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Sample records for rich microsecond isomers

  1. New neutron-rich microsecond isomers observed among fission products of {sup 238}U at 80 MeV/nucleon

    SciTech Connect

    Folden, C. M. III; Ginter, T. N.; Hausmann, M.; Portillo, M.; Nettleton, A. S.; Amthor, A. M.; Sherrill, B. M.; Kubo, T.; Takeda, H.; Loveland, W.; Manikonda, S. L.; Morrissey, D. J.; Nakao, T.; Souliotis, G. A.; Strong, B. F.; Tarasov, O. B.

    2009-06-15

    Eight new isomeric states in neutron-rich nuclides have been discovered in fission fragments produced by the reaction of an 80 MeV/nucleon {sup 238}U beam with a {sup 9}Be target and separated in-flight using the A1900 fragment separator. The experiment was conducted at the National Superconducting Cyclotron Laboratory (NSCL) at Michigan State University. Gamma rays were detected in a high-purity germanium detector located at the focal plane within a time window of 20 {mu}s following ion implantation. In some cases the isomers were observed to decay into previously reported states, allowing us to assign the initial decay from the isomeric state. Among the outcomes, the results suggest that many studies on the nuclear structure of medium-mass neutron-rich nuclei are feasible at projectile fragmentation facilities using induced fission.

  2. Observation of new neutron-rich micro-second isomers among fission products of ^238U at 345 MeV/u

    NASA Astrophysics Data System (ADS)

    Kameda, Daisuke; Nakao, Taro; Kubo, Toshiyuki; Ohnishi, Tetsuya; Takeda, Hiroyuki; Fukuda, Naoki; Kusaka, Kensuke; Yoshida, Atsushi; Yoshida, Koichi; Ohtake, Masao; Inabe, Naohito; Yanagisawa, Yoshiyuki; Tanaka, Kanenobu; Gono, Yasuyuki

    2009-10-01

    In the production of the radioactive isotope (RI) beam using projectile fragment separators, γ rays emitted from metastable states, isomers, of the reaction products can be used as a fingerprint of the isotope that is analyzed in the separator. In the operation of the superconducting in-flight RI beam separator BigRIPS [1] at RIKEN RI Beam Factory, the detection of such γ rays plays important roles not only in the identification of the RI beam [2] but also in searching for new isomers, providing valuable spectroscopic information on the isotopes. In the recent new-isotope production experiment with BigRIPS using in-flight fission of 345 MeV/nucleon ^238U at the beam intensity around 0.3 pnA, we have observed a number of short-lived isomeric decays which include unknown decays from more than 10 isotopes, using three clover-type Ge detectors with a beam stopper of aluminum. The primal result of the observations will be reported. [1] T. Kubo: Nucl. Instr. and Meth. B 204 (2003) 97. [2] T. Ohnishi et al.: J. Phys. Soc. Japan, 77 (2008) 083201.

  3. Configuration assignments to isomers in the neutron-rich 186Ta (Z =73 ) nucleus

    NASA Astrophysics Data System (ADS)

    Sood, P. C.; Gowrishankar, R.

    2014-12-01

    Though the neutron-rich odd-odd nucleus Ta18673113 was first produced in 1955, even after 60 years its ground state (g.s.) and both of its two other isomers remain undefined. We use the well-tested two-quasiparticle rotor model, which explicitly includes residual neutron-proton n -p interaction and other contributing factors, to evaluate the bandhead energies of the physically admissible low-lying two-particle structures in 186Ta with inputs from experimentally observed structures in neighboring isotopes and isotones to characterize these levels. Our analysis assigns Kπ = 5-{p :7 /2 [404 ]⊗n :3 /2 [512 ]} configuration to the 10.5 min 186Ta (g.s.) and the antiparallel-spin Kπ=2- of the same configuration to the 1.54 min isomer with Ex = 90(10) keV. We further assign Kπ=8-{p :7 /2 [404 ]⊗n :9 /2 [505 ]} configuration to the recently identified 3.0 min isomer with Ex=336 (20) keV. These assignments are shown to be consistent with all the available experimental data. Further, they are seen to fit nicely as another instance of highly hindered Δ I =3 isomeric transitions, and also of low-lying long-lived isomer triplets, frequently observed in numerous odd-odd Z =61 (2 )75 nuclides.

  4. Isomers of Pm Isotopes on the Neutron-Rich Frontier of the Deformed Z ~ 60 Region

    NASA Astrophysics Data System (ADS)

    Yokoyama, Rin; Ideguchi, Eiji; Simpson, Gary; Tanaka, Mana; Nishimura, Shunji; Doornnbal, Pieter; Söderström, Pär-Anders; Lorusso, Giuseppe; Xu, Zhengyu; Wu, Jin; Sumikama, Toshiyuki; Aoi, Nori; Baba, Hidetada; Bello, Frank; Browne, Frank; Daido, Rie; Fang, Yifan; Fukuda, Naoki; Gey, Guillaume; Go, Shintaro; Inabe, Naohiro; Isobe, Tadaaki; Kameda, Daisuke; Kobayashi, Kazuma; Kobayashi, Motoki; Komatsubara, Tetsuro; Kubo, Toshiyuki; Kuti, Istvan; Li, Zhihuan; Matsushita, Masafumi; Michimasa, Shin'ichiro; Moon, Chang-Bum; Nishibata, Hiroki; Nishizuka, Ippei; Odahara, Atsuko; Patel, Zena; Rice, Simon; Sahin, Eda; Sinclair, Laura; Suzuki, Hiroshi; Takeda, Hiroyuki; Taprogge, Jan; Vajta, Zsolt; Watanabe, Hiroshi; Yagi, Ayumi

    Neutron-rich Pm (Z = 61) isotopes were studied by delayed γ-ray spectroscopy at RIBF, Riken Nishina Center using the in-flight fission of 345 MeV/u 238U beam. An array of cluster-type Ge detectors, EURICA, was used to measure the delayed γ rays from stopped ions. Isomers were observed in 158Pm, 159Pm and 161Pm with half-lives of >16, 4.64(21), and 0.88(10) µs respectively. Preliminary level schemes for 159Pm and 161Pm were constructed in this study. They have ground-state bands similar to those of 153Pm and 155Pm. The isomeric state of 161Pm could be interpreted as a two quasi-particle excitation of neutrons with configuration of ν 7/2[633] otimes ν 1/2[521] as other Kπ = 4 - isomers observed systematically in other N = 100 isotones.

  5. K-isomers in Hf nuclei at and beyond the neutron-rich edge of {beta}-stability.

    SciTech Connect

    Chowdhury, P.; Alarcao, R. D.; Seabury, E. H.; Walker, P. M.; Wheldon, C.; Ahmad. I.; Carpenter, M. P.; Hackman, G.; Janssens, R. V. F.; Khoo, T. L.; Nisius, D.; Reiter, P.

    1999-03-30

    New high-K isomers are populated in {sup 180,181,182}Hf nuclei via inelastic excitation and transfer reactions, using pulsed {sup 238}U beams on Hf targets. The new data explore K-hindrances for different multipolarities and the role of residual spin-spin interactions for multi-quasiparticle (qp) configurations at the neutron-rich edge of the {beta}-stability line. The mapping of 4-qp K-isomers in the A {approx} 180 region is extended into neutron-rich territory.

  6. Searching for high-K isomers in the proton-rich A ˜ 80 mass region

    NASA Astrophysics Data System (ADS)

    Bai, Zhi-Jun; Jiao, Chang-Feng; Gao, Yuan; Xu, Fu-Rong

    2016-09-01

    Configuration-constrained potential-energy-surface calculations have been performed to investigate the K isomerism in the proton-rich A ˜ 80 mass region. An abundance of high-K states are predicted. These high-K states arise from two and four-quasi-particle excitations, with Kπ = 8+ and Kπ = 16+, respectively. Their excitation energies are comparatively low, making them good candidates for long-lived isomers. Since most nuclei under study are prolate spheroids in their ground states, the oblate shapes of the predicted high-K states may indicate a combination of K isomerism and shape isomerism. Supported by National Key Basic Research Program of China (2013CB834402) and National Natural Science Foundation of China (11235001, 11320101004 and 11575007)

  7. New K isomers in the neutron-rich N =100 isotones 162Sm, 163Eu, and 164Gd

    NASA Astrophysics Data System (ADS)

    Yokoyama, R.; Go, S.; Kameda, D.; Kubo, T.; Inabe, N.; Fukuda, N.; Takeda, H.; Suzuki, H.; Yoshida, K.; Kusaka, K.; Tanaka, K.; Yanagisawa, Y.; Ohtake, M.; Sato, H.; Shimizu, Y.; Baba, H.; Kurokawa, M.; Nishimura, D.; Ohnishi, T.; Iwasa, N.; Chiba, A.; Yamada, T.; Ideguchi, E.; Fujii, T.; Nishibata, H.; Ieki, K.; Murai, D.; Momota, S.; Sato, Y.; Hwang, J. W.; Kim, S.; Tarasov, O. B.; Morrissey, D. J.; Sherrill, B. M.; Simpson, G.; Praharaj, C. R.

    2017-03-01

    Very neutron-rich Z ˜60 isotopes produced by in-flight fission of a 345 MeV/nucleon 238U beam at the RI Beam Factory, RIKEN Nishina Center, have been studied by delayed γ -ray spectroscopy. New isomers were discovered in the neutron-rich N =100 isotones 162Sm, 163Eu, and 164Gd. Half-lives, γ -ray energies, and relative intensities of these isomers were obtained. Level schemes were proposed for these nuclei and the first 2+ and 4+ states were assigned for the even-even nuclei. The first 2+ and 4+ state energies decrease as the proton numbers get smaller. The energies and the half-lives of the new isomers are very similar to those of 4- isomers known in less neutron-rich N =100 isotones 168Er and 170Yb. A deformed Hartree-Fock with angular momentum projection model suggests Kπ=4- two-quasiparticle states with ν 7 /2 [633 ]⊗ν 1 /2 [521 ] configurations with similar excitation energy. The results suggest that neutron-rich N =100 nuclei are well deformed and the deformation gets larger as Z decreases to 62. The onset of K isomers with the same configuration at almost the same energy in N =100 isotones indicates that the neutron single-particle structures of neutron-rich isotones down to Z =62 do not change significantly from those of the Z =70 stable nuclei. Systematics of the excitation energies of new isomers can be explained without the predicted N =100 shell gap.

  8. E2 transition probabilities for decays of isomers observed in neutron-rich odd Sn isotopes

    SciTech Connect

    Iskra, Ł. W.; Broda, R.; Janssens, R. V.F.; Wrzesiński, J.; Chiara, C. J.; Carpenter, M. P.; Fornal, B.; Hoteling, N.; Kondev, F. G.; Królas, W.; Lauritsen, T.; Pawłat, T.; Seweryniak, D.; Stefanescu, I.; Walters, W. B.; Zhu, S.

    2015-01-01

    High-spin states were investigated with gamma coincidence techniques in neutron-rich Sn isotopes produced in fission processes following ⁴⁸Ca + ²⁰⁸Pb, ⁴⁸Ca + ²³⁸U, and ⁶⁴Ni + ²³⁸U reactions. By exploiting delayed and cross-coincidence techniques, level schemes have been delineated in odd ¹¹⁹⁻¹²⁵Sn isotopes. Particular attention was paid to the occurrence of 19/2⁺ and 23/2⁺ isomeric states for which the available information has now been significantly extended. Reduced transition probabilities, B(E2), extracted from the measured half-lives and the established details of the isomeric decays exhibit a striking regularity. This behavior was compared with the previously observed regularity of the B(E2) amplitudes for the seniority ν = 2 and 3, 10⁺ and 27/2⁻ isomers in even- and odd-Sn isotopes, respectively.

  9. E2 transition probabilities for decays of isomers observed in neutron-rich odd Sn isotopes

    DOE PAGES

    Iskra, Ł. W.; Broda, R.; Janssens, R. V.F.; ...

    2015-01-01

    High-spin states were investigated with gamma coincidence techniques in neutron-rich Sn isotopes produced in fission processes following ⁴⁸Ca + ²⁰⁸Pb, ⁴⁸Ca + ²³⁸U, and ⁶⁴Ni + ²³⁸U reactions. By exploiting delayed and cross-coincidence techniques, level schemes have been delineated in odd ¹¹⁹⁻¹²⁵Sn isotopes. Particular attention was paid to the occurrence of 19/2⁺ and 23/2⁺ isomeric states for which the available information has now been significantly extended. Reduced transition probabilities, B(E2), extracted from the measured half-lives and the established details of the isomeric decays exhibit a striking regularity. This behavior was compared with the previously observed regularity of the B(E2) amplitudesmore » for the seniority ν = 2 and 3, 10⁺ and 27/2⁻ isomers in even- and odd-Sn isotopes, respectively.« less

  10. Lycopene from heat-induced cis-isomer-rich tomato sauce is more bioavailable than from all-trans-rich tomato sauce in human subjects.

    PubMed

    Unlu, Nuray Z; Bohn, Torsten; Francis, David M; Nagaraja, Haikady N; Clinton, Steven K; Schwartz, Steven J

    2007-07-01

    Lycopene is present mainly as cis-isomers in human serum and tissues whereas all-trans-lycopene predominates in tomato products, suggesting that all-trans-lycopene is isomerised in the body or is less bioavailable. The objectives of the present study were to develop processing conditions for tomatoes to obtain products with different cis-trans-lycopene isomer distribution and to assess their bioavailability. Healthy adult subjects (n 12) were recruited for this randomised cross-over trial. Each intervention was preceded by a 2-week washout period. Two tomato sauces, one rich in all-trans-lycopene (32.5 mg total lycopene/100 g sauce; 5 % cis-isomers), the other high in cis-lycopene (26.4 mg total lycopene/100 g sauce; 45 % cis-isomers), were produced by different heat-processing techniques. Each sauce (150 g) was served in a standardised meal at 08.00 hours after overnight fasting. Plasma TAG-rich lipoprotein fractions over 9.5 h following test-meal consumption as a measure of lycopene absorption were obtained and expressed as baseline-corrected area under the concentration v. time curves (AUC), using HPLC-electrochemical detection. AUC values adjusted for the amount lycopene consumed showed that total, total cis-, and all-trans-lycopene responses were significantly higher from the cis-isomer-rich sauce, compared with the all-trans-rich sauce, being 7.30 (sem 1.45) v. 4.74 (sem 1.08) nmol x h/l (P = 0.002), 3.80 (sem 0.76) v. 1.98 (sem 0.37) nmol x h/l (P = 0.0005) and 3.50 (sem 0.76) v. 2.76 (sem 0.76) nmol x h/l (P = 0.01), respectively. The present study demonstrates significant lycopene bioavailability from cis-lycopene-rich tomato sauce and highlights the importance of considering isomer-distribution for lycopene bioavailability. Furthermore, processing parameters can be controlled to alter isomer patterns of tomato products and influence lycopene bioavailability.

  11. Discovery of Highly Excited Long-Lived Isomers in Neutron-Rich Hafnium and Tantalum Isotopes through Direct Mass Measurements

    SciTech Connect

    Reed, M. W.; Cullen, I. J.; Walker, P. M.; Deo, A. Y.; Kempley, R. S.; Swan, T. P. D.; Litvinov, Yu. A.; Winckler, N.; Blaum, K.; Bosch, F.; Dimopoulou, C.; Farinon, F.; Heil, M.; Knoebel, R.; Kozhuharov, C.; Kurcewicz, J.; Kuzminchuk, N.; Litvinov, S.; Nociforo, C.; Nolden, F.

    2010-10-22

    A study of cooled {sup 197}Au projectile-fragmentation products has been performed with a storage ring. This has enabled metastable nuclear excitations with energies up to 3 MeV, and half-lives extending to minutes or longer, to be identified in the neutron-rich nuclides {sup 183,184,186}Hf and {sup 186,187}Ta. The results support the prediction of a strongly favored isomer region near neutron number 116.

  12. Reactions of Atomic Carbon with Butene Isomers: Implications for Molecular Growth in Carbon-Rich Environments

    DOE PAGES

    Bourgalais, J.; Spencer, Michael; Osborn, David L.; ...

    2016-10-31

    We carried out the product detection studies of C(3P) atom reactions with butene (C4H8) isomers (but-1-ene, cis-but-2-ene, trans-but-2-ene) in a flow tube reactor at 353 K and 4 Torr under multiple collision conditions. Ground state carbon atoms are generated by 248 nm laser photolysis of tetrabromomethane, CBr4, in a buffer of helium. Thermalized reaction products are detected using synchrotron tunable VUV photoionization and time-of-flight mass spectrometry. The temporal profiles of the detected ions are used to discriminate products from side or secondary reactions. Furthermore, for the C(3P) + trans-but-2-ene and C(3P) + cis-but-2-ene reactions, various isomers of C4H5 and C5H7more » are identified as reaction products formed via CH3 and H elimination. Assuming equal ionization cross sections for all C4H5 and C5H7 isomers, C4H5:C5H7 branching ratios of 0.63:1 and 0.60:1 are derived for the C(3P) + trans-but-2-ene and the C(3P) + cis-but-2-ene reactions, respectively. For the C(3P) + but-1-ene reaction, two reaction channels are observed: the H-elimination channel, leading to the formation of the ethylpropargyl isomer, and the C3H3 + C2H5 channel. Assuming equal ionization cross sections for ethylpropargyl and C3H3 radicals, a branching ratio of 1:0.95 for the C3H3 + C2H5 and H + ethylpropargyl channels is derived. Finally, the experimental results are compared to previous H atom branching ratios and used to propose the most likely mechanisms for the reaction of ground state carbon atoms with butene isomers.« less

  13. Reactions of Atomic Carbon with Butene Isomers: Implications for Molecular Growth in Carbon-Rich Environments

    NASA Astrophysics Data System (ADS)

    Bourgalais, J.; Spencer, Michael; Osborn, David L.; Goulay, F.; Le Picard, S. D.

    2016-10-01

    Product detection studies of C(3P) atom reactions with butene (C4H8) isomers (but-1-ene, cis-but-2-ene, trans-but-2-ene) are carried out in a flow tube reactor at 353 K and 4 Torr under multiple collision conditions. Ground state carbon atoms are generated by 248 nm laser photolysis of tetrabromomethane, CBr4, in a buffer of helium. Thermalized reaction products are detected using synchrotron tunable VUV photoionization and time-of-flight mass spectrometry. The temporal profiles of the detected ions are used to discriminate products from side or secondary reactions. For the C(3P) + trans-but-2-ene and C(3P) + cis-but-2-ene reactions, various isomers of C4H5 and C5H7 are identified as reaction products formed via CH3 and H elimination. Assuming equal ionization cross sections for all C4H5 and C5H7 isomers, C4H5:C5H7 branching ratios of 0.63:1 and 0.60:1 are derived for the C(3P) + trans-but-2-ene and the C(3P) + cis-but-2-ene reactions, respectively. For the C(3P) + but-1ene reaction, two reaction channels are observed: the H-elimination channel, leading to the formation of the ethylpropargyl isomer, and the C3H3 + C2H5 channel. Assuming equal ionization cross sections for ethylpropargyl and C3H3 radicals, a branching ratio of 1:0.95 for the C3H3 + C2H5 and H + ethylpropargyl channels is derived. The experimental results are compared to previous H atom branching ratios and used to propose the most likely mechanisms for the reaction of ground state carbon atoms with butene isomers.

  14. Reactions of Atomic Carbon with Butene Isomers: Implications for Molecular Growth in Carbon-Rich Environments

    SciTech Connect

    Bourgalais, J.; Spencer, Michael; Osborn, David L.; Goulay, F.; Le Picard, S. D.

    2016-10-31

    We carried out the product detection studies of C(3P) atom reactions with butene (C4H8) isomers (but-1-ene, cis-but-2-ene, trans-but-2-ene) in a flow tube reactor at 353 K and 4 Torr under multiple collision conditions. Ground state carbon atoms are generated by 248 nm laser photolysis of tetrabromomethane, CBr4, in a buffer of helium. Thermalized reaction products are detected using synchrotron tunable VUV photoionization and time-of-flight mass spectrometry. The temporal profiles of the detected ions are used to discriminate products from side or secondary reactions. Furthermore, for the C(3P) + trans-but-2-ene and C(3P) + cis-but-2-ene reactions, various isomers of C4H5 and C5H7 are identified as reaction products formed via CH3 and H elimination. Assuming equal ionization cross sections for all C4H5 and C5H7 isomers, C4H5:C5H7 branching ratios of 0.63:1 and 0.60:1 are derived for the C(3P) + trans-but-2-ene and the C(3P) + cis-but-2-ene reactions, respectively. For the C(3P) + but-1-ene reaction, two reaction channels are observed: the H-elimination channel, leading to the formation of the ethylpropargyl isomer, and the C3H3 + C2H5 channel. Assuming equal ionization cross sections for ethylpropargyl and C3H3 radicals, a branching ratio of 1:0.95 for the C3H3 + C2H5 and H + ethylpropargyl channels is derived. Finally, the experimental results are compared to previous H atom branching ratios and used to propose the most likely mechanisms for the reaction of ground state carbon atoms with butene isomers.

  15. Characterization of isomers in the neutron-rich odd-odd nucleus {sup 156}Pm

    SciTech Connect

    Sood, P. C.; Gowrishankar, R; Sai, K. Vijay; Sainath, M.

    2011-02-15

    Critical examination of the experimental data from {sup 156}Nd and {sup 156}Pm {beta} decays and the observed location of relevant neutron and proton orbitals in the neighboring odd-A isotones and isotopes, taken together with the low-lying two-quasiparticle (2qp) structures expected in {sup 156}Pm from the rotor-particle model, lead to the conclusion that a consistent description of all the available data is achieved with the I{sup {pi}}=4{sup +} spin-parity assignment to the 26.7s {sup 156}Pm ground state (g.s.) and assignment of I{sup {pi}}=1{sup +} to its 150.3-keV isomer with the 2qp configuration 4{sub g.s.}{sup +}{l_brace}p{sub o}:5/2[532{up_arrow}]{+-}n{sub o}:3/2[521{up_arrow}]{r_brace}1{sub 150}{sup +}. In the process, a two-neutron configuration is also suggested for the 1509-keV 4{sup +} level in the daughter nucleus {sup 156}Sm. The present analysis reiterates the important question of whether the {beta}-decay log ft value, by itself, can be employed to deduce the relative parity of the {beta}-connected states.

  16. Bands and Isomers in Neutron-Rich Rare-Earth Nuclei in PHF Model

    NASA Astrophysics Data System (ADS)

    Praharaj, C. R.; Ghorui, S. K.; Naik, Z.; Sahu, B. B.

    Rotational structures of neutron-rich Gd and Dy nuclei in the REE peak region are studied with deformed Hartee-Fock (HF) and angular momentum (J) projection model. Spectra of ground band and a few more excited, positive and negative parity bands have been studied up to high spin values. Some 4-quasiparticle K-isomeric bands and their electromagnetic properties are predicted.

  17. Decay of a {pi}h{sub 11/2} x {nu}h{sub 11/2} microsecond isomer in {sub 61}{sup 136}Pm{sub 75}

    SciTech Connect

    Rigby, S. V.; Cullen, D. M.; Mason, P. J. R.; Scholes, D. T.; Scholey, C.; Rahkila, P.; Eeckhaudt, S.; Grahn, T.; Greenlees, P.; Jones, P. M.; Julin, R.; Juutinen, S.; Kettunen, H.; Leino, M.; Leppaenen, A.-P.; Nieminen, P.; Nyman, M.; Pakarinen, J.; Uusitalo, J.

    2008-09-15

    An experiment has been performed to populate several extremely neutron-deficient nuclei around the mass-140 region of the nuclear chart, using a beam of {sup 54}Fe on a {sup 92}Mo target at an energy of 315 MeV. Analysis of these data using recoil-isomer tagging has established that the yrast {pi}h{sub 11/2} x {nu}h{sub 11/2},J{sup {pi}}=(8{sup +}), bandhead state in {sup 136}Pm is isomeric with a half-life of 1.5(1) {mu}s. This isomeric state decays via a 43-keV, probable-E1 transition to a J{sup {pi}}=(7{sup -}) state. Consideration of the theoretical Nilsson orbitals near the Fermi surface suggests that the J{sup {pi}}=(8{sup +}) state has a {nu}h{sub 11/2}[505](11/2){sup -} x {pi}h{sub 11/2}[532](5/2){sup -} configuration, which decays to the J{sup {pi}}=(7{sup -}) state with a {nu}h{sub 11/2}[505](11/2){sup -} x {pi}d{sub 5/2}[411](3/2){sup +} configuration. Differences in the shape-driving effects for these two configurations is reasoned to be responsible for the long half-life of the J{sup {pi}}=(8{sup +}) isomeric state. The non-observation of other {gamma} rays in prompt or delayed coincidence with the 43-keV transition suggests that this transition may feed another, longer lived isomeric state with a half-life of the order of milliseconds or greater. However, the present experiment was not sensitive to the decay of this new J{sup {pi}}=(7{sup -}) state by internal conversion or even {beta} decay.

  18. Microsecond switchable thermal antenna

    SciTech Connect

    Ben-Abdallah, Philippe Benisty, Henri; Besbes, Mondher

    2014-07-21

    We propose a thermal antenna that can be actively switched on and off at the microsecond scale by means of a phase transition of a metal-insulator material, the vanadium dioxide (VO{sub 2}). This thermal source is made of a periodically patterned tunable VO{sub 2} nanolayer, which support a surface phonon-polariton in the infrared range in their crystalline phase. Using electrodes properly registered with respect to the pattern, the VO{sub 2} phase transition can be locally triggered by ohmic heating so that the surface phonon-polariton can be diffracted by the induced grating, producing a highly directional thermal emission. Conversely, when heating less, the VO{sub 2} layers cool down below the transition temperature, the surface phonon-polariton cannot be diffracted anymore so that thermal emission is inhibited. This switchable antenna could find broad applications in the domain of active thermal coatings or in those of infrared spectroscopy and sensing.

  19. Three hen strains fed photoisomerized trans,trans CLA-rich soy oil exhibit different yolk accumulation rates and source-specific isomer deposition.

    PubMed

    Shinn, Sara E; Gilley, Alex D; Proctor, Andrew; Anthony, Nicholas B

    2015-04-01

    Most CLA chicken feeding trials used cis,trans (c,t) and trans,cis (t,c) CLA isomers to produce CLA-rich eggs, while reports of trans,trans (t,t) CLA enrichment in egg yolks are limited. The CLA yolk fatty acid profile changes and the 10-12 days of feeding needed for maximum CLA are well documented, but there is no information describing CLA accumulation during initial feed administration. In addition, no information on CLA accumulation rates in different hen strains is available. The aim of this study was to determine a mathematical model that described yolk CLA accumulation and depletion in three hen strains by using t,t CLA-rich soybean oil produced by photoisomerization. Diets of 30-week Leghorns, broilers, and jungle fowl were supplemented with 15% CLA-rich soy oil for 16 days, and eggs were collected for 32 days. Yolk fatty acid profiles were measured by GC-FID. CLA accumulation and depletion was modeled by both quadratic and piecewise regression analysis. A strong quadratic model was proposed, but it was not as effective as piecewise regression in describing CLA accumulation and depletion. Broiler hen eggs contained the greatest concentration of CLA at 3.2 mol/100 g egg yolk, then jungle fowl at 2.9 mol CLA, and Leghorns at 2.3 mol CLA. The t,t CLA isomer levels remained at 55% of total yolk CLA during CLA feeding. However, t-10,c-12 (t,c) CLA concentration increased slightly during CLA accumulation and was significantly greater than c-9,t-11 CLA. Jungle fowl had the smallest increase in yolk saturated fat with CLA yolk accumulation.

  20. Interstellar isomers

    NASA Technical Reports Server (NTRS)

    Defrees, D.; Mclean, D.; Herbst, E.

    1986-01-01

    Both observational and theoretical studies of molecular clouds are hindered by many difficulties. One way to partially circumvent the difficulties of characterizing the chemistry within these objects is to study the relative abundances of isomers which are synthesized from a common set of precursors. Unfortunately, only one such system has been confirmed, the HCN/HNC pair of isomers. While the basic outlines of its chemistry have been known for some years, there are still many aspects of the chemistry which are unclear. Another potential pair of isomers is HCO+/HOC+; HCO+ is an abundant instellar molecule and a tentative identification of HOC+ has been made in Sgr B2. This identification is being challenged, however, based on theoretical and laboratory evidence that HOC+ reacts with H2. Another potential pair of interstellar isomers is methyl cyanide (CH3CN, acetonitrile) and methyl isocyanide (CH3NC). The cyanide is well known, however the isocyanide has yet to be observed despite theoretical predictions that appreciable quantities should be present.

  1. Onset of isomers in Cd125,126,127,128 and weakened neutron-neutron interaction strength

    NASA Astrophysics Data System (ADS)

    Hoteling, N.; Walters, W. B.; Tomlin, B. E.; Mantica, P. F.; Pereira, J.; Becerril, A.; Fleckenstein, T.; Hecht, A. A.; Lorusso, G.; Quinn, M.; Pinter, J. S.; Stoker, J. B.

    2007-10-01

    The presence of isomeric levels with half-lives in the microsecond range has been identified in Cd125,126,127,128. Neutron-rich Cd isotopes were produced from the fragmentation of a 120 MeV/nucleon Xe136 beam and uniquely identified through their time-of-flight, energy loss, and total kinetic energy. γ rays from these isomeric levels were measured with an array of Ge detectors that were gated for 15 μs by a particle implantation trigger from a stack of Si detectors. The γ rays observed in the decay of Cd126,128 isomers populate low-energy levels previously identified in the β decay of Ag126,128. The γ rays found in the decay of Cd125,127 isomers are consistent with expected yrast structures observed in lighter, odd-mass Cd isotopes. The appearance of these isomers at the point where N/Z exceeds 1.6 is interpreted as an indication of the onset of a weakened neutron-neutron interaction that has been proposed for Sn134, whose N/Z also exceeds 1.6.

  2. Long-lived K isomer and enhanced γ vibration in the neutron-rich nucleus 172Dy: Collectivity beyond double midshell

    NASA Astrophysics Data System (ADS)

    Watanabe, H.; Zhang, G. X.; Yoshida, K.; Walker, P. M.; Liu, J. J.; Wu, J.; Regan, P. H.; Söderström, P.-A.; Kanaoka, H.; Korkulu, Z.; Lee, P. S.; Nishimura, S.; Yagi, A.; Ahn, D. S.; Alharbi, T.; Baba, H.; Browne, F.; Bruce, A. M.; Carroll, R. J.; Chae, K. Y.; Dombradi, Zs.; Doornenbal, P.; Estrade, A.; Fukuda, N.; Griffin, C.; Ideguchi, E.; Inabe, N.; Isobe, T.; Kanaya, S.; Kojouharov, I.; Kondev, F. G.; Kubo, T.; Kubono, S.; Kurz, N.; Kuti, I.; Lalkovski, S.; Lane, G. J.; Lee, C. S.; Lee, E. J.; Lorusso, G.; Lotay, G.; Moon, C.-B.; Nishizuka, I.; Nita, C. R.; Odahara, A.; Patel, Z.; Phong, V. H.; Podolyák, Zs.; Roberts, O. J.; Sakurai, H.; Schaffner, H.; Shand, C. M.; Shimizu, Y.; Sumikama, T.; Suzuki, H.; Takeda, H.; Terashima, S.; Vajta, Zs.; Valiente-Dóbon, J. J.; Xu, Z. Y.

    2016-09-01

    The level structure of 172Dy has been investigated for the first time by means of decay spectroscopy following in-flight fission of a 238U beam. A long-lived isomeric state with T1/2 = 0.71 (5) s and Kπ =8- has been identified at 1278 keV, which decays to the ground-state and γ-vibrational bands through hindered electromagnetic transitions, as well as to the daughter nucleus 172Ho via allowed β decays. The robust nature of the Kπ =8- isomer and the ground-state rotational band reveals an axially-symmetric structure for this nucleus. Meanwhile, the γ-vibrational levels have been identified at unusually low excitation energy compared to the neighboring well-deformed nuclei, indicating the significance of the microscopic effect on the non-axial collectivity in this doubly mid-shell region. The underlying mechanism of enhanced γ vibration is discussed in comparison with the deformed Quasiparticle Random-Phase Approximation based on a Skyrme energy-density functional.

  3. Sub-microsecond-resolution probe microscopy

    DOEpatents

    Ginger, David; Giridharagopal, Rajiv; Moore, David; Rayermann, Glennis; Reid, Obadiah

    2014-04-01

    Methods and apparatus are provided herein for time-resolved analysis of the effect of a perturbation (e.g., a light or voltage pulse) on a sample. By operating in the time domain, the provided method enables sub-microsecond time-resolved measurement of transient, or time-varying, forces acting on a cantilever.

  4. New Isomers in the Full Seniority Scheme of Neutron-Rich Lead Isotopes: The Role of Effective Three-Body Forces

    NASA Astrophysics Data System (ADS)

    Gottardo, A.; Valiente-Dobón, J. J.; Benzoni, G.; Nicolini, R.; Gadea, A.; Lunardi, S.; Boutachkov, P.; Bruce, A. M.; Górska, M.; Grebosz, J.; Pietri, S.; Podolyák, Zs.; Pfützner, M.; Regan, P. H.; Weick, H.; Alcántara Núñez, J.; Algora, A.; Al-Dahan, N.; de Angelis, G.; Ayyad, Y.; Alkhomashi, N.; Allegro, P. R. P.; Bazzacco, D.; Benlliure, J.; Bowry, M.; Bracco, A.; Bunce, M.; Camera, F.; Casarejos, E.; Cortes, M. L.; Crespi, F. C. L.; Corsi, A.; Denis Bacelar, A. M.; Deo, A. Y.; Domingo-Pardo, C.; Doncel, M.; Dombradi, Zs.; Engert, T.; Eppinger, K.; Farrelly, G. F.; Farinon, F.; Farnea, E.; Geissel, H.; Gerl, J.; Goel, N.; Gregor, E.; Habermann, T.; Hoischen, R.; Janik, R.; Klupp, S.; Kojouharov, I.; Kurz, N.; Lenzi, S. M.; Leoni, S.; Mandal, S.; Menegazzo, R.; Mengoni, D.; Million, B.; Morales, A. I.; Napoli, D. R.; Naqvi, F.; Nociforo, C.; Prochazka, A.; Prokopowicz, W.; Recchia, F.; Ribas, R. V.; Reed, M. W.; Rudolph, D.; Sahin, E.; Schaffner, H.; Sharma, A.; Sitar, B.; Siwal, D.; Steiger, K.; Strmen, P.; Swan, T. P. D.; Szarka, I.; Ur, C. A.; Walker, P. M.; Wieland, O.; Wollersheim, H.-J.; Nowacki, F.; Maglione, E.; Zuker, A. P.

    2012-10-01

    The neutron-rich lead isotopes, up to Pb216, have been studied for the first time, exploiting the fragmentation of a primary uranium beam at the FRS-RISING setup at GSI. The observed isomeric states exhibit electromagnetic transition strengths which deviate from state-of-the-art shell-model calculations. It is shown that their complete description demands the introduction of effective three-body interactions and two-body transition operators in the conventional neutron valence space beyond Pb208.

  5. Microsecond flares in gamma-ray bursts

    NASA Technical Reports Server (NTRS)

    Schaefer, Bradley E.; Cohen, Justin; Teegarden, Bonnard J.; Cline, Thomas L.; Fishman, Gerald J.; Meegan, Charles A.; Wilson, Robert B.; Paciesas, William S.; Pendleton, Geoffrey N.; Matteson, James L.

    1993-01-01

    It has been suggested that gamma-ray burst light curves may consist of many superposed flares with a duration shorter than 30/microsec. If true, the implications for the interpretation of burst data are enormous. With the launch of the Compton Gamma-Ray Observatory, four predictions of Mitrofanov's (1989) suggestion can be tested. Our results which contradict this suggestion are (1) the photon arrival times are not correlated between independent detectors, (2) the spectral hardness and intensity does not depend on the detector area, (3) the bursts seen by detectors which measure photon positions do not see microsecond flares, and (4) burst positions deduced from detectors with different projected areas are close to the positions deduced from time-of-flight differences between separated spacecraft. We conclude, therefore, that gamma-ray bursts are not composed of microsecond flares.

  6. The proportion of lycopene isomers in human plasma is modulated by lycopene isomer profile in the meal but not by lycopene preparation.

    PubMed

    Richelle, Myriam; Lambelet, Pierre; Rytz, Andreas; Tavazzi, Isabelle; Mermoud, Anne-France; Juhel, Christine; Borel, Patrick; Bortlik, Karlheinz

    2012-05-01

    Dietary lycopene consists mostly of the (all-E) isomer. Upon absorption, (all-E) lycopene undergoes isomerisation into various (Z)-isomers. Because these isomers offer potentially better health benefits than the (all-E) isomer, the aim of the present study was to investigate if the profile of lycopene isomers in intestinal lipoproteins is affected by the profile of lycopene isomers in the meal and by the tomato preparation. Six postprandial, crossover tests were performed in healthy men. Three meals provided about 70 % of the lycopene as (Z)-isomers, either mainly as 5-(Z) or 13-(Z), or as a mixture of 9-(Z) and 13-(Z) lycopene, while three tomato preparations provided lycopene mainly as the (all-E) isomer. Consumption of the 5-(Z) lycopene-rich meal led to a high (60 %) proportion of this isomer in TAG-rich lipoproteins (TRL), indicating a good absorption and/or a low intestinal conversion of this isomer. By contrast, consumption of meals rich in 9-(Z) and 13-(Z) lycopene isomers resulted in a low level of these isomers but high amounts of the 5-(Z) and (all-E) isomers in TRL. This indicates that the 9-(Z) and 13-(Z) isomers were less absorbed or were converted into 5-(Z) and (all-E) isomers. Dietary (Z)-lycopene isomers were, therefore, differently isomerised and released in TRL during their intestinal absorption in men. Consuming the three meals rich in (all-E) lycopene resulted in similar proportions of lycopene isomers in TRL: 60 % (all-E), 20 % 5-(Z), 9 % 13-(Z), 2 % 9-(Z) and 9 % unidentified (Z)-isomers. These results show that the tomato preparation has no impact on the lycopene isomerisation occurring during absorption in humans.

