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Sample records for ionized tetrahydrofuran studied

  1. An (e, 2e + ion) study of low-energy electron-impact ionization and fragmentation of tetrahydrofuran with high mass and energy resolutions

    SciTech Connect

    Ren, Xueguang Pflüger, Thomas; Weyland, Marvin; Baek, Woon Yoon; Rabus, Hans; Ullrich, Joachim; Dorn, Alexander

    2014-10-07

    We study the low-energy (E{sub 0} = 26 eV) electron-impact induced ionization and fragmentation of tetrahydrofuran using a reaction microscope. All three final-state charged particles, i.e., two outgoing electrons and one fragment ion, are detected in triple coincidence such that the momentum vectors and, consequently, the kinetic energies for charged reaction products are determined. The ionic fragments are clearly identified in the experiment with a mass resolution of 1 amu. The fragmentation pathways of tetrahydrofuran are investigated by measuring the ion kinetic energy spectra and the binding energy spectra where an energy resolution of 1.5 eV has been achieved using the recently developed photoemission electron source. Here, we will discuss the fragmentation reactions for the cations C{sub 4}H{sub 8}O{sup +}, C{sub 4}H{sub 7}O{sup +}, C{sub 2}H{sub 3}O{sup +}, C{sub 3}H{sub 6}{sup +}, C{sub 3}H{sub 5}{sup +}, C{sub 3}H{sub 3}{sup +}, CH{sub 3}O{sup +}, CHO{sup +}, and C{sub 2}H{sub 3}{sup +}.

  2. Tetrahydrofuran

    Integrated Risk Information System (IRIS)

    Tetrahydrofuran ; CASRN 109 - 99 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic E

  3. Theoretical and experimental quantification of doubly and singly differential cross sections for electron-induced ionization of isolated tetrahydrofuran molecules

    NASA Astrophysics Data System (ADS)

    Champion, Christophe; Quinto, Michele A.; Bug, Marion U.; Baek, Woon Y.; Weck, Philippe F.

    2014-07-01

    Electron-induced ionization of the tetrahydrofuran molecule, the commonly used surrogate of the DNA sugar-phosphate backbone, is theoretically described in this study within the 1st Born approximation. Comparisons between theory and recent experiments are reported in terms of doubly and singly differential cross sections.

  4. Experimental and theoretical triple-differential cross sections for tetrahydrofuran ionized by low-energy 26-eV-electron impact

    NASA Astrophysics Data System (ADS)

    Ali, Esam; Ren, XueGuang; Dorn, Alexander; Ning, Chuangang; Colgan, James; Madison, Don

    2016-06-01

    We report an experimental and theoretical study of low-energy electron-impact ionization of tetrahydrofuran, which is a molecule of biological interest. The experiments were performed using an advanced reaction microscope specially built for electron-impact ionization studies. The theoretical calculations were performed within the molecular three-body distorted-wave model. Reasonably good agreement is found between experiment and theory.

  5. Cross sections for ionization of tetrahydrofuran by protons at energies between 300 and 3000 keV

    NASA Astrophysics Data System (ADS)

    Wang, Mingjie; Rudek, Benedikt; Bennett, Daniel; de Vera, Pablo; Bug, Marion; Buhr, Ticia; Baek, Woon Yong; Hilgers, Gerhard; Rabus, Hans

    2016-05-01

    Double-differential cross sections for ionization of tetrahydrofuran by protons with energies from 300 to 3000 keV were measured at the Physikalisch-Technische Bundesanstalt ion accelerator facility. The electrons emitted at angles between 15∘ and 150∘ relative to the ion-beam direction were detected with an electrostatic hemispherical electron spectrometer. Single-differential and total ionization cross sections have been derived by integration. The experimental results are compared to the semiempirical Hansen-Kocbach-Stolterfoht model as well as to the recently reported method based on the dielectric formalism. The comparison to the latter showed good agreement with experimental data in a broad range of emission angles and energies of secondary electrons. The scaling property of ionization cross sections for tetrahydrofuran was also investigated. Compared to molecules of different size, the ionization cross sections of tetrahydrofuran were found to scale with the number of valence electrons at large impact parameters.

  6. Pseudorotation motion in tetrahydrofuran: an ab initio study.

    PubMed

    Rayón, Víctor M; Sordo, Jose A

    2005-05-22

    The use of different models based on experimental information about the observed level splitings, rotational constants, and far-infrared transition frequencies leads to different predictions on the equilibrium geometry for tetrahydrofuran. High-level ab initio calculations [coupled cluster singles, doubles (triples)/complete basis set (second order Moller-Plesset triple, quadrupole, quintuple)+zero-point energy(anharmonic)] suggest that the equilibrium conformation of tetrahydrofuran is an envelope C(s) structure. The theoretical geometrical parameters might be helpful to plan further microwave spectroscopic studies in order to get a physical interpretation of the measurements.

  7. Theoretical and experimental quantification of doubly and singly differential cross sections for electron-induced ionization of isolated tetrahydrofuran molecules

    DOE PAGESBeta

    Champion, Christophe; Quinto, Michele A.; Bug, Marion U.; Baek, Woon Y.; Weck, Philippe F.

    2014-07-29

    Electron-induced ionization of the commonly used surrogate of the DNA sugar-phosphate backbone, namely, the tetrahydrofuran molecule, is here theoretically described within the 1st Born approximation by means of quantum-mechanical approach. Comparisons between theory and recent experiments are reported in terms of doubly and singly differential cross sections.

  8. Theoretical and experimental quantification of doubly and singly differential cross sections for electron-induced ionization of isolated tetrahydrofuran molecules

    SciTech Connect

    Champion, Christophe; Quinto, Michele A.; Bug, Marion U.; Baek, Woon Y.; Weck, Philippe F.

    2014-07-29

    Electron-induced ionization of the commonly used surrogate of the DNA sugar-phosphate backbone, namely, the tetrahydrofuran molecule, is here theoretically described within the 1st Born approximation by means of quantum-mechanical approach. Comparisons between theory and recent experiments are reported in terms of doubly and singly differential cross sections.

  9. Inhalation developmental toxicology studies: Teratology study of tetrahydrofuran in mice and rats: Final report

    SciTech Connect

    Mast, T.J.; Evanoff, J.J.; Stoney, K.H.; Westerberg, R.B.; Rommereim, R.L.; Weigel, R.J.

    1988-08-01

    Tetrahydrofuran (THF), a four-carbon cyclic ether, is widely used as an industrial solvent. Although it has been used in large quantities for many years, few long-term toxicology studies, and no reproductive or developmental studies, have been conducted on THF. This study addresses the potential for THF to cause developmental toxicity in rodents by exposing Sprague-Dawley rats and Swiss (CD-1) mice to 0, 600, 1800, or 5000 ppm tetrahydrofuran (THF) vapors, 6 h/day, 7 dy/wk. Each treatment group consisted of 10 virgin females (for comparison), and approx.33 positively mated rats or mice. Positively mated mice were exposed on days 6--17 of gestation (dg), and rats on 6--19 dg. The day of plug or sperm detection was designated as O dg. Body weights were obtained throughout the study period, and uterine and fetal body weights were obtained at sacrifice (rats, 20 dg; mice, 18 dg). Implants were enumerated and their status recorded and live fetuses were examined for gross, visceral, skeletal, and soft-tissue craniofacial defects. 27 refs., 6 figs., 23 tabs.

  10. Analytical validation applied to simultaneous determination of solvents dichloromethane (DCM), methyl isobutyl ketone (MIBK), tetrahydrofuran (THF) and toluene (TOL) in urine by headspace extraction and injection on chromatographic system with a flame ionization detector

    NASA Astrophysics Data System (ADS)

    Muna, E. D. M.; Pereira, R. P.

    2016-07-01

    The determination of the volatile organic solvents dichloromethane (DCM), methyl isobutyl ketone (MIBK), tetrahydrofuran (THF) and toluene (TOL) is applied on toxicological monitoring of employees in various industrial activities. The gas chromatography technique with flame ionization detector and headspace injection system has been applied. The analytical procedure developed allows the simultaneous determination of the above-mentioned solvents and the accuracy of the method was tested following the INMETRO guidelines through the DOQ-CGRE 008 Rev.04-July/2011.

  11. Observations related to tetrahydrofuran and methane hydrates for laboratory studies of hydrate-bearing sediments

    NASA Astrophysics Data System (ADS)

    Lee, J. Y.; Yun, T. S.; Santamarina, J. C.; Ruppel, C.

    2007-06-01

    The interaction among water molecules, guest gas molecules, salts, and mineral particles determines the nucleation and growth behavior of gas hydrates in natural sediments. Hydrate of tetrahydrofuran (THF) has long been used for laboratory studies of gas hydrate-bearing sediments to provide close control on hydrate concentrations and to overcome the long formation history of methane hydrate from aqueous phase methane in sediments. Yet differences in the polarizability of THF (polar molecule) compared to methane (nonpolar molecule) raise questions about the suitability of THF as a proxy for methane in the study of hydrate-bearing sediments. From existing data and simple macroscale experiments, we show that despite its polar nature, THF's large molecular size results in low permittivity, prevents it from dissolving precipitated salts, and hinders the solvation of ions on dry mineral surfaces. In addition, the interfacial tension between water and THF hydrate is similar to that between water and methane hydrate. The processes that researchers choose for forming hydrate in sediments in laboratory settings (e.g., from gas, liquid, or ice) and the pore-scale distribution of the hydrate that is produced by each of these processes likely have a more pronounced effect on the measured macroscale properties of hydrate-bearing sediments than do differences between THF and methane hydrates themselves.

  12. Observations related to tetrahydrofuran and methane hydrates for laboratory studies of hydrate-bearing sediments

    USGS Publications Warehouse

    Lee, J.Y.; Yun, T.S.; Santamarina, J.C.; Ruppel, C.

    2007-01-01

    The interaction among water molecules, guest gas molecules, salts, and mineral particles determines the nucleation and growth behavior of gas hydrates in natural sediments. Hydrate of tetrahydrofuran (THF) has long been used for laboratory studies of gas hydrate-bearing sediments to provide close control on hydrate concentrations and to overcome the long formation history of methane hydrate from aqueous phase methane in sediments. Yet differences in the polarizability of THF (polar molecule) compared to methane (nonpolar molecule) raise questions about the suitability of THF as a proxy for methane in the study of hydrate-bearing sediments. From existing data and simple macroscale experiments, we show that despite its polar nature, THF's large molecular size results in low permittivity, prevents it from dissolving precipitated salts, and hinders the solvation of ions on dry mineral surfaces. In addition, the interfacial tension between water and THF hydrate is similar to that between water and methane hydrate. The processes that researchers choose for forming hydrate in sediments in laboratory settings (e.g., from gas, liquid, or ice) and the pore-scale distribution of the hydrate that is produced by each of these processes likely have a more pronounced effect on the measured macroscale properties of hydrate-bearing sediments than do differences between THF and methane hydrates themselves.

  13. Experimental study on the effect of ammonia on the phase behavior of tetrahydrofuran clathrates.

    PubMed

    Vu, Tuan Hoang; Gloesener, Elodie; Choukroun, Mathieu; Ibourichene, Anaïs; Hodyss, Robert

    2014-11-26

    Clathrate hydrates, ice-like crystalline compounds in which small guest molecules are enclosed inside cages formed by tetrahedrally hydrogen-bonded water molecules, are naturally abundant on Earth and are generally expected to exist on icy celestial bodies. A prototypical example is Saturn's moon Titan, where dissociation of methane clathrates, a major crustal component, could contribute significantly to the replenishment of atmospheric methane. Ammonia is an important clathrate inhibiting agent that may be present (potentially at high concentrations) in Titan's interior. In this study, low-temperature Raman experiments are conducted to examine the dissociation point of tetrahydrofuran clathrates, an ambient-pressure analogue of methane clathrates, over a wide range of ammonia concentrations from 0 to 25 wt %. A phase diagram for the H2O-THF-NH3 system is generated, showing two main results: (i) ammonia lowers the dissociation point of clathrate hydrates to a similar extent compared to the melting of water ice and (ii) THF clathrate exhibits a "liquidus-like" behavior in the presence of ammonia, with a eutectic temperature of about 203.6 K. As temperatures higher than this estimated eutectic are anticipated within Titan's icy crust, these results imply that partial dissociation of clathrates can occur readily and may contribute to outgassing from the interior.

  14. Experimental study on the effect of ammonia on the phase behavior of tetrahydrofuran clathrates.

    PubMed

    Vu, Tuan Hoang; Gloesener, Elodie; Choukroun, Mathieu; Ibourichene, Anaïs; Hodyss, Robert

    2014-11-26

    Clathrate hydrates, ice-like crystalline compounds in which small guest molecules are enclosed inside cages formed by tetrahedrally hydrogen-bonded water molecules, are naturally abundant on Earth and are generally expected to exist on icy celestial bodies. A prototypical example is Saturn's moon Titan, where dissociation of methane clathrates, a major crustal component, could contribute significantly to the replenishment of atmospheric methane. Ammonia is an important clathrate inhibiting agent that may be present (potentially at high concentrations) in Titan's interior. In this study, low-temperature Raman experiments are conducted to examine the dissociation point of tetrahydrofuran clathrates, an ambient-pressure analogue of methane clathrates, over a wide range of ammonia concentrations from 0 to 25 wt %. A phase diagram for the H2O-THF-NH3 system is generated, showing two main results: (i) ammonia lowers the dissociation point of clathrate hydrates to a similar extent compared to the melting of water ice and (ii) THF clathrate exhibits a "liquidus-like" behavior in the presence of ammonia, with a eutectic temperature of about 203.6 K. As temperatures higher than this estimated eutectic are anticipated within Titan's icy crust, these results imply that partial dissociation of clathrates can occur readily and may contribute to outgassing from the interior. PMID:24940841

  15. Anisotropy in growth kinetics of tetrahydrofuran clathrate hydrate: a molecular dynamics study.

    PubMed

    Nada, Hiroki

    2009-04-01

    The growth kinetics of a tetrahydrofuran (THF) clathrate hydrate at the interface between the clathrate and an aqueous THF solution were investigated by means of a molecular dynamic simulation. The simulation was carried out for the interface of both the {100} and {111} planes of the THF clathrate. The simulation indicated the same anisotropic growth as that observed in real systems: the growth of the THF clathrate was much slower at the {111} interface than at the {100} interface. When the THF clathrate grew, THF molecules that were dissolved in the solution first were arranged at both large and small cage sites on the interface. Subsequently, the formation of cages by H(2)O molecules occurred in regions surrounded or sandwiched by those arranged THF molecules. As the formation of cages progressed, the THF molecules that had once been arranged at small cage sites gradually moved away from the sites, and finally the structure of the clathrate was completely formed. Simulation results strongly suggested that the rate-determining process for clathrate growth was the rearrangement of THF molecules at the interface from a disordered state to a state in which THF molecules were ideally arranged at large cage sites only. This rearrangement occurred much more slowly at the {111} interface than at the {100} interface, owing to the formation of a modified structure in which large and small cages were formed at opposite positions of the {111} interface. The anisotropic growth kinetics of the THF clathrate, which were obtained in this study, are consistent with the fact that growth shapes of THF clathrates in real systems are octahedral with flat {111} planes.

  16. Photofragmentation of tetrahydrofuran molecules in the vacuum-ultraviolet region via superexcited states studied by fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Wasowicz, Tomasz J.; Kivimäki, Antti; Dampc, Marcin; Coreno, Marcello; de Simone, Monica; Zubek, Mariusz

    2011-03-01

    Photofragmentation of tetrahydrofuran molecules in the vacuum-ultraviolet region, producing excited atomic and molecular fragments, has been studied over the energy range 14-68 eV using photon-induced fluorescence spectroscopy. Excited hydrogen atoms H(n), n = 3-11, have been detected by observation of the Hα to Hı lines of the Balmer series. The diatomic CH(A2Δ), CH(B2Σ-) and C2(d3Πg) fragments, which are excited to low vibrational and high rotational levels are identified by their A2Δ→X2Πr, B2Σ-→X2Πr and d3Πg→a3Πu emission bands, respectively. Dissociation efficiency curves for CH(A2Δ) and H(n), n = 3-7, have been obtained in the photon energy ranges from their appearance thresholds up to 68 eV. The appearance energies for CH(A2Δ) and H(n), n = 3-7, have been determined and are compared with estimated fragmentation energy limits in order to discuss the possible fragmentation processes. In the present studies, superexcited states of tetrahydrofuran are found, which dissociate into the above excited atomic and molecular fragments.

  17. Molecular dynamics study on the nucleation of methane + tetrahydrofuran mixed guest hydrate.

    PubMed

    Wu, Jyun-Yi; Chen, Li-Jen; Chen, Yan-Ping; Lin, Shiang-Tai

    2016-04-21

    The nucleation of methane (CH4), tetrahydrofuran (THF), and CH4 + THF hydrates are investigated by microsecond MD simulations. These three systems exhibit distinct structural developments in the aqueous phase quantified by the formation of cage structures of hydrogen bonded water molecules. The development of a cluster of cages in the CH4 system is limited by the scarce CH4 molecules in the solution, while in the THF system it is limited by the short lifetime of cages. In the CH4 + THF mixed guest system, a small cluster of caged CH4 molecules can be rapidly stabilized by abundant neighboring cages of THF molecules. Therefore, the induction time of the CH4 + THF mixed guest system is found to be significantly shorter than that of the pure CH4 and pure THF systems. Furthermore, the structure of cages found in the initially formed cage clusters are often different from the typical 5(12)6(n) (n = 0, 2, 3, 4) cages observed in clathrate hydrate systems. The cluster of cages may grow or transform into structure I or II clathrate hydrate in the later stages. PMID:26750660

  18. Acoustical studies of some derivatives of 1,5-benzodiazepines formamide and tetrahydrofuran solutions at 298.15 K

    NASA Astrophysics Data System (ADS)

    Baluja, S.; Movaliya, J.; Godvani, N.

    2009-12-01

    Some derivatives of 1,5-benzodiazepines have been synthesized and characterized by TLC, IR, NMR, and Mass Spectral data. The ultrasonic velocity, density and viscosity of these synthesized compounds have been measured in dimethyl formamide and tetrahydrofuran at 298.15 K. From these experimental data, various acoustical parameters such as isentropic compressibility, intermolecular free path length, molar compressibility, Rao’s molar sound function, relaxation strength, internal pressure, free volume etc., have been calculated which helps in understanding the molecular interactions occurring in these solutions.

  19. Inter- versus intra-molecular cyclization of tripeptides containing tetrahydrofuran amino acids: a density functional theory study on kinetic control.

    PubMed

    Kumar, N V Suresh; Priyakumar, U Deva; Singh, Harjinder; Roy, Saumya; Chakraborty, Tushar Kanti

    2012-07-01

    Density functional B3LYP method was used to investigate the preference of intra- and inter-molecular cyclizations of linear tripeptides containing tetrahydrofuran amino acids. Two distinct model pathways were conceived for the cyclization reaction, and all possible transition states and intermediates were located. Analysis of the energetics indicate intermolecular cyclization being favored by both thermodynamic and kinetic control. Geometric and NBO analyses were performed to explain the trends obtained along both the reaction pathways. Conceptual density functional theory-based reactive indices also show that reaction pathways leading to intermolecular cyclization of the tripeptides are relatively more facile compared to intramolecular cyclization.

  20. Synthetic studies towards 1α-hydroxysolasodine from diosgenin and the unexpected tetrahydrofuran ring opening in the Birch reduction process.

    PubMed

    Liu, Chao; Xie, Fei; Zhao, Guo-Dong; Wang, De-Feng; Lou, Hong-Xiang; Liu, Zhao-Peng

    2015-12-01

    The synthesis of 1α-hydroxysolasodine from diosgenin was attempted. The Pd/C catalyst mediated dehydrogenation of diosgenin generated the 1,4,6-trien-3-one (3), which was reacted with Ac2O in pyridine in the presence of a catalytic amount of POCl3 followed by hydrolysis to give the 22-hydroxyfurostan (4) in 65% yield. Conversion of the primary 26-OH group into the azide and simultaneously 22-OH dehydration were achieved in one step by Mitsunobu reaction. Treatment of the (25R)-26-azidofurosta-1,4,6,20(22)-tetraen-3-one (5) with chlorotrimethylsilane (TMSCl)/NaI/MeCN and cyclisation in situ provided the (22R,25R)-spirosola-1,4,6-trien-3-one (6) in good yield. Stereoselective and regioselective epoxidation of trienone (6) with 30% H2O2 and 5% NaOH in methanol gave the 1α,2α-epoxy-(22R,25R)-spirosola-4,6-dien-3-one (7). Birch reduction of the epoxide (7) with Li/NH3 in THF followed by the treatment with NH4Cl, however, failed to generate the expected 1α-hydroxysolasodine, but provided a tetrahydrofuran ring opening product, (22S,25R)-1α,16β-dihydroxy-22,26-epiminocholest-4-en-3-one (8). Compounds 3 and 5-8 as well as solasodine were evaluated for their cell growth inhibitory activities against human prostate cancer PC3, human cervical carcinoma Hela, and human hepatoma HepG2 cells. At the concentration of 10 μM, only epoxide 7 displayed moderate inhibitory rates towards these cells (40-54%). PMID:26476186

  1. Structure and component dynamics in binary mixtures of poly(2-(dimethylamino)ethyl methacrylate) with water and tetrahydrofuran: A diffraction, calorimetric, and dielectric spectroscopy study.

    PubMed

    Goracci, G; Arbe, A; Alegría, A; Su, Y; Gasser, U; Colmenero, J

    2016-04-21

    We have combined X-ray diffraction, neutron diffraction with polarization analysis, small angle neutron scattering,differential scanning calorimetry, and broad band dielectric spectroscopy to investigate the structure and dynamics of binary mixtures of poly(2-(dimethylamino)ethyl methacrylate) with either water or tetrahydrofuran (THF) at different concentrations. Aqueous mixtures are characterized by a highly heterogeneous structure where water clusters coexist with an underlying nano-segregation of main chains and side groups of the polymeric matrix. THF molecules are homogeneously distributed among the polymeric nano-domains for concentrations of one THF molecule/monomer or lower. A more heterogeneous situation is found for higher THF amounts, but without evidences for solvent clusters. In THF-mixtures, we observe a remarkable reduction of the glass-transition temperature which is enhanced with increasing amount of solvent but seems to reach saturation at high THF concentrations. Adding THF markedly reduces the activation energy of the polymer β-relaxation. The presence of THF molecules seemingly hinders a slow component of this process which is active in the dry state. The aqueous mixtures present a strikingly broad glass-transition feature, revealing a highly heterogeneous behavior in agreement with the structural study. Regarding the solvent dynamics, deep in the glassy state all data can be described by an Arrhenius temperature dependence with a rather similar activation energy. However, the values of the characteristic times are about three orders of magnitude smaller for THF than for water. Water dynamics display a crossover toward increasingly higher apparent activation energies in the region of the onset of the glass transition, supporting its interpretation as a consequence of the freezing of the structuralrelaxation of the surrounding matrix. The absence of such a crossover (at least in the wide dynamic window here accessed) in THF is attributed to

  2. Low latitude middle atmosphere ionization studies

    NASA Technical Reports Server (NTRS)

    Bassi, J. P.

    1976-01-01

    Low latitude middle atmosphere ionization was studied with data obtained from three blunt conductivity probes and one Gerdien condenser. An investigation was conducted into the effects of various ionization sources in the 40 to 65 Km altitude range. An observed enhancement of positive ion conductivity taking place during the night can be explained by an atmsopheric effect, with cosmic rays being the only source of ionization only if the ion-ion recombination coefficient (alpha sub i) is small(10 to the -7 power cu cm/s) and varies greatly with altitude. More generally accepted values of alpha sub i ( approximately equal to 3x10 to the -7 power cu cm/s) require an additional source of ionization peaking at about 65 Km, and corresponding approximately to the integrated effect of an X-ray flux measured on a rocket flown in conjunction with the ionization measurements. The reasonable assumption of an alpha sub i which does not vary with altitude in the 50-70 Km range implies an even greater value alpha sub i and a more intense and harder X-ray spectrum.

  3. Study of collective effect in ionization cooling

    SciTech Connect

    Huang, D.; Ng, K.Y.; Roberts, T.J.; /MUONS Inc., Batavia

    2009-09-01

    As a charged particle passes through a non-gaseous medium, it polarizes the medium and induces wake fields behind it. Same thing happens in ionization cooling. The interaction with wake fields perturbs the stopping power of beam particles. The perturbation strongly depends on the densities of both the incident beam and the medium. To understand this collective effect, detailed studies have been carried out. Both analytic and simulation results are obtained and compared.

  4. Transition-metal triflate catalyzed unprecedented formation of oxime ketals of tetrahydrofuran via C-H functionalization

    NASA Astrophysics Data System (ADS)

    Shafi, Syed

    2015-02-01

    Benzaldehyde O-tetrahydrofuran-2-yl oximes were formed through the C-H functionalization from the reaction between benzaldoximes and aqueous tetrahydrofuran catalyzed by water tolerant transition metal triflates (Lewis acids). The formation of oxime ketal has been confirmed from 2D NMR analysis (HMBC and HSQC studies).

  5. 21 CFR 178.3950 - Tetrahydrofuran.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... of articles intended for packaging, transporting, or storing foods, subject to the provisions of this... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Tetrahydrofuran. 178.3950 Section 178.3950 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR...

  6. 21 CFR 178.3950 - Tetrahydrofuran.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... packaging, transporting, or storing foods, subject to the provisions of this section. (a) It is used as a... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Tetrahydrofuran. 178.3950 Section 178.3950 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED)...

  7. 21 CFR 178.3950 - Tetrahydrofuran.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... the fabrication of articles intended for packaging, transporting, or storing foods, subject to the... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Tetrahydrofuran. 178.3950 Section 178.3950 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD...

  8. 21 CFR 178.3950 - Tetrahydrofuran.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... the fabrication of articles intended for packaging, transporting, or storing foods, subject to the... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Tetrahydrofuran. 178.3950 Section 178.3950 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD...

  9. 21 CFR 178.3950 - Tetrahydrofuran.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... the fabrication of articles intended for packaging, transporting, or storing foods, subject to the... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Tetrahydrofuran. 178.3950 Section 178.3950 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD...

  10. Liquid-to-glass transition of tetrahydrofuran and 2-methyltetrahydrofuran

    NASA Astrophysics Data System (ADS)

    Tan, Rong-Ri; Shen, Xin; Hu, Lin; Zhang, Feng-Shou

    2012-08-01

    Both tetrahydrofuran (THF) and 2-methyltetrahydrofuran (MTHF) are studied systematically at desired temperatures using molecular dynamics simulations. The results show that the calculated densities are well consistent with experiment. Their glass transition temperatures are obtained: 115 K ~ 130 K for THF and 131 K ~ 142 K for MTHF. The calculated results from the dipolar orientational time correlation functions indicate that the “long time" behavior is often associated with a glass transition. From the radial and spatial distributions, we also find that the methyl has a direct impact on the structural symmetry of molecules, which leads to the differences of physical properties between THF and MTHF.

  11. Structure and reactivity of lithium amides. /sup 6/Li, /sup 13/C, and /sup 15/N NMR spectroscopic studies and colligative measurements of lithium diphenylamide and lithium diphenylamide-lithium bromide complex solvated by tetrahydrofuran

    SciTech Connect

    DePue, J.S.; Collum, D.B.

    1988-08-03

    /sup 6/Li, /sup 13/C, and /sup 15/N NMR spectroscopic studies of lithium diphenylamide in THF/hydrocarbon solutions (THF = tetrahydrofuran) detected two different species. /sup 6/Li and /sup 15/N NMR spectroscopic studies of (/sup 6/Li, /sup 15/N)lithium diphenylamide showed the species observed at low THF concentrations to be a cyclic oligomer. Structural analogies provided strong support for a dimer while colligative measurements at 0/degrees/C indicated the dimer to be di- or trisolvated. On the basis of the observed mass action effects, the species appearing at intermediate THF concentrations is assigned as a contact or solvent-separated ion-paired monomer. Lithium diphenylamide forms a 1:1 adduct with lithium bromide at low THF concentrations. A combination of /sup 6/Li-/sup 15/N double labeling studies and colligative measurements supports a trisolvated cyclic mixed dimer structure. Although detailed spectroscopic studies at elevated THF concentrations were precluded by high fluctionality, the similarity of the /sup 13/C chemical shifts of lithium diphenylamide in the presence and absence of lithium bromide provide indirect evidence that the mixed dimer undergoes a THF concentration dependent dissociation to the monomeric amide and free lithium bromide. 24 references, 9 figures, 2 tables.

  12. Simulation study of the ionizing front in the critical ionization velocity phenomenon

    NASA Technical Reports Server (NTRS)

    Machida, S.; Goertz, C. K.; Lu, G.

    1988-01-01

    The simulation of the critical ionization velocity for a neutral gas cloud moving across the static magnetic field is presented. A low-beta plasma is studied, using a two and a half-dimensional electrostatic code linked with the Plasma and Neutral Interaction Code (Goertz and Machida, 1987). The physics of the ionizing front and the instabilities which occur there are discussed. Results are presented from four numerical runs designed so that the effects of the charge separation field can be distinguished from the wave heating.

  13. Trehalose promotes Rhodococcus sp. strain YYL colonization in activated sludge under tetrahydrofuran (THF) stress

    PubMed Central

    He, Zhixing; Zhang, Kai; Wang, Haixia; Lv, Zhenmei

    2015-01-01

    Few studies have focused on the role of compatible solutes in changing the microbial community structure in bioaugmentation systems. In this study, we investigated the influence of trehalose as a biostimulant on the microbial community in tetrahydrofuran (THF)-treated wastewater bioaugmentation systems with Rhodococcus sp. YYL. Functional gene profile changes were used to study the variation in the microbial community. Soluble di-iron monooxygenases (SDIMO), particularly group-5 SDIMOs (i.e., tetrahydrofuran and propane monooxygenases), play a significant role in the initiation of the ring cleavage of tetrahydrofuran. Group-5 SDIMOs genes are enriched upon trehalose addition, and exogenous tetrahydrofuran monooxygenase (thmA) genes can successfully colonize bioaugmentation systems. Cytochrome P450 monooxygenases (P450s) have a significant role in catalyzing the region- and stereospecific oxidation of non-activated hydrocarbons, and THF was reported to inhibit P450s in the environment. The CYP153 family was chosen as a representative P450 to study the inhibitory effects of THF. The results demonstrated that CYP153 family genes exhibited significant changes upon THF treatment and that trehalose helped maintain a rich diversity and high abundance of CYP153 family genes. Biostimulation with trehalose could alleviate the negative effects of THF stress on microbial diversity in bioaugmentation systems. Our results indicated that trehalose as a compatible solute plays a significant role for environmental strains under extreme conditions. PMID:26029182

  14. Experimental Resonance Enhanced Multiphoton Ionization (REMPI) studies of small molecules

    NASA Technical Reports Server (NTRS)

    Dehmer, J. L.; Dehmer, P. M.; Pratt, S. T.; Ohalloran, M. A.; Tomkins, F. S.

    1987-01-01

    Resonance enhanced multiphoton ionization (REMPI) utilizes tunable dye lasers to ionize an atom or molecule by first preparing an excited state by multiphoton absorption and then ionizing that state before it can decay. This process is highly selective with respect to both the initial and resonant intermediate states of the target, and it can be extremely sensitive. In addition, the products of the REMPI process can be detected as needed by analyzing the resulting electrons, ions, fluorescence, or by additional REMPI. This points to a number of exciting opportunities for both basic and applied science. On the applied side, REMPI has great potential as an ultrasensitive, highly selective detector for trace, reactive, or transient species. On the basic side, REMPI affords an unprecedented means of exploring excited state physics and chemistry at the quantum-state-specific level. An overview of current studies of excited molecular states is given to illustrate the principles and prospects of REMPI.

  15. IRIS Toxicological Review of Tetrahydrofuran (Thf) (External Review Draft)

    EPA Science Inventory

    EPA is conducting a peer review and public comment of the scientific basis supporting the human health hazard and dose-response assessment of tetrahydrofuran (THF) that when finalized will appear on the Integrated Risk Information System (IRIS) database.

  16. Biodegradation kinetics of tetrahydrofuran, benzene, toluene, and ethylbenzene as multi-substrate by Pseudomonas oleovorans DT4.

    PubMed

    Chen, Dong-Zhi; Ding, Yun-Feng; Zhou, Yu-Yang; Ye, Jie-Xu; Chen, Jian-Meng

    2015-01-01

    The biodegradation kinetics of tetrahydrofuran, benzene (B), toluene (T), and ethylbenzene (E) were systematically investigated individually and as mixtures by a series of aerobic batch degradation experiments initiated by Pseudomonas oleovorans DT4. The Andrews model parameters, e.g., maximum specific growth rates (μmax), half saturation, and substrate inhibition constant, were obtained from single-substrate experiments. The interaction parameters in the sum kinetics model (SKIP) were obtained from the dual substrates. The μmax value of 1.01 for tetrahydrofuran indicated that cell growth using tetrahydrofuran as carbon source was faster than the growth on B (μmax, B = 0.39) or T (μmax, T = 0.39). The interactions in the dual-substrate experiments, including genhancement, inhibition, and co-metabolism, in the mixtures of tetrahydrofuran with B or T or E were identified. The degradation of the four compounds existing simultaneously could be predicted by the combination of SKIP and co-metabolism models. This study is the first to quantify the interactions between tetrahydrofuran and BTE. PMID:25561017

  17. Biodegradation Kinetics of Tetrahydrofuran, Benzene, Toluene, and Ethylbenzene as Multi-substrate by Pseudomonas oleovorans DT4

    PubMed Central

    Chen, Dong-Zhi; Ding, Yun-Feng; Zhou, Yu-Yang; Ye, Jie-Xu; Chen, Jian-Meng

    2014-01-01

    The biodegradation kinetics of tetrahydrofuran, benzene (B), toluene (T), and ethylbenzene (E) were systematically investigated individually and as mixtures by a series of aerobic batch degradation experiments initiated by Pseudomonas oleovorans DT4. The Andrews model parameters, e.g., maximum specific growth rates (μmax), half saturation, and substrate inhibition constant, were obtained from single-substrate experiments. The interaction parameters in the sum kinetics model (SKIP) were obtained from the dual substrates. The μmax value of 1.01 for tetrahydrofuran indicated that cell growth using tetrahydrofuran as carbon source was faster than the growth on B (μmax, B = 0.39) or T (μmax, T = 0.39). The interactions in the dual-substrate experiments, including genhancement, inhibition, and co-metabolism, in the mixtures of tetrahydrofuran with B or T or E were identified. The degradation of the four compounds existing simultaneously could be predicted by the combination of SKIP and co-metabolism models. This study is the first to quantify the interactions between tetrahydrofuran and BTE. PMID:25561017

  18. Theoretical studies of photoexcitation and ionization in H2O

    NASA Technical Reports Server (NTRS)

    Diercksen, G. H. F.; Kraemer, W. P.; Rescigno, T. N.; Bender, C. F.; Mckoy, B. V.; Langhoff, S. R.; Langhoff, P. W.

    1982-01-01

    Theoretical studies using Franck-Condon and static-exchange approximations are reported for the complete dipole excitation and ionization spectrum in H2O, where (1) large Cartesian Gaussian basis sets are used to represent the required discrete and continuum electronic eigenfunctions at the ground state equilibrium geometry, and (2) previously devised moment-theory techniques are employed in constructing the continuum oscillator-strength densities from the calculated spectra. Comparisons are made of the calculated excitation and ionization profiles with recent experimental photoabsorption studies and corresponding spectral assignments, electron impact-excitation cross sections, and dipole and synchrotron-radiation studies of partial-channel photoionization cross sections. The calculated partial-channel cross sections are found to be atomic-like, and dominated by 2p-kd components. It is suggested that the latter transition couples with the underlying 1b(1)-kb(1) channel, accounting for a prominent feature in recent synchrotron-radiation measurements.

  19. Cleave and capture chemistry illustrated through bimetallic-induced fragmentation of tetrahydrofuran

    NASA Astrophysics Data System (ADS)

    Mulvey, Robert E.; Blair, Victoria L.; Clegg, William; Kennedy, Alan R.; Klett, Jan; Russo, Luca

    2010-07-01

    The cleavage of ethers is commonly encountered in organometallic chemistry, although rarely studied in the context of new, emerging bimetallic reagents. Recently, it was reported that a bimetallic sodium-zinc base can deprotonate cyclic tetrahydrofuran under mild conditions without opening its heterocyclic (OC4) ring. In marked contrast to this synergic sedation, herein we show that switching to the more reactive sodium-magnesium or sodium-manganese bases promotes cleavage of at least six bonds in tetrahydrofuran, but uniquely the ring fragments are captured in separate crystalline complexes. Oxide fragments occupy guest positions in bimetallic, inverse crown ethers and C4 fragments ultimately appear in bimetallated butadiene molecules. These results demonstrate the special synergic reactivity that can be executed by bimetallic reagents, which include the ability to capture and control, and thereby study, reactive fragments from sensitive substrates.

  20. Cleave and capture chemistry illustrated through bimetallic-induced fragmentation of tetrahydrofuran.

    PubMed

    Mulvey, Robert E; Blair, Victoria L; Clegg, William; Kennedy, Alan R; Klett, Jan; Russo, Luca

    2010-07-01

    The cleavage of ethers is commonly encountered in organometallic chemistry, although rarely studied in the context of new, emerging bimetallic reagents. Recently, it was reported that a bimetallic sodium-zinc base can deprotonate cyclic tetrahydrofuran under mild conditions without opening its heterocyclic (OC(4)) ring. In marked contrast to this synergic sedation, herein we show that switching to the more reactive sodium-magnesium or sodium-manganese bases promotes cleavage of at least six bonds in tetrahydrofuran, but uniquely the ring fragments are captured in separate crystalline complexes. Oxide fragments occupy guest positions in bimetallic, inverse crown ethers and C(4) fragments ultimately appear in bimetallated butadiene molecules. These results demonstrate the special synergic reactivity that can be executed by bimetallic reagents, which include the ability to capture and control, and thereby study, reactive fragments from sensitive substrates. PMID:20571579

  1. Thermodynamic Functions of Solvation of Hydrocarbons, Noble Gases, and Hard Spheres in Tetrahydrofuran-Water Mixtures.

    PubMed

    Sedov, I A; Magsumov, T I

    2015-07-16

    Thermodynamic solvation properties of mixtures of water with tetrahydrofuran at 298 K are studied. The Gibbs free energies and enthalpies of solvation of n-octane and toluene are determined experimentally. For molecular dynamics simulations of the binary solvent, we have modified a TraPPE-UA model for tetrahydrofuran and combined it with the SPC/E potential for water. The excess thermodynamic functions of neon, xenon, and hard spheres with two different radii are calculated using the particle insertion method. Simulated and real systems share the same characteristic trends for the thermodynamic functions. A maximum is present on dependencies of the enthalpy of solvation from the composition of solvent at 70-90 mol % water, making it higher than in both of the cosolvents. It is caused by a high enthalpy of cavity formation in the mixtures rich with water due to solvent reorganization around the cavity, which is shown by calculation of the enthalpy of solvation of hard spheres. Addition of relatively small amounts of tetrahydrofuran to water effectively suppresses the hydrophobic effect, leading to a quick increase of both the entropy and enthalpy of cavity formation and solvation of low polar molecules. PMID:26115405

  2. Laser ionization/MS study of smog formation

    SciTech Connect

    Hewitt, A.D.; Lee, C.M.; Quimpo, B.C.

    1995-12-01

    Resonance-enhanced multiphoton ionization/time-of-flight mass spectrometry (REMPI/TOFMS) is a highly sensitive and selective technique which we are using to study atmospheric chemistry kinetics and reaction mechanisms. We are presently focusing our attention on toluene, the most abundant of the aromatic hydrocarbons in the troposphere, in order to understand the oxidation pathways which lead to smog formation. Our most recent results monitoring toluene and products of the OH + toluene reaction will be discussed, as well as our future plans to detect short-lived reaction intermediates, such as the methylhydroxycyclohexadienyl radical, formed by the addition of OH to the aromatic ring of toluene.

  3. Aspartame degradation study using electrospray ionization mass spectrometry.

    PubMed

    Pattanaargson, S; Sanchavanakit, C

    2000-01-01

    Electrospray mass spectrometry was used to simultaneously determine aspartame (APM) and five of its degradation products; aspartic acid, aspartylphenylalanine, 5-benzyl-3,6-dioxo-2-piperazieacetic acid (diketopiperazine), phenylalanine, and phenylalanine methyl ester. Under the ionization conditions used, there was no interfering fragmentation for any of the six compounds, i.e., no fragmentation of the compound being tested into other species also being monitored. A study of APM degradation in solution at various pH's and at various temperatures using this method was performed.

  4. IRIS Toxicological Review of Tetrahydrofuran (THF) (Interagency Science Discussion Draft)

    EPA Science Inventory

    EPA is releasing the draft report, Toxicological Review of Tetrahydrofuran, that was distributed to Federal agencies and White House Offices for comment during the Science Discussion step of the IRIS Assessment Development Proc...

  5. Study of the surface ionization detector for gas chromatography.

    PubMed

    Li, Weiwei; Wu, Dapeng; Chen, Shiheng; Peng, Hong; Guan, Yafeng

    2011-09-23

    The structure of the surface ionization detector (SID) and the operation parameters of GC-SID were investigated to reduce peak tailing and to enhance sensitivity. The performances of the GC-SID, including its repeatability, linearity, sensitivity, selectivity, and tolerance towards water vapor, were evaluated systematically. Compared with nitrogen-phosphorus detector (NPD), the SID was able to detect fg level triethylamine, and selectively respond to alkylamines, some anilines, and some nitrogen heterocyclic compounds. Among alkylamines, the SID sensitivity to diisobutylamine was rather small. Even so, it was also still 10 times higher than that on NPD. The SID selectivity, defined as the sensitivity ratio between triethylamine and various tested non-nitrogen compounds, was higher than 10(6). It was found that the SID is highly tolerant towards water vapor, allowing direct injection of water sample. Finally, the GC-SID was applied to directly measure trace amines in headspace gases of rotted meat and trace simazine in tap water. The SID sensitivity to simazine was proven to be 5 times higher than that on flame ionization detector (FID). This study suggests that the SID is a promising GC detector. PMID:21839459

  6. Design of HIV-1 Protease Inhibitors with Amino-bis-tetrahydrofuran Derivatives as P2-Ligands to Enhance Backbone-Binding Interactions. Synthesis, Biological Evaluation, and Protein-Ligand X-ray Studies

    SciTech Connect

    Ghosh, Arun K.; Martyr, Cuthbert D.; Osswald, Heather L.; Sheri, Venkat Reddy; Kassekert, Luke A.; Chen, Shujing; Agniswamy, Johnson; Wang, Yuan-Fang; Hayashi, Hironori; Aoki, Manabu; Weber, Irene T.; Mitsuya, Hiroaki

    2015-10-30

    Structure-based design, synthesis, and biological evaluation of a series of very potent HIV-1 protease inhibitors are described. In an effort to improve backbone ligand–binding site interactions, we have incorporated basic-amines at the C4 position of the bis-tetrahydrofuran (bis-THF) ring. We speculated that these substituents would make hydrogen bonding interactions in the flap region of HIV-1 protease. Synthesis of these inhibitors was performed diastereoselectively. A number of inhibitors displayed very potent enzyme inhibitory and antiviral activity. Inhibitors 25f, 25i, and 25j were evaluated against a number of highly-PI-resistant HIV-1 strains, and they exhibited improved antiviral activity over darunavir. Two high resolution X-ray structures of 25f- and 25g-bound HIV-1 protease revealed unique hydrogen bonding interactions with the backbone carbonyl group of Gly48 as well as with the backbone NH of Gly48 in the flap region of the enzyme active site. These ligand–binding site interactions are possibly responsible for their potent activity.

  7. Extractive electrospray ionization mass spectrometry for uranium chemistry studies.

    PubMed

    Chen, Huanwen; Luo, Mingbiao; Xiao, Saijin; Ouyang, Yongzhong; Zhou, Yafei; Zhang, Xinglei

    2013-01-01

    Uranium chemistry is of sustainable interest. Breakthroughs in uranium studies make serious impacts in many fields including chemistry, physics, energy and biology, because uranium plays fundamentally important roles in these fields. Substantial progress in uranium studies normally requires development of novel analytical tools. Extractive electrospray ionization mass spectrometry (EESI-MS) is a sensitive technique for trace detection of various analytes in complex matrices without sample pretreatment. EESI-MS shows excellent performance for monitoring uranium species in various samples at trace levels since it tolerates extremely complex matrices. Therefore, EESI-MS is an alternative choice for studying uranium chemistry, especially when it combines ion trap mass spectrometry. In this presentation, three examples of EESI-MS for uranium chemistry studies will be given, illustrating the potential applications of EESI-MS in synthesis chemistry, physical chemistry, and analytical chemistry of uranium. More specifically, case studies on EESI-MS for synthesis and characterization of novel uranium species, and for rapid detection of uranium and its isotope ratios in various samples will be presented. Novel methods based on EESI-MS for screening uranium ores and radioactive iodine-129 will be presented. PMID:24349940

  8. Ionization of vitamin C in gas phase: Theoretical study.

    PubMed

    Abyar, Fatemeh; Farrokhpour, Hossein

    2016-07-01

    In this work, the gas phase ionization energies and photoelectron spectra of four important conformers of vitamin C were calculated. Symmetry adapted cluster/configuration interaction methodology employing the single and double excitation operators (SAC-CI SD-R) along with D95++(d,p) basis set were used for the calculations. Thermochemistry calculations were also performed on all possible conformers of vitamin C to find the relative stability of conformers in the gas phase. The calculated ionization bands of each conformer were assigned by calculating the contribution of natural bonding orbital (NBO) in the calculated canonical molecular orbitals involved in the ionization. SAC-CI calculations showed that the first ionization band of vitamin C is related to the π electrons of CC bond of the ring of molecule although, there is the lone electron pairs of oxygen atoms and π electrons of CO bond in the molecule. PMID:27092998

  9. New adjacent Bis-tetrahydrofuran Annonaceous acetogenins from Annona muricata.

    PubMed

    Chang, Fang-Rong; Liaw, Chih-Chuang; Lin, Chih-Yuan; Chou, Chi-Jung; Chiu, Hui-Fen; Wu, Yang-Chang

    2003-03-01

    Bioactivity-guided fractionation led to the isolation of two new Annonaceous acetogenins, annocatacin A ( 1). and annocatacin B ( 2). from the seeds and the leaves, respectively, of Annona muricata. Compounds 1 and 2 are the first examples where the adjacent bis-tetrahydrofuran ring system is located at C-15. The new structures were elucidated and characterized by spectral and chemical methods. Both Annonaceous acetogenins 1 and 2 showed significant in vitro cytotoxicity toward the human hepatoma cell lines, Hep G2 and 2,2,15, and were compared with the known adjacent bis-tetrahydrofuran acetogenins, neoannonin ( 3). desacetyluvaricin ( 4). bullatacin ( 5). asimicin ( 6). annoglaucin ( 7). squamocin ( 8). and rollimusin ( 9).

  10. Molecular Driving Forces behind the Tetrahydrofuran-Water Miscibility Gap.

    PubMed

    Smith, Micholas Dean; Mostofian, Barmak; Petridis, Loukas; Cheng, Xiaolin; Smith, Jeremy C

    2016-02-01

    The tetrahydrofuran-water binary system exhibits an unusual closed-loop miscibility gap (transitions from a miscible regime to an immiscible regime back to another miscible regime as the temperature increases). Here, using all-atom molecular dynamics simulations, we probe the structural and dynamical behavior of the binary system in the temperature regime of this gap at four different mass ratios, and we compare the behavior of bulk water and tetrahydrofuran. The changes in structure and dynamics observed in the simulations indicate that the temperature region associated with the miscibility gap is distinctive. Within the miscibility-gap temperature region, the self-diffusion of water is significantly altered and the second virial coefficients (pair-interaction strengths) show parabolic-like behavior. Overall, the results suggest that the gap is the result of differing trends with temperature of minor structural changes, which produces interaction virials with parabolic temperature dependence near the miscibility gap. PMID:26734991

  11. Single- and multi-photon ionization studies of organosulfur species

    SciTech Connect

    Cheung, Y.S.

    1999-02-12

    Accurate ionization energies (IE`s) for molecular species are used for prediction of chemical reactivity and are of fundamental importance to chemists. The IE of a gaseous molecule can be determined routinely in a photoionization or a photoelectron experiment. IE determinations made in conventional photoionization and photoelectron studies have uncertainties in the range of 3--100 meV (25--250 cm{sup {minus}1}). In the past decade, the most exciting development in the field of photoionization and photoelectron spectroscopy has been the availability of high resolution, tunable ultraviolet (UV) and vacuum ultraviolet (VUV) laser sources. The laser pulsed field ionization photoelectron (PFI-PE) scheme is currently the state-of-the-art photoelectron spectroscopic technique and is capable of providing photoelectron energy resolution close to the optical resolution. The author has focused attention on the photoionization processes of some sulfur-containing species. The studies of the photoionization and photodissociation on sulfur-containing compounds [such as CS{sub 2}, CH{sub 3}SH, CH{sub 3}SSCH{sub 3}, CH{sub 3}CH{sub 2}SCH{sub 2}CH{sub 3}, HSCH{sub 2}CH{sub 2}SH and C{sub 4}H{sub 4}S (thiophene) and sulfur-containing radicals, such as HS, CS, CH{sub 3}S, CH{sub 3}CH{sub 2}S and CH{sub 3}SS], have been the major subjects in the group because sulfur is an important species contributing to air pollution in the atmosphere. The modeling of the combustion and oxidation of sulfur compounds represents important steps for the control of both the production and the elimination of sulfur-containing pollutants. Chapter 1 is a general introduction of the thesis. Chapters 2 and 6 contain five papers published in, or accepted for publication in, academic periodicals. In Chapter 7, the progress of the construction in the laboratory of a new vacuum ultraviolet laser system equipped with a reflectron mass spectrometer is presented. Chapters 2 through 7 have been removed for separate

  12. Ionization efficiency studies for xenon ions with thesuperconducting ECR ion source VENUS

    SciTech Connect

    Leitner, Daniela; Lyneis, Claude M.; Todd, DamonS.; Tarvainen,Olli

    2007-06-05

    Ionization efficiency studies for high charge state xenon ions using a calibrated gas leak are presented. A 75% enriched {sup 129}Xe gas leak with a gas flow equivalent to 5.11p{mu}A was used in all the measurements. The experiments were performed at the VENUS (Versatile ECR ion source for Nuclear Science) ion source for 18 GHz, 28 GHz and double frequency operation. Overall, total ionization efficiencies close to 100% and ionization efficiencies into a single charge state up to 22% were measured. The influence of the biased disk on the ionization efficiency was studied and the results were somewhat surprising. When the biased disk was removed from the plasma chamber, the ionization efficiency was dramatically reduced for single frequency operation. However, using double frequency heating the ionization efficiencies achieved without the biased disk almost matched the ionization efficiencies achieved with the biased probe. In addition, we have studied the influence of the support gas on the charge state distribution of the xenon ions. Either pure oxygen or a mixture of oxygen and helium were used as support gases. The addition of a small amount of helium can increase the ionization efficiency into a single charge state by narrowing the charge state distribution. Furthermore by varying the helium flow the most efficient charge state can be shifted over a wide range without compromising the ionization efficiency. This is not possible using only oxygen as support gas. Results from these studies are presented and discussed.

  13. Lithium cycling performance in improved lithium hexafluoroarsenate/2-Methyl tetrahydrofuran electrolytes

    SciTech Connect

    Desjardins, C.D.; Cadge, T.G.; Casey, E.J.; Donaldson, G.; Salter, R.S.

    1985-03-01

    Lithium hexafluoroarsenate/2-methyl tetrahydrofuran electrolytes have been prepared, purified, and evaluated using half-cell galvanostatic lithium cycling, cyclic voltammetry, plus colorimetric, gas chromatographic, and UV absorption techniques. Superior electrolytes have been prepared yielding reproducible cycling efficiencies in excess of 97%. Static aging trials at ambient temperature clearly demonstrate deterioration in cycling performance with time. This decline in performance is related to electrolyte degradation, possibly arising from the formation of peroxides. However, studies of various battery testing regimes on 1M LiAsF/sub 6//2Me-THF electrolyte support the system' battery potential with respect to both rate capability and shelf-life characteristics.

  14. Preliminary studies of a new monitor ionization chamber.

    PubMed

    Yoshizumi, Maíra T; Vivolo, Vitor; Caldas, Linda V E

    2010-01-01

    A new monitor ionization chamber was developed at Instituto de Pesquisas Energéticas e Nucleares (IPEN) in order to monitor X-ray beams. The main difference of this monitor ionization chamber in relation to other monitor chambers is its geometry, which consists of a ring-shaped sensitive volume. Because of this geometry, the monitor chamber has a central hole through which the direct radiation beam passes. The operational characteristics of the monitor chamber were evaluated: saturation, ion collection efficiency and polarity effect. Besides these tests, the short- and medium-term stabilities of its response were also evaluated. During the tests the leakage current was always negligible. All results showed values within those recommended internationally (IEC, 1997. Medical electrical equipment-dosimeters with ionization chambers and/or semi-conductor detectors as used in X-ray diagnostic imaging. IEC 61674. International Electrotechnical Commission, Genève).

  15. Ionization and capture in water: a multi-differential cross sections study

    NASA Astrophysics Data System (ADS)

    Champion, Christophe; Galassi, Mariel E.; Weck, Philippe F.; Fojón, Omar; Hanssen, Jocelyn; Rivarola, Roberto D.

    2012-11-01

    Two quantum mechanical models (CB1 and CDW-EIS) are here presented to provide accurate multiple differential and total cross sections for describing the two most important ionizing processes, namely, ionization and capture induced by heavy charged particles in water. A detailed study of the influence of the target description on the cross section calculations is also provided.

  16. Elastic Scattering of Low-Energy Electrons byTetrahydrofuran

    SciTech Connect

    Trevisan, Cynthia S.; Orel, Ann E.; Rescigno, Thomas N.

    2006-05-09

    We present the results of ab initio calculations for elasticelectron scattering by tetrahydrofuran (THF) using the complex Kohnvariational method. We carried out fixed-nuclei calculations at theequilibrium geometry of the target molecule for incident electronenergies up to 20 eV. The calculated momentum transfer cross sectionsclearly reveal the presence of broad shape resonance behavior in the 8-10eV energy range, in agreement with recent experiments. The calculateddifferential cross sections at 20 eV, which include the effects of thelong-range electron-dipole interaction, are alsofound to be in agreementwith the most recent experimental findings.

  17. DNA fragmentation induced by ionizing radiation - Atomic Force Microscopy study .

    NASA Astrophysics Data System (ADS)

    Gudowska-Nowak, E.; Psonka, K.; Elsaesser, Th.; Brons, S.; Taucher-Scholz, G.

    DNA as a carrier of genetic information is considered to be the critical target for radiation induced damage Especially severe are DNA double-strand breaks DSBs formed when breaks occur in both strands of the molecule The DSBs production is determined by the spatial distribution of ionization events dependent on the physical properties of the energy deposition and the chemical environment of the DNA According to theoretical predictions high LET charged particle radiation induces lesions in close proximity forming so called clustered damage in the DNA Atomic Force Microscopy AFM was newly established as a technique allowing the direct visualization of DNA fragments resulting from DSBs induced in small DNA molecules plasmids by ionizing radiation We have used AFM to visualize the DNA fragmentation induced by heavy ions high LET radiation and to compare it to the fragmentation pattern obtained after X-rays low LET radiation Plasmid supercoiled DNA was irradiated in vitro with X-rays and 3 9 MeV u Ni ions within a dose range 0 -- 3000 Gy Afterwards the samples were analyzed using AFM which allowed the detection and length measurement of individual fragments with a nanometer resolution Recording of the length of the induced fragments allowed to distinguish between molecules broken by a single DSB or by multiple DSBs The fragment length distributions were derived for different doses and different radiation qualities The first results of the measurement of radiation-induced DNA fragmentation show an influence of radiation quality on

  18. Computational study on Kerr constants of neutral and ionized gases

    NASA Astrophysics Data System (ADS)

    Sato, M.; Kumada, A.; Hidaka, K.

    2015-08-01

    In order to quantitatively examine the measurement capability of Poisson's field using electro-optic Kerr-effect (EOKE), Kerr constants of neutral molecules and ions are examined by means of first principle calculations. We have systematically computed Kerr constants of neutral molecules and ions of several molecular symmetry groups, with consistent theory level and basis sets. Computed Kerr constants of neutral molecules (N2, CO2, SF6, and CF3I) ranging across two orders of magnitudes are within 50% error of the experimental values, which are comparable to the scattering between experimental values itself. The results show that SF6 has smaller Kerr constant due to its high molecular symmetry compared to those of N2 and CO2. In contrast, CF3I has large Kerr constant due to its permanent dipole. Computed Kerr constants for anions are larger by two orders of magnitude than those of neutral molecules, probably due to the shielding effect. For cations, the opposite holds true; however, due to anisotropic polarizability, computed Kerr constants for some cations are comparable to neutral molecules, while others show smaller values. The ratio of Kerr constants of ions to those of neutral molecules are at most 102; EOKE is valid for measuring electric field in weakly ionized gas whose ionization degree is smaller than 10-3.

  19. VUV Photo-processing of PAH Cations: Quantitative Study on the Ionization versus Fragmentation Processes

    NASA Astrophysics Data System (ADS)

    Zhen, Junfeng; Rodriguez Castillo, Sarah; Joblin, Christine; Mulas, Giacomo; Sabbah, Hassan; Giuliani, Alexandre; Nahon, Laurent; Martin, Serge; Champeaux, Jean-Philippe; Mayer, Paul M.

    2016-05-01

    Interstellar polycyclic aromatic hydrocarbons (PAHs) are strongly affected by the absorption of vacuum ultraviolet (VUV) photons in the interstellar medium (ISM), yet the branching ratio between ionization and fragmentation is poorly studied. This is crucial for the stability and charge state of PAHs in the ISM in different environments, affecting in turn the chemistry, the energy balance, and the contribution of PAHs to the extinction and emission curves. We studied the interaction of PAH cations with VUV photons in the 7-20 eV range from the synchrotron SOLEIL beamline, DESIRS. We recorded by action spectroscopy the relative intensities of photo-fragmentation and photo-ionization for a set of eight PAH cations ranging in size from 14 to 24 carbon atoms, with different structures. At photon energies below ˜13.6 eV fragmentation dominates for the smaller species, while for larger species ionization is immediately competitive after the second ionization potential (IP). At higher photon energies all species behave similarly; the ionization yield gradually increases, leveling off between 0.8 and 0.9 at ˜18 eV. Among isomers, PAH structure appears to mainly affect the fragmentation cross section but not the ionization cross section. We also measured the second IP for all species and the third IP for two of them; all are in good agreement with theoretical ones, confirming that PAH cations can be further ionized in the diffuse ISM. Determining actual PAH dication abundances in the ISM will require detailed modeling. Our measured photo-ionization yields for several PAH cations provide a necessary ingredient for such models.

  20. VUV photo-processing of PAH cations: quantitative study on the ionization versus fragmentation processes

    PubMed Central

    Zhen, Junfeng; Castillo, Sarah Rodriguez; Joblin, Christine; Mulas, Giacomo; Sabbah, Hassan; Giuliani, Alexandre; Nahon, Laurent; Martin, Serge; Champeaux, Jean-Philippe; Mayer, Paul M.

    2016-01-01

    Interstellar polycyclic aromatic hydrocarbons (PAHs) are strongly affected by the absorption of vacuum ultraviolet (VUV) photons in the interstellar medium (ISM), yet the branching ratio between ionization and fragmentation is poorly studied. This is crucial for the stability and charge state of PAHs in the ISM in different environments, affecting in turn the chemistry, the energy balance, and the contribution of PAHs to the extinction and emission curves. We studied the interaction of PAH cations with VUV photons in the 7 – 20 eV range from the synchrotron SOLEIL beamline, DESIRS. We recorded by action spectroscopy the relative intensities of photo-fragmentation and photo-ionization for a set of eight PAH cations ranging in size from 14 to 24 carbon atoms, with different structures. At photon energies below ~13.6 eV fragmentation dominates for the smaller species, while for larger species ionization is immediately competitive after the second ionization potential (IP). At higher photon energies, all species behave similarly, the ionization yield gradually increases, leveling off between 0.8 and 0.9 at ~18 eV. Among isomers, PAH structure appears to mainly affect the fragmentation cross section, but not the ionization cross section. We also measured the second IP for all species and the third IP for two of them, all are in good agreement with theoretical ones confirming that PAH cations can be further ionized in the diffuse ISM. Determining actual PAH dication abundances in the ISM will require detailed modeling. Our measured photo-ionization yields for several PAH cations provide a necessary ingredient for such models. PMID:27212712

  1. Rotational spectrum and internal dynamics of tetrahydrofuran-krypton.

    PubMed

    Gou, Qian; Feng, Gang; Evangelisti, Luca; Maris, Assimo; Marchini, Marianna; Velino, Biagio; Caminati, Walther

    2012-01-16

    The rotational spectrum of the tetrahydrofuran-krypton van der Waals complex has been investigated by pulsed-jet Fourier transform microwave spectroscopy. The spectra of the (84)Kr and (86)Kr isotopologues have been assigned and the krypton atom is located nearly over the oxygen atom, almost perpendicular to the COC plane. Each rotational transition is split into two component lines due to, according to the observed Coriolis coupling term between the tunneling states, the residual pseudorotational effects of the ring in the complex. The splitting between the two vibrational sublevels is 87.462(2) and 87.062(2) MHz for the (84)Kr and (86)Kr isotopologues, respectively. These splittings have been used to determine the barrier to inversion, B(2) = 67 cm(-1). The dissociation energy has been estimated to be 3.7 kJ  mol(-1) from centrifugal distortion effects.

  2. Vacuum Ultraviolet Pulsed Field Ionization-Photoelectron and Infrared-Photoinduced Rydberg Ionization Study of trans-1,3-butadiene

    SciTech Connect

    Hou, Yu; Woo, H. K.; Wang, P.; Xing, X.; Ng, Cheuk-Yiu; Lau, Kai Chung

    2008-09-17

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The vacuum ultraviolet (VUV) laser pulsed field ionization-photoelectron (PFI-PE) spectrum of trans-1,3-butadiene (trans-CH2==CHCH==CH2+) has been measured in the region of 0–1700 cm-1 above its ionization energy (IE) to probe the vibrational modes vi + (i=1–18) of trans-CH2==CHCH==CH2 +. The high-frequency vibrational modes vi + (i=19, 22, and 23) of trans-CH2==CHCH==CH2 + have also been probed by the VUV-infrared-photoinduced Rydberg ionization (VUV-IR-PIRI) measurement. On the basis of the semiempirical simulation of the origin VUV-PFI-PE band, the IE(trans-CH2==CHCH==CH2) is determined to be 73 150.1±1.5 cm-1 (9.06946±0.00019 eV). This value has been used to benchmark the state-of-the-art theoretical IE prediction based on the CCSD(T,Full)/CBS procedures, the calculation of which is reported in the present study. The vibrational bands observed in the VUV-PFI-PE and VUV-IR-PIRI spectra were assigned based on ab initio anharmonic vibrational frequencies and Franck–Condon factor calculations for the photoionization transitions. Combining the VUV-PFI-PE and VUV-IR-PIRI measurements, 17 fundamental vibrational frequencies of trans-CH2==CHCH==CH2 + have been determined, including v1 +=182±3, v2 +=300±3, v3 +=428±3, v4 +=514±3, v5 +=554±5, v6 + =901±3, v7 +=928±5, v8 +=994±3, v

  3. Spectroscopic Study of ThCl+ by Two-Photon Ionization

    NASA Astrophysics Data System (ADS)

    Bartlett, Joshua; VanGundy, Robert A.; Heaven, Michael; Peterson, Kirk

    2016-06-01

    Despite the irreplaceable role experimental data plays for evaluating the performance of computational predictions, diatomic actinide species have not received much spectroscopic attention. As an early actinide element, thorium-containing species are ideal candidates for these types of studies. The electronic structure is expected to be relatively simple compared to later actinides, and therefore allows straightforward assessment of calculations. Here, we have studied ThCl+ for the first time via resonant two-photon ionization of jet-cooled ThCl produced by laser ablation of the metal reacted with dilute Cl2. Laser-induced Fluorescence (LIF) spectra have been recorded for the neutral molecule from 16000 - 23500 cm-1 in search of a suitable intermediate state for subsequent two-photon ionization experiments. Monochromator dispersion of the fluorescence has recovered the ground state vibration and anharmonic constants of ThCl. Resonant Two-Photon Ionization (R2PI) within a time-of-flight mass spectrometer was used to confirm ThCl production, and Pulsed Field Ionization Zero Kinetic Energy photoelectron spectroscopy (PFI-ZEKE) has been performed to identify the ionization energy as well as several of the low-lying states of the ThCl+ molecule. These constants have been predicted at the CASPT2 and CCSD(T) levels of theory, and a discussion of the calculations' performance will be presented alongside the recorded spectra.

  4. Numerical studies of wall-plasma interactions and ionization phenomena in an ablative pulsed plasma thruster

    NASA Astrophysics Data System (ADS)

    Yang, Lei; Zeng, Guangshang; Tang, Haibin; Huang, Yuping; Liu, Xiangyang

    2016-07-01

    Wall-plasma interactions excited by ablation controlled arcs are very critical physical processes in pulsed plasma thrusters (PPTs). Their effects on the ionization processes of ablated vapor into discharge plasma directly determine PPT performances. To reveal the physics governing the ionization phenomena in PPT discharge, a modified model taking into account the pyrolysis effect of heated polytetrafluoroethylene propellant on the wall-plasma interactions was developed. The feasibility of the modified model was analyzed by creating a one-dimensional simulation of a rectangular ablative PPT. The wall-plasma interaction results based on this modified model were found to be more realistic than for the unmodified model; this reflects the dynamic changes of the inflow parameters during discharge in our model. Furthermore, the temporal and spatial variations of the different plasma species in the discharge chamber were numerically studied. The numerical studies showed that polytetrafluoroethylene plasma was mainly composed of monovalent ions; carbon and fluorine ions were concentrated in the upstream and downstream discharge chamber, respectively. The results based on this modified model were in good agreement with the experimental formation times of the various plasma species. A large number of short-lived and highly ionized carbon and fluorine species (divalent and trivalent ions) were created during initial discharge. These highly ionized species reached their peak density earlier than the singly ionized species.

  5. Epoxygenase Eicosanoids: Synthesis of Tetrahydrofuran-Diol Metabolites and Their Vasoactivity

    PubMed Central

    Falck, J. R.; Reddy, L. Manmohan; Byun, Kihwan; Campbell, William B.; Yi, Xiu-Yu

    2007-01-01

    Eight members of a recently identified family of tetrahydrofuran-diols (THFDs), originating from epoxyeicosatrienoic acids (EETs), were prepared stereospecifically from D-(+)-glucose. The THFDs potently induced relaxation of pre-contracted bovine arteries. PMID:17293113

  6. Hot-cavity studies for the Resonance Ionization Laser Ion Source

    NASA Astrophysics Data System (ADS)

    Henares, J. L.; Lecesne, N.; Hijazi, L.; Bastin, B.; Kron, T.; Lassen, J.; Le Blanc, F.; Leroy, R.; Osmond, B.; Raeder, S.; Schneider, F.; Wendt, K.

    2016-09-01

    The Resonance Ionization Laser Ion Source (RILIS) has emerged as an important technique in many Radioactive Ion Beam (RIB) facilities for its reliability, and ability to ionize target elements efficiently and element selectively. GISELE is an off-line RILIS test bench to study the implementation of an on-line laser ion source at the GANIL separator facility. The aim of this project is to determine the best technical solution which combines high selectivity and ionization efficiency with small ion beam emittance and stable long term operation. The ion source geometry was tested in several configurations in order to find a solution with optimal ionization efficiency and beam emittance. Furthermore, a low work function material was tested to reduce the contaminants and molecular sidebands generated inside the ion source. First results with ZrC ionizer tubes will be presented. Furthermore, a method to measure the energy distribution of the ion beam as a function of the time of flight will be discussed.

  7. Effects of ionization on stability of 1-methylcytosine - DFT and PCM studies.

    PubMed

    Raczyńska, Ewa D; Michalec, Piotr; Zalewski, Marcin; Sapuła, Mariusz

    2016-07-01

    Consequences of ionization were studied by quantum-chemical methods (DFT and PCM) for 1-methylcytosine (MC)-a model of the nucleobase cytosine (C) connected with sugar in DNA. For calculations, three prototropic tautomers (one amino and two imino forms) and two imino zwitterions were considered, including conformational or configurational isomerism of exo heterogroups. Ionization and interactions between neighboring groups affect intramolecular proton-transfers, geometric and thermodynamic parameters, and electron delocalization for individual isomers. We discovered that an imino isomer is present in the isomeric mixture in the highest amount for positively ionized MC. Its contribution in neutral and negatively ionized MC is considerably smaller. Acid-base parameters for selected radical ions were estimated in the gas phase and compared to those of neutral MC. Gas-phase acidity of radical cations is close to that of the conjugate acid of MC, and gas-phase basicity of radical anions is close to that of the conjugate base of MC. Various routes of amino-imino conversion between neutral and ionized isomers were considered. Energetic-barrier for intramolecular proton-transfer in MC is close to that in the parent system-formamidine. PMID:27259531

  8. Surface ionization mass spectrometry of drugs in the thermal and hyperthermal energy range -- a comparative study

    NASA Astrophysics Data System (ADS)

    Dagan, Shai; Amirav, Aviv; Fujü, Toshihiro

    1995-12-01

    Thermal and hyperthermal surface ionization (SI) mass spectra of nicotine, caffeine and lidocaine were obtained using a rhenium oxide surface. Thermal surface ionization was studied on an oxidized surface positioned inside an electron impact ion source, while hyperthermal surface ionization (HSI) was obtained upon seeding the compounds into a hydrogen or helium supersonic molecular beam that scattered from the rhenium oxide surface. Both HSI and SI provide rich, informative and complementary mass spectral information. The results indicate that SI follows thermal dissociation processes on the surface prior to the desorption of the ion, while in HSI no thermal equilibrium is established and the ionization process is impulsive, followed by mostly unimolecular ion dissociation. HSI mass spectra are similar to electron impact mass spectra in the fragment ion masses, but the observed relative intensities are different. HSI is a softer ionization method compared to SI, and enables the degree of ion fragmentation to be tuned so that it can be minimized to a low level at low molecular kinetic energy. In SI, limited control over the degree of fragmentation is possible through the surface temperature. The analytical mass spectrometric applications of SI and HSI are briefly mentioned.

  9. Numerical Study on Blast Wave Propagation Driven by Unsteady Ionization Plasma

    SciTech Connect

    Ogino, Yousuke; Sawada, Keisuke; Ohnishi, Naofumi

    2008-04-28

    Understanding the dynamics of laser-produced plasma is essential for increasing the available thrust and energy conversion efficiency from a pulsed laser to a blast wave in a gas-driven laser-propulsion system. The performance of a gas-driven laser-propulsion system depends heavily on the laser-driven blast wave dynamics as well as on the ionizing and/or recombining plasma state that sustains the blast wave. In this study, we therefore develop a numerical simulation code for a laser-driven blast wave coupled with time-dependent rate equations to explore the formation of unsteady ionizing plasma produced by laser irradiation. We will also examine the various properties of blast waves and unsteady ionizing plasma for different laser input energies.

  10. The study of ionization by electron impact of a substance simulating spent nuclear fuel components

    NASA Astrophysics Data System (ADS)

    Antonov, N. N.; Bochkarev, E. I.; Gavrikov, A. V.; Samokhin, A. A.; Smirnov, V. P.

    2015-11-01

    Plasma sources of model substances are necessary to solve problems associated with development of the spent nuclear fuel (SNF) plasma separation method. Lead was chosen to simulate kinetic and dynamic properties of the heavy SNF components. In this paper we present the results of a study of a lead vapor discharge with a lead concentration of 1012-1013 cm-3. Ionization was carried out by an electron beam (with energy of up to 500 eV per electron) inside a centimeter gap between planar electrodes. The discharge was numerically modeled using the hydrodynamic and single-particle approximation. Current-voltage characteristics and single ionization efficiency were obtained as functions of the vapors concentration and thermoelectric current. An ion current of hundreds of microamperes at the ionization efficiency near tenths of a percent was experimentally obtained. These results are in good agreement with our model.

  11. Numerical quasi-linear study of the critical ionization velocity phenomenon

    NASA Technical Reports Server (NTRS)

    Moghaddam-Taaheri, E.; Goertz, C. K.

    1993-01-01

    The critical ionization velocity (CIV) for a neutral barium (Ba) gas cloud moving across the static magnetic field is studied numerically using quasi-linear equations and a parameter range which is typical for the shaped-charge Ba gas release experiments in space. For consistency the charge exchange between the background oxygen ions and neutral atoms and its reverse process, as well as the excitation of the neutral Ba atoms, are included. The numerical results indicate that when the ionization rate due to CIV becomes comparable to the charge exchange rate the energy lost to the ionization and excitation collisions by the superthermal electrons exceeds the energy gain from the waves that are excited by the ion beam. This results in a CIV yield less than the yield by the charge exchange process.

  12. [Characteristics of tetrahydrofuran degradation by Pseudomonas oleovorans DT4].

    PubMed

    Zhou, Yu-Yang; Chen, Dong-Zhi; Jin, Xiao-Jun; Chen, Jian-Meng; He, Jie

    2011-01-01

    A tetrahydrofuran (THF)-degrading strain Pseudomonas oleovorans DT4 was isolated from the activated sludge of a pharmaceutical plant. P. oleovorans DT4 was able to utilize THF as the sole carbon and energy source under aerobic condition. 5 mmol/L of THF could be completely degraded by 3.2 mg/L inoculums of P. oleovorans DT4 in 14 h at pH 7.2 and 30 degrees C, with the cells concentration increasing to 188.6 mg/L. After the complete consumption of THF, no TOC could be detected but IC reached the stable value of about 46 mg/L, with pH decreasing to 6.54, which indicated that the substance was totally mineralized by P. oleovorans DT4. The optimum conditions for THF biodegradation in shaking flasks were pH 7.5 and temperature 37 degrees C, respectively. Results from the oxygen control experiments revealed that the oxygen supply by shaking was the satisfactory growth condition. Additionally, as the important elements for DT4, Mg2+ and Ca2+ at concentrations of 0.80 mmol/L and 0.20 mmol/L, respectively, were suitable for THF degradation. All the results contribute to the efficient bioremediation for the THF contaminated. PMID:21404697

  13. Hirshfeld surface analysis of sulfameter (polymorph III), sulfameter dioxane monosolvate and sulfameter tetrahydrofuran monosolvate, all at 296 K.