  7. Efficient illumination for microsecond tracking microscopy.

    PubMed

    Dulin, David; Barland, Stephane; Hachair, Xavier; Pedaci, Francesco

    2014-01-01

    The possibility to observe microsecond dynamics at the sub-micron scale, opened by recent technological advances in fast camera sensors, will affect many biophysical studies based on particle tracking in optical microscopy. A main limiting factor for further development of fast video microscopy remains the illumination of the sample, which must deliver sufficient light to the camera to allow microsecond exposure times. Here we systematically compare the main illumination systems employed in holographic tracking microscopy, and we show that a superluminescent diode and a modulated laser diode perform the best in terms of image quality and acquisition speed, respectively. In particular, we show that the simple and inexpensive laser illumination enables less than 1 μs camera exposure time at high magnification on a large field of view without coherence image artifacts, together with a good hologram quality that allows nm-tracking of microscopic beads to be performed. This comparison of sources can guide in choosing the most efficient illumination system with respect to the specific application.

  8. Microsecond subdomain folding in dihydrofolate reductase.

    PubMed

    Arai, Munehito; Iwakura, Masahiro; Matthews, C Robert; Bilsel, Osman

    2011-07-08

    The characterization of microsecond dynamics in the folding of multisubdomain proteins has been a major challenge in understanding their often complex folding mechanisms. Using a continuous-flow mixing device coupled with fluorescence lifetime detection, we report the microsecond folding dynamics of dihydrofolate reductase (DHFR), a two-subdomain α/β/α sandwich protein known to begin folding in this time range. The global dimensions of early intermediates were monitored by Förster resonance energy transfer, and the dynamic properties of the local Trp environments were monitored by fluorescence lifetime detection. We found that substantial collapse occurs in both the locally connected adenosine binding subdomain and the discontinuous loop subdomain within 35 μs of initiation of folding from the urea unfolded state. During the fastest observable ∼550 μs phase, the discontinuous loop subdomain further contracts, concomitant with the burial of Trp residue(s), as both subdomains achieve a similar degree of compactness. Taken together with previous studies in the millisecond time range, a hierarchical assembly of DHFR--in which each subdomain independently folds, subsequently docks, and then anneals into the native conformation after an initial heterogeneous global collapse--emerges. The progressive acquisition of structure, beginning with a continuously connected subdomain and spreading to distal regions, shows that chain entropy is a significant organizing principle in the folding of multisubdomain proteins and single-domain proteins. Subdomain folding also provides a rationale for the complex kinetics often observed.

  9. Power optimization in logic isomers

    NASA Technical Reports Server (NTRS)

    Panwar, Ramesh; Rennels, David; Alkalaj, Leon

    1993-01-01

    Logic isomers are labeled, 2-isomorphic graphs that implement the same logic function. Logic isomers may have significantly different power requirements even though they have the same number of transistors in the implementation. The power requirements of the isomers depend on the transition activity of the input signals. The power requirements of isomorphic graph isomers of n-input NAND and NOR gates are shown. Choosing the less power-consuming isomer instead of the others can yield significant power savings. Experimental results on a ripple-carry adder are presented to show that the implementation using the least power-consuming isomers requires approximately 10 percent less power than the implementation using the most power-consuming isomers. Simulations of other random logic designs also confirm that designs using less power-consuming isomers can reduce the logic power demand by approximately 10 percent as compared to designs using more power-consuming isomers.

  10. Atlas of Nuclear Isomers

    SciTech Connect

    Jain, Ashok Kumar; Maheshwari, Bhoomika; Garg, Swati; Patial, Monika; Singh, Balraj

    2015-09-15

    We present an atlas of nuclear isomers containing the experimental data for the isomers with a half-life ≥ 10 ns together with their various properties such as excitation-energy, half-life, decay mode(s), spin-parity, energies and multipolarities of emitted gamma transitions, etc. The ENSDF database complemented by the XUNDL database has been extensively used in extracting the relevant data. Recent literature from primary nuclear physics journals, and the NSR bibliographic database have been searched to ensure that the compiled data Table is as complete and current as possible. The data from NUBASE-12 have also been checked for completeness, but as far as possible original references have been cited. Many interesting systematic features of nuclear isomers emerge, some of them new; these are discussed and presented in various graphs and figures. The cutoff date for the extraction of data from the literature is August 15, 2015.

  11. Microsecond protein dynamics observed at the single-molecule level

    PubMed Central

    Otosu, Takuhiro; Ishii, Kunihiko; Tahara, Tahei

    2015-01-01

    How polypeptide chains acquire specific conformations to realize unique biological functions is a central problem of protein science. Single-molecule spectroscopy, combined with fluorescence resonance energy transfer, is utilized to study the conformational heterogeneity and the state-to-state transition dynamics of proteins on the submillisecond to second timescales. However, observation of the dynamics on the microsecond timescale is still very challenging. This timescale is important because the elementary processes of protein dynamics take place and direct comparison between experiment and simulation is possible. Here we report a new single-molecule technique to reveal the microsecond structural dynamics of proteins through correlation of the fluorescence lifetime. This method, two-dimensional fluorescence lifetime correlation spectroscopy, is applied to clarify the conformational dynamics of cytochrome c. Three conformational ensembles and the microsecond transitions in each ensemble are indicated from the correlation signal, demonstrating the importance of quantifying microsecond dynamics of proteins on the folding free energy landscape. PMID:26151767

  12. Microsecond delays on non-real time operating systems

    SciTech Connect

    Angstadt, R.; Estrada, J.; Diehl, H.T.; Flaugher, B.; Johnson, M.; /Fermilab

    2007-05-01

    We have developed microsecond timing and profiling software that runs on standard Windows and Linux based operating systems. This software is orders of magnitudes better than most of the standard native functions in wide use. Our software libraries calibrate RDTSC in microseconds or seconds to provide two different types of delays: a ''Guaranteed Minimum'' and a precision ''Long Delay'', which releases to the kernel. Both return profiling information of the actual delay.

  13. Nuclear shape isomers

    NASA Astrophysics Data System (ADS)

    Möller, P.; Sierk, A. J.; Bengtsson, R.; Sagawa, H.; Ichikawa, T.

    2012-03-01

    We calculate potential-energy surfaces as functions of spheroidal (ɛ2), hexadecapole (ɛ4), and axial-asymmetry (γ) shape coordinates for 7206 nuclei from A=31 to A=290. We tabulate the deformations and energies of all minima deeper than 0.2 MeV and of the saddles between all pairs of minima. The tabulation is terminated at N=160. Our study is based on the FRLDM macroscopic-microscopic model defined in ATOMIC DATA AND NUCLEAR DATA TABLES [P. Möller, J.R. Nix, W.D. Myers, W.J. Swiatecki, At. Data Nucl. Data Tables 59 (1995) 185]. We also present potential-energy contour plots versus ɛ2 and γ for 1224 even-even nuclei in the region studied. We can identify nuclei for which a necessary condition for shape isomers occurs, namely multiple minima in the calculated potential-energy surface. We find that the vast majority of nuclear shape isomers occur in the A=80 region, the A=100 region, and in a more extended region centered around 208Pb. A calculated region of shape isomers that has so far not been extensively explored is the region of neutron-deficient actinides "north-east" of 208Pb.

  14. Microsecond Scale Vibrational Spectroscopic Imaging by Multiplex Stimulated Raman Scattering Microscopy

    PubMed Central

    Liao, Chien-Sheng; Slipchenko, Mikhail N.; Wang, Ping; Li, Junjie; Lee, Seung-Young; Oglesbee, Robert A.; Cheng, Ji-Xin

    2015-01-01

    Real-time vibrational spectroscopic imaging is desired for monitoring cellular states and cellular processes in a label-free manner. Raman spectroscopic imaging of highly dynamic systems is inhibited by relatively slow spectral acquisition on millisecond to second scale. Here, we report microsecond scale vibrational spectroscopic imaging by lock-in free parallel detection of spectrally dispersed stimulated Raman scattering signal. Using a homebuilt tuned amplifier array, our method enables Raman spectral acquisition, within the window defined by the broadband pulse, at the speed of 32 microseconds and with close to shot-noise limited detection sensitivity. Incorporated with multivariate curve resolution analysis, our platform allows compositional mapping of lipid droplets in single live cells, observation of intracellular retinoid metabolism, discrimination of fat droplets from protein-rich organelles in Caenorhabditis elegans, spectral detection of fast flowing tumor cells, and monitoring drug diffusion through skin tissue in vivo. The reported technique opens new opportunities for compositional analysis of cellular compartment in a microscope setting and high-throughput spectral profiling of single cells in a flow cytometer setting. PMID:26167336

  15. Optical Pumping and Laser Induced Nuclear Orientation of a Microsecond Isomeric Level in BARIUM-134

    NASA Astrophysics Data System (ADS)

    Bell, Curtis John

    Using optical pumping techniques, on and off-line experiments were performed on a microsecond nuclear isomer (('134m)Ba 10('+) ). Shifts in atomic resonances detected by changes in the angular distribution of characteristic nuclear radiations (expressed as changes in shape and size) yield information on changes in nuclear structure. The 10('+) isomeric state was produced using a 49 MeV pulsed beam of ('13)C on an isotopically enriched ('124)Sn target. The reaction products recoil out of the target and are slowed to thermal velocities in 10 torr of xenon in a region illuminated with circularly polarized light (553.5 nm) from a Coherent 699-21 dye laser. Nuclear parameters measured were the lifetime (3.8(2)(mu)s) and g-factor (g = -.20(1)) of the 10('+) state. Atomic parameters measured for barium were the depolarization cross sections of the ('1)P(,1) atomic level (6.0(6) nm('2)) in xenon, the quenching cross section for hydrogen (0.042(4) nm('2)), and the branching ratio of the metastable (('1,3)D(,1,2,3)) atomic states (0.011(1)). A possible anisotropy signal and the cumulative results (no measurable anisotropy) are presented. Difficulties encountered were insufficient neutralization, and unexpectedly large spatial distribution, and 'trapping' in metastable atomic states.

  16. Microsecond-resolved SDR-based cavity ring down ellipsometry.

    PubMed

    Sofikitis, D; Spiliotis, A K; Stamataki, K; Katsoprinakis, G E; Bougas, L; Samartzis, P C; Loppinet, B; Rakitzis, T P; Surligas, M; Papadakis, S

    2015-06-20

    We present an experimental apparatus that allows microsecond-resolved ellipsometric and absorption measurements. The apparatus is based on an optical cavity containing a Dove prism, in which light undergoes total internal reflection (TIR), while the data acquisition is based on software defined radio technology and custom-built drivers. We demonstrate the ability to sense rapid variations in the refractive index above the TIR interface for arbitrarily long times with a temporal resolution of at least 2 μs.

  17. Developing Single-Molecule Technique with Microsecond Resolution

    NASA Astrophysics Data System (ADS)

    Akhterov, Maxim V.

    Molecular machines like proteins are responsible for many regulatory and catalytic functions. Specifically, molecular motions of proteins and their flexibility determine conformational states required for enzyme catalysis, signal transduction, and protein-protein interactions. However, the mechanisms for protein transitions between conformational states are often poorly understood, especially in the milli- to microsecond ranges where conventional optical techniques and computational modeling are most limited. This work describes development of an electronic single-molecule technique for monitoring microsecond motions of biological molecules. Dynamic changes of conductance through a transistor made of a single-walled carbon nanotube (SWNT-FET) report conformational changes of a protein molecule tethered to the SWNT sidewall. In principle, the high operating speed of SWNT-FETs could allow this technique to resolve molecular events with nanosecond resolution. This project focused on improving the technique to a 200 kHz effective bandwidth in order to resolve microsecond-scale dynamics. The improvement was achieved with a home-built electrochemical flow cell. By minimizing parasitic capacitance due to liquid coupling to electrodes and eliminating noise pickup, the flow cell enabled low-noise, high bandwidth measurement of molecular events as short as 2 mus. The apparatus was used to observe closing and opening motions of lysozyme. Preliminary results suggest that lysozyme has a distribution of possible velocities with the most probable speed approaching our experimental resolution of 2 mus.

  18. [The sub-microsecond pulser applied for electroporation effect].

    PubMed

    Tan, Yafang; Yang, Hongchun; Wu, Jianxing; Yang, Xiaolin; Zhang, Yi; Zeng, Gang; Zhang, Xiaoyu

    2012-08-01

    A sub-microsecond pulse generation applied for electroporation effects of tumor cell is presented in this paper. The principle of the generator is that the expected pulse waveform is intercepted from the RC discharge curve by controlling the on-off states of two IGBT modules with a synchronous controller. Experimental tests indicate that the generator can produce adjustable pulse waveform parameters with 0.5-3.5kV amplitude, 300-800 ns pulse duration, 1-400Hz repetition frequency rate, and it is suitable for the study of the electroporation effect experiments.

  19. Microsecond Microfluidic Mixing for Investigation of Protein Folding Kinetics

    SciTech Connect

    Hertzog, D E; Santiago, J G; Bakajin, O

    2005-02-10

    We have developed and characterized a mixer to study the reaction kinetics of protein folding on a microsecond timescale. The mixer uses hydrodynamic focusing of pressure-driven flow in a microfluidic channel to reduce diffusion times as first demonstrated by Knight et al.[1]. Features of the mixer include 1 {micro}s mixing times, sample consumptions of order 1 nl/s, loading sample volumes on the order of microliters, and the ability to manufacture in fused silica for compatibility with most spectroscopic methods.

  20. X-rays from a microsecond X-pinch

    SciTech Connect

    Appartaim, R. K.

    2013-08-28

    The characteristics of x-rays emitted by X-pinches driven by discharging a current of ∼320 kA with a quarter period of 1 μs in crossed 25 μm wires have been investigated. The x-ray emissions are studied using filtered silicon photodiodes, diamond radiation detectors, and pinhole cameras. The results show that predominantly x-rays from the microsecond X-pinch tend to be emitted in two distinct sets of bursts. The first is predominantly “soft,” i.e., with photon energy hν < 5 keV, followed by a second set of bursts beginning up to 100 ns following the initial bursts, and usually consisting of higher photon energies. Our results show, however, that the x-ray emissions do not contain a significant component with hν > 10 keV as might be expected from electron beam activity within the plasma or from the X-pinch diode. High-resolution images obtained with the observed x-rays suggest a well-defined small source of soft x-rays that demonstrates the potential of the microsecond X-pinch.

  1. Differences in CLA isomer distribution of cow's milk lipids.

    PubMed

    Kraft, Jana; Collomb, Marius; Möckel, Peter; Sieber, Robert; Jahreis, Gerhard

    2003-06-01

    The uniqueness of ruminant milk lipids is based on their high concentration of CLA. Maximal CLA concentrations in milk lipids require optimal conditions of ruminal fermentation and substrate availability, conditions like those present in pasture-fed cows. Our previous work showed that farm management (indoor feeding vs. pasture feeding) markedly influenced the CLA concentration. In this study, the objective was to evaluate the influence of the farm management system as dependent on different locations. Milk samples from different locations (Thuringia and the Alps, representing diverse altitudes) were collected during the summer months and analyzed for FA profile and CLA isomer distribution. The proportion of PUFA and total CLA in milk fat was significantly lower in milk from indoor cows compared with the pasture cows in the Alps. The trans-11 18:1 in milk fat of Alpine cows was elevated, in contrast to lower values for trans-10 18:1. Milk from cows grazing pasture in the Alps was higher in EPA and lower in arachidonic acid than milk from indoor-fed cows. The proportion of cis,trans/trans,cis isomers of CLA was 10 times higher from the indoor cows than from the Alpine cows. In addition to the major isomer cis-9,trans-11, this difference also occurred for the trans-11,cis-13 isomer, which represented more than a fourth of the total CLA present in milk fat. This is the first report showing a special isomer distribution in the milk fat of cows living under very natural conditions. We hypothesize that the CLA isomer trans-11,cis-13 is formed in large quantity as a result of grazing mountain pasture, which is rich in alpha-linolenic acid.

  2. Virus capsid dissolution studied by microsecond molecular dynamics simulations.

    PubMed

    Larsson, Daniel S D; Liljas, Lars; van der Spoel, David

    2012-01-01

    Dissolution of many plant viruses is thought to start with swelling of the capsid caused by calcium removal following infection, but no high-resolution structures of swollen capsids exist. Here we have used microsecond all-atom molecular simulations to describe the dynamics of the capsid of satellite tobacco necrosis virus with and without the 92 structural calcium ions. The capsid expanded 2.5% upon removal of the calcium, in good agreement with experimental estimates. The water permeability of the native capsid was similar to that of a phospholipid membrane, but the permeability increased 10-fold after removing the calcium, predominantly between the 2-fold and 3-fold related subunits. The two calcium binding sites close to the icosahedral 3-fold symmetry axis were pivotal in the expansion and capsid-opening process, while the binding site on the 5-fold axis changed little structurally. These findings suggest that the dissociation of the capsid is initiated at the 3-fold axis.

  3. Microsecond-scale electric field pulses in cloud lightning discharges

    NASA Technical Reports Server (NTRS)

    Villanueva, Y.; Rakov, V. A.; Uman, M. A.; Brook, M.

    1994-01-01

    From wideband electric field records acquired using a 12-bit digitizing system with a 500-ns sampling interval, microsecond-scale pulses in different stages of cloud flashes in Florida and New Mexico are analyzed. Pulse occurrence statistics and waveshape characteristics are presented. The larger pulses tend to occur early in the flash, confirming the results of Bils et al. (1988) and in contrast with the three-stage representation of cloud-discharge electric fields suggested by Kitagawa and Brook (1960). Possible explanations for the discrepancy are discussed. The tendency for the larger pulses to occur early in the cloud flash suggests that they are related to the initial in-cloud channel formation processes and contradicts the common view found in the atmospheric radio-noise literature that the main sources of VLF/LF electromagnetic radiation in cloud flashes are the K processes which occur in the final, or J type, part of the cloud discharge.

  4. Substrate recognition by norovirus polymerase: microsecond molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Maláč, Kamil; Barvík, Ivan

    2013-04-01

    Molecular dynamics simulations of complexes between Norwalk virus RNA dependent RNA polymerase and its natural CTP and 2dCTP (both containing the O5'-C5'-C4'-O4' sequence of atoms bridging the triphosphate and sugar moiety) or modified coCTP ( C5' -O5'-C4'-O4'), cocCTP ( C5' -O5'-C4'- C4'') substrates were produced by means of CUDA programmable graphical processing units and the ACEMD software package. It enabled us to gain microsecond MD trajectories clearly showing that similar nucleoside triphosphates can bind surprisingly differently into the active site of the Norwalk virus RNA dependent RNA polymerase. It corresponds to their different modes of action (CTP—substrate, 2dCTP—poor substrate, coCTP—chain terminator, cocCTP—inhibitor). Moreover, extremely rare events—as repetitive pervasion of Arg182 into a potentially reaction promoting arrangement—were captured.

  5. Plasma dynamics in microsecond megaampere plasma opening switches

    SciTech Connect

    Loginov, S. V.

    2011-10-15

    The paper considers the transport of a magnetic field in highly ionized plasma of microsecond megaampere plasma opening switches. Self-similar solutions for plasma aggregation by a linearly increasing magnetic field are derived. For these solutions, the magnetic field energy in the current channel is much lower than the energy of the accelerated plasma flow. The effect of Joule heating of the plasma becomes profound only with a uniform current density. It is shown that the evolution of the magnetic field in the accelerated flow is reduced to diffusion with an effective electrical conductivity proportional to the harmonic average of the Spitzer conductivity and conductivity dependent on the magnetic field in the current channel. Thus, during about the first 100 ns of the current pulse the conductivity of the current channel increases due to the plasma heating and, as the plasma is accelerated, its conductivity decreases.

  6. Ab initio study of cyanoguanidine isomers

    NASA Astrophysics Data System (ADS)

    Arbuznikov, A. V.; Sheludyakova, L. A.; Burgina, E. B.

    1995-06-01

    An ab initio quantum chemical study of the geometric structure and stability of cyanoguanidine isomers was carried out at the Hartree-Fock and Møller-Plesset levels of theory. Two stable separable isomers ('cyanioime' and 'cyanoamine') are found. This gives evidence in favour of the vibrational spectroscopy data showing the existence of both isomers.

  7. Ab initio study of cyanoguanidine isomers

    NASA Astrophysics Data System (ADS)

    Arbuznikov, A. V.; Sheludyakova, L. A.; Burgina, E. B.

    1995-06-01

    An ab initio quantum chemical study of the geometric structure and stability of cyanoguanidine isomers was carried out at the Hartree-Fock and Møller-Plesset levels of theory. Two stable separable isomers (‘cyanioime' and ‘cyanoamine') are found. This gives evidence in favour of the vibrational spectroscopy data showing the existence of both isomers.

  8. LAS bioconcentration is isomer specific

    SciTech Connect

    Tolls, J.; Haller, M.; Graaf, I. de; Thijssen, M.H.C.; Sijm, D.T.H.M.

    1995-12-31

    The authors measured parent compound specific bioconcentration data for linear alkylbenzene sulfonates in Pimephales promelas. They did so by using cold, custom synthesized sulfophenyl alkanes. They observed that, within homologous series of isomers, the uptake rate constants (k{sub 1}) and the bioconcentration factor (BCF) increase with increasing number of carbon atoms in the alkyl chain (n{sub C-atoms}). In contrast, the elimination rate constant k{sub 2} appears to be independent of the alkyl chain length. Regressions of log BCF vs n{sub C-atoms} yielded different slopes for the homologous groups of the 5- and the 2-sulfophenyl alkane isomers. Regression of all log BCF-data vs log 1/CMC yielded a good description of the data. However, when regressing the data for both homologous series separately again very different slopes are obtained. The results therefore indicate that hydrophobicity-bioconcentration relationships may be different for different homologous groups of sulfophenyl alkanes.

  9. Microsecond-sustained lasing from colloidal quantum dot solids

    PubMed Central

    Adachi, Michael M.; Fan, Fengjia; Sellan, Daniel P.; Hoogland, Sjoerd; Voznyy, Oleksandr; Houtepen, Arjan J.; Parrish, Kevin D.; Kanjanaboos, Pongsakorn; Malen, Jonathan A.; Sargent, Edward H.

    2015-01-01

    Colloidal quantum dots have grown in interest as materials for light amplification and lasing in view of their bright photoluminescence, convenient solution processing and size-controlled spectral tunability. To date, lasing in colloidal quantum dot solids has been limited to the nanosecond temporal regime, curtailing their application in systems that require more sustained emission. Here we find that the chief cause of nanosecond-only operation has been thermal runaway: the combination of rapid heat injection from the pump source, poor heat removal and a highly temperature-dependent threshold. We show microsecond-sustained lasing, achieved by placing ultra-compact colloidal quantum dot films on a thermally conductive substrate, the combination of which minimizes heat accumulation. Specifically, we employ inorganic-halide-capped quantum dots that exhibit high modal gain (1,200 cm−1) and an ultralow amplified spontaneous emission threshold (average peak power of ∼50 kW cm−2) and rely on an optical structure that dissipates heat while offering minimal modal loss. PMID:26493282

  10. Detonation initiation on the microsecond time scale: DDTs

    SciTech Connect

    Kuehn, Jeffery A; Kassoy, Dr. David R; Nabity, Mr. Matthew W.; Clarke, Dr. John F.

    2006-01-01

    Spatially resolved, thermal power deposition of limited duration into a finite volume of reactive gas is the initiator for a deflagration-to-detonation transition (DDT) on the microsecond time scale. The reactive Euler equations with one-step Arrhenius kinetics are used to derive novel formulas for velocity and temperature variation that describe the physical phenomena characteristic of DDTs. A nonlinear transformation of the variables is shown to yield a canonical equation system, independent of the activation energy. Numerical solutions of the reactive Euler equations are used to describe the detailed sequence of reactive gas dynamic processes leading to an overdriven planar detonation far from the power deposition location. Results are presented for deposition into a region isolated from the planar boundary of the reactive gas as well as for that adjacent to the boundary. The role of compressions and shocks reflected from the boundary into the partially reacted hot gas is described. The quantitative dependences of DDT evolution on the magnitude of thermal power deposition and activation energy are identified.

  11. Detonation initiation on the microsecond time scale: DDTs

    SciTech Connect

    Kassoy, Dr. David R; Kuehn, Jeffery A; Nabity, Mr. Matthew W.; Clarke, Dr. John F.

    2008-01-01

    Spatially resolved, thermal power deposition of limited duration into a finite volume of reactive gas is the initiator for a deflagration-to-detonation transition (DDT) on the microsecond time scale. The reactive Euler equations with one-step Arrhenius kinetics are used to derive novel formulas for velocity and temperature variation that describe the physical phenomena characteristic of DDTs. A transformation of the variables is shown to yield a canonical equation system, independent of the activation energy. Numerical solutions of the reactive Euler equations are used to describe the detailed sequence of reactive gasdynamic processes leading to an overdriven planar detonation far from the power deposition location. Results are presented for deposition into a region isolated from the planar boundary of the reactive gas as well as for that adjacent to the boundary. The role of compressions and shocks reflected from the boundary into the partially reacted hot gas is described. The quantitative dependences of DDT evolution on the magnitude of thermal power deposition and activation energy are identified.

  12. Understanding High Voltage Vacuum Insulators for Microsecond Pulses

    SciTech Connect

    J.B., J; D.A., G; T.L., H; E.J., L; R.D., S; L.K., T; G.E., V

    2007-08-15

    High voltage insulation is one of the main areas of pulsed power research and development since the surface of an insulator exposed to vacuum can fail electrically at an applied field more than an order or magnitude below the bulk dielectric strength of the insulator. This is troublesome for applications where high voltage conditioning of the insulator and electrodes is not practical and where relatively long pulses, on the order of several microseconds, are required. Here we give a summary of our approach to modeling and simulation efforts and experimental investigations for understanding flashover mechanism. The computational work is comprised of both filed and particle-in-cell modeling with state-of-the-art commercial codes. Experiments were performed in using an available 100-kV, 10-{micro}s pulse generator and vacuum chamber. The initial experiments were done with polyethylene insulator material in the shape of a truncated cone cut at +45{sup o} angle between flat electrodes with a gap of 1.0 cm. The insulator was sized so there were no flashovers or breakdowns under nominal operating conditions. Insulator flashover or gap closure was induced by introducing a plasma source, a tuft of velvet, in proximity to the insulator or electrode.

  13. Microsecond-sustained lasing from colloidal quantum dot solids.

    PubMed

    Adachi, Michael M; Fan, Fengjia; Sellan, Daniel P; Hoogland, Sjoerd; Voznyy, Oleksandr; Houtepen, Arjan J; Parrish, Kevin D; Kanjanaboos, Pongsakorn; Malen, Jonathan A; Sargent, Edward H

    2015-10-23

    Colloidal quantum dots have grown in interest as materials for light amplification and lasing in view of their bright photoluminescence, convenient solution processing and size-controlled spectral tunability. To date, lasing in colloidal quantum dot solids has been limited to the nanosecond temporal regime, curtailing their application in systems that require more sustained emission. Here we find that the chief cause of nanosecond-only operation has been thermal runaway: the combination of rapid heat injection from the pump source, poor heat removal and a highly temperature-dependent threshold. We show microsecond-sustained lasing, achieved by placing ultra-compact colloidal quantum dot films on a thermally conductive substrate, the combination of which minimizes heat accumulation. Specifically, we employ inorganic-halide-capped quantum dots that exhibit high modal gain (1,200 cm(-1)) and an ultralow amplified spontaneous emission threshold (average peak power of ∼50 kW cm(-2)) and rely on an optical structure that dissipates heat while offering minimal modal loss.

  14. Characterization of a microsecond-conduction-time plasma opening switch

    NASA Astrophysics Data System (ADS)

    Commisso, R. J.; Goodrich, P. J.; Grossmann, J. M.; Hinshelwood, D. D.; Ottinger, P. F.; Weber, B. V.

    1992-07-01

    This paper presents data and analyses from which emerges a physical picture of microsecond-conduction-time plasma opening switch operation. During conduction, a broad current channel penetrates axially through the plasma, moving it toward the load. Opening occurs when the current channel reaches the load end of the plasma, far from the load. During conduction, the axial line density in the interelectrode region is reduced from its value with no current conduction as a result of radial hydrodynamic forces associated with the current channel. A factor of 20 reduction is observed at opening in a small, localized region between the electrodes. When open, the switch plasma behaves like a section of magnetically insulated transmission line with an effective gap of 2 to 3 mm. Increasing the magnetic field in this gap by 50% results in an improvement of 50% in the peak load voltage and load current rise time, to 1.2 MV and 20 nsec, respectively. An erosion opening mechanism explains the inferred gap growth rate using the reduced line density at opening. Improved switch performance results when the maximum gap size is increased by using a rising load impedance.

  15. Structure of three-quasiparticle isomers in {sup 169}Ho and {sup 171}Tm.

    SciTech Connect

    Dracoulis, G. D.; Lane, G. J.; Hughes, R. O.; Kondev, F. G.; Watanabe, H.; Seweryniak, D.; Zhu, S.; Carpenter, M. P.; Chiara, C. J.; Janssens, R. V. F.; Lauritsen, T.; Lister, C. J.; McCutchan, E. A.; Stefanescu, I.; Chowdhury, P.

    2010-09-17

    A three-quasiparticle isomer with {tau}=170(8) {micro}s and K{sup {pi}} = (19/2{sup +}) has been identified in the neutron-rich isotope {sup 169}Ho. The isomer decays with K-forbidden transitions to members of a band associated with the 7/2-[523] proton configuration, whose structure is characterized through analysis of the in-band {gamma}-ray branching ratios. In the isotone {sup 171}Tm, the rotational band based on the known 19/2{sup +}, three-quasiparticle isomer has also been observed. Alternative one-proton two-neutron configurations for the isomer in {sup 169}Ho are discussed in terms of multiquasiparticle calculations and through a comparison with the structures observed in {sup 171}Tm.

  16. Structure of three-quasiparticle isomers in {sup 169}Ho and {sup 171}Tm

    SciTech Connect

    Dracoulis, G. D.; Lane, G. J.; Hughes, R. O.; Kondev, F. G.; Chiara, C. J.; Watanabe, H.; Seweryniak, D.; Zhu, S.; Carpenter, M. P.; Janssens, R. V. F.; Lauritsen, T.; Lister, C. J.; McCutchan, E. A.; Stefanescu, I.; Chowdhury, P.

    2010-09-15

    A three-quasiparticle isomer with {tau}=170(8) {mu}s and K{sup {pi}=} (19/2{sup +}) has been identified in the neutron-rich isotope {sup 169}Ho. The isomer decays with K-forbidden transitions to members of a band associated with the 7/2{sup -}[523] proton configuration, whose structure is characterized through analysis of the in-band {gamma}-ray branching ratios. In the isotone {sup 171}Tm, the rotational band based on the known 19/2{sup +}, three-quasiparticle isomer has also been observed. Alternative one-proton two-neutron configurations for the isomer in {sup 169}Ho are discussed in terms of multiquasiparticle calculations and through a comparison with the structures observed in {sup 171}Tm.

  17. Interconversion of diborane(4) isomers

    NASA Technical Reports Server (NTRS)

    Stanton, John F.; Gauss, Juergen; Bartlett, Rodney J.; Helgaker, Trygve; Jorgensen, Poul; Jensen, Hans J. A.; Taylor, Peter R.

    1992-01-01

    Highly correlated electronic structure computations using many-body perturbation theory and coupled-cluster gradient techniques are used to study the reaction pathway that links the two forms (C2u and D2d) of diborane(4). The results obtained indicate that a low-energy pathway exists for interconversion of the two low-lying isomers of diborane(4). The proposed mechanism consists of a single concerted but nonsynchronous rotation of the BH2 groups. The pathway first follows an idealized reaction coordinate which preserves C2 symmetry, but then bifurcates at a branch point, leading to two equivalent transition states which lack nontrivial elements of symmetry.

  18. High spin isomer beam line at RIKEN

    SciTech Connect

    Kishida, T.; Ideguchi, E.; Wu, H.Y.

    1996-12-31

    Nuclear high spin states have been the subject of extensive experimental and theoretical studies. For the production of high spin states, fusion reactions are usually used. The orbital angular momentum brought in the reaction is changed into the nuclear spin of the compound nucleus. However, the maximum induced angular momentum is limited in this mechanism by the maximum impact parameter of the fusion reaction and by the competition with fission reactions. It is, therefore, difficult to populate very high spin states, and as a result, large {gamma}-detector arrays have been developed in order to detect subtle signals from such very high spin states. The use of high spin isomers in the fusion reactions can break this limitation because the high spin isomers have their intrinsic angular momentum, which can bring the additional angular momentum without increasing the excitation energy. There are two methods to use the high spin isomers for secondary reactions: the use of the high spin isomers as a target and that as a beam. A high spin isomer target has already been developed and used for several experiments. But this method has an inevitable shortcoming that only {open_quotes}long-lived{close_quotes} isomers can be used for a target: {sup 178}Hf{sup m2} (16{sup +}) with a half-life of 31 years in the present case. By developing a high spin isomer beam, the authors can utilize various short-lived isomers with a short half-life around 1 {mu}s. The high spin isomer beam line of RIKEN Accelerator Facility is a unique apparatus in the world which provides a high spin isomer as a secondary beam. The combination of fusion-evaporation reaction and inverse kinematics are used to produce high spin isomer beams; in particular, the adoption of `inverse kinematics` is essential to use short-lived isomers as a beam.

  19. 10 microsecond time resolution studies of Cygnus X-1

    SciTech Connect

    Wen, H. C.

    1997-06-01

    Time variability analyses have been applied to data composed of event times of X-rays emitted from the binary system Cygnus X-1 to search for unique black hole signatures. The X-ray data analyzed was collected at ten microsecond time resolution or better from two instruments, the High Energy Astrophysical Observatory (HEAO) A-1 detector and the Rossi X-ray Timing Explorer (XTE) Proportional Counter Array (PCA). HEAO A-1 and RXTE/PCA collected data from 1977--79 and from 1996 on with energy sensitivity from 1--25 keV and 2--60 keV, respectively. Variability characteristics predicted by various models of an accretion disk around a black hole have been searched for in the data. Drop-offs or quasi-periodic oscillations (QPOs) in the Fourier power spectra are expected from some of these models. The Fourier spectral technique was applied to the HEAO A-1 and RXTE/PCA data with careful consideration given for correcting the Poisson noise floor for instrumental effects. Evidence for a drop-off may be interpreted from the faster fall off in variability at frequencies greater than the observed breaks. Both breaks occur within the range of Keplerian frequencies associated with the inner edge radii of advection-dominated accretion disks predicted for Cyg X-1. The break between 10--20 Hz is also near the sharp rollover predicted by Nowak and Wagoner`s model of accretion disk turbulence. No QPOs were observed in the data for quality factors Q > 9 with a 95% confidence level upper limit for the fractional rms amplitude at 1.2% for a 16 M⊙ black hole.

  20. Erratum: Discovery of Microsecond Time Lags in Kilohertz QPOs

    NASA Astrophysics Data System (ADS)

    Vaughan, B. A.; van der Klis, M.; Méndez, M.; van Paradijs, J.; Wijnands, R. A. D.; Lewin, W. H. G.; Lamb, F. K.; Psaltis, D.; Kuulkers, E.; Oosterbroek, T.

    1998-12-01

    In the Letter ``Discovery of Microsecond Time Lags in Kilohertz QPOs'' by B. A. Vaughan, M. van der Klis, M. Méndez, J. van Paradijs, R. A. D. Wijnands, W. H. G. Lewin, F. K. Lamb, D. Psaltis, E. Kuulkers, and T. Oosterbroek (ApJ, 483, L115 [1997]), the reported time lags, while correct in magnitude, have a sign that is incorrect. We reanalyzed the data and checked the sign of our results using the hard lags in Cyg X-1 and GX 339-4 and the soft lags in the accreting millisecond pulsar SAX J1808.4-3658, as well as by using test signals. The true time delays for 4U 1608-52 are in the sense of the soft photons lagging the hard ones. Any lags in the reported energy and frequency ranges for 4U 0614+091 are between -80 and +15 μs and for 4U 1636-53 are between -50 and +25 μs (95% confidence), respectively, where a positive sign indicates a hard lag. This strengthens the conclusion of the Letter that in simple scattering models any time lags due to inverse Compton scattering are small and imply very small (<~1-10 km) scattering geometries. The time-lag data provide no independent evidence for inverse Compton scattering affecting the X-rays in these sources; another mechanism, perhaps related to the generation of the QPOs, must be operating to produce the soft lags in 4U 1608-52.

  1. Understanding and Improving High Voltage Vacuum Insulators for Microsecond Pulses

    SciTech Connect

    Javedani, J B; Goerz, D A; Houck, T L; Lauer, E J; Speer, R D; Tully, L K; Vogtlin, G E; White, A D

    2007-03-05

    High voltage insulation is one of the main areas of pulsed power research and development, and dielectric breakdown is usually the limiting factor in attaining the highest possible performance in pulsed power devices. For many applications the delivery of pulsed power into a vacuum region is the most critical aspect of operation. The surface of an insulator exposed to vacuum can fail electrically at an applied field more than an order or magnitude below the bulk dielectric strength of the insulator. This mode of breakdown, called surface flashover, imposes serious limitations on the power flow into a vacuum region. This is especially troublesome for applications where high voltage conditioning of the insulator and electrodes is not practical and for applications where relatively long pulses, on the order of several microseconds, are required. The goal of this project is to establish a sound fundamental understanding of the mechanisms that lead to surface flashover, and then evaluate the most promising techniques to improve vacuum insulators and enable high voltage operation at stress levels near the intrinsic bulk breakdown limits of the material. The approach we proposed and followed was to develop this understanding through a combination of theoretical and computation methods coupled with experiments to validate and quantify expected behaviors. In this report we summarize our modeling and simulation efforts, theoretical studies, and experimental investigations. The computational work began by exploring the limits of commercially available codes and demonstrating methods to examine field enhancements and defect mechanisms at microscopic levels. Plasma simulations with particle codes used in conjunction with circuit models of the experimental apparatus enabled comparisons with experimental measurements. The large scale plasma (LSP) particle-in-cell (PIC) code was run on multiprocessor platforms and used to simulate expanding plasma conditions in vacuum gap regions

  2. E/Z Isomers and Isomerization

    NASA Astrophysics Data System (ADS)

    Liaaen-Jensen, Synnøve; Lutnœes, Bjart Frode

    The natural occurrence of several carotenoid cis isomers and their biological significance were not anticipated in 1962, when the classical monograph on cis-trans isomeric carotenoids [1] was published. More recent research has demonstrated that various cis isomers occur naturally in bacteria plants, algae and invertebrate animals, and are present in human blood and tissues. The participation of cis isomers in the biosynthethic route to coloured carotenoids is well established (Volume 3, Chapter 2). Important biological functions of (15Z)-carotenoids in photosynthesis have been revealed [2]. In relation to health aspects of carotenoids, the bioavailability of cis isomers may be higher than that of the all-trans isomer [3], and accumulated evidence suggests that cis/trans isomerization may occur in biological tissues, particularly of lycopene (31) in human serum [4] (Volume 5, Chapter 7).

  3. Microsecond kinetics in model single- and double-stranded amylose polymers.

    PubMed

    Sattelle, Benedict M; Almond, Andrew

    2014-05-07

    Amylose, a component of starch with increasing biotechnological significance, is a linear glucose polysaccharide that self-organizes into single- and double-helical assemblies. Starch granule packing, gelation and inclusion-complex formation result from finely balanced macromolecular kinetics that have eluded precise experimental quantification. Here, graphics processing unit (GPU) accelerated multi-microsecond aqueous simulations are employed to explore conformational kinetics in model single- and double-stranded amylose. The all-atom dynamics concur with prior X-ray and NMR data while surprising and previously overlooked microsecond helix-coil, glycosidic linkage and pyranose ring exchange are hypothesized. In a dodecasaccharide, single-helical collapse was correlated with linkages and rings transitioning from their expected syn and (4)C1 chair conformers. The associated microsecond exchange rates were dependent on proximity to the termini and chain length (comparing hexa- and trisaccharides), while kinetic features of dodecasaccharide linkage and ring flexing are proposed to be a good model for polymers. Similar length double-helices were stable on microsecond timescales but the parallel configuration was sturdier than the antiparallel equivalent. In both, tertiary organization restricted local chain dynamics, implying that simulations of single amylose strands cannot be extrapolated to dimers. Unbiased multi-microsecond simulations of amylose are proposed as a valuable route to probing macromolecular kinetics in water, assessing the impact of chemical modifications on helical stability and accelerating the development of new biotechnologies.

  4. Spectral identification of fullerene C82 isomers

    NASA Astrophysics Data System (ADS)

    Gao, Bin; Liu, Lei; Wang, ChunRu; Wu, ZiYu; Luo, Yi

    2007-10-01

    Ultraviolet photoelectron spectra (UPS) of C82 isomers have been calculated using hybrid density functional theory in combination with the Gelius model [Proceedings of the International Conference on Electron spectroscopy, edited by D. A. Shirley (North-Holland, Amsterdam, 1972), p. 311; J. Electron Spectrosc. Relat. Phenom. 5, 985 (1974)]. The calculated UPS spectra are found to be isomer dependent and in good agreement with the experimental counterparts. Near-edge x-ray absorption fine structure (NEXAFS), x-ray photoelectron spectroscopy (XPS), x-ray emission spectroscopy, and the resonant inelastic x-ray scattering (RIXS) spectra of three important isomers [3(C2), 6(Cs), and 9(C2v)] have also been simulated. Strong isomer dependence has also been found for NEXAFS, XPS, and RIXS spectra.

  5. First Demonstration of Laser-Assisted Charge Exchange for Microsecond Duration H- Beams

    NASA Astrophysics Data System (ADS)

    Cousineau, Sarah; Rakhman, Abdurahim; Kay, Martin; Aleksandrov, Alexander; Danilov, Viatcheslav; Gorlov, Timofey; Liu, Yun; Plum, Michael; Shishlo, Andrei; Johnson, David

    2017-02-01

    This Letter reports on the first demonstration of laser-assisted H- charge exchange for microsecond duration H- beam pulses. Laser-assisted charge exchange injection is a breakthrough technology that overcomes long-standing limitations associated with the traditional method of producing high intensity, time structured beams of protons in accelerators via the use of carbon foils for charge exchange injection. The central theme of this experiment is the demonstration of novel techniques that reduce the laser power requirement to allow high efficiency stripping of microsecond duration beams with commercial laser technology.

  6. Design and Performance of a 560-Microsecond Ku-Band Binary Fiber-Optic Delay Line

    DTIC Science & Technology

    2015-05-14

    photodiode. 5. Press the laser power button on the front panel. The ring illuminator on the button will light. This button activates the current drivers for...Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/5650--15-9545 Design and Performance of a 560-Microsecond Ku-Band Binary Fiber -Optic Delay...THIS PAGE 18. NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Design and Performance of a 560-Microsecond Ku-Band Binary Fiber -Optic Delay Line Joseph M

  7. Energetic and Structural Study of Diphenylpyridine Isomers

    NASA Astrophysics Data System (ADS)

    Rocha, Marisa A. A.; Gomes, Lígia R.; Low, John N.; Santos, Luís M. N. B. F.

    2009-09-01

    The energetic and structural study of three diphenylpyridine isomers is presented in detail. The three isomers, 2,6-, 2,5-, and 3,5-diphenylpyridines, were synthesized via Suzuki-Miyaura methodology based on palladium catalysis, and the crystal structures of the isomers were obtained by X-ray diffraction. The relative energetic stabilities in the condensed and gaseous phases as well as volatilities and structures of the three studied isomers were evaluated, regarding the position of the phenyl groups relative to the nitrogen atom of the pyridine ring. The temperature, standard molar enthalpies, and entropies of fusion were measured and derived by differential scanning calorimetry. The vapor pressures of the considered isomers were determined by a static apparatus based on a MKS capacitance diaphragm manometer. The standard molar enthalpies, entropies, and Gibbs energies of sublimation, at T = 298.15 K, were derived, and the phase diagram near the triple point coordinates were determined for all isomers. The standard (p° = 0.1 MPa) molar enthalpies of combustion of all crystalline isomers were determined, at T = 298.15 K, by static bomb combustion calorimetry. The standard molar enthalpies of formation, in the crystalline and gaseous phases, at T = 298.15 K, were derived. The experimental results for the energetics in the gaseous phase of the three compounds were compared and assessed with the values obtained by ab initio calculations at different levels of theory (DFT and MP2) showing that, at this level of theory, the computational methods underestimate the energetic stability, in the gaseous phase, for these molecules. In order to understand the aromaticity in the central ring of each isomer, calculations of NICS (B3LYP/6-311G++(d,p) level of theory) values on the pyridine ring were also performed.

  8. Maternal dietary Alpine butter intake affects human milk: fatty acids and conjugated linoleic acid isomers.

    PubMed

    Bertschi, Isabelle; Collomb, Marius; Rist, Lukas; Eberhard, Pius; Sieber, Robert; Bütikofer, Ulrich; Wechsler, Daniel; Folkers, Gerd; von Mandach, Ursula

    2005-06-01

    Consumption of CLA by lactating women affects the composition of their milk, but the pattern of the different CLA isomers is still unknown. We determined the effects of short maternal supplementation with CLA-rich Alpine butter on the occurrence of FA and CLA isomers in human milk. In an open randomized controlled study with a two-period cross-over design, milk FA and CLA isomer concentrations were measured on postpartum days > or = 20 in two parallel groups of lactating women before, during, and after consumption of defined quantities of Alpine butter or margarine with comparable fat content (10 d of butter followed by 10 d of margarine for one group, and vice versa in the other). In the 16 women who completed the study (8/group), Alpine butter supplementation increased the C16 and C18 FA, the sum of saturated FA, the 18:1 trans FA, and the trans FA with CLA. The CLA isomer 18:2 c9,t11 increased by 49.7%. Significant increases were also found for the isomers t9,t11, t7,c9, t11,c13, and t8,c10 18:2. The remaining nine of the total 14 detectable isomers showed no changes, and concentrations were <5 mg/100 g fat. A breastfeeding mother can therefore modulate the FA/CLA supply of her child by consuming Alpine butter. Further studies will show whether human milk containing this FA and CLA isomer pattern acts as a functional food for newborns.

  9. Parallel line raster eliminates ambiguities in reading timing of pulses less than 500 microseconds apart

    NASA Technical Reports Server (NTRS)

    Horne, A. P.

    1966-01-01

    Parallel horizontal line raster is used for precision timing of events occurring less than 500 microseconds apart for observation of hypervelocity phenomena. The raster uses a staircase vertical deflection and eliminates ambiguities in reading timing of pulses close to the end of each line.

  10. Plasma Emission Spectra of Opuntia Nopalea Obtained with Microsecond Laser Pulses

    NASA Astrophysics Data System (ADS)

    Ponce, L.; Flores, T.; Arronte, A.; Flores, A.

    2008-04-01

    Laser-induced Plasma Spectroscopy was performed during the spines ablation of Opuntia by using Nd:YAG microsecond laser pulses. The results show strong absorption in Glochids that causes the intense electronic noise on the spectra. This process is consider suitable for practical elimination of spines in alimentary products like opuntia.

  11. Plasma Emission Spectra of Opuntia Nopalea Obtained with Microsecond Laser Pulses

    SciTech Connect

    Ponce, L.; Flores, T.; Arronte, A.; Flores, A.

    2008-04-15

    Laser-induced Plasma Spectroscopy was performed during the spines ablation of Opuntia by using Nd:YAG microsecond laser pulses. The results show strong absorption in Glochids that causes the intense electronic noise on the spectra. This process is consider suitable for practical elimination of spines in alimentary products like opuntia.

  12. High-harmonic spectroscopy of molecular isomers

    SciTech Connect

    Wong, M. C. H.; Brichta, J.-P.; Bhardwaj, V. R.; Spanner, M.; Patchkovskii, S.

    2011-11-15

    We demonstrate that high-order-harmonic generation (HHG) spectroscopy can be used to probe stereoisomers of randomly oriented 1,2-dichloroethylene (C{sub 2}H{sub 2}Cl{sub 2}) and 2-butene (C{sub 4}H{sub 8}). The high-harmonic spectra of these isomers are distinguishable over a range of laser intensities and wavelengths. Time-dependent numerical calculations of angle-dependent ionization yields for 1,2-dichloroethylene suggest that the harmonic spectra of molecular isomers reflect differences in their strong-field ionization. The subcycle ionization yields for the cis isomer are an order of magnitude higher than those for the trans isomer. The sensitivity in discrimination of the harmonic spectra of cis- and trans- isomers is greater than 8 and 5 for 1,2-dichloroethylene and 2-butene, respectively. We show that HHG spectroscopy cannot differentiate the harmonic spectra of the two enantiomers of the chiral molecule propylene oxide (C{sub 3}H{sub 6}O).

  13. Cis and Trans Isomers of Cycloalkenes

    NASA Astrophysics Data System (ADS)

    Barrows, Susan E.; Eberlein, Thomas H.

    2005-09-01

    As a rule, a trans disubstituted alkene is more stable than the corresponding cis isomer. For cycloalkenes of fewer than eleven members, cis isomers are more stable than their trans counterparts. Although this exception to the normal rule is occasionally noted in beginning organic chemistry textbooks, it is often done without a careful analysis of the reasons behind it. The purpose of this article is to provide that analysis. In order for a cycloalkene to accommodate a trans double bond one or more of the following nonideal geometries must occur: a twisted π bond; pyramidal sp 2 -carbon atoms; nonideal sp 3 bond angles; or longer than normal C C single and double bonds. This article provides a list of experimentally determined relative energies of the cis and trans isomers within the series cycloheptene cycloundecene, along with computationally derived energies at several levels of theory. It also examines the geometric distortions through which cycloalkenes relieve the strain introduced by a trans double bond.

  14. K isomers as probes of nuclear structure

    SciTech Connect

    Tandel, S. K.

    2014-08-14

    K isomers are studied in Pu and Cm isotopes, and also in Hf and W nuclei. Many high-K states, several of which are isomeric, are identified. Lifetime measurements spanning the ns-s range have been performed, and decay paths of isomers established. Rotational bands built on high-K states are also identified in many cases. Isomer decays are considerably hindered in many instances, both in the A≈180 and 250 regions indicating that K is an approximately conserved quantum number. High-K states become the favored excitation mode at high spins in the A≈180 region. The energies of the 2-quasiparticle high-K states in Cm isotopes suggest the presence of a deformed subshell gap at N=152.

  15. Nuclear isomer suitable for gamma ray laser

    NASA Technical Reports Server (NTRS)

    Jha, S.

    1979-01-01

    The operation of gamma ray lasers (gasers) are studied. It is assumed that the nuclear isomers mentioned in previously published papers have inherent limitations. It is further assumed that the judicious use of Bormann effect or the application of the total external reflection of low energy gamma radiation at grazing angle of incidence may permit the use of a gaser crystal sufficiently long to achieve observable stimulated emission. It is suggested that a long lived 0(+) isomer decaying by low energy gamma ray emission to a short lived 2(+) excited nuclear state would be an attractive gaser candidate. It is also suggested that the nuclear isomer be incorporated in a matrix of refractory material having an electrostatic field gradient whose principal axis lies along the length of the medium. This results in the preferential transmission of electric quadrupole radiation along the length of the medium.

  16. An Assessment of Nuclear Isomers as an Energy Storage Medium

    SciTech Connect

    Hartouni, E P

    2008-12-08

    Nuclear Isomers have been suggested as a potential high energy density medium that might be used to store energy. This talk assesses the state of the science supporting key elements of using nuclear isomers in energy storage applications. The focus is on the nuclear isomer {sup 178m2}Hf which has been most widely suggested for energy storage applications. However, the science issues apply to all nuclear isomer. The assessment addresses the production of the nuclear isomer, and inducing the release of the isomer. Also discussed are novel speculations on photon and/or neutron chain reactions, both as a 'pure' material as well as mixed with other materials.

  17. New Millisecond Isomer Lifetime Measurements at LANSCE

    SciTech Connect

    Devlin, M. Nelson, R.O.; Fotiades, N.; O'Donnell, J.M.

    2014-06-15

    New half-life measurements have been made of the millisecond isomers {sup 71m}Ge, {sup 114m2}I, {sup 208m}Bi, {sup 88m1}Y, {sup 88m2}Y, and {sup 75m}As populated in neutron-induced reactions. These measurements were made using the unique time structure of the LANSCE/WNR neutron source, by observing the γ-ray decays of the isomers during the time between the LANSCE proton macropulses. Two different LANSCE proton beam time structures were used. The GEANIE array of HPGe detectors was used to detect the γ-ray decays.

  18. 'Melatonin isomer' in wine is not an isomer of the melatonin but tryptophan-ethylester.

    PubMed

    Gardana, Claudio; Iriti, Marcello; Stuknytė, Milda; De Noni, Ivano; Simonetti, Paolo

    2014-11-01

    Melatonin is a neurohormone, chronobiotic, and antioxidant compound found in wine and deriving directly from grapes and/or synthesized by yeast during alcoholic fermentation. In addition, a melatonin isomer has been detected in different foods, wine among them. The special interest for melatonin isomer related to the fact that it was found in greater quantities than melatonin and probably shares some of its biological properties. Despite this, its chemical structure has not yet been defined; although some researchers hypothesize, it could be melatonin with the ethylacetamide group shifted into position N1. Thus, the aim of our study was to identify the structures of the melatonin isomer. For this purpose, melatonin and melatonin isomer in Syrah wine were separated chromatographically by a sub-2 μm particle column and detected by tandem mass spectrometry. The sample was then purified and concentrated by solid-phase extraction, hydrolyzed with alkali or esterase, and substrates and products quantified by UPLC-MS/MS. Moreover, melatonin, melatonin isomer, and their product ions were evaluated by high-resolution mass spectrometry. The amount of melatonin isomer and melatonin in the wine was 84 ± 4 and 3 ± 0 ng/mL, respectively. In the solutions, containing diluted alkali or esterase, melatonin isomer was hydrolyzed in about 8 min. Correspondingly, tryptophan was detected, and its amount increased and reached the maximum concentration in about 8 min. Melatonin concentration was not affected by diluted alkali or esterase. The fragmentation pattern of melatonin isomer was different from that of melatonin but comparable to that of tryptophan-ethylester. Finally, the so-called melatonin isomer identity was verified by cochromatography with authentic standard of tryptophan-ethylester.

  19. Analyzing ion distributions around DNA: sequence-dependence of potassium ion distributions from microsecond molecular dynamics

    PubMed Central

    Pasi, Marco; Maddocks, John H.; Lavery, Richard

    2015-01-01

    Microsecond molecular dynamics simulations of B-DNA oligomers carried out in an aqueous environment with a physiological salt concentration enable us to perform a detailed analysis of how potassium ions interact with the double helix. The oligomers studied contain all 136 distinct tetranucleotides and we are thus able to make a comprehensive analysis of base sequence effects. Using a recently developed curvilinear helicoidal coordinate method we are able to analyze the details of ion populations and densities within the major and minor grooves and in the space surrounding DNA. The results show higher ion populations than have typically been observed in earlier studies and sequence effects that go beyond the nature of individual base pairs or base pair steps. We also show that, in some special cases, ion distributions converge very slowly and, on a microsecond timescale, do not reflect the symmetry of the corresponding base sequence. PMID:25662221

  20. Organometallic chemistry: Heavyweight isomer brings stability

    NASA Astrophysics Data System (ADS)

    Scheschkewitz, David

    2016-11-01

    Due to its high reactivity, vinylidene -- the sole 'electron-precise' isomer of acetylene -- is only known to exist in the gas phase. Now, a stable base-free digermanium version of a vinylidene has been isolated by the clever use of suitable substituents.

  1. Introduction of Branching Degrees of Octane Isomers.

    PubMed

    Perdih, Anton

    2016-01-01

    The concept of branching degrees is introduced. In the case of octane isomers it is derived from the values of a set of their physicochemical properties, calculating for each isomer the average of the normalized values and these averages are defined as branching degrees of octane isomers. The sequence of these branching degrees of octane isomers does not differ much from the »regular« one defined earlier. 2,2-Dimethylhexane appears to be less branched than 3,4-dimethylhexane and 3-ethyl, 2-methylpentane, whereas 2,3,4-trimethylpentane appears to be less branched than 3-ethyl, 3-methylpentane. While the increasing number of branches gives rise to increasing branching degrees, the peripheral position of branches and the separation between branches decreases the value of the branching degree. The central position of branches increases it. A bigger branch increases it more than a smaller one. The quantification of these structural features and their correlations with few indices is given as well.

  2. Use of microsecond current prepulse for dramatic improvements of wire array Z-pinch implosion

    SciTech Connect

    Calamy, H.; Lassalle, F.; Loyen, A.; Zucchini, F.; Chittenden, J. P.; Hamann, F.; Maury, P.; Georges, A.; Bedoch, J. P.; Morell, A.

    2008-01-15

    The Sphinx machine [F. Lassalle et al., 'Status on the SPHINX machine based on the 1microsecond LTD technology'] based on microsecond linear transformer driver (LTD) technology is used to implode an aluminium wire array with an outer diameter up to 140 mm and maximum current from 3.5 to 5 MA. 700 to 800 ns implosion Z-pinch experiments are performed on this driver essentially with aluminium. Best results obtained before the improvement described in this paper were 1-3 TW radial total power, 100-300 kJ total yield, and 20-30 kJ energy above 1 keV. An auxiliary generator was added to the Sphinx machine in order to allow a multi microsecond current to be injected through the wire array load before the start of the main current. Amplitude and duration of this current prepulse are adjustable, with maxima {approx}10 kA and 50 {mu}s. This prepulse dramatically changes the ablation phase leading to an improvement of the axial homogeneity of both the implosion and the final radiating column. Total power was multiplied by a factor of 6, total yield by a factor of 2.5 with a reproducible behavior. This paper presents experimental results, magnetohydrodynamic simulations, and analysis of the effect of such a long current prepulse.

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

    PubMed Central

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

    2009-01-01

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

  4. Excitation of nuclear isomers by X rays from laser plasma

    SciTech Connect

    Andreev, Aleksandr A; Karpeshin, F; Trzhaskovskaya, M B; Platonov, Konstantin Yu; Rozhdestvenskii, Yu V

    2010-06-23

    The possibility of obtaining isomer nuclei is studied by the example of the molybdenum isomer {sup 93}Mo upon irradiation of a niobium {sup 93}Nb target by {approx}50-J, 100-fs laser pulses. It is shown that the modern laser technique allows production of isomer nuclei by accelerated protons and radiative de-excitation of isomer nuclear states by thermal or line X-rays from laser plasma. (interaction of laser radiation with matter. laser plasma)

  5. Anomalous dependence of the lasing parameters of dye solutions on the spectrum of microsecond pump laser pulses

    SciTech Connect

    Tarkovsky, V V; Kurstak, V Yu; Anufrik, S S

    2003-10-31

    The anomalous dependence of the lasing parameters of ethanol solutions of coumarin, rhodamine, oxazine, and laser dyes of other classes on the spectrum of microsecond pump laser pulses is found. The dependence is determined by the shape of the induced singlet - singlet absorption spectra and absorption spectra of short-lived photoproducts. The elucidation of the influence of these factors makes it possible to choose optimal pump spectra and to enhance the efficiency and stability of microsecond dye lasers. (active media)

  6. Pairing correlations in high-spin isomers

    SciTech Connect

    Odahara, A.; Gono, Y.; Fukuchi, T.; Wakabayashi, Y.; Sagawa, H.; Satula, W.; Nazarewicz, W.

    2005-12-15

    High-spin isomers with J{sup {pi}}=49/2{sup +} and 27{sup +} have been systematically observed in a number of N=83 isotones with 60{<=}Z{<=}67 at excitation energies {approx}9 MeV. Based on experimental excitation energies, an odd-even binding energy staggering has been extracted for the first time for these multi-quasiparticle states. Surprisingly, the magnitude of the odd-even effect in high-spin isomers turned out to be very close to that in ground states, thus challenging conventional wisdom that pairing correlations are reduced in highly excited states. Theoretical analysis based on mean-field theory explains the observed proton number dependence of the odd-even effect as a manifestation of strong pairing correlations in the highly excited states. Mean-field effects and the proton-neutron residual interaction on the odd-even staggering are also examined.

  7. Modelling Study of Interstellar Ethanimine Isomers

    NASA Astrophysics Data System (ADS)

    Quan, Donghui; Herbst, Eric; Corby, Joanna F.; Durr, Allison; Hassel, George

    2016-06-01

    Ethanimine (CH3CHNH) , including both the E- and Z- isomers, were detected towards the star-forming region Sgr B2(N) using the GBT PRIMOS data (Loomis et al 2013), and were recently imaged by the ACTA (Corby et al. 2015). These aldimines can serve as precursors of biological molecules such as amino acids thus are considered prebiotic molecules in interstellar medium. In this study, we present chemical simulations of ethanimine with various physical conditions. From models for Sgr B2(N) and environs, calculated ethanimine abundances show reasonable agreement with observed values, while the translucent cloud models yield much lower abundances. These results agree with locations suggested by observations that ethanimine isomers were detected in the foreground of the shells of the hot core.

  8. Measurements of Short-Lived Fission Isomers

    NASA Astrophysics Data System (ADS)

    Finch, Sean; Bhike, Megha; Howell, Calvin; Krishichayan, Fnu; Tornow, Werner

    2016-09-01

    Fission yields of the short lived isomers 134mTe (T1 / 2 = 162 ns) and 136mXe (T1 / 2 = 2 . 95 μs) were measured for 235U and 238U. The isomers were detected by the γ rays associated with the decay of the isomeric states using high-purity germanium detectors. Fission was induced using both monoenergetic γ rays and neutrons. At TUNL's High-Intensity Gamma-ray Source (HI γS), γ rays of 9 and 11 MeV were produced . Monoenergetic 8 MeV neutrons were produced at TUNL's tandem accelerator laboratory. Both beams were pulsed to allow for precise time-gated spectroscopy of both prompt and delayed γ rays following fission. This technique offers a non-destructive probe of special nuclear materials that is sensitive to the isotopic identity of the fissile material.

  9. Porphycenes and Related Isomers: Synthetic Aspects.

    PubMed

    Anguera, Gonzalo; Sánchez-García, David

    2017-02-22

    Porphyrins, called the pigments of life, have been studied for decades. However, the first constitutional isomer of porphyrin, porphycene, was not synthesized until 1986. This milestone marked the beginning of a new era in the field of porphyrinoids and presented opportunities for the creation of an abundance of new pigments. The unique structural and electronic features of these compounds give rise to interesting physical and optical properties with applications in biomedicine and materials science. This review focuses on the synthetic methodologies available for the preparation of porphycenes (functionalized porphycenes, extended porphycenes, benzoporphycenes, naphthoporphycenes, and heteroanalogues) and the other known isomers, namely, corrphycene, hemiporphycene, and isoporphycene. Although the classical synthetic approaches are discussed, particular emphasis is placed on improvements to the known methodologies and recent advances in the field.

  10. K Isomer in {sup 252}No

    SciTech Connect

    Sulignano, B.; Theisen, Ch.; Drouart, A.; Goergen, A.; Korten, W.; Obertelli, A.; Ackermann, D.; Hessberger, F. P.; Hofmann, S.; Antalic, S.; Venhart, M.; Dorvaux, O.; Piot, J.; Greenlees, P. T.; Jakobsson, U.; Jones, P.; Julin, R.; Juutinen, S.

    2010-04-30

    In this paper we discuss the discovery of an isomeric state in {sup 252}No and a recent experiment studying the rotational band built upon this isomeric state. Results from the later experiment help to assign the structure of the isomer on the basis of purely experimental data, and to disentangle between different theoretical interpretations. Comparison with similar states in {sup 250}Fm and {sup 254}No provides important information and helps the development of self -consistent theories.

  11. Biodegradation of cresol isomers in anoxic aquifers.

    PubMed Central

    Smolenski, W J; Suflita, J M

    1987-01-01

    The biodegradation of o-, m-, and p-cresol was examined in material obtained from a shallow anaerobic alluvial sand aquifer. The cresol isomers were preferentially metabolized, with p-cresol being the most easily degraded. m-Cresol was more persistent than the para-isomer, and o-cresol persisted for over 90 days. Biodegradation of cresol isomers was favored under sulfate-reducing conditions (SRC) compared with that under methanogenic conditions (MC). Slurries that were acclimated to p-cresol metabolism transformed this substrate at 18 and 330 nmol/h per g (dry weight) for MC and SRC, respectively. Inhibition of electron flow to sulfate reduction with 2.0 mM molybdate reduced p-cresol metabolism in incubations containing sulfate. When methanogenesis was blocked with 5 mM bromoethanesulfonic acid in incubations lacking sulfate, p-cresol catabolism was retarded. Under SRC 3.4 mol of sulfate was consumed per mol of p-cresol metabolized. The addition of sulfate to methanogenic incubations stimulated p-cresol degradation. Simultaneous adaptation studies in combination with spectrophotometric and chromatographic analysis of metabolites indicated that p-cresol was oxidized under SRC to p-hydroxybenzoate via the corresponding alcohol and aldehyde. This series of reactions was inhibited under sulfate-limited or aerobic conditions. Therefore, the primary catabolic event for p-cresol decomposition under SRC appears to involve the hydroxylation of the aryl methyl group. PMID:3579279

  12. Conjugated linoleic acid isomers: differences in metabolism and biological effects.

    PubMed

    Churruca, Itziar; Fernández-Quintela, Alfredo; Portillo, Maria Puy

    2009-01-01

    The term conjugated linoleic acid (CLA) refers to a mixture of linoleic acid positional and geometric isomers, characterized by having conjugated double bonds, not separated by a methylene group as in linoleic acid. CLA isomers appear as a minor component of the lipid fraction, found mainly in meat and dairy products from cows and sheep. The most abundant isomer is cis-9,trans-11, which represents up to 80% of total CLA in food. These isomers are metabolized in the body through different metabolic pathways, but important differences, that can have physiological consequences, are observed between the two main isomers. The trans-10,cis-12 isomer is more efficiently oxidized than the cis-9,trans-11 isomer, due to the position of its double bounds. Interest in CLA arose in its anticarcinogenic action but there is an increasing amount of specific scientific literature concerning the biological effects and properties of CLA. Numerous biological effects of CLA are due to the separate action of the most studied isomers, cis-9,trans-11 and trans-10,cis-12. It is also likely that some effects are induced and/or enhanced by these isomers acting synergistically. Although the cis-9,trans-11 isomer is mainly responsible for the anticarcinogenic effect, the trans-10,cis-12 isomer reduces body fat and it is referred as the most effective isomer affecting blood lipids. As far as insulin function is concerned, both isomers seem to be responsible for insulin resistance in humans. Finally, with regard to the immune system it is not clear whether individual isomers of CLA could act similarly or differently.

  13. CYANOMETHANIMINE ISOMERS IN COLD INTERSTELLAR CLOUDS: INSIGHTS FROM ELECTRONIC STRUCTURE AND KINETIC CALCULATIONS

    SciTech Connect

    Vazart, Fanny; Latouche, Camille; Skouteris, Dimitrios; Barone, Vincenzo; Balucani, Nadia

    2015-09-10

    New insights into the formation of interstellar cyanomethanimine, a species of great relevance in prebiotic chemistry, are provided by electronic structure and kinetic calculations for the reaction CN + CH{sub 2} = NH. This reaction is a facile formation route of Z,E-C-cyanomethanimine, even under the extreme conditions of density and temperature typical of cold interstellar clouds. E-C-cyanomethanimine has been recently identified in Sgr B2(N) in the Green Bank Telescope (GBT) PRIMOS survey by P. Zaleski et al. and no efficient formation routes have been envisaged so far. The rate coefficient expression for the reaction channel leading to the observed isomer E-C-cyanomethanimine is 3.15 × 10-10 × (T/300){sup 0.152} × e{sup (−0.0948/T)}. According to the present study, the more stable Z-C-cyanomethanimine isomer is formed with a slightly larger yield (4.59 × 10{sup −10} × (T/300){sup 0.153} × e{sup (−0.0871/T)}. As the detection of E-isomer is favored due to its larger dipole moment, the missing detection of the Z-isomer can be due to the sensitivity limit of the GBT PRIMOS survey and the detection of the Z-isomer should be attempted with more sensitive instrumentation. The CN + CH{sub 2} = NH reaction can also play a role in the chemistry of the upper atmosphere of Titan where the cyanomethanimine products can contribute to the buildup of the observed nitrogen-rich organic aerosols that cover the moon.

  14. Microsecond fiber laser pumped, single-frequency optical parametric oscillator for trace gas detection.

    PubMed

    Barria, Jessica Barrientos; Roux, Sophie; Dherbecourt, Jean-Baptiste; Raybaut, Myriam; Melkonian, Jean-Michel; Godard, Antoine; Lefebvre, Michel

    2013-07-01

    We report on the first microsecond doubly resonant optical parametric oscillator (OPO). It is based on a nested cavity OPO architecture allowing single longitudinal mode operation and low oscillation threshold (few microjoule). The combination with a master oscillator-power amplifier fiber pump laser provides a versatile optical source widely tunable in the 3.3-3.5 μm range with an adjustable pulse repetition rate (from 40 to 100 kHz), high duty cycle (~10(-2)) and mean power (up to 25 mW in the idler beam). The potential for trace gas sensing applications is demonstrated through photoacoustic detection of atmospheric methane.

  15. Cooling rate and stress relaxation in silica melts and glasses via microsecond molecular dyanmics

    SciTech Connect

    Lane, J. Matthew D.

    2015-07-22

    We have conducted extremely long molecular dynamics simulations of glasses to microsecond times, which close the gap between experimental and atomistic simulation time scales by two to three orders of magnitude. The static, thermal, and structural properties of silica glass are reported for glass cooling rates down to 5×109 K/s and viscoelastic response in silica melts and glasses are studied over nine decades of time. We finally present results from relaxation of hydrostatic compressive stress in silica and show that time-temperature superposition holds in these systems for temperatures from 3500 to 1000 K.

  16. Cooling rate and stress relaxation in silica melts and glasses via microsecond molecular dyanmics

    DOE PAGES

    Lane, J. Matthew D.

    2015-07-22

    We have conducted extremely long molecular dynamics simulations of glasses to microsecond times, which close the gap between experimental and atomistic simulation time scales by two to three orders of magnitude. The static, thermal, and structural properties of silica glass are reported for glass cooling rates down to 5×109 K/s and viscoelastic response in silica melts and glasses are studied over nine decades of time. We finally present results from relaxation of hydrostatic compressive stress in silica and show that time-temperature superposition holds in these systems for temperatures from 3500 to 1000 K.

  17. Cold Microsecond Spark Discharge Plasma Production of Active Species and Their Delivery into Tissue

    NASA Astrophysics Data System (ADS)

    Dobrynin, Danil; Fridman, Gregory; Friedman, Gary; Fridman, Alexander

    Mechanisms of the Plasma Medicine techniques, first of all plasma ­sterilization and healing of wounds, are immediately related to the effects of ­reactive neutral and charged species produced by plasma and delivered to the treated object. Here we report experimental results on measurement of production of reactive ­oxygen species in liquid media and their delivery into tissue by microsecond spark discharge plasma. We also show that a simple agarose gel model may closely mimic physicochemical characteristics of tissue.

  18. The content of conjugated linoleic acid (CLA) isomer groups in milk of two Polish sheep breeds determined by silver ion liquid chromatography (Ag(+)-HPLC).

    PubMed

    Rozbicka-Wieczorek, Agnieszka; Radzik-Rant, Aurelia; Rant, Witold; Czauderna, Marian

    2013-01-01

    Sheep milk is rich in CLA isomers which are biologically active components influencing human health. There are four geometric CLA isomer pairs: cis, trans; trans, cis; trans, trans and cis, cis. The aim of the present study was the analysis of CLA isomer groups content by Ag+-HPLC in milk fat of Zelazneńska (ZS) and Wrzosówka (WS) sheep breeds. The ewes of both breeds were kept under the same environmental and nutritional conditions. Milk samples were collected from 60 suckling ewes (30 from each breed), at the age of 3-4 years and in their 4th week of lactation. A higher total amount of all CLA isomer groups was obtained in milk of ZS ewes, however, this result was statistically insignificant. The percentage of the main c9, t11 isomer in total CLA was higher in Wrzosówka milk (68% vs. 74%). The content of the trans, trans isomer group in milk fat of the studied breeds was similar. The percentage of this group in total CLA in milk of WS and ZS constitutes 7.2% and 7.7%, respectively. The amount of cis,cis isomers in milk fat of ZS was higher thanWS (P < or = 0.01).

  19. A study of low-current-density microsecond electron beam diodes

    NASA Astrophysics Data System (ADS)

    Ramirez, J. J.; Cook, D. L.

    1980-09-01

    The performances of various field emitters and plasma-injected diodes for the generation of low-current-density microsecond electron beams to be used in gas laser excitation are investigated and compared. The output from a microsecond high-voltage pulse-forming network was fed to a large-area vacuum diode containing metal-oxide matrix and carbon fiber field emitters and to diodes filled with plasma and containing preformed plasma on the cathode surface. Of the field emitters, a brush cathode made with 10-micron carbon filaments is found to give the best performance, with emission at fields as low as 10 kV/cm, space charge-limited flow established in 60 nsec and apparent gap closure velocities of 1.5 cm/sec. Although substantial control of the diode impedance was obtained when the plasma was allowed to fill the anode-cathode volume, the constraining of the plasma to the cathode surface is found to improve the uniformity and reproducibility of anode current density, with apparent gap closure velocities as low as 2 cm/sec.

  20. Microsecond Time Resolution Optical Photometry using a H.E.S.S. Cherenkov Telescope

    SciTech Connect

    Deil, Christoph; Domainko, Wilfried; Hermann, German

    2008-02-22

    We have constructed an optical photometer with microsecond time resolution, which is currently being operated on one of the H.E.S.S. telescopes. H.E.S.S. is an array of four Cherenkov telescopes, each with a 107 m{sup 2} mirror, located in the Khomas highland in Namibia. In its normal mode of operation H.E.S.S. observes Cherenkov light from air showers generated by very high energy gamma-rays in the upper atmosphere. Our detector consists of seven photomultipliers, one in the center to record the lightcurve from the target and six concentric photomultipliers as a veto system to reject disturbing signals e.g. from meteorites or lightning at the horizon. The data acquisition system has been designed to continuously record the signals with zero deadtime. The Crab pulsar has been observed to verify the performance of the instrument and the GPS timing system. Compact galactic targets were observed to search for flares on timescales of a few microseconds to {approx}100 ms. The design and sensitivity of the instrument as well as the data analysis method are presented.

  1. Development of a microsecond X-ray protein footprinting facility at the Advanced Light Source

    PubMed Central

    Gupta, Sayan; Celestre, Richard; Petzold, Christopher J.; Chance, Mark R.; Ralston, Corie

    2014-01-01

    X-ray footprinting (XF) is an important structural biology tool used to determine macromolecular conformations and dynamics of both nucleic acids and proteins in solution on a wide range of timescales. With the impending shut-down of the National Synchrotron Light Source, it is ever more important that this tool continues to be developed at other synchrotron facilities to accommodate XF users. Toward this end, a collaborative XF program has been initiated at the Advanced Light Source using the white-light bending-magnet beamlines 5.3.1 and 3.2.1. Accessibility of the microsecond time regime for protein footprinting is demonstrated at beamline 5.3.1 using the high flux density provided by a focusing mirror in combination with a micro-capillary flow cell. It is further reported that, by saturating samples with nitrous oxide, the radiolytic labeling efficiency is increased and the imprints of bound versus bulk water can be distinguished. These results both demonstrate the suitability of the Advanced Light Source as a second home for the XF experiment, and pave the way for obtaining high-quality structural data on complex protein samples and dynamics information on the microsecond timescale. PMID:24971962

  2. Foundations of Isomer Physics for Energy Applications

    DTIC Science & Technology

    2008-10-16

    expected to impact the values of detector efficiencies determined from the counts within full-energy peaks. If the goal of the miniball system was to be...This occurs because F(t) is a very steep function . The shortest half-life is expected for decay that reaches the 6* level of the daughter, giving...10-16-2008 2. REPORT TYPE Final Technical Report 3. DATES COVERED (From - To) 9/15/2005 - 5-31-2006 4. TITLE AND SUBTITLE Foundations of Isomer

  3. The interstellar chemistry of H2C3O isomers.

    PubMed

    Loison, Jean-Christophe; Agúndez, Marcelino; Marcelino, Núria; Wakelam, Valentine; Hickson, Kevin M; Cernicharo, José; Gerin, Maryvonne; Roueff, Evelyne; Guélin, Michel

    2016-03-11

    We present the detection of two H2C3O isomers, propynal and cyclopropenone, toward various starless cores and molecular clouds, together with upper limits for the third isomer propadienone. We review the processes controlling the abundances of H2C3O isomers in interstellar media showing that the reactions involved are gas-phase ones. We show that the abundances of these species are controlled by kinetic rather than thermodynamic effects.