    PubMed

    Tailor, Sanjay M; Patel, Urmila H

    2015-11-01

    The ability of the antibacterial agent sulfameter (SMT) to form solvates is investigated. The X-ray crystal structures of sulfameter solvates have been determined to be conformational polymorphs. Both 1,4-dioxane and tetrahydrofuran form solvates with sulfameter in a 1:1 molar ratio. 4-Amino-N-(5-methoxypyrimidin-2-yl)benzenesulfonamide (polymorph III), C11H12N4O3S, (1), has two molecules of sulfameter in the asymmetric unit cell. 4-Amino-N-(5-methoxypyrimidin-2-yl)benzenesulfonamide 1,4-dioxane monosolvate, C11H12N4O3S·C4H8O2, (2), and 4-amino-N-(5-methoxypyrimidin-2-yl)benzenesulfonamide tetrahydrofuran monosolvate, C11H12N4O3S·C4H8O, (3), crystallize in the imide form. Hirshfeld surface analyses and fingerprint analyses were performed to study the nature of the interactions and their quantitative contributions towards the crystal packing. Finally, Hirshfeld surfaces, fingerprint plots and structural overlays were employed for a comparison of the two independent molecules in the asymmetric unit of (1), and also for a comparison of (2) and (3) in the monoclinic crystal system. A three-dimensional hydrogen-bonding network exists in all three structures, involving one of the sulfone O atoms and the aniline N atom. All three structures are stabilized by strong intermolecular N-H···N interactions. The tetrahydrofuran solvent molecule also takes part in forming significant intermolecular C-H···O interactions in the crystal structure of (3), contributing to the stability of the crystal packing. PMID:26524165

  14. Multiphoton ionization studies of WF{sub 6} and UF{sub 6}

    SciTech Connect

    Harkins, D.A.; Armstrong, D.P.; Compton, R.N.; Ding, Dajun

    1993-07-01

    Multiphoton ionization of UF{sub 6} and WF{sub 6} has been studied from low ({approximately} 10{sup 5}) to high ({approximately}10{sup 16} W/cm{sup 2}) power density. The role of ``collective states`` in MPI is considered.

  15. Field ionization kinetic and electron impact studies of gas phase transition states - The cyclic bromonium ion

    NASA Technical Reports Server (NTRS)

    Green, M. M.; Giguere, R. J.; Falick, A. M.; Aberth, W.; Burlingame, A. L.

    1978-01-01

    Cis- and trans-isomers of 4-t-butylcyclohexyl bromide were studied to determine the mechanism of cyclic bromonium ion formation. The field ionization kinetic and electron impact data indicate that the formation of the cyclic structure occurs simultaneously with loss of the neutral fragment. The data also show that little or no gas-phase cis-trans isomerization occurs.

  16. Ionization of cytosine monomer and dimer studied by VUV photoionization and electronic structure calculations

    SciTech Connect

    Kostko, Oleg; Bravaya, Ksenia; Krylov, Anna; Ahmed, Musahid

    2009-12-14

    We report a combined theoretical and experimental study of ionization of cytosine monomers and dimers. Gas-phase molecules are generated by thermal vaporization of cytosine followed by expansion of the vapor in a continuous supersonic jet seeded in Ar. The resulting species are investigated by single photon ionization with tunable vacuum-ultraviolet (VUV) synchrotron radiation and mass analyzed using reflectron mass spectrometry. Energy onsets for the measured photoionization efficiency (PIE) spectra are 8.60+-0.05 eV and 7.6+-0.1 eV for the monomer and the dimer, respectively, and provide an estimate for the adiabatic ionization energies (AIE). The first AIE and the ten lowest vertical ionization energies (VIEs) for selected isomers of cytosine dimer computed using equation-of-motion coupled-cluster (EOM-IP-CCSD) method are reported. The comparison of the computed VIEs with the derivative of the PIE spectra, suggests that multiple isomers of the cytosine dimer are present in the molecular beam. The calculations reveal that the large red shift (0.7 eV) of the first IE of the lowest-energy cytosine dimer is due to strong inter-fragment electrostatic interactions, i.e., the hole localized on one of the fragments is stabilized by the dipole moment of the other. A sharp rise in the CH+ signal at 9.20+-0.05 eV is ascribed to the formation of protonated cytosine by dissociation of the ionized dimers. The dominant role of this channel is supported by the computed energy thresholds for the CH+ appearance and the barrierless or nearly barrierless ionization-induced proton transfer observed for five isomers of the dimer.

  17. Ionization of cytosine monomer and dimer studied by VUV photoionization and electronic structure calculations.

    PubMed

    Kostko, Oleg; Bravaya, Ksenia; Krylov, Anna; Ahmed, Musahid

    2010-03-28

    We report a combined theoretical and experimental study of ionization of cytosine monomers and dimers. Gas-phase molecules are generated by thermal vaporization of cytosine followed by expansion of the vapor in a continuous supersonic jet seeded in Ar. The resulting species are investigated by single photon ionization with tunable vacuum-ultraviolet (VUV) synchrotron radiation and mass analyzed using reflectron mass spectrometry. Energy onsets for the measured photoionization efficiency (PIE) spectra are 8.60 +/- 0.05 eV and 7.6 +/- 0.1 eV for the monomer and the dimer, respectively, and provide an estimate for the adiabatic ionization energies (AIE). The first AIE and the ten lowest vertical ionization energies (VIEs) for selected isomers of cytosine dimer computed using equation-of-motion coupled-cluster (EOM-IP-CCSD) method are reported. The comparison of the computed VIEs with the derivative of the PIE spectra suggests that multiple isomers of the cytosine dimer are present in the molecular beam. The calculations reveal that the large red shift (0.7 eV) of the first IE of the lowest-energy cytosine dimer is due to strong inter-fragment electrostatic interactions, i.e., the hole localized on one of the fragments is stabilized by the dipole moment of the other. A sharp rise in the protonated cytosine ion (CH(+)) signal at 9.20 +/- 0.05 eV is ascribed to the formation of protonated cytosine by dissociation of the ionized dimers. The dominant role of this channel is supported by the computed energy thresholds for the CH(+) appearance and the barrierless or nearly barrierless ionization-induced proton transfer observed for five isomers of the dimer.

  18. Studies of nanosecond pulse surface ionization wave discharges over solid and liquid dielectric surfaces

    NASA Astrophysics Data System (ADS)

    Petrishchev, Vitaly; Leonov, Sergey; Adamovich, Igor V.

    2014-12-01

    Surface ionization wave discharges generated by high-voltage nanosecond pulses, propagating over a planar quartz surface and over liquid surfaces (distilled water and 1-butanol) have been studied in a rectangular cross section test cell. The discharge was initiated using a custom-made, alternating polarity, high-voltage nanosecond pulse plasma generator, operated at a pulse repetition rate of 100-500 Hz, with a pulse peak voltage and current of 10-15 kV and 7-20 A, respectively, a pulse FWHM of ˜100 ns, and a coupled pulse energy of 2-9 mJ/pulse. Wave speed was measured using a capacitive probe. ICCD camera images demonstrated that the ionization wave propagated predominantly over the quartz wall or over the liquid surface adjacent to the grounded waveguide placed along the bottom wall of the test cell. Under all experimental conditions tested, the surface plasma ‘sheet’ was diffuse and fairly uniform, both for positive and negative polarities. The parameters of ionization wave discharge propagating over distilled water and 1-butanol surfaces were close to those of the discharge over a quartz wall. No perturbation of the liquid surface by the discharge was detected. In most cases, the positive polarity surface ionization wave propagated at a higher speed and over a longer distance compared to the negative polarity wave. For all three sets of experiments (surface ionization wave discharge over quartz, water and 1-butanol), wave speed and travel distance decreased with pressure. Diffuse, highly reproducible surface ionization wave discharge was also observed over the liquid butanol-saturated butanol vapor interface, as well as over the distilled water-saturated water vapor interface, without buffer gas flow. No significant difference was detected between surface ionization discharges sustained using single-polarity (positive or negative), or alternating polarity high-voltage pulses. Plasma emission images yielded preliminary evidence of charge removal from the

  19. Choosing populations to study the health effects of low-dose ionizing radiation.

    PubMed Central

    Dreyer, N A; Loughlin, J E; Friedlander, E R; Clapp, R W; Fahey, F H

    1981-01-01

    In January 1978, the United States Congress requested information about the utility of additional epidemiologic studies for quantifying the health effects of low-dose ionizing radiation. In our judgment, no single population can be recommended for study on purely scientific grounds, since the largest group offers only a small chance to obtain a definitive result. On the other hand, if social pressures and regulatory agencies mandate that such studies be attempted, we would recommend prospective cohort studies of occupational populations. We propose that a national worker registry be developed using ionizing radiation as the prototype for studying other occupational exposures. The problems related to studying low-level radiation are not unique, but apply equally to investigations dealing with a great variety of toxic agents. A national plan for collecting information on workers' exposure and health could provide a cost-efficient means to answer public health questions posed by the Congress, scientists and the public. PMID:7294269

  20. Studying the Effect of Ionization Radiation of 60Co on the Spirulina

    NASA Astrophysics Data System (ADS)

    Ai, Weidang; Guo, Shuang-Sheng; Ai, Weidang; Dong, Wen-Ping; Qin, Li-Feng; Tang, Yong-Kang

    It studied the effect of ionization radiation on the Spirulina plastensis(No.6) by using the γ-rays of 60 Co. In the experiment, Spirulina were irradiated, and the dose of the ionization radiation covered 0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0kGy. After irradiating, these Spirulina were cultured under the same conditions. During the course of the experiment, the growth rate, photosynthetic efficiency and nutrition quality of the Spirulina, were analyzed. From the results, low dose of γ-rays (less than 1.5kGy) could improve the content of phycobilin and protein of Spirulina. Only small changes in the morphology of algae filament were found at dose less than 1.0kGy. But with the increase of the dose of γ-rays (more than 1.5kGy), the filaments would break up or even disintegrate. Spirulina had stronger ionization radiation proof and self-rehabilitation capacity, but the growth of Spirulina was stagnated. The LD50 (i.e. the dose resulted in 50% death of the Spirulina) of the colony was 2.0kGy. Considering the capacity of being resistant to γ-rays irradiation, Spirulina can be considered as one of the key biological components in the Controlled Ecological Life Support System (CELSS) for future long-term space missions. Keywords: Controlled Ecological Life Support System (CELSS); Spirulina; ionization radiation; biological component

  1. Solid-state NMR and density functional theory studies of ionization states of thiamin.

    PubMed

    Paramasivam, Sivakumar; Balakrishnan, Anand; Dmitrenko, Olga; Godert, Amy; Begley, Tadhg P; Jordan, Frank; Polenova, Tatyana

    2011-02-01

    Thiamin diphosphate (ThDP) is a key coenzyme in sugar metabolism. The 4'-aminopyrimidine ring of ThDP cycles through several ionization and tautomeric states during enzyme catalysis, but it is not fully understood which states are adopted during the individual steps of the catalytic cycle. Thiamin has been synthesized with labels selectively inserted into the C2 and C6' positions, as well as into the amino group, creating [C2, C6'-(13)C(2)] thiamin and [N4'-(15)N] thiamin. Magic-angle spinning (MAS) NMR spectroscopy has been employed to record the (13)C and (15)N chemical shift anisotropy (CSA) tensors for C2, C6', and N4' atoms. Our results indicate that the isotropic chemical shifts as well as the principal components of the (13)C and (15)N CSA tensors are very sensitive to the protonation states in these compounds and, therefore, permit differentiating between the two ionization states, 4-aminopyrimidine and 4-aminopyrimidinium. Using density functional theory (DFT), we have calculated the magnetic shielding anisotropy tensors of C2, C6', and N4' and found excellent agreement between the computed and the experimental tensors. Our findings indicate that MAS NMR spectroscopy in conjunction with DFT calculations is a sensitive probe of ionization states in the thiamin cofactor. The results of this study will serve as a guide for characterization of ionization and tautomeric states of thiamin in complexes with thiamin-dependent enzymes.

  2. Hyperfine structure and isotope shift study in singly ionized lead

    NASA Astrophysics Data System (ADS)

    Wąsowicz, T. J.; Drozdowski, R.; Kwela, J.

    2005-12-01

    Hyperfine structure and isotope shifts in five optical transitions: 424.5 nm (6s^25f ^2textrm{F}_{7/2} 6s^26d^2 textrm{D}_{5/2}), 537.2 nm (6s^25f ^2textrm{F}_{7/2} 6s6p^2 ^4textrm{P}_{5/2}), 554.5 nm (6s^27d ^2textrm{D}_{5/2} 6s^27p ^2textrm{P}_{3/2}), 560.9 nm (6s^27p^2 textrm{P}_{3/2} 6s^27s ^2textrm{S}_{1/2}) and 666.0 nm (6s^27p ^2textrm{P}_{1/2} 6s^27s ^2textrm{S}_{1/2}) of Pb II have been measured. As a light source the discharge tube was used. The hyperfine structure measurements were performed using metallic isotope 207Pb. For isotope shifts measurements natural lead was used. The high resolution spectral apparatus consisted of a silver coated Fabry-Perot etalon and a grating spectrograph combined with a CCD camera used as a detector. In the analysis of the spectra a computer simulation technique was used. The hyperfine structure observations yielded the splitting constants A for seven levels of Pb II. The isotope shift studies enabled to separate the mass and the field shifts and to determine values of changes of the mean square nuclear charge radii.

  3. Optimal choice of pH for toxicity and bioaccumulation studies of ionizing organic chemicals.

    PubMed

    Rendal, Cecilie; Kusk, Kresten Ole; Trapp, Stefan

    2011-11-01

    It is recognized that the pH of exposure solutions can influence the toxicity and bioaccumulation of ionizing compounds. The present study investigates whether it can be considered a general rule that an ionizable compound is more toxic and more bioaccumulative when in the neutral state. Three processes were identified to explain the behavior of ionizing compounds with changing pH: the change in lipophilicity when a neutral compound becomes ionized, electrical attraction, and the ion trap. The literature was screened for bioaccumulation and toxicity tests of ionizing organic compounds performed at multiple pH levels. Toxicity and bioconcentration factors (BCFs) were higher for acids at lower pH values, whereas the opposite was true for bases. The effect of pH was most pronounced when pH - pK(a) was in the range of -1 to 3 for acids, and -3 to 1 for bases. The factor by which toxicity and BCF changed with pH was correlated with the lipophilicity of the compound (log K(OW) of the neutral compound). For both acids and bases, the correlation was positive, but it was significant only for acids. Because experimental data in the literature were limited, results were supplemented with model simulations using a dynamic flux model based on the Fick-Nernst-Planck diffusion equation known as the cell model. The cell model predicts that bases with delocalized charges may in some cases show declining bioaccumulation with increasing pH. Little information is available for amphoteric and zwitterionic compounds; however, based on simulations with the cell model, it is expected that the highest toxicity and bioaccumulation of these compounds will be found where the compounds are most neutral, at the isoelectric point. PMID:21823161

  4. Optimal choice of pH for toxicity and bioaccumulation studies of ionizing organic chemicals.

    PubMed

    Rendal, Cecilie; Kusk, Kresten Ole; Trapp, Stefan

    2011-11-01

    It is recognized that the pH of exposure solutions can influence the toxicity and bioaccumulation of ionizing compounds. The present study investigates whether it can be considered a general rule that an ionizable compound is more toxic and more bioaccumulative when in the neutral state. Three processes were identified to explain the behavior of ionizing compounds with changing pH: the change in lipophilicity when a neutral compound becomes ionized, electrical attraction, and the ion trap. The literature was screened for bioaccumulation and toxicity tests of ionizing organic compounds performed at multiple pH levels. Toxicity and bioconcentration factors (BCFs) were higher for acids at lower pH values, whereas the opposite was true for bases. The effect of pH was most pronounced when pH - pK(a) was in the range of -1 to 3 for acids, and -3 to 1 for bases. The factor by which toxicity and BCF changed with pH was correlated with the lipophilicity of the compound (log K(OW) of the neutral compound). For both acids and bases, the correlation was positive, but it was significant only for acids. Because experimental data in the literature were limited, results were supplemented with model simulations using a dynamic flux model based on the Fick-Nernst-Planck diffusion equation known as the cell model. The cell model predicts that bases with delocalized charges may in some cases show declining bioaccumulation with increasing pH. Little information is available for amphoteric and zwitterionic compounds; however, based on simulations with the cell model, it is expected that the highest toxicity and bioaccumulation of these compounds will be found where the compounds are most neutral, at the isoelectric point.

  5. Oxidative Cyclization of 1,5-Dienes with Hydrogen Peroxide Catalyzed by an Osmium(III) Complex: Synthesis of cis-Tetrahydrofurans.

    PubMed

    Sugimoto, Hideki; Kanetake, Takayuki; Maeda, Kazuki; Itoh, Shinobu

    2016-03-18

    Stereoselective oxidative cyclization of 1,5-dienes with hydrogen peroxide catalyzed by [Os(III)(OH)(H2O)(L-N4Me2)](PF6)2 (1: L-N4Me2 = N,N'-dimethyl-2,11-diaza-[3,3](2,6)pyridinophane) is explored. 1,5-Dienes involving geraniol derivatives are converted to the corresponding tetrahydrofurans in modest to high yields. The products exclusively have the cis-conformation with respect to the substituents at the 2- and 5-positions of the tetrahydrofuran ring. The products also have a syn-conformation with respect to the furan oxygen atom and the hydroxyl groups. Mechanistic studies including a direct reaction of the oxo-hydroxo-osmium(V) complex, 2, with a dihydroxylated geraniol derivative are performed.

  6. Oxidative Cyclization of 1,5-Dienes with Hydrogen Peroxide Catalyzed by an Osmium(III) Complex: Synthesis of cis-Tetrahydrofurans.

    PubMed

    Sugimoto, Hideki; Kanetake, Takayuki; Maeda, Kazuki; Itoh, Shinobu

    2016-03-18

    Stereoselective oxidative cyclization of 1,5-dienes with hydrogen peroxide catalyzed by [Os(III)(OH)(H2O)(L-N4Me2)](PF6)2 (1: L-N4Me2 = N,N'-dimethyl-2,11-diaza-[3,3](2,6)pyridinophane) is explored. 1,5-Dienes involving geraniol derivatives are converted to the corresponding tetrahydrofurans in modest to high yields. The products exclusively have the cis-conformation with respect to the substituents at the 2- and 5-positions of the tetrahydrofuran ring. The products also have a syn-conformation with respect to the furan oxygen atom and the hydroxyl groups. Mechanistic studies including a direct reaction of the oxo-hydroxo-osmium(V) complex, 2, with a dihydroxylated geraniol derivative are performed. PMID:26950609

  7. Computer study of convection of weakly ionized plasma in a nonuniform magnetic field.

    NASA Technical Reports Server (NTRS)

    Shiau, J. N.

    1972-01-01

    A weakly ionized plasma in a strong and nonuniform magnetic field exhibits an instability analogous to the flute instability in a fully ionized plasma. The instability sets in at a critical magnetic field. To study the final state of the plasma after the onset of the instability, the plasma equations are integrated numerically assuming a certain initial spectrum of small disturbances. In the regime studied, numerical results indicate a final steadily oscillating state consisting of a single finite amplitude mode together with a time-independent modification of the original equilibrium. These results agree with the analytic results obtained by Simon in the slightly supercritical regime. As the magnetic field is increased further, the wavelength of the final oscillation becomes nonunique. There exists a subinterval in the unstable wave band. Final stable oscillation with a wavelength in this subinterval can be established if the initial disturbance has a sufficiently strong component at the particular wavelength.

  8. A comparative study of three ionizing chambers for measurements of personal dose equivalent, Hp(10)

    NASA Astrophysics Data System (ADS)

    Oliveira, C.; Cardoso, J.; Silva, H.

    2015-11-01

    A comparative study of three ionization chambers which directly measure the quantity personal dose equivalent Hp(10), was performed. Results show that the ratio between the response (air kerma) determined by Monte Carlo and the experimental response (collected charge) normalized by the monitor unit is the same whatever is the chamber and that this ratio is proportional to the conversion coefficients for air kerma from photon fluence.

  9. Density functional theory study of multiply ionized weakly bound fullerene dimers.

    PubMed

    Zettergren, Henning; Wang, Yang; Lamsabhi, Al Mokhtar; Alcamí, Manuel; Martín, Fernando

    2009-06-14

    Multiply ionized fullerene dimers ([C(60)](2) (q+),q=1-6) have been studied by means of state-of-the-art density functional theory methods. We found that the singly charged dimer is more strongly bound than the corresponding neutral van der Waals dimer at the binding distance of the latter; in contrast, multiply charged dimers (q>or=2) are unstable. For the latter dimers, the calculated kinetic energy release in the binary fission yielding intact fullerenes is lower than those reported in recent experimental work. This implies that, in such experiments, there are significant internal excitations in the separating monomers. We also show that electron transfer within the charged dimers occurs on the subfemtosecond time scale, in accordance with the high charge mobility observed in dimers and larger clusters of fullerenes. This provides an explanation for the even-odd effects in the measured multiple ionization yields of fullerene dimers.

  10. Theoretical and Experimental Study of Valence-Shell Ionization Spectra of Guanine

    NASA Astrophysics Data System (ADS)

    Zaytseva, Irina L.; Trofimov, Alexander B.; Schirmer, Jochen; Plekan, Oksana; Feyer, Vitaliy; Richter, Robert; Coreno, Marcello; Prince, Kevin C.

    2009-10-01

    The full valence-shell ionization spectra of the four most stable guanine tautomers were studied theoretically. The third-order algebraic-diagrammatic construction (ADC(3)) method for the one-particle Green's function was used to calculate the energies and relative intensities of the vertical ionization transitions. For low-lying transitions, the influence of planar and nonplanar guanine configurations on the ionization energies, as well as the convergence of the results with respect to basis set was studied at the level of the outer-valence Green's function (OVGF) approximation scheme. The results of the calculations were used to interpret recent synchrotron radiation valence-shell photoionization spectra of guanine in the gas phase under thermal equilibrium conditions. The photoelectron spectrum was modeled by summing individual tautomer spectra weighted by Boltzmann population ratios (BPR) of tautomers from our previous high-level ab initio thermochemical calculations. The theoretical spectra are in good agreement with the experimental results, providing assignments of most observed structures and offering insight into tautomerism of guanine in the gas phase. The first six molecular orbitals give rise to single-hole states with a binding energy of about 7-12 eV. At higher binding energy the spectral features are mainly due to satellite states.

  11. A mass spectrometry study of n-octane: Electron impact ionization and ion-molecule reactions

    NASA Astrophysics Data System (ADS)

    Jiao, C. Q.; DeJoseph, C. A.; Garscadden, A.

    2001-02-01

    Electron impact ionization of n-octane over an energy range of 10-70 eV and the subsequent ion-molecule reactions with the parent molecule have been studied using Fourier-transform mass spectrometry. Molecular ion and fragment ions C1+-C6+ are produced from the electron impact with a total ionization cross section of 1.4±0.2×10-15 cm2 between 60 and 70 eV. C3H7+ is the most abundant ion at most of the ionizing energies with the exception for E⩽16 eV where C6H13+ and C6H12+ are the most abundant. Among the fragment ions only C4H7+ and smaller ions react readily with the parent molecule, primarily producing C5H11+ and C4H9+, with rate coefficients of 0.32-2.4×10-9 cm3s-1. Essentially all of the ions, including the molecular ion and the large fragment ions, undergo decomposition upon collision with neutral molecules after they are kinetically excited to an energy range of 1-5 eV, forming a variety of small hydrocarbon ions. Many of the decomposition product ions in turn are capable of further reacting with n-octane. Isotope reagents have been utilized in experiments to probe the type of the ion-molecule reactions studied.

  12. Sustainable Synthesis of Chiral Tetrahydrofurans through the Selective Dehydration of Pentoses.

    PubMed

    Foster, Robert W; Tame, Christopher J; Bučar, Dejan-Krešimir; Hailes, Helen C; Sheppard, Tom D

    2015-11-01

    L-Arabinose is an abundant resource available as a waste product of the sugar beet industry. Through use of a hydrazone-based strategy, L-arabinose was selectively dehydrated to form a chiral tetrahydrofuran on a multi-gram scale without the need for protecting groups. This approach was extended to other biomass-derived reducing sugars and the mechanism of the key cyclization investigated. This methodology was applied to the synthesis of a range of functionalized chiral tetrahydrofurans, as well as a formal synthesis of 3R-3-hydroxymuscarine.

  13. Encapsulation of saline solution by tetrahydrofuran clathrate hydrates and inclusion migration by recrystallization.

    PubMed

    Nagashima, Kazushige; Orihashi, Suguru; Yamamoto, Yoshitaka; Takahashi, Masayoshi

    2005-05-26

    Encapsulation of saline solution as an impurity in tetrahydrofuran clathrate hydrates grown in a stoichiometric solution with 3 wt % NaCl and the release of a saline solution during melting along with inclusion migration by hydrate recrystallization during annealing are studied using a directional growth apparatus in combination with a Mach-Zender interferometer. Interferometric observation revealed that the salt concentration increased locally in the solution near the growth interface. The time evolution of salt concentration in the solution was in accordance with the numerical results obtained from the diffusion equation for salt, assuming perfect rejection of salt by the hydrate. However, after the interfacial pattern developed into a serrated pattern (periodical array of trough and crest), the salt concentration in the solution ceased to increase, deviating from the theoretical value. This indicates that the saline solution was encapsulated by the growth hydrate. On the other hand, upon melting of the slowly grown hydrate, the salt concentration near the interface was observed to be locally high at the location of the trough during growth, whereas it was dilute at the location of the growth crest. Furthermore, when the hydrate was annealed under an applied temperature gradient, the inclusions (encapsulated saline solution) in the hydrate migrated toward the bulk solution and were finally expelled by hydrate recrystallization. The migration speed of the inclusions increased with a larger temperature gradient. By melting the sample over a sufficiently long anneal time, the melt was determined to be completely desalinated.

  14. a Study of Biophysical Mechanisms of Damage by Ionizing Radiation to Mammalian Cells in Vitro.

    NASA Astrophysics Data System (ADS)

    Chen, Chun-Zhang

    Available from UMI in association with The British Library. An extensive survey made of published survival data of damage by ionizing radiation to mammalian cells in vitro has led to the new conclusion that the damage is determined by the specific ionization or the mean free path between ionizing events along the charged particle tracks. The optimum damage is observed when the mean free path is equivalent to the DNA double strand spacing of 1.8 nm. Therefore, the biological mechanism of ionizing radiation to mammalian cells in vitro is intra track dominant. A 100 keV electron accelerator has been constructed and commissioned to produce a broad beam irradiation field of greater than 1 cm diameter. The fluence rate may be adjusted from 10^8cm^ {-2}sec^{-1} downwards to enable further development as a chronic irradiation facility. Another new feature of the accelerator is that it incorporates a differential vacuum system which permits irradiation of the monolayer cell cultures to be carried out in normal pressure. Experiments of irradiation to Chinese hamster cells, by ^{241}Am alpha particles at low fluence rate, have supplied satisfactory data for testing a new DNA-rupture model which is under development. For V79 cells irradiated at a low fluence rate of 10^5cm^{ -2}min^{-1}, when survival data were fitted into the model, new biophysical parameters were extracted and a proposal was made that the repair phenomenon of cellular survival at very low doses is determined by three time factors: the irradiation time, the damage fixation time and the repair time. The values obtained were 3-4 hours for the mean repair time, and more than 10 hours for the damage to be considered permanent. Details of the monolayer cell culture technique developed and used in the present experiments are described. Consideration has been given to the significance of the results obtained from the study in radiation protection and in radiotherapy. In future studies it is recommended that more

  15. Study of Electrochemical Reactions Using Nanospray Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Liu, Pengyuan; Lanekoff, Ingela T.; Laskin, Julia; Dewald, Howard D.; Chen, Hao

    2012-07-03

    The combination of electrochemistry (EC) and mass spectrometry (MS) is a powerful analytical tool for studying mechanisms of redox reactions, identification of products and intermediates, and online derivatization/recognition of analytes. This work reports a new coupling interface for EC/MS by employing nanospray desorption electrospray ionization (nano-DESI), a recently developed ambient ionization method. We demonstrate online coupling of nano-DESI-MS with a traditional electrochemical flow cell, in which the electrolyzed solution emanating from the cell is ionized by nano-DESI for MS analysis. Furthermore, we show first coupling of nano-DESI-MS with an interdigitated array (IDA) electrode enabling chemical analysis of electrolyzed samples directly from electrode surfaces. Because of its inherent sensitivity, nano-DESI enables chemical analysis of small volumes and concentrations of sample solution. Specifically, good-quality signal of dopamine and its oxidized form, dopamine ortho-quinone, was obtained using 10 μL of 1 μM solution of dopamine on the IDA. Oxidation of dopamine, reduction of benzodiazepines, and electrochemical derivatization of thiol groups were used to demonstrate the performance of the technique. Our results show the potential of nano-DESI as a novel interface for electrochemical mass spectrometry research.

  16. In-gas-cell laser ionization studies of plutonium isotopes at IGISOL

    NASA Astrophysics Data System (ADS)

    Pohjalainen, I.; Moore, I. D.; Kron, T.; Raeder, S.; Sonnenschein, V.; Tomita, H.; Trautmann, N.; Voss, A.; Wendt, K.

    2016-06-01

    In-gas-cell resonance laser ionization has been performed on long-lived isotopes of Pu at the IGISOL facility, Jyväskylä. This initiates a new programme of research towards high-resolution optical spectroscopy of heavy actinide elements which can be produced in sufficient quantities at research reactors and transported to facilities elsewhere. In this work a new gas cell has been constructed for fast extraction of laser-ionized elements. Samples of 238-240,242Pu and 244Pu have been evaporated from Ta filaments, laser ionized, mass separated and delivered to the collinear laser spectroscopy station. Here we report on the performance of the gas cell through studies of the mass spectra obtained in helium and argon, before and after the radiofrequency quadrupole cooler-buncher. This provides valuable insight into the gas phase chemistry exhibited by Pu, which has been additionally supported by measurements of ion time profiles. The resulting monoatomic yields are sufficient for collinear laser spectroscopy. A gamma-ray spectroscopic analysis of the Pu samples shows a good agreement with the assay provided by the Mainz Nuclear Chemistry department.

  17. Generation of naphthoquinone radical anions by electrospray ionization: solution, gas-phase, and computational chemistry studies.

    PubMed

    Vessecchi, Ricardo; Naal, Zeki; Lopes, José N C; Galembeck, Sérgio E; Lopes, Norberto P

    2011-06-01

    Radical anions are present in several chemical processes, and understanding the reactivity of these species may be described by their thermodynamic properties. Over the last years, the formation of radical ions in the gas phase has been an important issue concerning electrospray ionization mass spectrometry studies. In this work, we report on the generation of radical anions of quinonoid compounds (Q) by electrospray ionization mass spectrometry. The balance between radical anion formation and the deprotonated molecule is also analyzed by influence of the experimental parameters (gas-phase acidity, electron affinity, and reduction potential) and solvent system employed. The gas-phase parameters for formation of radical species and deprotonated species were achieved on the basis of computational thermochemistry. The solution effects on the formation of radical anion (Q(•-)) and dianion (Q(2-)) were evaluated on the basis of cyclic voltammetry analysis and the reduction potentials compared with calculated electron affinities. The occurrence of unexpected ions [Q+15](-) was described as being a reaction between the solvent system and the radical anion, Q(•-). The gas-phase chemistry of the electrosprayed radical anions was obtained by collisional-induced dissociation and compared to the relative energy calculations. These results are important for understanding the formation and reactivity of radical anions and to establish their correlation with the reducing properties by electrospray ionization analyses. PMID:21561138

  18. Infrared depletion spectroscopy of the doubly hydrogen-bonded aniline-(tetrahydrofuran) 2 complex produced in supersonic jet

    NASA Astrophysics Data System (ADS)

    Chowdhury, Pradyot K.

    2006-01-01

    The vibrational frequencies of the N-H stretching modes of aniline after forming a strong doubly H-bonded complex with tetrahydrofuran (THF) are measured with infrared depletion spectroscopy that uses cluster-size-selective resonance-enhanced multiphoton ionization (REMPI) time-of-flight mass spectrometry. Two strong infrared absorption features observed at 3355 and 3488 cm -1 are assigned to the symmetric and antisymmetric N-H stretching vibrations of the 1:2 aniline-THF complex, respectively. The red-shifts of the N-H stretching vibrations of aniline agree with the ab initio calculated (MP2/6-31G**) aniline-(THF) 2 structure in which both aniline N-H bonds interact with the oxygen atom of THF through two hydrogen bonds. The calculated binding energy is found to be 29.6 kJ mol -1 after corrections for basis set superposition error (BSSE) and zero-point energy. The calculated structure revealed that the angle between the N-H bonds in the NH 2 group increased to 112.5° in the aniline-(THF) 2 complex from that of 109.8° in the aniline. The electronic 0-0 band origin for the S1 ← S0 transition is observed at 32,900 cm -1 in the aniline-(THF) 2 complex, giving a red-shift of 1129 cm -1 from that of the aniline molecule.

  19. Manipulation of a Schlenk Line: Preparation of Tetrahydrofuran Complexes of Transition-Metal Chlorides

    ERIC Educational Resources Information Center

    Davis, Craig M.; Curran, Kelly A.

    2007-01-01

    Before taking an inorganic laboratory course few students have experience handling air-sensitive materials using Schlenk techniques. This exercise introduces them to techniques they will employ in later syntheses. The procedure involves the formation of anhydrous tetrahydrofuran complexes of transition-metal chlorides from metal-chloride hydrates;…

  20. Alkene Dioxygenation with Malonoyl Peroxides: Synthesis of γ-Lactones, Isobenzofuranones, and Tetrahydrofurans.

    PubMed

    Alamillo-Ferrer, Carla; Karabourniotis-Sotti, Marianna; Kennedy, Alan R; Campbell, Matthew; Tomkinson, Nicholas C O

    2016-07-01

    Treatment of homoallylic alcohols or carboxylic acids with malonoyl peroxide 1 provides a stereoselective method for the preparation of tetrahydrofurans, γ-lactones, and isobenzofuranones in 44-82% yield and up to 27:1 trans selectivity. Application of this simple and effective heterocyclization in the synthesis of the antidepressant citalopram is also described. PMID:27314605

  1. Mechanistic study and optimization of a hydrogen atmosphere flame ionization detector

    SciTech Connect

    Lillie, C.H.

    1985-01-01

    A residual gas analyzer was modified to study ions produced by flames similar to those used in the organometallic and organosilicon selective hydrogen atmosphere flame ionization detectors, HAFID and HAFID-Si, respectively. Flame ions traveled from 1 to 7 cm at atmospheric pressure prior to entering the vacuum chamber. The ions were then extracted and focused using an Einzel lens system into a quadrupole mass spectrometer. The mass spectrometry system was calibrated using the ions produced by a radioactive Ni-63 foil which had nitrogen gas blown over it. Optimization of the system was accomplished by varying parameters while the Ni-63 foil was the ionizing source and then with a hydrogen in air diffusion flame. The mass spectrum from a flame similar in composition to that used in the gas chromatographic flame ionization detector was compared to literature spectra to validate the results. Characterization studies of the HAFID indicated a linear range of two orders of magnitude for organics with a minimum detectable amount of 500 ng for tetradecane. An equal per carbon response pattern similar to that observed in the FID was observed with the HAFID for a homologous n-alkane series. A new detector design that allows the collector to jet tip height to be varied while the detector flame is burning was utilized in the simplex optimization of the detector. A computer program that utilizes variable sized steps in the simplex was developed to determine the next set of conditions to be tested and to determine when the optimum had been reached. A mechanism was developed to account for the selective response of the organometallic and organosilicon selective detectors. The mechanisms were based on the results of the mass spectrometric studies, characterization studies and thermodynamic data obtained from the literature.

  2. Case-control study of congenital malformations and occupational exposure to low-level ionizing radiation

    SciTech Connect

    Sever, L.E.; Gilbert, E.S.; Hessol, N.A.; McIntyre, J.M.

    1988-02-01

    In a case-control study, the authors investigated the association of parental occupational exposure to low-level external whole-body penetrating ionizing radiation and risk of congenital malformations in their offspring. Cases and controls were ascertained from births in two counties in southeastern Washington State, where the Hanford Site has been a major employer. A unique feature of this study was the linking of quantitative individual measurement of external whole-body penetrating ionizing radiation exposure of employees at the Hanford Site, using personal dosimeters, and the disease outcome, congenital malformations. The study population included 672 malformation cases and 977 matched controls from births occurring from 1957 through 1980. Twelve specific malformation types were analyzed for evidence of association with employment of the parents at Hanford and with occupational exposure to ionizing radiation. Two defects, congenital dislocation of the hip and tracheoesophageal fistula, showed statistically significant associations with employment of the parents at Hanford, but not with parental radiation exposure. Neural tube defects showed a significant association with parental preconception exposure, on the basis of a small number of cases. Eleven other defects, including Down syndrome, for which an association with radiation was considered most likely, showed no evidence of such an association. When all malformations were analyzed as a group, there was no evidence of an association with employment of the parents at Hanford, but the relation of parental exposure to radiation before conception was in the positive direction (one-tailed p value between 0.05 and 0.10). Given the number of statistical tests conducted, some or all of the observed positive correlations are likely to represent false positive findings. 30 references.

  3. Influence of electron impact ionization on the termination shock: model case studies

    SciTech Connect

    Soloviev, V.Y.; Schwadron, N.A.; McComas, D.J.

    2004-09-15

    We include a latitudinally localized increase in ionization and subsequent mass loading in a 2.5-dimensional magneto-hydrodynamic case study to analyze its impact on the magnetic field, the flow field geometry, and the TS location. The localized additional mass loading leads to deflection of the flow and weakens the TS. We suggest the possibility that Voyager 1 may have been inside such a region during the recent {approx} 6 month period in 2002 when Voyager 1 observed energetic particle signatures consistent with a TS crossing, but only moderate changes in the magnetic field intensity and ACR spectrum.

  4. Resonantly enhanced multiphoton ionization under XUV FEL radiation: a case study of the role of harmonics

    NASA Astrophysics Data System (ADS)

    Nikolopoulos, G. M.; Lambropoulos, P.

    2015-12-01

    We provide a detailed quantitative study of the possible role of a small admixture of harmonics on resonant two-photon ionization. The motivation comes from the occasional presence of 2nd and 3rd harmonics in FEL radiation. We obtain the dependence of ionic yields on the intensity of the fundamental, the percentage of 2nd harmonic and the detuning of the fundamental from resonance. Having examined the cases of one and two intermediate resonances, we arrive at results of general validity and global behaviour, showing that even a small amount of harmonic may seem deceptively innocuous.

  5. Fully differential study of wave packet scattering in ionization of helium by proton impact

    NASA Astrophysics Data System (ADS)

    Arthanayaka, T.; Lamichhane, B. R.; Hasan, A.; Gurung, S.; Remolina, J.; Borbély, S.; Járai-Szabó, F.; Nagy, L.; Schulz, M.

    2016-07-01

    We present a fully differential study of projectile coherence effects in ionization in p + He collisions. The experimental data are qualitatively reproduced by a non-perturbative ab initio time-dependent model, which treats the projectile coherence properties in terms of a wave packet. A comparison between first- and higher-order treatments shows that the observed interference structures are primarily due to a coherent superposition of different impact parameters leading to the same scattering angle. Higher-order contributions have a significant effect on the interference term.

  6. A combined electron-ion spectrometer for studying complete kinematics of molecular dissociation upon shell selective ionization

    SciTech Connect

    Saha, K.; Banerjee, S. B.; Bapat, B.

    2013-07-15

    A combined electron-ion spectrometer has been built to study dissociation kinematics of molecular ions upon various electronic decay processes ensuing from ionization of neutral molecules. The apparatus can be used with various ionization agents. Ion time-of-flight (ToF) spectra arising from various electronic decay processes are acquired by triggering the ToF measurement in coincidence with energy analyzed electrons. The design and the performance of the spectrometer in a photoionization experiment is presented in detail. Electron spectra and ion time of flight spectra resulting from valence and 2p{sub 1/2} ionization of Argon and those from valence ionization of CO are presented to demonstrate the capability of the instrument. The fragment ion spectra show remarkable differences (both kinematic and cross sectional) dependent on the energy of the ejected electron, corresponding to various electron loss and decay mechanisms in dissociative photoionization of molecules.

  7. Absolute vibrational cross sections for 1-19 eV electron scattering from condensed tetrahydrofuran (THF)

    NASA Astrophysics Data System (ADS)

    Lemelin, V.; Bass, A. D.; Cloutier, P.; Sanche, L.

    2016-02-01

    Absolute cross sections (CSs) for vibrational excitation by 1-19 eV electrons impacting on condensed tetrahydrofuran (THF) were measured with a high-resolution electron energy loss spectrometer. Experiments were performed under ultra-high vacuum (3 × 10-11 Torr) at a temperature of about 20 K. The magnitudes of the vibrational CSs lie within the 10-17 cm2 range. Features observed near 4.5, 9.5, and 12.5 eV in the incident energy dependence of the CSs were compared to the results of theoretical calculations and other experiments on gas and solid-phase THF. These three resonances are attributed to the formation of shape or core-excited shape resonances. Another maximum observed around 2.5 eV is not found in the calculations but has been observed in gas-phase studies; it is attributed to the formation of a shape resonance.

  8. A DFT study of the ionization and electron attachment of 2-azido pyridine

    NASA Astrophysics Data System (ADS)

    Elshakre, Mohamed

    2015-03-01

    A DFT study using B3LYP/6-31G(d,p) level of theory is pursued to investigate the energy and geometry changes of 2-azido pyridine isomers in the S0, D0+, and D0-. In S0, cis-2 azidopyridine is the most stable, followed by cyclic tetrazole and trans isomer is the least stable. In D0+, the cis isomer is the most stable, followed by trans isomer, and tetrazole isomer is the least stable. In the D0- state, the trans form is the most stable, followed by the cis and the tetrazolo form is the least stable. Single point vertical excitation energy calculations of the cis form gave four excited states at 266.4, 239.4, 199.4, and 196.1 nm, all having π-π∗ character. For trans isomer, five excited states at, 256.7, 250.3, 229.7, 199.0, 197.0 nm all resulting from π-π∗ transitions. For the tetrazole isomer, seven excited states at 269.3, 242.7, 198.0, 187.2, 183.9, 182.1, 178.7 nm all resulting from π-π∗ transitions. The geometries of the 3 isomers show noticeable changes in bond lengths, bond angles and dihedral angles, upon ionization and electron attachment. The ionization results in a remarkable variation of the NBO atomic charges as a result of ionization and electron attachment. where electron density of HOMO of the D0+ state is found to be much lower than that of the HOMO of the S0 in the case of ionization. The dipole moment calculations show that tetrazole isomer has the largest polarization in the S0 state, followed by cis isomer and trans isomer is the least polarized. The same pattern is found in the D0+ state. In the D0- state, trans isomer is the highest polarized, followed by the cis, and tetrazole isomer is the least polarized. The rotational constants calculations of cis- isomer show that the cation is elongated along the long in-plane axis and compressed along the two short out-of-plane axes while the anion is compressed along the long in-plane axis, and elongated along the two short out-of plane axes. The cation and anion of trans isomer show

  9. Studies of ground-state dynamics in isolated species by ionization-detected stimulated Raman techniques

    SciTech Connect

    Felker, P.M.

    1993-12-01

    First, the author aims to develop methods of nonlinear Raman spectroscopy for application in studies of sparse samples. Second, the author wishes to apply such methods to structural and dynamical studies of species (molecules, complexes, and clusters) in supersonic molecular beams. In the past year, the author has made progress in several areas. The first pertains to the application of mass-selective ionization-detected stimulated Raman spectroscopies (IDSRS) to the size-specific vibrational spectroscopy of solute-solvent{sub n} clusters. The second involves the application of IDSRS methods to studies of jet-cooled benzene clusters. The third pertains to the use of IDSRS methods in the study of intermolecular vibrational transitions in van der Waals complexes.

  10. Epidemiologic Study of One Million American Workers and Military Veterans Exposed to Ionizing Radiation

    SciTech Connect

    Boice, John D.

    2015-02-27

    A pilot study was completed demonstrating the feasibility of conducting an epidemiologic study assessing cancer and other disease mortality among nearly one million US veterans and workers exposed to ionizing radiation, a population 10 times larger than atomic bomb survivor study with high statistical power to evaluate low dose rate effects. Among the groups enumerated and/or studied were: (1) 194,000 Department of Energy Uranium Workers; (2) 6,700 Rocketdyne Radiation Workers; (3) 7,000 Mound Radiation Workers; (4) 156,000 DOE Plutonium Workers; (5) 212,000 Nuclear Power Plant Workers; (6) 130,000 Industrial Radiography Workers; (7) 1.7 million Medical Workers and (8) 135,000 Atomic Veterans.

  11. Valence ionized states of iron pentacarbonyl and eta5-cyclopentadienyl cobalt dicarbonyl studied by symmetry-adapted cluster-configuration interaction calculation and collision-energy resolved Penning ionization electron spectroscopy.

    PubMed

    Fukuda, Ryoichi; Ehara, Masahiro; Nakatsuji, Hiroshi; Kishimoto, Naoki; Ohno, Koichi

    2010-02-28

    Valence ionized states of iron pentacarbonyl Fe(CO)(5) and eta(5)-cyclopentadienyl cobalt dicarbonyl Co(eta(5)-C(5)H(5))(CO)(2) have been studied by ultraviolet photoelectron spectroscopy, two-dimensional Penning ionization electron spectroscopy (2D-PIES), and symmetry-adapted cluster-configuration interaction calculations. Theory provided reliable assignments for the complex ionization spectra of these molecules, which have metal-carbonyl bonds. Theoretical ionization energies agreed well with experimental observations and the calculated wave functions could explain the relative intensities of PIES spectra. The collision-energy dependence of partial ionization cross sections (CEDPICS) was obtained by 2D-PIES. To interpret these CEDPICS, the interaction potentials between the molecules and a Li atom were examined in several coordinates by calculations. The relation between the slope of the CEDPICS and the electronic structure of the ionized states, such as molecular symmetry and the spatial distribution of ionizing orbitals, was analyzed. In Fe(CO)(5), an attractive interaction was obtained for the equatorial CO, while the interaction for the axial CO direction was repulsive. For Co(eta(5)-C(5)H(5))(CO)(2), the interaction potential in the direction of both Co-C-O and Co-Cp ring was attractive. These anisotropic interactions and ionizing orbital distributions consistently explain the relative slopes of the CEDPICS.

  12. Recent advances in the study of ionizing radiation damage and repair.

    PubMed

    Arrand, J E; Michael, B D

    1992-06-01

    This workshop, organized under the auspices of the EC Concerted Action Programme on DNA Repair and Cancer, was held at the CRC Gray Laboratory, Northwood, Middlesex, UK, 23-25 October 1991. The 42 participants were drawn mainly from laboratories participating in the EC Concerted Action, with a few visitors from elsewhere. The discussions centred on the increasing convergence of classical radiobiology and biophysics with molecular biology and mammalian cell genetics to study mechanisms of DNA strand break accumulation and repair following exposure to ionizing radiation. There was a strong emphasis on the application of this research both to cancer radiotherapy and to detection of individuals at risk from cancer due to exposure to ionizing radiation. The first two days were organized as six workshop sessions; on the third day we joined forces with Julie Denekamp and dedicated a session to the memory of our late friend and colleague, Nic McNally. The rest of this day was devoted to reviews by his colleagues and collaborators of the fields of research to which he contributed so much. An evening of music and readings, organized by Joanna and Rachel McNally, completed the memorial. Here we review the first seven sessions of the workshop, emphasizing the more recent approaches and the new information they have given us.

  13. Heterogeneous clusters as a model system for the study of ionization dynamics within tampered samples

    SciTech Connect

    Ziaja, B.; Chapman, H. N.; Santra, R.; Laarmann, T.; Weckert, E.; Bostedt, C.; Moeller, T.

    2011-09-15

    Tampering of a sample with a layer of another material is a promising technique to slow down the expansion dynamics within laser irradiated samples, with sound implications for single-particle diffraction imaging. Ideally, if an imaged object is covered by a layer of another material, during the irradiation this layer will be primarily ionized and will expand fast due to Coulomb repulsion, whereas the object located within the net neutral core will expand more slowly (hydrodynamically). We investigate the details of the electronic damage within the tampered samples during their irradiation with an intense extreme ultraviolet (EUV) pulse. We study heterogeneous clusters composed of noble gas atoms, Xe and Ar, for which chemical-bond effects can be neglected. Using a fully nonequilibrium kinetic equation code, we demonstrate the influence of cluster composition on ionization dynamics; in particular, on the electronic damage. The results are obtained for the wavelength of 32 nm, which is available at the free-electron laser in Hamburg (FLASH) facility, but our conclusions can also have implications for samples with a more complex structure and irradiated at a much shorter wavelength.

  14. Studying the Chemistry of Cationized Triacylglycerols Using Electrospray Ionization Mass Spectrometry and Density Functional Theory Computations

    NASA Astrophysics Data System (ADS)

    Grossert, J. Stuart; Herrera, Lisandra Cubero; Ramaley, Louis; Melanson, Jeremy E.

    2014-08-01

    Analysis of triacylglycerols (TAGs), found as complex mixtures in living organisms, is typically accomplished using liquid chromatography, often coupled to mass spectrometry. TAGs, weak bases not protonated using electrospray ionization, are usually ionized by adduct formation with a cation, including those present in the solvent (e.g., Na+). There are relatively few reports on the binding of TAGs with cations or on the mechanisms by which cationized TAGs fragment. This work examines binding efficiencies, determined by mass spectrometry and computations, for the complexation of TAGs to a range of cations (Na+, Li+, K+, Ag+, NH4 +). While most cations bind to oxygen, Ag+ binding to unsaturation in the acid side chains is significant. The importance of dimer formation, [2TAG + M]+ was demonstrated using several different types of mass spectrometers. From breakdown curves, it became apparent that two or three acid side chains must be attached to glycerol for strong cationization. Possible mechanisms for fragmentation of lithiated TAGs were modeled by computations on tripropionylglycerol. Viable pathways were found for losses of neutral acids and lithium salts of acids from different positions on the glycerol moiety. Novel lactone structures were proposed for the loss of a neutral acid from one position of the glycerol moiety. These were studied further using triple-stage mass spectrometry (MS3). These lactones can account for all the major product ions in the MS3 spectra in both this work and the literature, which should allow for new insights into the challenging analytical methods needed for naturally occurring TAGs.

  15. Distributions of deposited energy and ionization clusters around ion tracks studied with Geant4 toolkit

    NASA Astrophysics Data System (ADS)

    Burigo, Lucas; Pshenichnov, Igor; Mishustin, Igor; Hilgers, Gerhard; Bleicher, Marcus

    2016-05-01

    The Geant4-based Monte Carlo model for Heavy-Ion Therapy (MCHIT) was extended to study the patterns of energy deposition at sub-micrometer distance from individual ion tracks. Dose distributions for low-energy 1H, 4He, 12C and 16O ions measured in several experiments are well described by the model in a broad range of radial distances, from 0.5 to 3000 nm. Despite the fact that such distributions are characterized by long tails, a dominant fraction of deposited energy (∼80%) is confined within a radius of about 10 nm. The probability distributions of clustered ionization events in nanoscale volumes of water traversed by 1H, 2H, 4He, 6Li, 7Li, and 12C ions are also calculated. A good agreement of calculated ionization cluster-size distributions with the corresponding experimental data suggests that the extended MCHIT can be used to characterize stochastic processes of energy deposition to sensitive cellular structures.

  16. Exposure to the atmospheric ionizing radiation environment: studies on Icelandic and Italian civilian aviation flight personnel

    NASA Astrophysics Data System (ADS)

    de Angelis, G.; Caldora, M.; Santaquilani, M.; Scipione, R.; Verdecchia, A.; Rafnsson, V.; Hrafnkelsson, J.; Sulem, P.; Gudjonsdottir, A. J.

    The largest source of data on human exposure to low dose rate radiation may be airline flight personnel, if enrolled for studies on health effects induced by the cosmic-ray-generated atmospheric ionizing radiation, whose total dose, increasing over the years, may cause delayed radiation-induced health effects, with the high-LET and highly ionizing neutron component typical of atmospheric radiation. With regards to this, the Italian civilian airline flight personnel have been studied by analyzing the atmospheric ionizing radiation exposure and associated effects. The study population includes all Italian civilian airline flight personnel, both cockpit and cabin crewmembers, whose work history records and actual flights (route, aircraft type, and date for each individual flight for each person where possible) were available. The dose calculations were performed along specific flight legs, taking into account the actual flight profiles for all different routes and the variations with time of solar and geomagnetic parameters, in order to take into account the whole atmospheric neutron spectrum. Dose values for each flight are applied to the flight history of study participants in order to estimate the individual annual and lifetime occupational radiation dose. Following the same protocols for both cohorts in terms of dose evaluation, a comparative study has been performed between the radiation exposure patterns of the Icelandic and the Italian civilian aviation flight personnel. These two populations represent two extremes within the group of worldwide airline personnel. The Icelandic crewmembers, like only in the world their Canadian colleagues, always fly over or very close to the geomagnetic pole, and are this way exposed to high doses within each flight leg, whereas the Italian crewmembers, apart from transatlantic flights, are always flying close to the geomagnetic equator or anyhow quite far from the geomagnetic pole, receiving a small dose rates for each flight

  17. Resonance ionization mass spectrometric study of the promethium/samarium isobaric pair

    SciTech Connect

    Shaw, R.W.; Young, J.P.; Smith, D.H.

    1988-01-01

    Samarium daughters are problematic in isotope ratio measurements of promethium because they are isobaric. Resonance ionization mass spectrometry was utilized to circumvent this problem. An ionization selectivity factor of at least 1000:1 has been measured for promethium over samarium at 584.6 nm. Resonance ionization spectra have been recorded for both elements over the 528-560 and 580-614 nm wavelength ranges.

  18. Nonlocal analysis to study of the impact ionization and avalanche characteristics of deep submicron Si devices

    NASA Astrophysics Data System (ADS)

    Masudy-Panah, Saeid

    2011-04-01

    In this paper, we have presented electric field dependence of the electron and hole impact ionization coefficients and threshold energies in submicron Si diodes with intrinsic region thicknesses down to 31 nm. To do so, we have used a nonlocal analysis, in order to take the effects of arbitrary distribution of ionization events in both space and time domains and the effects of enhancement in the average speed of those carriers which ionize early in their trajectories as well as nonuniform electric fields in the multiplication region and its surrounding ambient, carrier's dead space history and its spatial ionization rate, into consideration all in one comprehensive analytic model.

  19. Theoretical study of γ-aminobutyric acid conformers: Intramolecular interactions and ionization energies

    NASA Astrophysics Data System (ADS)

    Wang, Ke-Dong; Wang, Mei-Ting; Meng, Ju

    2014-10-01

    Allowing for all combinations of internal single-bond rotamers, 1,296 unique trial structures of γ-Aminobutyric acid (GABA) are obtained. All of these structures are optimized at the M06-2X level of theory and a total of 68 local minimal conformers are found. The nine low-lying conformers are used for further studies. According to the calculated relative Gibbs free energies at M06-2X level of theory, we find that the dispersion is important for the relative energy of GABA. The intramolecular hydrogen bonds and hyperconjugative interaction and their effects on the conformational stability are studied. The results show that both of them have great influence on the conformers. The vertical ionization energies (VIE) are calculated and match the experimental data well. The results show that the neutral GABA in the gas phase is a multi-conformer system and at least four conformations exist.

  20. Double ionization of helium by bare ions: Theoretical study of the fully differential cross sections

    NASA Astrophysics Data System (ADS)

    López, S. D.; Garibotti, C. R.; Otranto, S.

    2011-06-01

    This work presents a theoretical study of fully differential cross sections (FDCSs) for the double ionization of an He target by ion impact within a distorted wave model. The initial atomic system is described by two approximated wave functions of different accuracy proposed by Bonham and Kohl. For the final channel several models are considered based upon improvements and simplifications of the well-known three-body Coulomb (3C) model. The influence of the receding projectile on the resulting fragments is also studied by implementing a model with effective charges that depend on the momenta of the four particles. The FDCSs resulting for different electron energy sharing are discussed. The sensitivity of the FDCSs to the projectile charge sign and magnitude is explored over the energy range 700 keV/amu through 6 MeV/amu.

  1. Study of bis(bibenzyls) in bryophytes using electron ionization time-of-flight and electrospray ionization triple-quadrupole mass spectrometry.

    PubMed

    Guo, Huaifang; Xing, Jie; Xie, Chunfeng; Qu, Jianbo; Gao, Yanhui; Lou, Hongxiang

    2007-01-01

    A detailed analysis of mass spectra generated from bis(bibenzyl) compounds in bryophytes under electron ionization time-of-flight (EI-TOF) and electrospray ionization triple-quadrupole (ESI-TQ) mass spectrometry conditions is reported. Proposed structures of the fragment ions were obtained by tracking the functional groups of 15 bis(bibenzyls), the structures of which are similar except for some alkoxyl substituents and linkage sites of biphenyl ether bonds. The elucidation was aided by the use of accurate mass measurements. Attempts have been made to provide rational pathways for the formation of these fragment ions, and a generalized fragmentation mechanism is proposed. The bis(bibenzyls) mentioned in this study include three types according to their structure characteristics, i.e. one biphenyl ether bond (A-type), two biphenyl ether bonds (B-type), one biphenyl ether and one biphenyl bond (C-type). The three types display different EI-MS and ESI-MS/MS product profiles, by which the bis(bibenzyl) type and the number of alkoxyl substituents can be identified. Isomers of bis(bibenzyls) can be differentiated to some extent, while the linkage sites of biphenyl ether bonds are difficult to identify. The structure-fragmentation relationships will facilitate the characterization of other bis(bibenzyls) and this will be of value for the high-throughput screening of novel bis(bibenzyls) in bryophytes.

  2. First stereoselective synthesis of (+)-magnostellin C, a tetrahydrofuran type of lignan bearing a chiral secondary benzyl alcohol.

    PubMed

    Yamauchi, S; Kinoshita, Y

    2001-07-01

    (+)-Magnostellin C, which is a tetrahydrofuran type of lignan bearing a chiral secondary benzylic hydroxy group, was stereoselectively synthesized from L-arabinose by using threo selective aldol condensation.

  3. Double and single ionization of He and other targets studied using cold target recoil momentum spectroscopy

    SciTech Connect

    Doerner, R.; Feagin, J. M.; Brauning, H.; Jagutzki, O.; Jung, M.; Kanter, E. P.; Khemliche, H.; Kravis, S.; Mergel, V.; Prior, M. H.; Schmidt-Boeking, H.; Spielberger, L.; Ullrich, J.; Unverzagt, M.; Vogt, T.

    1997-04-01

    Double ionization of an atom by a single photon is the simplest and most fundamental many-electron process. The ejection of two electrons following the absorption of one photon is strictly prohibited in an independent electron approximation. Thus determining the probability of double photoionization alone is already a challenging test of the understanding of electron-electron correlation. Furthermore, in the slow breakup of a bound system into three charged particles, the final state wave function must represent a high degree of few-body Coulomb correlation involving the simultaneous interaction of all three particles. The case of double photoionization is again particularly well suited to study this problem as the energy and the angular momentum delivered to the system can be very well controlled. Helium, as the most basic three body system, has been the target of extensive studies over the past decades. The purpose of this project has been to study double and single ionization using cold target recoil ion momentum spectroscopy (COLTRIMS). This technique has been widely applied within the area of ion-atom collisions to study the dynamics of energy and momentum transfer in collisions between few-electron systems, and the entire technical machinery has been transferred to photon-atom collisions. The technique uses space- and time-imaging of He{sup +} and He{sup ++} recoil ions created in photon-He collisions to measure the full momentum vector of each ion produced. Event-mode recording is used and a solid angle of nearly 4{pi} is realized, allowing an extremely high data-collection efficiency. In order to reduce the initial momentum spread of the He target a precooled supersonic He jet is used.

  4. Ionizable Nitroxides for Studying Local Electrostatic Properties of Lipid Bilayers and Protein Systems by EPR

    PubMed Central

    Voinov, Maxim A.; Smirnov, Alex I.

    2016-01-01

    Electrostatic interactions are known to play one of the major roles in the myriad of biochemical and biophysical processes. In this Chapter we describe biophysical methods to probe local electrostatic potentials of proteins and lipid bilayer systems that is based on an observation of reversible protonation of nitroxides by EPR. Two types of the electrostatic probes are discussed. The first one includes methanethiosulfonate derivatives of protonatable nitroxides that could be used for highly specific covalent modification of the cysteine’s sulfhydryl groups. Such spin labels are very similar in magnetic parameters and chemical properties to conventional MTSL making them suitable for studying local electrostatic properties of protein-lipid interfaces. The second type of EPR probes is designed as spin-labeled phospholipids having a protonatable nitroxide tethered to the polar head group. The probes of both types report on their ionization state through changes in magnetic parameters and a degree of rotational averaging, thus, allowing one to determine the electrostatic contribution to the interfacial pKa of the nitroxide, and, therefore, determining the local electrostatic potential. Due to their small molecular volume these probes cause a minimal perturbation to the protein or lipid system while covalent attachment secure the position of the reporter nitroxides. Experimental procedures to characterize and calibrate these probes by EPR and also the methods to analyze the EPR spectra by least-squares simulations are also outlined. The ionizable nitroxide labels and the nitroxide-labeled phospholipids described so far cover an exceptionally wide pH range from ca. 2.5 to 7.0 pH units making them suitable to study a broad range of biophysical phenomena especially at the negatively charged lipid bilayer surfaces. The rationale for selecting proper electrostatically neutral interface for calibrating such probes and example of studying surface potential of lipid bilayer is

  5. Iron Catalyzed Dual-Oxidative Dehydrogenative (DOD) Tandem Annulation of Glycine Derivatives with Tetrahydrofurans.

    PubMed

    Huo, Congde; Chen, Fengjuan; Yuan, Yong; Xie, Haisheng; Wang, Yajun

    2015-10-16

    A novel iron-catalyzed dual-oxidative dehydrogenative (DOD) tandem annulation of glycine derivatives with tetrahydrofurans (THFs) for the synthesis of high value quinoline fused lactones has been developed. The reactions were performed under mild reaction conditions. And the use of cheap substrates (glycine derivatives and THF) and an even cheaper simple inorganic iron salt as the catalyst makes this protocol very attractive for potential synthetic applications. PMID:26430718

  6. Copper-Catalyzed Oxidative C-H Amination of Tetrahydrofuran with Indole/Carbazole Derivatives.

    PubMed

    Yang, Qingjing; Choy, Pui Ying; Fu, Wai Chung; Fan, Baomin; Kwong, Fuk Yee

    2015-11-01

    A simple α-C-H amination of cyclic ether with indole/carbazole derivatives has been accomplished by employing copper(II) chloride/bipy as the catalyst system. In the presence of the di-tert-butyl peroxide oxidant, cyclic ethers such as tetrahydrofuran, 1,4-dioxane, and tetrahydropyran successfully undergo C-H/N-H cross dehydrogenative coupling (CDC) with various carbazole or indole derivatives in good-to-excellent yields. PMID:26485515

  7. Environmental analysis of the life cycle emissions of 2-methyl tetrahydrofuran solvent manufactured from renewable resources.

    PubMed

    Slater, C Stewart; Savelski, Mariano J; Hitchcock, David; Cavanagh, Eduardo J

    2016-01-01

    An environmental analysis has been conducted to determine the cradle to gate life cycle emissions to manufacture the green solvent, 2-methyl tetrahydrofuran. The solvent is considered a greener chemical since it can be manufactured from renewable resources with a lower life cycle footprint. Analyses have been performed using different methods to show greenness in both its production and industrial use. This solvent can potentially be substituted for other ether and chlorinated solvents commonly used in organometallic and biphasic reactions steps in pharmaceutical and fine chemical syntheses. The 2-methyl tetrahydrofuran made from renewable agricultural by-products is marketed by Penn A Kem under the name ecoMeTHF™. The starting material, 2-furfuraldehyde (furfural), is produced from corn cob waste by converting the available pentosans by acid hydrolysis. An evaluation of each step in the process was necessary to determine the overall life cycle and specific CO2 emissions for each raw material/intermediate produced. Allocation of credits for CO2 from the incineration of solvents made from renewable feedstocks significantly reduced the overall carbon footprint. Using this approach, the overall life cycle emissions for production of 1 kg of ecoMeTHF™ were determined to be 0.191 kg, including 0.150 kg of CO2. Life cycle emissions generated from raw material manufacture represents the majority of the overall environmental impact. Our evaluation shows that using 2-methyl tetrahydrofuran in an industrial scenario results in a 97% reduction in emissions, when compared to typically used solvents such as tetrahydrofuran, made through a conventional chemical route.

  8. Stereodivergent Organocatalytic Intramolecular Michael Addition/Lactonization for the Asymmetric Synthesis of Substituted Dihydrobenzofurans and Tetrahydrofurans

    PubMed Central

    Belmessieri, Dorine; de la Houpliere, Alix; Calder, Ewen D D; Taylor, James E; Smith, Andrew D

    2014-01-01

    A stereodivergent asymmetric Lewis base catalyzed Michael addition/lactonization of enone acids into substituted dihydrobenzofuran and tetrahydrofuran derivatives is reported. Commercially available (S)-(−)-tetramisole hydrochloride gives products with high syn diastereoselectivity in excellent enantioselectivity (up to 99:1 d.r.syn/anti, 99 % eesyn), whereas using a cinchona alkaloid derived catalyst gives the corresponding anti-diastereoisomers as the major product (up to 10:90 d.r.syn/anti, 99 % eeanti). PMID:24989672

  9. Environmental analysis of the life cycle emissions of 2-methyl tetrahydrofuran solvent manufactured from renewable resources.

    PubMed

    Slater, C Stewart; Savelski, Mariano J; Hitchcock, David; Cavanagh, Eduardo J

    2016-01-01

    An environmental analysis has been conducted to determine the cradle to gate life cycle emissions to manufacture the green solvent, 2-methyl tetrahydrofuran. The solvent is considered a greener chemical since it can be manufactured from renewable resources with a lower life cycle footprint. Analyses have been performed using different methods to show greenness in both its production and industrial use. This solvent can potentially be substituted for other ether and chlorinated solvents commonly used in organometallic and biphasic reactions steps in pharmaceutical and fine chemical syntheses. The 2-methyl tetrahydrofuran made from renewable agricultural by-products is marketed by Penn A Kem under the name ecoMeTHF™. The starting material, 2-furfuraldehyde (furfural), is produced from corn cob waste by converting the available pentosans by acid hydrolysis. An evaluation of each step in the process was necessary to determine the overall life cycle and specific CO2 emissions for each raw material/intermediate produced. Allocation of credits for CO2 from the incineration of solvents made from renewable feedstocks significantly reduced the overall carbon footprint. Using this approach, the overall life cycle emissions for production of 1 kg of ecoMeTHF™ were determined to be 0.191 kg, including 0.150 kg of CO2. Life cycle emissions generated from raw material manufacture represents the majority of the overall environmental impact. Our evaluation shows that using 2-methyl tetrahydrofuran in an industrial scenario results in a 97% reduction in emissions, when compared to typically used solvents such as tetrahydrofuran, made through a conventional chemical route. PMID:26889729

  10. A surface penning ionization study of NH 3 on Ni(111)

    NASA Astrophysics Data System (ADS)

    Bozso, Ferenc; Arias, Jose M.; Hanrahan, Ciaran P.; Yates, John T.; Metiu, Horia; Martin, Richard M.

    1984-03-01

    Surface Penning ionization electron spectroscopy was used to investigate the properties of chemisorbed and condensed multilayers of ammonia on Ni(111). We find that the Penning spectroscopy of chemisorbed ammonia provides similar information to ultraviolet photoelectron spectroscopy: we detect emission from the 3a 1 and 1e molecular orbitals of NH 3. We also find a new peak which we assign to emission from Ni sites whose local work function differs from that of the clean Ni(111) surface. The Penning spectrum of condensed ammonia layers is similar to that of chemisorbed ammonia, but has higher intensity and different peak intensity ratios. Possible reasons for this behavior are suggested. Penning studies of NH 3 adsorbed on a Ni(111) surface precovered with hydrogen or oxygen show that the precoverage does not substantially modify the ammonia spectrum.

  11. Experimental and theoretical study on nonsequential double ionization of carbon disulfide in strong near-IR laser fields

    NASA Astrophysics Data System (ADS)

    Zuo, Wanlong; Ben, Shuai; Lv, Hang; Zhao, Lei; Guo, Jing; Liu, Xue-Shen; Xu, Haifeng; Jin, Mingxing; Ding, Dajun

    2016-05-01

    Nonsequential double ionization (NSDI) of carbon disulfide CS2 in strong 800-nm laser fields is studied experimentally and theoretically. A knee structure is observed in the intensity-dependent double ionization (DI) yield in linearly polarized laser fields, which exhibits a strong dependence on the laser ellipticity. The electron momentum distributions and energy trajectories after DI in both linearly and circularly polarized laser fields are investigated by employing the two-dimensional classical ensemble method. The results clearly show the evidence of NSDI in the strong-field DI of CS2 molecules. It is demonstrated that, similar to that of atoms, NSDI of CS2 molecules is produced via laser-driven electron recollision with the ion core and presents electron-electron correlations in the process. Analysis indicates that both mechanisms in atomic strong-field NSDI, i.e., recollision impact ionization and recollision excitation with subsequent ionization, may also be contributed to NSDI of CS2 in strong laser fields. Further studies are no doubt necessary for a full understanding of the underlying physical mechanism of molecular strong-field NSDI, due to the multicenter character of the molecular structure and the complex molecular excited states that could be involved in the ionization.

  12. Ionization states, cellular toxicity and molecular modeling studies of midazolam complexed with trimethyl-β-cyclodextrin.

    PubMed

    Shityakov, Sergey; Sohajda, Tamás; Puskás, István; Roewer, Norbert; Förster, Carola; Broscheit, Jens-Albert

    2014-01-01

    We investigated the ionization profiles for open-ring (OR) and closed-ring (CR) forms of midazolam and drug-binding modes with heptakis-(2,3,6-tri-O-methyl)-β-cyclodextrin (trimethyl-β-cyclodextrin; TRIMEB) using molecular modeling techniques and quantum mechanics methods. The results indicated that the total net charges for different molecular forms of midazolam tend to be cationic for OR and neutral for CR at physiological pH levels. The thermodynamic calculations demonstrated that CR is less water-soluble than OR, mainly due to the maximal solvation energy (ΔG(CR)(solv = -9.98 kcal·mol ⁻¹), which has a minimal ΔG(OR)(solv) of -67.01 kcal·mol⁻¹. A cell viability assay did not detect any signs of TRIMEB and OR/CR-TRIMEB complex toxicity on the cEND cells after 24 h of incubation in either Dulbecco's Modified Eagles Medium or in heat-inactivated human serum. The molecular docking studies identified the more flexible OR form of midazolam as being a better binder to TRIMEB with the fluorophenyl ring introduced inside the amphiphilic cavity of the host molecule. The OR binding affinity was confirmed by a minimal Gibbs free energy of binding (ΔG(bind)) value of -5.57 ± 0.02 kcal·mol⁻¹, an equilibrium binding constant (K(b)) of 79.89 ± 2.706 μM, and a ligand efficiency index (LE(lig)) of -0.21 ± 0.001. Our current data suggest that in order to improve the clinical applications of midazolam via its complexation with trimethyl-β-cyclodextrin to increase drug's overall aqueous solubility, it is important to concern the different forms and ionization states of this anesthetic. All mean values are indicated with their standard deviations. PMID:25338177

  13. Atmospheric pressure chemical ionization studies of non-polar isomeric hydrocarbons using ion mobility spectrometry and mass spectrometry with different ionization techniques

    NASA Technical Reports Server (NTRS)

    Borsdorf, H.; Nazarov, E. G.; Eiceman, G. A.

    2002-01-01

    The ionization pathways were determined for sets of isomeric non-polar hydrocarbons (structural isomers, cis/trans isomers) using ion mobility spectrometry and mass spectrometry with different techniques of atmospheric pressure chemical ionization to assess the influence of structural features on ion formation. Depending on the structural features, different ions were observed using mass spectrometry. Unsaturated hydrocarbons formed mostly [M - 1]+ and [(M - 1)2H]+ ions while mainly [M - 3]+ and [(M - 3)H2O]+ ions were found for saturated cis/trans isomers using photoionization and 63Ni ionization. These ionization methods and corona discharge ionization were used for ion mobility measurements of these compounds. Different ions were detected for compounds with different structural features. 63Ni ionization and photoionization provide comparable ions for every set of isomers. The product ions formed can be clearly attributed to the structures identified. However, differences in relative abundance of product ions were found. Although corona discharge ionization permits the most sensitive detection of non-polar hydrocarbons, the spectra detected are complex and differ from those obtained with 63Ni ionization and photoionization. c. 2002 American Society for Mass Spectrometry.

  14. Is ionized calcium a reliable predictor of hypocalcemia after total thyroidectomy? A before and after study

    PubMed Central

    TARTAGLIA, F.; GIULIANI, A.; SGUEGLIA, M.; PATRIZI, G.; DI ROCCO, G.; BLASI, S.; RUSSO, G.; TORTORELLI, G.; GIANNOTTI, D.; REDLER, A.

    2014-01-01

    Summary Wanting to find a way of identifying patients suitable for early discharge after thyroidectomy, we set out to establish whether ionized calcium concentration is a better predictor of post-surgical hypocalcemia than total serum calcium. Data were analyzed to establish whether serum ionized calcium concentrations are correlated with total serum calcium levels and symptomatic hypocalcemia after thyroidectomy. Sixty-two patients undergoing total thyroidectomy at the Department of Surgical Sciences of the “Sapienza” University of Rome, Italy, in 2010. Ionized calcium was measured before (day 0) and after surgery (days 1, 2 and 60) in all the patients. These measurements were compared with preoperative (day 0) and postoperative total serum calcium levels (days 1, 2 and 60). The preoperative ionized calcium levels differed from the ionized calcium levels recorded on days 1 and 2; this pattern was not observed for the total calcium concentrations. Conversely, total calcium on days I and II correlated significantly with the various ionized calcium measurements. The presence of parathyroid glands in the surgical specimen did not seem to affect suitability for discharge. The statistical analysis showed that ionized calcium measurements are more reliable than total calcium measurements in the immediate and long-term follow-up of total thyroidectomy patients. Applying a 95% confidence interval we established reference values for both total serum calcium and ionized calcium, below which all patients develop postoperative symptomatic hypocalcemia. In conclusion, measurement of ionized calcium, as opposed to total calcium, should be strongly recommended in the immediate and long-term follow-up of total thyroidectomy patients. PMID:24690338

  15. Is ionized calcium a reliable predictor of hypocalcemia after total thyroidectomy? A before and after study.

    PubMed

    Tartaglia, F; Giuliani, A; Sgueglia, M; Patrizi, G; Di Rocco, G; Blasi, S; Russo, G; Tortorelli, G; Giannotti, D; Redler, A

    2014-01-01

    Wanting to find a way of identifying patients suitable for early discharge after thyroidectomy, we set out to establish whether ionized calcium concentration is a better predictor of post-surgical hypocalcemia than total serum calcium. Data were analyzed to establish whether serum ionized calcium concentrations are correlated with total serum calcium levels and symptomatic hypocalcemia after thyroidectomy. Sixty-two patients undergoing total thyroidectomy at the Department of Surgical Sciences of the "Sapienza" University of Rome, Italy, in 2010. Ionized calcium was measured before (day 0) and after surgery (days 1, 2 and 60) in all the patients. These measurements were compared with preoperative (day 0) and postoperative total serum calcium levels (days 1, 2 and 60). The preoperative ionized calcium levels differed from the ionized calcium levels recorded on days 1 and 2; this pattern was not observed for the total calcium concentrations. Conversely, total calcium on days I and II correlated significantly with the various ionized calcium measurements. The presence of parathyroid glands in the surgical specimen did not seem to affect suitability for discharge. The statistical analysis showed that ionized calcium measurements are more reliable than total calcium measurements in the immediate and long-term follow-up of total thyroidectomy patients. Applying a 95% confidence interval we established reference values for both total serum calcium and ionized calcium, below which all patients develop postoperative symptomatic hypocalcemia. In conclusion, measurement of ionized calcium, as opposed to total calcium, should be strongly recommended in the immediate and longterm follow-up of total thyroidectomy patients. PMID:24690338

  16. Study of genetic effects of high energy radiations with different ionizing capacities on extracellular phages.

    PubMed

    Bresler, S E; Kalinin, V L; Kopylova, Y U; Krivisky, A S; Rybchin, V N; Shelegedin, V N

    1975-07-01

    The inactivating and mutagenic action of high-energy radiations with different ionizing capacities (gamma-rays, protons, alpha-particles and accelerated ions of 12C and 20Ne) was studied by using coliphages lambda11 and SD as subjects. In particular the role of irradiation conditions (broth suspension, pure buffer, dry samples) and of the host functions recA, exrA and polA was investigated. The dose-response curve of induced mutagenesis was studied by measuring the yield of vir mutants in lambda11 and plaque mutants in SD. The following results were obtained. (1) The inactivation kinetics of phages under the action of gamma-rays and protons was first order to a survival of 10(-7). Heavy ions also showed exponential inactivation kinetics to a survival of 10(-4). At higher doses of 20Ne ion bombardment some deviation from one-hit kinetics was observed. For dry samples of phages the dimensions of targets for all types of radiation were approximately proportional to the molecular weights of phage DNA's. For densely ionizing radiation (heavy ions) the inactivating action was 3-5 times weaker than for gamma-rays and protons. (2) Mutagenesis was observed for all types of radiation, but heavy ions were 1-5-2 times less efficient than gamma-rays. For both phages studied the dose-response curve of mutagenesis was non-linear. The dependence on the dose was near to parabolic for lambda11. For SD a plateau or maximum of mutagenesis was observed for the relative number of mutants at a survival of about 10(-4). (3) Host-cell functions recA and exrA were practically indifferent for survival of gamma-irradiated phage lambda11, but indispensable for mutagenesis. Mutation recAI3 abolished induced vir mutations totally and exrA- reduced them significantly. The absence of the function polA had a considerable influence on phage survival, but no effect on vir mutation yield (if compared at the same survival level). (4) In conditions of indirect action of gamma-rays no vir mutations were

  17. Background Ionizing Radiation and the Risk of Childhood Cancer: A Census-Based Nationwide Cohort Study

    PubMed Central

    Lupatsch, Judith E.; Zwahlen, Marcel; Röösli, Martin; Niggli, Felix; Grotzer, Michael A.; Rischewski, Johannes; Egger, Matthias; Kuehni, Claudia E.

    2015-01-01

    Background Exposure to medium or high doses of ionizing radiation is a known risk factor for cancer in children. The extent to which low-dose radiation from natural sources contributes to the risk of childhood cancer remains unclear. Objectives In a nationwide census-based cohort study, we investigated whether the incidence of childhood cancer was associated with background radiation from terrestrial gamma and cosmic rays. Methods Children < 16 years of age in the Swiss National Censuses in 1990 and 2000 were included. The follow-up period lasted until 2008, and incident cancer cases were identified from the Swiss Childhood Cancer Registry. A radiation model was used to predict dose rates from terrestrial and cosmic radiation at locations of residence. Cox regression models were used to assess associations between cancer risk and dose rates and cumulative dose since birth. Results Among 2,093,660 children included at census, 1,782 incident cases of cancer were identified including 530 with leukemia, 328 with lymphoma, and 423 with a tumor of the central nervous system (CNS). Hazard ratios for each millisievert increase in cumulative dose of external radiation were 1.03 (95% CI: 1.01, 1.05) for any cancer, 1.04 (95% CI: 1.00, 1.08) for leukemia, 1.01 (95% CI: 0.96, 1.05) for lymphoma, and 1.04 (95% CI: 1.00, 1.08) for CNS tumors. Adjustment for a range of potential confounders had little effect on the results. Conclusions Our study suggests that background radiation may contribute to the risk of cancer in children, including leukemia and CNS tumors. Citation Spycher BD, Lupatsch JE, Zwahlen M, Röösli M, Niggli F, Grotzer MA, Rischewski J, Egger M, Kuehni CE, for the Swiss Pediatric Oncology Group and the Swiss National Cohort. 2015. Background ionizing radiation and the risk of childhood cancer: a census-based nationwide cohort study. Environ Health Perspect 123:622–628; http://dx.doi.org/10.1289/ehp.1408548 PMID:25707026

  18. High-resolution pulsed-field ionization photoelectron study of O{sub 2}

    SciTech Connect

    Hsu, C.W.; Evans, M.; Stimson, S.

    1997-04-01

    There have been numerous photoionization studies of O{sub 2} over the past 10 years. Using the pulsed field ionization (PFI) photoelectron spectroscopy (PES) technique, the electronic ground state of O{sub 2}{sup +} (X{sup 2}{Pi}{sub g}{sup {minus}}) has been well studied on the rotationally resolved level by several groups. However, due to the difficulty of producing photon energies above 18 eV using the tunable lasers, the electronic excited states of O{sub 2}{sup +} have been mostly studied on the vibrationally resolved level using the threshold photoelectron spectroscopy (TPES) and the synchrotron radiation. Recently, the authors developed a new technique for performing the PFI-PE experiments using multi-bunch synchrotron radiation at the Chemical Dynamics Beamline of the Advanced Light Source (ALS). Using the high resolution VUV light from the ALS, they have obtained the PFI-PE spectra of O{sub 2} between 12 and 24 eV. In this abstract, the authors report for the first time the rotationally resolved spectra of O{sub 2}{sup +} (b{sup 4}{Sigma}{sub g}{sup {minus}}, v{sup +}=0).

  19. Electron ionization of acetylene

    NASA Astrophysics Data System (ADS)

    King, Simon J.; Price, Stephen D.

    2007-11-01

    Relative partial ionization cross sections and precursor specific relative partial ionization cross sections for fragment ions formed by electron ionization of C2H2 have been measured using time-of-flight mass spectrometry coupled with a 2D ion-ion coincidence technique. We report data for the formation of H+, H2+, C2+, C+/C22+, CH +/C2H22+, CH2+, C2+, and C2H + relative to the formation of C2H2+, as a function of ionizing electron energy from 30-200eV. While excellent agreement is found between our data and one set of previously published absolute partial ionization cross sections, some discrepancies exist between the results presented here and two other recent determinations of these absolute partial ionization cross sections. We attribute these differences to the loss of some translationally energetic fragment ions in these earlier studies. Our relative precursor-specific partial ionization cross sections enable us, for the first time, to quantify the contribution to the yield of each fragment ion from single, double, and triple ionization. Analysis shows that at 50eV double ionization contributes 2% to the total ion yield, increasing to over 10% at an ionizing energy of 100eV. From our ion-ion coincidence data, we have derived branching ratios for charge separating dissociations of the acetylene dication. Comparison of our data to recent ab initio/RRKM calculations suggest that close to the double ionization potential C2H22+ dissociates predominantly on the ground triplet potential energy surface (Σg-3) with a much smaller contribution from dissociation via the lowest singlet potential energy surface (Δg1). Measurements of the kinetic energy released in the fragmentation reactions of C2H22+ have been used to obtain precursor state energies for the formation of product ion pairs, and are shown to be in good agreement with available experimental data and with theory.

  20. Ionizing radiation-induced mutagenesis: radiation studies in Neurospora predictive for results in mammalian cells

    NASA Technical Reports Server (NTRS)

    Evans, H. H.; DeMarini, D. M.

    1999-01-01

    Ionizing radiation was the first mutagen discovered and was used to develop the first mutagenicity assay. In the ensuing 70+ years, ionizing radiation became a fundamental tool in understanding mutagenesis and is still a subject of intensive research. Frederick de Serres et al. developed and used the Neurospora crassa ad-3 system initially to explore the mutagenic effects of ionizing radiation. Using this system, de Serres et al. demonstrated the dependence of the frequency and spectra of mutations induced by ionizing radiation on the dose, dose rate, radiation quality, repair capabilities of the cells, and the target gene employed. This work in Neurospora predicted the subsequent observations of the mutagenic effects of ionizing radiation in mammalian cells. Modeled originally on the mouse specific-locus system developed by William L. Russell, the N. crassa ad-3 system developed by de Serres has itself served as a model for interpreting the results in subsequent systems in mammalian cells. This review describes the primary findings on the nature of ionizing radiation-induced mutagenesis in the N. crassa ad-3 system and the parallel observations made years later in mammalian cells.

  1. Nature of sodium atoms/(Na(+), e(-)) contact pairs in liquid tetrahydrofuran.

    PubMed

    Glover, William J; Larsen, Ross E; Schwartz, Benjamin J

    2010-09-01

    With no internal vibrational or rotational degrees of freedom, atomic solutes serve as the simplest possible probe of a condensed-phase environment's influence on solute electronic structure. Of the various atomic species that can be formed in solution, the quasi-one-electron alkali atoms in ether solvents have been the most widely studied experimentally, primarily due to the convenient location of their absorption spectra at visible wavelengths. The nature of solvated alkali atoms, however, remains controversial: the consensus view is that solvated alkali atoms exist as (Na(+), e(-)) tight-contact pairs (TCPs), species in which the alkali valence electron is significantly displaced from the alkali nucleus and confined primarily by the first solvent shell. Thus, to shed light on the nature of alkali atoms in solution and to further our understanding of condensed-phase effects on solutes' electronic structure, we have performed mixed quantum/classical molecular dynamics simulations of sodium atoms in liquid tetrahydrofuran (Na(0)/THF). Our interest in this particular system stems from recent pump-probe experiments in our group, which found that the rate at which this species is solvated depends on how it was created ( Science 2008 , 321 , 1817 ); in other words, the solvation dynamics of this system do not obey linear response. Our simulations reproduce the experimental spectroscopy of this system and clearly indicate that neutral Na atoms exist as (Na(+), e(-)) TCPs in solution. We find that the driving force for the displacement of sodium's valence electron is the formation of a tight solvation shell around the partially exposed Na(+). On average, four THF oxygens coordinate the cation end of the TCP; however, we also observe fluctuations to other solvent coordination numbers. Furthermore, we find that species with different solvent coordination numbers have unique absorption spectra and that interconversion between species with different solvent coordination

  2. Deciphering the bipolar planetary nebula Abell 14 with 3D ionization and morphological studies

    NASA Astrophysics Data System (ADS)

    Akras, S.; Clyne, N.; Boumis, P.; Monteiro, H.; Gonçalves, D. R.; Redman, M. P.; Williams, S.

    2016-04-01

    Abell 14 is a poorly studied object despite being considered a born-again planetary nebula. We performed a detailed study of its 3D morphology and ionization structure using the SHAPE and MOCASSIN codes. We found that Abell 14 is a highly evolved, bipolar nebula with a kinematical age of ˜19 400 yr for a distance of 4 kpc. The high He abundance, and N/O ratio indicate a progenitor of 5 M⊙ that has experienced the third dredge-up and hot bottom burning phases. The stellar parameters of the central source reveal a star at a highly evolved stage near to the white dwarf cooling track, being inconsistent with the born-again scenario. The nebula shows unexpectedly strong [N I] λ5200 and [O I] λ6300 emission lines indicating possible shock interactions. Abell 14 appears to be a member of a small group of highly evolved, extreme type-I planetary nebulae (PNe). The members of this group lie at the lower-left corner of the PNe regime on the [N II]/Hα versus [S II]/Hα diagnostic diagram, where shock-excited regions/objects are also placed. The low luminosity of their central stars, in conjunction with the large physical size of the nebulae, result in a very low photoionization rate, which can make any contribution of shock interaction easily perceptible, even for small velocities.

  3. New Modeling Approaches to Study DNA Damage by the Direct and Indirect Effects of Ionizing Radiation

    NASA Technical Reports Server (NTRS)

    Plante, Ianik; Cucinotta, Francis A.

    2012-01-01

    DNA is damaged both by the direct and indirect effects of radiation. In the direct effect, the DNA itself is ionized, whereas the indirect effect involves the radiolysis of the water molecules surrounding the DNA and the subsequent reaction of the DNA with radical products. While this problem has been studied for many years, many unknowns still exist. To study this problem, we have developed the computer code RITRACKS [1], which simulates the radiation track structure for heavy ions and electrons, calculating all energy deposition events and the coordinates of all species produced by the water radiolysis. In this work, we plan to simulate DNA damage by using the crystal structure of a nucleosome and calculations performed by RITRACKS. The energy deposition events are used to calculate the dose deposited in nanovolumes [2] and therefore can be used to simulate the direct effect of the radiation. Using the positions of the radiolytic species with a radiation chemistry code [3] it will be possible to simulate DNA damage by indirect effect. The simulation results can be compared with results from previous calculations such as the frequencies of simple and complex strand breaks [4] and with newer experimental data using surrogate markers of DNA double ]strand breaks such as . ]H2AX foci [5].

  4. Studies on laser-assisted Penning ionization by the optogalvanic effect in Ne/Eu hollow cathode discharge.

    PubMed

    Saini, V K; Kumar, P; Dixit, S K; Nakhe, S V

    2015-02-01

    Laser-assisted Penning ionization (LAPI) is detected in a Ne/Eu hollow cathode (HC) discharge lamp using the pulsed optogalvanic (OG) method. In the Ne/Eu discharge, doubly ionized europium excited energy levels Eu[4f(7)(P(7/2,5/2)6)] lie within the thermal limit (∼kT) from the laser-excited neon's energy level [2p(5)(P3/202)3p or 2p(8) (in Paschen notation)] lying at 149,848  cm(-1). Therefore, Penning ionization (PI) of europium atoms likely to occur into its highly excited ionic states is investigated. To probe the PI of europium, the temporal profiles of its counterpart neon OG signal are studied as a function of discharge current for the transitions (1s(4)→2p(8)) and (1s(2)→2p(2)), corresponding to 650.65 and 659.89 nm wavelengths, respectively. It is observed that PI of europium alters the overall discharge characteristics significantly and, hence, modifies the temporal profile of the OG signals accordingly. The quasi-resonant ionizing energy transfer collisions between laser-excited Ne 2p(8) atoms and electronically excited europium P(9/2)10 atoms are used to explain the LAPI mechanism. Such LAPI studies carried out in HC discharge could be useful for the discharge of a metal-vapor laser with appropriate Penning mixtures.

  5. Amifostine, a radioprotectant agent, protects rat brain tissue lipids against ionizing radiation induced damage: An FTIR microspectroscopic imaging study

    SciTech Connect

    Cakmak G.; Miller L.; Zorlu, F.; Severcan, F.

    2012-03-03

    Amifostine is the only approved radioprotective agent by FDA for reducing the damaging effects of radiation on healthy tissues. In this study, the protective effect of amifostine against the damaging effects of ionizing radiation on the white matter (WM) and grey matter (GM) regions of the rat brain were investigated at molecular level. Sprague-Dawley rats, which were administered amifostine or not, were whole-body irradiated at a single dose of 800 cGy, decapitated after 24 h and the brain tissues of these rats were analyzed using Fourier transform infrared microspectroscopy (FTIRM). The results revealed that the total lipid content and CH{sub 2} groups of lipids decreased significantly and the carbonyl esters, olefinic=CH and CH{sub 3} groups of lipids increased significantly in the WM and GM after exposure to ionizing radiation, which could be interpreted as a result of lipid peroxidation. These changes were more prominent in the WM of the brain. The administration of amifostine before ionizing radiation inhibited the radiation-induced lipid peroxidation in the brain. In addition, this study indicated that FTIRM provides a novel approach for monitoring ionizing radiation induced-lipid peroxidation and obtaining different molecular ratio images can be used as biomarkers to detect lipid peroxidation in biological systems.

  6. Studies on laser-assisted Penning ionization by the optogalvanic effect in Ne/Eu hollow cathode discharge.

    PubMed

    Saini, V K; Kumar, P; Dixit, S K; Nakhe, S V

    2015-02-01

    Laser-assisted Penning ionization (LAPI) is detected in a Ne/Eu hollow cathode (HC) discharge lamp using the pulsed optogalvanic (OG) method. In the Ne/Eu discharge, doubly ionized europium excited energy levels Eu[4f(7)(P(7/2,5/2)6)] lie within the thermal limit (∼kT) from the laser-excited neon's energy level [2p(5)(P3/202)3p or 2p(8) (in Paschen notation)] lying at 149,848  cm(-1). Therefore, Penning ionization (PI) of europium atoms likely to occur into its highly excited ionic states is investigated. To probe the PI of europium, the temporal profiles of its counterpart neon OG signal are studied as a function of discharge current for the transitions (1s(4)→2p(8)) and (1s(2)→2p(2)), corresponding to 650.65 and 659.89 nm wavelengths, respectively. It is observed that PI of europium alters the overall discharge characteristics significantly and, hence, modifies the temporal profile of the OG signals accordingly. The quasi-resonant ionizing energy transfer collisions between laser-excited Ne 2p(8) atoms and electronically excited europium P(9/2)10 atoms are used to explain the LAPI mechanism. Such LAPI studies carried out in HC discharge could be useful for the discharge of a metal-vapor laser with appropriate Penning mixtures. PMID:25967764

  7. A MULTIWAVELENGTH STUDY ON THE FATE OF IONIZING RADIATION IN LOCAL STARBURSTS

    SciTech Connect

    Hanish, D. J.; Oey, M. S.; Rigby, J. R.; Lee, J. C.; De Mello, D. F.

    2010-12-20

    The fate of ionizing radiation is vital for understanding cosmic ionization, energy budgets in the interstellar and intergalactic medium, and star formation rate indicators. The low observed escape fractions of ionizing radiation have not been adequately explained, and there is evidence that some starbursts have high escape fractions. We examine the spectral energy distributions (SEDs) of a sample of local star-forming galaxies, containing 13 local starburst galaxies and 10 of their ordinary star-forming counterparts, to determine if there exist significant differences in the fate of ionizing radiation in these galaxies. We find that the galaxy-to-galaxy variations in the SEDs are much larger than any systematic differences between starbursts and non-starbursts. For example, we find no significant differences in the total absorption of ionizing radiation by dust, traced by the 24 {mu}m, 70 {mu}m, and 160 {mu}m MIPS bands of the Spitzer Space Telescope, although the dust in starburst galaxies appears to be hotter than that of non-starburst galaxies. We also observe no excess ultraviolet flux in the Galaxy Evolution Explorer bands that could indicate a high escape fraction of ionizing photons in starburst galaxies. The small H{alpha} fractions of the diffuse, warm ionized medium (WIM) in starburst galaxies are apparently due to temporarily boosted H{alpha} luminosity within the star-forming regions themselves, with an independent, constant WIM luminosity. This independence of the WIM and starburst luminosities contrasts with WIM behavior in non-starburst galaxies and underscores our poor understanding of radiation transfer in both ordinary and starburst galaxies.

  8. Study of Hydrophobic and Ionizable Hydrophilic Copolymers at Polymer/Solid and Polymer/Liquid Interfaces

    SciTech Connect

    Perahia, Dvora

    2011-11-01

    Joint experimental-computational efforts were set to characterize the interfacial effects on the structure and dynamics of polymers consisting of highly rigid hydrophilic-ionizable and hydrophobic sub-units within one polymeric chain casted into thin films of several molecular dimensions. Focusing on the ultra thin film region we separate out the interfacial effects from bulk characteristics. Specifically, the study sought to: identify the parameters that control the formation of a stable polymer-solid interface. The study consists of two components, experimental investigations and computational efforts. The experimental component was designed to derive empirical trends that can be used to correlate the set of coupled polymer molecular parameters with the interfacial characteristics of these polymers, and their response to presence of solvents. The computational study was designed to provide molecular insight into the ensemble averages provided by the experimental efforts on multiple length scales from molecular dimensions, to the nanometer lengths to a macroscopic understanding of solvent interactions with structured polymers. With the ultimate goal of correlating molecular parameters to structure, dynamics and properties of ionic polymers, the first stage of the research began with the study of two systems, one which allowed tailoring the flexibility of the backbone without the presence of ionic groups, but with a potential to sulfonate groups at a later stage, and a polymer whose backbone is rigid and the density of the ionic group can be varied. The combined experimental and computational studies significantly extended the understanding of polymers at interfaces from model systems to polydispersed copolymers with blocks of varying nature and complexity. This new insight directly affects the design of polymers for sustainable energy applications from batteries and fuel cells to solar energy.

  9. Study of the Ionization Dynamics and Equation of State of a Strongly Coupled Plasma

    SciTech Connect

    Shepherd, R; Audebert, P; Geindre, J P; Iglesias, C; Foord, M; Rogers, F; Gauthier, J C; Springer, P

    2003-02-06

    Preliminary experiments to study the ionization dynamics and equation of state of a strongly coupled plasma have been performed at the LLNL COMET laser facility. In these experiment, a 1.0 J, 500 fs, 532 nm laser was used to create a uniform, warm dense plasma.The primary diagnostic, Fourier Domain Interferometry (FDI), was used to provide information about the position of the critical density of the target and thus the expansion hydrodynamics, laying the ground work for the plasma characterization. The plasmas were determined to be strongly coupled. In addition work was performed characterizing the back-lighter. A von Hamos spectrograph coupled to a 500 fs X-ray streak camera (TREX-VHS) developed at LLNL was used for these measurements. This diagnostic combines high collection efficiency ({approx} 10{sup -4} steradians) with fast temporal response ({approx} 500 fs), allowing resolution of extremely transient spectral variations. The TREX-VHS will be used to determine the time history, intensity, and spectral content of the back-lighter resulting in absorption measurements that provide insight into bound states in strongly coupled conditions.

  10. Time-Dependent Ionized Reflection: Major Implications for Fe Kα Reverberation Studies of AGN.

    NASA Astrophysics Data System (ADS)

    Nayakshin, S.; Begelman, Mitchell C.; Kazanas, D.

    2000-12-01

    We discuss the influence of the thermal ionization instability (see Nayakshin, Kazanas & Kallman 2000) on the studies of Fe Kα reverberation in AGN. We show that the density structure of the illuminated gas reacts slowly to changes in the incident X-rays, which leads to a very complex line variability behavior under certain conditions. We find that if X-ray luminosity of the source exceeds ~ a percent of the Eddington limit, then rapid variations in the X-ray flux will result in rather complex and observationally seemingly chaotic changes in the integrated flux of the line and its profile. We also discuss the implications of our results for current and future Fe Kα line reverberations missions, such as Constellation-X. In particular, we point out the importance of the high energy part of the spectrum that is not going to be measured by Constellation-X. We show that AGN that are only moderately bright and/or have steep X-ray spectrum should be the best candidates in which to observe the line reverberation. This work was supported by the National Research Council.

  11. Review of certain low-level ionizing radiation studies in mice and guinea pigs

    SciTech Connect

    Congdon, C.C.

    1987-05-01

    Starting in the early 1940s, Egon Lorenz and collaborators at the National Cancer Institute began an extended study of chronic low-level ionizing radiation effects in what was then the tolerance range for man. Observations on life span, body weight and radiation carcinogenesis, among others, were made in mice, guinea pigs and rabbits. At the then-permissible exposure level, 0.1 R** per 8-h day until natural death, experimental mice and guinea pigs had a slightly greater mean life span compared to control animals. In addition, there was marked weight gain during the growth phase in both species. Increased tumor incidence was also observed at the 0.1-R level in mice. The primary hypothesis for increased median life span has been rebound regenerative hyperplasia during the early part of the exposure; in the presence of continuing injury, there is physiological enhancement of defense mechanisms against intercurrent infection. The body weight gain has not been explained. 32 references.

  12. A new dynamical atmospheric ionizing radiation (AIR) model for epidemiological studies

    NASA Technical Reports Server (NTRS)

    De Angelis, G.; Clem, J. M.; Goldhagen, P. E.; Wilson, J. W.

    2003-01-01

    A new Atmospheric Ionizing Radiation (AIR) model is currently being developed for use in radiation dose evaluation in epidemiological studies targeted to atmospheric flight personnel such as civilian airlines crewmembers. The model will allow computing values for biologically relevant parameters, e.g. dose equivalent and effective dose, for individual flights from 1945. Each flight is described by its actual three dimensional flight profile, i.e. geographic coordinates and altitudes varying with time. Solar modulated primary particles are filtered with a new analytical fully angular dependent geomagnetic cut off rigidity model, as a function of latitude, longitude, arrival direction, altitude and time. The particle transport results have been obtained with a technique based on the three-dimensional Monte Carlo transport code FLUKA, with a special procedure to deal with HZE particles. Particle fluxes are transformed into dose-related quantities and then integrated all along the flight path to obtain the overall flight dose. Preliminary validations of the particle transport technique using data from the AIR Project ER-2 flight campaign of measurements are encouraging. Future efforts will deal with modeling of the effects of the aircraft structure as well as inclusion of solar particle events. Published by Elsevier Ltd on behalf of COSPAR.

  13. Numerical studies of the behavior of ionized residual gas in an energy recovering linac

    NASA Astrophysics Data System (ADS)

    Pöplau, Gisela; van Rienen, Ursula; Meseck, Atoosa

    2015-04-01

    Next generation light sources such as energy recovering linacs (ERLs) are highly sensitive to instabilities due to ionized residual gas, which must be mitigated for successful operation. Vacuum pumps are insufficient for removal of the ions, as the ions are trapped by the beam's electrical potential. Two effective measures are (i) introducing clearing gaps in the bunch train, and (ii) installing clearing electrodes which pull out the trapped ions from the electrical potential of the beam. In this paper, we present numerical studies on the behavior of ion clouds that interact with bunch trains in an ERL taking into account the effects of the clearing gaps and clearing electrodes. We present simulations with different compositions of the residual gas. Simulations are done using the MOEVE PIC Tracking software package developed at Rostock University, which has been upgraded to include the behavior of ion clouds in the environment of additional electromagnetic fields, such as generated by clearing electrodes. The simulations use the parameters of the Berlin Energy Recovery Linac Project (bERLinPro) to allow for the deduction of appropriate measures for bERLinPro 's design and operation.

  14. Study of the behaviour of the equatorial ionization anomaly (EIA) during solar flares

    NASA Astrophysics Data System (ADS)

    Aggarwal, Malini; Astafyeva, Elvira

    2014-05-01

    A solar flare occurring in the sun's chromosphere is observed in various wavebands (radio to x-rays). The response of the solar flare which causes sudden changes in the earth's ionosphere is not yet well understood though investigations suggested that its impact depends on the size and location of occurrence of solar flare on sun. Considering this, we have carried an investigation to study the response of two strong and gradual solar flares: 2 Apr 2001 (X20, limb) and 7 Feb 2010 (M6.4, disk) on the earth's equatorial-low latitude regions using multi-technique observations of satellite and ground-based instruments. We found a weakening of strength of equatorial ionization anomaly (EIA) in total electron content during both the flares as observed by TOPEX, JASON-1 and JASON-2 altimeter measurements. The H component of the geomagnetic field also shows a sudden change at equatorial and low latitude stations in the sunlit hemisphere during the flare. The observations of ionosonde at low-latitudes indicate a strong absorption of higher-frequency radio signals. The detail response of these flare on EIA of the earth's ionosphere will be presented and discussed.

  15. Difluorocarbene studied with threshold photoelectron spectroscopy (TPES): measurement of the first adiabatic ionization energy (AIE) of CF(2).

    PubMed

    Innocenti, Fabrizio; Eypper, Marie; Lee, Edmond P F; Stranges, Stefano; Mok, Daniel K W; Chau, Foo-tim; King, George C; Dyke, John M

    2008-01-01

    The first photoelectron band of difluorocarbene CF(2), has been studied by threshold photoelectron (TPE) spectroscopy. CF(2) was prepared by microwave discharge of a flowing mixture of hexafluoropropene, C(3)F(6), and argon. A vibrationally resolved band was observed in which at least twenty-two components were observed. In the first PE band of CF(2), the adiabatic ionization energy differs significantly from the vertical ionization energy because, for the ionization CF(2) (+) (X(2)A(1))+e(-) <-- CF(2) (X(1)A(1)), there is an increase in the FCF bond angle (by approximately 20 degrees ) and a decrease in the C--F bond length (by approximately 0.7 A). The adiabatic component was not observed in the experimental TPE spectrum. However, on comparing this spectrum with an ab initio/Franck-Condon simulation of this band, using results from high-level ab initio calculations, the structure associated with the vibrational components could be assigned. This led to alignment of the experimental TPE spectrum and the computed Franck-Condon envelope, and a determination of the first adiabatic ionization energy of CF(2) as (11.362+/-0.005) eV. From the assignment of the vibrational structure, values were obtained for the harmonic and fundamental frequencies of the symmetric stretching mode (nu(1)') and symmetric bending mode (nu(2)') in CF(2) (+) (X(2)A(1)). PMID:19006171

  16. Comparative Study of the Dissociative Ionization of 1,1,1-Trichloroethane Using Nanosecond and Femtosecond Laser Pulses

    PubMed Central

    du Plessis, Anton; Strydom, Christien; Botha, Lourens

    2010-01-01

    Changes in the laser induced molecular dissociation of 1,1,1-trichloroethane (TCE) were studied using a range of intensities and standard laser wavelengths with nanosecond and femtosecond pulse durations. TCE contains C-H, C-C and C-Cl bonds and selective bond breakage of one or more of these bonds is of scientific interest. Using laser ionization time of flight mass spectrometry, it was found that considerable variation of fragment ion peak heights as well as changes in relative peak ratios is possible by varying the laser intensity (by attenuation), wavelength and pulse duration using standard laser sources. The nanosecond laser dissociation seems to occur via C-Cl bond breakage, with significant fragmentation and only a few large mass ion peaks observed. In contrast, femtosecond laser dissociative ionization results in many large mass ion peaks. Evidence is found for various competing dissociation and ionization pathways. Variation of the nanosecond laser intensity does not change the fragmentation pattern, while at high femtosecond intensities large changes are observed in relative ion peak sizes. The total ionization yield and fragmentation ratios are presented for a range of wavelengths and intensities, and compared to the changes observed due to a linear chirp variation. PMID:20480004

  17. Spectroscopic investigation of heterogeneous Ziegler-Natta catalysts: Ti and Mg chloride tetrahydrofuranates, their interaction compound, and the role of the activator.

    PubMed

    Seenivasan, Kalaivani; Sommazzi, Anna; Bonino, Francesca; Bordiga, Silvia; Groppo, Elena

    2011-07-25

    X-ray powder diffraction (XRPD), Infrared, Raman, and UV/Vis spectroscopy have been used to investigate the structural, vibrational, and optical properties of Ti and Mg chloride tetrahydrofuranates as precursors of heterogeneous Ziegler-Natta catalysts for polyethylene production; as well as their interaction compound (pro-catalyst) and the final catalyst obtained after interaction with the AlR(3) activator. Although the structure of the precursors and of the pro-catalyst were well known, that of the catalyst (obtained by reaction of the pro-catalyst with AlR(3)) was not easily obtainable from XRPD data. IR and Raman spectroscopy provided important information on tetrahydrofuran (thf) coordination and on the ν(M-Cl) region; whereas UV/Vis spectroscopy gave the direct proof on both the formal oxidation state and the coordination environment of the active Ti sites. Those presented herein are among the first direct experimental data on the structure of the active Ti sites in Ziegler-Natta catalysts, and can be used to validate the many computational studies that have been increasing exponentially in the last few decades.

  18. Fragmentation of tetrahydrofuran molecules by H(+), C(+), and O(+) collisions at the incident energy range of 25-1000 eV.

    PubMed

    Wasowicz, Tomasz J; Pranszke, Bogusław

    2015-01-29

    We have studied fragmentation processes of the gas-phase tetrahydrofuran (THF) molecules in collisions with the H(+), C(+), and O(+) cations. The collision energies have been varied between 25 and 1000 eV and thus covered a velocity range from 10 to 440 km/s. The following excited neutral fragments of THF have been observed: the atomic hydrogen H(n), n = 4-9, carbon atoms in the 2p3s (1)P1, 2p4p (1)D2, and 2p4p (3)P states and vibrationally and rotationally excited diatomic CH fragments in the A(2)Δ and B(2)Σ(-) states. Fragmentation yields of these excited fragments have been measured as functions of the projectile energy (velocity). Our results show that the fragmentation mechanism depends on the projectile cations and is dominated by electron transfer from tetrahydrofuran molecules to cations. It has been additionally hypothesized that in the C(+)+THF collisions a [C-C4H8O](+) complex is formed prior to dissociation. The possible reaction channels involved in fragmentation of THF under the H(+), C(+), and O(+) cations impact are also discussed. PMID:25565161

  19. Tandem Olefin Metathesis/Oxidative Cyclization: Synthesis of Tetrahydrofuran Diols from Simple Olefins.

    PubMed

    Dornan, Peter K; Lee, Daniel; Grubbs, Robert H

    2016-05-25

    A tandem olefin metathesis/oxidative cyclization has been developed to synthesize 2,5-disubstituted tetrahydrofuran (THF) diols in a stereocontrolled fashion from simple olefin precursors. The ruthenium metathesis catalyst is converted into an oxidation catalyst in the second step and is thus responsible for both catalytic steps. The stereochemistry of the 1,5-diene intermediate can be controlled through the choice of catalyst and the type of metathesis conducted. This olefin stereochemistry then controls the THF diol stereochemistry through a highly stereospecific oxidative cyclization.

  20. Gymnothelignans A-O: conformation and absolute configuration analyses of lignans bearing tetrahydrofuran from Gymnotheca chinensis.

    PubMed

    He, Dahai; Ding, Lisheng; Xu, Hongxi; Lei, Xinxiang; Xiao, Hongping; Zhou, Yan

    2012-10-01

    Fifteen new lignans, gymnothelignans A-O (1-15), bearing tetrahydrofuran with variable conformations belonging to three potentially related skeletons were isolated from Gymnotheca chinensis Decne. The structures were elucidated by means of detailed spectroscopic analysis. Absolute configurations were assigned using X-ray single-crystal diffraction and chemical transformations. Moreover, by the homology, compounds 1-11 and eupomatilones were confirmed to have uniform R-configuration at C-5. However, a synthesized congener has long been mistaken as 5-epimer of eupomatilone-6. This work provides guidance for the absolute configuration establishment of the subeupomatilone family with trans-H-4-H-5 configuration.

  1. Tandem Olefin Metathesis/Oxidative Cyclization: Synthesis of Tetrahydrofuran Diols from Simple Olefins.

    PubMed

    Dornan, Peter K; Lee, Daniel; Grubbs, Robert H

    2016-05-25

    A tandem olefin metathesis/oxidative cyclization has been developed to synthesize 2,5-disubstituted tetrahydrofuran (THF) diols in a stereocontrolled fashion from simple olefin precursors. The ruthenium metathesis catalyst is converted into an oxidation catalyst in the second step and is thus responsible for both catalytic steps. The stereochemistry of the 1,5-diene intermediate can be controlled through the choice of catalyst and the type of metathesis conducted. This olefin stereochemistry then controls the THF diol stereochemistry through a highly stereospecific oxidative cyclization. PMID:27133576

  2. Differential cross sections for electron-impact vibrational-excitation of tetrahydrofuran at intermediate impact energies

    SciTech Connect

    Do, T. P. T.; Lopes, M. C. A.; Konovalov, D. A.; White, R. D.; Brunger, M. J. E-mail: darryl.jones@flinders.edu.au; Jones, D. B. E-mail: darryl.jones@flinders.edu.au

    2015-03-28

    We report differential cross sections (DCSs) for electron-impact vibrational-excitation of tetrahydrofuran, at intermediate incident electron energies (15-50 eV) and over the 10°-90° scattered electron angular range. These measurements extend the available DCS data for vibrational excitation for this species, which have previously been obtained at lower incident electron energies (≤20 eV). Where possible, our data are compared to the earlier measurements in the overlapping energy ranges. Here, quite good agreement was generally observed where the measurements overlapped.

  3. Tetrahydrofuran amino acid-containing gramicidin S analogues with improved biological profiles.

    PubMed

    Pal, Sudip; Singh, Gajendra; Singh, Shyam; Tripathi, Jitendra Kumar; Ghosh, Jimut Kanti; Sinha, Sudhir; Ampapathi, Ravi Sankar; Chakraborty, Tushar Kanti

    2015-06-28

    Gramicidin S (GS) is a cyclic cationic antimicrobial peptide (CAP) with a wide spectrum of antibiotic activities whose usage has been limited to topical applications owing to its cytotoxic side effects. We have synthesized tetrahydrofuran amino acid (Taa)-containing GS analogues, and we have carried out conformational analysis and explored their structure activity relationships by evaluating their antitubercular, antibacterial and cytotoxic properties. Two of these analogues showed impressive as well as selective activity against Mycobacterium tuberculosis (MTB) without toxicity towards mammalian Vero cells or human RBCs, and are promising as potential leads.

  4. New MOF based on lithium tetrahydrofuran-2,3,4,5-tetracarboxylate: Its structure and conductivity behavior

    SciTech Connect

    Zima, Vitezslav; Patil, Deepak S.; Raja, Duraisamy Senthil; Chang, Ting-Guang; Lin, Chia-Her; Shimakawa, Koichi; Wagner, Tomas

    2014-09-15

    A novel metal–organic framework, [Li{sub 6}(HTFTA){sub 2}(H{sub 2}O){sub 3}]·3H{sub 2}O (LiTFTA, H{sub 4}TFTA is tetrahydrofuran-2,3,4,5-tetracarboxylic acid), has been synthesized under solvothermal conditions and its structure was determined by single-crystal X-ray diffraction studies. It has six different LiO{sub 4} tetrahedra which forms two kinds of tetranuclear clusters that are coordinated to the ligands and form an overall three-dimensional structure with channels running along the crystallographic a axis. Some of the carboxylate groups of the ligand moiety jut out into the channels and the channels are occupied by water molecules. The proton conductivity behavior of LiTFTA with respect to temperature and relative humidity was analyzed by our newly developed impedance data analysis method called a random-walk approach. The results were compared with the data obtained by an analysis using an equivalent electric circuit model. Based on the physical parameters obtained by the random-walk method and the known structure we suggested the mechanism of the proton conductivity in this material. The proton conduction proceeds most probably by a vehicle conduction mechanism which employs mainly water molecules of crystallization present in the channels of LiTFTA. The value of the diffusion coefficient increases with temperature whereas the number of charge carriers remains constant. On the other hand, both the number of charge carriers and diffusion coefficient increase with increasing relative humidity. - Graphical abstract: Structure of a new metal organic framework was determined and its ionic conductivity was evaluated using a random-walk approach. - Highlights: • Lithium tetrahydrofuran-2,3,4,5-tetracarboxylate is a MOF with water-filled pores. • The impedance spectra indicate that this material is ion conductive. • Conductivity was evaluated using a random walk approach. • The number of charge carriers and diffusion coefficient was determined.

  5. Abnormal ionization in sonoluminescence

    NASA Astrophysics Data System (ADS)

    Zhang, Wen-Juan; An, Yu

    2015-04-01

    Sonoluminescence is a complex phenomenon, the mechanism of which remains unclear. The present study reveals that an abnormal ionization process is likely to be present in the sonoluminescing bubble. To fit the experimental data of previous studies, we assume that the ionization energies of the molecules and atoms in the bubble decrease as the gas density increases and that the decrease of the ionization energy reaches about 60%-70% as the bubble flashes, which is difficult to explain by using previous models. Project supported by the Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20120002110031) and the National Natural Science Foundation of China (Grant No. 11334005).

  6. Mechanical properties of sand, silt, and clay containing tetrahydrofuran hydrate

    USGS Publications Warehouse

    Yun, T.S.; Santamarina, C.J.; Ruppel, C.

    2007-01-01

    The mechanical behavior of hydrate-bearing sediments subjected to large strains has relevance for the stability of the seafloor and submarine slopes, drilling and coring operations, and the analysis of certain small-strain properties of these sediments (for example, seismic velocities). This study reports on the results of comprehensive axial compression triaxial tests conducted at up to 1 MPa confining pressure on sand, crushed silt, precipitated silt, and clay specimens with closely controlled concentrations of synthetic hydrate. The results show that the stress-strain behavior of hydrate-bearing sediments is a complex function of particle size, confining pressure, and hydrate concentration. The mechanical properties of hydrate-bearing sediments at low hydrate concentration (probably 50% of pore space), the behavior becomes more independent of stress because the hydrates control both stiffness and strength and possibly the dilative tendency of sediments by effectively increasing interparticle coordination, cementing particles together, and filling the pore space. The cementation contribution to the shear strength of hydrate-bearing sediments decreases with increasing specific surface of soil minerals. The lower the effective confining stress, the greater the impact of hydrate formation on normalized strength.

  7. Theoretical study of Jesse effect in tritium measurements using ionization chambers

    NASA Astrophysics Data System (ADS)

    Chen, Zhilin; Peng, Shuming; Lu, Hanghang; Tan, Zhaoyi; Wang, Heyi; Long, Xingui; Masao, Matsuyama

    2016-01-01

    Jesse effect caused by impurities in helium might enhance the output signal significantly in tritium measurements with ionization chamber, which will lead to overestimation of tritium concentration in experiments. A theoretical method was proposed to evaluate Jesse effect quantitatively. Results indicate that besides Penning ionization, sub-excitation electrons also place very important influence on ionization enhancement by Jesse effect. An experiential expression about the relationship between enhancement factor and impurity concentration was established, in which second order of it fits experimental results very well. Theoretical calculation method in this paper is also applicable to evaluate Jesse effect in other kinds of mixtures besides hydrogen as impurities in helium. In addition, Jesse effects about tritium molecules as impurities have also been investigated.

  8. Cosmic ray studies with a gas Cherenkov counter in association with an ionization spectrometer

    NASA Technical Reports Server (NTRS)

    Balasubrahmanyan, V. K.; Ormes, J. F.; Arens, J. F.; Siohan, F.; Yodh, G. B.; Simon, M.; Spiegelhauer, H.

    1980-01-01

    The results from a balloon-borne gas Cherenkov counter (threshold 16.5 GeV/nucleon) and an ionization spectrometer are presented. The gas Cherenkov counter provides an absolute energy distribution for the response of the calorimeter for 5 or = Z 26 nuclei of cosmic rays. The contribution of scintillation to the gas Cherenkov pulse height was obtained by independently selecting particles below the gas Cherenkov threshold using the ionization spectrometer. Energy spectra were derived by minimizing the chi squared between Monte Carlo simulted data and flight data. Best fit power laws, dN/dE = AE-gamma, were determined for C, N, O, Ne, Mg, and Si. The power laws, all consistent with E (-2.7) are not good fits to the data. A better fit is obtained using the spectrum derived from the spectrometer. The data from the ionization calorimeter and the gas Cherenkov are thus completely self-consistent.

  9. Muon Tracking Studies in a Skew Parametric Resonance Ionization Cooling Channel

    SciTech Connect

    Sy, Amy; Afanaciev, Andre; Derbenev, Yaroslav S.; Johnson, Rolland; Morozov, Vasiliy

    2015-09-01

    Skew Parametric-resonance Ionization Cooling (SPIC) is an extension of the Parametric-resonance Ionization Cooling (PIC) framework that has previously been explored as the final 6D cooling stage of a high-luminosity muon collider. The addition of skew quadrupoles to the PIC magnetic focusing channel induces coupled dynamic behavior of the beam that is radially periodic. The periodicity of the radial motion allows for the avoidance of unwanted resonances in the horizontal and vertical transverse planes, while still providing periodic locations at which ionization cooling components can be implemented. A first practical implementation of the magnetic field components required in the SPIC channel is modeled in MADX. Dynamic features of the coupled correlated optics with and without induced parametric resonance are presented and discussed.

  10. Shock tube study of ionization rates of NaCl-contaminated argon

    NASA Technical Reports Server (NTRS)

    Schneider, K.-P.; Park, C.

    1975-01-01

    Electron density, electron temperature, and concentration of excited sodium atoms are measured in the weakly ionized regime behind a shock wave in impure argon in a shock tube using microwave techniques and spectrally resolved radiometry. Evidence is presented to show that an apparent increase in the rate of ionization is due to electron detachment of negative chlorine ions produced from sodium chloride vapor contained as an impurity. To be consistent with this chemical model, rate coefficients are found in the temperature range between 5500 and 8600 K for the dissociation of NaCl into an ion pair, dissociation of NaCl into a neutral pair, and electron detachment of a negative chlorine ion. Electron temperature is lower than heavy-particle temperature by roughly 1000 K. The electron-argon impact-ionization rate coefficient is a weak function of electron temperature in contradiction to expectation.

  11. Physician exposure to ionizing radiation during trauma resuscitation: A prospective clinical study

    SciTech Connect

    Weiss, E.L.; Singer, C.M.; Benedict, S.H.; Baraff, L.J.

    1990-02-01

    A prospective study of emergency physician whole body and extremity exposure to ionizing radiation during trauma resuscitation over a three-month period was conducted. Radiation film badges and thermoluminescent dosimeter finger rings were permanently attached to leaded aprons worn by emergency medicine residents during all trauma resuscitations. One set of apron and finger ring dosimeters was designated for the resident who managed the airway and stabilized the neck, when necessary, during cervical spine radiography (A-CS resident). A separate set of dosimeters was designated for the resident supervising the resuscitation. During the study period, 150 major trauma patients requiring 481 radiographic studies were treated. The mean monthly cumulative whole body exposures were 136.7 +/- 85.0 and 103.3 +/- 60.3 mrem for A-CS and supervising residents, respectively. The mean weekly cumulative extremity exposures were 523.3 +/- 611.0 and 46.7 +/- 18.6 mrem for A-CS and supervising residents, respectively. Calculated whole body exposures per patient were 2.7 mrem for the A-CS resident and 2.1 mrem for the supervising resident. Calculated extremity exposures per patient were 41.9 +/- 48.9 and 3.7 +/- 1.5 mrem, respectively. To exceed the annual whole body exposure limit established by the National Council of Radiologic Protection, the A-CS resident, working 200 shifts per year, would have to treat 9.2 trauma patients per shift. To exceed the annual extremity exposure limit, the A-CS resident would have to treat 5.9 trauma patients per shift. Of note, European exposure limits are 10% of current US limits. We conclude that significant exposures may occur to physicians working in trauma centers and that the use of shielding devices is indicated.

  12. Electron impact ionization in plasma technologies; studies on atomic boron and BN molecule

    NASA Astrophysics Data System (ADS)

    Joshi, Foram M.; Joshipura, K. N.; Chaudhari, Asha S.

    2016-05-01

    Electron impact ionization plays important role in plasma technologies. Relevant cross sections on atomic boron are required to understand the erosion processes in fusion experiments. Boronization of plasma exposed surfaces of tokomaks has proved to be an effective way to produce very pure fusion plasmas. This paper reports comprehensive theoretical investigations on electron scattering with atomic Boron and Boron Nitride in solid phases. Presently we determine total ionization cross-section Qion and the summed-electronic excitation cross section ΣQexc in a standard quantum mechanical formalism called SCOP and CSP-ic methods. Our calculated cross sections are examined as functions of incident electron energy along with available comparisons.

  13. X-ray laser studies using plasmas created by optical field ionization

    SciTech Connect

    Krushelnick, K.M.; Tighe, W.; Suckewer, S.

    1995-01-01

    X-ray laser experiments involving the creation of fast recombining plasmas by optical field ionization of preformed targets were conducted. A nonlinear increase in the intensity of the 13.5nm Lyman-{alpha} line in Li III with the length of the target plasma was observed but only for distances less than the laser confocal parameter and for low plasma electron temperatures. Multiphoton pumping of resonant atomic transitions was also examined and the process of multiphoton ionization of FIII was found to be more probable than multiphoton excitation.

  14. Occupational exposure to non-ionizing radiation and an association with heart disease: an exploratory study.

    PubMed

    Hamburger, S; Logue, J N; Silverman, P M

    1983-01-01

    Exploratory analyses for dose-related exposure to non-ionizing radiation and adverse health effects among male physical therapists were done from a mail questionnaire survey. The cohort consisted of 3004 respondents who were stratified into subgroups according to exposure across and within the various types of non-ionizing radiation energy emitted from diathermy equipment. The radiation modalities considered were ultrasound, microwave, shortwave, and infrared. An association between heart disease and exposure to shortwave radiation was the only consistently significant finding when high and low exposure groups were compared. PMID:6643646

  15. Ionization energies of argon clusters: A combined experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Echt, O.; Fiegele, T.; Rümmele, M.; Probst, M.; Matt-Leubner, S.; Urban, J.; Mach, P.; Leszczynski, J.; Scheier, P.; Märk, T. D.

    2005-08-01

    We have measured appearance energies of Arn+,n⩽30, by electron impact of gas phase clusters. Quantum-chemical calculations have been performed to determine the adiabatic and vertical ionization energies of argon clusters up to n =4 and 6, respectively. The experimental appearance energy of the dimer ion approaches, under suitable cluster source conditions, the adiabatic ionization energy. The agreement with values obtained by photoionization and threshold photoelectron-photoion coincidence (TPEPICO) spectra demonstrates that autoionizing Rydberg states are accessible by electron impact. Appearance energies of larger clusters, though, exceed the TPEPICO values by about 0.5 eV.

  16. Shock tube study of ionization rates of NaCl-contaminated argon

    NASA Technical Reports Server (NTRS)

    Scheneider, C.-P.; Park, C.

    1975-01-01

    Spectrally resolved radiometry and a microwave technique were used to measure the electron density, electron temperature, and concentration, and the concentration of sodium atoms in the weakly ionized region behind a shock wave in an argon shock tube. It is shown that the observed increase in the ionization rate is due to electron detachment of negative chlorine ions produced from sodium chloride vapor contained as an impurity in the argon gas. The observed behavior of the electron temperature in time and the reactions controlled by the electron temperature are analyzed in the light of the impurity reaction scheme.

  17. Fine Substituent Effects in Sandwich Complexes: A Threshold Ionization Study of Monosubstituted Chromium Bisarene Compounds.

    PubMed

    Ketkov, Sergey Yu; Markin, Gennady V; Tzeng, Sheng Y; Tzeng, Wen B

    2016-03-24

    Mass-analyzed threshold ionization spectra of jet-cooled [(η(6) -PhMe)(η(6) -PhH)Cr] and [(η(6) -Ph2 )(η(6) -PhH)Cr] reveal with unprecedented accuracy the effects of methyl and phenyl groups on the electronic structure of bis(η(6) -benzene)chromium. These "pure" substituent effects allow quantitative experimental determination of the ionization energy changes caused by the mutual substituent influence in bisarene systems. Two types of such influence have been revealed for the first time in bis(η(6) -toluene)chromium. PMID:26995399

  18. A Comparative PCET Study of a Donor-Acceptor Pair Linked by Ionized and Non-ionized Asymmetric Hydrogen-Bonded Interfaces

    PubMed Central

    Young, Elizabeth R.; Rosenthal, Joel; Hodgkiss, Justin M.

    2012-01-01

    A Zn(II) porphyrin-amidinium is the excited state electron donor (D) to a naphthalene diimide acceptor (A) appended with either a carboxylate or sulfonate functionality. The two-point hydrogen bond (---[H+]---) formed between the amidinium and carboxylate or sulfonate establishes a proton-coupled electron transfer (PCET) pathway for charge transfer. The two D---[H+]---A assemblies differ only by the proton configuration within the hydrogen bonding interface. Specifically, the amidinium transfers a proton to the carboxylate to form a non-ionized amidine-carboxylic acid two-point hydrogen network whereas the amidinium maintains both protons when bound to the sulfonate functionality forming an ionized amidinium-sulfonate two-point hydrogen network. These two interface configurations within the dyads thus allow for a direct comparison of PCET kinetics for the same donor and acceptor juxtaposed by an ionized and non-ionized hydrogen-bonded interface. Analysis of PCET kinetics ascertained from transient absorption and transient emission spectroscopy reveal that the ionized interface is more strongly impacted by the local solvent environment, thus establishing that the initial static configuration of the proton interface is a critical determinant to the kinetics of PCET. PMID:19489645

  19. Raman Spectroscopic Study of Radioresistant Oral Cancer Sublines Established by Fractionated Ionizing Radiation

    PubMed Central

    Yasser, Mohd; Shaikh, Rubina; Chilakapati, Murali Krishna; Teni, Tanuja

    2014-01-01

    Radiotherapy is an important treatment modality for oral cancer. However, development of radioresistance is a major hurdle in the efficacy of radiotherapy in oral cancer patients. Identifying predictors of radioresistance is a challenging task and has met with little success. The aim of the present study was to explore the differential spectral profiles of the established radioresistant sublines and parental oral cancer cell lines by Raman spectroscopy. We have established radioresistant sublines namely, 50Gy-UPCI:SCC029B and 70Gy-UPCI:SCC029B from its parental UPCI:SCC029B cell line, by using clinically admissible 2Gy fractionated ionizing radiation (FIR). The developed radioresistant character was validated by clonogenic cell survival assay and known radioresistance-related protein markers like Mcl-1, Bcl-2, Cox-2 and Survivin. Altered cellular morphology with significant increase (p<0.001) in the number of filopodia in radioresistant cells with respect to parental cells was observed. The Raman spectra of parental UPCI:SCC029B, 50Gy-UPCI:SCC029B and 70Gy-UPCI:SCC029B cells were acquired and spectral features indicate possible differences in biomolecules like proteins, lipids and nucleic acids. Principal component analysis (PCA) provided three clusters corresponding to radioresistant 50Gy, 70Gy-UPCI:SCC029B sublines and parental UPCI:SCC029B cell line with minor overlap, which suggest altered molecular profile acquired by the radioresistant cells due to multiple doses of irradiation. The findings of this study support the potential of Raman spectroscopy in prediction of radioresistance and possibly contribute to better prognosis of oral cancer. PMID:24841281

  20. Semiclassical Study of the Wave Vector Dependence of the Interband Impact Ionization Rate in Bulk Silicon

    NASA Technical Reports Server (NTRS)

    Wang, Yang; Brennan, Kevin F.

    1994-01-01

    We present calculations of the interband impact ionization rate calculated using a wave vector dependent (k-dependent) semiclassical formulation of the transition rate. The transition rate is determined using Fermi's golden rule from a two-body screened Coulomb interaction assuming energy and momentum conservation. The transition rate is calculated for the first two conduction bands of silicon by numerically integrating over the full Brillouin zone. The overlap integrals in the expression for the transition rate are determined numerically using a 15 band k-p calculation. It is found that the transition rate depends strongly on the initiating electron wave vector (k vector) and that the transition rate is greatest for electrons originating within the second conduction band than the first conduction band. An ensemble Monte Carlo simulation, which includes the numerically determined ionization transition rate as well as the full details of the first two conduction bands, is used to calculate the total impact ionization rate in bulk silicon. Good agreement with the experimentally determined electron ionization rate data is obtained.

  1. Optical Emission Line Studies and the Warm, Ionized Component of the Local Interstellar Medium

    NASA Technical Reports Server (NTRS)

    Reynolds, R. J.

    1984-01-01

    Observations of diffuse, galactic H alpha, N2 lambda 6583, and S2 6716 emission lines provide evidence for a warm (10,000K), primarily ionized component of the interstellar medium distribution throughout the galactic disk. This component of the interstellar gas has an electron density approximately equals 0.1-0.2/cu cm and occupies about 10 to 30% of the interstellar volume. Interstellar H alpha emission near the galactic poles, the dispersion measure of a nearby pulsar, and observations of interstellar gas flowing into the solar system indicate that this ionized component is an important constituent of the interstellar medium in the solar neighborhood. The intensity of the H alpha background at high galactic latitudes implies that this component is maintained by an average hydrogen ionization rate in the vicinity of the Sun of (2-4) x 100,000 s(-1) per square cm of galactic disk. The emission measure is 1.3 to 2.3 cm (-6) pc toward the galactic poles. The sources of this ionization were not identified but may include escaping Lyman continuum radiation from planetary nebulae, hot white dwarfs, and early type stars.

  2. A study of inter-species ion suppression in electrospray ionization-mass spectrometry of some phospholipid classes.

    PubMed

    Khoury, Spiro; El Banna, Nadine; Tfaili, Sana; Chaminade, Pierre

    2016-02-01

    Phospholipid quantification in biological samples is crucial and is increasingly studied in lipidomics. Quantitative studies are often performed using commercially available standards of phospholipid classes in order to mimic the composition of biological samples. For this, studies are conducted by liquid chromatography coupled to electrospray ionization-mass spectrometry. In liquid chromatography coupled to mass spectrometry (LC-MS) analysis, the matrix components and the co-elution of several phospholipid species lead to the phenomenon of ion suppression. As a result, a decrease in the response of phospholipid species in mass spectrometry MS is observed. In fact, inter-species ion suppression affects the efficiency of phospholipid (PL) ionization and might also influence the quantitative results. The aim of this work is to study the PL inter-species ion suppression phenomenon in electrospray ionization (ESI)-mass spectrometry on a triple quadrupole TQ and an LTQ-Orbitrap in order to improve quantification in natural and biological samples. Thus, the phospholipid MS response was evaluated to study the effect of acyl chain length, the degree, and the position of unsaturation on acyl chain and the effect of the polar head group structure. A number of saturated and unsaturated phospholipid species and mixtures were analyzed in different ionization modes to a better understanding of inter-species ion suppression phenomenon. PL molecular species responded differently according to the length of fatty acid chains, the number of unsaturation, and the nature of the polar head group. Fatty acid chain length showed to have the most marked effect on MS response.

  3. Divergent Synthesis of Multisubstituted Tetrahydrofurans and Pyrrolidines via Intramolecular Aldol-type Trapping of Onium Ylide Intermediates.

    PubMed

    Jing, Changcheng; Xing, Dong; Gao, Lixin; Li, Jia; Hu, Wenhao

    2015-12-21

    This paper reports a divergent strategy for the synthesis of multisubstituted tetrahydrofurans and pyrrolidines, starting from easily accessible β-hydroxyketones or β-aminoketones to react with diazo compounds. Under Rh(II) catalysis, this transformation is proposed to proceed through a metal-carbene-induced oxonium ylide or ammonium ylide formation followed by an intramolecular aldol-type trapping of these active intermediates. A series of highly substituted tetrahydrofurans and pyrrolidines are synthesized in high yields with good to excellent diastereoselectivities. Preliminary biological evaluations revealed that both types of heterocycles show good PTP1B inhibitory activities. PMID:26592374

  4. Understanding the Phase Behavior of Tetrahydrofuran + Carbon Dioxide, + Methane, and + Water Binary Mixtures from the SAFT-VR Approach.

    PubMed

    Míguez, J M; Piñeiro, M M; Algaba, J; Mendiboure, B; Torré, J P; Blas, F J

    2015-11-01

    The high-pressure phase diagrams of the tetrahydrofuran(1) + carbon dioxide(2), + methane(2), and + water(2) mixtures are examined using the SAFT-VR approach. Carbon dioxide molecule is modeled as two spherical segments tangentially bonded, water is modeled as a spherical segment with four associating sites to represent the hydrogen bonding, methane is represented as an isolated sphere, and tetrahydrofuran is represented as a chain of m tangentially bonded spherical segments. Dispersive interactions are modeled using the square-well intermolecular potential. In addition, two different molecular model mixtures are developed to take into account the subtle balance between water-tetrahydrofuran hydrogen-bonding interactions. The polar and quadrupolar interactions present in water, tetrahydrofuran, and carbon dioxide are treated in an effective way via square-well potentials of variable range. The optimized intermolecular parameters are taken from the works of Giner et al. (Fluid Phase Equil. 2007, 255, 200), Galindo and Blas (J. Phys. Chem. B 2002, 106, 4503), Patel et al. (Ind. Eng. Chem. Res. 2003, 42, 3809), and Clark et al. (Mol. Phys. 2006, 104, 3561) for tetrahydrofuran, carbon dioxide, methane, and water, respectively. The phase diagrams of the binary mixtures exhibit different types of phase behavior according to the classification of van Konynenburg and Scott, ranging from types I, III, and VI phase behavior for the tetrahydrofuran(1) + carbon dioxide(2), + methane(2), and + water(2) binary mixtures, respectively. This last type is characterized by the presence of a Bancroft point, positive azeotropy, and the so-called closed-loop curves that represent regions of liquid-liquid immiscibility in the phase diagram. The system exhibits lower critical solution temperatures (LCSTs), which denote the lower limit of immiscibility together with upper critical solution temperatures (UCSTs). This behavior is explained in terms of competition between the incompatibility

  5. Understanding the Phase Behavior of Tetrahydrofuran + Carbon Dioxide, + Methane, and + Water Binary Mixtures from the SAFT-VR Approach.

    PubMed

    Míguez, J M; Piñeiro, M M; Algaba, J; Mendiboure, B; Torré, J P; Blas, F J

    2015-11-01

    The high-pressure phase diagrams of the tetrahydrofuran(1) + carbon dioxide(2), + methane(2), and + water(2) mixtures are examined using the SAFT-VR approach. Carbon dioxide molecule is modeled as two spherical segments tangentially bonded, water is modeled as a spherical segment with four associating sites to represent the hydrogen bonding, methane is represented as an isolated sphere, and tetrahydrofuran is represented as a chain of m tangentially bonded spherical segments. Dispersive interactions are modeled using the square-well intermolecular potential. In addition, two different molecular model mixtures are developed to take into account the subtle balance between water-tetrahydrofuran hydrogen-bonding interactions. The polar and quadrupolar interactions present in water, tetrahydrofuran, and carbon dioxide are treated in an effective way via square-well potentials of variable range. The optimized intermolecular parameters are taken from the works of Giner et al. (Fluid Phase Equil. 2007, 255, 200), Galindo and Blas (J. Phys. Chem. B 2002, 106, 4503), Patel et al. (Ind. Eng. Chem. Res. 2003, 42, 3809), and Clark et al. (Mol. Phys. 2006, 104, 3561) for tetrahydrofuran, carbon dioxide, methane, and water, respectively. The phase diagrams of the binary mixtures exhibit different types of phase behavior according to the classification of van Konynenburg and Scott, ranging from types I, III, and VI phase behavior for the tetrahydrofuran(1) + carbon dioxide(2), + methane(2), and + water(2) binary mixtures, respectively. This last type is characterized by the presence of a Bancroft point, positive azeotropy, and the so-called closed-loop curves that represent regions of liquid-liquid immiscibility in the phase diagram. The system exhibits lower critical solution temperatures (LCSTs), which denote the lower limit of immiscibility together with upper critical solution temperatures (UCSTs). This behavior is explained in terms of competition between the incompatibility

  6. Synergy Between Theory and Experiment in Physical Chemistry: Studies on Thermochemistry, Sites of Ionization and Reaction Mechanisms

    NASA Astrophysics Data System (ADS)

    Notario, Rafael

    2008-03-01

    The word "synergy" means "working together". Synergy refers to the interaction of two or more agents or forces so that their combined effect is greater than the sum of their individual effects. Several examples are presented on the synergy between theory and experiment in physical chemistry taken from studies on the thermochemistry of oxygen- and sulfur-containing six-membered heterocycles, the site of ionization in bifunctional species, and the mechanism of thermolysis reactions.

  7. Secondary electrospray ionization-mass spectrometry: breath study on a control group.

    PubMed

    Martínez-Lozano, P; Zingaro, L; Finiguerra, A; Cristoni, S

    2011-03-01

    A series of fatty acids among other compounds have recently been detected in breath in real time by secondary electrospray ionization mass spectrometry (SESI-MS) (Martínez-Lozano P and Fernández de la Mora J 2008 Anal. Chem. 80 8210). Our main aim in this work was to (1) quantify their abundance in breath calibrating the system with standard vapors and (2) extend the study to a control group for several days, both under fasting conditions and after sucrose intake. For the quantitative study, we fed our system with controlled amounts (∼140-1440 ppt) of fatty acid vapors (i.e. propanoic, butanoic, pentanoic and hexanoic acids). As a result, we found sensitivities ranging between 1 and 2.2 cps/ppt. Estimated concentrations of these particular acids in the breath of a fasting subject were in the order of 100 ppt. These values were in reasonable agreement with those expected from reported typical plasma concentrations and Henry constants. A second set of experiments on three fasting individuals before and after ingesting 15 g of sucrose showed that the concentration of propionic and butanoic acids increased rapidly in breath for two subjects. This response was attributed to bacterial activity in mouth and pharynx. In contrast, a third subject showed no response to the administration of sucrose. In addition, we performed a survey among six fasting subjects comparing nasal and mouth exhalations during 11 days, 4 months apart. The signal intensity was comparable for mouth and nose breath. This observation, in conjunction with the quantitative study, suggests that these compounds are mostly systemic when measured under fasting conditions. We finally used the NIST MS search algorithm to evaluate the possibility of recognizing a breathing subject based on his/her breath signature. The global recognition score was 63% (41 out of 65), while the probability by chance alone was 6 × 10(-17). This indicates that (i) there are statistically recognizable differences in

  8. Diffuse, Warm Ionized Gas

    NASA Astrophysics Data System (ADS)

    Haffner, L. M.

    2002-05-01

    Over the past decade, new high-sensitivity observations have significantly advanced our knowledge of the diffuse, ionized gas in spiral galaxies. This component of the interstellar medium, often referred to as Warm Ionized Medium (WIM) or Diffuse Ionized Gas (DIG), plays an important role in the complex stellar-interstellar matter and energy cycle. In examining the distribution and physical properties of this gas, we learn not only about the conditions of the medium but also about processes providing heating and ionization in the halos of spiral galaxies. For the Milky Way, three new Hα surveys are available providing large sky coverage, arc-minute spatial resolution, and the ability to kinematically resolve this prominent optical emission line. These new, global views show that the Warm Ionized Medium of the Galaxy is ubiquitous as previously suspected, is rich with filamentary structure down to current resolution limits, and can be traced into the halo at large distances from the Galactic plane. Observations of additional optical emission lines are beginning to probe the physical conditions of the WIM. Early results suggest variations in the temperature and ionization state of the gas which are not adequately explained by Lyman continuum stellar photoionization alone. In parallel with this intensive work in the Milky Way have been numerous studies about the diffuse, ionized gas in other spiral galaxies. Here, deep, face-on spiral investigations provide some of the best maps of the global DIG distribution in a galaxy and begin to allow a probe of the local link between star formation and the powering of ionized gas. In addition, ionized gas has been traced out to impressive distances (z > 3 kpc) in edge-on spirals, revealing out large-scale changes in the physical conditions and kinematics of galactic halos.

  9. A new in-gas-laser ionization and spectroscopy laboratory for off-line studies at KU Leuven

    NASA Astrophysics Data System (ADS)

    Kudryavtsev, Yu.; Creemers, P.; Ferrer, R.; Granados, C.; Gaffney, L. P.; Huyse, M.; Mogilevskiy, E.; Raeder, S.; Sels, S.; Van den Bergh, P.; Van Duppen, P.; Zadvornaya, A.

    2016-06-01

    The in-gas laser ionization and spectroscopy (IGLIS) technique is used to produce and to investigate short-lived radioactive isotopes at on-line ion beam facilities. In this technique, the nuclear reaction products recoiling out of a thin target are thermalized and neutralized in a high-pressure noble gas, resonantly ionized by the laser beams in a two-step process, and then extracted from the ion source to be finally accelerated and mass separated. Resonant ionization of radioactive species in the supersonic gas jet ensures very high spectral resolution because of essential reduction of broadening mechanisms. To obtain the maximum efficiency and the best spectral resolution, properties of the supersonic jet and the laser beams must be optimized. To perform these studies a new off-line IGLIS laboratory, including a new high-repetition-rate laser system and a dedicated off-line mass separator, has been commissioned. In this article, the specifications of the different components necessary to achieve optimum conditions in laser-spectroscopy studies of radioactive beams using IGLIS are discussed and the results of simulations are presented.

  10. Matrix-Free UV-Laser Desorption Ionization Mass Spectrometry as a Versatile Approach for Accelerating Dereplication Studies on Lichens.

    PubMed

    Le Pogam, Pierre; Schinkovitz, Andreas; Legouin, Béatrice; Le Lamer, Anne-Cécile; Boustie, Joël; Richomme, Pascal

    2015-10-20

    The present study examined the suitability of laser desorption/ionization time-of-flight mass spectrometry (LDI-MS) for the rapid chemical fingerprinting of lichen extracts. Lichens are known to produce a wide array of secondary metabolites. Most of these compounds are unique to the symbiotic condition but some can be found in many species. Therefore, dereplication, that is, the rapid identification of known compounds within a complex mixture is crucial in the search for novel natural products. Over the past decade, significant advances were made in analytical techniques and profiling methods specifically adapted to crude lichen extracts, but LDI-MS has never been applied in this context. However, most classes of lichen metabolites have UV chromophores, which are quite similar to commercial matrix molecules used in matrix-assisted laser desorption ionization (MALDI). It is consequently postulated that these molecules could be directly detectable by matrix-free LDI-MS. The present study evaluated the versatility of this technique by investigating the LDI properties of a vast array of single lichen metabolites as well as lichen extracts of known chemical composition. Results from the LDI experiments were compared with those obtained by direct ESI-MS detection as well as LC-ESI-MS. It was shown that LDI ionization leads to strong molecular ion formation with little fragmentation, thus, facilitating straightforward spectra interpretation and representing a valuable alternative to time-consuming LC-MS analysis.

  11. Studies of Flow in Ionized Gas: Historical Perspective, Contemporary Experiments, and Applications

    SciTech Connect

    Popovic, S.; Vuskovic, L.

    2007-04-23

    Since the first observations that a very small ionized fraction (order of 1 ppm) could strongly affect the gas flow, numerous experiments with partially or fully wall-free discharges have demonstrated the dispersion of shock waves, the enhancement of lateral forces in the flow, the prospects of levitation, and other aerodynamic effects with vast potential of application. A review of physical effects and observations are given along with current status of their interpretation. Special attention will be given to the physical problems of energy efficiency in generating wall-free discharges and the phenomenology of filamentary discharges. Comments and case examples are given on the current status of availability of necessary data for modelling and simulation of the aerodynamic phenomena in weakly ionized gas.

  12. Cosmic ray studies with a gas Cerenkov counter in association with an ionization spectrometer

    NASA Technical Reports Server (NTRS)

    Balasubrahmanyan, V. K.; Ormes, J. F.; Arens, J. F.; Siohan, F.; Simon, M.; Spiegelhauer, H.; Yodh, G. B.

    1980-01-01

    The results from a balloon-borne gas Cerenkov counter (threshold 16.5 GeV/nuc) and an ionization spectrometer are presented. The gas Cerenkov counter provides an absolute energy calibration for the response of the calorimeter for the Z range of 5-26 nuclei of cosmic rays. The contribution of scintillation to the gas Cerenkov pulse height has been obtained by independently selecting particles below the gas Cerenkov threshold using the ionization spectrometer. Energy spectra were derived by minimizing the chi-squared between a Monte Carlo simulated data and flight data. Best fit power laws were determined for C, N, O, Ne, Mg, and Si. The power laws, all consistent with E exp-2.7, are not good fits to the data. A better fit is obtained using the spectrum derived from the spectrometer.

  13. Ionization chamber

    DOEpatents

    Walenta, Albert H.

    1981-01-01

    An ionization chamber has separate drift and detection regions electrically isolated from each other by a fine wire grid. A relatively weak electric field can be maintained in the drift region when the grid and another electrode in the chamber are connected to a high voltage source. A much stronger electric field can be provided in the detection region by connecting wire electrodes therein to another high voltage source. The detection region can thus be operated in a proportional mode when a suitable gas is contained in the chamber. High resolution output pulse waveforms are provided across a resistor connected to the detection region anode, after ionizing radiation enters the drift region and ionize the gas.

  14. Ionization chamber

    DOEpatents

    Walenta, A.H.

    An ionization chamber is described which has separate drift and detection regions electrically isolated from each other by a fine wire grid. A relatively weak electric field can be maintained in the drift region when the grid and another electrode in the chamber are connected to a high voltage source. A much stronger electric field can be provided in the detection region by connecting wire electrodes therein to another high voltage source. The detection region can thus be operated in a proportional mode when a suitable gas is contained in the chamber. High resolution output pulse waveforms are provided across a resistor connected to the detection region anode, after ionizing radiation enters the drift region and ionizes the gas.