  4. The interstellar chemistry of H2C3O isomers

    PubMed Central

    Loison, Jean-Christophe; Agúndez, Marcelino; Marcelino, Núria; Wakelam, Valentine; Hickson, Kevin M.; Cernicharo, José; Gerin, Maryvonne; Roueff, Evelyne; Guélin, Michel

    2016-01-01

    We present the detection of two H2C3O isomers, propynal and cyclopropenone, toward various starless cores and molecular clouds, together with upper limits for the third isomer propadienone. We review the processes controlling the abundances of H2C3O isomers in interstellar media showing that the reactions involved are gas-phase ones. We show that the abundances of these species are controlled by kinetic rather than thermodynamic effects. PMID:27013768

  5. Unprecedented χ isomers of single-side triol-functionalized Anderson polyoxometalates and their proton-controlled isomer transformation.

    PubMed

    Zhang, Jiangwei; Liu, Zhenhua; Huang, Yichao; zhang, Jin; Hao, Jian; Wei, Yongge

    2015-06-04

    The μ2-O atom in Anderson polyoxometalates was regioselectively activated by the introduction of protons, which, upon functionalization with triol ligands, could afford a series of unique χ isomers of the organically-derived Anderson cluster {[RCC(CH2O)3]MMo6O18(OH)3}(3-). Herein proton-controlled isomer transformation between the δ and χ isomer was observed by using the fingerprint region in the IR spectra and (13)C NMR spectra.

  6. The truth about the lower plasma concentration of the (-)-isomer after racemic doxazosin administration in rats: Stereoselective inhibition of the (-)-isomer by the (+)-isomer at CYP3A.

    PubMed

    Kong, Dezhi; Li, Qing; Zhang, Panpan; Zhang, Wei; Zhen, Yaqin; Ren, Leiming

    2015-09-18

    Doxazosin (DOX), a long-lasting α1-adrenoceptor antagonist, is used clinically as a racemate that consists of two optical isomers. In humans and rats, following oral administration of racemic DOX [(±)-DOX], the plasma concentration of the (-)-isomer is lower than that of the (+)-isomer, but the mechanism for this interaction is not known. In this study, a chiral HPLC with fluorescence detection was used to measure the drug concentrations for analysis of the stereoselective metabolism of DOX in in vivo and in vitro experiments. We found that the plasma levels of the (-)-isomer were significantly lower than those of the (+)-enantiomer following i.v. administration of (±)-DOX to the rats and that the depletion rate constant (kdep) of (-)-DOX (0.0107±0.0007L/min) was significantly larger than that of (+)-DOX (kdep 0.0088±0.0005L/min) (p<0.05) when (±)-DOX was incubated with rat liver microsomes (RLMs). However, (-)-DOX was not depleted faster than (+)-DOX following their separate incubation with RLMs. The metabolism of (-)- or (+)-isomer in RLMs was catalysed by CYP3A because the depletion of the compounds was inhibited by ketoconazole (a potent CYP3A-selective inhibitor) similarly. More importantly, the kdep of (+)-DOX in the 1.0/2.0 and 0.5/2.5 (+)-DOX/(-)-DOX mixtures was significantly lower than that of (-)-DOX in the 1.0/2.0 and 0.5/2.5 (-)-DOX/(+)-DOX mixtures (p<0.05). In conclusion, although (-)-DOX is not depleted faster than (+)-DOX when only a single isomer of DOX is incubated with rat liver microsomes, it is depleted much faster than (+)-DOX when a mixture of the two isomers was used, suggesting a prominent and stereoselective inhibition of the (-)-isomer over the (+)-isomer at the CYP3A enzyme.

  7. Effects of ingestion of tomatoes, tomato juice and tomato purée on contents of lycopene isomers, tocopherols and ascorbic acid in human plasma as well as on lycopene isomer pattern.

    PubMed

    Fröhlich, Kati; Kaufmann, Karin; Bitsch, Roland; Böhm, Volker

    2006-04-01

    Tomatoes are an important part of the diet. Lycopene, the predominant carotenoid in tomatoes, is hypothesised to mainly mediate the health benefits of tomato products. Anticancer activity of tomato products and lycopene has been suggested by numerous studies. The aim of the present study was to investigate the effect of ingestion of three different tomato-based foodstuffs on plasma contents of lycopene, tocopherols and ascorbic acid. Because isomers of lycopene may have different biological activities, a special interest was to look how the lycopene isomer pattern is changed depending on the matrix of tomato products. Following a 2-week depletion phase volunteers ingested 12.5 mg lycopene/d for 4 weeks comprising tomatoes, tomato juice or tomato purée. The basal levels of lycopene in plasma were comparable for all groups and decreased significantly during the 2 weeks of depletion to approximately half of the basal values. Following intervention, plasma lycopene concentration increased significantly. Conversely, supplementation did not significantly affect levels of tocopherols and ascorbic acid in plasma. Regarding isomers of lycopene, the (Z)-lycopene:(all-E)-lycopene plasma isomer ratio was significantly changed during the study for all groups. A remarkable enrichment of the relative contents of (5Z)-lycopene was observed during the depletion period, which supports the hypothesis that lycopene (Z)-isomers are formed within the human body after ingestion of (all-E)-lycopene. After dietary intervention with lycopene-rich products the isomer ratios returned to those observed at the start of the study. Further investigations will clarify the process of isomerisation in more detail.

  8. Study of Vacuum Insulator Flashover for Pulse Lengths of Multi-Microseconds

    SciTech Connect

    Houck, T; Goerz, D; Javedani, J; Lauer, E; Tully, L; Vogtlin, G

    2006-07-31

    We are studying the flashover of vacuum insulators for applications where high voltage conditioning of the insulator and electrodes is not practical and for pulse lengths on the order of several microseconds. The study is centered about experiments performed with a 100-kV, 10-ms pulsed power system and supported by a combination of theoretical and computational modeling. The base line geometry is a cylindrically symmetric, +45{sup o} insulator between flat electrodes. In the experiments, flashovers or breakdowns are localized by operating at field stresses slightly below the level needed for explosive emissions with the base line geometry. The electrodes and/or insulator are then seeded with an emission source, e.g. a tuft of velvet, or a known mechanical defect. Various standard techniques are employed to suppress cathode-originating flashovers/breakdowns. We present the results of our experiments and discuss the capabilities of modeling insulator flashover.

  9. Physical chemistry and membrane properties of two phosphatidylinositol bisphosphate isomers.

    PubMed

    Slochower, David R; Wang, Yu-Hsiu; Radhakrishnan, Ravi; Janmey, Paul A

    2015-05-21

    The most highly charged phospholipids, polyphosphoinositides, are often involved in signaling pathways that originate at cell-cell and cell-matrix contacts, and different isomers of polyphosphoinositides have distinct biological functions that cannot be explained by separate highly specific protein ligand binding sites [Lemmon, Nat. Rev. Mol. Cell Biol., 2008, 9, 99-111]. PtdIns(3,5)P2 is a low abundance phosphoinositide localized to cytoplasmic-facing membrane surfaces, with relatively few known ligands, yet PtdIns(3,5)P2 plays a key role in controlling membrane trafficking events and cellular stress responses that cannot be duplicated by other phosphoinositides [Dove et al., Nature, 1997, 390, 187-192; Michell, FEBS J., 2013, 280, 6281-6294]. Here we show that PtdIns(3,5)P2 is structurally distinct from PtdIns(4,5)P2 and other more common phospholipids, with unique physical chemistry. Using multiscale molecular dynamics techniques on the quantum level, single molecule, and in bilayer settings, we found that the negative charge of PtdIns(3,5)P2 is spread over a larger area, compared to PtdIns(4,5)P2, leading to a decreased ability to bind divalent ions. Additionally, our results match well with experimental data characterizing the cluster forming potential of these isomers in the presence of Ca(2+) [Wang et al., J. Am. Chem. Soc., 2012, 134, 3387-3395; van den Bogaart et al., Nature, 2011, 479, 552-555]. Our results demonstrate that the different cellular roles of PtdIns(4,5)P2 and PtdIns(3,5)P2in vivo are not simply determined by their localization by enzymes that produce or degrade them, but also by their molecular size, ability to chelate ions, and the partial dehydration of those ions, which might affect the ability of PtdIns(3,5)P2 and PtdIns(4,5)P2 to form phosphoinositide-rich clusters in vitro and in vivo.

  10. 27 CFR 21.120 - Nitropropane, mixed isomers of.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2012-04-01 2012-04-01 false Nitropropane, mixed isomers of. 21.120 Section 21.120 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE... Denaturants § 21.120 Nitropropane, mixed isomers of. (a) Nitropropane content. A minimum of 94 percent...

  11. Stereospecific Synthesis of the Geometrical Isomers of a Natural Product

    ERIC Educational Resources Information Center

    Grove, T.; DiLella, D.; Volker, E.

    2006-01-01

    Stereospecific synthesis of a geometrical isomer is not a common topic for the introductory organic chemistry laboratory. We have developed and tested an experiment for the synthesis of (Z) and (E) isomers that has been performed successfully by undergraduate students. The experiment is presented to the students as a puzzle in which they must…

  12. 27 CFR 21.120 - Nitropropane, mixed isomers of.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2013-04-01 2013-04-01 false Nitropropane, mixed isomers of. 21.120 Section 21.120 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE... Denaturants § 21.120 Nitropropane, mixed isomers of. (a) Nitropropane content. A minimum of 94 percent...

  13. 27 CFR 21.120 - Nitropropane, mixed isomers of.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2011-04-01 2011-04-01 false Nitropropane, mixed isomers of. 21.120 Section 21.120 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE... Denaturants § 21.120 Nitropropane, mixed isomers of. (a) Nitropropane content. A minimum of 94 percent...

  14. 27 CFR 21.120 - Nitropropane, mixed isomers of.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Nitropropane, mixed isomers of. 21.120 Section 21.120 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE... Denaturants § 21.120 Nitropropane, mixed isomers of. (a) Nitropropane content. A minimum of 94 percent...

  15. 27 CFR 21.120 - Nitropropane, mixed isomers of.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2014-04-01 2014-04-01 false Nitropropane, mixed isomers of. 21.120 Section 21.120 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE... Denaturants § 21.120 Nitropropane, mixed isomers of. (a) Nitropropane content. A minimum of 94 percent...

  16. ASTROPULSE: A SEARCH FOR MICROSECOND TRANSIENT RADIO SIGNALS USING DISTRIBUTED COMPUTING. I. METHODOLOGY

    SciTech Connect

    Von Korff, J.; Heien, E.; Korpela, E.; Werthimer, D.; Cobb, J.; Lebofsky, M.; Anderson, D.; Bankay, B.; Siemion, A.; Demorest, P.

    2013-04-10

    We are performing a transient, microsecond timescale radio sky survey, called 'Astropulse', using the Arecibo telescope. Astropulse searches for brief (0.4 {mu}s to 204.8 {mu}s ), wideband (relative to its 2.5 MHz bandwidth) radio pulses centered at 1420 MHz. Astropulse is a commensal (piggyback) survey, and scans the sky between declinations of -1. Degree-Sign 33 and 38. Degree-Sign 03. We obtained 1540 hr of data in each of seven beams of the ALFA receiver, with two polarizations per beam. The data are one-bit complex sampled at the Nyquist limit of 0.4 {mu}s per sample. Examination of timescales on the order of microseconds is possible because we used coherent dedispersion, a technique that has frequently been used for targeted observations, but has never been associated with a radio sky survey. The more usual technique, incoherent dedispersion, cannot resolve signals below a minimum timescale which depends on the signal's dispersion measure (DM) and frequency. However, coherent dedispersion requires more intensive computation than incoherent dedispersion. The required processing power was provided by BOINC, the Berkeley Open Infrastructure for Network Computing. BOINC is a distributed computing system, allowing us to utilize hundreds of thousands of volunteers' computers to perform the necessary calculations for coherent dedispersion. Astrophysical events that might produce brief radio pulses include giant pulses from pulsars, rotating radio transients, exploding primordial black holes, or new sources yet to be imagined. Radio frequency interference and noise contaminate the data; these are mitigated by a number of techniques including multi-polarization correlation, DM repetition detection, and frequency profiling.

  17. From microseconds to seconds and minutes—time computation in insect hearing

    PubMed Central

    Hartbauer, Manfred; Römer, Heiner

    2014-01-01

    The computation of time in the auditory system of insects is of relevance at rather different time scales, covering a large range from microseconds to several minutes. At the one end of this range, only a few microseconds of interaural time differences are available for directional hearing, due to the small distance between the ears, usually considered too small to be processed reliably by simple nervous systems. Synapses of interneurons in the afferent auditory pathway are, however, very sensitive to a time difference of only 1–2 ms provided by the latency shift of afferent activity with changing sound direction. At a much larger time scale of several tens of milliseconds to seconds, time processing is important in the context species recognition, but also for those insects where males produce acoustic signals within choruses, and the temporal relationship between song elements strongly deviates from a random distribution. In these situations, some species exhibit a more or less strict phase relationship of song elements, based on phase response properties of their song oscillator. Here we review evidence on how this may influence mate choice decisions. In the same dimension of some tens of milliseconds we find species of katydids with a duetting communication scheme, where one sex only performs phonotaxis to the other sex if the acoustic response falls within a very short time window after its own call. Such time windows show some features unique to insects, and although its neuronal implementation is unknown so far, the similarity with time processing for target range detection in bat echolocation will be discussed. Finally, the time scale being processed must be extended into the range of many minutes, since some acoustic insects produce singing bouts lasting quite long, and female preferences may be based on total signaling time. PMID:24782783

  18. Astropulse: A Search for Microsecond Transient Radio Signals Using Distributed Computing. I. Methodology

    NASA Astrophysics Data System (ADS)

    Von Korff, J.; Demorest, P.; Heien, E.; Korpela, E.; Werthimer, D.; Cobb, J.; Lebofsky, M.; Anderson, D.; Bankay, B.; Siemion, A.

    2013-04-01

    We are performing a transient, microsecond timescale radio sky survey, called "Astropulse," using the Arecibo telescope. Astropulse searches for brief (0.4 μs to 204.8 μs ), wideband (relative to its 2.5 MHz bandwidth) radio pulses centered at 1420 MHz. Astropulse is a commensal (piggyback) survey, and scans the sky between declinations of -1.°33 and 38.°03. We obtained 1540 hr of data in each of seven beams of the ALFA receiver, with two polarizations per beam. The data are one-bit complex sampled at the Nyquist limit of 0.4 μs per sample. Examination of timescales on the order of microseconds is possible because we used coherent dedispersion, a technique that has frequently been used for targeted observations, but has never been associated with a radio sky survey. The more usual technique, incoherent dedispersion, cannot resolve signals below a minimum timescale which depends on the signal's dispersion measure (DM) and frequency. However, coherent dedispersion requires more intensive computation than incoherent dedispersion. The required processing power was provided by BOINC, the Berkeley Open Infrastructure for Network Computing. BOINC is a distributed computing system, allowing us to utilize hundreds of thousands of volunteers' computers to perform the necessary calculations for coherent dedispersion. Astrophysical events that might produce brief radio pulses include giant pulses from pulsars, rotating radio transients, exploding primordial black holes, or new sources yet to be imagined. Radio frequency interference and noise contaminate the data; these are mitigated by a number of techniques including multi-polarization correlation, DM repetition detection, and frequency profiling.

  19. Isomer Spectroscopy of the Heaviest Elements

    NASA Astrophysics Data System (ADS)

    Clark, Roderick

    2009-05-01

    A new generation of experiments on the structure and properties of the heaviest elements is being performed in laboratories around the world. These studies are addressing fundamental questions such as the maximum mass and charge that a nucleus can attain. Long-lived high-K isomers are found in the region of prolate-deformed trans-fermium nuclei and by studying their decay one can learn about the single-particle structure, pairing correlations, and excitation modes of the heaviest nuclei. Recent decay spectroscopy experiments using the Berkeley Gas-Filled Separator (BGS) at the 88-Inch Cyclotron of the Lawrence Berkeley National Laboratory have yielded a wealth of detailed new information on many nuclei in the trans-fermium region. I will discuss these new results and their implications.

  20. Complete Hexose Isomer Identification with Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Nagy, Gabe; Pohl, Nicola L. B.

    2015-04-01

    The first analytical method is presented for the identification and absolute configuration determination of all 24 aldohexose and 2-ketohexose isomers, including the D and L enantiomers for allose, altrose, galactose, glucose, gulose, idose, mannose, talose, fructose, psicose, sorbose, and tagatose. Two unique fixed ligand kinetic method combinations were discovered to create significant enough energetic differences to achieve chiral discrimination among all 24 hexoses. Each of these 24 hexoses yields unique ratios of a specific pair of fragment ions that allows for simultaneous determination of identification and absolute configuration. This mass spectrometric-based methodology can be readily employed for accurate identification of any isolated monosaccharide from an unknown biological source. This work provides a key step towards the goal of complete de novo carbohydrate analysis.

  1. Fission and Properties of Neutron-Rich Nuclei - Proceedings of the Second International Conference

    NASA Astrophysics Data System (ADS)

    Hamilton, J. H.; Phillips, W. R.; Carter, H. K.

    The Table of Contents for the book is as follows: * Preface * Structure of Elementary Matter: Cold Valleys and Their Importance in Fission, Fusion and for Superheavy Nuclei * Tunnelling Phenomena in Nuclear Physics * Heavy Nuclei Studies Using Transfer Reactions * Isomeric Properties of Nuclei Near 78Ni * Investigation of Light Actinide Nuclei at Yale and Beyond * U-Projectile Fission at Relativistic Energies * Cluster Description of Cold Fission Modes in 252Cf * Neutron-pair Transfer Theory for Pear-shaped Ba Fission Fragments * New RMFA Parameters of Normal and Exotic Nuclei * Study of Fission Fragments from 12C+238U Reactions: Prompt and Delayed Spectroscopy * γ-Ray Angular Correlations in 252Cf and 248Cm Fission Fragments * Fragment Angular Momentum and Descent Dynamics in 252Cf Spontaneous Fission * The Experimental Investigation of Neutron-Rich Nuclei * High-Spin Structure of Some Odd-Z Nuclei with A ≈ 100 From Heavy-Ion Induced Fission * Coexistence of Symmetric and Asymmetric Nuclear Shapes and 10Be Ternary Fission * Octupole Effects in the Lanthanides * High Spin Structure of the 113-1l6Cd Isotopes Produced by Heavy-Ion Induced Fission Reaction * Temperature-Dependent Fission Barriers and Mass Distributions for 239U * Strength Distributions for Gamow Teller Transitions in Very Weakly Bound Systems * High Spin Fragmentation Spectroscopy * Search for a Four-Neutron Transfer From 8He to 4He * Microsecond Isomers in Fission Fragments in the Vicinity of the Doubly Magic 132Sn * Recent On-Line NMR/on Nuclear Magnetic Dipole Moments Near 132Sn: Meson Exchange Current Effects at the Shell Closure and Shell Model Treatment of Variation with Proton and Neutron Number * High-spin K-Isomers Beyond the Fusion Limit * High Energy Neutron Induced Fission: Charge Yield Distributions and Search and Spectroscopy of New Isomers * Hartree-Fock Mean-Field Models Using Separable Interactions * Variation of Fission Characteristics Over the Nuclear Chart * Investigation of

  2. Nuclear structure and depletion of nuclear isomers using electron linacs

    SciTech Connect

    Carroll, J. J.; Litz, M. S.; Henriquez, S. L.; Burns, D. A.; Netherton, K. A.; Pereira, N. R.; Karamian, S. A.

    2013-04-19

    Long-lived nuclear excited states (isomers) have proven important to understanding nuclear structure. With some isomers having half-lives of decades or longer, and intrinsic energy densities reaching 10{sup 12} J/kg, they have also been suggested for a wide range of applications. The ability to effectively transfer a population of nuclei from an isomer to shorter-lived levels will determine the feasibility of any applications. Here is described a first demonstration of the induced depletion of a population of the 438 year isomer of {sup 108}Ag to its 2.38 min ground state, using 6 MeV bremsstrahlung from a modified medical electron linac. The experiment suggests refinements to be implemented in the future and how a similar approach might be applied to study induced depletion of the 1200 year isomer of {sup 166}Ho.

  3. Failures of fractional crystallization: ordered co-crystals of isomers and near isomers.

    PubMed

    Kelley, Steven P; Fábián, László; Brock, Carolyn Pratt

    2011-02-01

    A list of 270 structures of ordered co-crystals of isomers, near isomers and molecules that are almost the same has been compiled. Searches for structures containing isomers could be automated by the use of IUPAC International Chemical Identifier (InChI™) strings but searches for co-crystals of very similar molecules were more labor intensive. Compounds in which the heteromolecular A···B interactions are clearly better than the average of the homomolecular A···A and B···B interactions were excluded. The two largest structural classes found include co-crystals of configurational diastereomers and of quasienantiomers (or quasiracemates). These two groups overlap. There are 114 co-crystals of diastereomers and the same number of quasiracemates, with 71 structures being counted in both groups; together the groups account for 157 structures or 58% of the total. The large number of quasiracemates is strong evidence for inversion symmetry being very favorable for crystal packing. Co-crystallization of two diastereomers is especially likely if a 1,1 switch of a methyl group and an H atom, or of an inversion of a [2.2.1] or [2.2.2] cage, in one of the diastereomers would make the two molecules enantiomers.

  4. Near-IR absorbance changes and electrogenic reactions in the microsecond-to-second time domain in Photosystem I.

    PubMed

    Vassiliev, I R; Jung, Y S; Mamedov, M D; Semenov AYu; Golbeck, J H

    1997-01-01

    The back-reaction kinetics in Photosystem I (PS I) were studied on the microsecond-to-s time scale in cyanobacterial preparations, which differed in the number of iron-sulfur clusters to assess the contributions of particular components to the reduction of P700+. In membrane fragments and in trimeric P700-FA/FB complexes, the major contribution to the absorbance change at 820 nm (delta A820) was the back-reaction of FA- and/or FB- with lifetimes of approximately 10 and 80 ms (approximately 10% and 40% relative amplitude). The decay of photoinduced electric potential (delta psi) across a membrane with directionally incorporated P700-FA/FB complexes had similar kinetics. HgCl2-treated PS I complexes, which contain FA but no FB, retain both of these kinetic components, indicating that neither can be assigned uniquely to a specific acceptor. These results suggest that FA- reduces P700+ directly and argue for a rapid electron equilibration between FA and FB, which would eliminate their kinetic distinction in a back-reaction. In PsaC-depleted P700-Fx cores, as well as in P700-FA/FB complexes with chemically reduced FA and FB, the major contribution to the delta A820 and the delta psi decay is a biphasic back-reaction of F-X (approximately 400 microseconds and 1.5 ms) with some contribution from A-1 (approximately 10 microseconds and 100 microseconds), the latter of which is variable depending on experimental conditions. The delta A820 decay in a P700-A1 core devoid of all iron-sulfur clusters comprises two phases with lifetimes of 10 microseconds and 130 microseconds (2.7:1 ratio). The biexponential back-reaction kinetics found for each of the electron acceptors may be related to existence of different conformational states of the PS I complex. In all preparations studied, excitation at 532 nm with flash energies exceeding 10 mJ gives rise to formation of antenna 3Chl, which also contributes to delta A820 decay on the tens-of-microsecond time scale. A distinction between

  5. Identification of conjugated linoleic acid (CLA) isomers by silver ion-liquid chromatography/in-line ozonolysis/mass spectrometry (Ag+-LC/O3-MS).

    PubMed

    Sun, Chenxing; Black, Brenna A; Zhao, Yuan-Yuan; Gänzle, Michael G; Curtis, Jonathan M

    2013-08-06

    A novel method for the identification of conjugated linoleic acid (CLA) isomers has been developed in which silver ion liquid chromatography is coupled to in-line ozonolysis/mass spectrometry (Ag(+)-LC/O3-MS). The mobile phase containing CLA isomers eluting from the Ag(+)-LC column flows through a length of gas-permeable tubing within an ozone rich environment. Ozone penetrating the tubing wall reacts with the conjugated double bonds forming ozonolysis product aldehydes. These, and their corresponding methanol loss fragment ions formed within the atmospheric pressure photoionization (APPI) source, were detected by in-line MS and used for the direct assignment of double bond positions. Assignment of positional isomers is based entirely on the two pairs of diagnostic ions seen in the in-line O3-MS mass spectra. In this way, de novo identification of CLA positional isomers, i.e. without requiring comparison to CLA standards, was achieved. The Ag(+)-LC/O3-MS method was applied to the analysis of CLA isomers in a commercial CLA supplement, milk fat, and the lipid extract from a Lactobacillus plantarum TMW1460 culture. The results demonstrate how Ag(+)-LC/O3-MS can be used for the direct and fast determination of CLA isomers at low concentrations and in complex lipid mixtures.

  6. Conversion electron spectroscopy at the FMA focal plane: Decay studies of proton-rich N {approximately} 82 nuclei

    SciTech Connect

    Nisius, D.; Janssens, R.V.F.; Ahmad, I.

    1995-08-01

    The FMA has proven to be an ideal instrument for the detailed study of the decay of microsecond isomers behind the focal plane following mass selection. In reactions leading to the population of nuclei with isomeric lifetimes longer than their flight time through the device, decay gamma rays and conversion electrons can be detected in an environment free from the backgrounds of prompt radiation and delta electrons. This was a very successful technique to study proton (h{sub 11/2}){sup n} seniority isomers in nuclei with Z > 64 and N {approximately} 82. Since isomeric decay gamma rays are emitted isotropically, conversion electrons are essential for the assignment of multipolarities in these nuclei. Furthermore, the low-energy transitions that depopulate isomeric states are typically highly converted and can escape gamma-ray detection, but they can be identified by their conversion electrons.

  7. Isomers and Enhanced Stability of Superheavy Elements

    NASA Astrophysics Data System (ADS)

    Kondev, Filip; Anl, Lbnl, Anu, Csnsm, Llnl, Usna, U. Of Edinburgh, U. Of Jyväskylä, U. Of Massachusetts, Lowell Collaboration

    2014-09-01

    There has been continuing activity addressing the complex question of whether excited isomeric states would lead to enhanced stability of superheavy nuclei, given changes in the fission barriers, α-decay probabilities and the effects of nuclear structure (such as K-hindrance). Recently, we have carried out new studies of the 254Rf isotope using the 50Ti + 206Pb reaction at Argonne National Laboratory and Lawrence Berkeley National Laboratory. A digital data acquisition system was deployed in both experiments, which allowed the identification of implant and decay events that were separated by time as short as hundreds of nanoseconds. Two isomeric states were discovered in 254Rf with half-lives of ~4 μs and ~300 μs, the latter being an order of magnitude longer lived than the ground state. In addition, K-isomers in 244Cm and 246Cm were also studied following β- decays of 244Am (Kπ = 6+) and 246Am (Kπ = 7-) mass-separated sources, respectively. The emphasis was on elucidating details of the level schemes, which allowed reliable values for the strength of the K-forbidden transitions to be determined and compared with systematics in other regions of the nuclear chart. There has been continuing activity addressing the complex question of whether excited isomeric states would lead to enhanced stability of superheavy nuclei, given changes in the fission barriers, α-decay probabilities and the effects of nuclear structure (such as K-hindrance). Recently, we have carried out new studies of the 254Rf isotope using the 50Ti + 206Pb reaction at Argonne National Laboratory and Lawrence Berkeley National Laboratory. A digital data acquisition system was deployed in both experiments, which allowed the identification of implant and decay events that were separated by time as short as hundreds of nanoseconds. Two isomeric states were discovered in 254Rf with half-lives of ~4 μs and ~300 μs, the latter being an order of magnitude longer lived than the ground state. In

  8. Detection of Actinides via Nuclear Isomer De-Excitation

    SciTech Connect

    Francy, Christopher J.

    2009-07-01

    This dissertation discusses a data collection experiment within the Actinide Isomer Identification project (AID). The AID project is the investigation of an active interrogation technique that utilizes nuclear isomer production, with the goal of assisting in the interdiction of illicit nuclear materials. In an attempt to find and characterize isomers belonging to 235U and its fission fragments, a 232Th target was bombarded with a monoenergetic 6Li ion beam, operating at 45 MeV.

  9. Observations of multi-microsecond VHF pulsetrains in energetic intracloud lightning discharges

    NASA Astrophysics Data System (ADS)

    Jacobson, A. R.; Holzworth, R. H.; Shao, X.-M.

    2011-09-01

    Certain intracloud lightning discharges emit energetic, multi-microsecond pulsetrains of radio noise. Observations of this distinctive form of lightning date from 1980 and have involved both ground-based and satellite-based radio recording systems. The underlying intracloud lightning discharges have been referred to as "Narrow Bipolar Pulses", "Narrow Bipolar Events", and "Compact Intracloud Discharges". An important discriminant for this species of radio emission is that, in the range above ~30 MHz, it consists of several microseconds of intense radio noise. When the intracloud emission is viewed from a satellite, each radio pulsetrain is received both from a direct lightning-to-satellite path, and after some delay, from a path via ground. Thus one recording of the radio emission, if of sufficient length, contains the "view" of the intracloud emission from two different angles. One view is of radiation exiting the emitter into the upper hemisphere, the other for radiation exiting into the lower hemisphere. However, the propagation conditions are similar, except that one path includes a ground reflection, while the other does not. One would normally expect a stereoscopic double view of the "same" emission process to provide two almost congruent time series, one delayed from the other, and also differing due to the different propagation effects along the two signal paths, namely, the ground reflection. We present somewhat unexpected results on this matter, using recordings from the FORTE satellite at a passband 118-141 MHz, with simultaneous data at 26-49 MHz. We find that the 118-141 MHz pulsetrain's detailed time-dependence is completely uncorrelated between the two views of the process. We examine statistics of the 118-141 MHz pulsetrain's integrated power and show that the power emitted into the lower hemisphere, on average, exceeds the power emitted into the upper hemisphere. Finally, we examine statistical measures of the amplitude distribution and show that

  10. Electropolymerization mechanisms of hydroxyphenylacetic acid isomers

    NASA Astrophysics Data System (ADS)

    Rodrigues, Luciano P.; Ferreira, Deusmaque C.; Sonoda, Milton Taidi; Madurro, Ana Graci B.; Abrahão, Odonírio; Madurro, João M.

    2014-08-01

    Three different films of conducting polymers with free carboxylic functional groups were obtained from 2,3 and 4-hydroxyphenylacetic acid isomers (HPA) and the respective electropolymerization mechanisms were elucidated by DFT calculations. The different properties observed at these new material characterizations, obtained by means of cyclic voltammetry on graphite, are in agreement with theoretical interpretation presented for each reaction mechanisms, which involves the different radical cation coupling and formation of aromatic polyethers with free carboxyl groups, characterized by FTIR spectrometry and electrochemical tests. The computational chemistry analysis of the radical cations spin densities and partial atomic charges variation during the monomer oxidations, indicates the most probably reactive sites for their coupling, allowing the proposition of HPA electropolymerization mechanisms. The poly(2-HPA) had the largest yield in the electropolymerization reaction and the lowest electron transfer. The poly(4-HPA) displayed the lowest yield and the largest electron transfer coefficient, with poly(3-HPA) presenting intermediate values between the former two. Therefore, poly(3-HPA) is a very promising polymer for the platform development for electronic systems, which require materials with good electronic conductivity allied to intrinsic flexibility of polymeric materials.

  11. Isomer spectroscopy of {sup 127}Cd

    SciTech Connect

    Naqvi, F.; Gorska, M.; Grawe, H.; Beck, T.; Doornenbal, P.; Geissel, H.; Gerl, J.; Kojouharov, I.; Kurz, N.; Montes, F.; Prokopowicz, W.; Schaffner, H.; Tashenov, S.; Wollersheim, H. J.; Caceres, L.; Jungclaus, A.; Pfuetzner, M.; Werner-Malento, E.; Nowacki, F.; Sieja, K.

    2010-09-15

    The spin and configurational structure of excited states of {sup 127}Cd, the two-proton and three-neutron hole neighbor of {sup 132}Sn, has been studied. An isomeric state with a half-life of 17.5(3) {mu}s was populated in the fragmentation of a {sup 136}Xe beam on a {sup 9}Be target at a beam energy of 750 MeV/u. Time distributions of the delayed {gamma} transitions and {gamma}{gamma} coincidence relations were exploited to construct a decay scheme. The observed yrast (19/2){sup +} isomer is proposed to have dominant configurations of {nu}(h{sub 11/2}{sup -3}){pi}(g{sub 9/2}{sup -1},p{sub 1/2}{sup -1}), {nu}(h{sub 11/2}{sup -2}d{sub 3/2}{sup -1}){pi}(g{sub 9/2}{sup -2}), and {nu}(h{sub 11/2}{sup -2},s{sub 1/2}{sup -1}){pi}(g{sub 9/2}{sup -2}) and to decay by two competing stretched M2 and E3 transitions. Experimental results are compared with the isotone {sup 129}Sn. The new information provides input for the proton-neutron interaction and the evolution of neutron hole energies in nuclei around the doubly magic {sup 132}Sn core.

  12. A Comparative Study on the Effects of Millisecond- and Microsecond-Pulsed Electric Field Treatments on the Permeabilization and Extraction of Pigments from Chlorella vulgaris.

    PubMed

    Luengo, Elisa; Martínez, Juan Manuel; Coustets, Mathilde; Álvarez, Ignacio; Teissié, Justin; Rols, Marie-Pierre; Raso, Javier

    2015-10-01

    The interdependencies of the two main processing parameters affecting "electroporation" (electric field strength and pulse duration) while using pulse duration in the range of milliseconds and microseconds on the permeabilization, inactivation, and extraction of pigments from Chlorella vulgaris was compared. While irreversible "electroporation" was observed above 4 kV/cm in the millisecond range, electric field strengths of ≥10 kV/cm were required in the microseconds range. However, to cause the electroporation of most of the 90 % of the population of C. vulgaris in the millisecond (5 kV/cm, 20 pulses) or microsecond (15 kV/cm, 25 pulses) range, the specific energy that was delivered was lower for microsecond treatments (16.87 kJ/L) than in millisecond treatments (150 kJ/L). In terms of the specific energy required to cause microalgae inactivation, treatments in the microsecond range also resulted in greater energy efficiency. The comparison of extraction yields in the range of milliseconds (5 kV, 20 ms) and microseconds (20, 25 pulses) under the conditions in which the maximum extraction was observed revealed that the improvement in the carotenoid extraction was similar and chlorophyll a and b extraction was slightly higher for treatments in the microsecond range. The specific energy that was required for the treatment in the millisecond range (150 kJ/L) was much higher than those required in the microsecond range (30 kJ/L). The comparison of the efficacy of both types of pulses on the extraction enhancement just after the treatment and after a post-pulse incubation period seemed to indicate that PEF in the millisecond range created irreversible alterations while, in the microsecond range, the defects were a dynamic structure along the post-pulse time that caused a subsequent increment in the extraction yield.

  13. Molecular structure of uranium carbides: isomers of UC3.

    PubMed

    Zalazar, M Fernanda; Rayón, Víctor M; Largo, Antonio

    2013-03-21

    In this article, the most relevant isomers of uranium tricarbide are studied through quantum chemical methods. It is found that the most stable isomer has a fan geometry in which the uranium atom is bonded to a quasilinear C3 unit. Both, a rhombic and a ring CU(C2) structures are found about 104-125 kJ/mol higher in energy. Other possible isomers including linear geometries are located even higher. For each structure, we provide predictions for those molecular properties (vibrational frequencies, IR intensities, dipole moments) that could eventually help in their experimental detection. We also discuss the possible routes for the formation of the different UC3 isomers as well as the bonding situation by means of a topological analysis of the electron density.

  14. Carotenoids and their isomers: color pigments in fruits and vegetables.

    PubMed

    Khoo, Hock-Eng; Prasad, K Nagendra; Kong, Kin-Weng; Jiang, Yueming; Ismail, Amin

    2011-02-18

    Fruits and vegetables are colorful pigment-containing food sources. Owing to their nutritional benefits and phytochemicals, they are considered as 'functional food ingredients'. Carotenoids are some of the most vital colored phytochemicals, occurring as all-trans and cis-isomers, and accounting for the brilliant colors of a variety of fruits and vegetables. Carotenoids extensively studied in this regard include β-carotene, lycopene, lutein and zeaxanthin. Coloration of fruits and vegetables depends on their growth maturity, concentration of carotenoid isomers, and food processing methods. This article focuses more on several carotenoids and their isomers present in different fruits and vegetables along with their concentrations. Carotenoids and their geometric isomers also play an important role in protecting cells from oxidation and cellular damages.

  15. Tocopherol isomers in intravenous lipid emulsions and resultant plasma concentrations.

    PubMed

    Gutcher, G R; Lax, A A; Farrell, P M

    1984-01-01

    Conflicting reports exist regarding the relative tocopherol isomer content of Intralipid ranging from 99% as alpha-tocopherol to as much as 90% as gamma-tocopherol. Our direct assay of Intralipid as well as plasma levels measured in premature infants receiving Intralipid confirm the existence of a low alpha, high gamma-tocopherol content and imply the need for alpha-tocopherol supplementation in patients receiving Intralipid, particularly the relatively tocopherol-deficient premature infant. Furthermore, the observation of abnormal erythrocyte hemolysis test values despite "normal" total tocopherol plasma concentrations may be explained by high plasma levels of non-alpha, biologically less active isomers. The quantitation of tocopherol isomers helps explain this discrepancy and suggests the need for future studies of vitamin E status to employ measurements of tocopherol isomers in reporting results.

  16. Enhanced Raman spectroscopic study of rotational isomers on metal surfaces

    NASA Technical Reports Server (NTRS)

    Loo, B. H.; Lee, Y. G.; Frazier, D. O.