  15. Studies of the Twin Helix Parametric-resonance Ionization Cooling Channel with COSY INFINITY

    SciTech Connect

    J.A. Maloney, K.B. Beard, R.P. Johnson, A. Afanasev, S.A. Bogacz, Y.S. Derbenev, V.S. Morozov, B. Erdelyi

    2012-07-01

    A primary technical challenge to the design of a high luminosity muon collider is an effective beam cooling system. An epicyclic twin-helix channel utilizing parametric-resonance ionization cooling has been proposed for the final 6D cooling stage. A proposed design of this twin-helix channel is presented that utilizes correlated optics between the horizontal and vertical betatron periods to simultaneously focus transverse motion of the beam in both planes. Parametric resonance is induced in both planes via a system of helical quadrupole harmonics. Ionization cooling is achieved via periodically placed wedges of absorbing material, with intermittent rf cavities restoring longitudinal momentum necessary to maintain stable orbit of the beam. COSY INFINITY is utilized to simulate the theory at first order. The motion of particles around a hyperbolic fixed point is tracked. Comparison is made between the EPIC cooling channel and standard ionization cooling effects. Cooling effects are measured, after including stochastic effects, for both a single particle and a distribution of particles.

  16. Multielectron coincidence study of the double Auger decay of 3d-ionized krypton

    SciTech Connect

    Andersson, E.; Hedin, L.; Rubensson, J.-E.; Karlsson, L.; Feifel, R.; Fritzsche, S.; Linusson, P.; Eland, J. H. D.

    2010-10-15

    Multielectron coincidence data for triple ionization of krypton have been recorded above the 3d ionization threshold at two photon energies (140 and 150 eV). Three principal transition pathways have been observed, two involving double Auger transitions from Kr{sup +}, and one involving single Auger transitions from Kr{sup 2+} created by direct single-photon double ionization. The decay of the 3d{sup 9} {sup 2}D{sub 5/2,3/2} states in Kr{sup +} has been analyzed in some detail and is found to be strongly dominated by cascade processes where two electrons with well-defined energies are emitted. The decay paths leading to the 4s{sup 2}4p{sup 3} {sup 4}S, {sup 2}D, and {sup 2}P states of Kr{sup 3+} are analyzed and energies of seven intermediate states in Kr{sup 2+} are given. A preliminary investigation of the decay paths from Kr{sup +} 3d{sup 9}4p{sup 5}nl shake-up states has also been carried out.

  17. IONIZATION CHAMBER

    DOEpatents

    Redman, W.C.; Shonka, F.R.

    1958-02-18

    This patent describes a novel ionization chamber which is well suited to measuring the radioactivity of the various portions of a wire as the wire is moved at a uniform speed, in order to produce the neutron flux traverse pattern of a reactor in which the wire was previously exposed to neutron radiation. The ionization chamber of the present invention is characterized by the construction wherein the wire is passed through a tubular, straight electrode and radiation shielding material is disposed along the wire except at an intermediate, narrow area where the second electrode of the chamber is located.

  18. Study of the replacement correction factors for ionization chamber dosimetry by Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Wang, Lilie

    In ionization chamber radiation dosimetry, the introduction of the ion chamber into medium will unavoidably distort the radiation field near the chamber because the chamber cavity material (air) is different from the medium. A replacement correction factor, Prepl was introduced in order to correct the chamber readings to give an accurate radiation dose in the medium without the presence of the chamber. Generally it is very hard to measure the values of Prepl since they are intertwined with the chamber wall effect. In addition, the P repl values always come together with the stopping-power ratio of the two media involved. This makes the problem of determining the P repl values even more complicated. Monte Carlo simulation is an ideal method to investigate the replacement correction factors. In this study, four different methods of calculating the values of Prepl by Monte Carlo simulation are discussed. Two of the methods are designated as 'direct' methods in the sense that the evaluation of the stopping-power ratio is not necessary. The systematic uncertainties of the two direct methods are estimated to be about 0.1-0.2% which comes from the ambiguous definition of the energy cutoff Delta used in the Spencer-Attix cavity theory. The two direct methods are used to calculate the values of P repl for both plane-parallel chambers and cylindrical thimble chambers in either electron beams or photon beams. The calculation results are compared to measurements. For electron beams, good agreements are obtained. For thimble chambers in photon beams, significant discrepancies are observed between calculations and measurements. The experiments are thus investigated and the procedures are simulated by the Monte Carlo method. It is found that the interpretation of the measured data as the replacement correction factors in dosimetry protocols are not correct. In applying the calculation to the BIPM graphite chamber in a 60Co beam, the calculated values of P repl differ from those

  19. High-resolution X-ray study of the multiple ionization of Pd atoms by fast oxygen ions

    NASA Astrophysics Data System (ADS)

    Czarnota, M.; Banaś, D.; Berset, M.; Chmielewska, D.; Dousse, J.-Cl.; Hoszowska, J.; Maillard, Y.-P.; Mauron, O.; Pajek, M.; Polasik, M.; Raboud, P. A.; Rzadkiewicz, J.; Słabkowska, K.; Sujkowski, Z.

    2010-04-01

    The multiple ionization of the L- and M-shells of Pd by fast oxygen ions has been studied by measuring with high-resolution the satellite structures of the Lα1,2 X-ray transitions. Relativistic multi-configuration Dirac-Fock (MCDF) calculations were used to interpret the complex X-ray spectrum, allowing to derive the number of L- and M-shell spectator vacancies at the moment of the X-ray emission. After correcting these numbers for the atomic vacancy rearrangement processes that take place prior to the X-ray emission, the ionization probabilities corresponding to the collision time were obtained. The latter were compared to predictions of the semiclassical approximation (SCA) and the geometrical model. The SCA calculations were performed using relativistic hydrogenic and self-consistent Dirac-Hartree-Fock (DHF) electronic wave functions. It was found that the use of the more realistic DHF wave functions in the SCA calculations leads to a much better description of the measured ionization probabilities for both the L- and M-shells.

  20. A comparative study of disinfection efficiency and regrowth control of microorganism in secondary wastewater effluent using UV, ozone, and ionizing irradiation process.

    PubMed

    Lee, O-Mi; Kim, Hyun Young; Park, Wooshin; Kim, Tae-Hun; Yu, Seungho

    2015-09-15

    Ionizing radiation technology was suggested as an alternative method to disinfection processes, such as chlorine, UV, and ozone. Although many studies have demonstrated the effectiveness of irradiation technology for microbial disinfection, there has been a lack of information on comparison studies of disinfection techniques and a regrowth of each treatment. In the present study, an ionizing radiation was investigated to inactivate microorganisms and to determine the critical dose to prevent the regrowth. As a result, it was observed that the disinfection efficiency using ionizing radiation was not affected by the seasonal changes of wastewater characteristics, such as temperature and turbidity. In terms of bacterial regrowth after disinfection, the ionizing radiation showed a significant resistance of regrowth, whereas, on-site UV treatment is influenced by the suspended solid, temperature, or precipitation. The electric power consumption was also compared for the economic feasibility of each technique at a given value of disinfection efficiency of 90% (1-log), showing 0.12, 36.80, and 96.53 Wh/(L/day) for ionizing radiation, ozone, and UV, respectively. The ionizing radiation requires two or three orders of magnitude lower power consumption than UV and ozone. Consequently, ionizing radiation can be applied as an effective and economical alternative technique to other conventional disinfection processes.

  1. "Magic" Ionization Mass Spectrometry.

    PubMed

    Trimpin, Sarah

    2016-01-01

    The systematic study of the temperature and pressure dependence of matrix-assisted ionization (MAI) led us to the discovery of the seemingly impossible, initially explained by some reviewers as either sleight of hand or the misinterpretation by an overzealous young scientist of results reported many years before and having little utility. The “magic” that we were attempting to report was that with matrix assistance, molecules, at least as large as bovine serum albumin (66 kDa), are lifted into the gas phase as multiply charged ions simply by exposure of the matrix:analyte sample to the vacuum of a mass spectrometer. Applied heat, a laser, or voltages are not necessary to achieve charge states and ion abundances only previously observed with electrospray ionization (ESI). The fundamentals of how solid phase volatile or nonvolatile compounds are converted to gas-phase ions without added energy currently involves speculation providing a great opportunity to rethink mechanistic understanding of ionization processes used in mass spectrometry. Improved understanding of the mechanism(s) of these processes and their connection to ESI and matrix-assisted laser desorption/ionization may provide opportunities to further develop new ionization strategies for traditional and yet unforeseen applications of mass spectrometry. This Critical Insights article covers developments leading to the discovery of a seemingly magic ionization process that is simple to use, fast, sensitive, robust, and can be directly applied to surface characterization using portable or high performance mass spectrometers. PMID:26486514

  2. "Magic" Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Trimpin, Sarah

    2016-01-01

    The systematic study of the temperature and pressure dependence of matrix-assisted ionization (MAI) led us to the discovery of the seemingly impossible, initially explained by some reviewers as either sleight of hand or the misinterpretation by an overzealous young scientist of results reported many years before and having little utility. The "magic" that we were attempting to report was that with matrix assistance, molecules, at least as large as bovine serum albumin (66 kDa), are lifted into the gas phase as multiply charged ions simply by exposure of the matrix:analyte sample to the vacuum of a mass spectrometer. Applied heat, a laser, or voltages are not necessary to achieve charge states and ion abundances only previously observed with electrospray ionization (ESI). The fundamentals of how solid phase volatile or nonvolatile compounds are converted to gas-phase ions without added energy currently involves speculation providing a great opportunity to rethink mechanistic understanding of ionization processes used in mass spectrometry. Improved understanding of the mechanism(s) of these processes and their connection to ESI and matrix-assisted laser desorption/ionization may provide opportunities to further develop new ionization strategies for traditional and yet unforeseen applications of mass spectrometry. This Critical Insights article covers developments leading to the discovery of a seemingly magic ionization process that is simple to use, fast, sensitive, robust, and can be directly applied to surface characterization using portable or high performance mass spectrometers.

  3. "Magic" Ionization Mass Spectrometry.

    PubMed

    Trimpin, Sarah

    2016-01-01

    The systematic study of the temperature and pressure dependence of matrix-assisted ionization (MAI) led us to the discovery of the seemingly impossible, initially explained by some reviewers as either sleight of hand or the misinterpretation by an overzealous young scientist of results reported many years before and having little utility. The “magic” that we were attempting to report was that with matrix assistance, molecules, at least as large as bovine serum albumin (66 kDa), are lifted into the gas phase as multiply charged ions simply by exposure of the matrix:analyte sample to the vacuum of a mass spectrometer. Applied heat, a laser, or voltages are not necessary to achieve charge states and ion abundances only previously observed with electrospray ionization (ESI). The fundamentals of how solid phase volatile or nonvolatile compounds are converted to gas-phase ions without added energy currently involves speculation providing a great opportunity to rethink mechanistic understanding of ionization processes used in mass spectrometry. Improved understanding of the mechanism(s) of these processes and their connection to ESI and matrix-assisted laser desorption/ionization may provide opportunities to further develop new ionization strategies for traditional and yet unforeseen applications of mass spectrometry. This Critical Insights article covers developments leading to the discovery of a seemingly magic ionization process that is simple to use, fast, sensitive, robust, and can be directly applied to surface characterization using portable or high performance mass spectrometers.

  4. [Biodegradation of tetrahydrofuran by combined immobilized of Pseudomonas oleovorans DT4].

    PubMed

    Shao, Qian; Ye, Jie-Xu; Ouyang, Du-Juan; Chen, Jian-Meng; Chen, Dong-Zhi

    2013-08-01

    A new composite matrix, calcium alginate (CA) coupled with activated carbon fiber (ACF) was designed to immobilize the cells of Pseudomonas oleovorans DT4 for tetrahydrofuran (THF) degradation. The average removal rate of the CA-ACF immobilized cells reached 24.0 mg x (L x h)(-1) with an initial THF concentration of 360 mg x L(-1) when the concentration of CA and ACF was 3% and 1.5% respectively. The mechanical strength of the mobilized cells was also significantly improved with the addition of ACF. Compared to the free suspended cells, higher stable removal efficiency (more than 80%) of CA-ACF cells was detected under different conditions of temperature and pH. The feasibility of the newly designed matrix was also reflected by the repeated batch degradation which showed that the removal activity decreased insignificantly after 80 cycles with the modified reaction system (PNS). PMID:24191576

  5. Five novel mono-tetrahydrofuran ring acetogenins from the seeds of Annona muricata.

    PubMed

    Rieser, M J; Gu, Z M; Fang, X P; Zeng, L; Wood, K V; McLaughlin, J L

    1996-02-01

    Bioactivity-directed fractionation of the seeds of Annona muricata L. (Annonaceae) resulted in the isolation of five new compounds: cis-annonacin (1), cis-annonacin-10-one (2), cis-goniothalamicin (3), arianacin (4), and javoricin (5). Three of these (1-3) are among the first cis mono-tetrahydrofuran ring acetogenins to be reported. NMR analyses of published model synthetic compounds, prepared cyclized formal acetals, and prepared Mosher ester derivatives permitted the determinations of absolute stereochemistries. Bioassays of the pure compounds, in the brine shrimp test, for the inhibition of crown gall tumors, and in a panel of human solid tumor cell lines for cytotoxicity, evaluated relative potencies. Compound 1 was selectively cytotoxic to colon adenocarcinoma cells (HT-29) in which it was 10,000 times the potency of adriamycin.

  6. Synthesis and characterization of polyurethanes made from copolymers of epoxidized natural oil and tetrahydrofuran.

    PubMed

    Hoong, Seng Soi; Yeong, Shoot Kian; Hassan, Hazimah Abu; Din, Ahmad Kushairi; Choo, Yuen May

    2015-01-01

    Polyols were synthesized from epoxidized natural oils and tetrahydrofuran through ring opening copolymerization catalyzed by Lewis acid. The properties of these polyols depend on the type of natural oils as well as the reaction conditions (monomer concentration, catalyst amount, reaction temperature and reaction time). These polyols were evaluated as a raw material for making polyurethane (PU) in order to understand the structure-property relationship between a natural oil and PU made from it. The tensile test analysis shows that the incorporation of natural oil moiety into the PU polymer network improves the elasticity of these PU samples when compared to a benchmark PU sample. In addition, the PU samples made from palm oil and soybean oil based polyols exhibit better tensile strength than benchmark PU. These polyols samples are suitable for making elastomeric PU, where high flexibility (high elongation at break) of PU is a common requirement. PMID:25492233

  7. Stereospecific cross-coupling reactions of aryl-substituted tetrahydrofurans, tetrahydropyrans, and lactones.

    PubMed

    Tollefson, Emily J; Dawson, David D; Osborne, Charlotte A; Jarvo, Elizabeth R

    2014-10-22

    The stereospecific ring-opening of O-heterocycles to provide acyclic alcohols and carboxylic acids with controlled formation of a new C-C bond is reported. These reactions provide new methods for synthesis of acyclic polyketide analogs with complex stereochemical arrays. Stereoselective synthesis of the cyclic template is utilized to control relative configuration; subsequent stereospecific nickel-catalyzed ring-opening affords the acyclic product. Aryl-substituted tetrahydrofurans and tetrahydropyrans undergo nickel-catalyzed Kumada-type coupling with a range of Grignard reagents to furnish acyclic alcohols with high diastereoselectivity. Enantioenriched lactones undergo Negishi-type cross-coupling with dimethylzinc to afford enantioenriched carboxylic acids. Application in a two-step enantioselective synthesis of an anti-dyslipidemia agent is demonstrated. PMID:25308512

  8. The role of electron-impact vibrational excitation in electron transport through gaseous tetrahydrofuran

    SciTech Connect

    Duque, H. V.; Do, T. P. T.; Konovalov, D. A.; White, R. D.; Brunger, M. J. E-mail: darryl.jones@flinders.edu.au; Jones, D. B. E-mail: darryl.jones@flinders.edu.au

    2015-03-28

    In this paper, we report newly derived integral cross sections (ICSs) for electron impact vibrational excitation of tetrahydrofuran (THF) at intermediate impact energies. These cross sections extend the currently available data from 20 to 50 eV. Further, they indicate that the previously recommended THF ICS set [Garland et al., Phys. Rev. A 88, 062712 (2013)] underestimated the strength of the electron-impact vibrational excitation processes. Thus, that recommended vibrational cross section set is revised to address those deficiencies. Electron swarm transport properties were calculated with the amended vibrational cross section set, to quantify the role of electron-driven vibrational excitation in describing the macroscopic swarm phenomena. Here, significant differences of up to 17% in the transport coefficients were observed between the calculations performed using the original and revised cross section sets for vibrational excitation.

  9. A DEEP CHANDRA ACIS STUDY OF NGC 4151. III. THE LINE EMISSION AND SPECTRAL ANALYSIS OF THE IONIZATION CONE

    SciTech Connect

    Wang, Junfeng; Fabbiano, Giuseppina; Elvis, Martin; Risaliti, Guido; Karovska, Margarita; Zezas, Andreas; Mundell, Carole G.; Dumas, Gaelle; Schinnerer, Eva

    2011-11-20

    This paper is the third in a series in which we present deep Chandra ACIS-S imaging spectroscopy of the Seyfert 1 galaxy NGC 4151, devoted to study its complex circumnuclear X-ray emission. Emission features in the soft X-ray spectrum of the bright extended emission (L{sub 0.3-2{sub keV}} {approx} 10{sup 40} erg s{sup -1}) at r > 130 pc (2'') are consistent with blended brighter O VII, O VIII, and Ne IX lines seen in the Chandra HETGS and XMM-Newton RGS spectra below 2 keV. We construct emission line images of these features and find good morphological correlations with the narrow-line region clouds mapped in [O III] {lambda}5007. Self-consistent photoionization models provide good descriptions of the spectra of the large-scale emission, as well as resolved structures, supporting the dominant role of nuclear photoionization, although displacement of optical and X-ray features implies a more complex medium. Collisionally ionized emission is estimated to be {approx}<12% of the extended emission. Presence of both low- and high-ionization spectral components and extended emission in the X-ray image perpendicular to the bicone indicates leakage of nuclear ionization, likely filtered through warm absorbers, instead of being blocked by a continuous obscuring torus. The ratios of [O III]/soft X-ray flux are approximately constant ({approx}15) for the 1.5 kpc radius spanned by these measurements, indicating similar relative contributions from the low- and high-ionization gas phases at different radial distances from the nucleus. If the [O III] and X-ray emission arise from a single photoionized medium, this further implies an outflow with a wind-like density profile. Using spatially resolved X-ray features, we estimate that the mass outflow rate in NGC 4151 is {approx}2 M{sub Sun} yr{sup -1} at 130 pc and the kinematic power of the ionized outflow is 1.7 Multiplication-Sign 10{sup 41} erg s{sup -1}, approximately 0.3% of the bolometric luminosity of the active nucleus in

  10. Sonic and resistivity measurements on Berea sandstone containing tetrahydrofuran hydrates: a possible analogue to natural-gas-hydrate deposits. [Tetrahydrofuran hydrates

    SciTech Connect

    Pearson, C.; Murphy, J.; Halleck, P.; Hermes, R.; Mathews, M.

    1983-01-01

    Deposits of natural gas hydrates exist in arctic sedimentary basins and in marine sediments on continental slopes and rises. However, the physical properties of such sediments are largely unknown. In this paper, we report laboratory sonic and resistivity measurements on Berea sandstone cores saturated with a stoichiometric mixture of tetrahydrofuran (THF) and water. We used THF as the guest species rather than methane or propane gas because THF can be mixed with water to form a solution containing proportions of the proper stoichiometric THF and water. Because neither methane nor propane is soluble in water, mixing the guest species with water sufficiently to form solid hydrate is difficult. Because THF solutions form hydrates readily at atmospheric pressure it is an excellent experimental analogue to natural gas hydrates. Hydrate formation increased the sonic P-wave velocities from a room temperature value of 2.5 km/s to 4.5 km/s at -5/sup 0/C when the pores were nearly filled with hydrates. Lowering the temperature below -5/sup 0/C did not appreciably change the velocity however. In contrast, the electrical resistivity increases nearly two orders of magnitude upon hydrate formation and continues to increase more slowly as the temperature is further decreased. In all cases the resistivities are nearly frequency independent to 30 kHz and the loss tangents are high, always greater than 5. The dielectric loss shows a linear decrease with frequency suggesting that ionic conduction through a brine phase dominates at all frequencies, even when the pores are nearly filled with hydrates. We find that the resistivities are strongly a function of the dissolved salt content of the pore water. Pore water salinity also influences the sonic velocity, but this effect is much smaller and only important near the hydrate formation temperature.

  11. Study of Simvastatin Self-Association Using Electrospray-Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Vetrova, E. V.; Lekar, A. V.; Filonova, O. V.; Borisenko, S. N.; Maksimenko, E. V.; Borisenko, N. I.

    2015-07-01

    Self-association of simvastatin, which is widely used to treat coronary heart disease, was investigated using electrospray-ionization mass spectrometry. Formation of simvastatin self-associates in various solvents was demonstrated using mass spectrometry. Solvation effects were shown to play a special role in the formation of the self-associates. Self-associates containing from two to fi ve simvastatin molecules were detected in mass spectra of an aqueous MeOH (20%) solution of simvastatin. The formation of simvastatin self-associates could compete with the complexation of supramolecular structures during the synthesis of new generation drugs.

  12. Electron ionization mass spectrometric study of substituted alloxazine-5-oxides and iso-alloxazine-5-oxide.

    PubMed

    Prukała, Dorota; Sikorski, Marek

    2009-03-01

    The fragmentation pathways in electron ionization (EI) mass spectra of a series of new N(5)-oxides of alloxazines and iso-alloxazine are presented, and compared with those of substituted alloxazines and iso-alloxazine. The EI mass spectra of these compounds showed characteristic fragmentation pathways A, B and C, started by the ejection of atomic oxygen, a HNCO molecule and an OH(*) radical, respectively. On the basis of B/E and B(2)/E spectra, the mechanism of elimination of the OH(*) radical is discussed. The influence of the methyl substituent in the benzene ring of alloxazine on the mass fragmentation pathways is described. PMID:19165754

  13. Evaluation of a hydrophilic ionic liquid as a salting-out phase separation agent to a water-tetrahydrofuran homogeneous system for aqueous biphasic extraction separation.

    PubMed

    Hirayama, Naoki; Higo, Takaaki; Imura, Hisanori

    2012-01-01

    The use of a hydrophilic ionic liquid (IL), 1-butyl-3-methylimidazolium chloride (C(4)mimCl), as a salting-out phase separation agent to a water-tetrahydrofuran homogeneous system was studied for possible applications to novel aqueous biphasic extraction separation. The IL showed a salting-out phase-separation ability. Also, differences in the polarity between the formed two phases were smaller than that when using NaCl as a salting-out agent. This result suggested that C(4)mimCl remaining in water-rich phase acts not only as a salting-out agent, but also a component of a mixed-solvent. Possible uses of C(4)mimCl/NaCl mixed salting-out agent system were also discussed.

  14. Time-resolved study of excited states of N2 near its first ionization threshold

    NASA Astrophysics Data System (ADS)

    Moise, Angelica; Prince, Kevin C.; Richter, Robert

    2011-03-01

    Two-photon, two-color double-resonance ionization spectroscopy combining synchrotron vacuum ultraviolet radiation with a tunable near-infrared (NIR) laser has been used to investigate gerade symmetry states of the nitrogen molecule. The rotationally resolved spectrum of an autoionizing 1Σg- state has been excited via the intermediate c4 (v = 0) 1Πu Rydberg state. We present the analysis of the band located at Tv = 10 800.7 ± 2 cm-1 with respect to the intermediate state, 126 366 ± 11 cm-1 with respect to the ground state, approximately 700 cm-1 above the first ionization threshold. From the analysis a rotational constant of Bv = 1.700 ± 0.005 cm-1 has been determined for this band. Making use of the pulsed structure of the two radiation beams, lifetimes of several rotational levels of the intermediate state have been measured. We also report rotationally-averaged fluorescence lifetimes (300 K) of several excited electronic states accessible from the ground state by absorption of one photon in the range of 13.85-14.9 eV. The averaged lifetimes of the c4 (0) and c5 (0) states are 5.6 and 4.4 ns, respectively, while the b' (12), c'4 (4, 5, 6), and c'5 (0) states all have lifetimes in the range of hundreds of picoseconds.

  15. Study of Ozone-Initiated Limonene Reaction Products by Low Temperature Plasma Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Nørgaard, Asger W.; Vibenholt, Anni; Benassi, Mario; Clausen, Per Axel; Wolkoff, Peder

    2013-07-01

    Limonene and its ozone-initiated reaction products were investigated in situ by low temperature plasma (LTP) ionization quadrupole time-of-flight (QTOF) mass spectrometry. Helium was used as discharge gas and the protruding plasma generated ~850 ppb ozone in front of the glass tube by reaction with the ambient oxygen. Limonene applied to filter paper was placed in front of the LTP afterglow and the MS inlet. Instantly, a wide range of reaction products appeared, ranging from m/ z 139 to ca. 1000 in the positive mode and m/ z 115 to ca. 600 in the negative mode. Key monomeric oxidation products including levulinic acid, 4-acetyl-1-methylcyclohexene, limonene oxide, 3-isopropenyl-6-oxo-heptanal, and the secondary ozonide of limonene could be identified by collision-induced dissociation. Oligomeric products ranged from the nonoxidized dimer of limonene (C20H30) and up to the hexamer with 10 oxygen atoms (C60H90O10). The use of LTP for in situ ozonolysis and ionization represents a new and versatile approach for the assessment of ozone-initiated terpene chemistry.

  16. Time resolved studies of interfacial reactions of ozone with pulmonary phospholipid surfactants using field induced droplet ionization mass spectrometry.

    PubMed

    Kim, Hugh I; Kim, Hyungjun; Shin, Young Shik; Beegle, Luther W; Goddard, William A; Heath, James R; Kanik, Isik; Beauchamp, J L

    2010-07-29

    Field induced droplet ionization mass spectrometry (FIDI-MS) comprises a soft ionization method to sample ions from the surface of microliter droplets. A pulsed electric field stretches neutral droplets until they develop dual Taylor cones, emitting streams of positively and negatively charged submicrometer droplets in opposite directions, with the desired polarity being directed into a mass spectrometer for analysis. This methodology is employed to study the heterogeneous ozonolysis of 1-palmitoyl-2-oleoyl-sn-phosphatidylglycerol (POPG) at the air-liquid interface in negative ion mode using FIDI mass spectrometry. Our results demonstrate unique characteristics of the heterogeneous reactions at the air-liquid interface. We observe the hydroxyhydroperoxide and the secondary ozonide as major products of POPG ozonolysis in the FIDI-MS spectra. These products are metastable and difficult to observe in the bulk phase, using standard electrospray ionization (ESI) for mass spectrometric analysis. We also present studies of the heterogeneous ozonolysis of a mixture of saturated and unsaturated phospholipids at the air-liquid interface. A mixture of the saturated phospholipid 1,2-dipalmitoyl-sn-phosphatidylglycerol (DPPG) and unsaturated POPG is investigated in negative ion mode using FIDI-MS while a mixture of 1,2-dipalmitoyl-sn-phosphatidylcholine (DPPC) and 1-stearoyl-2-oleoyl-sn-phosphatidylcholine (SOPC) surfactant is studied in positive ion mode. In both cases FIDI-MS shows the saturated and unsaturated pulmonary surfactants form a mixed interfacial layer. Only the unsaturated phospholipid reacts with ozone, forming products that are more hydrophilic than the saturated phospholipid. With extensive ozonolysis only the saturated phospholipid remains at the droplet surface. Combining these experimental observations with the results of computational analysis provides an improved understanding of the interfacial structure and chemistry of a surfactant layer system when

  17. Electron-correlation effects in enhanced ionization of molecules: A time-dependent generalized-active-space configuration-interaction study

    NASA Astrophysics Data System (ADS)

    Chattopadhyay, S.; Bauch, S.; Madsen, L. B.

    2015-12-01

    We numerically study models of H2 and LiH molecules, aligned collinearly with the linear polarization of the external field, to elucidate the possible role of correlation in the enhanced-ionization (EI) phenomena. Correlation is considered at different levels of approximation with the time-dependent generalized-active-space configuration-interaction method. The results of our studies show that enhanced ionization occurs in multielectron molecules and that correlation is important, and they also demonstrate significant deviations between the results of the single-active-electron approximation and more accurate configuration-interaction methods. We further investigate the role of low-lying excited states in the EI phenomena. With the inclusion of correlation we show strong carrier-envelope-phase effects in the enhanced ionization of the asymmetric heteronuclear LiH -like molecule. The correlated calculation shows an intriguing feature of crossover in enhanced ionization with two carrier-envelope phases at critical internuclear separation.

  18. Time-dependent close-coupling studies of the electron-impact ionization of excited-state helium

    SciTech Connect

    Colgan, J.; Pindzola, M. S.

    2002-12-01

    The time-dependent close-coupling theory is applied to the study of the electron-impact ionization of helium from the excited (1s2s) configuration. Calculations are made in an effort to resolve the discrepancy between theoretical calculations and existing experimental measurements for this cross section. We find good agreement with the existing convergent close-coupling calculations of Bray and Fursa [J. Phys. B 28, L197 (1995)], but are in substantial disagreement with the experimental measurements of this quantity by Dixon et al. [J. Phys. B 9, 2617 (1976)].

  19. BCH-1868 [(-)-2-R-dihydroxyphosphinoyl-5-(S)-(guanin-9'-yl-methyl) tetrahydrofuran]: a cyclic nucleoside phosphonate with antitumor activity.

    PubMed

    Leblond, Lorraine; Attardo, Giorgio; Hamelin, Bettina; Bouffard, David Y; Nguyen-Ba, Nghe; Gourdeau, Henriette

    2002-07-01

    Nucleoside phosphonates are widely used therapeutic agents with a broad spectrum of antiviral activity. However, only a few of them are reported to have antitumor activity. In this study, we show that a tetrahydrofuran phosphonate analogue of guanosine, (-)-2-R-dihydroxyphosphinoyl-5-(S)-(guanin-9'-ylmethyl) tetrahydrofuran (BCH-1868), previously reported as having antiviral activity, also displays antitumor activity. In vitro, BCH-1868 inhibited the proliferation of several murine and human cancer cell lines with IC50s in the microM range independently of the tissue type or the presence of multidrug resistance protein MRP/gp190. In vivo, BCH-1868 was active against a variety of human tumor xenograft models (Caki-1, HT-29, DU 145, COLO 205, and CCRF-CEM). In all tumors tested, a significant tumor growth inhibition was noted at 40-50 mg/kg (daily x 5), but no tumor regression was observed in the settings used. To better understand these results, we partially characterized, at the cellular level, the mechanism of action of this new cyclic nucleoside phosphonate and investigated its pharmacokinetic characteristics in mice. We showed that BCH-1868 exerts its antitumor activity by an inhibitory mechanism at the level of DNA polymerase a, resulting in arrest of DNA synthesis and a block of cell division at the S phase of the cell cycle. Low-circulating plasma concentration (Cmax = 87 microM; area under the curve = 1138 micromol x min/liters; after a bolus i.v. injection of 10 mg/kg) and rapid clearance of the drug (terminal half-life, t1/2 = 16 min) may contribute to the modest antitumor efficacy observed in vivo.

  20. The Chandra X-Ray Observatory and its Role for the Study of Ionized Plasmas

    NASA Technical Reports Server (NTRS)

    Weisskopf, Martin C.

    2010-01-01

    NASA's Chandra X-Ray Observatory was launched in July of 1999. Featuring a 1000cm2-class X-ray telescope with sub-arcsecond angular resolution, the Observatory has observed targets from the solar system including the earth s moon, comets, and planets to the most distant galaxy clusters and active galactic nuclei. Capable of performing moderate energy resolution image-resolved spectroscopy using its CCD detectors, and high-resolution grating spectroscopy, the Observatory has produced, and continues to produce, valuable data and insights into the emission mechanisms of the ionized plasmas in which the X-rays originate. We present a brief overview of the Observatory to provide insight as to how to use it for your investigations. We also present an, admittedly brief and biased, overview of some of the results of investigations performed with Chandra that may be of interest to this audience.

  1. Further studies of double ionization of He, Ne, and Ar by fast and slow antiprotons

    NASA Astrophysics Data System (ADS)

    Andersen, L. H.; Hvelplund, P.; Knudsen, H.; Møller, S. P.; Pedersen, J. O. P.; Tang-Petersen, S.; Uggerhøj, E.; Elsener, K.; Morenzoni, E.

    1989-12-01

    Measurements of the ratio R between double- and single-ionization cross sections for antiproton impact on He, Ne, and Ar targets are reported for impact energies ranging from 65 keV to 20 MeV. At high energies the results are found to merge with proton results at around 20 MeV, and the high-energy limit of the common ratio is in good agreement with recent first-Born-calculation results for the helium target. The large difference previously observed in the ratio R for protons and antiprotons at energies between 0.5 and 5 MeV is found to persist down to the lowest energies investigated here.

  2. Molecular beam resonant two-photon ionization study of caffeine and its hydrated clusters

    NASA Astrophysics Data System (ADS)

    Kim, Doory; Kim, Hyung Min; Yang, Key Young; Kim, Seong Keun; Kim, Nam Joon

    2008-04-01

    We investigated electronically excited states of caffeine and its 1:1 complex with water by using resonant two-photon ionization (R2PI) and UV-UV hole-burning techniques. Strong vibronic coupling between a pair of close-lying π-π * and n-π * transitions is proposed to be responsible for the broad spectral feature observed. By comparing the experimental results with those of theoretical calculations, both the O-bonded and N-bonded forms were suggested to be initially produced for the 1:1 complex. The electronic transitions of the O-bonded complex were blueshifted in the R2PI spectrum. For the N-bonded complex, the excited state undergoes an ultrafast decay process, followed by dissociation on a repulsive potential energy surface, which gives rise to a characteristically anomalous cluster distribution in nanosecond experiments.

  3. Theoretical study of the ionospheric plasma cave in the equatorial ionization anomaly region

    NASA Astrophysics Data System (ADS)

    Chen, Yu-Tsung; Lin, C. H.; Chen, C. H.; Liu, J. Y.; Huba, J. D.; Chang, L. C.; Liu, H.-L.; Lin, J. T.; Rajesh, P. K.

    2014-12-01

    This paper investigates the physical mechanism of an unusual equatorial electron density structure, plasma cave, located underneath the equatorial ionization anomaly by using theoretical simulations. The simulation results provide important new understanding of the dynamics of the equatorial ionosphere. It has been suggested previously that unusual E>⇀×B>⇀ drifts might be responsible for the observed plasma cave structure, but model simulations in this paper suggest that the more likely cause is latitudinal meridional neutral wind variations. The neutral winds are featured by two divergent wind regions at off-equator latitudes and a convergent wind region around the magnetic equator, resulting in plasma divergences and convergence, respectively, to form the plasma caves structure. The tidal-decomposition analysis further suggests that the cave related meridional neutral winds and the intensity of plasma cave are highly associated with the migrating terdiurnal tidal component of the neutral winds.

  4. Studying interfacial reactions of cholesterol sulfate in an unsaturated phosphatidylglycerol layer with ozone using field induced droplet ionization mass spectrometry.

    PubMed

    Ko, Jae Yoon; Choi, Sun Mi; Rhee, Young Min; Beauchamp, J L; Kim, Hugh I

    2012-01-01

    Field-induced droplet ionization (FIDI) is a recently developed ionization technique that can transfer ions from the surface of microliter droplets to the gas phase intact. The air-liquid interfacial reactions of cholesterol sulfate (CholSO(4)) in a 1-palmitoyl-2-oleoyl-sn-phosphatidylglycerol (POPG) surfactant layer with ozone (O(3)) are investigated using field-induced droplet ionization mass spectrometry (FIDI-MS). Time-resolved studies of interfacial ozonolysis of CholSO(4) reveal that water plays an important role in forming oxygenated products. An epoxide derivative is observed as a major product of CholSO(4) oxidation in the FIDI-MS spectrum after exposure of the droplet to O(3) for 5 s. The abundance of the epoxide product then decreases with continued O(3) exposure as the finite number of water molecules at the air-liquid interface becomes exhausted. Competitive oxidation of CholSO(4) and POPG is observed when they are present together in a lipid surfactant layer at the air-liquid interface. Competitive reactions of CholSO(4) and POPG with O(3) suggest that CholSO(4) is present with POPG as a well-mixed interfacial layer. Compared with CholSO(4) and POPG alone, the overall ozonolysis rates of both CholSO(4) and POPG are reduced in a mixed layer, suggesting the double bonds of both molecules are shielded by additional hydrocarbons from one another. Molecular dynamics simulations of a monolayer comprising POPG and CholSO(4) correlate well with experimental observations and provide a detailed picture of the interactions between CholSO(4), lipids, and water molecules in the interfacial region.

  5. Single cell ionization by a laser trap: a preliminary study in measuring radiation dose and charge in BT20 breast carcinoma cells

    PubMed Central

    Kelley, Michele; Gao, Ying; Erenso, Daniel

    2016-01-01

    In this work, a preliminary study in the application of a laser trap for ionization of living carcinoma cells is presented. The study was conducted using BT20 breast carcinoma cells cultured and harvested in our laboratory. Each cell, for a total of 50 cells, was trapped and ionized by a high intensity infrared laser at 1064 nm. The threshold radiation dose and the resultant charge from the ionization for each cell were determined. With the laser trap serving as a radiation source, the cell underwent dielectric breakdown of the membrane. When this process occurs, the cell becomes highly charged and its dielectric susceptibility changes. The charge creates an increasing electrostatic force while the changing dielectric susceptibility diminishes the strength of the trapping force. Consequently, at some instant of time the cell gets ejected from the trap. The time inside the trap while the cell is being ionized, the intensity of the radiation, and the post ionization trajectory of the cell were used to determine the threshold radiation dose and the charge for each cell. The measurement of the charge vs ionization radiation dose at single cell level could be useful in the accuracy of radiotherapy as the individual charges can collectively create a strong enough electrical interaction to cause dielectric breakdown in other cells in a tumor. PMID:27699110

  6. Single cell ionization by a laser trap: a preliminary study in measuring radiation dose and charge in BT20 breast carcinoma cells

    PubMed Central

    Kelley, Michele; Gao, Ying; Erenso, Daniel

    2016-01-01

    In this work, a preliminary study in the application of a laser trap for ionization of living carcinoma cells is presented. The study was conducted using BT20 breast carcinoma cells cultured and harvested in our laboratory. Each cell, for a total of 50 cells, was trapped and ionized by a high intensity infrared laser at 1064 nm. The threshold radiation dose and the resultant charge from the ionization for each cell were determined. With the laser trap serving as a radiation source, the cell underwent dielectric breakdown of the membrane. When this process occurs, the cell becomes highly charged and its dielectric susceptibility changes. The charge creates an increasing electrostatic force while the changing dielectric susceptibility diminishes the strength of the trapping force. Consequently, at some instant of time the cell gets ejected from the trap. The time inside the trap while the cell is being ionized, the intensity of the radiation, and the post ionization trajectory of the cell were used to determine the threshold radiation dose and the charge for each cell. The measurement of the charge vs ionization radiation dose at single cell level could be useful in the accuracy of radiotherapy as the individual charges can collectively create a strong enough electrical interaction to cause dielectric breakdown in other cells in a tumor.

  7. RF Pre-Ionization to Create Faster, Hotter MHD-Driven Jets and Studies of Plasma Expansion Into a Vacuum

    NASA Astrophysics Data System (ADS)

    Chaplin, Vernon; Bellan, Paul

    2013-10-01

    We are studying MHD-driven jets relevant to astrophysical jets and fusion plasmas. Previous experiments at Caltech have focused on plasmas created by breaking down neutral gas using high voltage. The Paschen breakdown criterion governing this process sets an undesirable lower limit for the jet density. To overcome this constraint, we have developed a pre-ionization system powered by a pulsed, battery-powered, 3 kW 13.56 MHz RF amplifier. Pre-ionization of plasma in a tube behind the jet experiment's center electrode is expected to enable the formation of lower density, hotter, faster jets. Thus far, argon jets have been created with v >30 km/s, twice as fast as was previously achievable. The expansion of the RF plasma into the chamber prior to the discharge of the main capacitor bank involves surprisingly complex dynamics. There are two phases: initially plasma expansion along the background magnetic field is inhibited and the primary source of emission away from the RF antenna appears to be neutral atoms excited by fast electrons or photons from the RF source. At a later time, either before or after RF turn-off depending on the magnetic field configuration, a relatively high density (ne >1018 m-3) , cold (Te < 0.5 eV) cloud of plasma emerges from the source tube.

  8. Three new anti-proliferative Annonaceous acetogenins with mono-tetrahydrofuran ring from graviola fruit (Annona muricata).

    PubMed

    Sun, Shi; Liu, Jingchun; Kadouh, Hoda; Sun, Xiuxiu; Zhou, Kequan

    2014-06-15

    Bioassay-guided fractionation of the fruit powder of graviola (Annona muricata) yielded three novel compounds: muricins J, K, and L. The compounds are all C35 Annonaceous acetogenins with a mono-tetrahydrofuran ring and four hydroxyls. Their structures were elucidated by spectral methods and chemical modification after isolation via chromatographic techniques and HPLC purification. These three acetogenins demonstrated an antiproliferative against human prostate cancer PC-3 cells.

  9. Occupational exposure to low doses of ionizing radiation and cataract development: a systematic literature review and perspectives on future studies.

    PubMed

    Hammer, Gaël P; Scheidemann-Wesp, Ulrike; Samkange-Zeeb, Florence; Wicke, Henryk; Neriishi, Kazuo; Blettner, Maria

    2013-08-01

    Ionizing radiation is a well-known but little understood risk factor for lens opacities. Until recently, cataract development was considered to be a deterministic effect occurring at lens doses exceeding a threshold of 5-8 Gy. Substantial uncertainty about the level and the existence of a threshold subsists. The International Commission on Radiation Protection recently revised it to 0.5 Gy. Based on a systematic literature review of epidemiological studies on exposure to low levels of ionizing radiation and the occurrence of lens opacities, a list of criteria for new epidemiological studies was compiled, and a list of potential study populations was reviewed. Among 24 publications finally identified, six report analyses of acute exposures in atomic bomb survivors and Chernobyl liquidators, and the others report analyses of protracted exposures in occupationally, medically or accidentally exposed populations. Three studies investigated a dose threshold: in atomic bomb survivors, the best estimates were 1 Sv (95 % CI <0-0.8 Sv) regarding lensectomies; in survivors exposed as children, 0.6 Sv (90 % CI <0.0-1.2 Sv) for cortical cataract prevalence and 0.7 Sv (90 % CI 0.0-2.8 Sv) for posterior subcapsular cataract; and in Chernobyl liquidators, 0.34 Sv (95 % CI 0.19-0.68 Sv) for stage 1 cataract. Current studies are heterogeneous and inconclusive regarding the dose-response relationship. Protracted exposures and high lens doses occur in several occupational groups, for instance, in physicians performing fluoroscopy-guided interventional procedures, and in accidentally exposed populations. New studies with a good retrospective exposure assessment are feasible and should be initiated.

  10. Ionization and fragmentation of complex molecules studied with a density functional theory based approach

    NASA Astrophysics Data System (ADS)

    Kirchner, Tom

    2013-05-01

    Ion-impact induced ionization and fragmentation of complex molecules have important applications in many branches of science. If the molecule is H2O an obvious topic to address is the radiobiological relevance of these processes, e.g. in the context of hadron therapy, to name just one example. From a more fundamental physics viewpoint ion-molecule collision systems constitute interesting many-body systems, whose analysis poses challenges to both experimentalists and theorists. This talk will describe a theoretical approach to ion-molecule collisions, which is based on density functional theory to describe the nonperturbative electron dynamics. The basis generator method applied in the past successfully to ion-atom collisions is adapted to deal with the multi-center problem one faces when one considers molecular targets. Cross sections for single- and multiple-electron processes (capture and transfer to the continuum) are obtained directly from solving time-dependent Kohn-Sham-type orbital equations and using a Slater determinant based analysis. Fragmentation yields are predicted on the basis of a semi-phenomenological model which uses the calculated cross sections as input. Results will be presented for various ions impacting on water molecules in the energy range of 10-5000 keV/amu and compared with experimental data and previous theoretical calculations where available. First applications of the model to collisions involving CH4 molecules will also be discussed. This work has been supported by SHARCNET and NSERC Canada.

  11. Fragmentation studies and electrospray ionization mass spectrometry of lapachol: protonated, deprotonated and cationized species.

    PubMed

    Vessecchi, Ricardo; Emery, Flavio S; Galembeck, Sérgio E; Lopes, Norberto P

    2010-07-30

    Electrospray ionization mass spectrometric analysis of lapachol (2-hydroxy-3-(3-methyl-2-butenyl)-1,4-naphthoquinone) was accomplished in order to elucidate the gas-phase dissociation reactions of this important biologically active natural product. The occurrence of protonated and cationized species in the positive mode and of deprotonated species in the negative mode was explored by means of collision-induced dissociation (CID) experiments. For the protonated molecule, the H(2)O and C(4)H(8) losses occur by two competitive channels. For the deprotonated molecule, the even-electron rule is not conserved, and the radicalar species are eliminated by formation of distonic anions. The fragmentation mechanism for each ion was suggested on the basis of computational thermochemistry. Atomic charges, relative energies, and frontier orbitals were employed aiming at a better understanding of the gas-phase reactivity of lapachol. Potential energy surfaces for fragmentation reactions were obtained by the B3LYP/6-31+G(d,p) model. PMID:20552691

  12. Long-Term Effects of Exposure to Ionizing Irradiation on Periodontal Health Status – The Tinea capitis Cohort Study

    PubMed Central

    Sadetzki, Siegal; Chetrit, Angela; Sgan-Cohen, Harold D.; Mann, Jonathan; Amitai, Tova; Even-Nir, Hadas; Vered, Yuval

    2015-01-01

    Studies among long-term survivors of childhood cancer who had received high-dose irradiation therapy of 4–60 Gy, demonstrated acute and chronic dental effects, including periodontal diseases. However, the possible effects of low to moderate doses of radiation on dental health are sparse. The aim of this study is to investigate the association between childhood exposure to low–moderate doses of ionizing radiation and periodontal health following 50 years since exposure. The study population included 253 irradiated subjects (treated for Tinea capitis in the 1950s) and, 162 non-irradiated subjects. The estimated dose to the teeth was 0.2–0.4 Gy. Dental examination was performed according to the community periodontal index (CPI). Socioeconomic and health behavior variables were obtained through a personal questionnaire. Periodontal disease was operationally defined as “deep periodontal pockets.” A multivariate logistic regression model was used for the association of irradiation status and other independent variables with periodontal status. The results showed that among the irradiated subjects, 23%, (95% CI 18–28%) demonstrated complete edentulousness or insufficient teeth for CPI scoring as compared to 13% (95% CI 8–19%) among the non-irradiated subjects (p = 0.01). Periodontal disease was detected among 54% of the irradiated subjects as compared to 40% of the non-irradiated (p = 0.008). Controlling for education and smoking, the ORs for the association between radiation and periodontal disease were 1.61 (95% CI 1.01–2.57) and 1.95 (95% CI 1.1–3.5) for ever never and per 1 Gy absorbed in the salivary gland, respectively. In line with other studies, a protective effect for periodontal diseases among those with high education and an increased risk for ever smokers were observed. In conclusion, childhood exposure to low-moderate doses of ionizing radiation might be associated with later outcomes of dental health. The results add

  13. Long-Term Effects of Exposure to Ionizing Irradiation on Periodontal Health Status - The Tinea capitis Cohort Study.

    PubMed

    Sadetzki, Siegal; Chetrit, Angela; Sgan-Cohen, Harold D; Mann, Jonathan; Amitai, Tova; Even-Nir, Hadas; Vered, Yuval

    2015-01-01

    Studies among long-term survivors of childhood cancer who had received high-dose irradiation therapy of 4-60 Gy, demonstrated acute and chronic dental effects, including periodontal diseases. However, the possible effects of low to moderate doses of radiation on dental health are sparse. The aim of this study is to investigate the association between childhood exposure to low-moderate doses of ionizing radiation and periodontal health following 50 years since exposure. The study population included 253 irradiated subjects (treated for Tinea capitis in the 1950s) and, 162 non-irradiated subjects. The estimated dose to the teeth was 0.2-0.4 Gy. Dental examination was performed according to the community periodontal index (CPI). Socioeconomic and health behavior variables were obtained through a personal questionnaire. Periodontal disease was operationally defined as "deep periodontal pockets." A multivariate logistic regression model was used for the association of irradiation status and other independent variables with periodontal status. The results showed that among the irradiated subjects, 23%, (95% CI 18-28%) demonstrated complete edentulousness or insufficient teeth for CPI scoring as compared to 13% (95% CI 8-19%) among the non-irradiated subjects (p = 0.01). Periodontal disease was detected among 54% of the irradiated subjects as compared to 40% of the non-irradiated (p = 0.008). Controlling for education and smoking, the ORs for the association between radiation and periodontal disease were 1.61 (95% CI 1.01-2.57) and 1.95 (95% CI 1.1-3.5) for ever never and per 1 Gy absorbed in the salivary gland, respectively. In line with other studies, a protective effect for periodontal diseases among those with high education and an increased risk for ever smokers were observed. In conclusion, childhood exposure to low-moderate doses of ionizing radiation might be associated with later outcomes of dental health. The results add valuable data on the long

  14. Cosolvent pretreatment in cellulosic biofuel production: Effect of tetrahydrofuran-water on lignin structure and dynamics

    DOE PAGESBeta

    Smith, Micholas Dean; Mostofian, Barmak; Cheng, Xiaolin; Petridis, Loukas; Cai, Charles M.; Wyman, Charles E.; Smith, Jeremy C.

    2015-10-05

    The deconstruction of cellulose is an essential step in the production of ethanol from lignocellulosic biomass. However, the presence of lignin hinders this process. Recently, a novel cosolvent based biomass pretreatment method called CELF (Cosolvent Enhanced Lignocellulosic Fractionation) which employs tetrahydrofuran (THF) in a single phase mixture with water, was found to be highly effective at solubilizing and extracting lignin from lignocellulosic biomass and achieving high yields of fermentable sugars. Here, using all-atom molecular-dynamics simulation, we find that THF preferentially solvates lignin, and in doing so, shifts the equilibrium configurational distribution of the biopolymer from a crumpled globule to coil,more » independent of temperature. Whereas pure water is a bad solvent for lignin, the THF : water cosolvent acts as a "theta" solvent, in which solvent : lignin and lignin : lignin interactions are approximately equivalent in strength. Furthermore, under these conditions, polymers do not aggregate, thus providing a mechanism for the observed lignin solubilization that facilitates unfettered access of celluloytic enzymes to cellulose.« less

  15. Cosolvent pretreatment in cellulosic biofuel production: Effect of tetrahydrofuran-water on lignin structure and dynamics

    SciTech Connect

    Smith, Micholas Dean; Mostofian, Barmak; Cheng, Xiaolin; Petridis, Loukas; Cai, Charles M.; Wyman, Charles E.; Smith, Jeremy C.

    2015-10-05

    The deconstruction of cellulose is an essential step in the production of ethanol from lignocellulosic biomass. However, the presence of lignin hinders this process. Recently, a novel cosolvent based biomass pretreatment method called CELF (Cosolvent Enhanced Lignocellulosic Fractionation) which employs tetrahydrofuran (THF) in a single phase mixture with water, was found to be highly effective at solubilizing and extracting lignin from lignocellulosic biomass and achieving high yields of fermentable sugars. Here, using all-atom molecular-dynamics simulation, we find that THF preferentially solvates lignin, and in doing so, shifts the equilibrium configurational distribution of the biopolymer from a crumpled globule to coil, independent of temperature. Whereas pure water is a bad solvent for lignin, the THF : water cosolvent acts as a "theta" solvent, in which solvent : lignin and lignin : lignin interactions are approximately equivalent in strength. Furthermore, under these conditions, polymers do not aggregate, thus providing a mechanism for the observed lignin solubilization that facilitates unfettered access of celluloytic enzymes to cellulose.

  16. An efficient and economical process for lignin depolymerization in biomass-derived solvent tetrahydrofuran.

    PubMed

    Long, Jinxing; Zhang, Qi; Wang, Tiejun; Zhang, Xinghua; Xu, Ying; Ma, Longlong

    2014-02-01

    The depolymerization of renewable lignin for phenolic monomer, a versatile biochemical and precursor for biofuel, has attracted increasing attention. Here, an efficient base-catalyzed depolymerization process for this natural aromatic polymer is presented with cheap industrial solid alkali MgO and biomass-derived solvent tetrahydrofuran (THF). Results showed that more than 13.2% of phenolic monomers were obtained under 250°C for 15 min, because of the excellent lignin dissolution of THF and its promotion effect on the catalytic activity of MgO. Furthermore, comparison characterization on the raw material, products and residual solid using elemental analysis, FT-IR, TG-DSC, Py-GC-MS and chemo-physical absorption and desorption demonstrated that this base-catalyzed process can inhibit char formation significantly. Whereas, the fact that thermal repolymerization of oligomer on the pore and surface of catalyst resulting in the declination of the catalytic performance is responsible for the residue formation. PMID:24370950

  17. Dichlorido(3-phenyl-indenyl-idene)bis-(triphenyl-phosphane)ruthenium(II) tetra-hydro-furan disolvate.

    PubMed

    Bats, Jan W; Pérez Gomes, Jessica; Doppiu, Angelino; Hashmi, A Stephen K

    2011-06-01

    The Ru(II) atom in the title compound, [RuCl(2)(C(15)H(10))(C(18)H(15)P)(2)]·2C(4)H(8)O, has a distorted square-pyramidal conformation. The P and Cl atoms are at the base of the pyramid and the Ru-C(indenyl-idene) bond is in the axial position. The two Cl ligands and the two phosphane ligands are in trans positions. The Cl-Ru-Cl and P-Ru-P angles are 157.71 (2) and 166.83 (2)°, respectively. The two independent tetra-hydro-furan (THF) solvent mol-ecules are disordered. One THF mol-ecule was refined using a split-atom model. The second THF mol-ecule was accounted for by using program PLATON/SQUEEZE [Spek (2009 ▶). Acta Cryst. D65, 148-155]. The molecular conformation shows three intramolecular C-H⋯Cl contacts and two C-H⋯π interactions while the crystal packing features an intermolecular C-H⋯Cl contact and two very weak intermolecular C-H⋯π contacts. PMID:21754621

  18. Characteristics of tetrahydrofuran-based electrolytes with magnesium alkoxide additives for rechargeable magnesium batteries

    NASA Astrophysics Data System (ADS)

    Kim, In-Tae; Yamabuki, Kazuhiro; Sumimoto, Michinori; Tsutsumi, Hiromori; Morita, Masayuki; Yoshimoto, Nobuko

    2016-08-01

    The electrochemical behavior of magnesium (Mg) metal was investigated in tetrahydrofuran (THF)-based solutions containing magnesium bromide (MgBr2) and/or magnesium ethoxide (Mg(OEt)2). THF solutions containing a single solute, MgBr2 or Mg(OEt)2, show no visible faradaic current based on Mg deposition and/or dissolution. However, the electrolyte system containing both solutes, MgBr2 + Mg(OEt)2/THF, gives a reversible current response of Mg deposition and dissolution. The ionic structure of the electrolyte system containing the binary solute was examined by infrared (IR) spectroscopy and density functional theory (DFT) calculations. It was confirmed that MgBr2 and Mg(OEt)2 are coordinated (solvated) with THF molecules to form an EtOsbnd Mgsbnd Br·4THF complex. The DFT calculations also suggest the possible formation of μ-complexes for the MgBr2/Mg(OEt)2 binary system in THF. The voltammetric responses at the Pt electrode indicate low overpotential and high coulombic efficiency for Mg deposition and dissolution in THF-based solutions containing suitable molar ratios of MgBr2 and Mg(OEt)2. The constant-current charge-discharge cycling of Mg in MgBr2 + Mg(OEt)2/THF electrolyte also shows low overpotential and good cyclability over 300 cycles.

  19. Studies of the mechanism of the cluster formation in a thermally sampling atmospheric pressure ionization mass spectrometer.

    PubMed

    Albrecht, Sascha; Klopotowski, Sebastian; Derpmann, Valerie; Klee, Sonja; Brockmann, Klaus J; Stroh, Fred; Benter, Thorsten

    2014-01-01

    In this study a thermally sampling atmospheric pressure ionization mass spectrometer is described and characterized. The ion transfer stage offers the capability to sample cluster ions at thermal equilibrium and during this transfer fundamental processes possibly affecting the cluster distribution are also readily identified. Additionally, the transfer stage combines optional collision-induced dissociation (CID) analysis of the cluster composition with thermal equilibrium sampling of clusters. The performance of the setup is demonstrated with regard to the proton-bound water cluster system. The benefit of the studied processes is that they can help to improve future transfer stages and to understand cluster ion reactions in ion mobility tubes and high-pressure ion sources. In addition, the instrument allows for the identification of fragmentation and protonation reactions caused by CID. PMID:24517784

  20. Studies of the mechanism of the cluster formation in a thermally sampling atmospheric pressure ionization mass spectrometer

    SciTech Connect

    Albrecht, Sascha Stroh, Fred; Klopotowski, Sebastian Derpmann, Valerie Klee, Sonja Brockmann, Klaus J. Benter, Thorsten

    2014-01-15

    In this study a thermally sampling atmospheric pressure ionization mass spectrometer is described and characterized. The ion transfer stage offers the capability to sample cluster ions at thermal equilibrium and during this transfer fundamental processes possibly affecting the cluster distribution are also readily identified. Additionally, the transfer stage combines optional collision-induced dissociation (CID) analysis of the cluster composition with thermal equilibrium sampling of clusters. The performance of the setup is demonstrated with regard to the proton-bound water cluster system. The benefit of the studied processes is that they can help to improve future transfer stages and to understand cluster ion reactions in ion mobility tubes and high-pressure ion sources. In addition, the instrument allows for the identification of fragmentation and protonation reactions caused by CID.

  1. Electrospray Ionization Mechanisms for Large Polyethylene Glycol Chains Studied Through Tandem Ion Mobility Spectrometry

    NASA Astrophysics Data System (ADS)

    Larriba, Carlos; de la Mora, Juan Fernandez; Clemmer, David E.

    2014-08-01

    Ion mobility mass spectrometry (IMS-MS) is used to investigate the abundance pattern, n z (m) of Poly-(ethyleneglycol) (PEG) electrosprayed from water/methanol as a function of mass and charge state. We examine n z (m) patterns from a diversity of solution cations, primarily dimethylammonium and triethylammonium. The ability of PEG chains to initially attach to various cations in the spraying chamber, and to retain them (or not) on entering the MS, provide valuable clues on the ionization mechanism. Single chains form in highly charged and extended shapes in most buffers. But the high initial charge they hold under atmospheric pressure is lost on transit to the vacuum system for large cations. In contrast, aggregates of two or more chains carry in all buffers at most the Rayleigh charge of a water drop of the same volume. This shows either that they form via Dole's charge residue mechanism, or that highly charged and extended aggregates are ripped apart by Coulombic repulsion. IMS-IMS experiments in He confirm these findings, and provide new mechanistic insights on the stability of aggregates. When collisionally activated, initially globular dimers are stable. However, slightly nonglobular dimers projecting out a linear appendix are segregated into two monomeric chains. The breakup of a charged dimer is therefore a multi-step process, similar to the Fenn-Consta polymer extrusion mechanism. The highest activation barrier is associated to the first step, where a short chain segment carrying a single charge escapes (ion-evaporates) from a charged drop, leading then to gradual field extrusion of the whole chain out of the drop.

  2. H II Region Ionization of the Interstellar Medium: A Case Study of NGC 7538

    NASA Astrophysics Data System (ADS)

    Luisi, Matteo; Anderson, L. D.; Balser, Dana S.; Bania, T. M.; Wenger, Trey V.

    2016-06-01

    Using data from the Green Bank Telescope, we analyze the radio continuum (free–free) and radio recombination line (RRL) emission of the compact H ii region NGC 7538 (Sharpless 158). We detect extended radio continuum and hydrogen RRL emission beyond the photodissociation region (PDR) toward the north and east, but a sharp decrease in emission toward the south and west. This indicates that a non-uniform PDR morphology is affecting the amount of radiation “leaking” through the PDR. The strongest carbon RRL emission is found in the western PDR that appears to be dense. We compute a leaking fraction f R = 15 ± 5% of the radio continuum emission measured in the plane of the sky which represents a lower limit when accounting for the three-dimensional geometry of the region. We detect an average {}4{{{He}}}+/{{{H}}}+ abundance ratio by number of 0.088 ± 0.003 inside the H ii region and a decrease in this ratio with increasing distance from the region beyond the PDR. Using Herschel Space Observatory data, we show that small dust temperature enhancements to the north and east of NGC 7538 coincide with extended radio emission, but that the dust temperature enhancements are mostly contained within a second PDR to the east. Unlike the giant H ii region W43, the radiation leaking from NGC 7538 seems to only affect the local ambient medium. This suggests that giant H ii regions may have a large effect in maintaining the ionization of the interstellar medium.

  3. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometric and semi-empirical calculations study of five isoflavone aglycones.

    PubMed

    Madeira, Paulo J Amorim; Borges, Carlos M; Florêncio, M Helena

    2010-12-15

    Five isoflavones, daidzein, genistein, formononetin, prunetin and biochanin A, known for their biological properties, are investigated by electrospray ionization mass spectrometry in the positive ion mode. The most probable protonation sites are determined taking into account semi-empirical calculations using the PM6 Hamiltonian. Fragmentation mechanisms are proposed based on accurate mass measurements, MS(3) experiments and supported by the semi-empirical calculations. Some of the fragmentation pathways were found to be dependent on the substitution pattern of the B-ring and the ions afforded by these fragmentations can be considered as diagnostic. It was possible to distinguish between prunetin and biochanin A, two isobaric isoflavone aglycones included in this study. Furthermore, a comparison of the fragmentation patterns of genistein and biochanin A, two isoflavones, with those of their flavone counterparts, apigenin and acacetin, enabled us to identify some key ions mainly due to structural features, allowing distinction to be made between these two classes of compounds.

  4. Effect of noncovalent interactions on conformers of the n-butylbenzene monomer studied by mass analyzed threshold ionization spectroscopy and basis-set convergent ab initio computations.

    PubMed

    Tong, Xin; Cerný, Jirí; Müller-Dethlefs, Klaus; Dessent, Caroline E H

    2008-07-01

    Two conformational isomers of the aromatic hydrocarbon n-butylbenzene have been studied using two-color MATI (mass analyzed threshold ionization) spectroscopy to explore the effect of conformation on ionization dynamics. Cationic states of g auche-conformer III and anti- conformers IV were selectively produced by two-color excitation via the respective S 1 origins. Adiabatic ionization potentials of the gauche- and anti-conformations were determined to be 70146 and 69872 +/- 5 cm (-1) respectively. Spectral features and vibrational modes are interpreted with the aid of MP2/cc-pVDZ ab initio calculations, and ionization-induced changes in the molecular conformations are discussed. Complete basis set (CBS) ab initio studies at MP2 level reveal reliable energetics for all four n-butylbenzene conformers observed in earlier two-color REMPI (resonance enhanced multiphoton ionization) spectra. For the S 0 state, the energies of conformer III, IV and V are above conformer I by 130, 289, 73 cm (-1), respectively. Furthermore, the combination of the CBS calculations with the measured REMPI, MATI spectra allowed the determination of the energetics of all four conformers in the S 1 and D 0 states.

  5. Effect of noncovalent interactions on conformers of the n-butylbenzene monomer studied by mass analyzed threshold ionization spectroscopy and basis-set convergent ab initio computations.

    PubMed

    Tong, Xin; Cerný, Jirí; Müller-Dethlefs, Klaus; Dessent, Caroline E H

    2008-07-01

    Two conformational isomers of the aromatic hydrocarbon n-butylbenzene have been studied using two-color MATI (mass analyzed threshold ionization) spectroscopy to explore the effect of conformation on ionization dynamics. Cationic states of g auche-conformer III and anti- conformers IV were selectively produced by two-color excitation via the respective S 1 origins. Adiabatic ionization potentials of the gauche- and anti-conformations were determined to be 70146 and 69872 +/- 5 cm (-1) respectively. Spectral features and vibrational modes are interpreted with the aid of MP2/cc-pVDZ ab initio calculations, and ionization-induced changes in the molecular conformations are discussed. Complete basis set (CBS) ab initio studies at MP2 level reveal reliable energetics for all four n-butylbenzene conformers observed in earlier two-color REMPI (resonance enhanced multiphoton ionization) spectra. For the S 0 state, the energies of conformer III, IV and V are above conformer I by 130, 289, 73 cm (-1), respectively. Furthermore, the combination of the CBS calculations with the measured REMPI, MATI spectra allowed the determination of the energetics of all four conformers in the S 1 and D 0 states. PMID:18533642

  6. Studies of photoionization in liquids using a laser two-photon ionization conductivity technique. [Potoionization of pyrene, fluoranthene and TMPD in liquid n-pentane

    SciTech Connect

    Siomos, K.; Christophorou, L.G.

    1981-01-01

    One-photon ionization studies of solute molecules in a liquid medium are limited by the absorption of the host medium. A laser two-photon ionization (TPI) technique using a frequency tunable dye laser has been developed, whereby the photoionization threshold of a solute molecule was determined from the induced conductivity in the liquid medium under study due to electron-ion pair formation via two-photon ionization of the solute. The two-photon induced electron-ion current is measured as a function of the laser wavelength, lambda/sub laser/. In this paper, results are reported and discussed on the photoionization of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), pyrene and fluoranthene in liquid n-pentane (n-Pt).

  7. Double-ionization energies of some n-alkyl isocyanate molecules; studies with double-charge-transfer spectrometry and ab initio propagator theory

    NASA Astrophysics Data System (ADS)

    Bayliss, M. A.; Griffiths, I. W.; Harris, F. M.; Parry, D. E.

    2003-12-01

    Double-charge-transfer (DCT) collisions of H+, OH+ and F+ 3 keV beam ions with a series of alkyl isocyanate molecules were studied using mass spectrometric techniques. Measurement of the kinetic energies of H- ions so produced enabled the determination of double-ionization energies (DIE) for transitions to singlet doubly ionized states of the target molecules; those for triplet doubly ionized states were obtained similarly from measurements of the kinetic energies of OH- and F- ions. Values up to approximately 40 eV were obtained in most cases and were found to be in close agreement with the predictions of ab initio calculations using propagator theory, also presented here. For n-butyl isocyanate (and by implication heavier molecules in the series) the density of doubly ionized states above 30 eV was both observed and predicted to be too large and featureless for meaningful analysis, so establishing an effective upper limit on molecular size for the current application of these techniques. Significant configuration interaction was predicted for the final doubly ionized states, which justified theoretical analysis with a relatively complex method that accounts well for correlation effects.

  8. Electron-impact ionization and dissociative ionization of biomolecules

    NASA Astrophysics Data System (ADS)

    Huo, Winifred

    2006-05-01

    Oxidative damages by ionizing radiation are the source of radiation-induced damages to human health. It is recognized that secondary electrons play a role in the damage process, particularly important is the damage of DNA by electrons, potentially leading to mutagenesis. The damage can be direct, by creating a DNA lesion, or indirect, by producing radicals that attack the DNA. Molecular-level study of electron interaction with DNA provides information on the damage pathways and dominant mechanisms. This investigation focuses on ionization and dissociative ionization (DI) of DNA fragments by electron-impact. For ionization we use the improved binary-encounter dipole (iBED) model [W.M. Huo, Phys. Rev. A64, 042719-1 (2001)]. For DI it is assumed that electron motion is much faster than nuclear motion, allowing DI to be treated as a two-step process and the DI cross section given by the product of the ionization cross section and dissociation probability. The ionization study covers DNA bases, sugar phosphate backbone, and nucleotides. An additivity principle is observed. For example, the sum of the ionization cross sections of the separate deoxyribose and phosphate fragments is in close agreement with the C3'- and C5'-deoxyribose-phospate cross sections, differing by less than 5%. The result implies that certain properties of the DNA, like the total ionization cross section, are localized properties and an additivity principle may apply. This allows us to obtain properties of a larger molecular system built up from the results of smaller subsystem fragments. The DI of guanine and cytosine has been studied. For guanine, a proton is produced from the channel where the ionized electron originates from a molecular orbital with significant charge density along the N(1)-H bond. The interaction of the proton with cytosine was also studied.

  9. Preparations, structures and properties of heterobimetallic complexes based on tetrahydrofuran-2,3,4,5-tetracarboxylate

    SciTech Connect

    Jia, Tian-Jing; Li, Shu-Mu; Cao, Wei; Li, Li-Cun; Zheng, Xiang-Jun; Yuan, Da-Qiang

    2013-05-01

    Transition heterobimetallic metal-organic frameworks based on tetrahydrofuran-2,3,4,5-tetracarboxylicate (FTA), namely [M(H₂O)₆][Cu₂M(FTA)₂(H₂O)₂]·4H₂O [M=Mn (1), Co (2)], and [CuZn(FTA)(H₂O)₅]·H₂O (3) have been synthesized and characterized. Single-crystal X-ray diffraction indicates that complexes 1 and 2 are isomorphic. In 1 and 2, FTA ligand links the metal ions to a 2-D wave-like negative-charged layer with a topology of (4;6²)₂(4;6³;8²)₂(6). They possess 1-D channels with [M(H₂O)₆]²⁺ and lattice water molecules enclathrated. While in the complex 3, Cu²⁺ and Zn²⁺ ions are bridged by FTA to a 2-D neutral layer structure with a (8)₂(8⁴;12²) topology. Magnetic properties of 1–3 were analyzed in connection with their structures, which show that there exist weak antiferromagnetic interactions between metal ions. - Graphical abstract: Three heterobimetallic MOFs were constructed through the size-selectivity of TFA coordination sites for different transition metal ions based on the concept of “Hard and Soft Acids and Bases”. Highlights: • Complexes 1 and 3 contain 2-D wave-like negative-charged layers. • Complex 2 is a 2-D neutral layer structure with a (8)₂(8⁴;12²) topology. • Complexes 1–3 are the first example of heterobimetallic MOFs based on FTA. • The coordination sites of FTA show size-selectivity to metal ions.

  10. A patient-specific quality assurance study on absolute dose verification using ionization chambers of different volumes in RapidArc treatments

    SciTech Connect

    Syam Kumar, S.A.; Sukumar, Prabakar; Sriram, Padmanaban; Rajasekaran, Dhanabalan; Aketi, Srinu; Vivekanandan, Nagarajan

    2012-01-01

    The recalculation of 1 fraction from a patient treatment plan on a phantom and subsequent measurements have become the norms for measurement-based verification, which combines the quality assurance recommendations that deal with the treatment planning system and the beam delivery system. This type of evaluation has prompted attention to measurement equipment and techniques. Ionization chambers are considered the gold standard because of their precision, availability, and relative ease of use. This study evaluates and compares 5 different ionization chambers: phantom combinations for verification in routine patient-specific quality assurance of RapidArc treatments. Fifteen different RapidArc plans conforming to the clinical standards were selected for the study. Verification plans were then created for each treatment plan with different chamber-phantom combinations scanned by computed tomography. This includes Medtec intensity modulated radiation therapy (IMRT) phantom with micro-ionization chamber (0.007 cm{sup 3}) and pinpoint chamber (0.015 cm{sup 3}), PTW-Octavius phantom with semiflex chamber (0.125 cm{sup 3}) and 2D array (0.125 cm{sup 3}), and indigenously made Circular wax phantom with 0.6 cm{sup 3} chamber. The measured isocenter absolute dose was compared with the treatment planning system (TPS) plan. The micro-ionization chamber shows more deviations when compared with semiflex and 0.6 cm{sup 3} with a maximum variation of -4.76%, -1.49%, and 2.23% for micro-ionization, semiflex, and farmer chambers, respectively. The positive variations indicate that the chamber with larger volume overestimates. Farmer chamber shows higher deviation when compared with 0.125 cm{sup 3}. In general the deviation was found to be <1% with the semiflex and farmer chambers. A maximum variation of 2% was observed for the 0.007 cm{sup 3} ionization chamber, except in a few cases. Pinpoint chamber underestimates the calculated isocenter dose by a maximum of 4.8%. Absolute dose

  11. Studies of 4-CHLORO-2-FLUOROANISOLE by Two-Color Resonant Two-Photon Mass-Analyzed Threshold Ionization Spectroscopy

    NASA Astrophysics Data System (ADS)

    Wu, Pei-Ying; Tzeng, Wen-Bih

    2016-06-01

    We applied the two-color resonant two-photon mass analyzed threshold ionization technique to record the cation spectra of 4-chloro-2-fluoroanisole by ionizing via five intermediate vibronic levels. The excitation and adiabatic ionization energies were determined to be 35 227, and 67 218 wn, respectively. Spectral analysis and theoretical calculation suggest that the geometry of the aromatic ring of the neutral species in the S1 state is non-planar, but that of the cation in the D0 state is planar.

  12. Comparative study of ionization chamber detectors vis-a-vis a CCD detector for dispersive XAS measurement in transmission geometry

    SciTech Connect

    Poswal, A. K.; Agrawal, A.; Bhattachryya, D.; Jha, S. N.; Sahoo, N. K.

    2013-02-05

    We have designed and fabricated parallel plate ionization chamber detectors and voltage vs. current characteristics (V-I curve) of the detectors were recorded with synchrotron radiation to qualify for use in X-ray Absorption Spectroscopy (XAS) measurements. After qualifying the ionization chambers, the detectors were used in the dispersive EXAFS beamline (BL-08) at INDUS-2 SRS in Turbo-XAS geometry. Using the same setup and under the same setting, XAS spectra were also recorded with a CCD detector and the observation on relative performance of the ionization chamber vis-a-vis the CCD detector is presented in this paper.

  13. Numerical study of the wave-vector dependence of the electron interband impact ionization rate in bulk GaAs

    NASA Technical Reports Server (NTRS)

    Wang, Yang; Brennan, Kevin F.

    1994-01-01

    Ensemble Monte Carlo calculations of the electron interband impact ionization rate in bulk GaAs are presented using a wave-vector (k)-dependent formulation of the ionization transition rate. The transition rate is evaluated through the use of numerically generated wavefunctions determined via a k-p calculation within the first two conduction bands at numerous points within a finely spaced three-dimensional grid in k space. The transition rate is determined to be greatest for states within the second conduction band. Is is found that the interband impact ionization transition rate in bulk GaAs is best characterized as having an exceedingly soft threshold energy. As a consequence, the dead space, defined as the distance over which the ionization probability for a given carrier is assumed to be zero, is estimated to be much larger than that estimated using a harder threshold. These results have importance in the design of the multiquantum-well avalanche photodiodes.

  14. Numerical Study of the Wave-Vector Dependence of the Electron Interband Impact Ionization Rate in Bulk GaAs

    NASA Technical Reports Server (NTRS)

    Wang, Yang; Brennan, Kevin F.

    1994-01-01

    Ensemble Monte Carlo calculations of the electron interband impact ionization rate in bulk GaAs are presented using a wave-vector (k)-dependent formulation of the ionization transition rate. The transition rate is evaluated through use of numerically generated wavefunctions determined via a k-p calculation within the first two conduction bonds at numerous points within a finely spaced three-dimensional grid in k space. The transition rate is determined to be greatest for states within the second conduction band. It is found that the interband impact ionization transition rate in bulk GaAs is best characterized as having an exceedingly "soft" threshold energy. As a consequence, the dead space, defined as the distance over which the ionization probability for a given carrier is assumed to be zero, is estimated to be-much larger than that estimated using a "harder" threshold. These results have importance in the design of multiquantum-well avalanche photodiodes.

  15. INFLUENCE OF ELECTRON-IMPACT MULTIPLE IONIZATION ON EQUILIBRIUM AND DYNAMIC CHARGE STATE DISTRIBUTIONS: A CASE STUDY USING IRON

    SciTech Connect

    Hahn, M.; Savin, D. W.

    2015-02-10

    We describe the influence of electron-impact multiple ionization (EIMI) on the ionization balance of collisionally ionized plasmas. Previous ionization balance calculations have largely neglected EIMI. Here, EIMI cross-section data are incorporated into calculations of both equilibrium and non-equilibrium charge-state distributions (CSDs). For equilibrium CSDs, we find that EIMI has only a small effect and can usually be ignored. However, for non-equilibrium plasmas the influence of EIMI can be important. In particular, we find that for plasmas in which the temperature oscillates there are significant differences in the CSD when including versus neglecting EIMI. These results have implications for modeling and spectroscopy of impulsively heated plasmas, such as nanoflare heating of the solar corona.

  16. [Use of time-of-flight mass spectrometry with ionization division fragments of californium-252 for studying the mechanisms of action of drugs on DNA and its components].

    PubMed

    Sukhodub, L F; Grebenik, L I; Chivanov, V D

    1994-01-01

    Using soft-ionization mass spectrometry (252-Cf particle desorption mass spectrometry, PDMS) a minor adduct of anticancer drug prospidine and deoxyguanosine-5-phosphate (pdG) has been found. It has been shown experimentally that PDMS is very useful for study of biological mixtures as well as mechanisms of interactions between drugs and biomolecules.

  17. Effect of tanshinone IIA on the noncovalent interaction between warfarin and human serum albumin studied by electrospray ionization mass spectrometry.

    PubMed

    Liu, Jie; Wang, Xiaoru; Cai, Zongwei; Lee, Frank S C

    2008-10-01

    Enhanced anticoagulation and/or even bleeding are often observed when patients on long-term warfarin (WAR) therapy consumed Danshen, a well-known medicinal herb in traditional Chinese medicine (TCM). This study demonstrates that altered WAR metabolism, arising from its interaction with the active components in Danshen, played a significant role in this curative effect. Mass spectrometric techniques including ESI-ITMS (electrospray ionization ion-trap mass spectrometry) and ESI-TOF (time-of-flight)-MS have been developed for the study of such drug-herb interactions. The experimental approach involved a detailed analysis and comparison of WAR metabolites in vivo from blood or urine of rats that had been orally administrated with WAR, either singly or together with the representative bioactive component of Danshen-lipid soluble TIIA (Tanshinon IIA), and a study of the interaction of human serum albumin (HSA), WAR, and water-soluble sodium tanshinone IIA sulfonate (STS) in vitro. Results demonstrate that TIIA accelerates the metabolic rate of WAR, whereas STS displaces WAR from the WAR-HSA complex, resulting in an increase of free WAR concentration in blood. It is suggested that the elevated level and enhanced metabolism of WAR is responsible for the over-anticoagulation effect observed. PMID:18657993

  18. Determination of solubility products of complex compounds of certain lanthanide and actinide diiodies with 18-crown-6 in tetrahydrofuran

    SciTech Connect

    Mikheev, N.B.; Kamenskaya, A.N.; Kulyukhin, S.A.

    1988-09-01

    The existence of divalent americium in a tetrahydrofuran (THF) solution was proved for the first time. The values of the solubility products (SP) of the complex compounds with the composition of MeI{sub 2}{centered dot}18-crown-6 (Me = Sm, Eu, Yb, Am, Cf, Es, Fm) in the THF solutions were determined by the cocrystallization method. The SP values obtained are within (5.9-7.9){centered dot}10{sup {minus}12} and are close to the SP value for SrI{sub 2}{centered dot}10{sup {minus}12}, which indicates a similarity in the properties of these elements.

  19. High-resolution (e, 2e + ion) study of electron-impact ionization and fragmentation of methane

    SciTech Connect

    Ren, Xueguang Pflüger, Thomas; Weyland, Marvin; Baek, Woon Yong; Rabus, Hans; Ullrich, Joachim; Dorn, Alexander

    2015-05-07

    The ionization and fragmentation of methane induced by low-energy (E{sub 0} = 66 eV) electron-impact is investigated using a reaction microscope. The momentum vectors of all three charged final state particles, two outgoing electrons, and one fragment ion, are detected in coincidence. Compared to the earlier study [Xu et al., J. Chem. Phys. 138, 134307 (2013)], considerable improvements to the instrumental mass and energy resolutions have been achieved. The fragment products CH{sub 4}{sup +}, CH{sub 3}{sup +}, CH{sub 2}{sup +}, CH{sup +}, and C{sup +} are clearly resolved. The binding energy resolution of ΔE = 2.0 eV is a factor of three better than in the earlier measurements. The fragmentation channels are investigated by measuring the ion kinetic energy distributions and the binding energy spectra. While being mostly in consistence with existing photoionization studies the results show differences including missing fragmentation channels and previously unseen channels.

  20. On interfacial properties of tetrahydrofuran: Atomistic and coarse-grained models from molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Garrido, J. M.; Algaba, J.; Míguez, J. M.; Mendiboure, B.; Moreno-Ventas Bravo, A. I.; Piñeiro, M. M.; Blas, F. J.

    2016-04-01

    We have determined the interfacial properties of tetrahydrofuran (THF) from direct simulation of the vapor-liquid interface. The molecules are modeled using six different molecular models, three of them based on the united-atom approach and the other three based on a coarse-grained (CG) approach. In the first case, THF is modeled using the transferable parameters potential functions approach proposed by Chandrasekhar and Jorgensen [J. Chem. Phys. 77, 5073 (1982)] and a new parametrization of the TraPPE force fields for cyclic alkanes and ethers [S. J. Keasler et al., J. Phys. Chem. B 115, 11234 (2012)]. In both cases, dispersive and coulombic intermolecular interactions are explicitly taken into account. In the second case, THF is modeled as a single sphere, a diatomic molecule, and a ring formed from three Mie monomers according to the SAFT-γ Mie top-down approach [V. Papaioannou et al., J. Chem. Phys. 140, 054107 (2014)]. Simulations were performed in the molecular dynamics canonical ensemble and the vapor-liquid surface tension is evaluated from the normal and tangential components of the pressure tensor along the simulation box. In addition to the surface tension, we have also obtained density profiles, coexistence densities, critical temperature, density, and pressure, and interfacial thickness as functions of temperature, paying special attention to the comparison between the estimations obtained from different models and literature experimental data. The simulation results obtained from the three CG models as described by the SAFT-γ Mie approach are able to predict accurately the vapor-liquid phase envelope of THF, in excellent agreement with estimations obtained from TraPPE model and experimental data in the whole range of coexistence. However, Chandrasekhar and Jorgensen model presents significant deviations from experimental results. We also compare the predictions for surface tension as obtained from simulation results for all the models with

  1. Comparison of Rock Physics Properties of Tetrahydrofuran and Cyclopentane Hydrate-Bearing Sediments

    NASA Astrophysics Data System (ADS)

    Schindler, M.; Batzle, M. L.

    2013-12-01

    Laboratory rock physics measurements of gas hydrate-bearing sediments provided calibration for field geophysical data. The manner of how the hydrate is formed in the sediment will thereby affect the physical properties of the hydrated sediment. Methane hydrates in nature form either from the free or dissolved gas phase. MXCT images of tetrahydrofuran (THF) and cyclopentane (CP) hydrate-bearing porous media show that the manner of hydrate formation determines the hydrate distribution within the pore space. CP, which is immiscible in water forms hydrate that tends to be located at the grain contacts, whereas THF hydrate, which is formed out of solution, tends to occur in the pore space away from the grains. Consequently, we use THF and CP as proxy for CH4 in solution and as free gas phase, respectively. In addition, ultrasonic velocity measurements are conducted as a function of confining pressure on both types of hydrate-bearing porous media. Glass beads and unconsolidated quartz sand are used as host sediment. To form the THF hydrate-bearing samples, THF-water solution is mixed and injected into the dry and vacuumed sample. The ratio of THF to water determines the resulting hydrate saturation. CP hydrate-bearing samples are generated by injecting CP into partially water-saturated samples. Here, the initial water saturation determines the resulting hydrate saturation. Samples with hydrate saturations of 0, 40, 60, 80, and 100 percent are tested. In both cases hydrates are formed by slowly cooling the samples into the respective hydrate stability zone, which for both types of samples lies at temperatures above 273 K at atmospheric pressure. The results show an increase in velocity with hydrate saturation in both cases. Velocities of hydrate-bearing glass beads tend to be elevated compared to hydrate-bearing quartz sand. Analysis is still ongoing, but it is expected that the cyclopentane hydrate-bearing samples will exhibit a more significant increase in velocities

  2. On interfacial properties of tetrahydrofuran: Atomistic and coarse-grained models from molecular dynamics simulation.

    PubMed

    Garrido, J M; Algaba, J; Míguez, J M; Mendiboure, B; Moreno-Ventas Bravo, A I; Piñeiro, M M; Blas, F J

    2016-04-14

    We have determined the interfacial properties of tetrahydrofuran (THF) from direct simulation of the vapor-liquid interface. The molecules are modeled using six different molecular models, three of them based on the united-atom approach and the other three based on a coarse-grained (CG) approach. In the first case, THF is modeled using the transferable parameters potential functions approach proposed by Chandrasekhar and Jorgensen [J. Chem. Phys. 77, 5073 (1982)] and a new parametrization of the TraPPE force fields for cyclic alkanes and ethers [S. J. Keasler et al., J. Phys. Chem. B 115, 11234 (2012)]. In both cases, dispersive and coulombic intermolecular interactions are explicitly taken into account. In the second case, THF is modeled as a single sphere, a diatomic molecule, and a ring formed from three Mie monomers according to the SAFT-γ Mie top-down approach [V. Papaioannou et al., J. Chem. Phys. 140, 054107 (2014)]. Simulations were performed in the molecular dynamics canonical ensemble and the vapor-liquid surface tension is evaluated from the normal and tangential components of the pressure tensor along the simulation box. In addition to the surface tension, we have also obtained density profiles, coexistence densities, critical temperature, density, and pressure, and interfacial thickness as functions of temperature, paying special attention to the comparison between the estimations obtained from different models and literature experimental data. The simulation results obtained from the three CG models as described by the SAFT-γ Mie approach are able to predict accurately the vapor-liquid phase envelope of THF, in excellent agreement with estimations obtained from TraPPE model and experimental data in the whole range of coexistence. However, Chandrasekhar and Jorgensen model presents significant deviations from experimental results. We also compare the predictions for surface tension as obtained from simulation results for all the models with

  3. The electronic structure of NaCl adlayers on W(110) studied by ionizing radiation

    NASA Astrophysics Data System (ADS)

    Dieckhoff, S.; Müller, H.; Maus-Friedrichs, W.; Brenten, H.; Kempter, V.

    1992-12-01

    The electronic structure of thin NaCl adlayers deposited on W(110) at room temperature is studied with electron energy loss spectroscopy (EELS), ion impact electron spectroscopy (IIES) with He + and He 2+ ions, metastable impact electron spectroscopy (MIES) with He ∗ atoms, ultraviolet photoelectron spectroscopy (UPS), and AES. It is concluded that NaCl adsorbs molecularly under the studied conditions. The transition from the electronic structure of single adsorbed NaCl molecules to the well-known bulk structure could be studied by following the emergence of bulk properties, such as interband transitions and excitonic excitations, as a function of the NaCl exposure. Our results are consistent with lateral growth of two-dimensional islands during the formation of the first adlayer. The electronic transition processes at the surface induced by electrons as well as He projectiles in different excitation and charge states, in particular the vacancy production in the Cl - 3p valence band, are studied. Their relevance for desorption induced by electronic transitions (DIET) is discussed.

  4. Regio- and stereoselective Pd-catalyzed direct arylation of unactivated sp(3) C(3)-H bonds of tetrahydrofuran and 1,4-benzodioxane systems.

    PubMed

    Parella, Ramarao; Babu, Srinivasarao Arulananda

    2015-02-20

    An auxiliary-enabled Pd-catalyzed highly regio- and stereoselective sp(3) C-H activation and the direct arylation of the C3-position of oxygen heterocycles, such as tetrahydrofuran and 1,4-benzodioxane systems, are reported. An efficient stereoselective construction of cis 2,3-disubstituted tetrahydrofuran derivatives (analogues of norlignans) and cis 2,3-disubstituted 1,4-benzodioxane derivatives (analogues of neolignans) is described. The direct C(sp(3))-H arylation of the C3-position of (R)- or (S)- tetrahydrofuran-2-carboxamides furnished the corresponding (2R,3R) and (2S,3S) C3-arylated THF scaffolds as major compounds with very high regio- and diastereoselectivities. The stereochemistry of the products obtained in this work were unambiguously assigned on the basis of the X-ray structure analyses of representative compounds 3b, 3e, 4p, and 7.

  5. Stability studies of propoxur herbicide in environmental water samples by liquid chromatography-atmospheric pressure chemical ionization ion-trap mass spectrometry.

    PubMed

    Sun, Lei; Lee, Hian Kee

    2003-10-01

    Liquid chromatography-atmospheric pressure ionization ion-trap mass spectrometry has been investigated for the analysis of polar pesticides in water. The degradation behavior of propoxur, selected as a model pesticide belonging to the N-methylcarbamate group, in various aqueous matrices (Milli-Q water, drinking water, rain water, seawater and river water) was investigated. Two interfaces of atmospheric pressure ionization, atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI), were compared during the study. Propoxur and its transformation product (N-methylformamide) were best ionized as positive ions with both APCI and ESI, while another transformation product (2-isopropoxyphenol) yielded stronger signals as negative ions only with APCI. In addition, the effects of various pH, matrix type and irradiation sources (sunlight, darkness, indoor lighting and artificial UV lamp) on the chemical degradation (hydrolysis) were also assessed. From the kinetic studies of degradation, it was found that the half-life of propoxur was reduced from 327 to 161 h in Milli-Q water with variation of irradiation conditions from dark to sunlight exposure. Degradation rates largely increased with increasing pH. The half-life of the target compound dissolved in Milli-Q water under darkness decreased from 407 to 3 h when the pH of Milli-Q water was increased from 5 to 8.5. These suggest that hydrolysis of propoxur is light-intensity and pH-dependent. In order to mimic contaminated natural environmental waters, propoxur was spiked into real water samples at 30 microg/l. The degradation of propoxur in such water samples under various conditions were studied in detail and compared. With the ion trap run in a time-scheduled single ion monitoring mode, typical limits of detection of the instrument were in the range of 1-10 microg/l.

  6. A real-time kinetic study of luciferase inactivation by pulsed ionizing radiation

    SciTech Connect

    Bell, D.H.; Gould, J.M.; Patterson, L.K.

    1982-06-01

    The real-time kinetics of radiation-induced inactivation of the luminescent firefly luciferase-luciferin system were investigated. A single, microsecond pulse from a Van de Graaff accelerator delivered to the system is sufficient to decrease the luminescence by over 60%. This decrease exhibits exponential behavior and has a half-time of 46 +/- 6 msec. In both steady-state and pulsed studies, the dose dependence of the inactivation is independent of the dose rate. Likewise, the decay kinetics are independent of the dose per pulse. These studies suggest that the enzyme is altered in a way that inteferes with the initial steps of catalysis without affecting the subsequent steps which lead to light emission.

  7. Blood biomarkers in metal scrap workers accidentally exposed to ionizing radiation: a case study.

    PubMed

    Gupta, M L; Srivastava, N N; Dutta, S; Shukla, S K; Dutta, A; Verma, S; Devi, M

    2013-12-01

    The detrimental effect of nuclear accidents due to localized or whole body radiation exposure results in severe cellular damage. The current study was carried out to evaluate radiation-mediated variability in blood components of metal scrap workers exposed accidently to cobalt-60 source. Blood samples collected initially from five hospitalized patients, coded P1-P5, were processed for total leukocyte counts (TLC), platelet (PLT) counts, haemoglobin, estimation of DNA double strand breaks by measuring phosphorylated form of H2AX (γ-H2AX) and chromosomal aberrations (dicentrics). Blood cells count (TLC), in all the patients except P2, was found decreased. Dicentrics increased in all the five patients. γ-H2AX was found significantly elevated in patients P2 and P4. After 3 days, 21 subjects working in close vicinity of accident site were evaluated for the above-mentioned markers to confirm their possibility of radiation exposure; however, all the parameters in these subjects were found within normal limits. Blood from patients P1-P5 was collected again after 11 days. Studies revealed exorbitant increase in γ-H2AX in lymphocytes and monocytes of patients P1, P4 and P5. TLC and PLT count in these patients had fallen further. Dicentrics declined with time in all the five patients. Based on the studied blood biomarkers, we conclude that the five subjects showed signs of radiation exposure. Measurement on radiation dose could not be performed in the current study; however, the generated data particularly on dicentrics provide ample evidence of radiation exposure.

  8. Sanitation of chicken eggs by ionizing radiation: HACCP and inactivation studies

    NASA Astrophysics Data System (ADS)

    Verde, S. Cabo; Tenreiro, R.; Botelho, M. L.

    2004-09-01

    The aim of this study is to develop the application of irradiation technology to chicken eggs in order to get a product free of pathogenic microorganisms. Bioburden values of eggs from chickens of different ages ( n=150) were found to not be significantly different ( p<0.05) and an average value of (2.0±0.3). 10 5 cfu/egg was obtained for the shell. Two major microbial groups were characterized in the egg's natural microbiota, no Salmonella or Campylobacter were detected. HACCP studies indicated the feed as a critical point. Dosimetry studies were carried out in a γ facility to find the best geometry and dose rate for irradiation. Whole eggs were artificially contaminated with reference strains of Salmonella typhimurium, Salmonella enteritidis, Campylobacter coli and Campylobacter jejuni and irradiated in the γ facility at sub-lethal doses (0.2-1 kGy) with a dose rate of 1.0 kGy/h. Dvalue varied between 0.31-0.26 kGy and 0.20-0.19 kGy in S. typhimurium and S. enteritidis, and between 0.21-0.18 kGy and 0.07-0.09 in C. coli and C. jejuni, for shell and yolk+white. Using sub-lethal doses up to 5 kGy, the Dvalue of natural microbiota in whole eggs was 1.29 kGy. Results show that low irradiation doses could guarantee egg sanitation.

  9. Molecular Characterization of Organic Aerosol Using Nanospray Desorption/Electrospray Ionization Mass Spectrometry: CalNex 2010 field study

    SciTech Connect

    O'Brien, Rachel E.; Laskin, Alexander; Laskin, Julia; Liu, Shang; Weber, Robin; Russell, Lynn; Goldstein, Allen H.

    2013-04-01

    Aerosol samples from the CalNex 2010 field study were analyzed using high resolution mass spectrometry (HR-MS) coupled to a nanospray-desorption/electrospray ionization (nano-DESI) source. The samples were collected in Bakersfield, CA on June 22-23, 2010. The chemical formulas of over 1300 unique molecular species were detected in the mass range of 50-800 m/z. Our analysis focused on identification of two main groups: compounds containing only carbon, hydrogen, and oxygen (CHO only), and nitrogen-containing organic compounds (NOC). The NOC accounted for 35% (by number) of the compounds observed in the afternoon, and for 59% in the early morning samples. By comparing plausible reactant-product pairs, we propose that over 50% of the NOC in each sample could have been formed through reactions transforming carbonyls into imines. The CHO only compounds were dominant in the afternoon suggesting a photochemical source. The average O:C ratios of all observed compounds were fairly consistent throughout the day, ranging from 0.34 in the early morning to 0.37 at night. We conclude that both photooxidation and ammonia chemistry play important roles in forming the compounds observed in this mixed urban-rural environment.

  10. [Good laboratory practice of equilibrium solubility measurement II. Study of pH-dependent solubility of ionizable compounds].

    PubMed

    Völgyi, Gergely; Baka, Edit; Kovács, Márta; Takácsné, Novák Krisztina

    2011-01-01

    In this paper the pH-equilibrium solubility profiles of ionizable drugs are presented. The aim of the present work was to study the validity of the Henderson-Hasselbalch (HH) relationship in the case of structurally diverse weak bases. In the case of monoprotic bases, namely papaverine, promethazine and propafenone the experimental equilibrium solubility data precisely follow the theoretical HH curve until the limit of salt solubility. The common ion effect on salt solubility was found to be significant at low pHs. Deviation from the HH equation in the case of dibasic quetiapine hydrogen fumarate can be easily interpreted with the formation of different salt compositions. The significance of pH control and the effect of the salt form (e.g., fumarate) was also investigated. It is critical that the pKa value and the intrinsic solubility are accurately determined when the HH relationship is used to predict the pH-dependent aqueous solubility of drugs.

  11. Multiphoton dissociation/ionization of CHCl3 and CFCl3 at 355 nm: an experimental and theoretical study.

    PubMed

    Sharma, P; Vatsa, R K; Maity, D K; Kulshreshtha, S K

    2004-01-01

    Nonresonant laser-induced multiphoton dissociation/ionization studies have been conducted for trichloromethane (CHCl3) and trichlorofluoromethane (CFCl3) at 355 nm, using time-of-flight mass spectrometry (TOFMS). The molecular ion signal was found to be missing for both these compounds, and very similar fragmentation patterns were observed. Ab initio molecular electronic structure calculations were performed to help understand the fragmentation pattern of these molecules in the laser field. The energetics of different dissociation channels in the ground states of [CHCl3]+*, [CHCl2]+, [CFCl3]+* and [CFCl2]+, as well as neutral CHCl3, CHCl2*, CFCl3 and CFCl2* systems, were calculated. On comparing theoretical results with experimentally observed ion signals and their relative abundances in TOFMS, it is inferred that these molecules undergo sequential Cl atom elimination followed by photoionization of the fragments. The absence of [CFCl]+ has been interpreted on the basis of resonant A state-mediated two-photon absorption by CFCl, and the subsequent prompt photodissociation processes occurring for this state. PMID:15386631

  12. Photodegradation of secondary organic aerosol generated from limonene oxidation by ozone studied with chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pan, X.; Underwood, J. S.; Xing, J.-H.; Mang, S. A.; Nizkorodov, S. A.

    2009-06-01

    Photodegradation of secondary organic aerosol (SOA) prepared by ozone-initiated oxidation of D-limonene is studied with an action spectroscopy approach, which relies on detection of volatile photoproducts with chemical ionization mass-spectrometry as a function of the UV irradiation wavelength. Efficient photodegradation is observed for a broad range of ozone (0.1-300 ppm) and D-limonene (0.02-3 ppm) concentrations used in the preparation of SOA. The observed photoproducts are dominated by oxygenated C1-C3 compounds such as methanol, formic acid, acetaldehyde, acetic acid, and acetone. The irradiation wavelength dependence of the combined yield of the photoproducts closely tracks the absorption spectrum of the SOA material suggesting that photodegradation is not limited to the UV wavelengths. Kinetic simulations suggest that RO2+HO2/RO2 reactions represent the dominant route to photochemically active carbonyl and peroxide species in the limonene SOA prepared in these experiments. Similar photodegradation processes are likely to occur in realistic SOA produced by OH- or O3-initiated oxidation of biogenic volatile organic compounds in clean air.

  13. Photodegradation of secondary organic aerosol generated from limonene oxidation by ozone studied with chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Pan, X.; Underwood, J. S.; Xing, J.-H.; Mang, S. A.; Nizkorodov, S. A.

    2009-02-01

    Photodegradation of secondary organic aerosol (SOA) prepared by ozone-initiated oxidation of D-limonene is studied with an action spectroscopy approach, which relies on detection of volatile photoproducts with chemical ionization mass-spectrometry as a function of the UV irradiation wavelength. Efficient photodegradation is observed for a broad range of ozone and D-limonene concentrations (0.1-300 ppm) used in the preparation of SOA. The observed photoproducts are dominated by oxygenated C1-C3 compounds such as methanol, formic acid, acetaldehyde, acetic acid, and acetone. The irradiation wavelength dependence of the combined yield of the photoproducts closely tracks the absorption spectrum of the SOA material suggesting that photodegradation is not limited to the UV wavelengths. Kinetic simulations suggest that RO2+HO2/RO2 reactions represent the dominant route to photochemically active carbonyl and peroxide species in the limonene SOA material. Similar photodegradation processes are likely to occur in realistic SOA produced by OH- or O3-initiated oxidation of biogenic volatile organic compounds in clean air.

  14. Dissociative ionization of biomolecules

    NASA Astrophysics Data System (ADS)

    Huo, Winifred

    2004-09-01

    Dissociative ionization (DI) by electron impact plays a role in many different applications, including low-temperature plasma processing, the study of space and astrophysical plasmas, and the study of biological damages by high-energy radiation. In the present study, our goal is to understand the health hazard to humans from exposure to radiation during an extended space flight. DI by secondary electrons can damage the DNA, either directly by causing a DNA lesion, or indirectly by producing radicals and cations that attack the DNA. The theoretical model employed makes use of the fact that electronic motion is much faster than nuclear motion, allowing DI to be treated as a two-step process. The first step is electron-impact ionization resulting in a dissociative state of the molecular ion with the same geometry as the neutral molecule. In the second step the ion relaxes from the initial geometry and undergoes unimolecular dissociation. Thus the DI cross section is given by the product of the ionization cross section and the dissociation probability. For the ionization process we use the improved binary-encounter dipole (iBED) model. For unimolecular dissociation, we use the multiconfigurational self-consistent field (MCSCF) method to determine the minimum energy pathways to possible product channels. This model has been applied to study the DI of H_2O, NH_3, and CH_4, and the results are in good agreement with experiment. The DI from the low-lying channels of benzene has also been studied and the dissociation products are compared with photoionization measurements. The DI of the DNA bases guanine and cytosine are then discussed. Of the four DNA bases, guanine has the largest ionization cross section and cytosine has the smallest. The guanine radical cation is considered to be one of the precursors to the primary, direct-type lesions formed in DNA when it is irradiated. Comparison of DI products of guanine and cytosine will be made to understand the differences in

  15. Poly(2-methyl-2-oxazoline)-b-poly(tetrahydrofuran)-b-poly(2-methyl-2-oxazoline) amphiphilic triblock copolymers: synthesis, physicochemical characterizations, and hydrosolubilizing properties.

    PubMed

    Rasolonjatovo, Bazoly; Gomez, Jean-Pierre; Même, William; Gonçalves, Cristine; Huin, Cécile; Bennevault-Celton, Véronique; Le Gall, Tony; Montier, Tristan; Lehn, Pierre; Cheradame, Hervé; Midoux, Patrick; Guégan, Philippe

    2015-03-01

    Block copolymers assembled into micelles have gained a lot of attention to improve drug delivery. The recent drawbacks of the poly(ethylene oxide) blocks (PEO) contained in amphiphilic pluronics derivatives made of a central poly(propylene oxide) block surrounded by two PEO blocks were recently revealed, opening the way to the design of new amphiphilic block copolymers able to self-assemble in water and to entrap molecules of interest. Here, a family of p(methyloxazoline)-b-p(tetrahydrofuran)-b-p(methyloxazoline) triblock copolymers (called TBCP) is synthesized using cationic ring opening polymerization. Studies of micelle formation using dynamic light scattering, isothermal titration calorimetry (ITC), NMR diffusion-ordered spectroscopy (DOSY), and fluorescence experiments lead us to draw a relationship between copolymer structure and the physicochemical properties of the block copolymers (critical micellar concentration (CMC), Nagg, core diameter, shell thickness, etc.). The packing parameter of the block copolymers indicates the formation of a core-corona structure. Hydrosolubilizing properties of TBCPs were exemplified with curcumin selected as a highly insoluble drug model. Curcumin, a natural polyphenolic compound, has shown a large spectrum of biological and pharmacological activity, including anti-inflammatory, antimicrobial, antioxidant, and anticarcinogenic activities. An optimized formulation process reveals that the aggregation number is the parameter affecting drug encapsulation. Patch clamp experiments carried out to study the interaction of TBCP with the cell membrane demonstrate their permeation property suitable to promote the cellular internalization of curcumin. PMID:25517924

  16. A Study of Heterogeneous Catalysis by Nanoparticle-Embedded Paper-Spray Ionization Mass Spectrometry.

    PubMed

    Banerjee, Shibdas; Basheer, Chanbasha; Zare, Richard N

    2016-10-01

    We have developed nanoparticle-embedded paper-spray mass spectrometry for studying three types of heterogeneously catalyzed reactions: 1) Palladium-nanoparticle-catalyzed Suzuki cross-coupling reactions, 2) palladium- or silver-nanoparticle-catalyzed 4-nitrophenol reduction, and 3) gold-nanoparticle-catalyzed glucose oxidation. These reactions were almost instantaneous on the nanocatalyst-embedded paper, which subsequently transferred the transient intermediates and products to a mass spectrometer for their detection. This in situ method of capturing transient intermediates and products from heterogeneous catalysis is highly promising for investigating the mechanism of catalysis and rapidly screening catalytic activity under ambient conditions. PMID:27633445

  17. Two decades of studying non-covalent biomolecular assemblies by means of electrospray ionization mass spectrometry

    PubMed Central

    Hilton, Gillian R.; Benesch, Justin L. P.

    2012-01-01

    Mass spectrometry (MS) is a recognized approach for characterizing proteins and the complexes they assemble into. This application of a long-established physico-chemical tool to the frontiers of structural biology has stemmed from experiments performed in the early 1990s. While initial studies focused on the elucidation of stoichiometry by means of simple mass determination, developments in MS technology and methodology now allow researchers to address questions of shape, inter-subunit connectivity and protein dynamics. Here, we chart the remarkable rise of MS and its application to biomolecular complexes over the last two decades. PMID:22319100

  18. R-matrix study of ionization in barium via two-photon interfering routes

    NASA Astrophysics Data System (ADS)

    Aymar, M.; Luc-Koenig, E.; Lecomte, J. M.; Millet, M.; Lyras, A.

    2000-02-01

    A quantitative analysis of part of the experimental data reported by Wang, Chen and Elliott [1,3] who studied in barium coherent control through two-color resonant interfering paths is reported. Dynamics of the two-color photoionization process, described as an adiabatic process in the rotating wave approximation, is governed by the coherent excitation of the 6s6p and 6s7p 1P1 intermediate states. Interference effects are found to play a minor role. The required atomic parameters are obtained from a theoretical approach based on a combination of jj-coupled eigenchannel R-matrix and Multichannel Quantum Defect Theory.

  19. A Study of Heterogeneous Catalysis by Nanoparticle-Embedded Paper-Spray Ionization Mass Spectrometry.

    PubMed

    Banerjee, Shibdas; Basheer, Chanbasha; Zare, Richard N

    2016-10-01

    We have developed nanoparticle-embedded paper-spray mass spectrometry for studying three types of heterogeneously catalyzed reactions: 1) Palladium-nanoparticle-catalyzed Suzuki cross-coupling reactions, 2) palladium- or silver-nanoparticle-catalyzed 4-nitrophenol reduction, and 3) gold-nanoparticle-catalyzed glucose oxidation. These reactions were almost instantaneous on the nanocatalyst-embedded paper, which subsequently transferred the transient intermediates and products to a mass spectrometer for their detection. This in situ method of capturing transient intermediates and products from heterogeneous catalysis is highly promising for investigating the mechanism of catalysis and rapidly screening catalytic activity under ambient conditions.

  20. A discharge flow-photoionization mass spectrometric study of the FO(X 2 Pi i) radical. Photoionization efficiency spectrum and ionization energy

    NASA Technical Reports Server (NTRS)

    Zhang, Zhengyu; Kuo, Szu-Cherng; Klemm, R. Bruce; Monks, Paul S.; Stief, Louis J.

    1994-01-01

    Photoionization efficiency spectra of FO were measured over the wavelength range 80.0-100.0 nm and in the ionization threshold region, 94.0-100.0 nm, using a discharge flow-photoionization mass spectrometer apparatus coupled to a synchrotron radiation source. FO was generated by the reaction of F2P atoms with NO3 and via a F2O2 discharge. A value of 12.78 +/- 0.03 eV was obtained for the adiabatic ionization energy of FO from photoion thresholds which corresponds to FO(+)(X 3 Sigma -) from FO(X 2 Pi i). These results, which are the first to be obtained by direct Photo-ionization mass spectrometry (PIMS) measurements, corroborate those of a photoelectron spectroscopy (PES) study; however, the ionization energy determined here is free from interferences due to other species which complicated the PES measurement. A value of 109.5 +/- 8.0 kJ/mol for Delta f H 0 298(FO) is computed from the present value of IE(FO) and a previous appearance energy measurement, and a value for the proton affinity of FO is calculated to be 511.5 +/- 10.0 kJ/mol.

  1. A study of non-linear ionization processes in planetary atmospheres

    NASA Astrophysics Data System (ADS)

    El-Agamawi, Mohsen Mohamed

    A model was developed for studying the airglow emission from the resonant transition OI (3s' 3D0 yields 2p 3P; lambda 989 A) in the Earth's atmosphere. This model was used to investigate the role of the airglow emission OI lambda 989 A as a secondary source of photoionization of molecular oxygen and nitric oxide, in the ionosphere. The effect of this EUV radiation source on the ion composition at E-region altitudes, during the twilight and at night-time, was studied. The propagation of the OI lambda 989 A resonant photon was treated by using the Monte Carlo simulation technique for the entrapment of resonant radiation in an optically thick thermosphere. Using this simulation model the enhanced source function due to resonant scattering of these photons was calculated along with photoionization production rate of 02(+) and NO(+) ions due to this resonance source. A chemistry model for different ionic processes in the ionosphere was developed. Using this chemistry model the ion distributions in the ionosphere were calculated as a function of the solar zenith angle. The results obtained from this investigation show that the secondary photoionization source OI lambda 989 A airglow has a significant effect in the ion density distribution at E-region altitudes and the lower part of the F-region ionosphere. The largest effect of this secondary photoionization source occurs during the sunrise and sunset hours in the absence of direct solar radiation in the lower part of the ionosphere, and in eclipses.

  2. Using electrospray ionization FTICR mass spectrometry to study competitive binding of inhibitors to carbonic anhydrase

    SciTech Connect

    Cheng, X.; Chen, R.; Bruce, J.E.; Schwartz, B.L.; Anderson, G.A.; Hofstadler, S.A.; Gale, D.C.; Smith, R.D.; Gao, J.; Sigal, G.B.; Mammen, M.; Whitesides, G.M.

    1995-08-30

    We report a method based on mass spectrometry for the characterization of noncovalent complexes of proteins with mixtures of ligands; this method is relevant to the study of drug leads and may be useful in screening libraries for tight-binding compounds. This study describes the competitive binding of inhibitors derived from para-substituted benzenesulfonamides to bovine carbonic anhydrase II (BCAII, EC 4.2.1.1) using this technique. Relative binding constants and structural information for a mixture of inhibitors can be obtained in a single experiment using ESI-FTICR-MS. The work demonstrates that ESI-MS has significant potential for measuring relative binding affinities and characterizing the structures of ligands associated noncovalently to proteins. We have detected noncovalent complexes in the gas phase for ligands having values of K{sub b} as low as 1.7 x 10{sup 6} M{sup -1} in solution. The technique also allowed identification of tightbinding ligands from small libraries. The structures of inhibitors having similar masses can be identified by the high-resolution and multistep dissociation mass spectrometry of which FTICR is uniquely capable. This range of capabilities for ESI-FTICR-MS should be widely useful in medicinal chemistry. 22 refs., 2 figs.

  3. Ionization efficiency studies with charge breeder and conventional electron cyclotron resonance ion source

    SciTech Connect

    Koivisto, H. Tarvainen, O.; Toivanen, V.; Komppula, J.; Kronholm, R.; Lamy, T.; Angot, J.; Delahaye, P.; Maunoury, L.; Patti, G.; Standylo, L.; Steczkiewicz, O.; Choinski, J.

    2014-02-15

    Radioactive Ion Beams play an increasingly important role in several European research facility programs such as SPES, SPIRAL1 Upgrade, and SPIRAL2, but even more for those such as EURISOL. Although remarkable advances of ECRIS charge breeders (CBs) have been achieved, further studies are needed to gain insight on the physics of the charge breeding process. The fundamental plasma processes of charge breeders are studied in the frame of the European collaboration project, EMILIE, for optimizing the charge breeding. Important information on the charge breeding can be obtained by conducting similar experiments using the gas mixing and 2-frequency heating techniques with a conventional JYFL 14 GHz ECRIS and the LPSC-PHOENIX charge breeder. The first experiments were carried out with noble gases and they revealed, for example, that the effects of the gas mixing and 2-frequency heating on the production of high charge states appear to be additive for the conventional ECRIS. The results also indicate that at least in the case of noble gases the differences between the conventional ECRIS and the charge breeder cause only minor impact on the production efficiency of ion beams.

  4. D-region differential-phase measurements and ionization variability studies

    NASA Technical Reports Server (NTRS)

    Weiland, R. M.; Bowhill, S. A.

    1978-01-01

    Measurements of electron densities in the D region are made by the partial-reflection differential-absorption and differential-phase techniques. The differential-phase data are obtained by a hard-wired phase-measuring system. Electron-sensity profiles obtained by the two techniques on six occasions are plotted and compared. Electron-density profiles obtained at the same time on 30 occasions during the years 1975 through 1977 are averaged to form a single profile for each technique. The effect of varying the assumed collision-frequency profile on these averaged profiles is studied. Time series of D-region electron-sensity data obtained by 3.4 minute intervals on six days during the summer of 1977 are examined for wave-like disturbances and tidal oscillations.

  5. Ionizing radiation induces structural and functional damage on the molecules of rat brain homogenate membranes: a Fourier transform infrared (FT-IR) spectroscopic study.

    PubMed

    Demir, Pinar; Akkas, Sara B; Severcan, Mete; Zorlu, Faruk; Severcan, Feride

    2015-01-01

    Humans can be exposed to ionizing radiation, due to various reasons, whose structural effects on biological membranes are not well defined. The current study aims to understand the ionizing radiation-induced structural and functional alterations in biomolecules of brain membranes using Fourier transform infrared (FT-IR) spectroscopy using rat animal models. For this purpose, 1000 cGy of ionizing radiation was specifically directed to the head of Sprague Dawley rats. The rats were decapitated after 24 h. The results revealed that the lipid-to-protein ratio decreased and that irradiation caused lipid peroxidation and increases in the amounts of olefinic =CH, carbonyl, and methylene groups of lipids. In addition, ionizing radiation induced a decrease in membrane fluidity, disordering of membrane lipids, strengthening of the hydrogen bonding of the phosphate groups of lipid head-groups, and weakening in the hydrogen bonding of the interfacial carbonyl groups of lipids. Radiation further caused significant decrements in the α-helix and turns, and significant increments in the β-sheet and random coil contents in the protein structure. Hierarchical cluster analyses, performed in the whole region (3030-1000 cm(-1)), lipid (3030-2800 cm(-1)), and protein (1700-1600 cm(-1)) regions separately, successfully differentiated the control and irradiated groups of rat brain membranes and showed that proteins in the membranes are affected more than lipids from the damages induced with ionizing radiation. As a result, the current study showed that FT-IR spectroscopy can be used successfully as a novel method to monitor radiation-induced alterations on biological membranes.

  6. Sulfapyridine (polymorph III), sulfapyridine dioxane solvate, sulfapyridine tetrahydrofuran solvate and sulfapyridine piperidine solvate, all at 173 K.

    PubMed

    Pratt, Jamal; Hutchinson, Janna; Stevens, Cheryl L Klein

    2011-12-01

    The X-ray crystal structures of solvates of sulfapyridine have been determined to be conformational polymorphs. 4-Amino-N-(1,2-dihydropyridin-2-ylidene)benzenesulfonamide (polymorph III), C(11)H(11)N(3)O(2)S, (1), 4-amino-N-(1,2-dihydropyridin-2-ylidene)benzenesulfonamide 1,3-dioxane monosolvate, C(11)H(11)N(3)O(2)S·C(4)H(8)O(2), (2), and 4-amino-N-(1,2-dihydropyridin-2-ylidene)benzenesulfonamide tetrahydrofuran monosolvate, C(11)H(11)N(3)O(2)S·C(4)H(8)O, (3), crystallized as the imide form, while piperidin-1-ium 4-amino-N-(pyridin-2-yl)benzenesulfonamidate, C(5)H(12)N(+)·C(11)H(10)N(3)O(2)S(-), (4), crystallized as the piperidinium salt. The tetrahydrofuran and dioxane solvent molecules in their respective structures were disordered and were refined using a disorder model. Three-dimensional hydrogen-bonding networks exist in all structures between at least one sulfone O atom and the aniline N atom. PMID:22138921

  7. Effect of ionizing radiation on the primate pancreas: an endocrine and morphologic study

    SciTech Connect

    Du Toit, D.F.; Heydenrych, J.J.; Smit, B.; Zuurmond, T.; Louw, G.; Laker, L.; Els, D.; Weideman, A.; Wolfe-Coote, S.; Du Toit, L.B.

    1987-01-01

    In this study we evaluated the endocrine, biochemical, and haematological derangements as well as pancreatic and histological changes of the bonemarrow in the primate following external fractionated subtotal marrow irradiation without bonemarrow reconstitution. The irradiation was administered in preparation for pancreatic transplantation. Two groups of animals (ten in each group) received 800 rad (8 Gy) and 1000 rad (10 Gy) respectively over 4 to 5 weeks. A maximum of 200 rads (2 Gy) were administered weekly as photons from a 6 MV linear accelerator. During irradiation the animals remained normoglycaemic in the presence of transiently elevated liver enzymes and serum amylase values, which returned to normal on completion of the irradiation. Insulin release was significantly reduced in both groups during irradiation and was associated with minimally decreased K-values in the presence of mild glucose intolerance. Pancreatic light morphologic changes included structural changes of both exocrine and endocrine elements and included necrosis of the islet cells and acinar tissue. Islet histology demonstrated striking cytocavitary network changes of alpha and beta cells, including degranulation, vacuolization, mitochondrial destruction, and an increase in lysosomes. A hypoplastic bonemarrow ranging from moderate to severe was observed in all irradiated recipients. Near total fractionated body irradiation in the primate is therefore associated with elevated liver enzymes, pancytopenia, transient hyperamylasaemia, hypoinsulinaemia, a varying degree of pancreatitis, and bonemarrow hypoplasia.

  8. Study of solid/gas phase photocatalytic reactions by electron ionization mass spectrometry.

    PubMed

    Nuño, Manuel; Ball, Richard J; Bowen, Chris R

    2014-08-01

    This paper describes a novel methodology for the real-time study of solid-gas phase photocatalytic reactions in situ. A novel reaction chamber has been designed and developed to facilitate the investigation of photoactive materials under different gas compositions. UV irradiation in the wavelength of ranges 376-387 and 381-392 nm was provided using specially designed high efficiency light emitting diode arrays. The experiments used air containing 190 ppm NO2 in a moist environment with a relative humidity of 0.1%. Photocatalytic samples consisting of pressed pellets of rutile and anatase crystalline forms of TiO2 were monitored over a period of 150 min. An ultra-high vacuum right angled bleed valve allowed a controlled flow of gas from the main reaction chamber at atmospheric pressure to a residual gas analyser operating at a vacuum of 10(-5)  mbar. The apparatus and methodology have been demonstrated to provide high sensitivity (ppb). The rate of degradation of NO2 attributed to reaction at the TiO2 surface was sensitive to both crystal structures (anatase or rutile) and wavelength of irradiation.

  9. Diffuse gas in the interstellar medium: Studies involving coupled ionization, radiation and dynamics

    SciTech Connect

    Slavin, J.D.

    1990-01-01

    A study is presented of the consequences of a conductive boundary on the Local Cloud, the warm low density region immediately surrounding the Sun. The evaporation of the cloud is modeled assuming steady flow. The soft x ray and EUV emission from the interface are calculated and compared with observations. It is found that the emission in the softest x ray band, the Be band, is harder than that of an equilibrium, normal abundance, 10(exp 6)K plasma. The results are also presented of a 1-D (spherical symmetry) numerical simulation of the evolution of a supernova remnant in a homogeneous medium with a 5 micro-G magnetic field and density of 0.2/cu cm. The remnant evolution was followed from the early Sedov-Taylor phase through the final collapse of the hot bubble after 5.5 x 10(exp 6) years. It was found that the evolution of the remnant, once it has become radiative, differs substantially from the equivalent field-free case, having a smaller interior hot bubble and thicker cold shell. Examples of calculated EUV and FUV emission spectra from the hot bubble are presented and their observability discussed.

  10. Pressure-dependent competition among reaction pathways from first- and second-O2 additions in the low-temperature oxidation of tetrahydrofuran

    DOE PAGESBeta

    Antonov, Ivan O.; Zador, Judit; Rotavera, Brandon; Papajak, Ewa; Osborn, David L.; Taatjes, Craig A.; Sheps, Leonid

    2016-07-21

    Here, we report a combined experimental and quantum chemistry study of the initial reactions in low-temperature oxidation of tetrahydrofuran (THF). Using synchrotron-based time-resolved VUV photoionization mass spectrometry, we probe numerous transient intermediates and products at P = 10–2000 Torr and T = 400–700 K. A key reaction sequence, revealed by our experiments, is the conversion of THF-yl peroxy to hydroperoxy-THF-yl radicals (QOOH), followed by a second O2 addition and subsequent decomposition to dihydrofuranyl hydroperoxide + HO2 or to γ-butyrolactone hydroperoxide + OH. The competition between these two pathways affects the degree of radical chain-branching and is likely of central importancemore » in modeling the autoignition of THF. We interpret our data with the aid of quantum chemical calculations of the THF-yl + O2 and QOOH + O2 potential energy surfaces. On the basis of our results, we propose a simplified THF oxidation mechanism below 700 K, which involves the competition among unimolecular decomposition and oxidation pathways of QOOH.« less

  11. Continuous hydrogenation of ethyl levulinate to γ-valerolactone and 2-methyl tetrahydrofuran over alumina doped Cu/SiO2 catalyst: the potential of commercialization

    NASA Astrophysics Data System (ADS)

    Zheng, Junlin; Zhu, Junhua; Xu, Xuan; Wang, Wanmin; Li, Jiwen; Zhao, Yan; Tang, Kangjian; Song, Qi; Qi, Xiaolan; Kong, Dejin; Tang, Yi

    2016-07-01

    Hydrogenation of levulinic acid (LA) and its esters to produce γ-valerolactone (GVL) and 2-methyl tetrahydrofuran (2-MTHF) is a key step for the utilization of cellulose derived LA. Aiming to develop a commercially feasible base metal catalyst for the production of GVL from LA, with satisfactory activity, selectivity, and stability, Al2O3 doped Cu/SiO2 and Cu/SiO2 catalysts were fabricated by co-precipitation routes in parallel. The diverse physio-chemical properties of these two catalysts were characterized by XRD, TEM, dissociative N2O chemisorptions, and Py-IR methods. The catalytic properties of these two catalysts were systematically assessed in the continuous hydrogenation of ethyl levulinate (EL) in a fixed-bed reactor. The effect of acidic property of the SiO2 substrate on the catalytic properties was investigated. To justify the potential of its commercialization, significant attention was paid on the initial activity, proper operation window, by-products control, selectivity, and stability of the catalyst. The effect of reaction conditions, such as temperature and pressure, on the performance of the catalyst was also thoroughly studied. The development of alumina doped Cu/SiO2 catalyst strengthened the value-chain from cellulose to industrially important chemicals via LA and GVL.

  12. Continuous hydrogenation of ethyl levulinate to γ-valerolactone and 2-methyl tetrahydrofuran over alumina doped Cu/SiO2 catalyst: the potential of commercialization

    PubMed Central

    Zheng, Junlin; Zhu, Junhua; Xu, Xuan; Wang, Wanmin; Li, Jiwen; Zhao, Yan; Tang, Kangjian; Song, Qi; Qi, Xiaolan; Kong, Dejin; Tang, Yi

    2016-01-01

    Hydrogenation of levulinic acid (LA) and its esters to produce γ-valerolactone (GVL) and 2-methyl tetrahydrofuran (2-MTHF) is a key step for the utilization of cellulose derived LA. Aiming to develop a commercially feasible base metal catalyst for the production of GVL from LA, with satisfactory activity, selectivity, and stability, Al2O3 doped Cu/SiO2 and Cu/SiO2 catalysts were fabricated by co-precipitation routes in parallel. The diverse physio-chemical properties of these two catalysts were characterized by XRD, TEM, dissociative N2O chemisorptions, and Py-IR methods. The catalytic properties of these two catalysts were systematically assessed in the continuous hydrogenation of ethyl levulinate (EL) in a fixed-bed reactor. The effect of acidic property of the SiO2 substrate on the catalytic properties was investigated. To justify the potential of its commercialization, significant attention was paid on the initial activity, proper operation window, by-products control, selectivity, and stability of the catalyst. The effect of reaction conditions, such as temperature and pressure, on the performance of the catalyst was also thoroughly studied. The development of alumina doped Cu/SiO2 catalyst strengthened the value-chain from cellulose to industrially important chemicals via LA and GVL. PMID:27377401

  13. Pressure-Dependent Competition among Reaction Pathways from First- and Second-O2 Additions in the Low-Temperature Oxidation of Tetrahydrofuran.

    PubMed

    Antonov, Ivan O; Zádor, Judit; Rotavera, Brandon; Papajak, Ewa; Osborn, David L; Taatjes, Craig A; Sheps, Leonid

    2016-08-25

    We report a combined experimental and quantum chemistry study of the initial reactions in low-temperature oxidation of tetrahydrofuran (THF). Using synchrotron-based time-resolved VUV photoionization mass spectrometry, we probe numerous transient intermediates and products at P = 10-2000 Torr and T = 400-700 K. A key reaction sequence, revealed by our experiments, is the conversion of THF-yl peroxy to hydroperoxy-THF-yl radicals (QOOH), followed by a second O2 addition and subsequent decomposition to dihydrofuranyl hydroperoxide + HO2 or to γ-butyrolactone hydroperoxide + OH. The competition between these two pathways affects the degree of radical chain-branching and is likely of central importance in modeling the autoignition of THF. We interpret our data with the aid of quantum chemical calculations of the THF-yl + O2 and QOOH + O2 potential energy surfaces. On the basis of our results, we propose a simplified THF oxidation mechanism below 700 K, which involves the competition among unimolecular decomposition and oxidation pathways of QOOH. PMID:27441526

  14. Dynamics of tetrahydrofuran as minority component in a mixture with poly(2-(dimethylamino)ethyl methacrylate): A neutron scattering and dielectric spectroscopy investigation

    NASA Astrophysics Data System (ADS)

    Goracci, G.; Arbe, A.; Alegría, A.; Lohstroh, W.; Su, Y.; Colmenero, J.

    2015-09-01

    We have investigated a mixture of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and tetrahydrofuran (THF) (70 wt. % PDMAEMA/30 wt. % THF) by combining dielectric spectroscopy and quasielastic neutron scattering (QENS) on a labelled sample, focusing on the dynamics of the THF molecules. Two independent processes have been identified. The "fast" one has been qualified as due to an internal motion of the THF ring leading to hydrogen displacements of about 3 Å with rather broadly distributed activation energies. The "slow" process is characterized by an Arrhenius-like temperature dependence of the characteristic time which persists over more than 9 orders of magnitude in time. The QENS results evidence the confined nature of this process, determining a size of about 8 Å for the volume within which THF hydrogens' motions are restricted. In a complementary way, we have also investigated the structural features of the sample. This study suggests that THF molecules are well dispersed among side-groups nano-domains in the polymer matrix, ruling out a significant presence of clusters of solvent. Such a good dispersion, together with a rich mobility of the local environment, would prevent cooperativity effects to develop for the structural relaxation of solvent molecules, frustrating thereby the emergence of Vogel-Fulcher-like behavior, at least in the whole temperature interval investigated.

  15. Dynamics of tetrahydrofuran as minority component in a mixture with poly(2-(dimethylamino)ethyl methacrylate): A neutron scattering and dielectric spectroscopy investigation.

    PubMed

    Goracci, G; Arbe, A; Alegría, A; Lohstroh, W; Su, Y; Colmenero, J

    2015-09-01

    We have investigated a mixture of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and tetrahydrofuran (THF) (70 wt. % PDMAEMA/30 wt. % THF) by combining dielectric spectroscopy and quasielastic neutron scattering (QENS) on a labelled sample, focusing on the dynamics of the THF molecules. Two independent processes have been identified. The "fast" one has been qualified as due to an internal motion of the THF ring leading to hydrogen displacements of about 3 Å with rather broadly distributed activation energies. The "slow" process is characterized by an Arrhenius-like temperature dependence of the characteristic time which persists over more than 9 orders of magnitude in time. The QENS results evidence the confined nature of this process, determining a size of about 8 Å for the volume within which THF hydrogens' motions are restricted. In a complementary way, we have also investigated the structural features of the sample. This study suggests that THF molecules are well dispersed among side-groups nano-domains in the polymer matrix, ruling out a significant presence of clusters of solvent. Such a good dispersion, together with a rich mobility of the local environment, would prevent cooperativity effects to develop for the structural relaxation of solvent molecules, frustrating thereby the emergence of Vogel-Fulcher-like behavior, at least in the whole temperature interval investigated. PMID:26342375

  16. Reactivity of niobium and tantalum pentahalides with cyclic ethers and the isolation and characterization of intermediates in the polymerization of tetrahydrofuran.

    PubMed

    Marchetti, Fabio; Pampaloni, Guido; Zacchini, Stefano

    2008-01-01

    The complexes MX5(THF) (M = Nb, X = Cl, 2a; M = Ta, X = F, 2c, X = Cl, 2d) and [MX4(THF){O(CH2)4O(CH2)3CH2)}][MX6] (M = Nb, X = Cl, 3a; M = Ta, X = Cl, 3d, X = Br, 3e, X = I, 3f) result from reactions of MX5 with 0.5 and 1.5 equiv of THF, respectively. Compounds 3 contain the unprecedented 4-(tetrahydrofuran-1-ium)-butan-1-oxo ligand and are likely to play a role in the course of THF polymerization catalyzed by MX5. The addition of L (L = 2,5-dimethyltetrahydrofuran, tetrahydropyran, 1,4-dioxane) to MX5 results in the formation of the hexacoordinated complexes MX5(L). The molecular structures of 2d, 3d, and NbCl5(dioxane), 6a, have been ascertained by X-ray diffraction studies. PMID:18052371

  17. Dynamics of tetrahydrofuran as minority component in a mixture with poly(2-(dimethylamino)ethyl methacrylate): A neutron scattering and dielectric spectroscopy investigation

    SciTech Connect

    Goracci, G. Arbe, A.; Lohstroh, W.; Su, Y.; Colmenero, J.

    2015-09-07

    We have investigated a mixture of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and tetrahydrofuran (THF) (70 wt. % PDMAEMA/30 wt. % THF) by combining dielectric spectroscopy and quasielastic neutron scattering (QENS) on a labelled sample, focusing on the dynamics of the THF molecules. Two independent processes have been identified. The “fast” one has been qualified as due to an internal motion of the THF ring leading to hydrogen displacements of about 3 Å with rather broadly distributed activation energies. The “slow” process is characterized by an Arrhenius-like temperature dependence of the characteristic time which persists over more than 9 orders of magnitude in time. The QENS results evidence the confined nature of this process, determining a size of about 8 Å for the volume within which THF hydrogens’ motions are restricted. In a complementary way, we have also investigated the structural features of the sample. This study suggests that THF molecules are well dispersed among side-groups nano-domains in the polymer matrix, ruling out a significant presence of clusters of solvent. Such a good dispersion, together with a rich mobility of the local environment, would prevent cooperativity effects to develop for the structural relaxation of solvent molecules, frustrating thereby the emergence of Vogel-Fulcher-like behavior, at least in the whole temperature interval investigated.

  18. Studying the reducing potencies of antioxidants with the electrochemistry inherently present in electrospray ionization-mass spectrometry.

    PubMed

    Plattner, Sabine; Erb, Robert; Chervet, Jean-Pierre; Oberacher, Herbert

    2014-01-01

    In this proof-of-principle study, the applicability of electrospray ionization-mass spectrometry (ESI-MS) to characterize the reducing potencies of natural antioxidants is demonstrated. The ESI source represents a controlled-current electrochemical cell. The interfacial potential at the emitter electrode will be at or near the electrochemical potential of those reactions that sufficiently supply all the required current for the ESI circuit. Indicator molecules prone to oxidation in ESI such as amodiaquine were used to visualize the impact of reducing compounds on the interfacial potential. The extent of inhibition of the oxidation of the indicator molecule was found to be dependent on the kind and amount of antioxidant added. Concentration-inhibition curves were constructed and used to compare reducing potencies and to rank antioxidants. This ranking was found to be dependent on the electrode material-indicator molecule combination applied. For fast and automated characterization of the reducing potencies of electrochemically active molecules, a flow-injection system was combined with ESI-MS. Liquid chromatography was used to process complex biological samples, such as red and white wine. Due to their high content of different polyphenols, red wine fractions were found to exhibit higher reducing potencies than the corresponding white wine fractions. Furthermore, for 14 important natural antioxidants, the results obtained with the controlled-current EC-ESI-MS assay were compared to those obtained with chemical antioxidant assays. Irrespectively of the kind of assay used to test the reducing potency, gallic acid, quercetin, and epicatechin were found to be potent reductants. Other antioxidants performed well in one particular assay only. This observation suggests that different kinds of redox and antioxidant chemistry were assessed with each of the assays applied. Therefore, several assays should be used to comprehensively study antioxidants and their reducing

  19. Monte Carlo study of the depth-dependent fluence perturbation in parallel-plate ionization chambers in electron beams

    SciTech Connect

    Zink, K.; Czarnecki, D.; Voigts-Rhetz, P. von; Looe, H. K.; Harder, D.

    2014-11-01

    Purpose: The electron fluence inside a parallel-plate ionization chamber positioned in a water phantom and exposed to a clinical electron beam deviates from the unperturbed fluence in water in absence of the chamber. One reason for the fluence perturbation is the well-known “inscattering effect,” whose physical cause is the lack of electron scattering in the gas-filled cavity. Correction factors determined to correct for this effect have long been recommended. However, more recent Monte Carlo calculations have led to some doubt about the range of validity of these corrections. Therefore, the aim of the present study is to reanalyze the development of the fluence perturbation with depth and to review the function of the guard rings. Methods: Spatially resolved Monte Carlo simulations of the dose profiles within gas-filled cavities with various radii in clinical electron beams have been performed in order to determine the radial variation of the fluence perturbation in a coin-shaped cavity, to study the influences of the radius of the collecting electrode and of the width of the guard ring upon the indicated value of the ionization chamber formed by the cavity, and to investigate the development of the perturbation as a function of the depth in an electron-irradiated phantom. The simulations were performed for a primary electron energy of 6 MeV. Results: The Monte Carlo simulations clearly demonstrated a surprisingly large in- and outward electron transport across the lateral cavity boundary. This results in a strong influence of the depth-dependent development of the electron field in the surrounding medium upon the chamber reading. In the buildup region of the depth-dose curve, the in–out balance of the electron fluence is positive and shows the well-known dose oscillation near the cavity/water boundary. At the depth of the dose maximum the in–out balance is equilibrated, and in the falling part of the depth-dose curve it is negative, as shown here the

  20. Ionization levels of As vacancies in as-grown GaAs studied by positron-lifetime spectroscopy

    SciTech Connect

    Saarinen, K.; Hautojaervi, P.; Lanki, P. ); Corbel, C. )

    1991-11-15

    The properties of the native monovacancy defects are systematically investigated by positron-lifetime measurements in {ital n}-type GaAs with carrier concentrations of {ital n}=10{sup 15--}10{sup 18} cm{sup {minus}3}. The native defects present two ionization levels at {ital E}{sub {ital C}}{minus}30 meV and {ital E}{sub {ital C}}{minus}140 meV. The first corresponds to a charge transition 1{minus}{r arrow}0 and the second to 0{r arrow}1+. The transitions are attributed to ionizations of As vacancy, which may be isolated or part of a complex. In a simple identification of the defect with {ital V}{sub As}, the ionization level at {ital E}{sub {ital C}}{minus}30 meV is attributed to the transition {ital V}{sub As}{sup {minus}}{r arrow}{ital V}{sub As}{sup 0} and the ionization level at {ital E}{sub {ital C}}{minus}140 meV to the transition {ital V}{sub As}{sup 0}{r arrow}{ital V}{sub As}{sup +}. The results show further that the configuration of {ital V}{sub As}{sup {minus}} is strongly relaxed inwards compared to the structure of {ital V}{sub As}{sup 0}.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  2. Studies of Total Electron Content variations at low-latitude stations within the Equatorial Ionization Anomaly zone

    NASA Astrophysics Data System (ADS)

    Lilian, Olatunbosun

    2016-07-01

    The total electron content (TEC) is an important parameter to monitor for possible space weather impacts. The radio waves that pass through the earth's ionosphere travel more slowly than their free space velocity due to group path delay of the ionosphere. This group path delay is directly proportional to the TEC of the ionosphere. Using dual frequency GPS receiver at low latitude stations of Ile-Ife (7.52oN, 4.28oE), Addis Ababa (9.04oN, 38.77oE) and Bangalore (13.03oE, 77.57oE), all located within 0 - 15oN of the equatorial anomaly region, the measurement of ionospheric TEC for 2012 has been carried out. The data from the three stations were used to study the diurnal, monthly and seasonal variations of TEC. The diurnal variations maximize between 10:00 - 16:00UT, 08:00 - 14:00UT and 06:00 - 12:00UT for Ile-Ife, Addis Ababa and Bangalore stations respectively. The diurnal variations showed wave-like pertubation during disturbed and quiet periods at Bangalore and Addis Ababa stations. The monthly average TEC variations showed that the month of March recorded the highest TEC value of ~59TECu at about 16:00UT in Ile-Ife station, while TEC at Addis Ababa and Bangalore maximize in October with ~72TECu and 65TECu at about 11:00UT and 09:00UT respectively. Seasonal variations showed that TEC maximizes during the equinoctial months and least in summer, over the three stations. Keywords: Total Electron Content, Equatorial Ionization Anomaly, Global Positioning System co-author:E.A. Ariyibi(Department of Physics and Engineering Physics, Obafemi Awolowo University, Ile-Ife, Nigeria)

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

    PubMed

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

    2016-01-01

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

  4. Ionization potentials of seaborgium

    SciTech Connect

    Johnson, E.; Pershina, V.; Fricke, B.

    1999-10-21

    Multiconfiguration relativistic Dirac-Fock values were calculated for the first six ionization potentials of seaborgium and of the other group 6 elements. No experimental ionization potentials are available for seaborgium. Accurate experimental values are not available for all of the other ionization potentials. Ionic radii for the 4+ through 6+ ions of seaborgium are also presented. The ionization potentials and ionic radii obtained will be used to predict some physiochemical properties of seaborgium and its compounds.

  5. An experimental study of recombination and polarity effect in a set of customized plane parallel ionization chambers.

    PubMed

    Kron, T; McNiven, A; Witruk, B; Kenny, M; Battista, J

    2006-12-01

    Plane parallel ionization chambers are an important tool for dosimetry and absolute calibration of electron beams used for radiotherapy. Most dosimetric protocols require corrections for recombination and polarity effects, which are to be determined experimentally as they depend on chamber design and radiation quality. Both effects were investigated in electron beams from a linear accelerator (Varian 21CD) for a set of four tissue equivalent plane parallel ionization chambers customized for the present research by Standard Imaging (Madison WI). All four chambers share the same design and air cavity dimensions, differing only in the diameter of their collecting electrode and the corresponding width of the guard ring. The diameters of the collecting electrodes were 2 mm, 4 mm, 10 mm and 20 mm. Measurements were taken using electron beams of nominal energy 6 to 20 MeV in a 10 cm x 10 cm field size with a SSD of 100 cm at various depths in a Solid Water slab phantom. No significant variation of recombination effect was found with radiation quality, depth of measurement or chamber design. However, the polarity effect exceeded 5% for the chambers with small collecting electrode for an effective electron energy below 4 MeV at the point of measurement. The magnitude of the effect increased with decreasing electron energy in the phantom. The polarity correction factor calculated following AAPM protocol TG51 ranged from approximately 1.00 for the 20.0 mm chamber to less than 0.95 for the 2 mm chamber at 4.1 cm depth in a electron beam of nominally 12 MeV. By inverting the chamber it could be shown that the polarity effect did not depend on the polarity of the electrode first traversed by the electron beam. Similarly, the introduction of an air gap between the overlying phantom layer and the chambers demonstrated that the angular distribution of the electrons at the point of measurement had a lesser effect on the polarity correction than the electron energy itself. The

  6. Ionization Energies of Lanthanides

    ERIC Educational Resources Information Center

    Lang, Peter F.; Smith, Barry C.

    2010-01-01

    This article describes how data are used to analyze the pattern of ionization energies of the lanthanide elements. Different observed pathways of ionization between different ground states are discussed, and the effects of pairing, exchange, and orbital interactions on ionization energies of the lanthanides are evaluated. When all the above…

  7. Tetrahydrofuran-water extraction, in-line clean-up and selective liquid chromatography/tandem mass spectrometry for the quantitation of perfluorinated compounds in food at the low picogram per gram level.

    PubMed

    Ballesteros-Gómez, Ana; Rubio, Soledad; van Leeuwen, Stefan

    2010-09-17

    A new solvent extraction system was developed for extraction of PFCs from food. The extraction is carried out with 75:25 (v/v) tetrahydrofuran:water, a solvent mixture that provides an appropriate balance of hydrogen bonding, dispersion and dipole-dipole interactions to efficiently extract PFCs with chains containing 4-14 carbon atoms from foods. This mixture provided recoveries above 85% from foods including vegetables, fruits, fish, meat and bread; and above 75% from cheese. Clean-up with a weak anion exchange resin and Envi-carb SPE, which were coupled in line for simplicity, was found to minimize matrix effects (viz. enhancement or suppression of electrospray ionization). The target analytes (PFCs) were resolved on a perfluorooctyl phase column that proved effective in separating mass interferences for perfluorooctane sulfonate (PFOS) in fish and meat samples. The mass spectrometer was operated in the negative electrospray ionization mode and used to record two transitions per analyte and one per mass-labeled method internal standard. The target PFCs were quantified from solvent based calibration curves. The limits of detection (LODs) were as low as 1-5 pg analyte g(-1) food; by exception, those for C(4) and C(5) PFCs were somewhat higher (25-30 pg g(-1)) owing to their less favourable mass response. To the best of our knowledge these are among the best LODs for PFCs in foods reported to date. The analysis of a variety of foods revealed contamination with PFCs at levels from 4.5 to 75 pg g(-1) in 25% of samples (fish and packaged spinach). C(10)-C(14) PFCs were found in fish, which testifies to the need to control long-chain PFCs in this type of food. The proposed method is a useful tool for the development of a large-scale database for the presence of PFCs in foods. PMID:20709322

  8. Fluid hydrogen at high density - Pressure ionization

    NASA Technical Reports Server (NTRS)

    Saumon, Didier; Chabrier, Gilles

    1992-01-01

    The Helmholtz-free-energy model for nonideal mixtures of hydrogen atoms and molecules by Saumon and Chabrier (1991) is extended to describe dissociation and ionization in similar mixtures in chemical equilibrium. A free-energy model is given that describes partial ionization in the pressure and temperature ionization region. The plasma-phase transition predicted by the model is described for hydrogen mixtures including such components as H2, H, H(+), and e(-). The plasma-phase transition has a critical point at Tc = 15,300 K and Pc = 0.614 Mbar, and thermodynamic instability is noted in the pressure-ionization regime. The pressure dissociation and ionization of fluid hydrogen are described well with the model yielding information on the nature of the plasma-phase transition. The model is shown to be valuable for studying dissociation and ionization in astrophysical objects and in high-pressure studies where pressure and temperature effects are significant.

  9. Ionization probes of molecular structure and chemistry

    SciTech Connect

    Johnson, P.M.

    1993-12-01

    Various photoionization processes provide very sensitive probes for the detection and understanding of the spectra of molecules relevant to combustion processes. The detection of ionization can be selective by using resonant multiphoton ionization or by exploiting the fact that different molecules have different sets of ionization potentials. Therefore, the structure and dynamics of individual molecules can be studied even in a mixed sample. The authors are continuing to develop methods for the selective spectroscopic detection of molecules by ionization, and to use these methods for the study of some molecules of combustion interest.

  10. Collision-energy-resolved Penning ionization electron spectroscopy of p-benzoquinone: Study of electronic structure and anisotropic interaction with He*(2 3S) metastable atoms

    NASA Astrophysics Data System (ADS)

    Kishimoto, Naoki; Okamura, Kohji; Ohno, Koichi

    2004-06-01

    Collision energy dependence of partial ionization cross sections (CEDPICS) of p-benzoquinone with He*(2 3S) metastable atoms indicates that interaction potentials between p-benzoquinone and He*(2 3S) are highly anisotropic in the studied collision energy range (100-250 meV). Attractive interactions were found around the C=O groups for in-plane and out-of-plane directions, while repulsive interactions were found around CH bonds and the benzenoid ring. Assignment of the first four ionic states of p-benzoquinone and an analogous methyl-substituted compound was examined with CEDPICS and anisotropic distributions of the corresponding two nonbonding oxygen orbitals (nO+,nO-) and two πCC orbitals (πCC+,πCC-). An extra band that shows negative CEDPICS was observed at ca. 7.2 eV in Penning ionization electron spectrum.

  11. Water dissociation in a radio-frequency electromagnetic field with ex situ electrodes—decomposition of perfluorooctanoic acid and tetrahydrofuran

    NASA Astrophysics Data System (ADS)

    Schneider, Jens; Holzer, Frank; Kraus, Markus; Kopinke, Frank-Dieter; Roland, Ulf

    2016-10-01

    The application of radio waves with a frequency of 13.56 MHz on electrolyte solutions in a capillary reactor led to the formation of reactive hydrogen and oxygen species and finally to molecular oxygen and hydrogen. This process of water splitting can be principally used for the elimination of hazardous chemicals in water. Two compounds, namely perfluorooctanoic acid (PFOA) and tetrahydrofuran, were converted using this process. Their main decomposition products were highly volatile and therefore transferred to a gas phase, where they could be identified by GC-MS analyses. It is remarkable that the chemical reactions could benefit from both the oxidizing and reducing species formed in the plasma process, which takes place in gas bubbles saturated with water vapor. The breaking of C-C and C-F bonds was proven in the case of PFOA, probably initiated by electron impacts and radical reactions.

  12. Kinetic-energy release distributions of fragment anions from collisions of potassium atoms with D-Ribose and tetrahydrofuran*

    NASA Astrophysics Data System (ADS)

    Rebelo, André; Cunha, Tiago; Mendes, Mónica; da Silva, Filipe Ferreira; García, Gustavo; Limão-Vieira, Paulo

    2016-06-01

    Kinetic-energy release distributions have been obtained from the width and shapes of the time-of-flight (TOF) negative ion mass peaks formed in collisions of fast potassium atoms with D-Ribose (DR) and tetrahydrofuran (THF) molecules. Recent dissociative ion-pair formation experiments yielding anion formation have shown that the dominant fragment from D-Ribose is OH- [D. Almeida, F. Ferreira da Silva, G. García, P. Limão-Vieira, J. Chem. Phys. 139, 114304 (2013)] whereas in the case of THF is O- [D. Almeida, F. Ferreira da Silva, S. Eden, G. García, P. Limão-Vieira, J. Phys. Chem. A 118, 690 (2014)]. The results for DR and THF show an energy distribution profile reminiscent of statistical degradation via vibrational excitation and partly due to direct transformation of the excess energy in translational energy.

  13. [Saccharomyces cerevisiae as a model organism for studying the carcinogenicity of non-ionizing electromagnetic fields and radiation].

    PubMed

    Voĭchuk, S I

    2014-01-01

    Medical and biological aspects of the effects of non-ionizing electromagnetic (EM) fields and radiation on human health are the important issues that have arisen as a result of anthropogenic impact on the biosphere. Safe use of man-made sources of non-ionizing electromagnetic fields and radiation in a broad range of frequencies--static, radio-frequency and microwave--is a subject of discussions and speculations. The main problem is the lack of understanding of the mechanism(s) of reception of EMFs by living organisms. In this review we have analyzed the existing literature data regarding the effects of the electromagnetic radiation on the model eukaryotic organism--yeast Saccharomyces cerevisiae. An attempt was made to estimate the probability of induction of carcinogenesis in humans under the influence of magnetic fields and electromagnetic radiation of extremely low frequency, radio frequency and microwave ranges. PMID:24800516

  14. [Saccharomyces cerevisiae as a model organism for studying the carcinogenicity of non-ionizing electromagnetic fields and radiation].

    PubMed

    Voĭchuk, S I

    2014-01-01

    Medical and biological aspects of the effects of non-ionizing electromagnetic (EM) fields and radiation on human health are the important issues that have arisen as a result of anthropogenic impact on the biosphere. Safe use of man-made sources of non-ionizing electromagnetic fields and radiation in a broad range of frequencies--static, radio-frequency and microwave--is a subject of discussions and speculations. The main problem is the lack of understanding of the mechanism(s) of reception of EMFs by living organisms. In this review we have analyzed the existing literature data regarding the effects of the electromagnetic radiation on the model eukaryotic organism--yeast Saccharomyces cerevisiae. An attempt was made to estimate the probability of induction of carcinogenesis in humans under the influence of magnetic fields and electromagnetic radiation of extremely low frequency, radio frequency and microwave ranges.