    1986-01-01

    Surfaced-enhanced Raman spectroscopy has been used to study rotational isomers of succinonitrile and N-methyl-thioacetamide on Cu and Ag surfaces. Both the gauche and trans conformers of succinonitrile are found to chemisorb on the metal surface. The doubly degenerate nu(C-triple bond-N) in the free molecules is removed when succinonitrile adsorbs on copper, which indicates that the two (C-triple bond-N) groups are no longer chemically equivalent. Both conformers are found to coordinate to the copper surface through the pi system of one of the two (C-triple bond-N) groups. In the case of N-methyl-thioacetamide, the population of the cis isomer is greatly increased on Cu and Ag surfaces. This is probably due to surface-induced cis-trans isomerization, in which the predominant trans isomer is converted to the cis isomer.

  17. STROBE-X: X-ray Timing & Spectroscopy on Dynamical Timescales from Microseconds to Years

    NASA Astrophysics Data System (ADS)

    Ray, Paul; Wilson-Hodge, Colleen; Gendreau, Keith; Chakrabarty, Deepto; Feroci, Marco; Maccarone, Thomas; Arzoumanian, Zaven; Remillard, Ron; Wood, Kent; Griffith, Chris; Strobe-X Collaboration

    2017-01-01

    We describe a proposed probe-class mission concept that will provide an unprecedented view of the X-ray sky, performing timing and spectroscopy over a broad band (0.2-30 keV) probing timescale from microseconds to years. The Spectroscopic Time-Resolving Observatory for Broadband Energy X-rays (STROBE-X) comprises two primary instruments, one based on technology developed for the NICER mission and the other based on the European LOFT mission. The broad coverage will enable thermal components, non-thermal components, iron lines, and reflection features to be studied simultaneously from a single platform for the first time in accreting black holes at all scales. The massive collecting area will enable studies of the dense matter equation of state using multiple techniques. A broad range of other revolutionary science, such as high quality spectroscopy of clusters of galaxies and unprecedented timing investigations of active galactic nuclei, would also be obtained. We describe the mission concept and the planned trade studies that will optimize the mission to maximize the science return. This mission is being developed in collaboration with members of the European LOFT team, and a hardware contribution from Europe is expected.

  18. Microsecond light-induced proton transfer to flavin in the blue light sensor plant cryptochrome.

    PubMed

    Langenbacher, Thomas; Immeln, Dominik; Dick, Bernhard; Kottke, Tilman

    2009-10-14

    Plant cryptochromes are blue light photoreceptors that regulate key responses in growth and daily rhythm of plants and might be involved in magnetoreception. They show structural homology to the DNA repair enzyme photolyase and bind flavin adenine dinucleotide as chromophore. Blue light absorption initiates the photoreduction from the oxidized dark state of flavin to the flavin neutral radical, which is the signaling state of the sensor. Previous time-resolved studies of the photoreduction process have been limited to observation of the decay of the radical in the millisecond time domain. We monitored faster, light-induced changes in absorption of an algal cryptochrome covering a spectral range of 375-750 nm with a streak camera setup. Electron transfer from tryptophan to flavin is completed before 100 ns under formation of the flavin anion radical. Proton transfer takes place with a time constant of 1.7 micros leading to the flavin neutral radical. Finally, the flavin radical and a tryptophan neutral radical decay with a time constant >200 micros in the millisecond and second time domain. The microsecond proton transfer has not been observed in animal cryptochromes from insects or photolyases. Furthermore, the strict separation in time of electron and proton transfer is novel in the field of flavin-containing photoreceptors. The reaction rate implies that the proton donor is not in hydrogen bonding distance to the flavin N5. Potential candidates for the proton donor and the involvement of the tryptophan triad are discussed.

  19. Microsecond folding and domain motions of a spider silk protein structural switch.

    PubMed

    Ries, Julia; Schwarze, Simone; Johnson, Christopher M; Neuweiler, Hannes

    2014-12-10

    Web spiders rapidly assemble protein monomers, so-called spidroins, into extraordinarily tough silk fibers. The process involves the pH-triggered self-association of the spidroin N-terminal domain (NTD), which contains a structural switch connecting spidroins to supermolecules. Single-molecule spectroscopy can detect conformational heterogeneity that is hidden to conventional methods, but motions of the NTD are beyond the resolution limit. Here, we engineered probes for 1 nm conformational changes based on the phenomenon of fluorescence quenching by photoinduced electron transfer into the isolated NTD of a spidroin from the nursery web spider Euprosthenops australis. Correlation analysis of single-molecule fluorescence fluctuations uncovered site-dependent nanosecond-to-microsecond movement of secondary and tertiary structure. Kinetic amplitudes were most pronounced for helices that are part of the association interface and where structural studies show large displacements between monomeric and dimeric conformations. A single tryptophan at the center of the five-helix bundle toggled conformations in ∼100 μs and in a pH-dependent manner. Equilibrium denaturation and temperature-jump relaxation experiments revealed cooperative and ultrafast folding in only 60 μs. We deduced a free-energy surface that exhibits native-state ruggedness with apparently similar barrier heights to folding and native motions. Observed equilibrium dynamics within the domain suggest a conformational selection mechanism in the rapid association of spidroins through their NTDs during silk synthesis by web spiders.

  20. Three-dimensional multispectral hand-held optoacoustic imaging with microsecond-level delayed laser pulses

    NASA Astrophysics Data System (ADS)

    Deán-Ben, X. L.; Bay, Erwin; Razansky, Daniel

    2015-03-01

    Three-dimensional hand-held optoacoustic imaging comes with important advantages that prompt the clinical translation of this modality, with applications envisioned in cardiovascular and peripheral vascular disease, disorders of the lymphatic system, breast cancer, arthritis or inflammation. Of particular importance is the multispectral acquisition of data by exciting the tissue at several wavelengths, which enables functional imaging applications. However, multispectral imaging of entire three-dimensional regions is significantly challenged by motion artefacts in concurrent acquisitions at different wavelengths. A method based on acquisition of volumetric datasets having a microsecond-level delay between pulses at different wavelengths is described in this work. This method can avoid image artefacts imposed by a scanning velocity greater than 2 m/s, thus, does not only facilitate imaging influenced by respiratory, cardiac or other intrinsic fast movements in living tissues, but can achieve artifact-free imaging in the presence of more significant motion, e.g., abrupt displacements during handheld-mode operation in a clinical environment.

  1. Evaluating letter recognition, flicker fusion, and the Talbot-Plateau law using microsecond-duration flashes.

    PubMed

    Greene, Ernest

    2015-01-01

    Four experiments examined the ability of respondents to identify letters that were displayed on an LED array with flashes lasting little more than a microsecond. The first experiment displayed each letter with a single, simultaneous flash of all the dots forming the letter and established the relation of flash intensity to the probability of letter identification. The second experiment displayed the letters with multiple flashes at different frequencies to determine the probability that the sequence of flashes would be perceived as fused. The third experiment displayed the letters at a frequency that was above the flicker-fusion frequency, varying flash intensity to establish the amount needed to elicit a given probability of letter identification. The fourth experiment displayed each letter twice, once at a frequency where no flicker was perceived and also with steady light emission. The intensity of each flash was fixed and the steady intensity was varied; respondents were asked to judge whether the fused-flicker display and the steady display appeared to be the same brightness. Steady intensity was about double the average flash intensity where the two conditions were perceived as being equal in brightness. This is at odds with Talbot-Plateau law, which predicts that these two values should be equal. The law was formulated relative to a flash lasting half of each period, so it is surprising that it comes this close to being correct where the flash occupies only a millionth of the total period.

  2. Studies of the dynamics of a 1-microsecond X-pinch

    NASA Astrophysics Data System (ADS)

    Appartaim, Richard; Green, Danielle

    2015-11-01

    The 1- μs X-pinch (0.3 kA/ns) has been shown to produce intense soft x-rays with a spatially reproducible source location and fine size (i .e . < 10 μm) . For certain applications these x-rays are comparable in their utility to those produced on pulsed-power devices but have the advantage of a much lower component of hard x-rays. Many of the critical plasma dynamics are also similar to those observed in the fast rise-time (1 kA/ns) experiments. However, the longer rise time of the microsecond discharge can lead to important differences in wire ablation rates and transition to coronal plasma, plasma current distribution and plasma dynamics. We present recent results of these plasma dynamics using optical techniques such as shadowgraphy, schlieren and framing photography, as well as x-ray observation techniques including filtered PCD and Si diode measurements, pinhole photography and x-ray spectroscopy. We demonstrate potential applications including the relevance of the observed plasma jets to astrophysical jets. Supported by DOE Grant DE-FG02-0547253ER.

  3. Molecular recognition of oxygen by protein mimics: dynamics on the femtosecond to microsecond time scale.

    PubMed

    Zou, Shouzhong; Baskin, J Spencer; Zewail, Ahmed H

    2002-07-23

    Molecular recognition by biological macromolecules involves many elementary steps, usually convoluted by diffusion processes. Here we report studies of the dynamics, from the femtosecond to the microsecond time scale, of the different elementary processes involved in the bimolecular recognition of a protein mimic, cobalt picket-fence porphyrin, with varying oxygen concentration at controlled temperatures. Electron transfer, bond breakage, and thermal "on" (recombination) and "off" (dissociation) reactions are the different processes involved. The reaction on-rate is 30 to 60 times smaller than that calculated from standard Smoluchowski theory. Introducing a two-step recognition model, with reversibility being part of both steps, removes the discrepancy and provides consistency for the reported thermodynamics, kinetics, and dynamics. The transient intermediates are configurations defined by the contact between oxygen (diatomic) and the picket-fence porphyrin (macromolecule). This intermediate is critical in the description of the potential energy landscape but, as shown here, both enthalpic and entropic contributions to the free energy are important. In the recognition process, the net entropy decrease is -33 cal mol(-1) K(-1); Delta H is -13.4 kcal mol(-1).

  4. Microsecond gain-switched master oscillator power amplifier (1958 nm) with high pulse energy

    SciTech Connect

    Ke Yin; Weiqiang Yang; Bin Zhang; Ying Li; Jing Hou

    2014-02-28

    An all-fibre master oscillator power amplifier (MOPA) emitting high-energy pulses at 1958 nm is presented. The seed laser is a microsecond gain-switched thulium-doped fibre laser (TDFL) pumped with a commercial 1550-nm pulsed fibre laser. The TDFL operates at a repetition rate f in the range of 10 to 100 kHz. The two-stage thulium-doped fibre amplifier is built to scale the energy of the pulses generated by the seed laser. The maximum output pulse energy higher than 0.5 mJ at 10 kHz is achieved which is comparable with the theoretical maximum extractable pulse energy. The slope efficiency of the second stage amplifier with respect to the pump power is 30.4% at f = 10 kHz. The wavelength of the output pulse laser is centred near 1958 nm at a spectral width of 0.25 nm after amplification. Neither nonlinear effects nor significant amplified spontaneous emission (ASE) is observed in the amplification experiments. (lasers)

  5. Differential degradation of nonylphenol isomers by Sphingomonas xenophaga Bayram.

    PubMed

    Gabriel, Frédéric L P; Giger, Walter; Guenther, Klaus; Kohler, Hans-Peter E

    2005-03-01

    Sphingomonas xenophaga Bayram, isolated from the activated sludge of a municipal wastewater treatment plant, was able to utilize 4-(1-ethyl-1,4-dimethylpentyl)phenol, one of the main isomers of technical nonylphenol mixtures, as a sole carbon and energy source. The isolate degraded 1 mg of 4-(1-ethyl-1,4-dimethylpentyl)phenol/ml in minimal medium within 1 week. Growth experiments with five nonylphenol isomers showed that the three isomers with quaternary benzylic carbon atoms [(1,1,2,4-tetramethylpentyl)phenol, 4-(1-ethyl-1,4-dimethylpentyl)phenol, and 4-(1,1-dimethylheptyl)phenol] served as growth substrates, whereas the isomers containing one or two hydrogen atoms in the benzylic position [4-(1-methyloctyl)phenol and 4-n-nonylphenol] did not. However, when the isomers were incubated as a mixture, all were degraded to a certain degree. Differential degradation was clearly evident, as isomers with more highly branched alkyl side chains were degraded much faster than the others. Furthermore, the C9 alcohols 2,3,5-trimethylhexan-2-ol, 3,6-dimethylheptan-3-ol, and 2-methyloctan-2-ol, derived from the three nonylphenol isomers with quaternary benzylic carbon atoms, were detected in the culture fluid by gas chromatography-mass spectrometry, but no analogous metabolites could be found originating from 4-(1-methyloctyl)phenol and 4-n-nonylphenol. We propose that 4-(1-methyloctyl)phenol and 4-n-nonylphenol were cometabolically transformed in the growth experiments with the mixture but that, unlike the other isomers, they did not participate in the reactions leading to the detachment of the alkyl moiety. This hypothesis was corroborated by the observed accumulation in the culture fluid of an as yet unidentified metabolite derived from 4-(1-methyloctyl)phenol.

  6. Differential Degradation of Nonylphenol Isomers by Sphingomonas xenophaga Bayram

    PubMed Central

    Gabriel, Frédéric L. P.; Giger, Walter; Guenther, Klaus; Kohler, Hans-Peter E.

    2005-01-01

    Sphingomonas xenophaga Bayram, isolated from the activated sludge of a municipal wastewater treatment plant, was able to utilize 4-(1-ethyl-1,4-dimethylpentyl)phenol, one of the main isomers of technical nonylphenol mixtures, as a sole carbon and energy source. The isolate degraded 1 mg of 4-(1-ethyl-1,4-dimethylpentyl)phenol/ml in minimal medium within 1 week. Growth experiments with five nonylphenol isomers showed that the three isomers with quaternary benzylic carbon atoms [(1,1,2,4-tetramethylpentyl)phenol, 4-(1-ethyl-1,4-dimethylpentyl)phenol, and 4-(1,1-dimethylheptyl)phenol] served as growth substrates, whereas the isomers containing one or two hydrogen atoms in the benzylic position [4-(1-methyloctyl)phenol and 4-n-nonylphenol] did not. However, when the isomers were incubated as a mixture, all were degraded to a certain degree. Differential degradation was clearly evident, as isomers with more highly branched alkyl side chains were degraded much faster than the others. Furthermore, the C9 alcohols 2,3,5-trimethylhexan-2-ol, 3,6-dimethylheptan-3-ol, and 2-methyloctan-2-ol, derived from the three nonylphenol isomers with quaternary benzylic carbon atoms, were detected in the culture fluid by gas chromatography-mass spectrometry, but no analogous metabolites could be found originating from 4-(1-methyloctyl)phenol and 4-n-nonylphenol. We propose that 4-(1-methyloctyl)phenol and 4-n-nonylphenol were cometabolically transformed in the growth experiments with the mixture but that, unlike the other isomers, they did not participate in the reactions leading to the detachment of the alkyl moiety. This hypothesis was corroborated by the observed accumulation in the culture fluid of an as yet unidentified metabolite derived from 4-(1-methyloctyl)phenol. PMID:15746308

  7. Anaerobic Degradation of Phthalate Isomers by Methanogenic Consortia

    PubMed Central

    Kleerebezem, Robbert; Pol, Look W. Hulshoff; Lettinga, Gatze

    1999-01-01

    Three methanogenic enrichment cultures, grown on ortho-phthalate, iso-phthalate, or terephthalate were obtained from digested sewage sludge or methanogenic granular sludge. Cultures grown on one of the phthalate isomers were not capable of degrading the other phthalate isomers. All three cultures had the ability to degrade benzoate. Maximum specific growth rates (μSmax) and biomass yields (YXtotS) of the mixed cultures were determined by using both the phthalate isomers and benzoate as substrates. Comparable values for these parameters were found for all three cultures. Values for μSmax and YXtotS were higher for growth on benzoate compared to the phthalate isomers. Based on measured and estimated values for the microbial yield of the methanogens in the mixed culture, specific yields for the phthalate and benzoate fermenting organisms were calculated. A kinetic model, involving three microbial species, was developed to predict intermediate acetate and hydrogen accumulation and the final production of methane. Values for the ratio of the concentrations of methanogenic organisms, versus the phthalate isomer and benzoate fermenting organisms, and apparent half-saturation constants (KS) for the methanogens were calculated. By using this combination of measured and estimated parameter values, a reasonable description of intermediate accumulation and methane formation was obtained, with the initial concentration of phthalate fermenting organisms being the only variable. The energetic efficiency for growth of the fermenting organisms on the phthalate isomers was calculated to be significantly smaller than for growth on benzoate. PMID:10049876

  8. Site-specific protein glycosylation analysis with glycan isomer differentiation.

    PubMed

    Hua, Serenus; Nwosu, Charles C; Strum, John S; Seipert, Richard R; An, Hyun Joo; Zivkovic, Angela M; German, J Bruce; Lebrilla, Carlito B

    2012-05-01

    Glycosylation is one of the most common yet diverse post-translational modifications. Information on glycan heterogeneity and glycosite occupancy is increasingly recognized as crucial to understanding glycoprotein structure and function. Yet, no approach currently exists with which to holistically consider both the proteomic and glycomic aspects of a system. Here, we developed a novel method of comprehensive glycosite profiling using nanoflow liquid chromatography/mass spectrometry (nano-LC/MS) that shows glycan isomer-specific differentiation on specific sites. Glycoproteins were digested by controlled non-specific proteolysis in order to produce informative glycopeptides. High-resolution, isomer-sensitive chromatographic separation of the glycopeptides was achieved using microfluidic chip-based capillaries packed with graphitized carbon. Integrated LC/MS/MS not only confirmed glycopeptide composition but also differentiated glycan and peptide isomers and yielded structural information on both the glycan and peptide moieties. Our analysis identified at least 13 distinct glycans (including isomers) corresponding to five compositions at the single N-glycosylation site on bovine ribonuclease B, 59 distinct glycans at five N-glycosylation sites on bovine lactoferrin, 13 distinct glycans at one N-glycosylation site on four subclasses of human immunoglobulin G, and 20 distinct glycans at five O-glycosylation sites on bovine κ-casein. Porous graphitized carbon provided effective separation of glycopeptide isomers. The integration of nano-LC with MS and MS/MS of non-specifically cleaved glycopeptides allows quantitative, isomer-sensitive, and site-specific glycoprotein analysis.

  9. On-the-fly decoding luminescence lifetimes in the microsecond region for lanthanide-encoded suspension arrays

    NASA Astrophysics Data System (ADS)

    Lu, Yiqing; Lu, Jie; Zhao, Jiangbo; Cusido, Janet; Raymo, Françisco M.; Yuan, Jingli; Yang, Sean; Leif, Robert C.; Huo, Yujing; Piper, James A.; Paul Robinson, J.; Goldys, Ewa M.; Jin, Dayong

    2014-05-01

    Significant multiplexing capacity of optical time-domain coding has been recently demonstrated by tuning luminescence lifetimes of the upconversion nanoparticles called ‘τ-Dots’. It provides a large dynamic range of lifetimes from microseconds to milliseconds, which allows creating large libraries of nanotags/microcarriers. However, a robust approach is required to rapidly and accurately measure the luminescence lifetimes from the relatively slow-decaying signals. Here we show a fast algorithm suitable for the microsecond region with precision closely approaching the theoretical limit and compatible with the rapid scanning cytometry technique. We exploit this approach to further extend optical time-domain multiplexing to the downconversion luminescence, using luminescence microspheres wherein lifetimes are tuned through luminescence resonance energy transfer. We demonstrate real-time discrimination of these microspheres in the rapid scanning cytometry, and apply them to the multiplexed probing of pathogen DNA strands. Our results indicate that tunable luminescence lifetimes have considerable potential in high-throughput analytical sciences.

  10. On-the-fly decoding luminescence lifetimes in the microsecond region for lanthanide-encoded suspension arrays.

    PubMed

    Lu, Yiqing; Lu, Jie; Zhao, Jiangbo; Cusido, Janet; Raymo, Françisco M; Yuan, Jingli; Yang, Sean; Leif, Robert C; Huo, Yujing; Piper, James A; Paul Robinson, J; Goldys, Ewa M; Jin, Dayong

    2014-05-06

    Significant multiplexing capacity of optical time-domain coding has been recently demonstrated by tuning luminescence lifetimes of the upconversion nanoparticles called 'τ-Dots'. It provides a large dynamic range of lifetimes from microseconds to milliseconds, which allows creating large libraries of nanotags/microcarriers. However, a robust approach is required to rapidly and accurately measure the luminescence lifetimes from the relatively slow-decaying signals. Here we show a fast algorithm suitable for the microsecond region with precision closely approaching the theoretical limit and compatible with the rapid scanning cytometry technique. We exploit this approach to further extend optical time-domain multiplexing to the downconversion luminescence, using luminescence microspheres wherein lifetimes are tuned through luminescence resonance energy transfer. We demonstrate real-time discrimination of these microspheres in the rapid scanning cytometry, and apply them to the multiplexed probing of pathogen DNA strands. Our results indicate that tunable luminescence lifetimes have considerable potential in high-throughput analytical sciences.

  11. Infrared spectroscopy of the bent isomer of N 2O-HF

    NASA Astrophysics Data System (ADS)

    Dayton, D. C.; Miller, R. E.

    1988-02-01

    We report the infrared spectrum of the bent isomer of N 2O-HF in which the HF subnit is hydrogen bonded to the oxygen. This isomer was previously observed using microwave spectroscopy, while recent infrared measurements by Lovejoy and Nesbitt have shown that a linear (or slightly bent) ONNHF isomer also exists. We find that the linear ONNHF isomer is present under identical beam conditions to those used to record the spectrum of the bent isomer.

  12. Methods for the Detection and Characterization of Silica Colloids by Microsecond spICP-MS.

    PubMed

    Montaño, Manuel D; Majestic, Brian J; Jämting, Åsa K; Westerhoff, Paul; Ranville, James F

    2016-05-03

    The rapid development of nanotechnology has led to concerns over their environmental risk. Current analytical techniques are underdeveloped and lack the sensitivity and specificity to characterize these materials in complex environmental and biological matrices. To this end, single particle ICP-MS (spICP-MS) has been developed in the past decade, with the capability to detect and characterize nanomaterials at environmentally relevant concentrations in complex environmental and biological matrices. However, some nanomaterials are composed of elements inherently difficult to quantify by quadrupole ICP-MS due to abundant molecular interferences, such as dinitrogen ions interfering with the detection of silicon. Three approaches aimed at reducing the contribution of these background molecular interferences in the analysis of (28)Si are explored in an attempt to detect and characterize silica colloids. Helium collision cell gases and reactive ammonia gas are investigated for their conventional use in reducing the signal generated from the dinitrogen interference and background silicon ions leaching from glass components of the instrumentation. A new approach brought on by the advent of microsecond dwell times in single particle ICP-MS allows for the detection and characterization of silica colloids without the need for these cell gases, as at shorter dwell times the proportion of signal attributed to a nanoparticle event is greater relative to the constant dinitrogen signal. It is demonstrated that the accurate detection and characterization of these materials will be reliant on achieving a balance between reducing the contribution of the background interference, while still registering the maximum amount of signal generated by the particle event.

  13. Microsecond pulsed hydrogen/deuterium exchange of electrosprayed ubiquitin ions stored in a linear ion trap.

    PubMed

    Rajabi, Khadijeh

    2015-02-07

    A pulse of D2O vapour on the order of microseconds is allowed to react with the +6 to +9 charge states of ubiquitin confined in a linear ion trap (LIT). Two envelopes of peaks are detected for the ions of ubiquitin, corresponding to the ions that exchange more quickly and more slowly. The deuterium uptake of the protonated sites on ubiquitin ions accounts for the ion population with the fast exchange. The hydrogen/deuterium exchange (HDX) kinetics of ubiquitin ions trapped in the LIT for 200 ms showed comparable structural transitions to those trapped for 300 ms. When ions are trapped for longer, i.e. up to 2000 ms, mainly the slow exchanging ion population is detected. In all experiments the +7 ions exchange the most, suggesting a short distance between the surface protonated sites and nearby charged sites, and concomitantly high accessibility of surface protonated sites towards D2O. The +6 ions are more compact than the +7 ions but have one fewer protonated site, therefore fewer surface availabilities for D2O attack. The data suggest that the +6 ions keep most of their solution-phase contacts intact while the hydrophobic core is slightly interrupted in the +7 ions, possibly due to the exposure of charged His68 that is normally buried in the hydrophobic pocket. The +8 and +9 ions have more protonated sites but are less compact than the +7 ions because of Coulombic repulsion, resulting in a larger distance between the protonated sites and the basic sites. The data indicate that the HDX mechanism of ions with the slower exchange corresponding to the second envelope of peaks is primarily governed via a relay mechanism. The results suggest that the pulsed HDX MS method is sampling a population of ubiquitin ions with a similar backbone fold to the solution.

  14. A new high-spin isomer in 195Bi

    NASA Astrophysics Data System (ADS)

    Roy, T.; Mukherjee, G.; Madhavan, N.; Rana, T. K.; Bhattacharya, Soumik; Asgar, Md. A.; Bala, I.; Basu, K.; Bhattacharjee, S. S.; Bhattacharya, C.; Bhattacharya, S.; Bhattacharyya, S.; Gehlot, J.; Ghugre, S. S.; Gurjar, R. K.; Jhingan, A.; Kumar, R.; Muralithar, S.; Nath, S.; Pai, H.; Palit, R.; Raut, R.; Singh, R. P.; Sinha, A. K.; Varughese, T.

    2015-11-01

    A new high-spin isomer has been identified in 195Bi at the focal plane of the HYbrid Recoil mass Analyser (HYRA) used in the gas-filled mode. The fusion evaporation reactions 169Tm (30Si, x n) 193, 195Bi were used with the beam energies on targets of 168 and 146MeV for 6n and 4n channels, respectively. The evaporation residues, separated from the fission fragments, and their decays were detected at the focal plane of HYRA using MWPC, Si-Pad and clover HPGe detectors. The half-life of the new isomer in 195Bi has been measured to be 1.6(1)μs. The configuration of the new isomer has been proposed and compared with the other isomers in this region. The Total Routhian Surface (TRS) calculations for the three-quasiparticle configurations corresponding to the new isomer suggest an oblate deformation for this isomeric state. The same calculations for different configurations in 195Bi and for the even-even 194Pb core indicate that the proton i 13/2 orbital has a large shape driving effect towards oblate shape in these nuclei.

  15. Separation of Peptide Isomers with Variant Modified Sites by High-Resolution Differential Ion Mobility Spectrometry

    SciTech Connect

    Shvartsburg, Alexandre A.; Creese, Andrew; Smith, Richard D.; Cooper, Helen J.

    2010-10-01

    Many proteins and proteolytic peptides incorporate the same post-translational modification (PTM) at different sites, creating multiple localization variants with different functions or activities that may coexist in cells. Current analytical methods based on liquid chromatography (LC) followed by tandem mass spectrometry (MS/MS) are challenged by such isomers that often co-elute in LC and/or produce non-unique fragments. Application of ion mobility spectrometry (IMS) has previously been explored, but success was limited by insufficient resolution. We show that the recently developed high-resolution differential ion mobility spectrometry (FAIMS) using helium-rich gases can readily separate phosphopeptides with variant modified sites. Specifically, use of He/N2 mixtures containing up to 74% He has allowed separating to >95% three monophosphorylated peptides of identical sequence. Similar separation was achieved at 50% He, using an elevated electric field. Bisphosphorylated isomers that differ in only one modification site were separated to the same extent. We anticipate the FAIMS capabilities for such separations to extend to other PTMs.

  16. Preferential polymerization and adsorption of L-optical isomers of amino acids relative to D-optical isomers on kaolinite templates.

    NASA Technical Reports Server (NTRS)

    Jackson, T. A.

    1971-01-01

    Experiments on the polymerization of the L- and D-optical isomers of aspartic acid and serine using kaolinite as a catalyst showed that the L-optical isomers were polymerized at a much higher rate than the D-optical isomers; racemic (DL-) mixtures were polymerized at an intermediate rate. The peptides formed from the L-monomers were preferentially adsorbed by the clay. In the absence of kaolinite, no significant or consistent difference in the behavior of the L- and D-optical isomers was observed. In experiments on the adsorption of L- and D-phenylalanine by kaolinite, the L-optical isomer was preferentially adsorbed.

  17. Electronic structure and isomer shifts of neptunium compounds

    NASA Astrophysics Data System (ADS)

    Svane, A.; Petit, L.; Temmerman, W. M.; Szotek, Z.

    2002-08-01

    The electronic structures of αNp metal and 28 Np compounds are calculated with the generalized gradient approximation to density-functional theory, implemented with the full-potential linear-muffin-tin-orbital method. The calculations are compared to experimental isomer shifts providing a calibration of the 237Np isomeric transition with a value of Δ=(-40.1+/-1.3)×10- 3 fm2 for the difference in nuclear radius between the excited isomeric level and the ground state. The isomer shift is primarily determined by the chemical environment. Decreasing the volume, either by external or chemical pressure, causes an f-->s+d charge transfer on Np, which leads to a higher electron contact density. The possible f-electron localization in Np compounds is discussed using self-interaction corrections, and it is concluded that f-electron localization has only a minor influence on the isomer shift.

  18. FY2010 Annual Report for the Actinide Isomer Detection Project

    SciTech Connect

    Warren, Glen A.; Francy, Christopher J.; Ressler, Jennifer J.; Erikson, Luke E.; Miller, Erin A.; Hatarik, R.

    2011-01-01

    This project seeks to identify a new signature for actinide element detection in active interrogation. This technique works by exciting and identifying long-lived nuclear excited states (isomers) in the actinide isotopes and/or primary fission products. Observation of isomers in the fission products will provide a signature for fissile material. For the actinide isomers, the decay time and energy of the isomeric state is unique to a particular isotope, providing an unambiguous signature for Special Nuclear Materials (SNM). Future work will include a follow-up measurement scheduled for December 2010 at LBNL. Lessons learned from the July 2010 measurements will be incorporated into these new measurements. Analysis of both the July and December experiments will be completed in a few months. A research paper to be submitted to a peer-reviewed journal will be drafted if the conclusions from the measurements warrant publication.

  19. Metastable isomers - A new class of interstellar molecules

    NASA Technical Reports Server (NTRS)

    Green, S.; Herbst, E.

    1979-01-01

    The abundances of a variety of metastable isomers of small organic molecules, analogous to HNC/HCN, in dense interstellar clouds are considered. These metastable species, some of which are thought to exist as intermediates in laboratory organic chemical reactions, are of considerable interest to chemists. Current ideas of gas-phase, ion-molecule chemistry are utilized to demonstrate that such metastable species should often be present in dense clouds in sufficient abundance to be observed. Unfortunately, the spectral constants of metastable isomers have rarely been determined in the laboratory, and quantum chemical calculations of a varying degree of accuracy must be utilized; results are included of some new quantum chemical calculations. The interstellar chemistry and expected microwave spectra of a representative sample of possibly important interstellar metastable isomers are discussed.

  20. STROBE-X: X-ray Timing & Spectroscopy on Dynamical Timescales from Microseconds to Years

    NASA Astrophysics Data System (ADS)

    Wilson-Hodge, Colleen A.; Ray, Paul S.; Gendreau, Keith; Chakrabarty, Deepto; Feroci, Marco; Maccarone, Tom; Arzoumanian, Zaven; Remillard, Ronald A.; Wood, Kent; Griffith, Christopher; STROBE-X Collaboration

    2017-01-01

    We describe a proposed probe-class mission concept that will provide an unprecedented view of the X-ray sky, performing timing and spectroscopy over a broad band (0.2-30 keV) probing timescales from microseconds to years. The Spectroscopic Time-Resolving Observatory for Broadband Energy X-rays (STROBE-X) comprises two primary instruments. The soft band (0.2-12 keV) will be covered by an array of lightweight optics (3-m focal length) that concentrate incident photons onto small solid state detectors with CCD-level (85-130 eV) energy resolution, 100 ns time resolution, and low background rates. This technology, fully developed for NICER, would be scaled up with enhanced optics to take advantage of the longer focal length of STROBE-X. The harder band (2 to at least 30 keV) would be covered by large-area collimated silicon drift detectors,developed for the European LOFT mission concept. Each instrument would provide an order of magnitude improvement in effective area compared with its predecessor (NICER in the soft band and RXTE in the hard band). A sensitive sky monitor would act as a trigger for pointed observations, provide high duty cycle, high time resolution, high spectral resolution monitoring of the X-ray sky with ~20 times the sensitivity of the RXTE ASM, and enable multi-wavelength and multi-messenger studies on a continuous, rather than scanning basis.The broad coverage will enable thermal components, non-thermal components, iron lines, and reflection features to be studied simultaneously from a single platform for the first time in accreting black holes at all scales. The enormous collecting area will enable studies of the dense matter equation of state using both soft thermal emission from rotation-powered pulsars and harder emission from X-ray burst oscillations. Revolutionary science, such as high quality spectroscopy of clusters of galaxies and unprecedented timing investigations of active galactic nuclei, would also be obtained.We describe the mission

  1. μ s isomers of Nd,160158

    NASA Astrophysics Data System (ADS)

    Ideguchi, E.; Simpson, G. S.; Yokoyama, R.; Tanaka, Mn.; Nishimura, S.; Doornenbal, P.; Lorusso, G.; Söderström, P.-A.; Sumikama, T.; Wu, J.; Xu, Z. Y.; Aoi, N.; Baba, H.; Bello Garrote, F. L.; Benzoni, G.; Browne, F.; Daido, R.; Fang, Y.; Fukuda, N.; Gottardo, A.; Gey, G.; Go, S.; Inabe, N.; Isobe, T.; Kameda, D.; Kobayashi, K.; Kobayashi, M.; Kojouharov, I.; Komatsubara, T.; Kubo, T.; Kurz, N.; Kuti, I.; Li, Z.; Matsushita, M.; Michimasa, S.; Moon, C.-B.; Nishibata, H.; Nishizuka, I.; Odahara, A.; Patel, Z.; Rice, S.; Sahin, E.; Sakurai, H.; Schaffner, H.; Sinclair, L.; Suzuki, H.; Takeda, H.; Taprogge, J.; Vajta, Zs.; Watanabe, H.; Yagi, A.

    2016-12-01

    The neutron-rich nuclei Nd,160158 have been studied via delayed γ -ray spectroscopy of μ s isomeric states at the RIBF facility, RIKEN. These nuclei were produced following the projectile fission of a 345 A MeV 238U beam and delayed γ rays were detected by the EURICA cluster Ge array. The isomeric states have measured half-lives of 339(20) ns and 1.63(21) μ s for 158Nd and 160Nd, respectively. From the observed γ decays and the systematics of levels in the neighboring Nd isotopes first level schemes were constructed for these nuclei. The isomeric states of Nd,160158 have been assigned spins of (6-) and (4-) , with proposed ν 5 /2 [523 ]⊗ν 7 /2 [633 ] and ν 1 /2 [521 ]⊗ν 7 /2 [633 ] configurations, respectively.

  2. Energy spectrum and optical transitions in C80 fullerene isomers

    NASA Astrophysics Data System (ADS)

    Lobanov, B. V.; Murzashev, A. I.

    2013-04-01

    The energy spectra of all isomers of the C80 fullerene have been calculated in terms of the Schubin-Wonsowskii-Hubbard model. On this basis, their optical absorption spectra have also been calculated. The optical absorption spectra calculated for the endohedral Ca@C80, Ba@C80, and Sr@C80 fullerenes with the I h symmetry agree well with the experimental data. This circumstance allows us to conclude that the optical absorption spectra of other isomers (for which experimental data are unavailable) obtained in this work can be used for their identification.

  3. Differentiation of optical isomers through enhanced weak-field interactions

    NASA Technical Reports Server (NTRS)

    Aronowitz, S.

    1980-01-01

    The influence of weak field interaction terms due to the cooperative effects which arise from a macroscopic assemblage of interacting sites is studied. Differential adsorption of optical isomers onto an achiral surface is predicted to occur if the surface was continuous and sufficiently large. However, the quantity of discontinuous crystal surfaces did not enhance the percentage of differentiation and thus the procedure of using large quantities of small particles was not a viable technique for obtaining a detectable differentiation of optical isomers on an achiral surface.

  4. An Unusual Conformational Isomer of Verrucosidin Backbone from a Hydrothermal Vent Fungus, Penicillium sp. Y-50-10

    PubMed Central

    Pan, Chengqian; Shi, Yutong; Auckloo, Bibi Nazia; Chen, Xuegang; Chen, Chen-Tung Arthur; Tao, Xinyi; Wu, Bin

    2016-01-01

    A new verrucosidin derivative, methyl isoverrucosidinol (1), was isolated from the marine fungus Penicillium sp. Y-50-10, dwelling in sulfur rich sediment in the Kueishantao hydrothermal vents off Taiwan. The structure was established by spectroscopic means including HRMS and 2D-NMR spectroscopic analysis. The absolute configuration was defined mainly by comparison of quantum chemical TDDFT calculated and experimental ECD spectra. Among hitherto known compounds with a verrucosidine backbone isolated from natural resource, compound 1 represents the first example of a new conformational isomer of its skeleton, exhibiting antibiotic activity against Bacillus subtilis with MIC value 32 μg/mL. PMID:27548192

  5. Isomerism in the "south-east" of 132Sn and a predicted neutron-decaying isomer in 129Pd

    NASA Astrophysics Data System (ADS)

    Yuan, Cenxi; Liu, Zhong; Xu, Furong; Walker, P. M.; Podolyák, Zs.; Xu, C.; Ren, Z. Z.; Ding, B.; Liu, M. L.; Liu, X. Y.; Xu, H. S.; Zhang, Y. H.; Zhou, X. H.; Zuo, W.

    2016-11-01

    Excited states in neutron-rich nuclei located south-east of 132Sn are investigated by shell-model calculations. A new shell-model Hamiltonian is constructed for the present study. The proton-proton and neutron-neutron interactions of the Hamiltonian are obtained through the existing CD-Bonn G matrix results, while the proton-neutron interaction across two major shells is derived from the monopole based universal interaction plus the M3Y spin-orbit force. The present Hamiltonian can reproduce well the experimental data available in this region, including one-neutron separation energies, level energies and the experimental B (E 2) values of isomers in 134,136,138Sn, 130Cd, and 128Pd. New isomers are predicted in this region, e.g. in 135Sn, 131Cd, 129Pd, 132,134In and 130Ag, in which almost no excited states are known experimentally yet. In the odd-odd 132,134In and 130Ag, the predicted very long E2 life-times of the low-lying 5- states are discussed, demanding more information on the related proton-neutron interaction. The low-lying states of 132In are discussed in connection with the recently observed γ rays. The predicted 19 /2- isomer in 129Pd could decay by both electromagnetic transitions and neutron emission with comparable partial life-times, making it a good candidate for neutron radioactivity, a decay mode which is yet to be discovered.