  15. Nonresonant ionization of oxygen molecules by femtosecond pulses: Plasma dynamics studied by time-resolved terahertz spectroscopy

    SciTech Connect

    Mics, Zoltan; Kadlec, Filip; Kuzel, Petr; Jungwirth, Pavel; Bradforth, Stephen E.; Apkarian, V. Ara

    2005-09-08

    We show that optical pump-terahertz probe spectroscopy is a direct experimental tool for exploring laser-induced ionization and plasma formation in gases. Plasma was produced in gaseous oxygen by focused amplified femtosecond pulses. The ionization mechanisms at 400- and 800-nm excitation wavelengths differ significantly being primarily of a multiphoton character in the former case and a strong-field process in the latter case. The generation of the plasma in the focal volume of the laser and its expansion on subnanosecond time scale is directly monitored through its density-dependent susceptibility. A Drude model used to evaluate the plasma densities and electron-scattering rates successfully captures the observations for a wide range of pump intensities. In addition, rotational fingerprints of molecular and ionic species were also observed in the spectra.

  16. Photoexcitation and ionization in carbon dioxide - Theoretical studies in the separated-channel static-exchange approximation

    NASA Technical Reports Server (NTRS)

    Padial, N.; Csanak, G.; Mckoy, B. V.; Langhoff, P. W.

    1981-01-01

    Vertical-electronic static-exchange photoexcitation and ionization cross sections are reported which provide a first approximation to the complete dipole spectrum of CO2. Separated-channel static-exchange calculations of vertical-electronic transition energies and oscillator strengths, and Stieltjes-Chebyshev moment methods were used in the development. Detailed comparisons were made of the static-exchange excitation and ionization spectra with photoabsorption, electron-impact excitation, and quantum-defect estimates of discrete transition energies and intensities, and with partial-channel photoionization cross sections obtained from fluorescence measurements and from tunable-source and (e, 2e) photoelectron spectroscopy. Results show that the separate-channel static-exchange approximation is generally satisfactory in CO2.

  17. Effect of Chromatin Structure on the Extent and Distribution of DNA Double Strand Breaks Produced by Ionizing Radiation; Comparative Study of hESC and Differentiated Cells Lines

    PubMed Central

    Venkatesh, Priyanka; Panyutin, Irina V.; Remeeva, Evgenia; Neumann, Ronald D.; Panyutin, Igor G.

    2016-01-01

    Chromatin structure affects the extent of DNA damage and repair. Thus, it has been shown that heterochromatin is more protective against DNA double strand breaks (DSB) formation by ionizing radiation (IR); and that DNA DSB repair may proceed differently in hetero- and euchromatin regions. Human embryonic stem cells (hESC) have a more open chromatin structure than differentiated cells. Here, we study the effect of chromatin structure in hESC on initial DSB formation and subsequent DSB repair. DSB were scored by comet assay; and DSB repair was assessed by repair foci formation via 53BP1 antibody staining. We found that in hESC, heterochromatin is confined to distinct regions, while in differentiated cells it is distributed more evenly within the nuclei. The same dose of ionizing radiation produced considerably more DSB in hESC than in differentiated derivatives, normal human fibroblasts; and one cancer cell line. At the same time, the number of DNA repair foci were not statistically different among these cells. We showed that in hESC, DNA repair foci localized almost exclusively outside the heterochromatin regions. We also noticed that exposure to ionizing radiation resulted in an increase in heterochromatin marker H3K9me3 in cancer HT1080 cells, and to a lesser extent in IMR90 normal fibroblasts, but not in hESCs. These results demonstrate the importance of chromatin conformation for DNA protection and DNA damage repair; and indicate the difference of these processes in hESC. PMID:26729112

  18. Effect of Chromatin Structure on the Extent and Distribution of DNA Double Strand Breaks Produced by Ionizing Radiation; Comparative Study of hESC and Differentiated Cells Lines.

    PubMed

    Venkatesh, Priyanka; Panyutin, Irina V; Remeeva, Evgenia; Neumann, Ronald D; Panyutin, Igor G

    2016-01-02

    Chromatin structure affects the extent of DNA damage and repair. Thus, it has been shown that heterochromatin is more protective against DNA double strand breaks (DSB) formation by ionizing radiation (IR); and that DNA DSB repair may proceed differently in hetero- and euchromatin regions. Human embryonic stem cells (hESC) have a more open chromatin structure than differentiated cells. Here, we study the effect of chromatin structure in hESC on initial DSB formation and subsequent DSB repair. DSB were scored by comet assay; and DSB repair was assessed by repair foci formation via 53BP1 antibody staining. We found that in hESC, heterochromatin is confined to distinct regions, while in differentiated cells it is distributed more evenly within the nuclei. The same dose of ionizing radiation produced considerably more DSB in hESC than in differentiated derivatives, normal human fibroblasts; and one cancer cell line. At the same time, the number of DNA repair foci were not statistically different among these cells. We showed that in hESC, DNA repair foci localized almost exclusively outside the heterochromatin regions. We also noticed that exposure to ionizing radiation resulted in an increase in heterochromatin marker H3K9me3 in cancer HT1080 cells, and to a lesser extent in IMR90 normal fibroblasts, but not in hESCs. These results demonstrate the importance of chromatin conformation for DNA protection and DNA damage repair; and indicate the difference of these processes in hESC.

  19. Effect of noncovalent interactions on the n-butylbenzene...Ar cluster studied by mass analyzed threshold ionization spectroscopy and ab initio computations.

    PubMed

    Tong, Xin; Cerný, Jirí; Müller-Dethlefs, Klaus

    2008-07-01

    Clusters of Ar bound to isomers of the aromatic hydrocarbon n-butylbenzene (BB) have been studied using two-color REMPI (resonance enhanced multiphoton ionization) and MATI (mass analyzed threshold ionization) spectroscopy to explore noncovalent vdW interactions between these two moieties. Blue shifts of excitation energy were observed for gauche-BB...Ar clusters, and red shifts for anti-BB...Ar clusters were observed. Adiabatic ionization energies (IEs) of the conformer BB-I...Ar and BB-V...Ar were determined as 70052 and 69845 +/- 5 cm (-1), respectively. Spectral features and vibrational modes were interpreted with the aid of UMP2/cc-pVDZ ab initio calculations. Data of complexation shifts of the alkyl-benzenes and their argon clusters were collected and discussed. Using the CCSD(T) method at complete basis set (CBS) level, interaction energies for the neutral ground states of BB-I...Ar and BB-V...Ar were obtained as 650 and 558 cm (-1), respectively. Combining the CBS calculation results and the REMPI and MATI spectra allowed further the determination of the interaction energies and the energetics of BB...Ar in the excited neutral S 1 and the D 0 cationic ground states.

  20. Effect of noncovalent interactions on the n-butylbenzene...Ar cluster studied by mass analyzed threshold ionization spectroscopy and ab initio computations.

    PubMed

    Tong, Xin; Cerný, Jirí; Müller-Dethlefs, Klaus

    2008-07-01

    Clusters of Ar bound to isomers of the aromatic hydrocarbon n-butylbenzene (BB) have been studied using two-color REMPI (resonance enhanced multiphoton ionization) and MATI (mass analyzed threshold ionization) spectroscopy to explore noncovalent vdW interactions between these two moieties. Blue shifts of excitation energy were observed for gauche-BB...Ar clusters, and red shifts for anti-BB...Ar clusters were observed. Adiabatic ionization energies (IEs) of the conformer BB-I...Ar and BB-V...Ar were determined as 70052 and 69845 +/- 5 cm (-1), respectively. Spectral features and vibrational modes were interpreted with the aid of UMP2/cc-pVDZ ab initio calculations. Data of complexation shifts of the alkyl-benzenes and their argon clusters were collected and discussed. Using the CCSD(T) method at complete basis set (CBS) level, interaction energies for the neutral ground states of BB-I...Ar and BB-V...Ar were obtained as 650 and 558 cm (-1), respectively. Combining the CBS calculation results and the REMPI and MATI spectra allowed further the determination of the interaction energies and the energetics of BB...Ar in the excited neutral S 1 and the D 0 cationic ground states. PMID:18533640

  1. Asymmetry of above-threshold ionization of metal clusters in two-color laser fields: A time-dependent density-functional study

    SciTech Connect

    Nguyen, H.S.; Bandrauk, A.D.; Ullrich, C.A.

    2004-06-01

    Above threshold ionization (ATI) spectra of small metal clusters (e.g., Na{sub 4} and Na{sub 4}{sup +}) are calculated numerically using a spherical jellium model and time-dependent density functional theory for two-color (1064 and 532 nm) ultrashort (25 fs) laser pulses as a function of phase difference between the two fields. ATI spectra and ionized electron fluxes are obtained in the two opposite directions of the linearly polarized laser fields. The asymmetry, defined as the difference in electron yield, is shown to depend strongly on the carrier-envelope phase of the second-harmonic (2{omega}) field. The ATI spectra allow one to identify the range of kinetic energies of the ionized electrons where the asymmetry mainly occurs. Comparisons are made between calculations with and without self-interaction correction and also with previous exact numerical solutions of the one-electron systems H and H{sub 2}{sup +} [A. D. Bandrauk and S. Chelkowski, Phys. Rev. Lett. 84, 3562 (2000)] where such asymmetry effects had first been observed. We find that ATI spectra in the clusters generally have much longer energy plateaus than in previously studied one-electron systems, with cutoffs up to 30-40 times the ponderomotive energy U{sub p}. In high-harmonic generation spectra, on the other hand, no extended plateaus are observed.

  2. Coupling of HPLC with electrospray ionization mass spectrometry for studying the aging of ultrasmall multifunctional gadolinium-based silica nanoparticles.

    PubMed

    Truillet, Charles; Lux, François; Tillement, Olivier; Dugourd, Philippe; Antoine, Rodolphe

    2013-11-01

    Sub-5 nm multimodal nanoparticles have great potential for theranostic applications due to their easy renal elimination combined with complementary imaging properties and therapeutic facilities. Their potential clinical use requires the full characterization of not only the nanoparticle but also all its possible degradation products. We have recently proposed new ultrasmall gadolinium-based nanoparticles for multimodal imaging and radiosensitization. The aim of this article is to describe an analytical tool to characterize degradation products in a highly diluted medium. We demonstrate that HPLC coupled to electrospray ionization mass spectrometry (ESI-MS) can be used in order to determine precisely the composition of nanoparticles and their degradation fragments during aging.

  3. Aging effects on macadamia nut oil studied by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Proschogo, Nicholas W; Albertson, Peter L; Bursle, Johanna; McConchie, Cameron A; Turner, Athol G; Willett, Gary D

    2012-02-29

    High-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry is successfully used in the detailed molecular analysis of aged macadamia nut oils. The results are consistent with peroxide values, the current industry measure for rancidity, and provide detailed molecular information on the oxidative and hydrolytic degeneration of such oils. Mass analysis of macadamia oil samples stored for extended periods at 6 °C revealed that oils obtained by the cold press method are more susceptible to aging than those obtained using modified Soxhlet or accelerated solvent extraction methods.

  4. The Study of Complex (Ti, Zr, Cs) Nanopowder Influencing the Effective Ionization Potential of Arc Discharge When Mma Welding

    NASA Astrophysics Data System (ADS)

    Sapozhkov, S. B.; Burakova, E. M.

    2016-08-01

    Strength is one of the most important characteristics of a weld joint. Mechanical properties of a weld metal can be improved in a variety of ways. One of the possibilities is to add a nanopowder to the weld metal. Authors of the paper suggest changing the production process of MMA welding electrodes via adding nanopowder Ti, Zr, Cs to electrode components through liquid glass. Theoretical research into the nanopowder influence on the effective ionization potential (Ueff) of welding arc discharge is also necessitated. These measures support arcing stability, improve strength of a weld joint, as the consequence, ensure quality enhancing of a weld joint and the structure on the whole.

  5. Aging effects on macadamia nut oil studied by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Proschogo, Nicholas W; Albertson, Peter L; Bursle, Johanna; McConchie, Cameron A; Turner, Athol G; Willett, Gary D

    2012-02-29

    High-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry is successfully used in the detailed molecular analysis of aged macadamia nut oils. The results are consistent with peroxide values, the current industry measure for rancidity, and provide detailed molecular information on the oxidative and hydrolytic degeneration of such oils. Mass analysis of macadamia oil samples stored for extended periods at 6 °C revealed that oils obtained by the cold press method are more susceptible to aging than those obtained using modified Soxhlet or accelerated solvent extraction methods. PMID:22268609

  6. Micellization and related behavior of sodium dodecylsulfate in mixed binary solvent media of tetrahydrofuran (Tf) and formamide (Fa) with water: a detailed physicochemical investigation.

    PubMed

    Pan, A; Naskar, B; Prameela, G K S; Kumar, B V N Phani; Aswal, V K; Bhattacharya, S C; Mandal, A B; Moulik, S P

    2014-08-21

    The detailed aggregation behavior of sodiumdodecyl sulfate (SDS) in tetrahydrofuran (Tf)-water (W) and formamide (Fa)-water (W) media at varied volume percent compositions has been investigated. Surface tension (ST), conductance (Cond), viscosity (Visc), isothermal titration calorimetry (ITC), nuclear magnetic resonance (NMR) and small angle neutron scattering (SANS) were used in this study. The presence of nonaqueous solvents affected the critical micelle concentration (CMC) of SDS, the counter-ion binding of the micelle, the energetics of the air/water interfacial adsorption and micellization of the amphiphiles in the bulk, the ion-association (ion-pair, triple-ion, quadruple, etc. between Na(+) and DS(-) ions) as well as the weakly soluble (aggregation less) amphiphile solution. Tf has been observed to produce a "dead zone" or "non-micelle formation zone" in the mixed Tf-W domain of 10-40 vol%. Fa influenced the SDS aggregation up to 70 vol%, at higher proportions (below the Krafft temperature (K(T))), instead of the micelle, "randomly arranged globular assembly" (RAGA) was formed. The correlation of the standard free energy of micellization (ΔG(m)(0)) with different solvent parameters (1) dielectric constant (ε), (2) viscosity (η0), (3) Reichardt parameter (E(T)(30)), (4) Gordon parameter (G), and (5) Hansen-Hildebrand hydrogen bonding parameter (δ(h)) has been attempted. It has been found that δ(h) produced a master correlation between ΔG(m)(0) and δ(h) for different binary mixtures such as Tf-W, Fa-W, Ml-W and Dn-W.

  7. Moving solvated electrons with light: Nonadiabatic mixed quantum/classical molecular dynamics simulations of the relocalization of photoexcited solvated electrons in tetrahydrofuran (THF)

    SciTech Connect

    Bedard-Hearn, Michael J.; Larsen, Ross E.; Schwartz, Benjamin J.

    2006-11-21

    Motivated by recent ultrafast spectroscopic experiments [Martini et al., Science 293, 462 (2001)], which suggest that photoexcited solvated electrons in tetrahydrofuran (THF) can relocalize (that is, return to equilibrium in solvent cavities far from where they started), we performed a series of nonequilibrium, nonadiabatic, mixed quantum/classical molecular dynamics simulations that mimic one-photon excitation of the THF-solvated electron. We find that as photoexcited THF-solvated electrons relax to their ground states either by continuous mixing from the excited state or via nonadiabatic transitions, {approx}30% of them relocalize into cavities that can be over 1 nm away from where they originated, in close agreement with the experiments. A detailed investigation shows that the ability of excited THF-solvated electrons to undergo photoinduced relocalization stems from the existence of preexisting cavity traps that are an intrinsic part of the structure of liquid THF. This explains why solvated electrons can undergo photoinduced relocalization in solvents like THF but not in solvents like water, which lack the preexisting traps necessary to stabilize the excited electron in other places in the fluid. We also find that even when they do not ultimately relocalize, photoexcited solvated electrons in THF temporarily visit other sites in the fluid, explaining why the photoexcitation of THF-solvated electrons is so efficient at promoting recombination with nearby scavengers. Overall, our study shows that the defining characteristic of a liquid that permits the photoassisted relocalization of solvated electrons is the existence of nascent cavities that are attractive to an excess electron; we propose that other such liquids can be found from classical computer simulations or neutron diffraction experiments.

  8. Analytical instruments, ionization sources, and ionization methods

    DOEpatents

    Atkinson, David A.; Mottishaw, Paul

    2006-04-11

    Methods and apparatus for simultaneous vaporization and ionization of a sample in a spectrometer prior to introducing the sample into the drift tube of the analyzer are disclosed. The apparatus includes a vaporization/ionization source having an electrically conductive conduit configured to receive sample particulate which is conveyed to a discharge end of the conduit. Positioned proximate to the discharge end of the conduit is an electrically conductive reference device. The conduit and the reference device act as electrodes and have an electrical potential maintained between them sufficient to cause a corona effect, which will cause at least partial simultaneous ionization and vaporization of the sample particulate. The electrical potential can be maintained to establish a continuous corona, or can be held slightly below the breakdown potential such that arrival of particulate at the point of proximity of the electrodes disrupts the potential, causing arcing and the corona effect. The electrical potential can also be varied to cause periodic arcing between the electrodes such that particulate passing through the arc is simultaneously vaporized and ionized. The invention further includes a spectrometer containing the source. The invention is particularly useful for ion mobility spectrometers and atmospheric pressure ionization mass spectrometers.

  9. Attenuation and cross-attenuation in taste aversion learning in the rat: Studies with ionizing radiation, lithium chloride and ethanol

    SciTech Connect

    Rabin, B.M.; Hunt, W.A.; Lee, J.

    1988-12-01

    The preexposure paradigm was utilized to evaluate the similarity of ionizing radiation, lithium chloride and ethanol as unconditioned stimuli for the acquisition of a conditioned taste aversion. Three unpaired preexposures to lithium chloride (3.0 mEq/kg, IP) blocked the acquisition of a taste aversion when a novel sucrose solution was paired with either the injection of the same dose of lithium chloride or exposure to ionizing radiation (100 rad). Similar pretreatment with radiation blocked the acquisition of a radiation-induced aversion, but had no effect on taste aversions produced by lithium chloride (3.0 or 1.5 mEq/kg). Preexposure to ethanol (4 g/kg, PO) disrupted the acquisition of an ethanol-induced taste aversion, but not radiation- or lithium chloride-induced aversions. In contrast, preexposure to either radiation or lithium chloride attenuated an ethanol-induced taste aversion in intact rats, but not in rats with lesions of the area postrema. The results are discussed in terms of relationships between these three unconditioned stimuli and in terms of implications of these results for understanding the nature of the proximal unconditioned stimulus in taste aversion learning.

  10. Effects of Tailored Surface Chemistry on Desorption Electrospray Ionization Mass Spectrometry: a Surface-Analytical Study by XPS and AFM

    NASA Astrophysics Data System (ADS)

    Penna, Andrea; Careri, Maria; Spencer, Nicholas D.; Rossi, Antonella

    2015-08-01

    Since it was proposed for the first time, desorption electrospray ionization-mass spectrometry (DESI-MS) has been evaluated for applicability in numerous areas. Elucidations of the ionization mechanisms and the subsequent formation of isolated gas-phase ions have been proposed so far. In this context, the role of both surface and pneumatic effects on ion-formation yield has recently been investigated. Nevertheless, the effect of the surface chemistry has not yet been completely understood. Functionalized glass surfaces have been prepared, in order to tailor surface performance for ion formation. Three substrates were functionalized by depositing three different silanes [3-mercaptopropyltriethoxysilane (MTES), octyltriethoxysilane (OTES), and 1H,1H,2H,2H-perfluorooctyltriethoxy-silane (FOTES)] from toluene solution onto standard glass slides. Surface characterization was carried out by contact-angle measurements, tapping-mode atomic force microscopy, and X-ray photoelectron spectroscopy. Morphologically homogeneous and thickness-controlled films in the nm range were obtained, with surface free energies lying between 15 and 70 mJ/m2. These results are discussed, together with those of DESI-MS on low-molecular-weight compounds such as melamine, tetracycline, and lincomycin, also taking into account the effects of the sprayer potential and its correlation with surface wettability. The results demonstrate that ion-formation efficiency is affected by surface wettability, and this was demonstrated operating above and below the onset of the electrospray.

  11. IN-SITU PROBING OF RADIATION-INDUCED PROCESSING OF ORGANICS IN ASTROPHYSICAL ICE ANALOGS-NOVEL LASER DESORPTION LASER IONIZATION TIME-OF-FLIGHT MASS SPECTROSCOPIC STUDIES

    SciTech Connect

    Gudipati, Murthy S.; Yang Rui E-mail: ryang73@ustc.edu

    2012-09-01

    Understanding the evolution of organic molecules in ice grains in the interstellar medium (ISM) under cosmic rays, stellar radiation, and local electrons and ions is critical to our understanding of the connection between ISM and solar systems. Our study is aimed at reaching this goal of looking directly into radiation-induced processing in these ice grains. We developed a two-color laser-desorption laser-ionization time-of-flight mass spectroscopic method (2C-MALDI-TOF), similar to matrix-assisted laser desorption and ionization time-of-flight (MALDI-TOF) mass spectroscopy. Results presented here with polycyclic aromatic hydrocarbon (PAH) probe molecules embedded in water-ice at 5 K show for the first time that hydrogenation and oxygenation are the primary chemical reactions that occur in astrophysical ice analogs when subjected to Ly{alpha} radiation. We found that hydrogenation can occur over several unsaturated bonds and the product distribution corresponds to their stabilities. Multiple hydrogenation efficiency is found to be higher at higher temperatures (100 K) compared to 5 K-close to the interstellar ice temperatures. Hydroxylation is shown to have similar efficiencies at 5 K or 100 K, indicating that addition of O atoms or OH radicals to pre-ionized PAHs is a barrierless process. These studies-the first glimpses into interstellar ice chemistry through analog studies-show that once accreted onto ice grains PAHs lose their PAH spectroscopic signatures through radiation chemistry, which could be one of the reason for the lack of PAH detection in interstellar ice grains, particularly the outer regions of cold, dense clouds or the upper molecular layers of protoplanetary disks.

  12. Inner-orbital ionization of iodine

    NASA Astrophysics Data System (ADS)

    Gibson, George; Smith, Dale; Tagliamonti, Vincent; Dragan, James

    2016-05-01

    Many coincidence techniques exist to study multiple ionization of molecules by strong laser fields. However, the first ionization step is critical in many experiments, although it is more difficult to obtain information about this initial step. We studied the single electron ionization of I2, as it presents interesting opportunities in that it is heavy and does not expand significantly during the laser pulse. Moreover, there are several distinct low-lying valence orbitals from which the electron may be removed. Most importantly, the kinetic energy release of the I+ + I dissociation channel can be measured and should correspond to well-known valence levels and separated atom limits. As it turns out, we must invoke deep valence orbits, built from the 5s electrons, to explain our data. Ionization from deep orbitals may be possible, as they have a smaller critical internuclear separation for enhanced ionization. We would like to acknowledge support from the NSF under Grant No. PHY-1306845.

  13. Reverse-phase liquid chromatography with electrospray ionization/mass spectrometry for the quantification of pseudoephedrine in human plasma and application to a bioequivalence study.

    PubMed

    Kim, Jin-Ki; Jee, Jun-Pil; Park, Jeong-Sook; Kim, Hyung Tae; Kim, Chong-Kook

    2011-01-01

    A sensitive and selective reverse-phase liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS) method was developed and validated to quantify pseudoephedrine (CAS 90-82-4) in human plasma. Phenacetin was used as the internal standard (I.S.). Sample preparation was performed with a deproteinization step using acetonitrile. Pseudoephedrine and I.S. were successfully separated using gradient elution with 0.5% trifluoroacetic acid (TFA) in water and 0.5% TFA in methanol at a flow-rate of 0.2 mL/min. Detection was performed on a single quadrupole mass spectrometer by a selected ion monitoring (SIM) mode via electrospray ionization (ESI) source. The ESI source was set at positive ionization mode. The ion signals of m/z 166.3 and 180.2 were measured for the protonated molecular ions of pseudoephedrine and I.S., respectively. The lower limit of quantification (LLOQ) of pseudoephedrine in human plasma was 10 ng/mL and good linearity was observed in the range of concentrations 10-500 ng/mL (R2 = 1). The intra-day accuracy of the drug containing plasma samples was more than 97.60% with a precision of 3.99-11.82%. The inter-day accuracy was 99.36% or more, with a precision of 7.65-18.42%. By using this analytical method, the bioequivalence study of the pseudoephedrine preparation was performed and evaluated by statistical analysis of the log transformed mean ratios of pharmacokinetic parameters. All the results fulfilled the standard criteria of bioequivalence, being within the 80-125% range which is required by the Korea FDA, US FDA, and EMEA to conclude bioequivalence. Consequently, the developed reverse-phase LC-ESI-MS method was successfully applied to bioequivalence studies of pseudoephedrine in healthy male volunteers.

  14. Online atmospheric pressure chemical ionization ion trap mass spectrometry (APCI-IT-MSn) for measuring organic acids in concentrated bulk aerosol - a laboratory and field study

    NASA Astrophysics Data System (ADS)

    Vogel, A. L.; Äijälä, M.; Brüggemann, M.; Ehn, M.; Junninen, H.; Petäjä, T.; Worsnop, D. R.; Kulmala, M.; Williams, J.; Hoffmann, T.

    2012-08-01

    The field application of an aerosol concentrator in conjunction with an atmospheric pressure chemical ionization ion trap mass spectrometer (APCI-IT-MS) at the boreal forest station SMEAR II at Hyytiälä, Finland, is demonstrated in this study. APCI is a soft ionization technique allowing online measurements of organic acids in the gas and particle phase. The detection limit for the acid species in the particle phase was increased by a factor of 7.5 to 11 (e.g. ~40 ng m-3 for pinonic acid) by using the miniature Versatile Aerosol Concentration Enrichment System (mVACES) upstream of the mass spectrometer. The APCI-IT-MS was calibrated in the negative ion mode with two biogenic organic acid standards - pinic acid and pinonic acid. Pinic acid was used as a surrogate for the quantification of the total amount of organic acids in the ambient aerosol based on the total signal intensities in the negative ion mode. The results were compared with the total organic signal of a C-ToF-AMS during the HUMPPA-COPEC 2010 field campaign. The campaign average contribution of organic acids measured by APCI-IT-MS to the total sub-micron organic aerosol mass was estimated to be about 60%. Very good correlation between APCI-IT-MS and C-ToF-AMS (Pearson's R = 0.94) demonstrates soft ionization mass spectrometry as a complimentary technique to AMS with electron impact ionization. MS2 studies of specific m/z ratios recorded during the HUMPPA-COPEC 2010 field campaign were compared to MS2 studies of selected monoterpene oxidation products formed in simulation chamber experiments. The comparison of the resulting fragments shows that oxidation products of the main VOCs emitted at Hyytiälä (α-pinene and Δ3-carene) cannot account for all of the measured fragments, which illustrates the complexity of ambient aerosol and possibly indicates unidentified or underestimated biogenic SOA precursor in the boreal forest.

  15. Online atmospheric pressure chemical ionization ion trap mass spectrometry (APCI-IT-MSn) for measuring organic acids in concentrated bulk aerosol - a laboratory and field study

    NASA Astrophysics Data System (ADS)

    Vogel, A. L.; Äijälä, M.; Brüggemann, M.; Ehn, M.; Junninen, H.; Petäjä, T.; Worsnop, D. R.; Kulmala, M.; Williams, J.; Hoffmann, T.

    2013-02-01

    The field application of an aerosol concentrator in conjunction with an atmospheric pressure chemical ionization ion trap mass spectrometer (APCI-IT-MS) at the boreal forest station SMEAR II at Hyytiälä, Finland, is demonstrated in this study. APCI is a soft-ionization technique allowing online measurements of organic acids in the gas and particle phase. The detection limit for the acid species in the particle phase was improved by a factor of 7.5 to 11 (e.g. ∼40 ng m3 for pinonic acid) by using the miniature versatile aerosol concentration enrichment system (mVACES) upstream of the mass spectrometer. The APCI-IT-MS was calibrated in the negative ion mode with two biogenic organic acid standards - pinic acid and pinonic acid. Pinic acid was used as a surrogate for the quantification of the total amount of organic acids in the ambient aerosol based on the total signal intensities in the negative ion mode. The results were compared with the total organic signal of a C-ToF-AMS during the HUMPPA-COPEC 2010 field campaign. The campaign average contribution of organic acids measured by APCI-IT-MS to the total submicron organic aerosol mass was estimated to be about 60%, based on the response of pinic acid. Very good correlation between APCI-IT-MS and C-ToF-AMS (Pearson's R = 0.94) demonstrates soft-ionization mass spectrometry as a complimentary technique to AMS with electron impact ionization. MS2 studies of specific m/z ratios recorded during the HUMPPA-COPEC 2010 field campaign were compared to MS2 studies of selected monoterpene oxidation products formed in simulation chamber experiments. The comparison of the resulting fragments shows that oxidation products of the main VOCs emitted at Hyytiälä (α-pinene and Δ3-carene) cannot account for all of the measured fragments. Possible explanations for those unaccounted fragments are the presence of unidentified or underestimated biogenic SOA precursors, or that different products are formed by a different oxidant

  16. Multiphoton ionization of Uracil

    NASA Astrophysics Data System (ADS)

    Prieto, Eladio; Martinez, Denhi; Guerrero, Alfonso; Alvarez, Ignacio; Cisneros, Carmen

    2016-05-01

    Multiphoton ionization and dissociation of Uracil using a Reflectron time of flight spectrometer was performed along with radiation from the second harmonic of a Nd:YAG laser. Uracil is one of the four nitrogen bases that belong to RNA. The last years special interest has been concentrated on the study of the effects under UV radiation in nucleic acids1 and also in the role that this molecule could have played in the origin and development of life on our planet.2 The MPI mass spectra show that the presence and intensity of the resulting ions strongly depend on the density power. The identification of the ions in the mass spectra is presented. The results are compared with those obtained in other laboratories under different experimental conditions and some of them show partial agreement.3 The present work was supported by CONACYT-Mexico Grant 165410 and DGAPA UNAM Grant IN101215 and IN102613.

  17. Refreshing the Aged Latent Fingerprints with Ionizing Radiation Prior to the Cyanoacrylate Fuming Procedure: A Preliminary Study.

    PubMed

    Ristova, Mimoza M; Radiceska, Pavlina; Bozinov, Igorco; Barandovski, Lambe

    2016-05-01

    One of the crucial factors determining the cyanoacrylate deposit quality over latent fingerprints appeared to be the extent of the humidity. This work focuses on the enhancement/refreshment of age-degraded latent fingerprints by irradiating the samples with UV, X-ray, or thermal neutrons prior to the cyanoacrylate (CA) fuming. Age degradation of latent fingerprints deposited on glass surfaces was examined through the decrease in the number of characteristic minutiae counts over time. A term "critical day" was introduced for the time at which the average number of identifiable minutiae definitions drops to one-half. Fingerprints older than their "critical day" were exposed to either UV, X-ray, or thermal neutrons. Identical reference samples were kept unexposed. All samples, both reference and irradiated, were developed during a single CA fuming procedure. Comparative latent fingerprint analysis showed that exposure to ionizing radiation enhances the CA fuming, yielding a 20-30% increase in average minutiae count. PMID:27122421

  18. Refreshing the Aged Latent Fingerprints with Ionizing Radiation Prior to the Cyanoacrylate Fuming Procedure: A Preliminary Study.

    PubMed

    Ristova, Mimoza M; Radiceska, Pavlina; Bozinov, Igorco; Barandovski, Lambe

    2016-05-01

    One of the crucial factors determining the cyanoacrylate deposit quality over latent fingerprints appeared to be the extent of the humidity. This work focuses on the enhancement/refreshment of age-degraded latent fingerprints by irradiating the samples with UV, X-ray, or thermal neutrons prior to the cyanoacrylate (CA) fuming. Age degradation of latent fingerprints deposited on glass surfaces was examined through the decrease in the number of characteristic minutiae counts over time. A term "critical day" was introduced for the time at which the average number of identifiable minutiae definitions drops to one-half. Fingerprints older than their "critical day" were exposed to either UV, X-ray, or thermal neutrons. Identical reference samples were kept unexposed. All samples, both reference and irradiated, were developed during a single CA fuming procedure. Comparative latent fingerprint analysis showed that exposure to ionizing radiation enhances the CA fuming, yielding a 20-30% increase in average minutiae count.

  19. A novel technique for studying F-region ionization patches with the Resolute Bay Incoherent Scatter Radar - North

    NASA Astrophysics Data System (ADS)

    Perry, G. W.; Hosokawa, K.; St-Maurice, J.; Shiokawa, K.

    2013-12-01

    The northward facing Resolute Bay Incoherent Scatter Radar - North (RISR-N) and the soon to be operational southward facing RISR-Canada (RISR-C) systems are both exceptional platforms for investigating F-region ionization patches and the polar ionosphere. To advance patch research using these systems, an algorithm has been developed for detecting F-region ionization patches with the RISR-N system. The algorithm is based on the definition of a patch put forward by Crowley [1996]: a volume of F-region plasma with a density that is twice that of the background ionosphere. In this work, the algorithm is applied to the sizeable RISR-N dataset, providing valuable insight into the prevalence of patches over Resolute Bay over a time frame of several years. Additional questions concerning patches are also addressed using the algorithm, including: when compared to each other, do the occurrence rates of patches identified by the Optical Mesosphere and Thermosphere Imagers (OMTI), Polar Dual Auroral Radar Network (PolarDARN) and RISR-N instruments (whose fields-of-view overlap over Resolute Bay) agree? Namely, for every patch that is detected with RISR-N and/or PolarDARN, is there a corresponding patch seen optically? Lastly, using the algorithm, is it possible to advance our ability to distinguish patches from other coherent backscatter echoes detected by PolarDARN? Crowley, G. (1996), Critical review of ionospheric patches and blobs, in Review of Radio Science: 1993-1996, edited by W. R. Stone, pp. 619 648, Oxford Univ. Press, Oxford, U. K.

  20. Fundamental studies of matrix-assisted laser desorption/ionization, using time-of-flight mass spectrometry to identify biological molecules

    SciTech Connect

    Eades, D.; Wruck, D.; Gregg, H.

    1996-11-11

    MALDI MS was developed as a way of getting molecular weight information on small quantities (picomole to femtomole levels) of high-mass, thermally labile macromolecules. While most other analytical MS ionization techniques cause fragmentation, decomposition, or multiple charging, MALDI efficiently places intact macromolecules into the gas phase with little fragmentation or rearrangement. This project had 3 objectives: establish the MALDI capability at LLNL, perform fundamental studies of analyte-matrix interactions, and apply the technique for biochemical research. A retired time-of-flight instrument was adapted for MALDI analyses, relevant parameters influencing the MALDI process were identified for further study (matrix molar absorptivity, sample crystal preparation), and collaborations were established with research groups in the Biology and Biotechnology Research Program at LLNL. In MALDI, the macromolecule of interest is mixed with a high-molar excess (1:100 to 1:10,000) of an organic matrix which readily absorbs energy at the wavelength corresponding to a UV laser. Upon laser irradiation, the matrix absorbs the majority of the energy, causing it to desorb from the surface and gently release the macromolecule into the gas phase with little or no fragmentation. Once in the gas phase, ion-molecule reactions between excited matrix and neutral macromolecules generated ionized analyte species which then can be focused into a MS for detection.

  1. Biological Effects of Ionizing Radiation

    DOE R&D Accomplishments Database

    Ingram, M.; Mason, W. B.; Whipple, G. H.; Howland, J. W.

    1952-04-07

    This report presents a review of present knowledge and concepts of the biological effects of ionizing radiations. Among the topics discussed are the physical and chemical effects of ionizing radiation on biological systems, morphological and physiological changes observed in biological systems subjected to ionizing radiations, physiological changes in the intact animal, latent changes following exposure of biological systems to ionizing radiations, factors influencing the biological response to ionizing radiation, relative effects of various ionizing radiations, and biological dosimetry.

  2. A newly isolated strain capable of effectively degrading tetrahydrofuran and its performance in a continuous flow system.

    PubMed

    Chen, Jian-Meng; Zhou, Yu-Yang; Chen, Dong-Zhi; Jin, Xiao-Jun

    2010-08-01

    A Gram-negative strain DT4, capable of growing aerobically on tetrahydrofuran (THF) as the sole carbon and energy source was isolated from a pharmaceutical wastewater treatment plant. It was identified as Pseudomonas oleovorans by morphological and physiological characteristics as well as Biolog profiling and 16S rDNA sequence. Cells of P. oleovorans DT4 pre-cultured in THF could degrade 5 mM THF completely without lag phase. The generation time of 2.7 h and the maximum degradation rate of 203.9 mg THF/(h g dry weight) were observed, demonstrating that DT4 bears the highest THF-degrading activity in ever described strains. Furthermore, THF concentration as high as 100 mM was tolerated by the culture. Several important compounds including gamma-butyrrolactone and benzene could be directly metabolized, whereas other pollutants (e.g., tetrahydropyrane) could be cometabolized by DT4. THF removal was achieved in a continuous flow system with the maximum specific growth rate 0.113 h(-1) and half-saturation constant 1.224 mg/L, indicating the great potential of THF bioremediation in future full-scale application. PMID:20381342

  3. Quantitative determination of 1,4-dioxane and tetrahydrofuran in groundwater by solid phase extraction GC/MS/MS.

    PubMed

    Isaacson, Carl; Mohr, Thomas K G; Field, Jennifer A

    2006-12-01

    Groundwater contamination by cyclic ethers, 1,4-dioxane (dioxane), a probable human carcinogen, and tetrahydrofuran (THF), a co-contaminant at many chlorinated solvent release sites, are a growing concern. Cyclic ethers are readily transported in groundwater, yet little is known about their fate in environmental systems. High water solubility coupled with low Henry's law constants and octanol-water partition coefficients make their removal from groundwater problematic for both remedial and analytical purposes. A solid-phase extraction (SPE) method based on activated carbon disks was developed for the quantitative determination of dioxane and THF. The method requires 80 mL samples and a total of 1.2 mL of solvent (acetone). The number of steps is minimized due to the "in-vial" elution of the disks. Average recoveries for dioxane and THF were 98% and 95%, respectively, with precision, as indicated by the relative standard deviation of <2% to 6%. The method quantitation limits are 0.31 microg/L for dioxane and 3.1 microg/L for THF. The method was demonstrated by analyzing groundwater samples for dioxane and THF collected during a single sampling campaign at a TCA-impacted site. Dioxane concentrations and areal extent of dioxane in groundwater were greater than those of either TCA or THF.

  4. GAS-PHASE SYNTHESIS OF PRECURSORS OF INTERSTELLAR GLYCINE: A COMPUTATIONAL STUDY OF THE REACTIONS OF ACETIC ACID WITH HYDROXYLAMINE AND ITS IONIZED AND PROTONATED DERIVATIVES

    SciTech Connect

    Barrientos, Carmen; Redondo, Pilar; Largo, Laura; Rayon, Victor M.; Largo, Antonio

    2012-04-01

    A computational study of the reactions of hydroxylamine and its ionized and protonated derivatives with acetic acid is provided. The reaction of neutral hydroxylamine with acetic acid, despite being clearly exothermic, involves a very large energy barrier. The reaction of ionized hydroxylamine with acetic acid is also clearly exothermic, but again a significant energy barrier is found (around 24 kcal mol{sup -1} at the CCSD(T) level). The reaction of the most stable protonated isomer of hydroxylamine, NH{sub 3}OH{sup +}, with acetic acid also involves a high barrier (more than 27 kcal mol{sup -1} at the CCSD(T) level). Only the higher energy isomer, NH{sub 2}OH{sup +}{sub 2}, leads to a sensibly lower energy barrier (about 2.3 kcal mol{sup -1} at the CCSD(T) level). Nevertheless, an estimate of the reaction coefficient at low temperatures such as those reigning in the interstellar medium gives very low values. Therefore, it seems that precursors of interstellar glycine could not be efficiently produced from the reactions of hydroxylamine-derived ions with acetic acid.

  5. Theoretical study of orientation-dependent multiphoton ionization of polyatomic molecules in intense ultrashort laser fields: A new time-dependent Voronoi-cell finite difference method

    NASA Astrophysics Data System (ADS)

    Son, Sang-Kil; Chu, Shih-I.

    2009-12-01

    We present a new grid-based time-dependent method to investigate multiphoton ionization (MPI) of polyatomic molecules in intense ultrashort laser fields. The electronic structure of polyatomic molecules is treated by the density-functional theory (DFT) with proper long-range potential and the Kohn-Sham equation is accurately solved by means of the Voronoi-cell finite difference method on non-uniform and highly adaptive molecular grids utilizing geometrical flexibility of the Voronoi diagram. This method is generalized to the time-dependent problems with the split-operator time-propagation technique in the energy representation, allowing accurate and efficient non-perturbative treatment of attosecond electronic dynamics in strong fields. The new procedure is applied to the study of MPI of N 2 and H 2O molecules in intense linearly-polarized and ultrashort laser fields with arbitrary field-molecule orientation. Our results demonstrate that the orientation dependence of MPI is determined not just by the highest-occupied molecular orbital (HOMO) but also by the symmetries and dynamics of other contributing molecular orbitals. In particular, the inner orbitals can show dominant contributions to the ionization processes when the molecule is aligned in some specific directions with respect to the field polarization. This feature suggests a new way to selectively probe individual orbitals in strong-field electronic dynamics.

  6. Study of Milli-Jansky Seyfert Galaxies with Strong Forbidden High-Ionization Lines Using the Very Large Array Survey Images

    NASA Astrophysics Data System (ADS)

    Lal, Dharam V.

    2015-12-01

    We study the radio properties at 1.4 GHz of Seyfert galaxies with strong forbidden high-ionization lines (FHILs), selected from the Sloan Digital Sky Survey - a large-sized sample containing nearly equal proportion of diverse range of Seyfert galaxies showing similar redshift distributions compiled by tet{GMW2009} using the Very Large Array survey images. The radio detection rate is low, 49%, which is lower than the detection rate of several other known Seyfert galaxy samples. These galaxies show low star formation rates and the radio emission is dominated by the active nucleus with ≤10% contribution from thermal emission, and possibly, none show evidence for relativistic beaming. The radio detection rate, distributions of radio power, and correlations between radio power and line luminosities or X-ray luminosity for narrow-line Seyfert 1 (NLS1), Seyfert 1 and Seyfert 2 galaxies are consistent with the predictions of the unified scheme hypothesis. Using correlation between radio and [O III] λ 5007 Å luminosities, we show that ˜8% sample sources are radio-intermediate and the remaining are radio-quiet. There is possibly an ionization stratification associated with clouds on scales of 0.1-1.0 kpc, which have large optical depths at 1.4 GHz, and it seems these clouds are responsible for free-free absorption of radio emission from the core; hence, leading to low radio detection rate for these FHIL-emitting Seyfert galaxies.

  7. Study of pK values and effective dielectric constants of ionizable residues in pentapeptides and in staphylococcal nuclease (SNase) using a mean-field approach.

    PubMed

    Bossa, Guilherme Volpe; Fahr, Alfred; Pereira de Souza, Tereza

    2014-04-17

    The determination of pK values of amino acid residues as a function of temperature and ionic concentration is crucial to understanding the dynamics of various biological processes such as adsorption of peptides and their interactions with active sites of enzymes. In this study we developed a mean-field model to calculate the position-dependent dielectric constants of ionizable groups and the mean electrostatic potential on the surface. Such potential, which takes into account the contributions exerted by neighboring groups and ions in solution, is responsible for the fine-tuning of the pK value of each residue. The proposed model was applied to the amino acids Asp, Glu, Lys, His, Tyr, and Cys, and since the results were consistent with experimentally obtained values, the model was extended and applied to computation of pK values of Gly and Ala pentapeptides and of ionizable residues of the enzyme staphylococcal nuclease (SNase). In this latter case, we used an approach similar to a first-neighbors approximation, and the results turned out to be in good agreement with previously reported data when considering only the interactions of charged groups located at distances of maximally 20 Å. These considerations and the little computational cost involved turn the suggested approach into a promising tool for the modeling of force fields in computational simulations.

  8. Probing Angular Correlations in Sequential Double Ionization

    SciTech Connect

    Fleischer, A.; Woerner, H. J.; Arissian, L.; Liu, L. R.; Meckel, M.; Rippert, A.; Doerner, R.; Villeneuve, D. M.; Corkum, P. B.; Staudte, A.

    2011-09-09

    We study electron correlation in sequential double ionization of noble gas atoms and HCl in intense, femtosecond laser pulses. We measure the photoelectron angular distributions of Ne{sup +} relative to the first electron in a pump-probe experiment with 8 fs, 800 nm, circularly polarized laser pulses at a peak intensity of a few 10{sup 15} W/cm{sup 2}. Using a linear-linear pump-probe setup, we further study He, Ar, and HCl. We find a clear angular correlation between the two ionization steps in the sequential double ionization intensity regime.

  9. Oxidative degradation of bis (2,4,4-trimethylpentyl) dithiophosphinic acid in nitric acid studied by electrospray ionization mass spectrometry

    SciTech Connect

    G. S. Groenewold; D. R. Peterman

    2012-10-01

    Samples of bis(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex-301) were analyzed using direct infusion electrospray ionization mass spectrometry. Positive ion spectra of standard and stereo-pure acids displayed ions typical of the unmodified compound, cationized monomeric and dimeric cluster ion species. In addition, a significant ions 2 u less than the dimeric clusters were seen, that correspond to an oxidatively coupled species designated Cyx2 that is observed as H- or Na-cationized species in the electrospray analyses. Based on uncorrected ion intensities, Cyx2 is estimated to account for about 20% of the total in the standard materials. When samples that were contacted with 3 M HNO3 were analyzed, the positive ion spectrum consisted nearly entirely of ions derived from the oxidatively coupled product, indicating that the acid promotes coupling. The negative ion spectra of the standard acids consisted nearly entirely of the conjugate base that is formed by deprotonation of the acids, and cluster ions containing multiple acid molecules. The negative spectra of the HNO3-contacted samples also contained the conjugate base of the unmodified acid, but also two other species that correspond to the dioxo- and perthio- derivatives. It is concluded that HNO3 contact causes significant oxidation, forming at least three major products, Cyx2, the perthio-acid, and the dioxo-acid.

  10. Electron-Impact Ionization and Dissociative Ionization of Biomolecules

    NASA Technical Reports Server (NTRS)

    Huo, Winifred M.; Chaban, Galina M.; Dateo, Christopher E.

    2006-01-01

    It is well recognized that secondary electrons play an important role in radiation damage to humans. Particularly important is the damage of DNA by electrons, potentially leading to mutagenesis. Molecular-level study of electron interaction with DNA provides information on the damage pathways and dominant mechanisms. Our study of electron-impact ionization of DNA fragments uses the improved binary-encounter dipole model and covers DNA bases, sugar phosphate backbone, and nucleotides. An additivity principle is observed. For example, the sum of the ionization cross sections of the separate deoxyribose and phosphate fragments is in close agreement with the C3(sup prime)- and C5 (sup prime)-deoxyribose-phospate cross sections, differing by less than 5%. Investigation of tandem double lesion initiated by electron-impact dissociative ionization of guanine, followed by proton reaction with the cytosine in the Watson-Crick pair, is currently being studied to see if tandem double lesion can be initiated by electron impact. Up to now only OH-induced tandem double lesion has been studied.

  11. Multiphoton ionization of ions, neutrals, and clusters. Progress report

    SciTech Connect

    Wessel, J.

    1991-06-28

    Scientific results are summarized from a three year research program on multiphoton ionization in aromatic molecules, clusters, and their ions. As originally proposed, the studies elucidated a new cluster ionization mechanism, characterized properties of long range intermolecular interactions, and investigated electronic transitions of aromatic cations cooled in a supersonic beam. The studies indicate that the new cluster ionization mechanism is highly efficient and dominates conventional 1 + 1 resonant ionization. In the case of the dimer of the large aromatic molecule fluorene, the results suggest that excimer formation competes with a direct ionization process. Highly selective excitonic spectra have been identified for several cluster species.

  12. Speciation studies on DTPA using the complementary nature of electrospray ionization mass spectrometry and time-resolved laser-induced fluorescence.

    PubMed

    Moulin, Christophe; Amekraz, Badia; Steiner, Valerie; Plancque, Gabriel; Ansoborlo, Eric

    2003-09-01

    Decorporation of radionuclides is of continuous interest in order to reduce doses in case of occupational or accidental human exposure. In the present study, insights into the non-covalent interactions that hold the well-known chelating agent DTPA (diethylenetriaminepentaacetic acid) with inorganic elements of interest, such as europium and strontium, and their ability to form stable complexes, are investigated with two spectroscopic techniques, i.e., electrospray ionization mass spectrometry (ESI-MS) and time-resolved laser-induced fluorescence (TRLIF). First investigations are on DTPA and europium alone and end with a complete study of the Eu-DTPA system. The pH variation allows one to readily investigate whether different species (protonated, hydrolyzed, etc.) exist in the pH range 2-9 and evaluate the stoichiometry and conditional stability constant for the Eu-DTPA complex. Additional experiments by ESI-MS are reported for Sr(II) in interaction with DTPA and EDTA.

  13. Joint neutron crystallographic and NMR solution studies of Tyr residue ionization and hydrogen bonding: Implications for enzyme-mediated proton transfer

    DOE PAGESBeta

    Michalczyk, Ryszard; Unkefer, Clifford J.; Bacik, John -Paul; Schrader, Tobias E.; Ostermann, Andreas; Kovalevsky, Andrey Y.; McKenna, Robert; Fisher, Suzanne Zoe

    2015-05-05

    Proton transfer is a fundamental mechanism at the core of many enzyme-catalyzed reactions. It is also exquisitely sensitive to a number of factors, including pH, electrostatics, proper active-site geometry, and chemistry. Carbonic anhydrase has evolved a fast and efficient way to conduct protons through a combination of hydrophilic amino acid side chains that coordinate a highly ordered H-bonded water network. This study uses a powerful approach, combining NMR solution studies with neutron protein crystallography, to determine the effect of pH and divalent cations on key residues involved in proton transfer in human carbonic anhydrase. Lastly, the results have broad implicationsmore » for our understanding of proton transfer and how subtle changes in ionization and H-bonding interactions can modulate enzyme catalysis.« less

  14. Joint neutron crystallographic and NMR solution studies of Tyr residue ionization and hydrogen bonding: Implications for enzyme-mediated proton transfer

    SciTech Connect

    Michalczyk, Ryszard; Unkefer, Clifford J.; Bacik, John -Paul; Schrader, Tobias E.; Ostermann, Andreas; Kovalevsky, Andrey Y.; McKenna, Robert; Fisher, Suzanne Zoe

    2015-05-05

    Proton transfer is a fundamental mechanism at the core of many enzyme-catalyzed reactions. It is also exquisitely sensitive to a number of factors, including pH, electrostatics, proper active-site geometry, and chemistry. Carbonic anhydrase has evolved a fast and efficient way to conduct protons through a combination of hydrophilic amino acid side chains that coordinate a highly ordered H-bonded water network. This study uses a powerful approach, combining NMR solution studies with neutron protein crystallography, to determine the effect of pH and divalent cations on key residues involved in proton transfer in human carbonic anhydrase. Lastly, the results have broad implications for our understanding of proton transfer and how subtle changes in ionization and H-bonding interactions can modulate enzyme catalysis.

  15. Alkali metal ionization detector

    DOEpatents

    Bauerle, James E.; Reed, William H.; Berkey, Edgar

    1978-01-01

    Variations in the conventional filament and collector electrodes of an alkali metal ionization detector, including the substitution of helical electrode configurations for either the conventional wire filament or flat plate collector; or, the substitution of a plurality of discrete filament electrodes providing an in situ capability for transferring from an operationally defective filament electrode to a previously unused filament electrode without removing the alkali metal ionization detector from the monitored environment. In particular, the helical collector arrangement which is coaxially disposed about the filament electrode, i.e. the thermal ionizer, provides an improved collection of positive ions developed by the filament electrode. The helical filament design, on the other hand, provides the advantage of an increased surface area for ionization of alkali metal-bearing species in a monitored gas environment as well as providing a relatively strong electric field for collecting the ions at the collector electrode about which the helical filament electrode is coaxially positioned. Alternatively, both the filament and collector electrodes can be helical. Furthermore, the operation of the conventional alkali metal ionization detector as a leak detector can be simplified as to cost and complexity, by operating the detector at a reduced collector potential while maintaining the sensitivity of the alkali metal ionization detector adequate for the relatively low concentration of alkali vapor and aerosol typically encountered in leak detection applications.

  16. Study of atmospheric pressure weakly ionized plasma as surface compatibilization technique for improved plastic composites loaded with cellulose based fillers

    NASA Astrophysics Data System (ADS)

    Lekobou, William Pimakouon

    Atmospheric pressure plasmas have gained considerable interest from researchers recently for their unique prospective of engineering surfaces with plasma without the need of vacuum systems. They offer the advantage of low energy consumption, minimal capital cost and their simplicity as compared to conventional low pressure plasmas make them easy to upscale from laboratory to industry size. The present dissertation summarizes results of our attempt at applying atmospheric pressure weakly ionized plasma (APWIP) to the engineering of plastic composites filled with cellulose based substrates. An APWIP reactor was designed and built based on a multipoint-to-grounded ring and screen configurations. The carrier gas was argon and acetylene serves as the precursor molecule. The APWIP reactors showed capability of depositing plasma polymerized coating rich in carbon on substrates positioned within the electrode gap as well as downstream of the plasma discharge into the afterglow region. Our findings show that films grow by forming islands which for prolonged deposition time grow into thin films showing nodules, aggregates of nodules and microspheres. They also show chemical structure similar to films deposited from hydrocarbons with other conventional plasma techniques. The plasma polymerized deposits were used on substrates to modify their surface properties. Results show the surface of wood veneer and wood flour can be finely tuned from hydrophilic to hydrophobic. It was achieved by altering the topography of the surfaces along with their chemical composition. The wettability of wood veneer was investigated with contact angle measurements on capacitive drops and the capillary effect was utilized to assess surface properties of wood flour exposed to the discharges.

  17. P450-catalyzed vs. electrochemical oxidation of haloperidol studied by ultra-performance liquid chromatography/electrospray ionization mass spectrometry.

    PubMed

    Mali'n, Tove Johansson; Weidolf, Lars; Castagnoli, Neal; Jurva, Ulrik

    2010-05-15

    The metabolites formed via the major metabolic pathways of haloperidol in liver microsomes, N-dealkylation and ring oxidation to the pyridinium species, were produced by electrochemical oxidation and characterized by ultra-performance liquid chromatography/electrospray ionization mass spectrometry (UPLC/ESI-MS). Liver microsomal incubations and electrochemical oxidation in the presence of potassium cyanide (KCN) resulted in two diastereomeric cyano adducts, proposed to be generated from trapping of the endocyclic iminium species of haloperidol. Electrochemical oxidation of haloperidol in the presence of KCN gave a third isomeric cyano adduct, resulting from trapping of the exocyclic iminium species of haloperidol. In the electrochemical experiments, addition of KCN almost completely blocked the formation of the major oxidation products, namely the N-dealkylated products, the pyridinium species and a putative lactam. This major shift in product formation by electrochemical oxidation was not observed for the liver microsomal incubations where the N-dealkylation and the pyridinium species were the major metabolites also in the presence of KCN. The previously not observed dihydropyridinium species of haloperidol was detected in the samples, both from electrochemical oxidation and the liver microsomal incubations, in the presence of KCN. The presence of the dihydropyridinium species and the absence of the corresponding cyano adduct lead to the speculation that an unstable cyano adduct was formed, but that cyanide was eliminated to regenerate the stable conjugated system. The formation of the exocyclic cyano adduct in the electrochemical experiments but not in the liver microsomal incubations suggests that the exocyclic iminium intermediate, obligatory in the electrochemically mediated N-dealkylation, may not be formed in the P450-catalyzed reaction.

  18. Epicyclic Twin-Helix Ionization Cooling Simulations

    SciTech Connect

    Vasiliy Morozov, Yaroslav Derbenev, A. Afanaciev, R.P. Johnson

    2011-04-01

    Parametric-resonance Ionization Cooling (PIC) is proposed as the final 6D cooling stage of a highluminosity muon collider. For the implementation of PIC, we earlier developed an epicyclic twin-helix channel with correlated behavior of the horizontal and vertical betatron motions and dispersion. We now insert absorber plates with short energy-recovering units located next to them at the appropriate locations in the twin-helix channel. We first demonstrate conventional ionization cooling in such a system with the optics uncorrelated. We then adjust the correlated optics state and induce a parametric resonance to study ionization cooling under the resonant condition.

  19. The role of solvent structure in the absorption spectrum of solvated electrons: Mixed quantum/classical simulations in tetrahydrofuran

    NASA Astrophysics Data System (ADS)

    Bedard-Hearn, Michael J.; Larsen, Ross E.; Schwartz, Benjamin J.

    2005-04-01

    In polar fluids such as water and methanol, the peak of the solvated electron's absorption spectrum in the red has been assigned as a sum of transitions between an s-like ground state and three nearly degenerate p-like excited states bound in a quasispherical cavity. In contrast, in weakly polar solvents such as tetrahydrofuran (THF), the solvated electron has an absorption spectrum that peaks in the mid-infrared, but no definitive assignment has been offered about the origins of the spectrum or the underlying structure. In this paper, we present the results of adiabatic mixed quantum/classical molecular dynamic simulations of the solvated electron in THF, and provide a detailed explanation of the THF-solvated electron's absorption spectrum and electronic structure. Using a classical solvent model and a fully quantum mechanical excess electron, our simulations show that although the ground and first excited states are bound in a quasispherical cavity, a multitude of other, nearby solvent cavities support numerous, nearly degenerate, bound excited states that have little Franck-Condon overlap with the ground state. We show that these solvent cavities, which are partially polarized so that they act as electron trapping sites, are an inherent property of the way THF molecules pack in the liquid. The absorption spectrum is thus assigned to a sum of bound-to-bound transitions between a localized ground state and multiple disjoint excited states scattered throughout the fluid. Furthermore, we find that the usual spherical harmonic labels (e.g., s-like, p-like) are not good descriptors of the excited-state wave functions of the solvated electron in THF. Our observation of multiple disjoint excited states is consistent with femtosecond pump-probe experiments in the literature that suggest that photoexcitation of solvated electrons in THF causes them to relocalize into solvent cavities far from where they originated.

  20. Steady externally sustained discharge with electrodeless pulsed ionization in a closed-loop laser. III - Experimental study of the discharge and lasing

    NASA Astrophysics Data System (ADS)

    Generalov, N. A.; Kosynkin, V. D.; Zimakov, V. P.; Raizer, Iu. P.; Roitenburg, D. I.

    1980-09-01

    An experimental study is presented of the characteristics of a combination glow-discharge in a closed-cycle fast-flow CO2 laser and of the properties of closed-cycle laser action in this system. The discharge region was a plane channel 5.5 cm high and 76 cm wide; the cross-section area of the gas flow and the electric current was 420 sq cm; the discharge length was 65 cm; the discharge volume was 27 liters; and the gas velocity in the channel was varied from 0 to 220 m/sec. The following data were obtained: volt-ampere characteristics, limiting energy input and vibrational temperature, frequency of electron loss and attachment velocity, the effect of flow velocity on the volt-ampere characteristics, the dependence of energy input on the pulse repetition frequency, and the efficiency of excitation of oscillations. Evidence for the occurrence of ionization-overheating instability in the discharge is presented.

  1. An instrument combining an electrospray ionization source and a velocity-map imaging spectrometer for studying delayed electron emission of polyanions.

    PubMed

    Concina, Bruno; Papalazarou, Evangelos; Barbaire, Marc; Clavier, Christian; Maurelli, Jacques; Lépine, Franck; Bordas, Christian

    2016-03-01

    An instrument combining an electrospray ionization source and a velocity-map imaging (VMI) spectrometer has been developed in order to study the delayed electron emission of molecular anions and especially of polyanions. It operates at a high repetition rate (kHz) in order to increase the acquisition speed. The VMI spectrometer has been upgraded for nanosecond time resolution by gating the voltages applied on the position-sensitive detector. Kinetic energy release distribution of thermionic emission (without any contribution from direct detachment) can be recorded for well-defined delays after the nanosecond laser excitation. The capability of the instrument is demonstrated by recording photodetachment spectra of the benchmark C60(-) anion and C84(2-) dianion. PMID:27036754

  2. An instrument combining an electrospray ionization source and a velocity-map imaging spectrometer for studying delayed electron emission of polyanions

    NASA Astrophysics Data System (ADS)

    Concina, Bruno; Papalazarou, Evangelos; Barbaire, Marc; Clavier, Christian; Maurelli, Jacques; Lépine, Franck; Bordas, Christian

    2016-03-01

    An instrument combining an electrospray ionization source and a velocity-map imaging (VMI) spectrometer has been developed in order to study the delayed electron emission of molecular anions and especially of polyanions. It operates at a high repetition rate (kHz) in order to increase the acquisition speed. The VMI spectrometer has been upgraded for nanosecond time resolution by gating the voltages applied on the position-sensitive detector. Kinetic energy release distribution of thermionic emission (without any contribution from direct detachment) can be recorded for well-defined delays after the nanosecond laser excitation. The capability of the instrument is demonstrated by recording photodetachment spectra of the benchmark C60- anion and C842- dianion.

  3. Perceived Incidence and Importance of Lay-Ideas on Ionizing Radiation: Results of a Delphi-Study among Radiation-Experts.

    ERIC Educational Resources Information Center

    Eijkelhof, H. M. C.; And Others

    1990-01-01

    Described are lay-ideas which may exist about ionizing radiation, the importance of these ideas for risk management, and the relationships between various lay-ideas. Lay-ideas were used to gain a better insight into the problems of learning about ionizing radiation and to construct appropriate teaching materials and strategies. (KR)

  4. Atmospheric Chemistry of Tetrahydrofuran, 2-Methyltetrahydrofuran, and 2,5-Dimethyltetrahydrofuran: Kinetics of Reactions with Chlorine Atoms, OD Radicals, and Ozone.

    PubMed

    Andersen, Christina; Nielsen, Ole John; Østerstrøm, Freja F; Ausmeel, Stina; Nilsson, Elna J K; Sulbaek Andersen, Mads P

    2016-09-22

    FTIR smog chamber techniques were used to study the kinetics of the gas-phase reactions of Cl atoms, OD radicals, and O3 with the five-membered ring-structured compounds tetrahydrofuran (C4H8O, THF), 2-methyltetrahydrofuran (CH3C4H7O, 2-MTHF), 2,5-dimethyltetrahydrofuran ((CH3)2C4H5O, 2,5-DMTHF), and furan (C4H4O). The rate coefficients determined using relative rate methods were kTHF+Cl = (1.96 ± 0.24) × 10(-10), kTHF+OD = (1.81 ± 0.27) × 10(-11), kTHF+O3 = (6.41 ± 2.90) × 10(-21), k2-MTHF+Cl = (2.65 ± 0.43) × 10(-10), k2-MTHF+OD = (2.41 ± 0.51) × 10(-11), k2-MTHF+O3 = (1.87 ± 0.82) × 10(-20), k2,5-DMTHF+OD = (4.56 ± 0.68) × 10(-11), k2,5-DMTHF+Cl = (2.84 ± 0.34) × 10(-10), k2,5-DMTHF+O3 = (4.58 ± 2.18), kfuran+Cl = (2.39 ± 0.27) × 10(-10), and kfuran+O3 = (2.60 ± 0.31) × 10(-18) molecules cm(-3) s(-1). Rate coefficients of the reactions with ozone were also determined using the absolute rate method under pseudo-first-order conditions. OD radicals, in place of OH radicals, were produced from CD3ONO to avoid spectral overlap of isopropyl and methyl nitrite with the reactants. The kinetics of OD radical reactions are expected to resemble the kinetics of OH radical reactions, and the rate coefficients of the reactions with OD radicals were used to calculate the atmospheric lifetimes with respect to reactions with OH radicals. The lifetimes of THF, 2-MTHF, and 2,5-DMTHF are approximately 15, 12, and 6 h, respectively. PMID:27556743

  5. Neutral nanocluster chemistry studied by soft x-ray laser single-photon ionization: Application to soft x-ray optical surface contamination studies: Si mO n and Ti mO n

    NASA Astrophysics Data System (ADS)

    Heinbuch, S.; Dong, F.; Rocca, J. J.; Bernstein, E. R.

    2007-09-01

    Metal oxide clusters are employed in studies to help understand an important, specific, type of surface chemical problem: the contamination of soft x-ray mirrors by carbon deposits. Herein we report nanocluster chemistry studies that are relevant to the use of silicon oxide and titanium oxide capping layers. Systems involving Si mO n, and Ti mO n metal oxide nanoclusters are generated in a pulsed supersonic expansion/ablation source and passed through a reactor containing any reactant desired. The reaction products of these gas phase clusters are ionized using single photon ionization from a desk-top sized 46.9 nm Ne-like Ar laser providing the advantage of little or no fragmentation of desired nanoclusters. The ionized products are analyzed by a time of flight mass spectrometer and experimental results supply useful information related to condensed phase soft x-ray optical surfaces. The results illustrate the great potential of the use of very compact soft x-ray lasers in photochemistry and photophysics studies.

  6. Fuel cell with ionization membrane

    NASA Technical Reports Server (NTRS)

    Hartley, Frank T. (Inventor)

    2007-01-01

    A fuel cell is disclosed comprising an ionization membrane having at least one area through which gas is passed, and which ionizes the gas passing therethrough, and a cathode for receiving the ions generated by the ionization membrane. The ionization membrane may include one or more openings in the membrane with electrodes that are located closer than a mean free path of molecules within the gas to be ionized. Methods of manufacture are also provided.

  7. About the collapse of the 3.3 μm CH stretching band with ionization in polycyclic aromatic hydrocarbons: Configuration interaction and quantum Monte Carlo studies of the CH fragment

    NASA Astrophysics Data System (ADS)

    Pauzat, Françoise; Pilmé, Julien; Toulouse, Julien; Ellinger, Yves

    2010-08-01

    The puzzling difference between the IR spectra of polycyclic aromatic hydrocarbons (PAHs) and those of the corresponding positive ions (PAHs+) is a well documented fact, although the basic reason for it is far from clear. In this report, the CH fragment, in its neutral and ionized forms is taken as a case study for investigating the collapse of the CH stretching vibration with ionization. A comprehensive study of the dipole moment function around the equilibrium geometries of the fragments using large scale configuration interaction and quantum Monte Carlo methods shows very different variations with the CH distance: a marked decrease for neutral CH(Π2) and a perfect stability for ionized CH+(Σ1+). These results are consistent with strong/weak intensities of the CH vibrations in the neutral/ionized PAHs, the key point being the presence, or not, of a hole in the π shell. A topological analysis of the electronic densities shows that the collapse of the CH stretching with ionization is directly linked to the compensation between the internal charge transfer contribution and the distortion of the electronic density within the CH bond.

  8. Initial velocity distributions of ions generated by in-flight laser desorption/ionization of individual polystyrene latex microparticles as studied by the delayed ion extraction method.

    PubMed

    Vera, César Costa; Trimborn, Achim; Hinz, Klaus-Peter; Spengler, Bernhard

    2005-01-01

    The delayed ion extraction method has been used to study characteristics of the initial velocity distributions of positive and negative ions produced simultaneously by laser desorption/ionization (LDI) from non-impacted single aerosol polymeric particles, using a bipolar time-of-flight (TOF) instrument (LAMPAS 2). Due to the geometry of the setup and the characteristics of the ablation process, only the projections of the velocities on the axis of the mass spectrometer can be directly studied. Additionally, since the mean initial velocity under these conditions should be close to zero, it was necessary to extend the method by taking into account higher order contributions of the velocity distribution. Theoretical expressions for these higher order terms are presented and discussed. The bipolar characteristics of the instrument permit evaluation and treatment of a possible instrumental artifact caused by small inclinations of the ionizing laser with respect to the ideal incidence direction. Results of a number of experiments are presented and discussed in relation to the theoretical expressions presented, and to possible ablation scenarios. Evidence pointing out that, under our experimental conditions, only partial ablation of the latex particles occurs was obtained. The variance of the distribution of the projection of the initial velocities can be directly estimated from these results. By assuming that the total initial velocities of the ions are developed completely according to a single-temperature adiabatic expansion mechanism, temperatures of approximately 50 K/Da can be assigned to the ion clouds from the variance estimations. If a two-temperature model is used, a radial temperature of about 100 K/Da results. These values are in reasonable agreement with results for polymer ablation from the literature.

  9. A novel study of screening and confirmation of modafinil, adrafinil and their metabolite modafinilic acid under EI-GC-MS and ESI-LC-MS-MS ionization

    PubMed Central

    Dubey, S.; Ahi, S.; Reddy, I. M.; Kaur, T.; Beotra, A.; Jain, S.

    2009-01-01

    Objective: Adrafinil and modafinil have received wide publicity and have become controversial in the sporting world when several athletes were discovered allegedly using these drugs as doping agents. By acknowledging the facts, the World Anti-Doping Agency (WADA) banned these drugs in sports since 2004. The present study explores the possibility of differentiating adrafinil and modafinil and their major metabolites under electron impact ionization in gas chromatograph–mass spectrometer (GC-MSD) and electrospray ionization in liquid chromatograph–mass spectrometer (LC-MS/MS) by studying the fragmentation pattern of these drugs. Materials and Methods: Adrafinil, modafinil and their major metabolite, modafinilic acid were analyzed on EI-GC-MSD and ESI-LC-MS/MS using various individual parameters on both the instruments. The analytical technique and equipment used in the analysis were an Agilent 6890N GC with 5973 mass selective detector for the GC-MSD analysis and an Agilent 1100 HPLC with API-3200 Triple quadrupole mass spectrometer for the LC-MS/MS analysis. Validation of both methods was performed using six replicates at different concentrations. Result and Discussion: The results show that adrafinil, modafinil and their major metabolite modafinilic acid could be detected as a single artifact without differentiation under EI-GC-MSD analysis. However, all drugs could be detected and differentiated under ESI-LCMS/MS analysis without any artifaction. The GC-MSD analysis gives a single artifact for both the drugs without differentiation and thus can be used as a marker for screening purposes. Further, the Multiple Reaction Monitoring (MRM) method developed under LC-MS/MS is fit for the purpose for confirmation of suspicious samples in routine sports testing and in forensic and clinical analysis. PMID:20407560

  10. Risk of Cataract after Exposure to Low Doses of Ionizing Radiation: A 20-Year Prospective Cohort Study among US Radiologic Technologists

    PubMed Central

    Bekiroglu, Nural; Hauptmann, Michael; Alexander, Bruce H.; Freedman, D. Michal; Doody, Michele Morin; Cheung, Li C.; Simon, Steven L.; Weinstock, Robert M.; Bouville, André; Sigurdson, Alice J.

    2008-01-01

    The study aim was to determine the risk of cataract among radiologic technologists with respect to occupational and nonoccupational exposures to ionizing radiation and to personal characteristics. A prospective cohort of 35,705 cataract-free US radiologic technologists aged 24–44 years was followed for nearly 20 years (1983–2004) by using two follow-up questionnaires. During the study period, 2,382 cataracts and 647 cataract extractions were reported. Cigarette smoking for ≥5 pack-years; body mass index of ≥25 kg/m2; and history of diabetes, hypertension, hypercholesterolemia, or arthritis at baseline were significantly (p ≤ 0.05) associated with increased risk of cataract. In multivariate models, self-report of ≥3 x-rays to the face/neck was associated with a hazard ratio of cataract of 1.25 (95% confidence interval: 1.06, 1.47). For workers in the highest category (mean, 60 mGy) versus lowest category (mean, 5 mGy) of occupational dose to the lens of the eye, the adjusted hazard ratio of cataract was 1.18 (95% confidence interval: 0.99, 1.40). Findings challenge the National Council on Radiation Protection and International Commission on Radiological Protection assumptions that the lowest cumulative ionizing radiation dose to the lens of the eye that can produce a progressive cataract is approximately 2 Gy, and they support the hypothesis that the lowest cataractogenic dose in humans is substantially less than previously thought. PMID:18664497

  11. Multiphoton ionization studies of metal atom-solvent interactions from thevan der Waals dimer to the mesoscopic scale

    NASA Astrophysics Data System (ADS)

    Spotts, James Michael

    A unified molecular-level description of solute-solvent interactions within condensed-phase systems has remained elusive despite recent advances towards the detailed understanding of the fundamental electrostatic interactions between the atomic and/or molecular moieties that compose a bulk system. Through the use of simplified cluster model systems such as those employing metal atoms solvated by a rare gas solvent, however, microscopic details pertaining to the intrinsic composite nature of the atomic orbital interactions can be effectively dissected away from the complexity inherent to condensed- phase systems. This thesis work presents a systematic spectroscopic investigation of Al/cdot Arn/ (n /leq 60) clusters generated by standard laser ablation techniques using 1/sp'UV + 1vis two-color and 2vis+1vis single-color resonance-enhanced multiphoton ionization (REMPI) in the vicinity of the Al(3d) gets Al(3p) atomic transitions. UV absorption spectra were collected for Al/cdot Arn cluster sizes corresponding to solvation within the first icosahedral solvation shell ( 1/leq n/leq12) as well as the second icosahedral solvation shell (13/leq n/leq 54). These spectra exhibited significant red-shifted absorption features whose absolute peak positions were noted to be highly sensitive to the degree of solvation. Such behavior was strongly suggestive of an aluminum atom surface binding site. Nevertheless, classical Monte Carlo simulations failed to reproduce the observed magnitude of the spectral shifts. Consequently, the underlying origin of this anomalous spectral behavior was believed to derive from electronic state mixing interactions between those states originating from the Al(3d) and Al(4p) electronic manifolds. Evidence for such a coupling was sought at the level of the diatomic AlċAr molecule using both 1/sp'UV+1vis and 2vis+1vis REMPI to characterize all electronic states arising from the Al(3d)ċAr and Al(4p)ċAr asymptotes. Strong evidence for state mixing was

  12. Ionizing radiation and cancer prevention.

    PubMed Central

    Hoel, D G

    1995-01-01

    Ionizing radiation long has been recognized as a cause of cancer. Among environmental cancer risks, radiation is unique in the variety of organs and tissues that it can affect. Numerous epidemiological studies with good dosimetry provide the basis for cancer risk estimation, including quantitative information derived from observed dose-response relationships. The amount of cancer attributable to ionizing radiation is difficult to estimate, but numbers such as 1 to 3% have been suggested. Some radiation-induced cancers attributable to naturally occurring exposures, such as cosmic and terrestrial radiation, are not preventable. The major natural radiation exposure, radon, can often be reduced, especially in the home, but not entirely eliminated. Medical use of radiation constitutes the other main category of exposure; because of the importance of its benefits to one's health, the appropriate prevention strategy is to simply work to minimize exposures. PMID:8741791

  13. Martian Meteor Ionization Layers

    NASA Technical Reports Server (NTRS)

    Grebowsky, J. M.; Pesnell, W. D.

    1999-01-01

    Small interplanetary grains bombard Mars, like all the solar system planets, and, like all the planets with atmospheres, meteoric ion and atom layers form in the upper atmosphere. We have developed a comprehensive one-dimensional model of the Martian meteoric ionization layer including a full chemical scheme. A persistent layer of magnesium ions should exist around an altitude of 70 km. Unlike the terrestrial case, where the metallic ions are formed via charge-exchange with the ambient ions, Mg(+) in the Martian atmosphere is produced by photoionization. Nevertheless, the predicted metal layer peak densities for Earth and Mars are similar. Diffusion solutions, such as those presented here, should be a good approximation of the metallic ions in regions where the magnetic field is negligible and may provide a significant contribution to the nightside ionosphere. The low ultraviolet absorption of the Martian atmosphere may make Mars an excellent laboratory in which to study meteoric ablation. Resonance lines not seen in the spectra of terrestrial meteors may be visible to a surface observatory in the Martian highlands.

  14. Low-density ionization behavior

    SciTech Connect

    Baker, G.A. Jr.

    1995-04-01

    As part of a continuing study of the physics of matter under extreme conditions, I give some results on matter at extremely low density. In particular I compare a quantum mechanical calculation of the pressure for atomic hydrogen with the corresponding pressure given by Thomas-Fermi theory. (This calculation differs from the ``confined atom`` approximation in a physically significant way.) Since Thomas-Fermi theory in some sense, represents the case of infinite nuclear charge, these cases should represent extremes. Comparison is also made with Saha theory, which considers ionization from a chemical point of view, but is weak on excited-state effects. In this theory, the pressure undergoes rapid variation as electron ionization levels are passed. This effect is in contrast to the smooth behavior of the Thomas-Fermi fixed temperature, complete ionization occurs in the low density limit, I study the case where the temperature goes appropriately to zero with the density. Although considerable modification is required, Saha theory is closer to the actual results for this case than is Thomas-Fermi theory.

  15. Carbonic acid ionization and the stability of sodium bicarbonate and carbonate ion pairs to 200 °C - A potentiometric and spectrophotometric study

    NASA Astrophysics Data System (ADS)

    Stefánsson, Andri; Bénézeth, Pascale; Schott, Jacques

    2013-11-01

    Carbonic acid ionization and sodium bicarbonate and carbonate ion pair formation constants have been experimentally determined in dilute hydrothermal solutions to 200 °C. Two experimental approaches were applied, potentiometric acid-base titrations at 10-60 °C and spectrophotometric pH measurements using the pH indicators, 2-napthol and 4-nitrophenol, at 25-200 °C. At a given temperature, the first and second ionization constants of carbonic acid (K1, K2) and the ion pair formation constants for NaHCO(aq)(K) and NaCO3-(aq)(K) were simultaneously fitted to the data. Results of this study compare well with previously determined values of K1 and K2. The NaHCO(aq) and NaCO3-(aq) ion pair formation constants vary between 25 and 200 °C having values of logK=-0.18 to 0.58 and logK=1.01 to 2.21, respectively. These ion pairs are weak at low-temperatures but become increasingly important with increasing temperature under neutral to alkaline conditions in moderately dilute to concentrated NaCl solutions, with NaCO3-(aq) predominating over CO32-(aq) in ⩾0.1 M NaCl solution at temperatures above 100 °C. The results demonstrate that NaCl cannot be considered as an inert (non-complexing) electrolyte in aqueous carbon dioxide containing solutions at elevated temperatures.

  16. Mass spectrometry of solid samples in open air using combined laser ionization and ambient metastable ionization

    NASA Astrophysics Data System (ADS)

    He, X. N.; Xie, Z. Q.; Gao, Y.; Hu, W.; Guo, L. B.; Jiang, L.; Lu, Y. F.

    2012-01-01

    Mass spectrometry of solid samples in open air was carried out using combined laser ionization and metastable ionization time-of-flight mass spectrometry (LI-MI-TOFMS) in ambient environment for qualitative and semiquantitative (relative analyte information, not absolute information) analysis. Ambient metastable ionization using a direct analysis in realtime (DART) ion source was combined with laser ionization time-of-flight mass spectrometry (LI-TOFMS) to study the effects of combining metastable and laser ionization. A series of metallic samples from the National Institute of Standards and Technology (NIST 494, 495, 498, 499, and 500) and a pure carbon target were characterized using LI-TOFMS in open air. LI-MI-TOFMS was found to be superior to laser-induced breakdown spectroscopy (LIBS). Laser pulse energies between 10 and 200 mJ at the second harmonic (532 nm) of an Nd:YAG laser were applied in the experiment to obtain a high degree of ionization in plasmas. Higher laser pulse energy improves signal intensities of trace elements (such as Fe, Cr, Mn, Ni, Ca, Al, and Ag). Data were analyzed by numerically calculating relative sensitivity coefficients (RSCs) and limit of detections (LODs) from mass spectrometry (MS) and LIBS spectra. Different parameters, such as boiling point, ionization potential, RSC, LOD, and atomic weight, were shown to analyze the ionization and MS detection processes in open air.

  17. The keto- and imine-epoxide rearrangements in the formation of substituted tetrahydrofurans and piperidines: Synthesis of ([+-])-teneraic acid; approahces to ([+-])-nemorensic acid and (+)-desoxoprosopinine

    SciTech Connect

    Kucharczyk, R.

    1992-01-01

    Previous work by Wasserman and co-workers showed that 2,7-dioxabicyclo-[2.21]heptanes can be formed via a thermal of Lewis acid-catalyzed rearrangement of 3,4-epoxy ketones. The author utilized this keto-epoxide rearrangement in the approach to the synthesis of nemorensic acid. A novel reaction of Grignard reagents with bicyclic acetals was developed permitting the stereoselective construction o9f highly substituted tetrahydrofurans. Thus, treatment of 1,4-dimethy1-2,7-dioxa-bicyclo[2.21]heptane with vinyl magnesium bromide resulted in Lewis acid-catalyzed acetal opening with subsequent chelation-controlled addition of the vinyl group to afford the tetrasubstituted tetrahydrofuran. Further functional group transformations demonstrated the feasibility of this approach in forming substituted tetrahydrofurans related to nemorensic acid. The carbonyl-epoxide rearrangement described above has been extended to imine epoxides in earlier work by Rusiecki. The resulting bicyclic oxazolidines can be stereoselectively reduced with hydride reagents to form substituted piperidines. The utility was demonstrated of this rearrangement/reduction methodology in the synthesis of [+-]-teneraic acid. The key steps in the synthesis were the formation of the bicyclic oxazolidine via the imine-epoxide rearrangement, and stereoselective hydride reduction to yield the trans piperidine. Oxidation of the t-butyloxycarbonyl-protected piperidine diol to the diacid, followed by deprotection of the amine, completed the synthesis of [+-]-teneraic acid. In seeking to apply the imine-epoxide rearrangement/reduction methodology in enantioselective syntheses, the author investigated an approach to the synthesis of (+)-desoxoprosopinine. This work has resulted in the successful construction of the desired intermediate keto epoxide which, with zinc chloride, rearranges cleanly to the corresponding bicyclic acetal. The corresponding imine-epoxide rearrangement has not been accomplished.

  18. FT-Raman spectroscopic analysis of the most probable structures in aluminum chloride and tetrahydrofuran solutions

    NASA Astrophysics Data System (ADS)

    Alves, Carolina C.; Campos, Thiago B. C.; Alves, Wagner A.

    2012-11-01

    A study by concentration-dependent Raman spectroscopy is presented for solutions of AlCl3 in THF. The formation of small amounts of AlCl4- has been evidenced by the appearance of only one band at 348 cm-1 in the most diluted salt solution. Another band at 330 cm-1 starts rising with increasing salt concentration and it seems to belong to the [AlCl3(THF)3] complex. Indeed, this octahedral entity was confirmed by the quantitative analysis performed at the band envelope at 915 cm-1. At this region, additional bands at 927 and 858 cm-1 were observed and assigned to the C-C and C-O stretching modes, respectively, of THF molecules coordinated to the aluminum salt. Besides them, another band at 1042 cm-1 clearly reveals the existence of this population of molecules. Although neutral octahedral complexes seem to be the major species in more concentrated salt solutions, the Raman spectra show the presence of complex ions in whole studied concentration range.

  19. Theory of dissociative tunneling ionization

    NASA Astrophysics Data System (ADS)

    Svensmark, Jens; Tolstikhin, Oleg I.; Madsen, Lars Bojer

    2016-05-01

    We present a theoretical study of the dissociative tunneling ionization process. Analytic expressions for the nuclear kinetic energy distribution of the ionization rates are derived. A particularly simple expression for the spectrum is found by using the Born-Oppenheimer (BO) approximation in conjunction with the reflection principle. These spectra are compared to exact non-BO ab initio spectra obtained through model calculations with a quantum mechanical treatment of both the electronic and nuclear degrees of freedom. In the regime where the BO approximation is applicable, imaging of the BO nuclear wave function is demonstrated to be possible through reverse use of the reflection principle, when accounting appropriately for the electronic ionization rate. A qualitative difference between the exact and BO wave functions in the asymptotic region of large electronic distances is shown. Additionally, the behavior of the wave function across the turning line is seen to be reminiscent of light refraction. For weak fields, where the BO approximation does not apply, the weak-field asymptotic theory describes the spectrum accurately.

  20. Saffloflavonesides A and B, two rearranged derivatives of flavonoid C-glycosides with a furan-tetrahydrofuran ring from Carthamus tinctorius.

    PubMed

    He, Jun; Yang, Ya-Nan; Jiang, Jian-Shuang; Feng, Zi-Ming; Zhang, Pei-Cheng

    2014-11-01

    Two new rearranged derivatives of flavonoid C-glycosides, saffloflavonesides A (1) and B (2), were isolated from the florets of Carthamus tinctorius. Their structures were determined using UV, IR, HRESIMS, and 1D and 2D NMR data and by comparing experimental and calculated electronic circular dichroism (ECD) spectra. Compounds 1 and 2 were unprecedented chalcone and flavanone derivatives possessing a furan conjoining tetrahydrofuran ring. A potential biosynthetic pathway was proposed. At 10 μM, 1 and 2 both showed strong inhibitory activity against PC12 cell damage induced by rotenone.

  1. Mn-catalyzed three-component reactions of imines/nitriles, Grignard reagents, and tetrahydrofuran: an expedient access to 1,5-amino/keto alcohols.

    PubMed

    He, Ruoyu; Jin, Xiqing; Chen, Hui; Huang, Zhi-Tang; Zheng, Qi-Yu; Wang, Congyang

    2014-05-01

    An expedient Mn-catalyzed three-component synthesis of 1,5-amino/keto alcohols from Grignard reagents, imines/nitriles, and tetrahydrofuran (THF) is described, which deviates from the classic Grignard addition to imines/nitriles in THF solvent. THF is split and "sewn" in an unprecedented manner in the reaction, leading to the formation of two geminal C-C bonds via C-H and C-O cleavage. Mechanistic experiments and DFT calculations reveal radical and organo-Mn intermediates in the catalytic cycle and the α-arylative ring-opening of THF as the key reaction step. PMID:24754481

  2. NMR spectroscopy of organolithium compounds. XXVI--The aggregation behaviour of methyllithium in the presence of LiBr and LiI in diethyl ether and tetrahydrofuran.

    PubMed

    Fox, Thomas; Hausmann, Heike; Günther, Harald

    2004-09-01

    1H, 6Li and 13C NMR spectroscopy were used to determine the structure of aggregates formed in mixtures of methyllithium, H3CLi, and lithium bromide and iodide in diethyl ether and tetrahydrofuran. From the chemical shifts, the signal intensity distribution and the isotope shifts observed for partially deuterated systems, it was shown that generally tetrameric structures with different halogen contents dominate. For methyllithium-lithium bromide (1:1) in THF a considerable concentration of an H3CLi-LiBr dimer was found. For the first time, deuterium-induced 6Li isotope shifts over four bonds were observed.

  3. Simulations of ionization in a hot cavity surface ion source

    SciTech Connect

    Turek, M.; Drozdziel, A.; Pyszniak, K.; MaPczka, D.; Slowinski, B.

    2012-02-15

    A new numerical Monte Carlo method based model of a hot cavity surface ionization ion source is presented in this paper. The model, intended to support the studies on ionization phenomena in a widely used class of ion sources, takes into account geometry of the ion source and extraction system, ionizer temperature and other features. The results of ion source efficiency calculations for various configurations of the extraction field are reviewed. The dominant role of the ionizer region near the extraction opening is described. Simulated dependences of ionization efficiency on the working parameters like ionizer length and temperature, ionization potential of the substance, and extraction voltage are discussed. A good agreement of the experimental data (e.g., influence of ionizer temperature, current-voltage curve) and the predictions of the model is found. It is also shown that the contribution to the ionization yield from impact of thermionic electrons accelerated by the extraction field may be significant, especially for the substances of small surface ionization coefficient. The simulation results are compared to the predictions of different theoretical models of the ion source--the obtained simulation data are in accordance both with a well-known Kirchner formula and the so called spherical ionizer model.

  4. Ambient ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Lebedev, A. T.

    2015-07-01

    Ambient ionization mass spectrometry emerged as a new scientific discipline only about ten years ago. A considerable body of information has been reported since that time. Keeping the sensitivity, performance and informativity of classical mass spectrometry methods, the new approach made it possible to eliminate laborious sample preparation procedures and triggered the development of miniaturized instruments to work directly in the field. The review concerns the theoretical foundations and design of ambient ionization methods. Their advantages and drawbacks, as well as prospects for application in chemistry, biology, medicine, environmetal analysis, etc., are discussed. The bibliography includes 194 references.

  5. Diagnosing transient ionization in dynamic events

    NASA Astrophysics Data System (ADS)

    Doyle, J. G.; Giunta, A.; Madjarska, M. S.; Summers, H.; O'Mullane, M.; Singh, A.

    2013-09-01

    Aims: The present study aims to provide a diagnostic line ratio that will enable the observer to determine whether a plasma is in a state of transient ionization. Methods: We use the Atomic Data and Analysis Structure (ADAS) to calculate line contribution functions for two lines, Si iv 1394 Å and O iv 1401 Å, formed in the solar transition region. The generalized collisional-radiative theory is used. It includes all radiative and electron collisional processes, except for photon-induced processes. State-resolved direct ionization and recombination to and from the next ionization stage are also taken into account. Results: For dynamic bursts with a decay time of a few seconds, the Si iv 1394 Å line can be enhanced by a factor of 2-4 in the first fraction of a second with the peak in the line contribution function occurring initially at a higher electron temperature due to transient ionization compared to ionization equilibrium conditions. On the other hand, the O iv 1401 Å does not show such any enhancement. Thus the ratio of these two lines, which can be observed with the Interface Region Imaging Spectrograph, can be used as a diagnostic of transient ionization. Conclusions: We show that simultaneous high-cadence observations of two lines formed in the solar transition region may be used as a direct diagnostic of whether the observed plasma is in transient ionization. The ratio of these two lines can change by a factor of four in a few seconds owing to transient ionization alone.

  6. Alkali ionization detector

    DOEpatents

    Hrizo, John; Bauerle, James E.; Witkowski, Robert E.

    1982-01-01

    A calibration filament containing a sodium-bearing compound is included in combination with the sensing filament and ion collector plate of a sodium ionization detector to permit periodic generation of sodium atoms for the in-situ calibration of the detector.

  7. Advanced Thin Ionization Calorimeter (ATIC)

    NASA Technical Reports Server (NTRS)

    Wefel, John P.

    1998-01-01

    This is the final report for NASA grant NAGW-4577, "Advanced Thin Ionization Calorimeter (ATIC)". This grant covered a joint project between LSU and the University of Maryland for a Concept Study of a new type of fully active calorimeter to be used to measure the energy spectra of very high energy cosmic rays, particularly Hydrogen and Helium, to beyond 1014 eV. This very high energy region has been studied with emulsion chamber techniques, but never investigated with electronic calorimeters. Technology had advanced to the point that a fully active calorimeter based upon Bismuth Germanate (BGO) scintillating crystals appeared feasible for balloon flight (and eventually space) experiments.

  8. The effect of Non- ionizing electromagnetic field with a frequency of 50 Hz in Rat ovary: A transmission electron microscopy study

    PubMed Central

    Khaki, Amir Afshin; Khaki, Arash; Ahmadi, Seyed Shahin

    2016-01-01

    Background: Recently, there are increasing concerns and interests about the potential effects of Electromagnetic Field (EMF) on both human and animal health. Objective: The goal of this study was to evaluate the harmful effects of 50 Hz non-ionizing EMF on rat oocytes. Materials and Methods: In this experimental study 30 rats were randomly taken from laboratory animals and their ags and weights were determined. These 3 month's old rats were randomly divided into 3 groups. The control group consisted of 10 rats without receiving any treatment and kept under normal conditions. Experimental group 1 (10 rats) received EMF for 8 weeks (3 weeks intrauterine +5 weeks after births) and experimental group 2 (10 rats) received EMF for 13 weeks (3 weeks intrauterine +10 weeks after birth). After removing the ovaries and isolating follicles, granulosa cells were fixed in glutaraldehyde and osmium tetroxide. Electron microscopy was used to investigate the traumatic effects of EMF on follicles. Results: In control group nucleus membrane and mitochondria in follicle’s cytoplasm seemed normal in appearance. Theca layer of primary follicles in experimental group was separated clearly, zona layer demonstrated trot with irregular thickness and ovarian stroma seemed isolated with dilated vessels showing infiltration. Conclusion: According to the results of this study, it can be concluded that EMF has harmful effects on the ovarian follicles. PMID:27200427

  9. Modulated voltage metastable ionization detector

    NASA Technical Reports Server (NTRS)

    Carle, G. C.; Kojiro, D. R.; Humphrey, D. E. (Inventor)

    1985-01-01

    The output current from a metastable ionization detector (MID) is applied to a modulation voltage circuit. An adjustment is made to balance out the background current, and an output current, above background, is applied to an input of a strip chart recorder. For low level concentrations, i.e., low detected output current, the ionization potential will be at a maximum and the metastable ionization detector will operate at its most sensitive level. When the detected current from the metastable ionization detector increases above a predetermined threshold level, a voltage control circuit is activated which turns on a high voltage transistor which acts to reduce the ionization potential. The ionization potential applied to the metastable ionization detector is then varied so as to maintain the detected signal level constant. The variation in ionization potential is now related to the concentration of the constituent and a representative amplitude is applied to another input of said strip chart recorder.

  10. Use of 'small but smart' libraries to enhance the enantioselectivity of an esterase from Bacillus stearothermophilus towards tetrahydrofuran-3-yl acetate.

    PubMed

    Nobili, Alberto; Gall, Markus G; Pavlidis, Ioannis V; Thompson, Mark L; Schmidt, Marlen; Bornscheuer, Uwe T

    2013-07-01

    Two libraries of simultaneous double mutations in the active site region of an esterase from Bacillus stearothermophilus were constructed to improve the enantioselectivity in the hydrolysis of tetrahydrofuran-3-yl acetate. As screening of large mutant libraries is hampered by the necessity for GC/MS analysis, mutant libraries were designed according to a 'small but smart' concept. The design of focused libraries was based on data derived from a structural alignment of 3317 amino acid sequences of α/β-hydrolase fold enzymes with the bioinformatic tool 3DM. In this way, the number of mutants to be screened was substantially reduced as compared with a standard site-saturation mutagenesis approach. Whereas the wild-type esterase showed only poor enantioselectivity (E = 4.3) in the hydrolysis of (S)-tetrahydrofuran-3-yl acetate, the best variants obtained with this approach showed increased E-values of up to 10.4. Furthermore, some variants with inverted enantiopreference were found. PMID:23331978

  11. Crystal structure of (2',3,6'-tri-chloro-biphenyl-2-yl)boronic acid tetra-hydro-furan monosolvate.

    PubMed

    Durka, Krzysztof; Kliś, Tomasz; Serwatowski, Janusz

    2015-12-01

    The title compound, C12H8BCl3O2·C4H8O, crystallizes as a tetra-hydro-furan monosolvate. The boronic acid group adopts a syn-anti conformation and is significantly twisted along the carbon-boron bond by 69.2 (1)°, due to considerable steric hindrance from the 2',6'-di-chloro-phenyl group that is located ortho to the boronic acid substituent. The phenyl rings of the biphenyl are almost perpendicular to one another, with a dihedral angle of 87.9 (1)° between them. In the crystal, adjacent mol-ecules are linked via O-H⋯O inter-actions to form centrosymmetric dimers with R 2 (2)(8) motifs, which have recently been shown to be energetically very favourable. The hy-droxy groups are in an anti conformation and are also engaged in hydrogen-bonding inter-actions with the O atom of the tetra-hydro-furan solvent mol-ecule. Cl⋯Cl halogen-bonding inter-actions [Cl⋯Cl = 3.464 (1) Å] link neigbouring dimers into chains running along [010]. Further aggregation occurs due to an additional Cl⋯Cl halogen bond [Cl⋯Cl = 3.387 (1) Å]. PMID:26870407

  12. Simultaneous determination of Eleutheroside B and Eleutheroside E in rat plasma by high performance liquid chromatography-electrospray ionization mass spectrometry and its application in a pharmacokinetic study.

    PubMed

    Ma, Bo; Zhang, Qi; Liu, Yinhui; Li, Jing; Xu, Qiuyu; Li, Xiaotian; Yang, Xiaojing; Yao, Di; Sun, Jingjing; Cui, Guangbo; Ying, Hanjie

    2013-02-15

    Eleutheroside B and Eleutheroside E, two kinds of the major bioactive saponins of Eleutherococcus senticosus, play a pivotal role in biologic activity. In this study, a specific and sensitive high performance liquid chromatography-electrospray ionization-tandem mass spectrometry method (HPLC-MS/MS) was developed and validated for simultaneous determination of Eleutheroside B and Eleutheroside E in rat plasma. The analytes were extracted from rat plasma via a simple protein precipitation procedure with methanol and polygonin was used as internal standard. Chromatographic separation was achieved on a C18 column using a gradient elution program with acetonitrile and water containing 0.1% ammonium hydroxide solution as the mobile phase, with a flow rate of 0.2mL/min. The detection was performed on a triple-quadrupole tandem mass spectrometer by multiple reactions monitoring (MRM) mode in a negative ion mode via electrospray ionization (ESI). The transition monitored were m/z 371 [M-H](-)→209 for Eleutheroside B, m/z 741[M-H](-)→579 for Eleutheroside E and m/z 389[M-H](-)→277 for internal standard. Linear calibration curves were obtained in the concentration range of 1-2000ng/mL for both (Eleutheroside B and Eleutheroside E), with a lower limit of quantification of 1ng/mL. Extraction recovery was over 80% in plasma. The intra- and inter-day precision (RSD) values were below 12% and accuracy (RE) was -2.80 to 5.70% at three QC levels for both. The assay was successfully applied to study pharmacokinetics behavior in rats after oral and intravenous administration of the single substances (Eleutheroside B and Eleutheroside E). And further research was performed by comparing the difference in pharmacokinetic behavior between the single substances and an aqueous extract of E. senticosus after oral administration. Significant difference in pharmacokinetic characteristics between the single substances and an aqueous extract was found in rat, which would be beneficial for

  13. Utilization of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for structural studies related to biology and disease

    NASA Astrophysics Data System (ADS)

    Costello, Catherine E.; Helin, Jari; Ngoka, Lambert C. M.

    1996-04-01

    Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), because of its high sensitivity and relatively straightforward requirements for sample preparation, is contributing to the solution of structural problems in biology and to the development of therapeutic approaches through increased understanding of pharmacology and enhanced capabilities for quality control of pharmaceuticals. We are using a reflectron TOF- MS for the determination of molecular weights of individual compounds and the components of mixtures that are naturally occurring or are generated through enzymic digests, and employing the post-source decay mode to elucidate structural details. To maximize the sensitivity and information content of the spectra, varied matrices, derivative, and stepwise degradation procedures are being explored. Present studies include investigations of oligosaccharides, neutral glycolipids, gangliosides, glycoproteins, neuropeptides and proteins. Rules for fragmentation are being developed with model compounds and used for the structural elucidation of unknowns. When adequate sample amounts are available, the results are compared with low- and high-energy collision-induced decomposition spectra obtained with tandem MS in order to provide a data base for the correlation of spectral features and guidance in selection of approaches for scarce biological samples. Current projects include biophysical studies of glycoplipids, glycoproteins and oligosaccharides and investigations of the substance P receptor, transthyretin genetic variants and cisplatin-DNA interactions.

  14. A Genomic Study of DNA Alteration Events Caused by Ionizing Radiation in Human Embryonic Stem Cells via Next-Generation Sequencing

    PubMed Central

    Nguyen, Van; Panyutin, Irina V.; Panyutin, Igor G.; Neumann, Ronald D.

    2016-01-01

    Ionizing radiation (IR) is a known mutagen that is widely employed for medical diagnostic and therapeutic purposes. To study the extent of genetic variations in DNA caused by IR, we used IR-sensitive human embryonic stem cells (hESCs). Four hESC cell lines, H1, H7, H9, and H14, were subjected to IR at 0.2 or 1 Gy dose and then maintained in culture for four days before being harvested for DNA isolation. Irradiation with 1 Gy dose resulted in significant cell death, ranging from 60% to 90% reduction in cell population. Since IR is often implicated as a risk for inducing cancer, a primer pool targeting genomic “hotspot” regions that are frequently mutated in human cancer genes was used to generate libraries from irradiated and control samples. Using a semiconductor-based next-generation sequencing approach, we were able to consistently sequence these samples with deep coverage for reliable data analysis. A possible rare nucleotide variant was identified in the KIT gene (chr4:55593481) exclusively in H1 hESCs irradiated with 1 Gy dose. More extensive further studies are warranted to assess the extent and distribution of genetic changes in hESCs after IR exposure. PMID:26709353

  15. A Genomic Study of DNA Alteration Events Caused by Ionizing Radiation in Human Embryonic Stem Cells via Next-Generation Sequencing.

    PubMed

    Nguyen, Van; Panyutin, Irina V; Panyutin, Igor G; Neumann, Ronald D

    2016-01-01

    Ionizing radiation (IR) is a known mutagen that is widely employed for medical diagnostic and therapeutic purposes. To study the extent of genetic variations in DNA caused by IR, we used IR-sensitive human embryonic stem cells (hESCs). Four hESC cell lines, H1, H7, H9, and H14, were subjected to IR at 0.2 or 1 Gy dose and then maintained in culture for four days before being harvested for DNA isolation. Irradiation with 1 Gy dose resulted in significant cell death, ranging from 60% to 90% reduction in cell population. Since IR is often implicated as a risk for inducing cancer, a primer pool targeting genomic "hotspot" regions that are frequently mutated in human cancer genes was used to generate libraries from irradiated and control samples. Using a semiconductor-based next-generation sequencing approach, we were able to consistently sequence these samples with deep coverage for reliable data analysis. A possible rare nucleotide variant was identified in the KIT gene (chr4:55593481) exclusively in H1 hESCs irradiated with 1 Gy dose. More extensive further studies are warranted to assess the extent and distribution of genetic changes in hESCs after IR exposure. PMID:26709353

  16. Pharmacokinetic study of nobiletin and tangeretin in rat serum by high-performance liquid chromatography-electrospray ionization-mass spectrometry.

    PubMed

    Manthey, John A; Cesar, Thais B; Jackson, Erin; Mertens-Talcott, Susanne

    2011-01-12

    Nobiletin (NOB) and tangeretin (TAN), two of the main polymethoxylated flavones (PMFs) in citrus, influence a number of key biological pathways in mammalian cells. Although the impacts of NOB and TAN on glucose homeostasis and cholesterol regulation have been investigated in human clinical trials, much information is still lacking about the metabolism and oral bioavailability of these compounds in animals. In this study, NOB and TAN were administered to rats by gavage and intraperitoneal (ip) injection, and the blood serum concentrations of these compounds and their main metabolites were monitored by high-performance liquid chromatography-electrospray ionization-mass spectrometry (HPLC-ESI-MS). In addition to the administered compounds, two metabolites of TAN and eight metabolites of NOB were detected and measured over 24 h. With identical oral doses, nearly 10-fold higher absorption of NOB occurred compared to TAN. For both compounds, maximum levels of glucuronidated metabolites occurred in the blood serum at later time points (∼5-8 h) compared to the earlier T(max) values for NOB and TAN. In most cases the glucuronides occurred at substantially higher concentrations than the aglycone metabolites. Low levels of NOB and TAN and their metabolites were detectable in rat blood serum even at 24 h after treatment.

  17. Determination of bevantolol in human plasma using liquid chromatography-electrospray ionization tandem mass spectrometry and its application to a bioequivalence study.

    PubMed

    Ren, Li; Wang, Zheng; Lou, Yiceng; Zheng, Lu; Zheng, Heng; Yin, Chunping

    2014-05-15

    A liquid chromatography-electrospray ionization tandem mass spectrometry method was established and validated for the determination of bevantolol in human plasma using propranolol as the internal standard. The optimal chromatographic behavior of bevantolol and propranolol was achieved on a Welch Ultimate XB-C18 column (5 μm, 150 mm × 2.1mm, Maryland, USA) with a mobile phase of acetonitrile-water (40:60, v/v) containing 10mM ammonium acetate and 0.1% formic acid. The mass spectrometer was operated in selected reaction monitoring mode using the transition m/z 346.1>165.1 for bevantolol and m/z 260.3>116.1 for propranolol. Sample preparation was carried out through protein precipitation with acetonitrile. The calibration curves were linear over the range of 5.00-1,000 ng/ml. The intra- and inter-day precisions were less than 6.7% and 6.6%, respectively. This method was successfully applied to the bioequivalence study of two kinds of bevantolol hydrochloride tablets in 24 Chinese male volunteers in fasting and postprandial experiment.

  18. O 1s excitation and ionization processes in the CO2 molecule studied via detection of low-energy fluorescence emission

    NASA Astrophysics Data System (ADS)

    Kivimäki, A.; Alvarez-Ruiz, J.; Wasowicz, T. J.; Callegari, C.; de Simone, M.; Alagia, M.; Richter, R.; Coreno, M.

    2011-08-01

    Oxygen 1s excitation and ionization processes in the CO2 molecule have been studied with dispersed and non-dispersed fluorescence spectroscopy as well as with the vacuum ultraviolet (VUV) photon-photoion coincidence technique. The intensity of the neutral O emission line at 845 nm shows particular sensitivity to core-to-Rydberg excitations and core-valence double excitations, while shape resonances are suppressed. In contrast, the partial fluorescence yield in the wavelength window 300-650 nm and the excitation functions of selected O+ and C+ emission lines in the wavelength range 400-500 nm display all of the absorption features. The relative intensity of ionic emission in the visible range increases towards higher photon energies, which is attributed to O 1s shake-off photoionization. VUV photon-photoion coincidence spectra reveal major contributions from the C+ and O+ ions and a minor contribution from C2 +. No conclusive changes in the intensity ratios among the different ions are observed above the O 1s threshold. The line shape of the VUV-O+ coincidence peak in the mass spectrum carries some information on the initial core excitation.

  19. A study of the electron image due to ionizing events in a two-dimensional liquid argon TPC with a 24 cm drift gap

    NASA Astrophysics Data System (ADS)

    Bonetti, S.; Braggiotti, A.; Buckley, E.; Campanella, M.; Carugno, G.; Cecchet, G.; Cennini, P.; Centro, S.; Ciocio, A.; Cittolin, S.; Dainese, B.; Ferro-Luzzi, M.; Gasparini, F.; Gonidec, A.; Manfredi, P. F.; Meroni, E.; Muñoz, R.; Perreau, J.-M.; Pietropaolo, F.; Ptohos, F.; Ragusa, F.; Rossi, P.; Rubbia, C.; Schinzel, D.; Schmidt, W. F.; Seidl, W.

    1990-01-01

    We have tested a liquid argon time projection chamber with a novel wire configuration based on electrostatic focussing which allows the realization of a nondestructive detection of the electron image produced by ionizing events. The chamber was tested in a 5 GeV pion beam at the CERN proton synchrotron. The measured pulse shapes at both 200 V/cm and 500 V/cm were in very good agreement with the expected shapes, calculated taking into account the electron lifetime, the response of the electronics and the longitudinal diffusion of the electron cloud. The measured electron drift velocity was in good agreement with the results of other workers as well as with our previous measurements. We have also analysed a sample of events containing delta rays in order to study the behaviour of low-energy electrons in the liquid argon. We find that for electron energies greater than 5 MeV the measured energy spectrum agrees very well with the predicted spectrum after corrections for acceptance and energy loss, hence demonstrating the feasibility of recognizing low-energy electrons in liquid argon.

  20. Tevatron ionization profile monitoring

    SciTech Connect

    Jansson, A.; Bowie, K.; Fitzpatrick, T.; Kwarciany, R.; Lundberg, C.; Slimmer, D.; Valerio, L.; Zagel, J.; /Fermilab

    2006-06-01

    Ionization Profile monitors have been used in almost all machines at Fermilab. However, the Tevatron presents some particular challenges with its two counter-rotating, small beams, and stringent vacuum requirements. In order to obtain adequate beam size accuracy with the small signals available, custom made electronics from particle physics experiments was employed. This provides a fast (single bunch) and dead-timeless charge integration with a sensitivity in the femto-Coulomb range, bringing the system close to the single ionization electron detection threshold. The detector itself is based on a previous Main Injector prototype, albeit with many modifications and improvements. The first detector was installed at the end of 2005, and the second detector during the spring shutdown. The ultimate goal is to continuously monitor beam size oscillations at injection, as well as the beam size evolution during ramp and squeeze. Initial results are very encouraging.

  1. Gridded electron reversal ionizer

    NASA Technical Reports Server (NTRS)

    Chutjian, Ara (Inventor)

    1993-01-01

    A gridded electron reversal ionizer forms a three dimensional cloud of zero or near-zero energy electrons in a cavity within a filament structure surrounding a central electrode having holes through which the sample gas, at reduced pressure, enters an elongated reversal volume. The resultant negative ion stream is applied to a mass analyzer. The reduced electron and ion space-charge limitations of this configuration enhances detection sensitivity for material to be detected by electron attachment, such as narcotic and explosive vapors. Positive ions may be generated by generating electrons having a higher energy, sufficient to ionize the target gas and pulsing the grid negative to stop the electron flow and pulsing the extraction aperture positive to draw out the positive ions.

  2. Microwave Ionization of an Atomic Electron Wave Packet

    SciTech Connect

    Noel, Michael W.; Ko, Lung; Gallagher, T. F.

    2001-07-23

    A short microwave pulse is used to ionize a lithium Rydberg wave packet launched from the core at a well-defined phase of the field. We observe a strong dependence on the relative phase between the motion of the wave packet and the oscillations of the field. This phase dependent ionization is also studied as a function of the relative frequency. Our experimental observations are in good qualitative agreement with a one-dimensional classical model of wave packet ionization.

  3. Hysteresis of ionization waves

    SciTech Connect

    Dinklage, A.; Bruhn, B.; Testrich, H.; Wilke, C.

    2008-06-15

    A quasi-logistic, nonlinear model for ionization wave modes is introduced. Modes are due to finite size of the discharge and current feedback. The model consists of competing coupled modes and it incorporates spatial wave amplitude saturation. The hysteresis of wave mode transitions under current variation is reproduced. Sidebands are predicted by the model and found in experimental data. The ad hoc model is equivalent to a general--so-called universal--approach from bifurcation theory.

  4. Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Kelly, Ryan T.; Marginean, Ioan; Tang, Keqi

    2014-06-13

    Electrospray Ionization (ESI) is a process whereby gas phase ions are created from molecules in solution. As a solution exits a narrow tube in the presence of a strong electric field, an aerosol of charged droplets are is formed that produces gas phase ions as they it desolvates. ESI-MS comprises the creation of ions by ESI and the determination of their mass to charge ratio (m/z) by MS.

  5. Kinetic study of the oxidation and nitration of catechols in the presence of nitrous acid ionization equilibria.

    PubMed

    Khalafi, Lida; Rafiee, Mohammad

    2010-02-15

    Conversion of catechols to corresponding nitro derivatives in the presence of nitrous acid dissociation is studied using voltammetry and UV-vis spectrophotometry. The results indicate that the quinones derived from oxidation of catechols by nitrous acid participate in Michael addition reaction with nitrite ion in very mild acidic solutions. Rank annihilation factor analysis RAFA is applied to resolve the two-way kinetic spectra data measured from spectroscopic reactions. The rank of the original data matrix is reduced by one by annihilating the information of each component. It is shown that both reactions are drastically depends on pH and nitrous acid or nitrite ion percentage. The rate constants of oxidation and nitration reactions of catechol derivatives are obtained at the pHs around pK(a) of nitrous acid.

  6. Stability and dissociation dynamics of N2++ ions following core ionization studied by an Auger-electron-photoion coincidence method

    NASA Astrophysics Data System (ADS)

    Iwayama, H.; Kaneyasu, T.; Hikosaka, Y.; Shigemasa, E.

    2016-07-01

    An Auger-electron-photoion coincidence (AEPICO) method has been applied to study the stability and dissociation dynamics of dicationic states after the N K-shell photoionization of nitrogen molecules. From time-of-flight and kinetic energy analyses of the product ions, we have obtained coincident Auger spectra associated with metastable states of N2++ ions and dissociative states leading to N2++ → N+ + N+ and N++ + N. To investigate the production of dissociative states, we present two-dimensional AEPICO maps which reveal the correlations between the binding energies of the Auger final states and the ion kinetic energy release. These correlations have been used to determine the dissociation limits of individual Auger final states.

  7. Bizarre (pseudomalignant) granulation-tissue reactions following ionizing-radiation exposure. A microscopic, immunohistochemical, and flow-cytometric study

    SciTech Connect

    Weidner, N.; Askin, F.B.; Berthrong, M.; Hopkins, M.B.; Kute, T.E.; McGuirt, F.W.

    1987-04-15

    Two patients developed extremely bizarre (pseudomalignant) granulation-tissue reactions in the larynx and facial sinuses, following radiation therapy for carcinoma. Containing pleomorphic spindle cells and numerous (sometimes atypical) mitotic figures, both tumefactive lesions simulated high grade malignancies. While the pleomorphic cells contained vimentin immunoreactivity, they were nonreactive for low or high molecular weight keratin. Flowcytometric study of paraffin-embedded tissues revealed DNA indexes of 0.75 and 1.0. Neither recurred locally nor spread distantly after therapy. Their granulation-tissue growth pattern, and the presence of stromal and endothelial cells showing similar degrees of cytologic atypia were central to their recognition as benign. These findings show that severely atypical, sometimes aneuploid, granulation-tissue reactions can occur following radiation exposure. Care should be taken not to misinterpret these lesions as malignant.

  8. Simultaneous determination of nitroglycerin and dinitrate metabolites in metabolism studies using liquid chromatography-mass spectrometry with electrospray ionization.

    PubMed

    Miyayama, Takashi; Tsou, Pei-Suen; Fung, Sun-Mi; Fung, Ho-Leung

    2006-05-01

    We have developed a liquid chromatographic-mass spectrometric method for the simultaneous determination of nitroglycerin (NTG) and its active metabolites, glyceryl 1,2-dinitrate (1,2-GDN) and glyceryl 1,3-dinitrate (1,3-GDN), for metabolism studies in cell cultures. 1,2,4-Butanetriol-1,4-dinitrate was chosen as an internal standard. Using a linear gradient of water/methanol containing 0.025 mM NH(4)Cl, the compounds were eluted within 12.5 min on an Allure Aqueous C(18) column (100 mm x 2.1 mm). Detection and quantification was achieved with multiple reaction monitoring in the negative ion mode. Intra- and inter-day variabilities for simultaneous determination of the three nitrates were below 10 and 18%, respectively, over a range of NTG and GDN concentrations of 0.5-15 ng/ml. The lower limit of quantification was found to be about 0.01 ng on column. Application of this method was illustrated through in vitro metabolism studies of NTG in culture media bathing LLC-PK1 cells and human vascular smooth muscle cells (HA-VSMC) at 37 degrees C. The degradation half-life of NTG was found to be 4.5 +/- 0.4 h and 39.2 +/- 0.02 h, respectively, for LLC-PK1 cells versus HA-VSMC. At 5 h, the 1,2-GDN versus 1,3-GDN metabolite distribution ratio in the bathing medium was found to be 1.5 +/- 0.1 and 0.2 +/- 0.02 for LLC-PK1 and HA-VSMC cells, respectively. With this method, the degradation half-life of NTG in rat plasma at 37 degrees C was shown to be 26.8 +/- 1.8 min, consistent with previous values obtained using gas chromatography.

  9. Ultrafast Electronuclear Dynamics of H2 Double Ionization

    NASA Astrophysics Data System (ADS)

    Saugout, Sébastien; Cornaggia, Christian; Suzor-Weiner, Annick; Charron, Eric

    2007-06-01

    The ultrafast electronic and nuclear dynamics of H2 laser-induced double ionization is studied using a time-dependent wave packet approach that goes beyond the fixed nuclei approximation. The double ionization pathways are analyzed by following the evolution of the total wave function during and after the pulse. The rescattering of the first ionized electron produces a coherent superposition of excited molecular states which presents a pronounced transient H+H- character. This attosecond excitation is followed by field-induced double ionization and by the formation of short-lived autoionizing states which decay via double ionization. These two double ionization mechanisms may be identified by their signatures imprinted in the kinetic-energy distribution of the ejected protons.

  10. Ionizing Radiation and Its Risks

    PubMed Central

    Goldman, Marvin

    1982-01-01

    Penetrating ionizing radiation fairly uniformly puts all exposed molecules and cells at approximately equal risk for deleterious consequences. Thus, the original deposition of radiation energy (that is, the dose) is unaltered by metabolic characteristics of cells and tissue, unlike the situation for chemical agents. Intensely ionizing radiations, such as neutrons and alpha particles, are up to ten times more damaging than sparsely ionizing sources such as x-rays or gamma rays for equivalent doses. Furthermore, repair in cells and tissues can ameliorate the consequences of radiation doses delivered at lower rates by up to a factor of ten compared with comparable doses acutely delivered, especially for somatic (carcinogenic) and genetic effects from x- and gamma-irradiation exposure. Studies on irradiated laboratory animals or on people following occupational, medical or accidental exposures point to an average lifetime fatal cancer risk of about 1 × 10-4 per rem of dose (100 per 106 person-rem). Leukemia and lung, breast and thyroid cancer seem more likely than other types of cancer to be produced by radiation. Radiation exposures from natural sources (cosmic rays and terrestrial radioactivity) of about 0.1 rem per year yield a lifetime cancer risk about 0.1 percent of the normally occurring 20 percent risk of cancer death. An increase of about 1 percent per rem in fatal cancer risk, or 200 rem to double the “background” risk rate, is compared with an estimate of about 100 rem to double the genetic risk. Newer data suggest that the risks for low-level radiation are lower than risks estimated from data from high exposures and that the present 5 rem per year limit for workers is adequate. PMID:6761969

  11. Study of the molecular structure, ionization spectrum, and electronic wave function of 1,3-butadiene using electron momentum spectroscopy and benchmark Dyson orbital theories

    NASA Astrophysics Data System (ADS)

    Deleuze, M. S.; Knippenberg, S.

    2006-09-01

    The scope of the present work is to reconcile electron momentum spectroscopy with elementary thermodynamics, and refute conclusions drawn by Saha et al. in J. Chem. Phys. 123, 124315 (2005) regarding fingerprints of the gauche conformational isomer of 1,3-butadiene in electron momentum distributions that were experimentally inferred from gas phase (e,2e) measurements on this compound [M. J. Brunger et al., J. Chem. Phys. 108, 1859 (1998)]. Our analysis is based on thorough calculations of one-electron and shake-up ionization spectra employing one-particle Green's function theory along with the benchmark third-order algebraic diagrammatic construction [ADC(3)] scheme. Accurate spherically averaged electron momentum distributions are correspondingly computed from the related Dyson orbitals. The ionization spectra and Dyson orbital momentum distributions that were computed for the trans-conformer of 1,3-butadiene alone are amply sufficient to quantitatively unravel the shape of all available experimental (e,2e) electron momentum distributions. A comparison of theoretical ADC(3) spectra for the s-trans and gauche energy minima with inner- and outer-valence high-resolution photoelectron measurements employing a synchrotron radiation beam [D. M. P. Holland et al., J. Phys. B 29, 3091 (1996)] demonstrates that the gauche structure is incompatible with ionization experiments in high-vacuum conditions and at standard temperatures. On the other hand, outer-valence Green's function calculations on the s-trans energy minimum form and approaching basis set completeness provide highly quantitative insights, within ˜0.2eV accuracy, into the available experimental one-electron ionization energies. At last, analysis of the angular dependence of relative (e,2e) ionization intensities nicely confirms the presence of one rather intense π-2 π*+1 satellite at ˜13.1eV in the ionization spectrum of the s-trans conformer.

  12. Electron impact ionization of the gas-phase sorbitol

    NASA Astrophysics Data System (ADS)

    Chernyshova, Irina; Markush, Pavlo; Zavilopulo, Anatoly; Shpenik, Otto

    2015-03-01

    Ionization and dissociative ionization of the sorbitol molecule by electron impact have been studied using two different experimental methods. In the mass range of m/ z = 10-190, the mass spectra of sorbitol were recorded at the ionizing electron energies of 70 and 30 eV. The ion yield curves for the fragment ions have been analyzed and the appearance energies of these ions have been determined. The relative total ionization cross section of the sorbitol molecule was measured using monoenergetic electron beam. Possible fragmentation pathways for the sorbitol molecule were proposed.

  13. Nondipole effects in strong-field ionization

    NASA Astrophysics Data System (ADS)

    Ivanov, I. A.; Dubau, J.; Kim, Kyung Taec

    2016-09-01

    We present a study of the relativistic nondipole effects in strong-field tunneling ionization process driven by a linearly polarized laser pulse. We consider the role of these effects in breaking the symmetry with respect to the inversion of the momentum component perpendicular to the laser-field polarization direction, which the dipole differential ionization probabilities possess. The study is based on the solution of a three-dimensional time-dependent Schrödinger equation taking into account the leading-order relativistic corrections.

  14. Dissociative Ionization of Pyridine by Electron Impact

    NASA Technical Reports Server (NTRS)

    Dateo, Christopher; Huo, Winifred; Kwak, Dochan (Technical Monitor)

    2002-01-01

    In order to understand the damage of biomolecules by electrons, a process important in radiation damage, we undertake a study of the dissociative ionization (DI) of pyridine (C5H5N) from the low-lying ionization channels. The methodology used is the same as in the benzene study. While no experimental DI data are available, we compare the dissociation products from our calculations with the dissociative photoionization measurements of Tixier et al. using dipole (e, e(+) ion) coincidence spectroscopy. Comparisons with the DI of benzene is also made so as to understand the difference in DI between a heterocyclic and an aromatic molecule.

  15. Measurement of the first ionization potential of astatine by laser ionization spectroscopy.

    PubMed

    Rothe, S; Andreyev, A N; Antalic, S; Borschevsky, A; Capponi, L; Cocolios, T E; De Witte, H; Eliav, E; Fedorov, D V; Fedosseev, V N; Fink, D A; Fritzsche, S; Ghys, L; Huyse, M; Imai, N; Kaldor, U; Kudryavtsev, Yuri; Köster, U; Lane, J F W; Lassen, J; Liberati, V; Lynch, K M; Marsh, B A; Nishio, K; Pauwels, D; Pershina, V; Popescu, L; Procter, T J; Radulov, D; Raeder, S; Rajabali, M M; Rapisarda, E; Rossel, R E; Sandhu, K; Seliverstov, M D; Sjödin, A M; Van den Bergh, P; Van Duppen, P; Venhart, M; Wakabayashi, Y; Wendt, K D A

    2013-01-01

    The radioactive element astatine exists only in trace amounts in nature. Its properties can therefore only be explored by study of the minute quantities of artificially produced isotopes or by performing theoretical calculations. One of the most important properties influencing the chemical behaviour is the energy required to remove one electron from the valence shell, referred to as the ionization potential. Here we use laser spectroscopy to probe the optical spectrum of astatine near the ionization threshold. The observed series of Rydberg states enabled the first determination of the ionization potential of the astatine atom, 9.31751(8) eV. New ab initio calculations are performed to support the experimental result. The measured value serves as a benchmark for quantum chemistry calculations of the properties of astatine as well as for the theoretical prediction of the ionization potential of superheavy element 117, the heaviest homologue of astatine. PMID:23673620

  16. Amplitude distribution of ionization jerks in ionization-chamber ASK-1 according long-term measurements

    NASA Astrophysics Data System (ADS)

    Timofeev, Vladislav

    2016-07-01

    As part of the Yakut complex systems by measuring the intensity of cosmic rays has a unique device spherical - ionization chamber ASK-1 with a lead screen thickness of 12 cm. The camera allows you to explore the physical characteristics of the so-called "ionization jerks " - sharp increases ionization current caused by the passage through the device much ionizing particles of cosmic origin. Due to a large increase in current nuclear cascade "showers", formed mainly by particles of cosmic rays in the camera screen. Over the entire period of observation (50 years old) camera ASK-1 was registered 59125 aftershocks. Their nature and properties still does not sufficiently studied, especially in medium and large amplitudes.

  17. Measurement of the first ionization potential of astatine by laser ionization spectroscopy

    PubMed Central

    Rothe, S.; Andreyev, A. N.; Antalic, S.; Borschevsky, A.; Capponi, L.; Cocolios, T. E.; De Witte, H.; Eliav, E.; Fedorov, D. V.; Fedosseev, V. N.; Fink, D. A.; Fritzsche, S.; Ghys, L.; Huyse, M.; Imai, N.; Kaldor, U.; Kudryavtsev, Yuri; Köster, U.; Lane, J. F. W.; Lassen, J.; Liberati, V.; Lynch, K. M.; Marsh, B. A.; Nishio, K.; Pauwels, D.; Pershina, V.; Popescu, L.; Procter, T. J.; Radulov, D.; Raeder, S.; Rajabali, M. M.; Rapisarda, E.; Rossel, R. E.; Sandhu, K.; Seliverstov, M. D.; Sjödin, A. M.; Van den Bergh, P.; Van Duppen, P.; Venhart, M.; Wakabayashi, Y.; Wendt, K. D. A.

    2013-01-01

    The radioactive element astatine exists only in trace amounts in nature. Its properties can therefore only be explored by study of the minute quantities of artificially produced isotopes or by performing theoretical calculations. One of the most important properties influencing the chemical behaviour is the energy required to remove one electron from the valence shell, referred to as the ionization potential. Here we use laser spectroscopy to probe the optical spectrum of astatine near the ionization threshold. The observed series of Rydberg states enabled the first determination of the ionization potential of the astatine atom, 9.31751(8) eV. New ab initio calculations are performed to support the experimental result. The measured value serves as a benchmark for quantum chemistry calculations of the properties of astatine as well as for the theoretical prediction of the ionization potential of superheavy element 117, the heaviest homologue of astatine. PMID:23673620

  18. Measurement of the first ionization potential of astatine by laser ionization spectroscopy.

    PubMed

    Rothe, S; Andreyev, A N; Antalic, S; Borschevsky, A; Capponi, L; Cocolios, T E; De Witte, H; Eliav, E; Fedorov, D V; Fedosseev, V N; Fink, D A; Fritzsche, S; Ghys, L; Huyse, M; Imai, N; Kaldor, U; Kudryavtsev, Yuri; Köster, U; Lane, J F W; Lassen, J; Liberati, V; Lynch, K M; Marsh, B A; Nishio, K; Pauwels, D; Pershina, V; Popescu, L; Procter, T J; Radulov, D; Raeder, S; Rajabali, M M; Rapisarda, E; Rossel, R E; Sandhu, K; Seliverstov, M D; Sjödin, A M; Van den Bergh, P; Van Duppen, P; Venhart, M; Wakabayashi, Y; Wendt, K D A

    2013-01-01

    The radioactive element astatine exists only in trace amounts in nature. Its properties can therefore only be explored by study of the minute quantities of artificially produced isotopes or by performing theoretical calculations. One of the most important properties influencing the chemical behaviour is the energy required to remove one electron from the valence shell, referred to as the ionization potential. Here we use laser spectroscopy to probe the optical spectrum of astatine near the ionization threshold. The observed series of Rydberg states enabled the first determination of the ionization potential of the astatine atom, 9.31751(8) eV. New ab initio calculations are performed to support the experimental result. The measured value serves as a benchmark for quantum chemistry calculations of the properties of astatine as well as for the theoretical prediction of the ionization potential of superheavy element 117, the heaviest homologue of astatine.

  19. Measurement of the first ionization potential of astatine by laser ionization spectroscopy

    NASA Astrophysics Data System (ADS)

    Rothe, S.; Andreyev, A. N.; Antalic, S.; Borschevsky, A.; Capponi, L.; Cocolios, T. E.; de Witte, H.; Eliav, E.; Fedorov, D. V.; Fedosseev, V. N.; Fink, D. A.; Fritzsche, S.; Ghys, L.; Huyse, M.; Imai, N.; Kaldor, U.; Kudryavtsev, Yuri; Köster, U.; Lane, J. F. W.; Lassen, J.; Liberati, V.; Lynch, K. M.; Marsh, B. A.; Nishio, K.; Pauwels, D.; Pershina, V.; Popescu, L.; Procter, T. J.; Radulov, D.; Raeder, S.; Rajabali, M. M.; Rapisarda, E.; Rossel, R. E.; Sandhu, K.; Seliverstov, M. D.; Sjödin, A. M.; van den Bergh, P.; van Duppen, P.; Venhart, M.; Wakabayashi, Y.; Wendt, K. D. A.

    2013-05-01

    The radioactive element astatine exists only in trace amounts in nature. Its properties can therefore only be explored by study of the minute quantities of artificially produced isotopes or by performing theoretical calculations. One of the most important properties influencing the chemical behaviour is the energy required to remove one electron from the valence shell, referred to as the ionization potential. Here we use laser spectroscopy to probe the optical spectrum of astatine near the ionization threshold. The observed series of Rydberg states enabled the first determination of the ionization potential of the astatine atom, 9.31751(8) eV. New ab initio calculations are performed to support the experimental result. The measured value serves as a benchmark for quantum chemistry calculations of the properties of astatine as well as for the theoretical prediction of the ionization potential of superheavy element 117, the heaviest homologue of astatine.

  20. Determination of 21-hydroxydeflazacort in human plasma by high-performance liquid chromatography/atmospheric pressure chemical ionization tandem mass spectrometry. Application to bioequivalence study.

    PubMed

    Ifa, D R; Moraes, M E; Moraes, M O; Santagada, V; Caliendo, G; de Nucci, G

    2000-03-01

    A liquid chromatographic atmospheric pressure chemical ionization tandem mass spectrometric method is described for the determination of 21-hydroxydeflazacort in human plasma using dexamethasone 21-acetate as an internal standard. The procedure requires a single diethyl ether extraction. After evaporation of the solvent under a nitrogen flow, the analytes are reconstituted in the mobile phase, chromatographed on a C18 reversed-phase column and analyzed by mass spectrometry via a heated nebulizer interface where they are detected by multiple reaction monitoring. The method has a chromatographic run time of less than 5 min and a linear calibration curve with a range of 1-400 ng ml(-1) (r>0.999). The between-run precision, based on the relative standard deviation for replicate quality controls, was < or =5.5% (10 ng ml(-1)), 1.0% (50 ng ml(-1)) and 2.7% (200 ng ml(-1)). The between-run accuracy was +/-7.1, 3.8 and 4.8% for the above concentrations, respectively. This method was employed in a bioequivalence study of two DFZ tablet formulations (Denacen from Marjan Industria e Comercio, Brazil, as a test formulation, and Calcort from Merrell Lepetit, Brazil, as a reference formulation) in 24 healthy volunteers of both sexes who received a single 30 mg dose of each formulation. The study was conducted using an open, randomized, two-period crossover design with a 7-day washout interval. The 90% confidence interval (CI) of the individual geometric mean ratio for Denacen/Calcort was 89.8-109.5% for area under the curve AUC(0-24 h) and 80.7-98.5% for Cmax. Since both the 90% CI for AUC(0-24 h) and Cmax were included in the 80-125% interval proposed by the US Food and Drug Administration, Denacen was considered bioequivalent to Calcort according to both the rate and extent of absorption.

  1. Determination of 21-hydroxydeflazacort in human plasma by high-performance liquid chromatography/atmospheric pressure chemical ionization tandem mass spectrometry. Application to bioequivalence study.

    PubMed

    Ifa, D R; Moraes, M E; Moraes, M O; Santagada, V; Caliendo, G; de Nucci, G

    2000-03-01

    A liquid chromatographic atmospheric pressure chemical ionization tandem mass spectrometric method is described for the determination of 21-hydroxydeflazacort in human plasma using dexamethasone 21-acetate as an internal standard. The procedure requires a single diethyl ether extraction. After evaporation of the solvent under a nitrogen flow, the analytes are reconstituted in the mobile phase, chromatographed on a C18 reversed-phase column and analyzed by mass spectrometry via a heated nebulizer interface where they are detected by multiple reaction monitoring. The method has a chromatographic run time of less than 5 min and a linear calibration curve with a range of 1-400 ng ml(-1) (r>0.999). The between-run precision, based on the relative standard deviation for replicate quality controls, was < or =5.5% (10 ng ml(-1)), 1.0% (50 ng ml(-1)) and 2.7% (200 ng ml(-1)). The between-run accuracy was +/-7.1, 3.8 and 4.8% for the above concentrations, respectively. This method was employed in a bioequivalence study of two DFZ tablet formulations (Denacen from Marjan Industria e Comercio, Brazil, as a test formulation, and Calcort from Merrell Lepetit, Brazil, as a reference formulation) in 24 healthy volunteers of both sexes who received a single 30 mg dose of each formulation. The study was conducted using an open, randomized, two-period crossover design with a 7-day washout interval. The 90% confidence interval (CI) of the individual geometric mean ratio for Denacen/Calcort was 89.8-109.5% for area under the curve AUC(0-24 h) and 80.7-98.5% for Cmax. Since both the 90% CI for AUC(0-24 h) and Cmax were included in the 80-125% interval proposed by the US Food and Drug Administration, Denacen was considered bioequivalent to Calcort according to both the rate and extent of absorption. PMID:10767775

  2. Ionization Energy: Implications of Preservice Teachers' Conceptions

    ERIC Educational Resources Information Center

    Tan, Kim Chwee Daniel; Taber, Keith S.

    2009-01-01

    The results from a study to explore pre-service teachers' understanding of ionization energy, a topic that features in A-level (grade 11 and 12) chemistry courses. in Singapore , is described. A previous study using a two-tier multiple choice diagnostic test has shown that Singapore A-level students have considerable difficulty understanding the…

  3. Two-step laser ionization schemes for in-gas laser ionization and spectroscopy of radioactive isotopes

    SciTech Connect

    Kudryavtsev, Yu. Ferrer, R.; Huyse, M.; Van den Bergh, P.; Van Duppen, P.; Vermeeren, L.

    2014-02-15

    The in-gas laser ionization and spectroscopy technique has been developed at the Leuven isotope separator on-line facility for the production and in-source laser spectroscopy studies of short-lived radioactive isotopes. In this article, results from a study to identify efficient optical schemes for the two-step resonance laser ionization of 18 elements are presented.

  4. Laboratory simulation of cometary neutral gas ionization

    NASA Astrophysics Data System (ADS)

    Chang, T.-F.; Rahman, H. U.; White, R. S.

    1989-05-01

    The laboratory simulation of the interaction of the solar wind with a comet is used to study the cometary neural gas ionization. The experiment is carried out in the UCR T-1 facility with an ice ball as the comet model. Photographs and data are taken with a variety of values of the solar wind velocity, interplanetary magnetic field (IMF), and comet configurations. The results show that the cometary neutral gas ionization depends on both the velocity of the solar wind and the interplanetary magnetic field. The plasma cloud surrounding the comet is visible only when the solar wind velocity and IMF are both above certain minimum values. This velocity dependent phenomena is explained by Alfven's critical ionization velocity effect. The critical magnetic field may be explained by assuming two stream lower hybrid instability as a triggering mechanism for the ionization of the neutral gas by plasma flow. Critical upper and lower limits for the magnetic field, required by anomalous ionization, are also derived that satisfy the experimental observations.

  5. Multiphoton ionization of large water clusters.

    PubMed

    Apicella, B; Li, X; Passaro, M; Spinelli, N; Wang, X

    2014-05-28

    Water clusters are multimers of water molecules held together by hydrogen bonds. In the present work, multiphoton ionization in the UV range coupled with time of flight mass spectrometry has been applied to water clusters with up to 160 molecules in order to obtain information on the electronic states of clusters of different sizes up to dimensions that can approximate the bulk phase. The dependence of ion intensities of water clusters and their metastable fragments produced by laser ionization at 355 nm on laser power density indicates a (3+1)-photon resonance-enhanced multiphoton ionization process. It also explains the large increase of ionization efficiency at 355 nm compared to that at 266 nm. Indeed, it was found, by applying both nanosecond and picosecond laser ionization with the two different UV wavelengths, that no water cluster sequences after n = 9 could be observed at 266 nm, whereas water clusters up to m/z 2000 Th in reflectron mode and m/z 3000 Th in linear mode were detected at 355 nm. The agreement between our findings on clusters of water, especially true in the range with n > 10, and reported data for liquid water supports the hypothesis that clusters above a critical dimension can approximate the liquid phase. It should thus be possible to study clusters just above 10 water molecules, for getting information on the bulk phase structure.

  6. Multiphoton ionization of large water clusters

    SciTech Connect

    Apicella, B.; Li, X.; Passaro, M.; Spinelli, N.; Wang, X.

    2014-05-28

    Water clusters are multimers of water molecules held together by hydrogen bonds. In the present work, multiphoton ionization in the UV range coupled with time of flight mass spectrometry has been applied to water clusters with up to 160 molecules in order to obtain information on the electronic states of clusters of different sizes up to dimensions that can approximate the bulk phase. The dependence of ion intensities of water clusters and their metastable fragments produced by laser ionization at 355 nm on laser power density indicates a (3+1)-photon resonance-enhanced multiphoton ionization process. It also explains the large increase of ionization efficiency at 355 nm compared to that at 266 nm. Indeed, it was found, by applying both nanosecond and picosecond laser ionization with the two different UV wavelengths, that no water cluster sequences after n = 9 could be observed at 266 nm, whereas water clusters up to m/z 2000 Th in reflectron mode and m/z 3000 Th in linear mode were detected at 355 nm. The agreement between our findings on clusters of water, especially true in the range with n > 10, and reported data for liquid water supports the hypothesis that clusters above a critical dimension can approximate the liquid phase. It should thus be possible to study clusters just above 10 water molecules, for getting information on the bulk phase structure.

  7. Engineered Ionizable Side Chains.

    PubMed

    Cymes, Gisela D; Grosman, Claudio

    2015-01-01

    One of the great challenges of mechanistic ion-channel biology is to obtain structural information from well-defined functional states. In the case of neurotransmitter-gated ion channels, the open-channel conformation is particularly elusive owing to its transient nature and brief mean lifetime. In this Chapter, we show how the analysis of single-channel currents recorded from mutants engineered to contain single ionizable side chains in the transmembrane region can provide specific information about the open-channel conformation without any interference from the closed or desensitized conformations. The method takes advantage of the fact that the alternate binding and unbinding of protons to and from an ionizable side chain causes the charge of the protein to fluctuate by 1 unit. We show that, in mutant muscle acetylcholine nicotinic receptors (AChRs), this fluctuating charge affects the rate of ion conduction in such a way that individual proton-transfer events can be identified in a most straightforward manner. From the extent to which the single-channel current amplitude is reduced every time a proton binds, we can learn about the proximity of the engineered side chain to the lumen of the pore. And from the kinetics of proton binding and unbinding, we can calculate the side-chain's affinity for protons (pK a), and hence, we can learn about the electrostatic properties of the microenvironment around the introduced ionizable group. The application of this method to systematically mutated AChRs allowed us to identify unambiguously the stripes of the M1, M2 and M3 transmembrane α-helices that face the pore's lumen in the open-channel conformation in the context of a native membrane. PMID:26381938

  8. Guided ionization waves: Theory and experiments

    NASA Astrophysics Data System (ADS)

    Lu, X.; Naidis, G. V.; Laroussi, M.; Ostrikov, K.

    2014-07-01

    This review focuses on one of the fundamental phenomena that occur upon application of sufficiently strong electric fields to gases, namely the formation and propagation of ionization waves-streamers. The dynamics of streamers is controlled by strongly nonlinear coupling, in localized streamer tip regions, between enhanced (due to charge separation) electric field and ionization and transport of charged species in the enhanced field. Streamers appear in nature (as initial stages of sparks and lightning, as huge structures-sprites above thunderclouds), and are also found in numerous technological applications of electrical discharges. Here we discuss the fundamental physics of the guided streamer-like structures-plasma bullets which are produced in cold atmospheric-pressure plasma jets. Plasma bullets are guided ionization waves moving in a thin column of a jet of plasma forming gases (e.g., He or Ar) expanding into ambient air. In contrast to streamers in a free (unbounded) space that propagate in a stochastic manner and often branch, guided ionization waves are repetitive and highly-reproducible and propagate along the same path-the jet axis. This property of guided streamers, in comparison with streamers in a free space, enables many advanced time-resolved experimental studies of ionization waves with nanosecond precision. In particular, experimental studies on manipulation of streamers by external electric fields and streamer interactions are critically examined. This review also introduces the basic theories and recent advances on the experimental and computational studies of guided streamers, in particular related to the propagation dynamics of ionization waves and the various parameters of relevance to plasma streamers. This knowledge is very useful to optimize the efficacy of applications of plasma streamer discharges in various fields ranging from health care and medicine to materials science and nanotechnology.

  9. Hybrid plan verification for intensity-modulated radiation therapy (IMRT) using the 2D ionization chamber array I'mRT MatriXX--a feasibility study.

    PubMed

    Dobler, Barbara; Streck, Natalia; Klein, Elisabeth; Loeschel, Rainer; Haertl, Petra; Koelbl, Oliver

    2010-01-21

    The 2D ionization chamber array I'mRT MatriXX (IBA, Schwarzenbruck, Germany) has been developed for absolute 2D dosimetry and verification of intensity-modulated radiation therapy (IMRT) for perpendicular beam incidence. The aim of this study is to evaluate the applicability of I'mRT MatriXX for oblique beam incidence and hybrid plan verification of IMRT with original gantry angles. For the assessment of angular dependence, open fields with gantry angles in steps of 10 degrees were calculated on a CT scan of I'mRT MatriXX. For hybrid plan verification, 17 clinical IMRT plans and one rotational plan were used. Calculations were performed with pencil beam (PB), collapsed cone (CC) and Monte Carlo (MC) methods, which had been previously validated. Measurements were conducted on an Elekta SynergyS linear accelerator. To assess the potential and limitations of the system, gamma evaluation was performed with different dose tolerances and distances to agreement. Hybrid plan verification passed the gamma test with 4% dose tolerance and 3 mm distance to agreement in all cases, in 82-88% of the cases for tolerances of 3%/3 mm, and in 59-76% of the cases if 3%/2 mm were used. Separate evaluation of the low dose and high dose regions showed that I'mRT MatriXX can be used for hybrid plan verification of IMRT plans within 3% dose tolerance and 3 mm distance to agreement with a relaxed dose tolerance of 4% in the low dose region outside the multileaf collimator (MLC).

  10. Equatorial ionization anomaly development as studied by GPS TEC and foF2 over Brazil: A comparison of observations with model results from SUPIM and IRI-2012

    NASA Astrophysics Data System (ADS)

    Nogueira, P. A. B.; Abdu, M. A.; Souza, J. R.; Batista, I. S.; Bailey, G. J.; Santos, A. M.; Takahashi, H.

    2013-11-01

    The equatorial ionization anomaly (EIA) development is studied using the total electron content (TEC) observed by the Global Positioning System (GPS) satellites, the F2-layer critical frequency (foF2) as measured by digisondes operated in the Brazilian sector, and by model simulation using the SUPIM (Sheffield University Plasmasphere Ionosphere Model). We have used two indices based on foF2 and TEC to represent the strength of the EIA Southern Anomaly Crest (SAC), which are denoted, respectively, by SAC(foF2) and SAC(TEC). Significant differences in the local time variations of the EIA intensity, as represented by these two indices, are investigated. The observed SAC indices are compared with their values modeled by the SUPIM and also by the International Reference Ionosphere (IRI)-2012. The SUPIM simulations that use the standard E×B plasma drift and neutral air wind models are found to provide acceptable representations of the observed foF2 and TEC, and hence the indices SAC(foF2) and SAC(TEC) during daytime, whereas the IRI-2012 model is not, except during the post-midnight/sunrise hours. It is found that the differences in the local time variations between the SAC(foF2) and SAC(TEC) can be reduced by limiting the TEC integrations in height up to an altitude of 630 km in the SUPIM calculations. It is also found that when the EIA intensity is calculated for an intermediate dip latitude (12°S) the difference between the local time variation patterns of the two corresponding indices in the experimental data and in the SUPIM results is reduced. For the IRI-2012 values, the subequatorial station modification does not appear to have any effect.

  11. Polymerase-chain reaction/electrospray ionization-mass spectrometry for the detection of bacteria and fungi in bronchoalveolar lavage fluids: a prospective observational study.

    PubMed

    Huttner, A; Emonet, S; Harbarth, S; Renzi, G; Kaiser, L; Schrenzel, J

    2014-12-01

    PLEX-ID uses polymerase chain reaction-electrospray ionization/mass spectrometry for rapid identification of infectious agents in clinical samples. We evaluated its concordance with our centre's standard methods (SM) for bacterial and fungal detection in bronchoalveolar lavage (BAL) fluid in a prospective observational cohort study. The primary outcome was concordance (%) between SM and PLEX-ID. Secondary outcomes included concordance when excluding commensal oral flora, detection of resistance genes, and PLEX-ID's potential impact on clinical management, as determined by two independent reviewers. Included were 101 specimens from 94 patients. BALs were performed primarily for suspected pneumonia (76/101, 75%) and lung transplant work-ups (12/101, 12%). Most specimens yielded at least one organism by either method (92/101, 91%). Among all microorganisms detected (n = 218), 83% and 17% were bacterial and fungal, respectively. Overall concordance between SM and PLEX-ID was 45% (45/101). Concordance increased to 66% (67/101) when discordance for commensal flora was excluded. PLEX-ID failed to detect 21% of all 183 SM-identified organisms, while SM did not identify 28% of the 191 PLEX-ID-identified organisms (p <0.001). There was low concordance for mecA detection. Two infectious-disease specialists' analyses concluded that in most of the 31 discordant, non-commensal cases, PLEX-ID results would have had little or no impact on patient management; in eight cases, however, PLEX-ID would have led to 'wrong decision-making'. The tested version of PLEX-ID concurred weakly with standard methods in the detection of bacteria and fungi in BAL specimens, and is not likely to be useful as a standalone tool for microbiological diagnosis in suspected respiratory infections.

  12. Theoretical IR spectra of ionized naphthalene

    NASA Technical Reports Server (NTRS)

    Pauzat, F.; Talbi, D.; Miller, M. D.; DeFrees, D. J.; Ellinger, Y.

    1992-01-01

    We report the results of a theoretical study of the effect of ionization on the IR spectrum of naphthalene, using ab initio molecular orbital theory. For that purpose we determined the structures, band frequencies, and intensities of neutral and positively ionized naphthalene. The calculated frequencies and intensities allowed an assignment of the most important bands appearing in the newly reported experimental spectrum of the positive ion. Agreement with the experimental spectrum is satisfactory enough to take into consideration the unexpected and important result that ionization significantly affects the intensities of most vibrations. A possible consequence on the interpretation of the IR interstellar emission, generally supposed to originate from polycyclic aromatic hydrocarbons (PAHs), is briefly presented.

  13. Ionization of polarized hydrogen atoms

    SciTech Connect

    Alessi, J.G.

    1983-01-01

    Methods are discussed for the production of polarized H/sup -/ ions from polarized atoms produced in ground state atomic beam sources. Present day sources use ionizers of two basic types - electron ionizers for H/sup +/ Vector production followed by double charge exchange in a vapor, or direct H/sup -/ Vector production by charge exchange of H/sup 0/ with Cs/sup 0/. Both methods have ionization efficiencies of less than 0.5%. Ionization efficiencies in excess of 10% may be obtained in the future by the use of a plasma ionizer plus charge exchange in Cs or Sr vapor, or ionization by resonant charge exchange with a self-extracted D/sup -/ beam from a ring magnetron or HCD source. 36 references, 4 figures.

  14. New Results in Electron-Atom Ionization

    NASA Astrophysics Data System (ADS)

    Madison, Don

    1997-10-01

    A deeper insight into atomic ionization by electron impact is gained by studying electron-electron correlation in a model-independent approach for calculating (e,2e) triply-differential cross sections using correlated (three-body) wave functions of arbitrary complexity. Results will be presented from the continuum distorted wave (CDW) model, three Coulomb-wave (3C) model, three-body distorted-wave Born approximation (3DWBA), Alt and Mukhamedzhanov (AM) model, dynamic-screening three Coulomb-wave (DS3C) model, and the eikonal approximation (EA). The sucesses and failures of the above models can be used to gain a better understanding of ionization processes.

  15. Characterization of a homemade ionization chamber for radiotherapy beams.

    PubMed

    Neves, Lucio P; Perini, Ana P; dos Santos, Gelson P; Xavier, Marcos; Khoury, Helen J; Caldas, Linda V E

    2012-07-01

    A homemade cylindrical ionization chamber was studied for routine use in therapy beams of (60)Co and X-rays. Several characterization tests were performed: leakage current, saturation, ion collection efficiency, polarity effect, stability, stabilization time, chamber orientation and energy dependence. All results obtained were within international recommendations. Therefore the homemade ionization chamber presents usefulness for routine dosimetric procedures in radiotherapy beams.