  6. LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Spectral characteristics of fragmentation of kidney stones by microsecond laser radiation

    NASA Astrophysics Data System (ADS)

    Batishche, S. A.; Tarkovsky, V. V.

    1995-07-01

    A study of the action of single microsecond laser pulses on kidney stones revealed a strong spectral dependence of the efficiency K of mass removal. This should be taken into account in the development of apparatus for laser lithotripsy. An increase in the energy of the laser pulses acting on a stone resulted in saturation of K when a certain energy, specific to each wavelength, was exceeded. The radiation energy should be less than the saturation threshold in order to reduce the effects on the surrounding tissues.

  7. Characterization and determination of piperine and piperine isomers in eggs.

    PubMed

    Ternes, Waldemar; Krause, Edburga L

    2002-09-01

    A new analytical method for the determination of piperine and its isomers in egg yolk and albumen is described here. All four isomers were separated by HPLC and detected using UV, DAD and electrochemical detection. The absolute detection limit (UV detection, S/ N=3) of a standard solution of piperine was 370 pg piperine. The correlation coefficients for the linear calibration graphs (concentration range: c=100 ng-10 micro g piperine isomer/mL) are generally better than 0.996. The piperine isomers were characterized and identified by spectroscopy (MS, (1)H-NMR, FT-IR). The method was successfully applied to the determination of piperine deposits in eggs (egg yolk and albumen) after feeding hens with piperine-spiked feed. The detection limit for piperine (24.8(+/-0.2) ng/g egg yolk and 37.9(+/-4.9) ng/g albumen) and the recoveries (70.3(+/-7.7)% (egg yolk) and 75.7(+/-1.9)% (albumen)) of piperine were determined.

  8. Fermentation of five sucrose isomers by human dental plaque bacteria.

    PubMed

    Matsuyama, J; Sato, T; Hoshino, E; Noda, T; Takahashi, N

    2003-01-01

    Sucrose has five structural isomers: palatinose, trehalulose, turanose, maltulose and leucrose. Although these isomers have been reported to be noncariogenic disaccharides, which cannot be utilized by mutans streptococci, there is no information about their fermentability by other bacteria in dental plaque. The purpose of the present study was to examine whether these isomers were fermented by predominant bacteria in human dental plaque. Clinical bacterial isolates obtained from dental plaque from 3 children aged 22 months to 50 months (146 strains) were inoculated into 3 ml of peptone-yeast extract (PY medium) containing glucose for 1 day, then an aliquot of 20 microl of culture medium was inoculated into 1 ml of PY medium containing 1% (w/v) of the respective test carbohydrates. After incubation for 1 day, the pH values and the optical density at 660 nm of the cultures were measured. Fermentation ability was measured by pH or=0.5. Of the clinical isolates, 33% fermented palatinose, and 69% of these were Actinomyces species. All of the palatinose-fermenting bacterial strains fermented trehalulose, 25% fermented turanose, 70% fermented maltulose and 23% fermented leucrose. We therefore conclude that, in human dental plaque, there are significant numbers of bacteria that are able to ferment sucrose isomers.

  9. The molecular properties of nitrobenzanthrone isomers and their mutagenic activities.

    PubMed

    Ostojić, Bojana D; Stanković, Branislav; Ðorđević, Dragana S

    2014-06-01

    The mutagenic activity of five mono-substituted nitrobenzanthrones (NBA) has been determined in the Ames assay (Takamura-Enya et al., 2006). In the present study, a theoretical investigation of the electronic properties of all mono-substituted NBA isomers and their relation to mutagenic activity are presented. Equilibrium geometries, vertical ionization potentials (VIP), vertical electron affinities (VEA), relative energies, dipole moments and electronic dipole polarizabilities, and the IR and Raman spectra of NBA isomers calculated by Density Functional Theory (DFT) methods are presented. The position of the nitro group affects the spectral features of the IR and Raman spectra of the NBA isomers. The results show that a good linear relationship exists between the summation of Raman activities (∑ARaman) over all the 3N-6 vibrational modes and the mutagenic activity of the NBA isomers in Salmonella typhimurium strains. The spectroscopic results suggest that the unknown mutagenic activities of 4-NBA, 5-NBA, 6-NBA, 8-NBA and 10-NBA are predicted to follow the order 4-NBA>10-NBA>5-NBA>8-NBA>6-NBA.

  10. Short-lived isomers in 192Po and 194Po

    NASA Astrophysics Data System (ADS)

    Andel, B.; Andreyev, A. N.; Antalic, S.; Heßberger, F. P.; Ackermann, D.; Hofmann, S.; Huyse, M.; Kalaninová, Z.; Kindler, B.; Kojouharov, I.; Kuusiniemi, P.; Lommel, B.; Nishio, K.; Page, R. D.; Sulignano, B.; Van Duppen, P.

    2016-06-01

    Isomeric states in 194Po and 192Po were studied at the velocity filter SHIP. The isotopes were produced in the fusion-evaporation reactions 141Pr(56Fe, p 2 n )194Po and 144Sm(51V, p 2 n )192Po . Several new γ -ray transitions were attributed to the isomers and γ -γ coincidences for both isomers were studied for the first time. The 459-keV transition earlier, tentatively proposed as de-exciting the isomeric level in 194Po, was replaced by a new 248-keV transition, and the spin of this isomer was reassigned from (11-) to (10-). The de-excitation of the (11-) isomeric level in 192Po by the 154-keV transition was confirmed and a parallel de-excitation by a 733-keV (E 3 ) transition to (8+) level of the ground-state band was suggested. Moreover, side feeding to the (4+) level of the ground-state band was proposed. The paper also discusses strengths of transitions de-exciting 11- isomers in neighboring Po and Pb isotopes.

  11. Enantioselective separation of defined endocrine-disrupting nonylphenol isomers.

    PubMed

    Acir, Ismail-Hakki; Wüst, Matthias; Guenther, Klaus

    2016-08-01

    Nonylphenol is in the focus of worldwide endocrine-disrupter research and accounted for as a priority hazardous substance of the Water Framework Directive of the European Union. Technical nonylphenol consists of a very complex mixture of isomers and enantiomers. As estrogenic effect and degradation behavior in environmental processes of single nonylphenols are heavily dependent on the structure of the nonyl side chain, it is absolutely necessary to consider the nonylphenol problem from an isomer and enantiomer-specific viewpoint. In this study, an enantiomer-specific separation of eight defined synthesized nonylphenol isomers by five different special chiral cyclodextrin columns was performed underivatized and after methylation, silylation, and acylation. This work demonstrates that three columns out of the investigated five show an excellent separation behavior for the studied different nonylphenol isomers and can be used for the enantiomer-specific determination of nonylphenols in food, other biological matrices, and environmental samples in the future. Graphical abstract Enantiomeric pair of 4-NP170 (4-[1-ethyl-1,3,3-trimethylbutyl]phenol).

  12. Isomer-Specific Distribution of Perfluoroalkyl Substances in Blood.

    PubMed

    Jin, Hangbiao; Zhang, Yifeng; Jiang, Weiwei; Zhu, Lingyan; Martin, Jonathan W

    2016-07-19

    Perfluoroalkyl substances (PFASs) such as perfluorohexanesulfonate (PFHxS), perfluorooctanoate (PFOA), perfluorooctanesulfonate (PFOS) and PFOS-precursors are routinely measured in human plasma and serum, but their relative abundance in the blood cell fraction has not been carefully examined, particularly at the isomer-specific level. Human plasma and whole blood were collected and partitioning behaviors of PFASs and their isomers between plasma and blood cells were investigated. In human samples, mass fraction in plasma (Fp) for PFASs increased among perfluoroalkyl carboxylates as the carbon chain length increased from C6 (mean 0.24) to C11 (0.87), indicating preference for the plasma fraction with increasing chain length. However, among perfluoroalkyl sulfonates, PFHxS (mean 0.87) had a slightly higher Fp than PFOS (0.85). In vitro assays with spiked Sprague-Dawley rat blood were also conducted, and the results showed that PFOS-precursors had lower Fp values than perfluoroalkyl acids, with perfluoroctanesulfonamide having the lowest Fp (mean 0.24). Consistently, linear isomers of PFOS and PFOS-precursors had lower mean Fp than their corresponding total branched isomers. Multiplying by a factor of 2 is not a reasonable method to convert from whole blood to plasma PFAS concentrations, and current ratios could be used as more accurate conversion factors.

  13. High Spin Isomers and Super Heavy Elements (SHE) Synthesis

    SciTech Connect

    Popescu, Domitian G.

    2010-04-30

    To get closer to the SHE-Island the new radioactive beams are proposed for future fusion reaction. We suggest something different: to use the advantage of High Spin Isomer States, by tacking into account the importance of the G (spin-isospin cupling) suggested by Ripka 1.

  14. Conjugated Linoleic Acids and Inflammation: Isomer and Tissue Specific Responses

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Conjugated linoleic acids (CLAs) are a series of geometric and positional isomers of linoleic acid that have been studied for their effects against diabetes, cancer, and atherosclerosis, all conditions with an inflammatory component. Despite the continued interest in CLA, there are many controversi...

  15. Flexible metal–organic supramolecular isomers for gas separation

    SciTech Connect

    Motkuri, Radha K.; Tian, Jian; Thallapally, Praveen K.; Fernandez, Carlos A.; Dalgarno, Scott J.; Warren, John E.; McGrail, B. Peter; Atwood, Jerry L.

    2010-01-01

    Here in we report three porous metal-organic supramolecular isomers (PtS, Diamondoid and Lonsdaleite networks) generated from a single building block (tetrakis[4-(carboxyphenyl)oxamethyl]methane, 1), with the differences in solid-state packing, amount of gas uptake and selectivity towards other gases and so on

  16. Electronic Structure Mediated Vibrational Coherence in Methyl Acetophenone Isomers

    NASA Astrophysics Data System (ADS)

    Konar, Arkaprabha; Shu, Yinan; Lozovoy, Vadim; Levine, Benjamin; Dantus, Marcos

    2014-05-01

    The role of ground and excited state electronic structures in influencing the vibrational coherences in gas phase polyatomic molecules has been a hot topic for quite some time. Here we explore the time resolved dynamics of acetophenone and its methyl substituted isomer when excited by intense 800nm femtosecond pump and probe pulses. The parent ion yield show 500 fs modulations that die down within 3ps. Similar modulations having the same timescales in the parent ion yield are also observed for the p-methyl isomer. The o-methyl isomer however shows longer 1ps modulations. Interestingly enough no oscillations are observed for the meta isomer. Quantum chemical calculations at the CASSCF/6-311G level of theory predicts that upon excitation the neutral ground state is planar and the energy spacing between the levels is very small. Preliminary calculations also predict torsional motion coupled to electronic modulations on the D0 state and further calculations are being performed to ascertain the involvement of the D1 and D2 states. This could help us better understand the electronic effect of substitution on a benzene ring.

  17. Electronic Structure Mediated Vibrational Coherence in Methyl Acetophenone Isomers

    NASA Astrophysics Data System (ADS)

    Konar, Arkaprabha; Shu, Yinan; Levine, Benjamin; Lozovoy, Vadim; Dantus, Marcos

    2014-03-01

    The role of ground and excited state electronic structures in influencing the vibrational coherences in gas phase polyatomic molecules has been a hot topic for quite some time. Here we explore the time resolved dynamics of acetophenone and its methyl substituted isomer when excited by intense 800nm femtosecond pump and probe pulses. The parent ion yield show 500 fs modulations that die down within 3ps. Similar modulations having the same timescales in the parent ion yield are also observed for the p-methyl isomer. The o-methyl isomer however shows longer 1ps modulations. Interestingly enough no oscillations are observed for the meta isomer. Quantum chemical calculations at the CASSCF/6-311G level of theory predicts that upon excitation the neutral ground state is planar and the energy spacing between the levels is very small. Preliminary calculations also predict torsional motion coupled to electronic modulations on the D0 state and further calculations are being performed to ascertain the involvement of the D1 and D2 states. This could help us better understand the electronic effect of substitution on a benzene ring.

  18. FY2011 Annual Report for the Actinide Isomer Detection Project

    SciTech Connect

    Warren, Glen A.; Francy, Christopher J.; Ressler, Jennifer J.; Erikson, Luke E.; Tatishvili, Gocha; Hatarik, R.

    2011-10-01

    This project seeks to identify a new signature for actinide element detection in active interrogation. This technique works by exciting and identifying long-lived nuclear excited states (isomers) in the actinide isotopes and/or primary fission products. Observation of isomers in the fission products will provide a signature for fissile material. For the actinide isomers, the decay time and energy of the isomeric state is unique to a particular isotope, providing an unambiguous signature for SNM. This project entails isomer identification and characterization and neutron population studies. This document summarizes activities from its third year - completion of the isomer identification characterization experiments and initialization of the neutron population experiments. The population and decay of the isomeric state in 235U remain elusive, although a number of candidate gamma rays have been identified. In the course of the experiments, a number of fission fragment isomers were populated and measured [Ressler 2010]. The decays from these isomers may also provide a suitable signature for the presence of fissile material. Several measurements were conducted throughout this project. This report focuses on the results of an experiment conducted collaboratively by PNNL, LLNL and LBNL in December 2010 at LBNL. The measurement involved measuring the gamma-rays emitted from an HEU target when bombarded with 11 MeV neutrons. This report discussed the analysis and resulting conclusions from those measurements. There was one strong candidate, at 1204 keV, of an isomeric signature of 235U. The half-life of the state is estimated to be 9.3 {mu}s. The measured time dependence fits the decay time structure very well. Other possible explanations for the 1204-keV state were investigated, but they could not explain the gamma ray. Unfortunately, the relatively limited statistics of the measurement limit, and the lack of understanding of some of the systematic of the experiment, limit

  19. Fuel properties of heptadecene isomers prepared via tandem isomerization-decarboxylation of oleic acid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Heptadecene isomers were prepared via tandem isomerization-decarboxylation of oleic acid using catalytic triruthenium dodecacarbonyl [Ru3(CO)12]. Chromatographic and spectroscopic characterization of the isolated heptadecene mixture indicated that it consisted of 96% internal isomers and 4% aromatic...

  20. Computational Docking of the Isomers of Nonylphenol to the Ligand Binding Domain of the Estrogen Receptor

    EPA Science Inventory

    Nonylphenols are environmentally persistent endocrine disrupting chemicals. They exist in the environment as complex mixtures containing many nonylphenol isomers. Environmental mixtures of nonylphenols, along with a few single isomers have been tested for their capacity to inte...

  1. Breaking the millisecond barrier on SpiNNaker: implementing asynchronous event-based plastic models with microsecond resolution

    PubMed Central

    Lagorce, Xavier; Stromatias, Evangelos; Galluppi, Francesco; Plana, Luis A.; Liu, Shih-Chii; Furber, Steve B.; Benosman, Ryad B.

    2015-01-01

    Spike-based neuromorphic sensors such as retinas and cochleas, change the way in which the world is sampled. Instead of producing data sampled at a constant rate, these sensors output spikes that are asynchronous and event driven. The event-based nature of neuromorphic sensors implies a complete paradigm shift in current perception algorithms toward those that emphasize the importance of precise timing. The spikes produced by these sensors usually have a time resolution in the order of microseconds. This high temporal resolution is a crucial factor in learning tasks. It is also widely used in the field of biological neural networks. Sound localization for instance relies on detecting time lags between the two ears which, in the barn owl, reaches a temporal resolution of 5 μs. Current available neuromorphic computation platforms such as SpiNNaker often limit their users to a time resolution in the order of milliseconds that is not compatible with the asynchronous outputs of neuromorphic sensors. To overcome these limitations and allow for the exploration of new types of neuromorphic computing architectures, we introduce a novel software framework on the SpiNNaker platform. This framework allows for simulations of spiking networks and plasticity mechanisms using a completely asynchronous and event-based scheme running with a microsecond time resolution. Results on two example networks using this new implementation are presented. PMID:26106288

  2. Search of the energetic gamma-ray experiment telescope (EGRET) data for high-energy gamma-ray microsecond bursts

    NASA Technical Reports Server (NTRS)

    Fichtel, C. E.; Bertsch, D. L.; Dingus, B. L.; Esposito, J. A.; Hartman, R. C.; Hunter, S. D.; Kanbach, G.; Kniffen, D. A.; Lin, Y. C.; Mattox, J. R.

    1994-01-01

    Hawking (1974) and Page & Hawking (1976) investigated theoretically the possibility of detecting high-energy gamma rays produced by the quantum-mechanical decay of a small black hole created in the early universe. They concluded that, at the very end of the life of the small black hole, it would radiate a burst of gamma rays peaked near 250 MeV with a total energy of about 10(exp 34) ergs in the order of a microsecond or less. The characteristics of a black hole are determined by laws of physics beyond the range of current particle accelerators; hence, the search for these short bursts of high-energy gamma rays provides at least the possibility of being the first test of this region of physics. The Compton Observatory Energetic Gamma-Ray Experiment Telescope (EGRET) has the capability of detecting directly the gamma rays from such bursts at a much fainter level than SAS 2, and a search of the EGRET data has led to an upper limit of 5 x 10(exp -2) black hole decays per cu pc per yr, placing constraints on this and other theories predicting microsecond high-energy gamma-ray bursts.

  3. Breaking the millisecond barrier on SpiNNaker: implementing asynchronous event-based plastic models with microsecond resolution.

    PubMed

    Lagorce, Xavier; Stromatias, Evangelos; Galluppi, Francesco; Plana, Luis A; Liu, Shih-Chii; Furber, Steve B; Benosman, Ryad B

    2015-01-01

    Spike-based neuromorphic sensors such as retinas and cochleas, change the way in which the world is sampled. Instead of producing data sampled at a constant rate, these sensors output spikes that are asynchronous and event driven. The event-based nature of neuromorphic sensors implies a complete paradigm shift in current perception algorithms toward those that emphasize the importance of precise timing. The spikes produced by these sensors usually have a time resolution in the order of microseconds. This high temporal resolution is a crucial factor in learning tasks. It is also widely used in the field of biological neural networks. Sound localization for instance relies on detecting time lags between the two ears which, in the barn owl, reaches a temporal resolution of 5 μs. Current available neuromorphic computation platforms such as SpiNNaker often limit their users to a time resolution in the order of milliseconds that is not compatible with the asynchronous outputs of neuromorphic sensors. To overcome these limitations and allow for the exploration of new types of neuromorphic computing architectures, we introduce a novel software framework on the SpiNNaker platform. This framework allows for simulations of spiking networks and plasticity mechanisms using a completely asynchronous and event-based scheme running with a microsecond time resolution. Results on two example networks using this new implementation are presented.

  4. On-the-fly decoding luminescence lifetimes in the microsecond region for lanthanide-encoded suspension arrays

    PubMed Central

    Lu, Yiqing; Lu, Jie; Zhao, Jiangbo; Cusido, Janet; Raymo, Françisco M; Yuan, Jingli; Yang, Sean; Leif, Robert C.; Huo, Yujing; Piper, James A.; Paul Robinson, J; Goldys, Ewa M.; Jin, Dayong

    2014-01-01

    Significant multiplexing capacity of optical time-domain coding has been recently demonstrated by tuning luminescence lifetimes of the upconversion nanoparticles called ‘τ-Dots’. It provides a large dynamic range of lifetimes from microseconds to milliseconds, which allows creating large libraries of nanotags/microcarriers. However, a robust approach is required to rapidly and accurately measure the luminescence lifetimes from the relatively slow-decaying signals. Here we show a fast algorithm suitable for the microsecond region with precision closely approaching the theoretical limit and compatible with the rapid scanning cytometry technique. We exploit this approach to further extend optical time-domain multiplexing to the downconversion luminescence, using luminescence microspheres wherein lifetimes are tuned through luminescence resonance energy transfer. We demonstrate real-time discrimination of these microspheres in the rapid scanning cytometry, and apply them to the multiplexed probing of pathogen DNA strands. Our results indicate that tunable luminescence lifetimes have considerable potential in high-throughput analytical sciences. PMID:24796249

  5. Isomer-specific combustion chemistry in allene and propyne flames

    SciTech Connect

    Hansen, Nils; Miller, James A.; Westmoreland, Phillip R.; Kasper, Tina; Kohse-Hoeinghaus, Katharina; Wang, Juan; Cool, Terrill A.

    2009-11-15

    A combined experimental and modeling study is performed to clarify the isomer-specific combustion chemistry in flames fueled by the C{sub 3}H{sub 4} isomers allene and propyne. To this end, mole fraction profiles of several flame species in stoichiometric allene (propyne)/O{sub 2}/Ar flames are analyzed by means of a chemical kinetic model. The premixed flames are stabilized on a flat-flame burner under a reduced pressure of 25 Torr (=33.3 mbar). Quantitative species profiles are determined by flame-sampling molecular-beam mass spectrometry, and the isomer-specific flame compositions are unraveled by employing photoionization with tunable vacuum-ultraviolet synchrotron radiation. The temperature profiles are measured by OH laser-induced fluorescence. Experimental and modeled mole fraction profiles of selected flame species are discussed with respect to the isomer-specific combustion chemistry in both flames. The emphasis is put on main reaction pathways of fuel consumption, of allene and propyne isomerization, and of isomer-specific formation of C{sub 6} aromatic species. The present model includes the latest theoretical rate coefficients for reactions on a C{sub 3}H{sub 5} potential [J.A. Miller, J.P. Senosiain, S.J. Klippenstein, Y. Georgievskii, J. Phys. Chem. A 112 (2008) 9429-9438] and for the propargyl recombination reactions [Y. Georgievskii, S.J. Klippenstein, J.A. Miller, Phys. Chem. Chem. Phys. 9 (2007) 4259-4268]. Larger peak mole fractions of propargyl, allyl, and benzene are observed in the allene flame than in the propyne flame. In these flames virtually all of the benzene is formed by the propargyl recombination reaction. (author)

  6. Azaphthalocyanines with fused triazolo rings: formation of sterically stressed constitutional isomers.

    PubMed

    Novakova, Veronika; Roh, Jaroslav; Gela, Petr; Kuneš, Jiří; Zimcik, Petr

    2012-05-07

    The presented work deals with synthesis and isolation of constitutional isomers of triazolo-fused azaphthalocyanines. Distribution of the isomers did not follow the statistical calculations due to steric effects of the substituents preferring the least sterically stressed C(4h) isomer.

  7. 40 CFR 180.1073 - Isomate-M; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Isomate-M; exemption from the... Exemptions From Tolerances § 180.1073 Isomate-M; exemption from the requirement of a tolerance. The oriental fruit moth pheromone (Isomate-M) (Z-8-dodecen-l-yl acetate, E-8-dodecen-l-yl acetate,...

  8. 40 CFR 180.1073 - Isomate-M; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Isomate-M; exemption from the... Exemptions From Tolerances § 180.1073 Isomate-M; exemption from the requirement of a tolerance. The oriental fruit moth pheromone (Isomate-M) (Z-8-dodecen-l-yl acetate, E-8-dodecen-l-yl acetate,...

  9. Isomer selective ionization of chlorinated PAH's: Detection of impurities in technical 9-monochloroanthracene

    SciTech Connect

    Zimmermann, Ralf; Lermer, Christoph; Lenoir, Dieter; Boesl, Ulrich

    1995-04-01

    Two-color RIS of anthracene (A), of all of its monochloroisomers and one dichlorinated (DCA) isomer have been measured. The possibility of isomer selective resonance ionization of the monochloroanthracenes (MCA) is demonstrated. A technical sample of the 9-DCA isomer has been investigated; no impurities of monochroroisomers have been found but significant impurities of non-chlorinated A and 9, 10-DCA.

  10. 40 CFR 721.10564 - Mixed amino diaryl sulfone isomers (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixed amino diaryl sulfone isomers... Specific Chemical Substances § 721.10564 Mixed amino diaryl sulfone isomers (generic). (a) Chemical... as mixed amino diaryl sulfone isomers (PMN P-08-39) is subject to reporting under this section...

  11. 40 CFR 180.418 - Cypermethrin and an isomer zeta-cypermethrin; tolerances for residues.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Cypermethrin and an isomer zeta... FOOD Specific Tolerances § 180.418 Cypermethrin and an isomer zeta-cypermethrin; tolerances for... (±))(cis-trans 3-(2,2-dichloroethenyl)-2,2 dimethylcyclopropanecarboxylate and its inactive R-isomers in...

  12. 40 CFR 721.10564 - Mixed amino diaryl sulfone isomers (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixed amino diaryl sulfone isomers... Specific Chemical Substances § 721.10564 Mixed amino diaryl sulfone isomers (generic). (a) Chemical... as mixed amino diaryl sulfone isomers (PMN P-08-39) is subject to reporting under this section...

  13. Isomer-specific biodegradation of nonylphenol in an activated sludge bioreactor and structure-biodegradability relationship.

    PubMed

    Lu, Zhijiang; Reif, Rubén; Gan, Jay

    2015-01-01

    Nonylphenol (NP), one of the priority hazardous substances, is in fact a mixture of numerous isomers. It is inconclusive whether or not biodegradation during wastewater treatment process is isomer-specific, leading to the environmental release of NP in different isomer profiles. In this study, we evaluated the isomer selectivity of 19 NP isomers in a laboratory-scale continuous flow conventional activated sludge bioreactor under various operational conditions. The removal efficiency of NP isomers ranged from 90 to 99%, depending on the operational conditions and isomer structures. Isomer selective biodegradation resulted in the increase of composition of recalcitrant isomers, such as, NP₁₉₃a/b, NP₁₁₀a and NP₁₉₄ in the effluent. Moreover, biodegradability was related to the bulkiness of α-substituents and followed α-dimethyl > α-ethyl-α-methyl > α-methyl-α-n-propyl > α-iso-propyl-α-methyl. Steric effect index, a quantitative descriptor of steric hindrance, was linearly correlated with residues of NP isomers in the effluent (R² = 0.76). Decrease of temperature to 10 °C decreased the overall biodegradability and also enhanced the relative enrichment of recalcitrant isomers. These findings suggest that isomer compositions of NP entering the environment may be different from those in technical mixtures and that isomeric selectivity should be taken into account to better understand the occurrence, fate, and ecological risks of NP.

  14. Systematic trends in the237neptunium Mössbauer isomer shift: Overlap of IV, V and VI neptunium oxidation states and correlation between isomer shift and crystal structure

    NASA Astrophysics Data System (ADS)

    Jové, J.; Cousson, A.; Abazli, H.; Tabuteau, A.; Thévenin, T.; Pagès, M.

    1988-01-01

    The influence of the neptunium ion environment on the237Np Mössbauer isomer shifts has been studied in various metal coordination complexes: fluorides, oxides, oxide fluorides and polycarboxylates. A linear dependence between the isomer shift and the mean neptunium-ligand distance in a series of hexavalent Np compounds has been evidenced and the feasibility of overlapped isomer shift areas, namely Np(IV), Np(V) and Np(VI) has been established.

  15. Population and decay of a Kπ=8– two-quasineutron isomer in Pu244

    DOE PAGES

    Hota, S. S.; Tandel, S. K.; Chowdhury, P.; ...

    2016-08-22

    Here, the decay of a Kπ = 8– isomer in 244Pu and the collective band structures populating the isomer were studied using deep inelastic excitations with 47Ti and 208Pb beams, respectively. Precise measurements of M1/E2 branching ratios in the band confirm a 9/2–[734]νⓍ7/2+[624]ν configuration assignment for the isomer, validating the systematics of Kπ = 8–, two-quasineutron isomers observed in even-Z, N = 150 isotones. These isomers around the deformed shell gap at N = 152 provide critical benchmarks for theoretical predictions of single-particle energies in this gateway region to superheavy nuclei.

  16. Population and decay of a Kπ=8- two-quasineutron isomer in 244Pu

    NASA Astrophysics Data System (ADS)

    Hota, S. S.; Tandel, S. K.; Chowdhury, P.; Ahmad, I.; Carpenter, M. P.; Chiara, C. J.; Greene, J. P.; Hoffman, C. R.; Jackson, E. G.; Janssens, R. V. F.; Kay, B. P.; Khoo, T. L.; Kondev, F. G.; Lakshmi, S.; Lalkovski, S.; Lauritsen, T.; Lister, C. J.; McCutchan, E. A.; Moran, K.; Peterson, D.; Shirwadkar, U.; Seweryniak, D.; Stefanescu, I.; Toh, Y.; Zhu, S.

    2016-08-01

    The decay of a Kπ=8- isomer in 244Pu and the collective band structures populating the isomer were studied using deep inelastic excitations with 47Ti and 208Pb beams, respectively. Precise measurements of M 1 /E 2 branching ratios in the band confirm a 9 /2-[734] ν⊗7 /2+[624] ν configuration assignment for the isomer, validating the systematics of Kπ=8- , two-quasineutron isomers observed in even-Z , N =150 isotones. These isomers around the deformed shell gap at N =152 provide critical benchmarks for theoretical predictions of single-particle energies in this gateway region to superheavy nuclei.

  17. GPUbased, Microsecond Latency, HectoChannel MIMO Feedback Control of Magnetically Confined Plasmas

    NASA Astrophysics Data System (ADS)

    Rath, Nikolaus

    Feedback control has become a crucial tool in the research on magnetic confinement of plasmas for achieving controlled nuclear fusion. This thesis presents a novel plasma feedback control system that, for the first time, employs a Graphics Processing Unit (GPU) for microsecond-latency, real-time control computations. This novel application area for GPU computing is opened up by a new system architecture that is optimized for low-latency computations on less than kilobyte sized data samples as they occur in typical plasma control algorithms. In contrast to traditional GPU computing approaches that target complex, high-throughput computations with massive amounts of data, the architecture presented in this thesis uses the GPU as the primary processing unit rather than as an auxiliary of the CPU, and data is transferred from A-D/D-A converters directly into GPU memory using peer-to-peer PCI Express transfers. The described design has been implemented in a new, GPU-based control system for the High-Beta Tokamak - Extended Pulse (HBT-EP) device. The system is built from commodity hardware and uses an NVIDIA GeForce GPU and D-TACQ A-D/D-A converters providing a total of 96 input and 64 output channels. The system is able to run with sampling periods down to 4 μs and latencies down to 8 μs. The GPU provides a total processing power of 1.5 x 1012 floating point operations per second. To illustrate the performance and versatility of both the general architecture and concrete implementation, a new control algorithm has been developed. The algorithm is designed for the control of multiple rotating magnetic perturbations in situations where the plasma equilibrium is not known exactly and features an adaptive system model: instead of requiring the rotation frequencies and growth rates embedded in the system model to be set a priori, the adaptive algorithm derives these parameters from the evolution of the perturbation amplitudes themselves. This results in non-linear control

  18. Spectroscopic Studies of the Several Isomers of UO3

    SciTech Connect

    Sweet, Lucas E.; Reilly, Dallas D.; Abrecht, David G.; Buck, Edgar C.; Meier, David E.; Su, Yin-Fong; Brauer, Carolyn S.; Schwantes, Jon M.; Tonkyn, Russell G.; Szecsody, James E.; Blake, Thomas A.; Johnson, Timothy J.

    2013-09-26

    Uranium trioxide is known to adopt seven different structural forms. While these structural forms have been well characterized using x-ray or neutron diffraction techniques, little work has been done to characterize their spectroscopic properties, particularly of the pure phases. Since the structural isomers of UO3 all have similar thermodynamic stabilities and most tend to hydrolyze under open atmospheric conditions, mixtures of UO3 phases and the hydrolysis products are common. Much effort went into isolating pure phases of UO3. Utilizing x-ray diffraction as a sample identification check, UV/Vis/NIR spectroscopic signatures of α-UO3, β-UO3, γ-UO3 and UO2(OH)2 products were obtained. The spectra of the pure phases can now be used to characterize typical samples of UO3, which are often mixtures of isomers.

  19. [Beaded molecule imprinted polymer for stereo isomer separation].

    PubMed

    Meng, Z; Wang, J; Zhou, L; Wang, Q; Zhu, D

    1999-07-01

    Beaded molecule imprinted polymer (MIP) was made by suspension polymerization. Particles with the size of 50-70 microns in diameter were collected and evaluated in HPLC mode to separate stereo isomers. Stereo isomers cinchonine and cinchonidine were successfully discriminated with selectivity factor of 2.89 and resolution factor of 0.76. Stereo selectivity of the MIP was found to come from both the interaction between the analyte and carboxyl group on the MIP and the similarity between the stereo structure of imprinted molecule and the MIP. The thermal analysis results showed that the MIP had high thermal stability with initial thermal decomposition temperature of 320 degrees C. The pore volume of the MIP was 0.1849 mL/g, the specific surface area was 126.84 sqm/g and the average pore diameter was 5.8 nanometer. Scanning electron microscopy showed that MIP had perfect spherical morphology.

  20. Novel bioactive oxazolomycin isomers produced by Streptomyces albus JA3453.

    PubMed

    Kanzaki, H; Wada, K; Nitoda, T; Kawazu, K

    1998-03-01

    Two novel oxazolomycin isomers, oxazolomycins B (2) and C (3), were isolated from the fermentation broth of an oxazolomycin-producing strain, Streptomyces albus JA3453. Both compounds are geometrical isomers of oxazolomycin (1), the configurations of their triene moieties being (4'E, 6'E, 8'E) (2) and (4'Z, 6'E, 8'E) (3) while that of oxazolomycin (1) is (4'Z, 6'Z, 8'E). Compounds 2 and 3 exhibited potent inhibitory activity against crown gall formation with the same MIC (0.8 microgram/disk) as oxazolomycin. Compounds 2 and 3 showed no antibacterial activity against Agrobacterium tumefaciens, in contrast to oxazolomycin which has specific anti-A. tumefaciens activity.

  1. Characterization of geometric isomers of Norbornene end-capped imides

    NASA Technical Reports Server (NTRS)

    Young, P. R.; Chang, A. C.

    1983-01-01

    Three geometric isomers from the thermal isomerization of methylene-4,4' bis(endo-N-phenylbicyclo/2.2.1/hept-2-ene-5,6-di carboximide) (I) were chromatographically separated and isolated in order to investigate the thermal cure of norbornene end-capped imide oligomers, which display considerable promise for use in various aerospace adhesive and composite applications. Endo-endo (I), endo-exo (II), and exo-exo (III) configurations were assigned to each compound based on the results of NMR spectroscopy. Several chromatographic, spectroscopic, and thermal techniques were then used to characterize these three isomers which serve as model compounds for norbornene end-capped polyimides. It was found that each compound thermally isomerized to an equilibrium mixture of all three compounds prior to cure. It is proposed that these compounds react by different mechanisms in air and nitrogen.

  2. A simple, rapid method for HPLC analysis of lycopene isomers.

    PubMed

    Ishida, B K; Ma, J; Chan, B

    2001-01-01

    A rapid method for the extraction, separation and quantification of the geometric isomers of lycopene and beta-carotene from tomato fruit is described. Carotenoids in tomato were separated and eluted using a reversed-phase HPLC with a C30 column and a mobile phase consisting of methyl-t-butyl ether, methanol and ethyl acetate. The system provided sharp resolution of cis- and trans-isomers of lycopene within approximately 23 min in contrast to the longer and more complex gradient procedures required by previously described methods. Experiments indicate that the stability of extracts of fresh tomato may be improved if stored at -20 degrees C, and that the presence of the antioxidant BHA has no apparent effect on stability.

  3. Positional isomer differentiation of synthetic cannabinoid JWH-081 by GC-MS/MS.

    PubMed

    Kusano, Maiko; Zaitsu, Kei; Nakayama, Hiroshi; Nakajima, Junichi; Hisatsune, Kazuaki; Moriyasu, Takako; Matsuta, Shuntaro; Katagi, Munehiro; Tsuchihashi, Hitoshi; Ishii, Akira

    2015-03-01

    Like many new designer drugs of abuse, synthetic cannabinoids (SC) have structural or positional isomers which may or may not all be regulated under law. Differences in acute toxicity may exist between isomers which impose further burden in the fields of forensic toxicology, medicine and legislation. Isomer differentiation therefore becomes crucial from these standpoints as new designer drugs continuously emerge with just minor positional modifications to their preexisting analogs. The aim of this study was to differentiate the positional isomers of JWH-081. Purchased standard compounds of JWH-081 and its positional isomers were analyzed by gas chromatography-electron ionization-mass spectrometry (GC-EI-MS) first in scan mode to investigate those isomers who could be differentiated by EI scan spectra. Isomers with identical or near-identical EI spectra were further subjected to GC-tandem mass spectrometry (MS/MS) analysis with appropriate precursor ions. EI scan was able to distinguish 3 of the 7 isomers: 2-methoxy, 7-methoxy and 8-methoxy. The remaining isomers exhibited near-identical spectra; hence, MS/MS was performed by selecting m/z 185 and 157 as precursor ions. 3-Methoxy and 5-methoxy isomers produced characteristic product ions that enabled the differentiation between them. Product ion spectrum of 6-methoxy isomer resembled that of JWH-081; however, the relative ion intensities were clearly different from one another. The combination of EI scan and MS/MS allowed for the regioisomeric differentiation of the targeted compounds in this study.

  4. Isomer-specific biodegradation of nonylphenol in river sediments and structure-biodegradability relationship.

    PubMed

    Lu, Zhijiang; Gan, Jay

    2014-01-21

    Nonylphenol (NP), a well-known environmental estrogen with numerous isomers, is frequently found in surface water and sediments. Recent studies showed that NP isomers exhibited different estrogenicity. However, at present little information is available on its isomer-specific degradation in the bed sediment, which is the primary sink of NP in surface aquatic systems. In this study, we investigated the biodegradability of 19 NP isomers in two river sediments under oxic and anoxic conditions. Under oxic conditions, the half-lives of NP isomers in an upper river sediment ranged from 0.9 to 13.2 d. Under reduced conditions, the persistence of NP isomers generally increased, with negligible dissipation under strongly reduced conditions. In the well-aerated sediment, NP isomers with short side chain and/or bulky α-substituents were found to be more recalcitrant to degradation. Moreover, when a total of 57 molecular descriptors were examined, the degree of branching as quantified by IDWbar was found to result in the best linear correlation with half-lives of NP isomers (R(2) = 0.88). These results indicated that the isomer-specificity of NP in environmental processes should be considered, and that simple molecular descriptors may be used to identify the more recalcitrant isomers, thus allowing prioritization in the evaluation of environmental fate and risks of NP isomers.

  5. Condensations of single DNA molecules induced by heptaplatin and its chiral isomer

    SciTech Connect

    Zhang, Hong-Yan; Liu, Yu-Ru; Li, Wei; Li, Hui; Dou, Shuo-Xing; Xie, Ping; Wang, Wei-Chi; Wang, Peng-Ye

    2014-08-15

    Heptaplatin is a third-generation platinum antitumor drug. It has a chiral isomer. We studied the interactions between the two isomers and DNA by using magnetic tweezers and atomic force microscopy (AFM) to investigate the effect of chiralities of the isomers on the interactions. We found that the extension curves and average condensation rates of DNA molecules incubated with heptaplatin were nearly the same as those incubated with its chiral isomer. In addition, the structures of DNA molecules incubated with heptaplatin were also similar to those incubated with its chiral isomer. These results indicate the difference in chirality of the two isomers does not induce different interactions of the isomers with DNA. Our study may facilitate the understanding of interactions of platinum complexes with DNA and the design of new antitumor platinum complexes.

  6. Condensations of single DNA molecules induced by heptaplatin and its chiral isomer

    NASA Astrophysics Data System (ADS)

    Zhang, Hong-Yan; Liu, Yu-Ru; Li, Wei; Li, Hui; Dou, Shuo-Xing; Xie, Ping; Wang, Wei-Chi; Wang, Peng-Ye

    2014-08-01

    Heptaplatin is a third-generation platinum antitumor drug. It has a chiral isomer. We studied the interactions between the two isomers and DNA by using magnetic tweezers and atomic force microscopy (AFM) to investigate the effect of chiralities of the isomers on the interactions. We found that the extension curves and average condensation rates of DNA molecules incubated with heptaplatin were nearly the same as those incubated with its chiral isomer. In addition, the structures of DNA molecules incubated with heptaplatin were also similar to those incubated with its chiral isomer. These results indicate the difference in chirality of the two isomers does not induce different interactions of the isomers with DNA. Our study may facilitate the understanding of interactions of platinum complexes with DNA and the design of new antitumor platinum complexes.

  7. Virtual libraries of tetrapyrrole macrocycles. Combinatorics, isomers, product distributions, and data mining.

    PubMed

    Taniguchi, Masahiko; Du, Hai; Lindsey, Jonathan S

    2011-09-26

    A software program (PorphyrinViLiGe) has been developed to enumerate the type and relative amounts of substituted tetrapyrrole macrocycles in a virtual library formed by one of four different classes of reactions. The classes include (1) 4-fold reaction of n disubstituted heterocycles (e.g., pyrroles or diiminoisoindolines) to form β-substituted porphyrins, β-substituted tetraazaporphyrins, or α- or β-substituted phthalocyanines; (2) combination of m aminoketones and n diones to form m × n pyrroles, which upon 4-fold reaction give β-substituted porphyrins; (3) derivatization of an 8-point tetrapyrrole scaffold with n reagents, and (4) 4-fold reaction of n aldehydes and pyrrole to form meso-substituted porphyrins. The program accommodates variable ratios of reactants, reversible or irreversible reaction (reaction classes 1 and 2), and degenerate modes of formation. Pólya's theorem (for enumeration of cyclic entities) has also been implemented and provides validation for reaction classes 3 and 4. The output includes the number and identity of distinct reaction-accessible substituent combinations, the number and identity of isomers thereof, and the theoretical mass spectrum. Provisions for data mining enable assessment of the number of products having a chosen pattern of substituents. Examples include derivatization of an octa-substituted phthalocyanine with eight reagents to afford a library of 2,099,728 members (yet only 6435 distinct substituent combinations) and reversible reaction of six distinct disubstituted pyrroles to afford 2649 members (yet only 126 distinct substituent combinations). In general, libraries of substituted tetrapyrrole macrocycles occupy a synthetically accessible region of chemical space that is rich in isomers (>99% or 95% for the two examples, respectively).

  8. Combustion of butanol isomers - A detailed molecular beam mass spectrometry investigation of their flame chemistry

    SciTech Connect

    Osswald, Patrick; Gueldenberg, Hanna; Kohse-Hoeinghaus, Katharina; Yang, Bin; Yuan, Tao; Qi, Fei

    2011-01-15

    The combustion chemistry of the four butanol isomers, 1-, 2-, iso- and tert-butanol was studied in flat, premixed, laminar low-pressure (40 mbar) flames of the respective alcohols. Fuel-rich ({phi} = 1.7) butanol-oxygen-(25%)argon flames were investigated using different molecular beam mass spectrometry (MBMS) techniques. Quantitative mole fraction profiles are reported as a function of burner distance. In total, 57 chemical compounds, including radical and isomeric species, have been unambiguously assigned and detected quantitatively in each flame using a combination of vacuum ultraviolet (VUV) photoionization (PI) and electron ionization (EI) MBMS. Synchrotron-based PI-MBMS allowed to separate isomeric combustion intermediates according to their different ionization thresholds. Complementary measurements in the same flames with a high mass-resolution EI-MBMS system provided the exact elementary composition of the involved species. Resulting mole fraction profiles from both instruments are generally in good quantitative agreement. In these flames of the four butanol isomers, temperature, measured by laser-induced fluorescence (LIF) of seeded nitric oxide, and major species profiles are strikingly similar, indicating seemingly analog global combustion behavior. However, significant variations in the intermediate species pool are observed between the fuels and discussed with respect to fuel-specific destruction pathways. As a consequence, different, fuel-specific pollutant emissions may be expected, by both their chemical nature and concentrations. The results reported here are the first of their kind from premixed isomeric butanol flames and are thought to be valuable for improving existing kinetic combustion models. (author)

  9. Determination of aminocresol isomers by high-speed liquid chromatography.

    PubMed

    Sakurai, H; Kito, M

    Aminocresol isomers (4-hydroxy-m-toluidine [II], 3-hydroxy-p-toluidine [II], 2-hydroxy-p-toluidine [III]) and p-aminophenol have been separated and determined by a high-speed liquid Chromatographie method. Since this method is applicable in aqueous media, it was used to investigate the suitability of a haemin-cysteine system as a model for the cytochrome P-450 mono-oxygenase system, by determination of the [I], [II], [III] and p-aminophenol formed.

  10. Flame Propagation of Butanol Isomers/Air Mixtures

    SciTech Connect

    Veloo, Peter S.; Egolfopoulos, Fokion N.

    2011-01-01

    An experimental and computational study was conducted on the propagation of flames of saturated butanol isomers. The experiments were performed in the counterflow configuration under atmospheric pressure, unburned mixture temperature of 343 K, and for a wide range of equivalence ratios. The experiments were simulated using a recent kinetic model for the four isomers of butanol. Results indicate that n-butanol/air flames propagate somewhat faster than both sec-butanol/air and iso-butanol/air flames, and that tert-butanol/air flames propagate notably slower compared to the other three isomers. Reaction path analysis of tert-butanol/air flames revealed that iso-butene is a major intermediate, which subsequently reacts to form the resonantly stable iso-butenyl radical retarding thus the overall reactivity of tert-butanol/air flames relatively to the other three isomers. Through sensitivity analysis, it was determined that the mass burning rates of sec-butanol/air and iso-butanol/air flames are sensitive largely to hydrogen, carbon monoxide, and C{sub 1}–C{sub 2} hydrocarbon kinetics and not to fuel-specific reactions similarly to n-butanol/air flames. However, for tert-butanol/air flames notable sensitivity to fuel-specific reactions exists. While the numerical results predicted closely the experimental data for n-butanol/air and sec-butanol/air flames, they overpredicted and underpredicted the laminar flame speeds for iso-butanol/air and tert-butanol/air flames respectively. It was demonstrated further that the underprediction of the laminar flame speeds of tert-butanol/air flames by the model was most likely due to deficiencies of the C{sub 4}-alkene kinetics.

  11. Preignition and Autoignition Behavior of the Xylene Isomers

    DTIC Science & Technology

    2010-03-01

    for the addition of three additives – a fuel system icing inhibitor, a corrosion inhibitor, and a static dissipater additive. The consequences of...identified were p-tolualdehyde, toluene, and p- cresol . Of note, p- cresol was identified in this experiment but its ortho- and meta- isomers were not...methylbenzaldehyde (p-tolualdehyde) and hydrogen radical. Hydroxyl radical attack on p-tolualdehyde produces p- cresol and formyl radical. Another

  12. Spectroscopic and computational study of a new isomer of salinomycin

    NASA Astrophysics Data System (ADS)

    Pankiewicz, Radosław

    2013-09-01

    A new derivative of polyether ionophore salinomycin was obtained as a result of a rearrangement catalysed by sulphuric acid in two-phase medium of water/methylene chloride solution. The new isomer was fully characterized by multinuclear 2D NMR, NOESY and MALDI-TOF. The properties of the new compound were additionally study by semiempirical (PM5) and DFT (B3LYP) methods. A potential mechanism of the rearrangement was also proposed.

  13. Focal point analysis of torsional isomers of acrylic acid

    NASA Astrophysics Data System (ADS)

    Alev Çiftçioğlu, Gökçen; Trindle, Carl; Yavuz, Ilhan

    2010-10-01

    The thermochemistry of acrylic acid has presented challenges owing to its high reactivity, tendency to dimerize in the gas phase, and the existence of two very nearly equal energy conformational isomers. Well-tested thermochemical schemes including G2, G3, G4, and CBS-QB3 agree in the prediction that the s-cis syn structure is the most stable of the torsional isomers, with the s-cis anti form lying 3 kJ mol-1 or less higher in energy. Microwave spectra suggest a value of 0.63 kJ mol-1. The energy barrier between these forms is in the neighbourhood of 25 kJ mol-1 according to a MP2/cc-pVDZ calculation. We present estimates of the relative energies of all four torsional isomers and the rotational barrier based on a variant of the Focal Point Analysis developed by Császár and co-workers. These calculations, extending to the CCSD(T)/cc-pV5Z level, predict that the s-cis anti torsional isomer is the most stable form, in contrast to prior estimates. The s-cis syn form lies about 2.9 kJ mol-1 higher, while the s-trans syn and anti forms lie at about 21.7 and 23.3 kJ mol-1, respectively. We estimate the rotational barrier between the s-cis trans and s-cis anti structures to be about 23.9 kJ mol-1. Error ranges derived from the fit to extrapolation forms suggest that our estimates have an uncertainty of about 0.1 kJ mol-1.

  14. Biodegradation of Alpha TNT and Its Production Isomers

    DTIC Science & Technology

    1974-07-01

    1 ^*"* **».-._ BIODEGRADATION OF ALPHA TNT ANT) ITS PRODUCTION ISOMERS Annual Report-U by: Richard W. Traxler University of Rhode Island...associated with the burning process. If these nitrobodies are found to be biodegradable , they could be rendered ecologically safe by biological...molecules are biodegradable by some microbial form whereas the truly recalcitrant molecules are found in broad classes of the synthetic organic compounds

  15. A Rapid Compression Machine Modelling Study of the Heptane Isomers

    SciTech Connect

    Silke, E J; Curran, H J; Simmie, J M; Pitz, W J; Westbrook, C K

    2005-05-10

    Previously we have reported on the combustion behavior of all nine isomers of heptane in a rapid compression machine (RCM) with stoichiometric fuel and ''air'' mixtures at a compressed gas pressure of 15 atm. The dependence of autoignition delay times on molecular structure was illustrated. Here, we report some additional experimental work that was performed in order to address unusual results regarding significant differences in the ignition delay times recorded at the same fuel and oxygen composition, but with different fractions of nitrogen and argon diluent gases. Moreover, we have begun to simulate these experiments with detailed chemical kinetic mechanisms. These mechanisms are based on previous studies of other alkane molecules, in particular, n-heptane and iso-octane. We have focused our attention on n-heptane in order to systematically redevelop the chemistry and thermochemistry for this C{sub 7} isomer with the intention of extending our greater knowledge gained to the other eight isomers. The addition of new reaction types, that were not included previously, has had a significant impact on the simulations, particularly at low temperatures.

  16. Borromean halo, Tango halo, and halo isomers in atomic nuclei

    NASA Astrophysics Data System (ADS)

    Izosimov, Igor

    2016-01-01

    Structure of the ground and excited states in halo-like nuclei is discussed. Both the Borromean and tango halo types can be observed for n-p configurations of atomic nuclei.Structure of the halo may be different for the different levels and resonances in atomic nuclei. Isobar analog, double isobar analog, configuration, and double configuration states can simultaneously have n-n, n-p, and p-p halo components in their wave functions. When the halo structure of the excited state differs from that of the ground state, or the ground state has non-halo structure, the γ-transition from the excited state to the ground state can be essentially hindered, i.e. the formation of a specific type of isomers (halo isomers) becomes possible. B(Mγ) and B(Eγ) values for γ-transitions in 6,7,8Li, 8,9,10Be, 8,10,11B, 10,11,12,13,14C, 13,14,15,16,17N, 15,16,17,19O, and 17F are analyzed. Special attention is given to nuclei which ground state does not exhibit halo structure but the excited state (halo isomer) may have one.

  17. Three bilindione isomers: synthesis, characterization and reactivity of biliverdin analogs.

    PubMed

    Wang, Jun-Fei; Ma, Fang; Sun, Hao-Ling; Zhang, Jing; Zhang, Jun-Long

    2017-02-07

    Linear tetrapyrrole is the core structure of light-sensitive native cofactors such as phycocyanobilin, phytochromobilin and bile pigments, which attracts increasing attention in biomimetic chemistry, photochemistry and coordination chemistry. To decipher the relationship between structures and functions, in this work, we firstly reported the synthesis, isolation and characterization of three bilindione isomers (ZZZ, syn, syn, syn 1, EZE, syn, syn, anti 2 and EZE, anti, syn, anti 3) bearing meso-pentafluorophenyl groups. The structures were confirmed by X-ray diffraction and 2-D NMR spectroscopes. More importantly, the interconversion between three isomers under heating and light irradiation was investigated, and isomer 3 was found to be transformed to 1 and 2 more easily, which is in line with the results of DFT calculation. This work provides important insights for understanding the relationship between structures and functions and would be important to further construct metal complexes based on linear tetrapyrrole ligands, which are complementary to well-studied the cyclic analogs such as porphyrin and corroles.

  18. Oxidative Transformation of Aminodinitrotoluene Isomers by Multicomponent Dioxygenases

    PubMed Central

    Johnson, Glenn R.; Smets, Barth F.; Spain, Jim C.

    2001-01-01

    The electron-withdrawing nitro substituents of 2,4,6-trinitrotoluene (TNT) make the aromatic ring highly resistant to oxidative transformation. The typical biological transformation of TNT involves reduction of one or more of the nitro groups of the ring to produce the corresponding amine. Reduction of a single nitro substituent of TNT to an amino substituent increases the electron density of the aromatic nucleus considerably. The comparatively electron-dense nuclei of the aminodinitrotoluene (ADNT) isomers would be expected to be more susceptible to oxygenase attack than TNT. The hypothesis was tested by evaluating three nitroarene dioxygenases for the ability to hydroxylate the ADNT isomers. The predominant reaction was dioxygenation of the ring to yield nitrite and the corresponding aminomethylnitrocatechol. A secondary reaction was benzylic monooxygenation to form aminodinitrobenzyl alcohol. The substrate preferences and catalytic specificities of the three enzymes differed considerably. The discovery that the ADNT isomers are substrates for the nitroarene dioxygenases reveals the potential for extensive bacterial transformation of TNT under aerobic conditions. PMID:11722893

  19. Electron attachment and detachment: Electron affinities of isomers of trifluoromethylbenzonitrile

    NASA Astrophysics Data System (ADS)

    Miller, Thomas M.; Viggiano, A. A.; Friedman, Jeffrey F.; Van Doren, Jane M.

    2004-11-01

    Rate constants for electron attachment to the three isomers of trifluoromethylbenzonitrile [(CF3)(CN)C6H4, or TFMBN] were measured over the temperature range of 303-463 K in a 133-Pa He buffer gas, using a flowing-afterglow Langmuir-probe apparatus. At 303 K, the measured attachment rate constants are 9.0×10-8 (o-TFMBN), 5.5×10-8 (m-TFMBN), and 8.9×10-8 cm3 s-1 (p-TFMBN), estimated accurate to ±25%. The attachment process formed only the parent anion in all three cases. Thermal electron detachment was observed for all three anion isomers, and rate constants for this reverse process were also measured. From the attachment and detachment results, the electron affinities of the three isomers of TFMBN were determined to be 0.70(o-TFMBN), 0.67(m-TFMBN), and 0.83 eV (p-TFMBN), all ±0.05 eV. G3(MP2) [Gaussian-3 calculations with reduced Møller-Plesset orders (MP2)] calculations were carried out for the neutrals and anions. Electron affinities derived from these calculations are in good agreement with the experimental values.

  20. Electron attachment and detachment: electron affinities of isomers of trifluoromethylbenzonitrile.

    PubMed

    Miller, Thomas M; Viggiano, A A; Friedman, Jeffrey F; Van Doren, Jane M

    2004-11-22

    Rate constants for electron attachment to the three isomers of trifluoromethylbenzonitrile [(CF(3))(CN)C(6)H(4), or TFMBN] were measured over the temperature range of 303-463 K in a 133-Pa He buffer gas, using a flowing-afterglow Langmuir-probe apparatus. At 303 K, the measured attachment rate constants are 9.0 x 10(-8) (o-TFMBN), 5.5 x 10(-8) (m-TFMBN), and 8.9 x 10(-8) cm(3) s(-1) (p-TFMBN), estimated accurate to +/-25%. The attachment process formed only the parent anion in all three cases. Thermal electron detachment was observed for all three anion isomers, and rate constants for this reverse process were also measured. From the attachment and detachment results, the electron affinities of the three isomers of TFMBN were determined to be 0.70(o-TFMBN), 0.67(m-TFMBN), and 0.83 eV (p-TFMBN), all +/-0.05 eV. G3(MP2) [Gaussian-3 calculations with reduced Møller-Plesset orders (MP2)] calculations were carried out for the neutrals and anions. Electron affinities derived from these calculations are in good agreement with the experimental values.

  1. Isomer-specific biodegradation of methylphenanthrenes by soil bacteria.

    PubMed

    Lamberts, Rasmus F; Christensen, Jan H; Mayer, Philipp; Andersen, Ole; Johnsen, Anders R

    2008-07-01

    It is assumed that bacteria generally degrade 2-methylphenanthrene (2MPhe) in preference to 1-methylphenanthrene (1MPhe), and that environmental biodegradation of methylated PAHs therefore can be described qualitatively by changes in relative concentrations of these isomers. Our objective was to investigate whether microbial phenanthrene degraders (Sphingomonas and Mycobacterium) show such isomer-specific PAH degradation. Eleven out of twenty-nine phenanthrene degraders could grow on methylphenanthrene. The mycobacteria grew only on 2MPhe, the sphingomonads grew mostly on 1MPhe, and one sphingomonad could utilize both substrates. Seven strains were tested in a two-phase system where 1MPhe and 2MPhe were supplied in heptamethylnonane. For these strains, a consistent description of biodegradation based on the 2MPhe/1MPhe diagnostic ratio would not be possible because three Mycobacterium and one Sphingomonas degraded 2MPhe faster than 1MPhe, another Sphingomonas degraded 1MPhe and 2MPhe at almost equal rates, and two Sphingomonas degraded 1MPhe faster than 2MPhe. Thus, environmental biodegradation of phenanthrenes may theoretically proceed with only minor changes in 2MPhe/1MPhe ratios if individual members of the degrader community have different isomer preferences. However, two soil microcosms polluted with bunker oil confirmed the general decline in 2MPhe/1MPhe ratio during oil biodegradation.

  2. INTERACTION OF LASER RADIATION WITH MATTER. LASER PLASMA: Composition and dynamics of an erosion plasma produced by microsecond laser pulses

    NASA Astrophysics Data System (ADS)

    Anisimov, V. N.; Grishina, V. G.; Derkach, O. N.; Sebrant, A. Yu; Stepanova, M. A.

    1995-08-01

    The ion and energy compositions were determined and the dynamics was studied of an erosion plume formed by microsecond CO2 laser pulses incident on a graphite target. The ionic emission lines were used to find the electron density and temperature of the plasma on the target surface. The temperature of the plasma source did not change throughout the line emission time (4 μs). At the plasma recombination stage the lines of the C II, C III, and C IV ions were accompanied by bands of the C2 molecule near the target surface and also near the surface of an substrate when a plasma flow interacted with it. Ways were found for controlling the plume expansion anisotropy and for producing plasma flows with controlled parameters by selection of the conditions during formation of a quasisteady erosion plasma flow.

  3. Cholesterol Flip-Flop Dynamics in a Phospholipid Bilayer: A 10 Microsecond All-Atom Molecular Dynamics Simulation

    NASA Astrophysics Data System (ADS)

    Choubey, Amit; Nomura, Ken-Ichi; Kalia, Rajiv; Nakano, Aiichiro; Vashishta, Priya

    2012-02-01

    Cholesterol (CHOL) molecules play a key role in modulating the rigidity of cell membranes, and controlling intracellular transport and signal transduction. Using all-atom molecular dynamics and the parallel replica approach, we study the effect of CHOL molecules on mechanical stresses across a dipalmitoylphosphatidycholine (DPPC)-CHOL bilayer, and the mechanism by which CHOL molecules migrate from one bilayer leaflet to the other (flip-flop events). On average, we observe a CHOL flip-flop event in half-a-microsecond. Once a CHOL flip-flop event is triggered, the inter-leaflet migration occurs in about 62 nanoseconds. The energy barrier associated with flip-flop events is found to be 73 kJ/mol. Results for membrane rigidity as a function of CHOL concentration will also be presented.

  4. The action of microsecond-pulsed plasma-activated media on the inactivation of human lung cancer cells

    NASA Astrophysics Data System (ADS)

    Kumar, Naresh; Park, Ji Hoon; Jeon, Su Nam; Park, Bong Sang; Choi, Eun Ha; Attri, Pankaj

    2016-03-01

    In the present work, we have generated reactive species (RS) through microsecond-pulsed plasma (MPP) in the cell culture media using a Marx generator with point-point electrodes of approximately 0.06 J discharge energy/pulse. RS generated in culture media through MPP have a selective action between growth of the H460 lung cancer cells and L132 normal lung cells. We observed that MPP-activated media (MPP-AM) induced apoptosis on H460 lung cancer cells through an oxidative DNA damage cascade. Additionally, we studied the apoptosis-related mRNA expression, DNA oxidation and polymerase-1 (PARP-1) cleaved analysis from treated cancer cells. The result proves that radicals generated through MPP play a pivotal role in the activation of media that induces the selective killing effect.

  5. Evaluation of electrical conductivity and equations of state of non-ideal plasma through microsecond timescale underwater electrical wire explosion

    SciTech Connect

    Sheftman, D.; Krasik, Ya. E.

    2011-09-15

    Experimental and simulation results of underwater electrical Cu, Al, and W wire explosions in the microsecond timescale are presented. It was shown that the electrical conductivity results for Cu and Al agree well with modified Lee-More and quantum molecular dynamic models for temperatures above 10 kK. The equation of state (EOS) values based on SESAME tables for Cu and Al were slightly modified for intermediate temperatures in order to obtain fitting between experimental and simulated exploding wire radial expansion. Also, it was shown that the electrical conductivity results and the EOS evaluation differ significantly from the results obtained in nanosecond timescale experiments. Finally, it was found that underwater electrical W wire explosion is characterized by the appearance of non-uniformities along the z-axis of the wire. This phenomena adds uncertainty to the possibility of applying this type of experiments for evaluation of the electrical conductivity and EOS of W.

  6. Evaluation of electrical conductivity and equations of state of non-ideal plasma through microsecond timescale underwater electrical wire explosion

    NASA Astrophysics Data System (ADS)

    Sheftman, D.; Krasik, Ya. E.

    2011-09-01

    Experimental and simulation results of underwater electrical Cu, Al, and W wire explosions in the microsecond timescale are presented. It was shown that the electrical conductivity results for Cu and Al agree well with modified Lee-More and quantum molecular dynamic models for temperatures above 10 kK. The equation of state (EOS) values based on SESAME tables for Cu and Al were slightly modified for intermediate temperatures in order to obtain fitting between experimental and simulated exploding wire radial expansion. Also, it was shown that the electrical conductivity results and the EOS evaluation differ significantly from the results obtained in nanosecond timescale experiments. Finally, it was found that underwater electrical W wire explosion is characterized by the appearance of non-uniformities along the z-axis of the wire. This phenomena adds uncertainty to the possibility of applying this type of experiments for evaluation of the electrical conductivity and EOS of W.

  7. Outlook for the use of microsecond plasma opening switches to generate high-power nanosecond current pulses

    NASA Astrophysics Data System (ADS)

    Dolgachev, G. I.; Maslennikov, D. D.; Ushakov, A. G.

    2006-12-01

    An analysis is made of the current break process in microsecond plasma opening switches and their possible application in high-current generators. Necessary conditions are determined for generating megavolt pulses in the erosion mode of a plasma opening switch with the gap insulated by an external magnetic field. Under these conditions, efficient sharpening of high-power submegampere current pulses can be achieved. The possibility of using plasma opening switches operating at voltages of 5 6 MV to generate X-ray and gamma emission is discussed. The main operating and design parameters of a six-module plasma opening switch with a current pulse amplitude of 3.7 MA and voltage of 4 6 MV for use in the MOL generator, which is the prototype of one of the 24 modules of the projected Baikal multimegajoule generator, are estimated by using the available scalings.

  8. High pulse energy, high beam quality microsecond-pulse Ti:sapphire laser at 819.7 nm

    NASA Astrophysics Data System (ADS)

    Xu, Chang; Guo, Chuan; Yu, Hai-Bo; Wang, Zhi-Min; Zuo, Jun-Wei; Xia, Yuan-Qin; Bian, Qi; Bo, Yong; Gao, Hong-Wei; Guo, Ya-Ding; Zhang, Sheng; Cui, Da-Fu; Peng, Qin-Jun; Xu, Zu-Yan

    2017-03-01

    In this letter, a high pulse energy and high beam quality 819.7 nm Ti:sapphire laser pumped by a frequency-doubled Nd:YAG laser is demonstrated. At incident pump energy of 774 mJ, the maximum output energy of 89 mJ at 819.7 nm with a pulse width of 100 μs is achieved at a repetition rate of 5 Hz. To the best of our knowledge, this is the highest pulse energy at 819.7 nm with pulse width of hundred microseconds for a Ti:sapphire laser. The beam quality factor M 2 is measured to be 1.18. This specific wavelength with the high pulse energy and high beam quality at 819.7 nm is a promising light source to create a polychromatic laser guide star together with a home-made 589 nm laser via exciting the sodium atoms in the mesospheric atmosphere.

  9. Organometal halide perovskite solar cell materials rationalized: ultrafast charge generation, high and microsecond-long balanced mobilities, and slow recombination.

    PubMed

    Ponseca, Carlito S; Savenije, Tom J; Abdellah, Mohamed; Zheng, Kaibo; Yartsev, Arkady; Pascher, Tobjörn; Harlang, Tobias; Chabera, Pavel; Pullerits, Tonu; Stepanov, Andrey; Wolf, Jean-Pierre; Sundström, Villy

    2014-04-09

    Organometal halide perovskite-based solar cells have recently been reported to be highly efficient, giving an overall power conversion efficiency of up to 15%. However, much of the fundamental photophysical properties underlying this performance has remained unknown. Here, we apply photoluminescence, transient absorption, time-resolved terahertz and microwave conductivity measurements to determine the time scales of generation and recombination of charge carriers as well as their transport properties in solution-processed CH3NH3PbI3 perovskite materials. We found that electron-hole pairs are generated almost instantaneously after photoexcitation and dissociate in 2 ps forming highly mobile charges (25 cm(2) V(-1) s(-1)) in the neat perovskite and in perovskite/alumina blends; almost balanced electron and hole mobilities remain very high up to the microsecond time scale. When the perovskite is introduced into a TiO2 mesoporous structure, electron injection from perovskite to the metal oxide is efficient in less than a picosecond, but the lower intrinsic electron mobility of TiO2 leads to unbalanced charge transport. Microwave conductivity measurements showed that the decay of mobile charges is very slow in CH3NH3PbI3, lasting up to tens of microseconds. These results unravel the remarkable intrinsic properties of CH3NH3PbI3 perovskite material if used as light absorber and charge transport layer. Moreover, finding a metal oxide with higher electron mobility may further increase the performance of this class of solar cells.

  10. Coupling between Histone Conformations and DNA Geometry in Nucleosomes on a Microsecond Timescale: Atomistic Insights into Nucleosome Functions.

    PubMed

    Shaytan, Alexey K; Armeev, Grigoriy A; Goncearenco, Alexander; Zhurkin, Victor B; Landsman, David; Panchenko, Anna R

    2016-01-16

    An octamer of histone proteins wraps about 200bp of DNA into two superhelical turns to form nucleosomes found in chromatin. Although the static structure of the nucleosomal core particle has been solved, details of the dynamic interactions between histones and DNA remain elusive. We performed extensively long unconstrained, all-atom microsecond molecular dynamics simulations of nucleosomes including linker DNA segments and full-length histones in explicit solvent. For the first time, we were able to identify and characterize the rearrangements in nucleosomes on a microsecond timescale including the coupling between the conformation of the histone tails and the DNA geometry. We found that certain histone tail conformations promoted DNA bulging near its entry/exit sites, resulting in the formation of twist defects within the DNA. This led to a reorganization of histone-DNA interactions, suggestive of the formation of initial nucleosome sliding intermediates. We characterized the dynamics of the histone tails upon their condensation on the core and linker DNA and showed that tails may adopt conformationally constrained positions due to the insertion of "anchoring" lysines and arginines into the DNA minor grooves. Potentially, these phenomena affect the accessibility of post-translationally modified histone residues that serve as important sites for epigenetic marks (e.g., at H3K9, H3K27, H4K16), suggesting that interactions of the histone tails with the core and linker DNA modulate the processes of histone tail modifications and binding of the effector proteins. We discuss the implications of the observed results on the nucleosome function and compare our results to different experimental studies.

  11. Distribution of perfluorooctane sulfonate isomers and predicted risk of thyroid hormonal perturbation in drinking water.

    PubMed

    Yu, Nanyang; Wang, Xiaoxiang; Zhang, Beibei; Yang, Jingping; Li, Meiying; Li, Jun; Shi, Wei; Wei, Si; Yu, Hongxia

    2015-06-01

    We documented the distribution of seven perfluorooctane sulfonate (PFOS) isomers in drinking water in Jiangsu Province, China. Compared to the 30% proportion of branched PFOS in technical PFOS, the levels of branched PFOS in drinking water increased to 31.8%-44.6% of total PFOS. Because of previous risk assessment without considering the PFOS isomer profile and the toxicity of individual PFOS isomers, here we performed a new health risk assessment of PFOS for thyroid hormonal perturbation in drinking water with the contribution from individual PFOS isomers. The risk quotients (RQs) of individual PFOS isomers indicated that linear PFOS contributed most to the risk among all the target PFOS isomers (83.0%-90.2% of the total PFOS RQ), and that risk from 6m-PFOS (5.2%-11.9% of the total PFOS RQ) was higher than that from other branched PFOS isomers. We found that the risks associated with PFOS in drinking water would be overestimated by 10.0%-91.7% if contributions from individual PFOS isomers were not considered. The results revealed that the PFOS isomer profile and the toxicity of individual PFOS isomers were important factors in health risk assessment of PFOS and should be considered in the future risk assessments.

  12. Excited states of neutron rich Pd from fragmentation

    NASA Astrophysics Data System (ADS)

    Hecht, A. A.; Walters, W. B.; Hoteling, N.; Mantica, P. F.; Becerril, A.; Fleckenstein, T.; Lorusso, G.; Pereira, J.; Pinter, J.; Stoker, J.; Quinn, M.

    2007-04-01

    The neutron rich region approaching N=82 and Z=50 is interesting for nuclear structure and nuclear astrophysics, both as a test of the shell closures far from stability and as the path for r-process nucleosynthesis. This region is difficult to access with fusion-evaporation reactions and novel techniques must be used. At the National Superconducting Cyclotron Laboratory (NSCL) an experiment was recently performed by fragmentation of a Xe beam using a Be target to examine isomers and beta decay from these neutron rich nuclei. The radioisotope fragments passed through several Si planar detectors and were implanted in a double-sided Si strip detector (DSSD) in the Beta Counting System (BCS). Fragments were identified via δE and TOF. Particle emitting decays were tracked in several layers of single sided strip detectors following the DSSD, while the SEGA array surrounding the DSSD was used to collect gamma emission following beta and isomer decay. Several neutron rich nuclei were observed in this experiment, including Ru, Rh, Pd, Ag, Cd, and In. Results on Pd will be discussed.

  13. Differential adsorption of CHON isomers at interstellar grain surfaces

    NASA Astrophysics Data System (ADS)

    Lattelais, M.; Pauzat, F.; Ellinger, Y.; Ceccarelli, C.

    2015-06-01

    Context. The CHON generic chemical formula covers different isomers such as isocyanic acid (HNCO), cyanic acid (HOCN), fulminic acid (HCNO), and isofulminic acid (HONC); the first three have been identified in a large variety of environments in the interstellar medium (ISM). Several phenomena could be at the origin of the observed abundances, such as different pathways of formation and destruction involving gas phase reactions with different possible activation barriers and/or surface processes depending on the local temperature and the nature of the support. Aims: The scope of this article is to shed some light on the interaction of the CHON isomers with interstellar grains as a function of the nature of the surface and to determine the corresponding adsorption energies in order to find whether this phenomenon could play a role in the abundances observed in the ISM. Methods: The question was addressed by means of numerical simulations using first principle periodic density functional theory (DFT) to represent the grain support as a solid of infinite dimension. Results: Regardless of the nature of the model surface (water ice, graphene, silica), two different classes of isomers were identified: weakly bound (HNCO and HCNO) and strongly bound (HOCN and HONC), with the adsorption energies of the latter group being about twice those of the former. The range of the adsorption energies is (from highest to lowest) HOCN > HONC > HNCO > HCNO. They are totally disconnected from the relative stabilities, which range from HNCO > HOCN > HCNO > HONC. Conclusions: The possibility of hydrogen bonding is the discriminating factor in the trapping of CHON species on grain surfaces. Whatever the environment, differential adsorption is effective and its contribution to the molecular abundances should not be ignored. The theoretical adsorption energies provided here could be profitably used for a more realistic modeling of molecule-surfaces interactions.

  14. Structure, dynamics, and energetics of lysobisphosphatidic acid (LBPA) isomers.

    PubMed

    Goursot, A; Mineva, T; Bissig, C; Gruenberg, J; Salahub, D R

    2010-12-02

    Lysobisphosphatidic acid (LBPA), or bis(monoacylglycerol)phosphate, is a very interesting lipid, that is mainly found in late endosomes. It has several intriguing characteristics, which differ from those of other animal glycerophospholipids, that may be related to its specific functions, particularly in the metabolism of cholesterol. Its phosphodiester group is bonded at the sn-1 (sn-1') positions of the glycerols rather than at sn-3 (sn-3'); the position of the two fatty acid chains is still under debate but, increasingly, arguments favor the sn-2, sn-2' position in the native molecule, whereas isolation procedures or acidic conditions lead to the thermodynamically more stable sn-3, sn-3' structure. Because of these peculiar features, it can be expected that LBPA shape and interactions with membrane lipids and proteins are related to its structure at the molecular level. We applied quantum mechanical methods to study the structures and stabilities of the 2,2' and 3,3' LBPA isomers, using a step-by-step procedure from glycerol to precursors (in vitro syntheses) and to the final isoforms. The structures of the two positional LBPA isomers are substantially different, showing that the binding positions of the fatty acid chains on the glycerol backbone determine the shape of the LBPA molecule and thus, possibly, its functions. The 3,3' LBPA structures obtained are more stable with respect to the 2,2' form, as expected from experiment. If one argues that the in vivo synthesis starts from the present glycerol conformers and considering the most stable bis(glycero)phosphate structures, the 2,2' isoform should be the most probable isomer.

  15. Formation of melatonin and its isomer during bread dough fermentation and effect of baking.

    PubMed

    Yılmaz, Cemile; Kocadağlı, Tolgahan; Gökmen, Vural

    2014-04-02

    Melatonin is produced mainly by the pineal gland in vertebrates. Also, melatonin and its isomer are found in foods. Investigating the formation of melatonin and its isomer is of importance during bread dough fermentation and its degradation during baking since bread is widely consumed in high amounts. Formation of melatonin was not significant during dough fermentation. The melatonin isomer content of nonfermented dough was found to be 4.02 ng/g and increased up to 16.71 ng/g during fermentation. Lower amounts of isomer in crumb and crust than dough showed that the thermal process caused a remarkable degree of degradation in melatonin isomer. At the end of the 180 min fermentation Trp decreased by 58%. The results revealed for the first time the formation of a melatonin isomer in bread dough during yeast fermentation.

  16. Isomers of broparoestrol and antiestrogen action: comparison with tamoxifen.

    PubMed

    Edery, M; Barnova, A; Drosdowsky, M; Guggiari, M; Vives, C; Rudali, G

    1985-01-01

    This study compares the relative biological potencies of a known antiestrogen tamoxifen to two triarylethylene compounds which have been shown previously to be potent inhibitors of rodent mammary tumorigenesis. Based on a) uterotrophic and anti-uterotrophic tests, b) indexes of cellularity, and c) protein content, these studies indicate that the trans, as well as the cis, isomers of bromotriphenylethylene are partial estrogen antagonists with no estrogenic effects in rat uteri and partial agonists in mouse uteri, whereas tamoxifen shows partial antiestrogenic/estrogenic effects in rats and is fully estrogenic in mice.