  16. Spectroscopy of triply and quadruply ionized states of mercury

    SciTech Connect

    Huttula, M.; Huttula, S.-M.; Lablanquie, P.; Palaudoux, J.; Penent, F.; Andric, L.; Eland, J. H. D.

    2011-03-15

    Multielectron coincidence spectroscopy has been used to study multiple ionization of atomic mercury. The binding energies of triply and quadruply ionized states of Hg have been determined from three- and fourfold electron coincidences. Relativistic ab initio theory has been used to calculate the state energies and predict the experimental findings.

  17. Nonsequential double ionization of molecules

    SciTech Connect

    Prauzner-Bechcicki, Jakub S.; Sacha, Krzysztof; Zakrzewski, Jakub; Eckhardt, Bruno

    2005-03-01

    Double ionization of diatomic molecules by short linearly polarized laser pulses is analyzed. We consider the final stage of the ionization process, that is the decay of a highly excited two electron molecule, which is formed after rescattering. The saddles of the effective adiabatic potential energy close to which simultaneous escape of electrons takes place are identified. Numerical simulations of the ionization of molecules show that the process can be dominated by either sequential or nonsequential events. In order to increase the ratio of nonsequential to sequential ionizations very short laser pulses should be applied.

  18. Inter-rater agreement for a retrospective exposure assessment of asbestos, chromium, nickel and welding fumes in a study of lung cancer and ionizing radiation.

    PubMed

    Seel, E A; Zaebst, D D; Hein, M J; Liu, J; Nowlin, S J; Chen, P

    2007-10-01

    A retrospective exposure assessment of asbestos, welding fumes, chromium and nickel (in welding fumes) was conducted at the Portsmouth Naval Shipyard for a nested case-control study of lung cancer risk from external ionizing radiation. These four contaminants were included because of their potential to confound or modify the effect of a lung cancer-radiation relationship. The exposure assessment included three experienced industrial hygienists from the shipyard who independently assessed exposures for 3519 shop/job/time period combinations. A consensus process was used to resolve estimates with large differences. Final exposure estimates were linked to employment histories of the 4388 study subjects to calculate their cumulative exposures. Inter-rater agreement analyses were performed on the original estimates to better understand the estimation process. Although concordance was good to excellent (78-99%) for intensity estimates and excellent (96-99%) for frequency estimates, overall simple kappa statistics indicated only slight agreement beyond chance (kappa < 0.2). Unbalanced distributions of exposure estimates partly contributed to the weak observed overall inter-rater agreement. Pairwise weighted kappa statistics revealed better agreement between two of the three panelists (kappa = 0.19-0.65). The final consensus estimates were similar to the estimates made by these same two panelists. Overall welding fume exposures were fairly stable across time at the shipyard while asbestos exposures were higher in the early years and fell in the mid-1970s. Mean cumulative exposure for all study subjects was 520 fiber-days cc(-1) for asbestos and 1000 mg-days m(-3) for welding fumes. Mean exposure was much lower for nickel (140 microg-days m(-3)) and chromium (45 microg-days m(-3)). Asbestos and welding fume exposure estimates were positively associated with lung cancer in the nested case-control study. The radiation-lung cancer relationship was attenuated by the inclusion

  19. Ultrafast charge-transfer-to-solvent dynamics of iodide in tetrahydrofuran. 2. Photoinduced electron transfer to counterions in solution.

    PubMed

    Bragg, Arthur E; Schwartz, Benjamin J

    2008-04-24

    The excited states of atomic anions in liquids are bound only by the polarization of the surrounding solvent. Thus, the electron-detachment process following excitation to one of these solvent-bound states, known as charge-transfer-to-solvent (CTTS) states, provides a useful probe of solvent structure and dynamics. These transitions and subsequent relaxation dynamics also are influenced by other factors that alter the solution environment local to the CTTS anion, including the presence of cosolutes, cosolvents, and other ions. In this paper, we examine the ultrafast CTTS dynamics of iodide in liquid tetrahydrofuran (THF) with a particular focus on how the solvent dynamics and the CTTS electron-ejection process are altered in the presence of various counterions. In weakly polar solvents such as THF, iodide salts can be strongly ion-paired in solution; the steady-state UV-visible absorption spectroscopy of various iodide salts in liquid THF indicates that the degree of ion-pairing changes from strong to weak to none as the counterion is switched from Na+ to tetrabutylammonium (t-BA+) to crown-ether-complexed Na+, respectively. In our ultrafast experiments, we have excited the I- CTTS transition of these various iodide salts at 263 nm and probed the dynamics of the CTTS-detached electrons throughout the visible and near-IR. In the previous paper of this series (Bragg, A. E.; Schwartz, B. J. J. Phys. Chem. B 2008, 112, 483-494), we found that for "counterion-free" I- (obtained by complexing Na+ with a crown ether) the CTTS electrons were ejected approximately 6 nm from their partner iodine atoms, the result of significant nonadiabatic coupling between the CTTS excited state and extended electronic states supported by the naturally existing solvent cavities in liquid THF, which also serve as pre-existing electron traps. In contrast, for the highly ion-paired NaI/THF system, we find that approximately 90% of the CTTS electrons are "captured" by a nearby Na+ to form (Na

  20. Ion energies in high power impulse magnetron sputtering with and without localized ionization zones

    SciTech Connect

    Yang, Yuchen; Tanaka, Koichi; Liu, Jason; Anders, André

    2015-03-23

    High speed imaging of high power impulse magnetron sputtering discharges has revealed that ionization is localized in moving ionization zones but localization disappears at high currents for high yield targets. This offers an opportunity to study the effect ionization zones have on ion energies. We measure that ions have generally higher energies when ionization zones are present, supporting the concept that these zones are associated with moving potential humps. We propose that the disappearance of ionization zones is caused by an increased supply of atoms from the target which cools electrons and reduces depletion of atoms to be ionized.

  1. Studies on the Application of High Voltage Discharge Ionization and Ablation in Supersonic-Jets for the Generation of Intense Cluster Ion Beams.

    NASA Astrophysics Data System (ADS)

    Brock, Ansgar

    Glow discharge and pulsed capacitor discharge ionization in supersonic expansions were investigated for the production of intense beams of molecular cluster ions from seeded and ablated compounds. A low cost high voltage high current pulser based on a triggered spark gap switch is described as a mean for ionization and ablation. Besides, details of the molecular beam apparatus and modified pulsed valve are given. Cluster cations rm (Ar)_ {n}^+, rm (CO_2) _{n}^{+}, rm (C_6H_6)_{n}^+ and rm (H_2O)_{n }^+ were produced by pulsed capacitor discharge ionization in the expansion region of a seeded free-jet. The observed cluster mass spectra (CMS) for Ar, rm C_6H_6 and H _2O show the characteristic features (magic numbers) of electron beam and photo ionized clusters under molecular flow conditions. Indications for the presence of magic numbers in the CMS of {(CO _2)_{n}^+} cluster ions at n = 20, 26, 30 and 34 similar to those found for rare gas clusters have been found. Cationic metal ligand complexes Cu(Toluene) _{rm n}^+, Cu(Acetone) _{rm n}^+, Cu(Methanol)_{rm n}^+ , Cu(Ethylether)_{rm n }^+, Cu(Water)_{ rm n}^+, Al(Water)_ {rm n}^+ were synthesized by ablation of the metal from metallic discharge electrodes in a discharge gas mixture of helium seeded with the ligand of choice. The CMS of the expanded plasmas show little background ion signal besides the metal-ligand species. Charge exchange processes in the expansion guarantee high ionization yields of the desired species and account for low backgrounds. Changes in the successive binding energy of Cu(Water)_ {rm n}^+ clusters n = 1-4 are clearly observed in the CMS as step formation. A similar pattern found in the Cu(Acetone)_{ rm n}^+ CMS suggests the same trend in the successive binding energy as known for water. Ablation from a Cr(acac)_3 in a copper matrix was employed for the synthesis of Cr(Acetone) _{rm n}^+ and Cr(Benzene)^+ complexes demonstrating the ability to use nonconducting compounds as a metal source

  2. Laser resonance ionization scheme development for tellurium and germanium at the dual Ti:Sa-Dye ISOLDE RILIS

    NASA Astrophysics Data System (ADS)

    Day Goodacre, T.; Fedorov, D.; Fedosseev, V. N.; Forster, L.; Marsh, B. A.; Rossel, R. E.; Rothe, S.; Veinhard, M.

    2016-09-01

    The resonance ionization laser ion source (RILIS) is the principal ion source of the ISOLDE radioactive beam facility based at CERN. Using the method of in-source laser resonance ionization spectroscopy, a transition to a new autoionizing state of tellurium was discovered and applied as part of a three-step, three-resonance, photo-ionization scheme. In a second study, a three-step, two-resonance, photo-ionization scheme for germanium was developed and the ionization efficiency was measured at ISOLDE. This work increases the range of ISOLDE RILIS ionized beams to 31 elements. Details of the spectroscopy studies are described and the new ionization schemes are summarized.

  3. Electrospray ionization tandem mass spectrometric study on the effect of N-terminal beta- and gamma-carbo amino acids on fragmentation of GABA-hybrid peptides.

    PubMed

    Ramesh, V; Ramesh, M; Srinivas, R; Sharma, G V M; Jayaprakash, P

    2008-11-01

    The fragmentations of protonated and deprotonated ions of a new class of N-blocked hybrid Boc-carbopeptides containing repeats of gamma-Caa/gammaAbu- and beta-Caa/gammaAbu- (Caa==C-linked carbo gamma(4)-/beta(3)- amino acids derived from D-xylose, gammaAbu = gamma-aminobutyric acid) have been studied using electrospray ionization (ESI) ion-trap tandem mass spectrometry (MS/MS). MS/MS of a pair of these protonated diastereomers produces distinct fragmentation of the Boc group. The formation of [M + H-56](+) corresponding to loss of isobutylene is more pronounced for Boc-NH-(R)-gamma-Caa-gammaAbu-OH (2) whereas it is of low abundance for Boc-NH-(S)-gamma-Caa-gammaAbu--OH (1). Similarly, MS(2) of [M--H](-) of 2 produces an abundant [M--H--C(CH(3))(3)OH--CO(2)](-) ion, which is absent for its diastereomeric isomer 1. From this, it can be suggested that MS/MS of N-blocked Boc-protected carbopeptides may be helpful in distinguishing the stereochemistry of the N-terminus Caa. MS(3) of [M + H-Boc + H](+) ions of peptides with a gamma-amino acid (gamma-Caa/gammaAbu) at the N-terminus produces only abundant y(n) (+) ions. On the other hand, characteristic fragmentations involving the peptide backbone (b(n) (+) and y(n) (+)) and the side chain are seen when beta-Caa is at the N-terminus of the peptides. MS(3) of the [M--H--C(CH(3))(3)OH](-) ion of peptides containing gamma-Caa/gammaAbu at the N-terminus gave y(n) (-) and [M--H--C(CH(3))(3)OH--CO(2)](-) ions, whereas the presence of beta-Caa at the N-terminus yielded predominantly [M--H--C(CH(3))(3)OH--HNCO](-). Thus, on the basis of our previous study and that presented here we propose that the fragmentation of these hybrid carbopeptides is highly influenced by the type of carbo amino acid present at the N-terminus. PMID:18837002

  4. Laser plasma formation assisted by ultraviolet pre-ionization

    SciTech Connect

    Yalin, Azer P. Dumitrache, Ciprian; Wilvert, Nick; Joshi, Sachin; Shneider, Mikhail N.

    2014-10-15

    We present experimental and modeling studies of air pre-ionization using ultraviolet (UV) laser pulses and its effect on laser breakdown of an overlapped near-infrared (NIR) pulse. Experimental studies are conducted with a 266 nm beam (fourth harmonic of Nd:YAG) for UV pre-ionization and an overlapped 1064 nm NIR beam (fundamental of Nd:YAG), both having pulse duration of ∼10 ns. Results show that the UV beam produces a pre-ionized volume which assists in breakdown of the NIR beam, leading to reduction in NIR breakdown threshold by factor of >2. Numerical modeling is performed to examine the ionization and breakdown of both beams. The modeled breakdown threshold of the NIR, including assist by pre-ionization, is in reasonable agreement with the experimental results.

  5. Fossil Ionized Bubbles around Dead Quasars during Reionization

    NASA Astrophysics Data System (ADS)

    Furlanetto, Steven R.; Haiman, Zoltán; Oh, S. Peng

    2008-10-01

    One of the most dramatic signatures of the reionization era may be the enormous ionized bubbles around luminous quasars (with radii reaching ~40 comoving Mpc), which may survive as "fossil" ionized regions long after their source shuts off. Here we study how the inhomogeneous intergalactic medium (IGM) evolves inside such fossils. The average recombination rate declines rapidly with time, and the brief quasar episode significantly increases the mean free path inside the fossil bubbles. As a result, even a weak ionizing background generated by galaxies inside the fossil can maintain it in a relatively highly and uniformly ionized state. For example, galaxies that would ionize 20%-30% of hydrogen in a random patch of the IGM can maintain 80%-90% ionization inside the fossil for a duration much longer than the average recombination time in the IGM. Quasar fossils at zlesssim 10 thus retain their identity for nearly a Hubble time and appear "gray," distinct from both the average IGM (which has a "Swiss cheese" ionization topology and a lower mean ionized fraction) and the fully ionized bubbles around active quasars. More distant fossils, at zgtrsim 10, have a weaker galaxy-generated ionizing background and a higher gas density, so they can attain a Swiss cheese topology similar to the rest of the IGM, but with a smaller contrast between the ionized bubbles and the partially neutral regions separating them. Analogous He III fossils should exist around the epoch of He II/He III reionization at z ~ 3, although rapid recombination inside the He III fossils is more common. Our model of inhomogeneous recombination also applies to "double-reionization" models and shows that a nonmonotonic reionization history is even more unlikely than previously thought.

  6. Ionized cluster beam deposition

    NASA Astrophysics Data System (ADS)

    Kirkpatrick, A. R.

    1983-11-01

    Ionized Cluster Beam (ICB) deposition, a new technique originated by Takagi of Kyoto University in Japan, offers a number of unique capabilities for thin film metallization as well as for deposition of active semiconductor materials. ICB allows average energy per deposited atom to be controlled and involves impact kinetics which result in high diffusion energies of atoms on the growth surface. To a greater degree than in other techniques, ICB involves quantitative process parameters which can be utilized to strongly control the characteristics of films being deposited. In the ICB deposition process, material to be deposited is vaporized into a vacuum chamber from a confinement crucible at high temperature. Crucible nozzle configuration and operating temperature are such that emerging vapor undergoes supercondensation following adiabatic expansion through the nozzle.

  7. Ionizing radiation detector

    DOEpatents

    Thacker, Louis H.

    1990-01-01

    An ionizing radiation detector is provided which is based on the principle of analog electronic integration of radiation sensor currents in the sub-pico to nano ampere range between fixed voltage switching thresholds with automatic voltage reversal each time the appropriate threshold is reached. The thresholds are provided by a first NAND gate Schmitt trigger which is coupled with a second NAND gate Schmitt trigger operating in an alternate switching state from the first gate to turn either a visible or audible indicating device on and off in response to the gate switching rate which is indicative of the level of radiation being sensed. The detector can be configured as a small, personal radiation dosimeter which is simple to operate and responsive over a dynamic range of at least 0.01 to 1000 R/hr.

  8. Ionized cluster beam deposition

    NASA Technical Reports Server (NTRS)

    Kirkpatrick, A. R.

    1983-01-01

    Ionized Cluster Beam (ICB) deposition, a new technique originated by Takagi of Kyoto University in Japan, offers a number of unique capabilities for thin film metallization as well as for deposition of active semiconductor materials. ICB allows average energy per deposited atom to be controlled and involves impact kinetics which result in high diffusion energies of atoms on the growth surface. To a greater degree than in other techniques, ICB involves quantitative process parameters which can be utilized to strongly control the characteristics of films being deposited. In the ICB deposition process, material to be deposited is vaporized into a vacuum chamber from a confinement crucible at high temperature. Crucible nozzle configuration and operating temperature are such that emerging vapor undergoes supercondensation following adiabatic expansion through the nozzle.

  9. Electrospray Ionization on Solid Substrates

    PubMed Central

    So, Pui-Kin; Hu, Bin; Yao, Zhong-Ping

    2014-01-01

    Development of electrospray ionization on solid substrates (solid-substrate ESI) avoids the clogging problem encountered in conventional capillary-based ESI, allows more convenient sampling and permits new applications. So far, solid-substrate ESI with various materials, e.g., metals, paper, wood, fibers and biological tissue, has been developed, and applications ranging from analysis of pure compounds to complex mixtures as well as in vivo study were demonstrated. Particularly, the capability of solid-substrate ESI in direct analysis of complex samples, e.g., biological fluids and foods, has significantly facilitated mass spectrometric analysis in real-life applications and led to increasingly important roles of these techniques nowadays. In this review, various solid-substrate ESI techniques and their applications are summarized and the prospects in this field are discussed. PMID:26819900

  10. Kinematically complete study of low-energy electron-impact ionization of argon: Internormalized cross sections in three-dimensional kinematics

    NASA Astrophysics Data System (ADS)

    Ren, Xueguang; Amami, Sadek; Zatsarinny, Oleg; Pflüger, Thomas; Weyland, Marvin; Dorn, Alexander; Madison, Don; Bartschat, Klaus

    2016-06-01

    As a further test of advanced theoretical methods to describe electron-impact single-ionization processes in complex atomic targets, we extended our recent work on Ne (2 p ) ionization [X. Ren, S. Amami, O. Zatsarinny, T. Pflüger, M. Weyland, W. Y. Baek, H. Rabus, K. Bartschat, D. Madison, and A. Dorn, Phys. Rev. A 91, 032707 (2015), 10.1103/PhysRevA.91.032707] to Ar (3 p ) ionization at the relatively low incident energy of E0=66 eV. The experimental data were obtained with a reaction microscope, which can cover nearly the entire 4 π solid angle for the secondary electron emission. We present experimental data for detection angles of 10, 15, and 20∘ for the faster of the two outgoing electrons as a function of the detection angle of the secondary electron with energies of 3, 5, and 10 eV, respectively. Comparison with theoretical predictions from a B -spline R -matrix (BSR) with pseudostates approach and a three-body distorted-wave (3DW) approach, for detection of the secondary electron in three orthogonal planes as well as the entire solid angle, shows overall satisfactory agreement between experiment and the BSR results, whereas the 3DW approach faces difficulties in predicting some of the details of the angular distributions. These findings are different from our earlier work on Ne (2 p ), where both the BSR and 3DW approaches yielded comparable levels of agreement with the experimental data.

  11. An Experimental and Theoretical Study on the Ionization Energies of Polyynes (H-(C≡C) n -H; n = 1-9)

    NASA Astrophysics Data System (ADS)

    Kaiser, Ralf I.; Sun, Bian Jian; Mao Lin, Hong; Chang, Agnes H. H.; Mebel, Alexander M.; Kostko, Oleg; Ahmed, Musahid

    2010-08-01

    We present a combined experimental and theoretical work on the ionization energies of polyacetylene-organic molecules considered as important building blocks to form polycyclic aromatic hydrocarbons in protoplanetary nebulae such as CRL 618. This set of astrophysical data can be utilized with significant confidence in future astrochemical models of photon-dominated regions and also of the protoplanetary nebulae CRL 618. We recommend ionization energies of polyacetylenes from diacetylene up to heptaacetylene with an experimental accuracy of ±0.05 eV: 10.03 eV (diacetylene), 9.45 eV (triacetylene), 9.08 eV (tetraacetylene), 8.75 eV (pentaacetylene), 8.65 eV (hexaacetylene), and 8.50 eV (heptaacetylene). Further, ionization energies with an accuracy of ±0.1 eV: 8.32 eV (octaacetylene) and 8.24 eV (nonaacetylene), were computed. Implications of these energies to the redox chemistry involved in the multiply charged metal-ion mediated chemistry of hydrocarbon-rich atmospheres of planets and their moons such as Titan are also discussed.

  12. AN EXPERIMENTAL AND THEORETICAL STUDY ON THE IONIZATION ENERGIES OF POLYYNES (H-(C{identical_to}C) {sub n} -H; n = 1-9)

    SciTech Connect

    Kaiser, Ralf I.; Sun Bianjian; Lin Hongmao; Chang, Agnes H. H.; Mebel, Alexander M.; Kostko, Oleg; Ahmed, Musahid

    2010-08-20

    We present a combined experimental and theoretical work on the ionization energies of polyacetylene-organic molecules considered as important building blocks to form polycyclic aromatic hydrocarbons in protoplanetary nebulae such as CRL 618. This set of astrophysical data can be utilized with significant confidence in future astrochemical models of photon-dominated regions and also of the protoplanetary nebulae CRL 618. We recommend ionization energies of polyacetylenes from diacetylene up to heptaacetylene with an experimental accuracy of {+-}0.05 eV: 10.03 eV (diacetylene), 9.45 eV (triacetylene), 9.08 eV (tetraacetylene), 8.75 eV (pentaacetylene), 8.65 eV (hexaacetylene), and 8.50 eV (heptaacetylene). Further, ionization energies with an accuracy of {+-}0.1 eV: 8.32 eV (octaacetylene) and 8.24 eV (nonaacetylene), were computed. Implications of these energies to the redox chemistry involved in the multiply charged metal-ion mediated chemistry of hydrocarbon-rich atmospheres of planets and their moons such as Titan are also discussed.

  13. An Experimental and Theoretical Study on the Ionization Energies of Polyynes (H-(C = C)n-H; n = 1 - 9)

    SciTech Connect

    Kaiser, Ralf I.; Sun, Bian Jian; Lin, Hong Mao; Chang, Agnes H. H.; Mebel, Alexander M.; Kostko, Oleg; Ahmed, Musahid

    2010-05-17

    We present a combined experimental and theoretical work on the ionization energies of polyacetylene -- organic molecules considered as important building blocks to form polycyclic aromatic hydrocarbons (PAHs) in the proto planetary nebulae such as of CRL 618. This set of astrophysical data can be utilized with significant confidence in future astrochemical models of photon-dominated regions and also of the proto planetary nebulae CRL 618. We recommend ionization energies of polyacetylenes from diacetylene up to heptaacetylene with an experimental accuracy of +- 0.05 eV: 10.03 eV (diacetylene), 9.45 eV (triacetylene), 9.08 eV (tetraacetylene), 8.75 eV (pentaacetylene), 8.65 eV (hexaacetylene), and 8.50 eV (heptaacetylene); further, ionization energies and with an accuracy of +- 0.1 eV: 8.32 eV (octaacetylene) and 8.24 eV (nonaacetylene) were computed. Implications of these energies to the redox chemistry involved in the multiply charged metal-ion mediated chemistry of hydrocarbon-rich atmospheres of planets and their moons such as Titan are also discussed.

  14. Study of dust particle charging in weakly ionized inert gases taking into account the nonlocality of the electron energy distribution function

    SciTech Connect

    Filippov, A. V. Dyatko, N. A.; Kostenko, A. S.

    2014-11-15

    The charging of dust particles in weakly ionized inert gases at atmospheric pressure has been investigated. The conditions under which the gas is ionized by an external source, a beam of fast electrons, are considered. The electron energy distribution function in argon, krypton, and xenon has been calculated for three rates of gas ionization by fast electrons: 10{sup 13}, 10{sup 14}, and 10{sup 15} cm{sup −1}. A model of dust particle charging with allowance for the nonlocal formation of the electron energy distribution function in the region of strong plasma quasi-neutrality violation around the dust particle is described. The nonlocality is taken into account in an approximation where the distribution function is a function of only the total electron energy. Comparative calculations of the dust particle charge with and without allowance for the nonlocality of the electron energy distribution function have been performed. Allowance for the nonlocality is shown to lead to a noticeable increase in the dust particle charge due to the influence of the group of hot electrons from the tail of the distribution function. It has been established that the screening constant virtually coincides with the smallest screening constant determined according to the asymptotic theory of screening with the electron transport and recombination coefficients in an unperturbed plasma.

  15. Amorphous silicon ionizing particle detectors

    DOEpatents

    Street, Robert A.; Mendez, Victor P.; Kaplan, Selig N.

    1988-01-01

    Amorphous silicon ionizing particle detectors having a hydrogenated amorphous silicon (a--Si:H) thin film deposited via plasma assisted chemical vapor deposition techniques are utilized to detect the presence, position and counting of high energy ionizing particles, such as electrons, x-rays, alpha particles, beta particles and gamma radiation.

  16. Amorphous silicon ionizing particle detectors

    DOEpatents

    Street, R.A.; Mendez, V.P.; Kaplan, S.N.

    1988-11-15

    Amorphous silicon ionizing particle detectors having a hydrogenated amorphous silicon (a--Si:H) thin film deposited via plasma assisted chemical vapor deposition techniques are utilized to detect the presence, position and counting of high energy ionizing particles, such as electrons, x-rays, alpha particles, beta particles and gamma radiation. 15 figs.

  17. Multiple ionization and coupling effects in L-subshell ionization of heavy atoms by oxygen ions

    SciTech Connect

    Pajek, M.; Banas, D.; Semaniak, J.; Braziewicz, J.; Majewska, U.; Chojnacki, S.; Czyzewski, T.; Fijal, I.; Jaskola, M.; Glombik, A.; Kretschmer, W.; Trautmann, D.; Lapicki, G.; Mukoyama, T.

    2003-08-01

    The multiple-ionization and coupling effects in L-shell ionization of atoms by heavy-ion impact have been studied by measuring the L x-ray production cross sections in solid targets of Au, Bi, Th, and U bombarded by oxygen ions in the energy range 6.4-70 MeV. The measured L x-ray spectra were analyzed using the recently proposed method accounting for the multiple-ionization effects, such as x-ray line shifting and broadening, which enables one to obtain the ionization probabilities for outer shells. The L-subshell ionization cross sections have been obtained from measured x-ray production cross sections for resolved L{alpha}{sub 1,2}, L{gamma}{sub 1}, and L{gamma}{sub 2,3} transitions using the L-shell fluorescence and Coster-Kronig yields being substantially modified by the multiple ionization in the M and N shells. In particular, the effect of closing of strong L{sub 1}-L{sub 3}M{sub 4,5} Coster-Kronig transitions in multiple-ionized atoms was evidenced and discussed. The experimental ionization cross sections for the L{sub 1}, L{sub 2}, and L{sub 3} subshells have been compared with the predictions of the semiclassical approximation (SCA) and the ECPSSR theory that includes the corrections for the binding-polarization effect within the perturbed stationary states approximation, the projecticle energy loss, and Coulomb deflection effects as well as the relativistic description of inner-shell electrons. These approaches were further modified to include the L-subshell couplings within the ''coupled-subshell model'' (CSM). Both approaches, when modified for the coupling effects, are in better agreement with the data. Particularly, the predictions of the SCA-CSM calculations reproduce the experimental L-subshell ionization cross section reasonably well. Remaining discrepancies are discussed qualitatively, in terms of further modifications of the L-shell decay rates caused by a change of electronic wave functions in multiple-ionized atoms.

  18. Infrared-Vacuum Ultraviolet Pulsed Field Ionization-Photoelectron Study of C₂H₄ + Using a High-Resolution Infrared Laser

    SciTech Connect

    Xing, Xi; Reed, Beth; Bahng, Mi-Kyung; Ng, Cheuk-Yiu

    2008-02-20

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The infrared (IR)-vacuum ultraviolet (VUV)-pulsed field ionization-photoelectron (IR-VUV-PFI-PE) spectrum for C₂H₄(X 1Ag, V11 = 1, N'Ka'Kc'=3₀₃) in the VUV range of 83 000-84 800 cm-1 obtained using a single mode infrared laser revealed 24 rotationally resolved vibrational bands for the ion C₂H₄ +(X 2B3u) ground state. The frequencies and symmetry of the vibrational bands thus determined, together with the anharmonic frequency predictions calculated at the CCSD(T)/aug-cc-pVQZ level, have allowed the unambiguous assignment of these vibrational bands. These bands are mostly combination bands. The measured frequencies of these bands yield the fundamental frequencies for V8 + ) 1103± ( 10 cm-1 and V10 + ) 813 ( 10 cm-1 of C₂H₄ +(X 2B3u), which have not been determined previously. The present IR-VUV-PFI-PE study also provides truly rovibrationally selected and resolved state-to-state cross sections for the photoionization transitions C₂H₄(X~1Ag; V11, N'Ka'Kc') → C₂H₄ +(X~ 2B3u; Vi +, N+ Ka +Kc +), where N'Ka'Kc' denotes the rotational level of C₂H₄(X~ 1Ag; V11), and Vi + and N+ Ka +Kc + represent the vibrational and rotational states of the cation.

  19. IONIZED NITROGEN AT HIGH REDSHIFT

    SciTech Connect

    Decarli, R.; Walter, F.; Neri, R.; Cox, P.; Bertoldi, F.; Carilli, C.; Kneib, J. P.; Lestrade, J. F.; Maiolino, R.; Omont, A.; Richard, J.; Riechers, D.; Thanjavur, K.; Weiss, A.

    2012-06-10

    We present secure [N II]{sub 205{mu}m} detections in two millimeter-bright, strongly lensed objects at high redshift, APM 08279+5255 (z = 3.911) and MM 18423+5938 (z = 3.930), using the IRAM Plateau de Bure Interferometer. Due to its ionization energy [N II]{sub 205{mu}m} is a good tracer of the ionized gas phase in the interstellar medium. The measured fluxes are S([N II]{sub 205{mu}m}) = (4.8 {+-} 0.8) Jy km s{sup -1} and (7.4 {+-} 0.5) Jy km s{sup -1}, respectively, yielding line luminosities of L([N II]{sub 205{mu}m}) = (1.8 {+-} 0.3) Multiplication-Sign 10{sup 9} {mu}{sup -1} L{sub Sun} for APM 08279+5255 and L([N II]{sub 205{mu}m}) = (2.8 {+-} 0.2) Multiplication-Sign 10{sup 9} {mu}{sup -1} L{sub Sun} for MM 18423+5938. Our high-resolution map of the [N II]{sub 205{mu}m} and 1 mm continuum emission in MM 18423+5938 clearly resolves an Einstein ring in this source and reveals a velocity gradient in the dynamics of the ionized gas. A comparison of these maps with high-resolution EVLA CO observations enables us to perform the first spatially resolved study of the dust continuum-to-molecular gas surface brightness ({Sigma}{sub FIR}{proportional_to}{Sigma}{sup N}{sub CO}, which can be interpreted as the star formation law) in a high-redshift object. We find a steep relation (N = 1.4 {+-} 0.2), consistent with a starbursting environment. We measure a [N II]{sub 205{mu}m}/FIR luminosity ratio in APM 08279+5255 and MM 18423+5938 of 9.0 Multiplication-Sign 10{sup -6} and 5.8 Multiplication-Sign 10{sup -6}, respectively. This is in agreement with the decrease of the [N II]{sub 205{mu}m}/FIR ratio at high FIR luminosities observed in local galaxies.

  20. Ionization detection system for aerosols

    DOEpatents

    Jacobs, Martin E.

    1977-01-01

    This invention relates to an improved smoke-detection system of the ionization-chamber type. In the preferred embodiment, the system utilizes a conventional detector head comprising a measuring ionization chamber, a reference ionization chamber, and a normally non-conductive gas triode for discharging when a threshold concentration of airborne particulates is present in the measuring chamber. The improved system utilizes a measuring ionization chamber which is modified to minimize false alarms and reductions in sensitivity resulting from changes in ambient temperature. In the preferred form of the modification, an annular radiation shield is mounted about the usual radiation source provided to effect ionization in the measuring chamber. The shield is supported by a bimetallic strip which flexes in response to changes in ambient temperature, moving the shield relative to the source so as to vary the radiative area of the source in a manner offsetting temperature-induced variations in the sensitivity of the chamber.

  1. Hyphenation of Thermal Analysis to Ultrahigh-Resolution Mass Spectrometry (Fourier Transform Ion Cyclotron Resonance Mass Spectrometry) Using Atmospheric Pressure Chemical Ionization For Studying Composition and Thermal Degradation of Complex Materials.

    PubMed

    Rüger, Christopher P; Miersch, Toni; Schwemer, Theo; Sklorz, Martin; Zimmermann, Ralf

    2015-07-01

    In this study, the hyphenation of a thermobalance to an ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometer (UHR FTICR MS) is presented. Atmospheric pressure chemical ionization (APCI) is used for efficient ionization. The evolved gas analysis (EGA), using high-resolution mass spectrometry allows the time-resolved molecular characterization of thermally induced processes in complex materials or mixtures, such as biomass or crude oil. The most crucial part of the setup is the hyphenation between the thermobalance and the APCI source. Evolved gases are forced to enter the atmospheric pressure ionization interface of the MS by applying a slight overpressure at the thermobalance side of the hyphenation. Using the FTICR exact mass data, detailed chemical information is gained by calculation of elemental compositions from the organic species, enabling a time and temperature resolved, highly selective detection of the evolved species. An additional selectivity is gained by the APCI ionization, which is particularly sensitive toward polar compounds. This selectivity on the one hand misses bulk components of petroleum samples such as alkanes and does not deliver a comprehensive view but on the other hand focuses particularly on typical evolved components from biomass samples. As proof of principle, the thermal behavior of different fossil fuels: heavy fuel oil, light fuel oil, and a crude oil, and different lignocellulosic biomass, namely, beech, birch, spruce, ash, oak, and pine as well as commercial available softwood and birch-bark pellets were investigated. The results clearly show the capability to distinguish between certain wood types through their molecular patterns and compound classes. Additionally, typical literature known pyrolysis biomass marker were confirmed by their elemental composition, such as coniferyl aldehyde (C10H10O3), sinapyl aldehyde (C11H12O4), retene (C18H18), and abietic acid (C20H30O2). PMID:26024433

  2. Hyphenation of Thermal Analysis to Ultrahigh-Resolution Mass Spectrometry (Fourier Transform Ion Cyclotron Resonance Mass Spectrometry) Using Atmospheric Pressure Chemical Ionization For Studying Composition and Thermal Degradation of Complex Materials.

    PubMed

    Rüger, Christopher P; Miersch, Toni; Schwemer, Theo; Sklorz, Martin; Zimmermann, Ralf

    2015-07-01

    In this study, the hyphenation of a thermobalance to an ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometer (UHR FTICR MS) is presented. Atmospheric pressure chemical ionization (APCI) is used for efficient ionization. The evolved gas analysis (EGA), using high-resolution mass spectrometry allows the time-resolved molecular characterization of thermally induced processes in complex materials or mixtures, such as biomass or crude oil. The most crucial part of the setup is the hyphenation between the thermobalance and the APCI source. Evolved gases are forced to enter the atmospheric pressure ionization interface of the MS by applying a slight overpressure at the thermobalance side of the hyphenation. Using the FTICR exact mass data, detailed chemical information is gained by calculation of elemental compositions from the organic species, enabling a time and temperature resolved, highly selective detection of the evolved species. An additional selectivity is gained by the APCI ionization, which is particularly sensitive toward polar compounds. This selectivity on the one hand misses bulk components of petroleum samples such as alkanes and does not deliver a comprehensive view but on the other hand focuses particularly on typical evolved components from biomass samples. As proof of principle, the thermal behavior of different fossil fuels: heavy fuel oil, light fuel oil, and a crude oil, and different lignocellulosic biomass, namely, beech, birch, spruce, ash, oak, and pine as well as commercial available softwood and birch-bark pellets were investigated. The results clearly show the capability to distinguish between certain wood types through their molecular patterns and compound classes. Additionally, typical literature known pyrolysis biomass marker were confirmed by their elemental composition, such as coniferyl aldehyde (C10H10O3), sinapyl aldehyde (C11H12O4), retene (C18H18), and abietic acid (C20H30O2).

  3. The GODDESS ionization chamber: developing robust windows

    NASA Astrophysics Data System (ADS)

    Blanchard, Rose; Baugher, Travis; Cizewski, Jolie; Pain, Steven; Ratkiewicz, Andrew; Goddess Collaboration

    2015-10-01

    Reaction studies of nuclei far from stability require high-efficiency arrays of detectors and the ability to identify beam-like particles, especially when the beam is a cocktail beam. The Gammasphere ORRUBA Dual Detectors for Experimental Structure Studies (GODDESS) is made up of the Oak Ridge-Rutgers University Barrel Array (ORRUBA) of silicon detectors for charged particles inside of the gamma-ray detector array Gammasphere. A high-rate ionization chamber is being developed to identify beam-like particles. Consisting of twenty-one alternating anode and cathode grids, the ionization chamber sits downstream of the target chamber and is used to measure the energy loss of recoiling ions. A critical component of the system is a thin and robust mylar window which serves to separate the gas-filled ionization chamber from the vacuum of the target chamber with minimal energy loss. After construction, windows were tested to assure that they would not break below the required pressure, causing harm to the wire grids. This presentation will summarize the status of the ionization chamber and the results of the first tests with beams. This work is supported in part by the U.S. Department of Energy and National Science Foundation.

  4. Salt Tolerance of Desorption Electrospray Ionization (DESI)

    SciTech Connect

    Jackson, Ayanna U.; Talaty, Nari; Cooks, R G; Van Berkel, Gary J

    2007-01-01

    Suppression of ion intensity in the presence of high salt matrices is common in most mass spectrometry ionization techniques. Desorption electrospray ionization (DESI) is an ionization method that exhibits salt tolerance, and this is investigated. DESI analysis was performed on three different drug mixtures in the presence of 0, 0.2, 2, 5, 10, and 20% NaCl:KCl weight by volume from seven different surfaces. At physiological concentrations individual drugs in each mixture were observed with each surface. Collision-induced dissociation (CID) was used to provide additional confirmation for select compounds. Multiple stage experiments, to MS5, were performed for select compounds. Even in the absence of added salt, the benzodiazepine containing mixture yielded sodium and potassium adducts of carbamazepine which masked the ions of interest. These adducts were eliminated by adding 0.1% 7M ammonium acetate to the standard methanol:water (1:1) spray solvent. Comparison of the salt tolerance of DESI with that of electrospray ionization (ESI) demonstrated much better signal/noise characteristics for DESI in this study. The salt tolerance of DESI was also studied by performing limit of detection and dynamic range experiments. Even at a salt concentration significantly above physiological concentrations, select surfaces were effective in providing spectra that allowed the ready identification of the compounds of interest. The already high salt tolerance of DESI can be optimized further by appropriate choices of surface and spray solution.

  5. Dissociative Ionization of Benzene by Electron Impact

    NASA Technical Reports Server (NTRS)

    Huo, Winifred; Dateo, Christopher; Kwak, Dochan (Technical Monitor)

    2002-01-01

    We report a theoretical study of the dissociative ionization (DI) of benzene from the low-lying ionization channels. Our approach makes use of the fact that electron motion is much faster than nuclear motion and DI is treated as a two-step process. The first step is electron-impact ionization resulting in an ion with the same nuclear geometry as the neutral molecule. In the second step the nuclei relax from the initial geometry and undergo unimolecular dissociation. For the ionization process we use the improved binary-encounter dipole (iBED) model. For the unimolecular dissociation step, we study the steepest descent reaction path to the minimum of the ion potential energy surface. The path is used to analyze the probability of unimolecular dissociation and to determine the product distributions. Our analysis of the dissociation products and the thresholds of the productions are compared with the result dissociative photoionization measurements of Feng et al. The partial oscillator strengths from Feng et al. are then used in the iBED cross section calculations.

  6. Calculation of H2-He Flow with Nonequilibrium Ionization and Radiation: an Interim Report

    NASA Technical Reports Server (NTRS)

    Furudate, Michiko; Chang, Keun-Shik

    2005-01-01

    The nonequilibrium ionization process in hydrogen-helium mixture behind a strong shock wave is studied numerically using the detailed ionization rate model developed recently by Park which accounts for emission and absorption of Lyman lines. The study finds that, once the avalanche ionization is started, the Lyman line is self-absorbed. The intensity variation of the radiation at 5145 Angstroms found by Leibowitz in a shock tube experiment can be numerically reproduced by assuming that ionization behind the shock wave prior to the onset of avalanche ionization is 1.3%. Because 1.3% initial ionization is highly unlikely, Leibowitz s experimental data is deemed questionable. By varying the initial electron density value in the calculation, the calculated ionization equilibration time is shown to increase approximately as inverse square-root of the initial electron density value. The true ionization equilibration time is most likely much longer than the value found by Leibowitz.

  7. Isotope Effect in Tunneling Ionization of Neutral Hydrogen Molecules

    NASA Astrophysics Data System (ADS)

    Wang, X.; Xu, H.; Atia-Tul-Noor, A.; Hu, B. T.; Kielpinski, D.; Sang, R. T.; Litvinyuk, I. V.

    2016-08-01

    It has been recently predicted theoretically that due to nuclear motion light and heavy hydrogen molecules exposed to strong electric field should exhibit substantially different tunneling ionization rates [O. I. Tolstikhin, H. J. Worner, and T. Morishita, Phys. Rev. A 87, 041401(R) (2013)]. We studied that isotope effect experimentally by measuring relative ionization yields for each species in a mixed H2/D2 gas jet interacting with intense femtosecond laser pulses. In a reaction microscope apparatus, we detected ionic fragments from all contributing channels (single ionization, dissociation, and sequential double ionization) and determined the ratio of total single ionization yields for H2 and D2 . The measured ratio agrees quantitatively with the prediction of the generalized weak-field asymptotic theory in an apparent failure of the frozen-nuclei approximation.

  8. Resonant Ionization Laser Ion Source for Radioactive Ion Beams

    SciTech Connect

    Liu, Yuan; Beene, James R; Havener, Charles C; Vane, C Randy; Gottwald, T.; Wendt, K.; Mattolat, C.; Lassen, J.

    2009-01-01

    A resonant ionization laser ion source based on all-solid-state, tunable Ti:Sapphire lasers is being developed for the production of pure radioactive ion beams. It consists of a hot-cavity ion source and three pulsed Ti:Sapphire lasers operating at a 10 kHz pulse repetition rate. Spectroscopic studies are being conducted to develop ionization schemes that lead to ionizing an excited atom through an auto-ionization or a Rydberg state for numerous elements of interest. Three-photon resonant ionization of 12 elements has been recently demonstrated. The overall efficiency of the laser ion source measured for some of these elements ranges from 1 to 40%. The results indicate that Ti:Sapphire lasers could be well suited for laser ion source applications. The time structures of the ions produced by the pulsed lasers are investigated. The information may help to improve the laser ion source performance.

  9. Isotope Effect in Tunneling Ionization of Neutral Hydrogen Molecules.

    PubMed

    Wang, X; Xu, H; Atia-Tul-Noor, A; Hu, B T; Kielpinski, D; Sang, R T; Litvinyuk, I V

    2016-08-19

    It has been recently predicted theoretically that due to nuclear motion light and heavy hydrogen molecules exposed to strong electric field should exhibit substantially different tunneling ionization rates [O. I. Tolstikhin, H. J. Worner, and T. Morishita, Phys. Rev. A 87, 041401(R) (2013)]. We studied that isotope effect experimentally by measuring relative ionization yields for each species in a mixed H_{2}/D_{2} gas jet interacting with intense femtosecond laser pulses. In a reaction microscope apparatus, we detected ionic fragments from all contributing channels (single ionization, dissociation, and sequential double ionization) and determined the ratio of total single ionization yields for H_{2} and D_{2}. The measured ratio agrees quantitatively with the prediction of the generalized weak-field asymptotic theory in an apparent failure of the frozen-nuclei approximation. PMID:27588855

  10. Isotope Effect in Tunneling Ionization of Neutral Hydrogen Molecules.

    PubMed

    Wang, X; Xu, H; Atia-Tul-Noor, A; Hu, B T; Kielpinski, D; Sang, R T; Litvinyuk, I V

    2016-08-19

    It has been recently predicted theoretically that due to nuclear motion light and heavy hydrogen molecules exposed to strong electric field should exhibit substantially different tunneling ionization rates [O. I. Tolstikhin, H. J. Worner, and T. Morishita, Phys. Rev. A 87, 041401(R) (2013)]. We studied that isotope effect experimentally by measuring relative ionization yields for each species in a mixed H_{2}/D_{2} gas jet interacting with intense femtosecond laser pulses. In a reaction microscope apparatus, we detected ionic fragments from all contributing channels (single ionization, dissociation, and sequential double ionization) and determined the ratio of total single ionization yields for H_{2} and D_{2}. The measured ratio agrees quantitatively with the prediction of the generalized weak-field asymptotic theory in an apparent failure of the frozen-nuclei approximation.

  11. New Constraints on the Escape of Ionizing Photons from Starburst Galaxies Using Ionization-parameter Mapping

    NASA Astrophysics Data System (ADS)

    Zastrow, Jordan; Oey, M. S.; Veilleux, Sylvain; McDonald, Michael

    2013-12-01

    The fate of ionizing radiation in starburst galaxies is key to understanding cosmic reionization. However, the galactic parameters on which the escape fraction of ionizing radiation depend are not well understood. Ionization-parameter mapping provides a simple, yet effective, way to study the radiative transfer in starburst galaxies. We obtain emission-line ratio maps of [S III]/[S II] for six, nearby, dwarf starbursts: NGC 178, NGC 1482, NGC 1705, NGC 3125, NGC 7126, and He 2-10. The narrowband images are obtained with the Maryland-Magellan Tunable Filter at Las Campanas Observatory. Using these data, we previously reported the discovery of an optically thin ionization cone in NGC 5253, and here we also discover a similar ionization cone in NGC 3125. This latter cone has an opening angle of 40° ± 5° (0.4 sr), indicating that the passageways through which ionizing radiation may travel correspond to a small solid angle. Additionally, there are three sample galaxies that have winds and/or superbubble activity, which should be conducive to escaping radiation, yet they are optically thick. These results support the scenario that an orientation bias limits our ability to directly detect escaping Lyman continuum in many starburst galaxies. A comparison of the star formation properties and histories of the optically thin and thick galaxies is consistent with the model that high escape fractions are limited to galaxies that are old enough (gsim3 Myr) for mechanical feedback to have cleared optically thin passageways in the interstellar medium, but young enough (lsim5 Myr) that the ionizing stars are still present.

  12. New constraints on the escape of ionizing photons from starburst galaxies using ionization-parameter mapping

    SciTech Connect

    Zastrow, Jordan; Oey, M. S.; Veilleux, Sylvain; McDonald, Michael

    2013-12-10

    The fate of ionizing radiation in starburst galaxies is key to understanding cosmic reionization. However, the galactic parameters on which the escape fraction of ionizing radiation depend are not well understood. Ionization-parameter mapping provides a simple, yet effective, way to study the radiative transfer in starburst galaxies. We obtain emission-line ratio maps of [S III]/[S II] for six, nearby, dwarf starbursts: NGC 178, NGC 1482, NGC 1705, NGC 3125, NGC 7126, and He 2-10. The narrowband images are obtained with the Maryland-Magellan Tunable Filter at Las Campanas Observatory. Using these data, we previously reported the discovery of an optically thin ionization cone in NGC 5253, and here we also discover a similar ionization cone in NGC 3125. This latter cone has an opening angle of 40° ± 5° (0.4 sr), indicating that the passageways through which ionizing radiation may travel correspond to a small solid angle. Additionally, there are three sample galaxies that have winds and/or superbubble activity, which should be conducive to escaping radiation, yet they are optically thick. These results support the scenario that an orientation bias limits our ability to directly detect escaping Lyman continuum in many starburst galaxies. A comparison of the star formation properties and histories of the optically thin and thick galaxies is consistent with the model that high escape fractions are limited to galaxies that are old enough (≳3 Myr) for mechanical feedback to have cleared optically thin passageways in the interstellar medium, but young enough (≲5 Myr) that the ionizing stars are still present.

  13. Laser-Induced Ionization Efficiency Enhancement On A Filament For Thermal Ionization Mass Spectrometry

    SciTech Connect

    Siegfried, M.

    2015-10-14

    The evaluation of trace Uranium and Plutonium isotope ratios for nanogram to femtogram material quantities is a vital tool for nuclear counter-proliferation and safeguard activities. Thermal Ionization Mass Spectrometry (TIMS) is generally accepted as the state of the art technology for highly accurate and ultra-trace measurements of these actinide ratios. However, the very low TIMS ionization yield (typically less than 1%) leaves much room for improvement. Enhanced ionization of Nd and Sm from a TIMS filament was demonstrated using wavelength resonance with a nanosecond (pulse width) laser operating at 10 Hz when light was directed toward the filament.1 For this study, femtosecond and picosecond laser capabilities were to be employed to study the dissociation and ionization mechanisms of actinides/lanthanides and measure the enhanced ionization of the metal of interest. Since the underlying chemistry of the actinide/lanthanide carbides produced and dissociated on a TIMS filament is not well understood, the experimental parameters affecting the photodissociation and photoionization with one and two laser beams were to be investigated.

  14. High pressure xenon ionization detector

    DOEpatents

    Markey, J.K.

    1989-11-14

    A method is provided for detecting ionization comprising allowing particles that cause ionization to contact high pressure xenon maintained at or near its critical point and measuring the amount of ionization. An apparatus is provided for detecting ionization, the apparatus comprising a vessel containing a ionizable medium, the vessel having an inlet to allow high pressure ionizable medium to enter the vessel, a means to permit particles that cause ionization of the medium to enter the vessel, an anode, a cathode, a grid and a plurality of annular field shaping rings, the field shaping rings being electrically isolated from one another, the anode, cathode, grid and field shaping rings being electrically isolated from one another in order to form an electric field between the cathode and the anode, the electric field originating at the anode and terminating at the cathode, the grid being disposed between the cathode and the anode, the field shaping rings being disposed between the cathode and the grid, the improvement comprising the medium being xenon and the vessel being maintained at a pressure of 50 to 70 atmospheres and a temperature of 0 to 30 C. 2 figs.

  15. High pressure xenon ionization detector

    DOEpatents

    Markey, John K.

    1989-01-01

    A method is provided for detecting ionization comprising allowing particles that cause ionization to contact high pressure xenon maintained at or near its critical point and measuring the amount of ionization. An apparatus is provided for detecting ionization, the apparatus comprising a vessel containing a ionizable medium, the vessel having an inlet to allow high pressure ionizable medium to enter the vessel, a means to permit particles that cause ionization of the medium to enter the vessel, an anode, a cathode, a grid and a plurality of annular field shaping rings, the field shaping rings being electrically isolated from one another, the anode, cathode, grid and field shaping rings being electrically isolated from one another in order to form an electric field between the cathode and the anode, the electric field originating at the anode and terminating at the cathode, the grid being disposed between the cathode and the anode, the field shaping rings being disposed between the cathode and the grid, the improvement comprising the medium being xenon and the vessel being maintained at a pressure of 50 to 70 atmospheres and a temperature of 0.degree. to 30.degree. C.

  16. A high-resolution vacuum ultraviolet photoionization, photoelectron, and pulsed field ionization study of CS{sub 2} near the CS{sub 2}{sup +}(X{sup 2}{Pi}{sub 3/2,1/2}) thresholds

    SciTech Connect

    Huang, J.; Cheung, Y.; Evans, M.; Liao, C.; Ng, C.Y.; Hsu, C.; Heimann, P.; Lefebvre-Brion, H.; Cossart-Magos, C.

    1997-01-01

    High-resolution photoionization efficiency (PIE) and pulsed field ionization photoelectron (PFI-PE) spectra for CS{sub 2} have been measured using coherent vacuum ultraviolet (VUV) laser radiation in the energy range of 81050{endash}82100 cm{sup {minus}1}. The PIE and threshold photoelectron (TPE) spectra for CS{sub 2} in the energy range of 80850{endash}82750 cm{sup {minus}1} have also been obtained using synchrotron radiation. The analysis of the PIE spectra reveals three Rydberg series converging to the excited CS{sub 2}{sup +}({sup 2}{Pi}{sub 1/2}) spin{endash}orbit state. These series, with quantum defects of 1.430, 1.616, and 0.053, are associated with the [{sup 2}{Pi}{sub 1/2}]np{sigma}{sub u}, [{sup 2}{Pi}{sub 1/2}]np{pi}{sub u}, and [{sup 2}{Pi}{sub 1/2}]nf{sub u} configurations. The Stark shift effect on the ionization threshold of CS{sub 2} has been examined as a function of dc electric fields (F) in the range of 0.65{endash}1071 V/cm. The observed F dependence of the Stark shift for the ionization onset of CS{sub 2} is consistent with the prediction by the classical adiabatic field ionization formula. The extrapolation of the ionization onset to zero F yields accurate values for IE[CS{sub 2}{sup +}({tilde X}{sup 2}{Pi}{sub 3/2})]. In order to determine accurate IEs and to probe autoionizing structures for molecular species by PIE measurements, it is necessary to minimize the electric field used for ion extraction. Assignment of Renner{endash}Teller structures resolved in the VUV PFI-PE spectrum is guided by the recent nonresonant two-photon (N2P) PFI-PE and theoretical studies. Analysis of the PFI-PE spectrum also yields accurate values for IE[CS{sub 2}{sup +}({tilde X}{sup 2}{Pi}{sub 3/2,1/2})]. Taking average of the IE values determined by VUV-PFI-PE, N2P-PFI-PE, and Stark field extrapolation methods, we obtain a value of 81285.7{plus_minus}2.8 cm{sup {minus}1} for IE[CS{sub 2}{sup +}({tilde X}{sup 2}{Pi}{sub 3/2})]. (Abstract Truncated)

  17. Iron ionization and recombination rates and ionization equilibrium

    NASA Technical Reports Server (NTRS)

    Arnaud, M.; Raymond, J.

    1992-01-01

    In the past few years important progress has been made on the knowledge of ionization and recombination rates of iron, an astrophysically abundant heavy element and a major impurity in laboratory fusion devices. We make a critical review of the existing data on ionization and dielectronic recombination and present new computations of radiative recombination rate coefficients of Fe(+14) through Fe(+25) using the photoionization cross sections of Clark et al. (1986). We provide analytical fits to the recommended data (direct ionization and excitation-autoionization cross sections; radiative and dielectronic recombination rate coefficients). Finally we determine the iron ionic fractions at ionization equilibrium and compare them with previous computations as well as with observational data.

  18. Calculating Relative Ionization Probabilities of Plutonium for Resonance Ionization Mass Spectrometry to Support Nuclear Forensic Investigations

    NASA Astrophysics Data System (ADS)

    Lensegrav, Craig; Smith, Craig; Isselhardt, Brett

    2015-03-01

    Ongoing work seeks to apply the technology of Resonance Ionization Mass Spectrometry (RIMS) to problems related to nuclear forensics and, in particular, to the analysis and quantification of debris from nuclear detonations. As part of this effort, modeling and simulation methods are being applied to analyze and predict the potential for ionization by laser excitation of isotopes of both uranium and plutonium. Early work focused on the ionization potential of isotopes of uranium, and the present effort has expanded and extended the previous work by identifying and integrating new data for plutonium isotopes. In addition to extending the effort to this important new element, we have implemented more accurate descriptions of the spatial distribution of the laser beams to improve the accuracy of model predictions compared with experiment results as well as an ability to readily incorporate new experimental data as they become available. The model is used to estimate ionization cross sections and to compare relative excitation on two isotopes as a function of wavelength. This allows the study of sensitivity of these measurements to fluctuations in laser wavelength, irradiance, and bandwidth. We also report on initial efforts to include predictions of americium ionization probabilities into our modeling package. I would like to thank my co-authors, Gamani Karunasiri and Fabio Alves. My success is a product of their support and guidance.

  19. Laboratory study of the spectrum of highly ionized calcium in the 100-250 A range applied to solar flare diagnostics

    NASA Technical Reports Server (NTRS)

    Lippmann, S.; Finkenthal, M.; Huang, L. K.; Moos, H. W.; Stratton, B. C.; Yu, T. L.; Bhatia, A. K.

    1987-01-01

    Calcium was introduced into the TEXT tokamak, and its spectral emission was recorded in the 50-360 A range by an absolutely calibrated grazing incidence spectrometer. These observations of highly ionized species of calcium at known conditions of plasma electron temperature and density allow testing of line brightness ratio predictions based on theoretical values of temperature-dependent electron excitation rates. The confirmation of the expected ratios in Be I-like to O I-like calcium allows more confident use of these ratios as a density diagnostic of remote astrophysical sources such as solar flares.

  20. Resonance Enhanced Multi-Photon Ionization and Uv-Uv Hole-Burning Spectroscopic Studies of Jet-Cooled Acetanilide Derivatives

    NASA Astrophysics Data System (ADS)

    Moon, Ceol Joo; Min, Ahreum; Ahn, Ahreum; Lee, Seung Jun; Choi, Myong Yong; Kim, Seong Keun

    2013-06-01

    Conformational investigations and photochemistry of jet-cooled methacetine (MA) and phenacetine (PA) using one color resonant two-photon ionization (REMPI), UV-UV hole-burning and IR-dip spectroscopy are presented. MA and PA are derivatives of acetanilide, substituted by methoxyl, ethoxyl group in the para position of acetanilide, respectively. Moreover, we have investigated conformational information of the acetanilide derivatives (AAP, MA and PA)-water. In this work, we will present and discuss the solvent effects of the hydroxyl group of acetanilide derivatives in the excited state.

  1. Pulsed helium ionization detection system

    DOEpatents

    Ramsey, Roswitha S.; Todd, Richard A.

    1987-01-01

    A helium ionization detection system is provided which produces stable operation of a conventional helium ionization detector while providing improved sensitivity and linearity. Stability is improved by applying pulsed dc supply voltage across the ionization detector, thereby modifying the sampling of the detectors output current. A unique pulse generator is used to supply pulsed dc to the detector which has variable width and interval adjust features that allows up to 500 V to be applied in pulse widths ranging from about 150 nsec to about dc conditions.

  2. Pulsed helium ionization detection system

    DOEpatents

    Ramsey, R.S.; Todd, R.A.

    1985-04-09

    A helium ionization detection system is provided which produces stable operation of a conventional helium ionization detector while providing improved sensitivity and linearity. Stability is improved by applying pulsed dc supply voltage across the ionization detector, thereby modifying the sampling of the detectors output current. A unique pulse generator is used to supply pulsed dc to the detector which has variable width and interval adjust features that allows up to 500 V to be applied in pulse widths ranging from about 150 nsec to about dc conditions.

  3. Ionizing radiation promotes protozoan reproduction

    SciTech Connect

    Luckey, T.D.

    1986-11-01

    This experiment was performed to determine whether ionizing radiation is essential for maximum growth rate in a ciliated protozoan. When extraneous ionizing radiation was reduced to 0.15 mrad/day, the reproduction rate of Tetrahymena pyriformis was significantly less (P less than 0.01) than it was at near ambient levels, 0.5 or 1.8 mrad/day. Significantly higher growth rates (P less than 0.01) were obtained when chronic radiation was increased. The data suggest that ionizing radiation is essential for optimum reproduction rate in this organism.

  4. Microwave reflectometer ionization sensor

    NASA Technical Reports Server (NTRS)

    Seals, Joseph; Fordham, Jeffrey A.; Pauley, Robert G.; Simonutti, Mario D.

    1993-01-01

    The development of the Microwave Reflectometer Ionization Sensor (MRIS) Instrument for use on the Aeroassist Flight Experiment (AFE) spacecraft is described. The instrument contract was terminated, due to cancellation of the AFE program, subsequent to testing of an engineering development model. The MRIS, a four-frequency reflectometer, was designed for the detection and location of critical electron density levels in spacecraft reentry plasmas. The instrument would sample the relative magnitude and phase of reflected signals at discrete frequency steps across 4 GHz bandwidths centered at four frequencies: 20, 44, 95, and 140 GHz. The sampled data would be stored for later processing to calculate the distance from the spacecraft surface to the critical electron densities versus time. Four stepped PM CW transmitter receivers were located behind the thermal protection system of the spacecraft with horn antennas radiating and receiving through an insulating tile. Techniques were developed to deal with interference, including multiple reflections and resonance effects, resulting from the antenna configuration and operating environment.

  5. Optical ionization detector

    DOEpatents

    Wuest, C.R.; Lowry, M.E.

    1994-03-29

    An optical ionization detector wherein a beam of light is split so that one arm passes through a fiber optics and the other arm passes through a gas-filled region, and uses interferometry to detect density changes in a gas when charged particles pass through it. The gas-filled region of the detector is subjected to a high electric field and as a charged particle traverses this gas region electrons are freed from the cathode and accelerated so as to generate an electron avalanche which is collected on the anode. The gas density is effected by the electron avalanche formation and if the index or refraction is proportional to the gas density the index will change accordingly. The detector uses this index change by modulating the one arm of the split light beam passing through the gas, with respect to the other arm that is passed through the fiber optic. Upon recombining of the beams, interference fringe changes as a function of the index change indicates the passage of charged particles through the gaseous medium. 3 figures.

  6. Optical ionization detector

    DOEpatents

    Wuest, Craig R.; Lowry, Mark E.

    1994-01-01

    An optical ionization detector wherein a beam of light is split so that one arm passes through a fiber optics and the other arm passes through a gas-filled region, and uses interferometry to detect density changes in a gas when charged particles pass through it. The gas-filled region of the detector is subjected to a high electric field and as a charged particle traverses this gas region electrons are freed from the cathode and accelerated so as to generate an electron avalanche which is collected on the anode. The gas density is effected by the electron avalanche formation and if the index or refraction is proportional to the gas density the index will change accordingly. The detector uses this index change by modulating the one arm of the split light beam passing through the gas, with respect to the other arm that is passed through the fiber optic. Upon recombining of the beams, interference fringe changes as a function of the index change indicates the passage of charged particles through the gaseous medium.

  7. Ionization-based detectors for gas chromatography.

    PubMed

    Poole, Colin F

    2015-11-20

    The gas phase ionization detectors are the most widely used detectors for gas chromatography. The column and makeup gases commonly used in gas chromatography are near perfect insulators. This facilitates the detection of a minute number of charge carriers facilitating the use of ionization mechanisms of low efficiency while providing high sensitivity. The main ionization mechanism discussed in this report are combustion in a hydrogen diffusion flame (flame ionization detector), surface ionization in a plasma (thermionic ionization detector), photon ionization (photoionization detector and pulsed discharge helium ionization detector), attachment of thermal electrons (electron-capture detector), and ionization by collision with metastable helium species (helium ionization detector). The design, response characteristics, response mechanism, and suitability for fast gas chromatography are the main features summarized in this report. Mass spectrometric detection and atomic emission detection, which could be considered as ionization detectors of a more sophisticated and complex design, are not discussed in this report. PMID:25757823

  8. Ionization-based detectors for gas chromatography.

    PubMed

    Poole, Colin F

    2015-11-20

    The gas phase ionization detectors are the most widely used detectors for gas chromatography. The column and makeup gases commonly used in gas chromatography are near perfect insulators. This facilitates the detection of a minute number of charge carriers facilitating the use of ionization mechanisms of low efficiency while providing high sensitivity. The main ionization mechanism discussed in this report are combustion in a hydrogen diffusion flame (flame ionization detector), surface ionization in a plasma (thermionic ionization detector), photon ionization (photoionization detector and pulsed discharge helium ionization detector), attachment of thermal electrons (electron-capture detector), and ionization by collision with metastable helium species (helium ionization detector). The design, response characteristics, response mechanism, and suitability for fast gas chromatography are the main features summarized in this report. Mass spectrometric detection and atomic emission detection, which could be considered as ionization detectors of a more sophisticated and complex design, are not discussed in this report.

  9. Benchmark theoretical study of the ionization energies, electron affinities and singlet-triplet energy gaps of azulene, phenanthrene, pyrene, chrysene and perylene

    NASA Astrophysics Data System (ADS)

    Huzak, M.; Hajgató, B.; Deleuze, M. S.

    2012-10-01

    The vertical and adiabatic singlet-triplet energy gaps, electron affinities and ionization energies of azulene, phenanthrene, pyrene, chrysene, and perylene are computed by applying the principles of a focal point analysis onto a series of single-point calculations at the level of Hartree-Fock theory, second-, third-, and fourth-order Møller-Plesset perturbation theory, as well as coupled cluster theory including single, double and perturbative triple excitations, in conjunction with correlation consistent basis sets of improving quality. Results are supplemented with an extrapolation to the limit of an asymptotically complete basis set. According to our best estimates, azulene, phenanthrene, pyrene, chrysene, and perylene exhibit adiabatic singlet-triplet energy gaps of 1.79, 2.92, 2.22, 2.79 and 1.71 eV, respectively. In the same order, the corresponding adiabatic electron affinities (EAs) amount to 0.71, -0.08, -0.40, 0.24, and 0.87 eV, whereas benchmark values equal to 7.43, 8.01, 7.48, 7.66 and 7.15 eV, are found for the adiabatic ionization energies.

  10. Infrared Vacuum-Ultraviolet Laser Pulsed Field Ionization-Photoelectron Study of CH₃Br⁺(X˜ 2E3/2)

    SciTech Connect

    Xing, X.; Wang, P.; Reed, Beth; Baek, Sun-Jong; Ng, Cheuk-Yiu

    2008-10-02

    The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. By preparing methyl bromide (CH₃Br) in selected rotational levels of the CH₃Br(X˜ 1A1; V1 = 1) state with infrared (IR) laser excitation prior to vacuum-ultraviolet (VUV) laser pulsed field ionization-photoelectron (PFI-PE) measurements, we have observed rotationally resolved photoionization transitions to the CH₃Br⁺(X˜ 2E3/2; V1 + = 1) state, where V1 and V1 + are the symmetric C-H stretching vibrational mode for the neutral and cation, respectively. The VUV-PFI-PE origin band for CH₃Br⁺(X˜ 2E3/2) has also been measured. The simulation of these IR-VUV-PFI-PE and VUV-PFI-PE spectra have allowed the determination of the V1 + vibrational frequency (2901.8 ( 0.5 cm-1) and the ionization energies of the origin band (85 028.3 ( 0.5 cm-1) and the V1 + ) 1 r V1 ) 1 band (84 957.9 ( 0.5 cm-1).

  11. Attenuation and cross-attenuation in taste-aversion learning in the rat: Studies with ionizing radiation, lithium chloride, and ethanol. Scientific report

    SciTech Connect

    Rabin, B.M.; Hunt, W.A.; Lee, J.

    1989-01-01

    The pre-exposure paradigm was utilized to evaluate the similarity of ionizing radiation, lithium chloride, and ethanol as unconditioned stimuli for the acquisition of a conditioned taste aversion. Three unpaired pre-exposures to lithium chloride blocked the acquisition of a taste aversion when a novel sucrose solution was paired with either the injection of the same dose of lithium chloride or exposure to ionizing radiation (100 rad). Similar pretreatment with radiation blocked the acquisition of a radiation-induced aversion, but had no effect on taste aversions produced by lithium aversion, but not radiation- or lithium chloride-induced aversions. In contrast, preexposure to either radiation or lithium chloride attenuated an ethanol-induced taste aversion in intact rats, but not in rats with lesions of the area postrema. The results are discussed in terms of relationships between these three unconditioned stimuli and in terms of implications of these results for understanding the nature of the proximal unconditioned stimulus in taste aversion learning.

  12. Ionization of impurities in silicon

    NASA Astrophysics Data System (ADS)

    Kuźmicz, Wiesław

    1986-12-01

    A model for calculation of the percentage of ionized dopant atoms as a function of the doping concentration and temperature is proposed. The results are compared with experiment. Analytical approximations that facilitate practical applications of the model are given.

  13. Measuring Air-Ionizer Output

    NASA Technical Reports Server (NTRS)

    Lonborg, J. O.

    1985-01-01

    Test apparatus checks ion content of airstream from commercial air ionizer. Apparatus ensures ion output is sufficient to neutralize static charges in electronic assembly areas and concentrations of positive and negative ions are balanced.

  14. Ionization oscillations in Hall accelerators

    NASA Astrophysics Data System (ADS)

    Barral, S.; Peradzyński, Z.

    2010-01-01

    The underlying mechanism of low-frequency oscillations in Hall accelerators is investigated theoretically. It is shown that relaxation oscillations arise from a competition between avalanche ionization and the advective transport of the working gas. The model derived recovers the slow progression and fast recession of the ionization front. Analytical approximations of the shape of current pulses and of the oscillation frequency are provided for the case of large amplitude oscillations.

  15. Resonance ionization for analytical spectroscopy

    DOEpatents

    Hurst, George S.; Payne, Marvin G.; Wagner, Edward B.

    1976-01-01

    This invention relates to a method for the sensitive and selective analysis of an atomic or molecular component of a gas. According to this method, the desired neutral component is ionized by one or more resonance photon absorptions, and the resultant ions are measured in a sensitive counter. Numerous energy pathways are described for accomplishing the ionization including the use of one or two tunable pulsed dye lasers.

  16. Fragmentation study of rutin, a naturally occurring flavone glycoside cationized with different alkali metal ions, using post-source decay matrix-assisted laser desorption/ionization mass spectrometry.

    PubMed

    Kéki, S; Deák, G; Zsuga, M

    2001-12-01

    A post-source decay matrix-assisted laser desorption/ionization mass spectrometric (PSD-MALDI-MS) study of rutin, a naturally occurring flavone glycoside cationized with different alkali metal ions, is reported. The fragmentations of rutin were performed by selecting the [R + Cat]+ peaks for PSD, where R represents a rutin molecule and Cat an alkali metal ion (Li+, Na+, K+). The PSD-MALDI mass spectra showed, depending on Cat, different fragmentation patterns with respect to both the quality and quantity of the fragment ions formed. The intensity of fragmentation decreased in the order Li+ > Na+ > K+. The fragmentation mechanism and an explanation for the observed differences are suggested.

  17. Biodegradation of tetrahydrofuran by Pseudomonas oleovorans DT4 immobilized in calcium alginate beads impregnated with activated carbon fiber: mass transfer effect and continuous treatment.

    PubMed

    Chen, Dong-Zhi; Fang, Jun-Yi; Shao, Qian; Ye, Jie-Xu; Ouyang, Du-Juan; Chen, Jian-Meng

    2013-07-01

    A novel entrapment matrix, calcium alginate (CA) coupled with activated carbon fiber (ACF), was prepared to immobilize Pseudomonas oleovorans DT4 for degrading tetrahydrofuran (THF). The addition of 1.5% ACF increased the adsorption capacity of the immobilized bead, thus resulting in an enhanced average removal rate of 30.3mg/(Lh). The synergism between adsorption and biodegradation was observed in the hybrid CA-ACF beads instead of in the system comprising CA beads and freely suspended ACF. The effective diffusion coefficient of the CA-ACF bead was not significantly affected by bead size, but the bead's value of 1.14×10(-6)cm(2)/s (for the bead diameter of 0.4 cm) was larger than that of the CA bead by almost one order of magnitude based on the intraparticle diffusion-reaction kinetics analysis. Continuous treatment of the THF-containing wastewater was succeeded by CA-ACF immobilized cells in a packed-bed reactor for 54 d with a >90% removal efficiency. PMID:23644074

  18. Biodegradation of tetrahydrofuran by Pseudomonas oleovorans DT4 immobilized in calcium alginate beads impregnated with activated carbon fiber: mass transfer effect and continuous treatment.

    PubMed

    Chen, Dong-Zhi; Fang, Jun-Yi; Shao, Qian; Ye, Jie-Xu; Ouyang, Du-Juan; Chen, Jian-Meng

    2013-07-01

    A novel entrapment matrix, calcium alginate (CA) coupled with activated carbon fiber (ACF), was prepared to immobilize Pseudomonas oleovorans DT4 for degrading tetrahydrofuran (THF). The addition of 1.5% ACF increased the adsorption capacity of the immobilized bead, thus resulting in an enhanced average removal rate of 30.3mg/(Lh). The synergism between adsorption and biodegradation was observed in the hybrid CA-ACF beads instead of in the system comprising CA beads and freely suspended ACF. The effective diffusion coefficient of the CA-ACF bead was not significantly affected by bead size, but the bead's value of 1.14×10(-6)cm(2)/s (for the bead diameter of 0.4 cm) was larger than that of the CA bead by almost one order of magnitude based on the intraparticle diffusion-reaction kinetics analysis. Continuous treatment of the THF-containing wastewater was succeeded by CA-ACF immobilized cells in a packed-bed reactor for 54 d with a >90% removal efficiency.

  19. Tetrahydrofuran-induced K and Li doping onto poly(furfuryl alcohol)-derived activated carbon (PFAC): Influence on microstructure and H2 sorption properties

    SciTech Connect

    Saha, Dipendu; Contescu, Cristian I; Gallego, Nidia C

    2012-01-01

    We have doped polyfurfuryl alcohol derived activated carbon (PFAC) with two alkali metals, potassium (K) and lithium (Li) by prior reacting the metals with naphthalene in presence of tetrahydrofuran (THF) followed by introducing them to pristine PFAC. THF molecule causes minor alteration in the microstructure of PFAC as confirmed by the Raman spectra, X-ray diffraction and pore textural analysis. Raman spectra and X-ray diffraction indicated a slight localized ordering towards the stacking defects of disordered carbon, like PFAC which can be attributed to the movement of THF molecules within the internal planes of graphene sheets. Pore textural analysis confirmed the lowering specific surface area and pore volume of both K and Li doped PFACs.(BET SSA: 1378 m2/g (PFAC); 1252 m2/g (K-PFAC); 1081 m2/g (Li-PFAC)) Volumetric hydrogen adsorption measurement at the temperatures of 298, 288, 273 and 77 K and pressure up to 1 bar indicated the enhanced adsorption potential imposed by the presence of alkali metals, which can be reconfirmed by the additional heats of adsorption of metal doped PFACs (Li-PFAC: -(10 - 11) kJ/mol; K-PFAC: -(16 -19) kJ/mol) compared to pristine PFAC (-9.6 kJ/mol).

  20. Ionization sources and mass analyzers in MS imaging.

    PubMed

    Tsai, Yu-Hsuan; Menger, Robert F; Drexler, Dieter M; Yost, Richard A; Garrett, Timothy J

    2015-01-01

    Drug absorption, distribution, metabolism, excretion and toxicology study is one important step in drug discovery and development. MS imaging has become one of the popular methods in this field. Here, selected ionization methods such as matrix-assisted laser desorption/ionization, secondary ion MS and desorption electrospray ionization have been briefly discussed. To differentiate drug and drug metabolites from endogenous compounds present in the biological system, exact mass and/or tandem MS is necessary. As a result, mass analyzers such as time-of-flight, Fourier transform ion cyclotron resonance or Orbitrap are often the method of choice and are briefly introduced. PMID:26511148