  17. Periodicity of monoisotopic mass isomers and isobars in proteomics.

    PubMed

    Yu, Long; Xiong, Yan-Mei; Polfer, Nick C

    2011-10-15

    We report trends in the theoretically derived number of compositionally distinct peptides (i.e., peptides made up of different amino acid residues) up to a nominal mass of 1000. A total of 21 amino acid residues commonly found in proteomics studies are included in this study, 19 natural, nonisomeric amino acid residues as well as oxidated methione and acetamidated cysteine. The number of possibilities is found to increase in an exponential fashion with increasing nominal mass, and the data show a periodic oscillation that starts at mass ~200 and continues throughout to 1000. Note that similar effects are reported in the companion article on fragment ions from electron capture/transfer dissociation (ECD/ETD) (Mao et al. Anal. Chem.2011, DOI: 10.1021/ac201619t). The spacing of this oscillation is ~15 mass units at lower masses and ~14 mass units at higher nominal masses. This correlates with the most common mass differences between the amino acid building blocks. In other words, some mass differences are more common than others, thus determining the periodicity in this data. From an analytical point of view, nominal masses with a larger number of compositionally distinct peptides include a substantial number of isomers, which cannot be separated based on mass. Consequently, even ultrahigh mass accuracy (i.e., 0.5 ppm) does not lead to a substantially enhanced rate of identification. Conversely, for adjacent nominal masses with a lower number of isomers, moderately accurate mass (i.e., 10 ppm) gives a higher degree of certainty in identification. These effects are limited to the mass range between 200 and 500 Da. At higher masses, the percentage of uniquely identified peptides drops off to close to zero, independent of nominal mass, due the inherently high number of isomers. While the exact number of isobars/isomers at each nominal mass depends on the amino acid building blocks that are considered, the periodicity in the data is found to be remarkably robust; for

  18. Interstellar Isomers: The Importance of Bonding Energy Differences

    NASA Technical Reports Server (NTRS)

    Remijan, Anthony J.; Hollis, J. M.; Lovas, F. J.; Plusquellic, D. F.; Jewell, P. R.

    2005-01-01

    We present strong detections of methyl cyanide (CH3CN), vinyl cyanide (CH2CHCN), ethyl cyanide (CH3CH2CN) and cyanodiacetylene (HC4CN) molecules with the Green Bank Telescope (GBT) toward the Sgr B2(N) molecular cloud. Attempts to detect the corresponding isocyanide isomers were only successful in the case of methyl isocyanide (CH3NC) for its J(sub K) = 1(sub 0) - 0(sub 0) transition, which is the first interstellar report of this line. To determine the spatial distribution of CH3NC, we used archival Berkeley-Illinois-Maryland Association (BIMA) array data for the J(sub K) = 1(sub 0) - 0(sub 0) transitions but no emission was detected. From ab initio calculations, the bonding energy difference between the cyanide and isocyanide molecules is greater than 8500 per centimeter (greater than 12,000 K). Thus, cyanides are the more stable isomers and would likely be formed more preferentially over their isocyanide counterparts. That we detect CH3NC emission with a single antenna (Gaussian beamsize(omega(sub B))=1723 arcsec(sup 2)) but not with an interferometer (omega(sub b)=192 arcsec(sup 2)), strongly suggests that CH3NC has a widespread spatial distribution toward the Sgr B2(N) region. Other investigators have shown that CH3CN is present both in the LMH hot core of Sgr B2(N) and in the surrounding medium, while we have shown that CH3NC appears to be deficient in the LMH hot core. Thus, largescale, non-thermal processes in the surrounding medium may account for the conversion of CH3CN to CH3NC while the LMH hot core, which is dominated by thermal processes, does not produce a significant amount of CH3NC. Ice analog experiments by other investigators have shown that radiation bombardment of CH3CN can produce CH3NC, thus supporting our observations. We conclude that isomers separated by such large bonding energy differences are distributed in different interstellar environments, making the evaluation of column density ratios between such isomers irrelevant unless it can

  19. Multiquasiparticle states in the neutron-rich nucleus 174Tm

    NASA Astrophysics Data System (ADS)

    Hughes, R. O.; Lane, G. J.; Dracoulis, G. D.; Byrne, A. P.; Nieminen, P.; Watanabe, H.; Carpenter, M. P.; Chowdhury, P.; Janssens, R. V. F.; Kondev, F. G.; Lauritsen, T.; Seweryniak, D.; Zhu, S.

    2013-07-01

    Deep inelastic and transfer reactions with an 820-MeV, 136Xe beam and various ytterbium and lutetium targets have been employed to study high-spin structures in the neutron-rich thulium isotopes beyond 171Tm. Results in the doubly odd nucleus, 174Tm, include the identification of numerous new two- and four-quasiparticle intrinsic states including several isomers below 1 MeV, and the observation of the Kπ=4- ground state rotational band populated via direct decay from a τ=153(10)-μs, Kπ=14- isomer at 2092 keV. The 398-keV, M1 transition linking the isomer and ground state band is abnormally fast for a highly forbidden, ΔK=10 decay. This relative enhancement is explained in terms of mixing of the 13- level with the nearby 13- member of a Kπ=8- rotational band, with an interaction strength of V ≈ 1.4 keV. Multiquasiparticle calculations are compared with the observed states.

  20. Identification of absolute geometries of cis and trans molecular isomers by Coulomb Explosion Imaging

    PubMed Central

    Ablikim, Utuq; Bomme, Cédric; Xiong, Hui; Savelyev, Evgeny; Obaid, Razib; Kaderiya, Balram; Augustin, Sven; Schnorr, Kirsten; Dumitriu, Ileana; Osipov, Timur; Bilodeau, René; Kilcoyne, David; Kumarappan, Vinod; Rudenko, Artem; Berrah, Nora; Rolles, Daniel

    2016-01-01

    An experimental route to identify and separate geometric isomers by means of coincident Coulomb explosion imaging is presented, allowing isomer-resolved photoionization studies on isomerically mixed samples. We demonstrate the technique on cis/trans 1,2-dibromoethene (C2H2Br2). The momentum correlation between the bromine ions in a three-body fragmentation process induced by bromine 3d inner-shell photoionization is used to identify the cis and trans structures of the isomers. The experimentally determined momentum correlations and the isomer-resolved fragment-ion kinetic energies are matched closely by a classical Coulomb explosion model. PMID:27910943

  1. Isomer-Specific Binding Affinity of Perfluorooctanesulfonate (PFOS) and Perfluorooctanoate (PFOA) to Serum Proteins.

    PubMed

    Beesoon, Sanjay; Martin, Jonathan W

    2015-05-05

    Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are among the most prominent contaminants in human serum, and these were historically manufactured as technical mixtures of linear and branched isomers. The isomers display unique pharmacokinetics in humans and in animal models, but molecular mechanisms underlying isomer-specific PFOS and PFOA disposition have not previously been studied. Here, ultrafiltration devices were used to examine (i) the dissociation constants (Kd) of individual PFOS and PFOA isomers with human serum albumin (HSA) and (ii) relative binding affinity of isomers in technical mixtures spiked to whole calf serum and human serum. Measurement of HSA Kd's demonstrated that linear PFOS (Kd=8(±4)×10(-8) M) was much more tightly bound than branched PFOS isomers (Kd range from 8(±1)×10(-5) M to 4(±2)×10(-4) M). Similarly, linear PFOA (Kd=1(±0.9)×10(-4) M) was more strongly bound to HSA compared to branched PFOA isomers (Kd range from 4(±2)×10(-4) M to 3(±2)×10(-4) M). The higher binding affinities of linear PFOS and PFOA to total serum protein were confirmed when both calf serum and human serum were spiked with technical mixtures. Overall, these data provide a mechanistic explanation for the longer biological half-life of PFOS in humans, compared to PFOA, and for the higher transplacental transfer efficiencies and renal clearance of branched PFOS and PFOA isomers, compared to the respective linear isomer.

  2. Identification of absolute geometries of cis and trans molecular isomers by Coulomb Explosion Imaging

    NASA Astrophysics Data System (ADS)

    Ablikim, Utuq; Bomme, Cédric; Xiong, Hui; Savelyev, Evgeny; Obaid, Razib; Kaderiya, Balram; Augustin, Sven; Schnorr, Kirsten; Dumitriu, Ileana; Osipov, Timur; Bilodeau, René; Kilcoyne, David; Kumarappan, Vinod; Rudenko, Artem; Berrah, Nora; Rolles, Daniel

    2016-12-01

    An experimental route to identify and separate geometric isomers by means of coincident Coulomb explosion imaging is presented, allowing isomer-resolved photoionization studies on isomerically mixed samples. We demonstrate the technique on cis/trans 1,2-dibromoethene (C2H2Br2). The momentum correlation between the bromine ions in a three-body fragmentation process induced by bromine 3d inner-shell photoionization is used to identify the cis and trans structures of the isomers. The experimentally determined momentum correlations and the isomer-resolved fragment-ion kinetic energies are matched closely by a classical Coulomb explosion model.

  3. Hydrogen rich gas generator

    NASA Technical Reports Server (NTRS)

    Houseman, J. (Inventor)

    1976-01-01

    A process and apparatus is described for producing a hydrogen rich gas by introducing a liquid hydrocarbon fuel in the form of a spray into a partial oxidation region and mixing with a mixture of steam and air that is preheated by indirect heat exchange with the formed hydrogen rich gas, igniting the hydrocarbon fuel spray mixed with the preheated mixture of steam and air within the partial oxidation region to form a hydrogen rich gas.

  4. Rich catalytic injection

    DOEpatents

    Veninger, Albert

    2008-12-30

    A gas turbine engine includes a compressor, a rich catalytic injector, a combustor, and a turbine. The rich catalytic injector includes a rich catalytic device, a mixing zone, and an injection assembly. The injection assembly provides an interface between the mixing zone and the combustor. The injection assembly can inject diffusion fuel into the combustor, provides flame aerodynamic stabilization in the combustor, and may include an ignition device.

  5. The prenucleosome, a stable conformational isomer of the nucleosome.

    PubMed

    Fei, Jia; Torigoe, Sharon E; Brown, Christopher R; Khuong, Mai T; Kassavetis, George A; Boeger, Hinrich; Kadonaga, James T

    2015-12-15

    Chromatin comprises nucleosomes as well as nonnucleosomal histone-DNA particles. Prenucleosomes are rapidly formed histone-DNA particles that can be converted into canonical nucleosomes by a motor protein such as ACF. Here we show that the prenucleosome is a stable conformational isomer of the nucleosome. It consists of a histone octamer associated with ∼ 80 base pair (bp) of DNA, which is located at a position that corresponds to the central 80 bp of a nucleosome core particle. Monomeric prenucleosomes with free flanking DNA do not spontaneously fold into nucleosomes but can be converted into canonical nucleosomes by an ATP-driven motor protein such as ACF or Chd1. In addition, histone H3K56, which is located at the DNA entry and exit points of a canonical nucleosome, is specifically acetylated by p300 in prenucleosomes relative to nucleosomes. Prenucleosomes assembled in vitro exhibit properties that are strikingly similar to those of nonnucleosomal histone-DNA particles in the upstream region of active promoters in vivo. These findings suggest that the prenucleosome, the only known stable conformational isomer of the nucleosome, is related to nonnucleosomal histone-DNA species in the cell.

  6. Calculations of long-lived isomer production in neutron reactions

    SciTech Connect

    Chadwick, M.B.; Young, P.G.

    1991-01-01

    We have carried out theoretical calculations for the production of the long-lived isomers {sup 93m}Nb({1/2}{sup {minus}}, 16y), {sup 121m}Sn(11/2{minus}, 55 yr), {sup 166m}Ho(7-, 1200 yr), {sup 184m}Re(8+, 165 d), {sup 186m}Re(8+, 2{times}10{sup 5} yr), {sup 178m}Hf(16+, 31 yr), {sup 179m}Hf(25/2-, 25 d), {sup 192m}Ir(9+, 241 yr), all of which pose potential radiation activation problems in nuclear fusion reactors. We consider (n, 2n), (n,n{prime}), and (n, {gamma}) production modes and compare our results both with experimental data (where available) and systematic. We also investigate the dependence of the isomeric cross section ratio on incident neutron energy for the isomers under consideration. The statistical Hauser-Feshbach plus preequilibrium code GNASH was used for the calculations. Where discrete state experimental information was lacking, rotational band members above the isomeric state, which can be justified theoretically but have not been experimentally resolved, were reconstructed. 16 refs., 8 figs.

  7. Gamma-ray spectroscopy of the ^238U shape isomer.

    NASA Astrophysics Data System (ADS)

    Hauschild, K.; Bauer, R. W.; Becker, J. A.; Bernstein, L. A.; Britt, H. C.; Younes, W.; Fotiades, N.

    1997-04-01

    The γ--rays de--exciting the fission isomers ^236U and ^238U are very different despite similar excitation energies, lifetimes and low--lying yrast structures. The predominant γ--ray decay branch for ^236U^m is a 1.783 MeV E1 transition (J. Schirmer, et al., Phys. Rev. Lett. 63), 2196 (1989); and Refs. therein., while ^238U^m is depopulated by a 2.513 MeV E2 γ-ray (J. Kantele, et al., Phys. Rev. C 29), 1693 (1984); and Refs. therein.. Approximately 65% of the γ--branch de-exciting ^238U^m remains to be identified. To determine the multipolarity of the remaining γ-branch out of ^238U^m we used the Gammasphere array at LBNL and the ^238U(d,pn) reaction at Ed = 20 MeV. A search for excited states in the 2^nd well has also been conducted. Preliminary results will be presented, and the γ--decay of the shape isomers discussed in context with the recent A ~190 SD decay--out results (T. L. Khoo, et al., Phys. Rev. Lett. 76), 1583 (1996); A. Lopez-Martens, et al., Phys. Lett. B380, 18 (1996); K. Hauschild, et al., submitted to Phys. Rev. C (1996)..

  8. Chemical Simulations of Prebiotic Molecules: Interstellar Ethanimine Isomers

    NASA Astrophysics Data System (ADS)

    Quan, Donghui; Herbst, Eric; Corby, Joanna F.; Durr, Allison; Hassel, George

    2016-06-01

    The E- and Z-isomers of ethanimine (CH3CHNH) were recently detected toward the star-forming region Sagittarius (Sgr) B2(N) using the Green Bank Telescope PRIMOS cm-wave spectral data, and imaged by the Australia Telescope Compact Array. Ethanimine is not reported in the hot cores of Sgr B2, but only in gas that absorbs at +64 and +82 km s-1 in the foreground of continuum emission generated by H ii regions. The ethanimine isomers can serve as precursors of the amino acid alanine and may play important roles in forming biological molecules in the interstellar medium. Here we present a study of the chemistry of ethanimine using a gas-grain simulation based on rate equations, with both isothermal and warm-up conditions. In addition, the density, kinetic temperature, and cosmic ray ionization rate have been varied. For a variety of physical conditions in the warm-up models for Sgr B2(N) and environs, the simulations show reasonable agreement with observationally obtained abundances. Isothermal models of translucent clouds along the same line of sight yield much lower abundances, so that ethanimine would be much more difficult to detect in these sources despite the fact that other complex molecules have been detected there.

  9. Research: Rags to Rags? Riches to Riches?

    ERIC Educational Resources Information Center

    Bracey, Gerald W.

    2004-01-01

    Everyone has read about what might be called the "gold gap"--how the rich in this country are getting richer and controlling an ever-larger share of the nation's wealth. The Century Foundation has started publishing "Reality Check", a series of guides to campaign issues that sometimes finds gaps in these types of cherished delusions. The guides…

  10. New isomer and decay half-life of {sup 115}Ru

    SciTech Connect

    Kurpeta, J.; Plochocki, A.; Rissanen, J.; Elomaa, V.-V.; Eronen, T.; Hakala, J.; Jokinen, A.; Kankainen, A.; Karvonen, P.; Moore, I. D.; Penttilae, H.; Saastamoinen, A.; Weber, C.; Aeystoe, J.; Urban, W.; Malkiewicz, T.

    2010-12-15

    Exotic, neutron-rich nuclei of mass A=115 produced in proton-induced fission of {sup 238}U were extracted using the IGISOL mass separator. The beam of isobars was transferred to the JYFLTRAP Penning trap system for further separation to the isotopic level. Monoisotopic samples of {sup 115}Ru nuclei were used for {gamma}and {beta} coincidence spectroscopy. In {sup 115}Ru we have observed excited levels, including an isomer with a half-life of 76(6) ms and (7/2{sup -}) spin and parity. The first excited 61.7-keV level in {sup 115}Ru with spins and parity (3/2{sup +}) may correspond to an oblate 3/2{sup +}[431] Nilsson orbital. A half-life of 318(19) ms for the {beta}{sup -} decay of the (1/2{sup +}) ground state in {sup 115}Ru has been firmly established in two independent measurements, a value which is significantly shorter than that previously reported.

  11. Peptide kinetics from picoseconds to microseconds using boxed molecular dynamics: power law rate coefficients in cyclisation reactions.

    PubMed

    Shalashilin, Dmitrii V; Beddard, Godfrey S; Paci, Emanuele; Glowacki, David R

    2012-10-28

    Molecular dynamics (MD) methods are increasingly widespread, but simulation of rare events in complex molecular systems remains a challenge. We recently introduced the boxed molecular dynamics (BXD) method, which accelerates rare events, and simultaneously provides both kinetic and thermodynamic information. We illustrate how the BXD method may be used to obtain high-resolution kinetic data from explicit MD simulations, spanning picoseconds to microseconds. The method is applied to investigate the loop formation dynamics and kinetics of cyclisation for a range of polypeptides, and recovers a power law dependence of the instantaneous rate coefficient over six orders of magnitude in time, in good agreement with experimental observations. Analysis of our BXD results shows that this power law behaviour arises when there is a broad and nearly uniform spectrum of reaction rate coefficients. For the systems investigated in this work, where the free energy surfaces have relatively small barriers, the kinetics is very sensitive to the initial conditions: strongly non-equilibrium conditions give rise to power law kinetics, while equilibrium initial conditions result in a rate coefficient with only a weak dependence on time. These results suggest that BXD may offer us a powerful and general algorithm for describing kinetics and thermodynamics in chemical and biochemical systems.

  12. Artifact Free and Detection Profile Independent Higher Order Fluorescence Correlation Spectroscopy for Microsecond Resolved Kinetics. 2. Mixtures and Reactions.

    PubMed

    Abdollah-Nia, Farshad; Gelfand, Martin P; Van Orden, Alan K

    2017-02-09

    Fluorescence correlation spectroscopy (FCS) is a primary tool in the time-resolved analysis of non-reacting or reacting molecules in solution, based on fluorescence intensity fluctuations. However, conventional FCS alone is insufficient for complete determination of reaction or mixture parameters. In an accompanying article, a technique for computation of artifact-free higher-order correlations with microsecond time resolution was described. Here, we demonstrate applications of the technique to analyze systems of fast and slow reactions. As an example of slow- or non-reacting systems, the technique is applied to resolve two-component mixtures of labeled oligonucleotides. Next, the protonation reaction of fluorescein isothiocyanate (FITC) in phosphate buffer is analyzed as an example of fast reactions (relaxation time <1 μs ). By reference to an (apparent) non-reacting system, the simple factorized form of cumulant-based higher-order correlations is exploited to remove the dependence on the molecular detection function (MDF). Therefore, there is no need to model and characterize the experimental MDF, and the precision and the accuracy of the technique are enhanced. It is verified that higher-order correlation analysis enables complete and simultaneous determination of number and brightness parameters of mixing or reacting molecules, the reaction relaxation time, and forward and reverse reaction rates.

  13. Microsecond simulations of DNA and ion transport in nanopores with novel ion-ion and ion-nucleotides effective potentials.

    PubMed

    De Biase, Pablo M; Markosyan, Suren; Noskov, Sergei

    2014-04-05

    We developed a novel scheme based on the grand-canonical Monte Carlo/Brownian dynamics simulations and have extended it to studies of ion currents across three nanopores with the potential for single-stranded DNA (ssDNA) sequencing: solid-state nanopore Si₃N₄, α-hemolysin, and E111N/M113Y/K147N mutant. To describe nucleotide-specific ion dynamics compatible with ssDNA coarse-grained model, we used the inverse Monte Carlo protocol, which maps the relevant ion-nucleotide distribution functions from all-atom molecular dynamics (MD) simulations. Combined with the previously developed simulation platform for Brownian dynamics simulations of ion transport, it allows for microsecond- and millisecond-long simulations of ssDNA dynamics in the nanopore with a conductance computation accuracy that equals or exceeds that of all-atom MD simulations. In spite of the simplifications, the protocol produces results that agree with the results of previous studies on ion conductance across open channels and provide direct correlations with experimentally measured blockade currents and ion conductances that have been estimated from all-atom MD simulations.

  14. Physical and biological mechanisms of nanosecond- and microsecond-pulsed FE-DBD plasma interaction with biological objects

    NASA Astrophysics Data System (ADS)

    Dobrynin, Danil

    2013-09-01

    Mechanisms of plasma interaction with living tissues and cells can be quite complex, owing to the complexity of both the plasma and the tissue. Thus, unification of all the mechanisms under one umbrella might not be possible. Here, analysis of interaction of floating electrode dielectric barrier discharge (FE-DBD) with living tissues and cells is presented and biological and physical mechanisms are discussed. In physical mechanisms, charged species are identified as the major contributors to the desired effect and a mechanism of this interaction is proposed. Biological mechanisms are also addressed and a hypothesis of plasma selectivity and its effects is offered. Spatially uniform nanosecond and sub-nanosecond short-pulsed dielectric barrier discharge plasmas are gaining popularity in biological and medical applications due to their increased uniformity, lower plasma temperature, lower surface power density, and higher concentration of the active species produced. In this presentation we will compare microsecond pulsed plasmas with nanosecond driven systems and their applications in biology and medicine with specific focus on wound healing and tissue regeneration. Transition from negative to positive streamer will be discussed with proposed hypothesis of uniformity mechanisms of positive streamer and the reduced dependence on morphology and surface chemistry of the second electrode (human body) being treated. Uniform plasma offers a more uniform delivery of active species to the tissue/surface being treated thus leading to better control over the biological results.

  15. Membrane Permeabilization of Pathogenic Yeast in Alternating Sub-microsecond Electromagnetic Fields in Combination with Conventional Electroporation.

    PubMed

    Novickij, Vitalij; Lastauskienė, Eglė; Švedienė, Jurgita; Grainys, Audrius; Staigvila, Gediminas; Paškevičius, Algimantas; Girkontaitė, Irutė; Zinkevičienė, Auksė; Markovskaja, Svetlana; Novickij, Jurij

    2017-02-25

    Recently, a novel contactless treatment method based on high-power pulsed electromagnetic fields (PEMF) was proposed, which results in cell membrane permeabilization effects similar to electroporation. In this work, a new PEMF generator based on multi-stage Marx circuit topology, which is capable of delivering 3.3 T, 0.19 kV/cm sub-microsecond pulses was used to permeabilize pathogenic yeast Candida albicans separately and in combination with conventional square wave electroporation (8-17 kV/cm, 100 μs). Bursts of 10, 25, and 50 PEMF pulses were used. The yeast permeabilization rate was evaluated using flow cytometric analysis and propidium iodide (PI) assay. A statistically significant (P < 0.05) combinatorial effect of electroporation and PEMF treatment was detected. Also the PEMF treatment (3.3 T, 50 pulses) resulted in up to 21% loss of yeast viability, and a dose-dependent additive effect with pulsed electric field was observed. As expected, increase of the dB/dt and subsequently the induced electric field amplitude resulted in a detectable effect solely by PEMF, which was not achievable before for yeasts in vitro.

  16. FAST TRACK COMMUNICATION: Contrasting characteristics of sub-microsecond pulsed atmospheric air and atmospheric pressure helium-oxygen glow discharges

    NASA Astrophysics Data System (ADS)

    Walsh, J. L.; Liu, D. X.; Iza, F.; Rong, M. Z.; Kong, M. G.

    2010-01-01

    Glow discharges in air are often considered to be the ultimate low-temperature atmospheric pressure plasmas for numerous chamber-free applications. This is due to the ubiquitous presence of air and the perceived abundance of reactive oxygen and nitrogen species in air plasmas. In this paper, sub-microsecond pulsed atmospheric air plasmas are shown to produce a low concentration of excited oxygen atoms but an abundance of excited nitrogen species, UV photons and ozone molecules. This contrasts sharply with the efficient production of excited oxygen atoms in comparable helium-oxygen discharges. Relevant reaction chemistry analysed with a global model suggests that collisional excitation of O2 by helium metastables is significantly more efficient than electron dissociative excitation of O2, electron excitation of O and ion-ion recombination. These results suggest different practical uses of the two oxygen-containing atmospheric discharges, with air plasmas being well suited for nitrogen and UV based chemistry and He-O2 plasmas for excited atomic oxygen based chemistry.

  17. Numerical investigation of temperature field Induced by dual wavelength lasers in sub-microsecond laser annealing technology for insulated gate bipolar transistor

    NASA Astrophysics Data System (ADS)

    Cui, GuoDong; Ma, Mingying; Wang, Fan; Sun, Gang; Lan, Yanping; Xu, Wen

    2015-07-01

    To enhance the performance of the Insulated Gate Bipolar Transistor (IGBT), sub-microsecond laser annealing (LA) is propitious to achieve maximal dopant activation with minimal diffusion. In this work, two different lasers are used as annealing resource: a continuous 808 nm laser with larger spot is applied to preheat the wafer and another sub-microsecond pulsed 527 nm laser is responsible to activate the dopant. To optimize the system's performance, a physical model is presented to predict the thermal effect of two laser fields interacting on wafer. Using the Finite-Element method (FEM), we numerically investigate the temperature field induced by lasers in detail. The process window corresponding to the lasers is also acquired which can satisfy the requirements of the IGBT's annealing.

  18. Experimental characterization of a micro-hole drilling process with short micro-second pulses by a CW single-mode fiber laser

    NASA Astrophysics Data System (ADS)

    Tu, Jay; Paleocrassas, Alexander G.; Reeves, Nicholas; Rajule, Nilesh

    2014-04-01

    Laser ablation with pulse durations in a few microseconds is a viable solution for micro-hole drilling applications which require large material removal rate (MRR) with moderate hole quality. However, the body of work regarding short microsecond laser drilling/ablation is small. The objective of this paper is to experimentally characterize this short micro-second laser micro-hole drilling technique using a 300 W, CW, single-mode fiber laser. This CW fiber laser is controlled to produce modulated pulses from 1 μs to 8 μs and these modulated laser pulses have a unique profile which contains an initial spike with a peak power of 1500 W for 1 μs, followed by the steady state power of 300 W. Because of its excellent beam quality, the laser beam produced by this fiber laser can be focused to a small spot size of 10 μm to achieve very high power density up to 1.9 GW/cm2. With one single laser pulse at approximately 1 μs, a blind hole of 167 μm in depth and 23 μm in opening diameter can be created in a stainless substrate. The experimental characterization of this micro-hole drilling process includes laser control, laser beam characterization, hole formation, photodiode measurements of the vapor intensity, high-speed photography of vapor/plasma formation, and spectroscopic measurements of plasma. The results show that, due to very high irradiance of the fiber laser beam, the absorbed energy not only is sufficient to melt and vaporize the material, but also is able to dissociate vapor into intense plasma at temperatures over 16,000 K. The hole drilling mechanism by this short microsecond laser ablation is due to a combination of adiabatic evaporation and ejection of fine droplets.

  19. C3H3+ isomers: temperature dependencies of production in the H3+ reaction with allene and loss by dissociative recombination with electrons.

    PubMed

    McLain, Jason L; Poterya, Viktoriya; Molek, Christopher D; Jackson, Douglas M; Babcock, Lucia M; Adams, Nigel G

    2005-06-16

    A technique has been developed to simultaneously determine recombination rate coefficients, alpha e, and initial concentrations of ion types that coexist in a flowing afterglow plasma. This was tested using the H3(+) + allene reaction in which two different C3H3+ isomers are produced. Use of an electrostatic Langmuir probe enabled the C3H3+ isomer branching ratios for propargyl and cyclic C3H3+ from this allene reaction and their alpha e to be determined over the temperature range 172-489 K. The study showed that the cyclic C3H3+ to propargyl C3H3+ branching ratios from the allene reaction varied from 50/50 at 172 K to 18/82 at 489 K. Over this temperature range, the alpha e for both isomers change only slightly. The room temperature alpha e values for propargyl and cyclic C3H3+ are (1.15 +/- 0.2) x 10(-7) and (8.00 +/- 0.1) x 10(-7) cm3/s, respectively. The data are discussed relative to current theories and in relation to fuel-rich flame chemistry, interstellar molecular synthesis, and modeling of Titan's atmosphere.

  20. A Highly Sensitive Diketopyrrolopyrrole-Based Ambipolar Transistor for Selective Detection and Discrimination of Xylene Isomers.

    PubMed

    Wang, Bin; Huynh, Tan-Phat; Wu, Weiwei; Hayek, Naseem; Do, Thu Trang; Cancilla, John C; Torrecilla, Jose S; Nahid, Masrur Morshed; Colwell, John M; Gazit, Oz M; Puniredd, Sreenivasa Reddy; McNeill, Christopher R; Sonar, Prashant; Haick, Hossam

    2016-06-01

    An ambipolar poly(diketopyrrolopyrrole-terthiophene)-based field-effect transistor (FET) sensitively detects xylene isomers at low ppm levels with multiple sensing features. Combined with pattern-recognition algorithms, a sole ambipolar FET sensor, rather than arrays of sensors, can discriminate highly similar xylene structural isomers from one another.

  1. Theoretical Prediction of the Structures and Energies of Olympicene and its Isomers

    NASA Astrophysics Data System (ADS)

    Valentine, Andrew J. S.; Mazziotti, David A.

    2013-10-01

    Pentacene, a linear five-ringed polyaromatic hydrocarbon, has recently been used as an organic semiconductor in field-effect transistors. The recently synthesized olympicene molecule, so named because of its resemblance to the olympic rings, is a more compact five-ringed structure. This paper offers the first theoretical study of the kinetic stability of olympicene and its isomers. We use the parametric two-electron reduced density matrix (2-RDM) method, which takes the 2-RDM as the basic variable in lieu of the traditional wave function in calculations [ Mazziotti, D. A. Phys. Rev. Lett. 2008, 101, 253002 ]. Our calculations demonstrate that olympicene-s isomers may be separated into aromatic and diradical isomers, the latter of which require accurate treatment of strong electron correlation to detect multireference character. Albeit formally a single-reference method, the parametric 2-RDM captures the multireference correlation of the diradical isomers; relative to olympicene, the 2-RDM predicts five diradical isomers that are 16-22 kcal/mol lower in energy than those from coupled cluster with single and double excitations-a significant change that causes these isomers to be stable to dissociation by 2-20 kcal/mol. We characterize the transition states between olympicene-s isomers, observe differences in aromaticity among the different isomers, and compare the electronic properties of olympicene to those of pentacene. The olympicene molecule has the potential to complement pentacene as an organic semiconductor.

  2. Comparison of some specific polychlorinated biphenyl isomers in human and monkey milk

    SciTech Connect

    Mes, J.; Marchand, L.

    1987-11-01

    The presence and levels of polychlorinated biphenyls (PCBs) in monkey milk have been reported earlier as part of studies which investigated the overall toxicity of PCBs in commercial Aroclors. Some of this information has served as a basis for an estimation of the potential health hazard of PCB contaminated breast milk to human infants. To further support such extrapolation from one primate situation to another, it would be desirable to know not only the levels of PCBs in the milk of these primates, but also the isomeric distribution in order to better evaluate the contribution of each isomer to the overall toxicity. A large concentration in breast milk of an isomer of relatively low toxicity may have the same effect on an infant as a smaller concentration of a highly toxic isomer. This paper compares the relative amounts of 29 selected PCB isomers in human milk and monkey milk samples. The selection of isomers was based on the most prevalent PCB isomers in human milk and represented approximately 80% of all reported isomers. In addition, Aroclor 1254, whose toxicity in monkeys has been investigated recently by several investigators, was analyzed for the same 29 selected PCB isomers.

  3. Fuel properties of heptadecene isomers prepared via tandem isomerization-decarboxylation of oleic acid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Heptadecene isomers were prepared via tandem isomerization-decarboxylation of oleic acid using catalytic triruthenium dodecacarbonyl [Ru3(CO)12]. Chromatographic and spectroscopic characterization of the isolated heptadecene mixture indicated that it consisted of 96% internal trans isomers and 4% ar...

  4. Synthesis of the optical isomers of a new anticholinergic drug, penehyclidine hydrochloride (8018).

    PubMed

    Han, Xiang-Yu; Liu, He; Liu, Chun-He; Wu, Bo; Chen, Lan-Fu; Zhong, Bo-Hua; Liu, Ke-Liang

    2005-04-15

    A practical diastereoselective synthetic method for 8018 enantiopure isomers is described. The intramolecular asymmetric epoxidation of mono-sulfonate 4 was applied for the execution of the synthesis of the key chiral building block for the first time. The isomers were obtained with 70-76% yields in 99-100% ee.

  5. 40 CFR 180.418 - Cypermethrin and an isomer zeta-cypermethrin; tolerances for residues.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Cypermethrin and an isomer zeta-cypermethrin; tolerances for residues. 180.418 Section 180.418 Protection of Environment ENVIRONMENTAL... FOOD Specific Tolerances § 180.418 Cypermethrin and an isomer zeta-cypermethrin; tolerances...

  6. 40 CFR 180.418 - Cypermethrin and an isomer zeta-cypermethrin; tolerances for residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Cypermethrin and an isomer zeta-cypermethrin; tolerances for residues. 180.418 Section 180.418 Protection of Environment ENVIRONMENTAL... FOOD Specific Tolerances § 180.418 Cypermethrin and an isomer zeta-cypermethrin; tolerances...

  7. Enantiomers of a nonylphenol isomer: absolute configurations and estrogenic potencies.

    PubMed

    Zhang, Haifeng; Oppel, Iris M; Spiteller, Michael; Guenther, Klaus; Boehmler, Gabriele; Zuehlke, Sebastian

    2009-02-01

    Enantiomers of 4-(1,1,2-trimethylhexyl)phenol, a chiral isomer of the endocrine disrupting chemical nonylphenol, have been resolved and isolated by preparative chiral HPLC. The absolute configurations of the enantiomers were then determined by an X-ray crystallographic study of the (-)-camphanoyl derivative of the first eluted enantiomer NP(35)E1. The first enantiomer (NP(35)E1) and the second enantiomer (NP(35)E2) eluted were found to have the S and R absolute configurations, respectively. The estrogenic potencies of the S and R enantiomers were tested by the E-screen assay. A slight difference was observed in the relative proliferative effect between the S enantiomer and R enantiomer in the E-screen assay.

  8. Social isomers of picolines in a small space.

    PubMed

    Ajami, Dariush; Theodorakopoulos, Giannoula; Petsalakis, Ioannis D; Rebek, Julius

    2013-12-09

    Encapsulation complexes permit the observation of molecules under conditions of limited motion. Inside capsules, molecular encounters are prolonged, prearranged, and protected from the medium, in contrast to the short-lived and random encounters that occur in bulk solution. Herein, the interaction of α-, β-, and γ-picolines in a cylindrical capsule is described. Two picolines were taken up, and NMR spectra indicated dynamic combinations of various social isomers. The stabilities of the complexes are interpreted through computational methods. The shape of the space in the capsule allowed the alignment of molecules and revealed delicate, atom-to-atom interactions and attractive forces that elude observation in dilute solution. These weak forces were amplified in the isolated small space of the capsule.

  9. Theoretical study of structural patterns in CH₂OP₂ isomers.

    PubMed

    Septelean, Raluca; Petrar, Petronela Maria; Gabriela, Nemes; Escudié, Jean; Silaghi-Dumitrescu, Ioan

    2011-07-01

    DFT calculations have been performed on the derivatives of formula CH₂OP₂ to determine their total energy, the relative energy between the isomers and their geometry. Among compounds with a P-C-P linkage, the most stable one is the 2-hydroxy-1,2-diphosphirene II.1, a three-membered heterocycle with a P=C unsaturation. The phosphavinylidene(oxo)phosphorane HP=C=P(O)H IV.5 (which has the same skeleton as the experimentally obtained Mes*P=C=P(O)Mes*) lies 36.30 kcal mol⁻¹ above it. The least stable compounds are carbenes; the singlet carbenes are more stable than the triplet ones.

  10. Communication: "Position" does matter: The photofragmentation of the nitroimidazole isomers

    NASA Astrophysics Data System (ADS)

    Bolognesi, P.; Casavola, A. R.; Cartoni, A.; Richter, R.; Markus, P.; Borocci, S.; Chiarinelli, J.; Tošić, S.; Sa'adeh, H.; Masič, M.; Marinković, B. P.; Prince, K. C.; Avaldi, L.

    2016-11-01

    A combined experimental and theoretical approach has been used to disentangle the fundamental mechanisms of the fragmentation of the three isomers of nitroimidazole induced by vacuum ultra-violet (VUV) radiation, namely, 4-, 5-, and 2-nitroimidazole. The results of mass spectrometry as well as photoelectron-photoion coincidence spectroscopy display striking differences in the radiation-induced decomposition of the different nitroimidazole radical cations. Based on density functional theory (DFT) calculations, a model is proposed which fully explains such differences, and reveals the subtle fragmentation mechanisms leading to the release of neutral species like NO, CO, and HCN. Such species have a profound impact in biological media and may play a fundamental role in radiosensitising mechanisms during radiotherapy.

  11. Lifetime Measurement of the 229Th nuclear isomer

    NASA Astrophysics Data System (ADS)

    Seiferle, Benedict; von der Wense, Lars; Thirolf, Peter G.

    2017-01-01

    The first excited isomeric state of 229Th possesses the lowest energy among all known excited nuclear states. The expected energy is accessible with today's laser technology and in principle allows for a direct optical laser excitation of the nucleus. The isomer decays via three channels to its ground state (internal conversion, γ decay, and bound internal conversion), whose strengths depend on the charge state of Thm229 . We report on the measurement of the internal-conversion decay half-life of neutral Thm229 . A half-life of 7 ±1 μ s has been measured, which is in the range of theoretical predictions and, based on the theoretically expected lifetime of ≈1 04 s of the photonic decay channel, gives further support for an internal conversion coefficient of ≈1 09, thus constraining the strength of a radiative branch in the presence of internal conversion.

  12. Static and Dynamic Nanosheets from Selective Assembly of Geometric Macrocycle Isomers.

    PubMed

    Wang, Yanqiu; Kim, Yongju; Lee, Myongsoo

    2016-10-10

    In contrast to the significant advances that have been made in the construction of two-dimensional (2D) nanostructures, the rational modification from static to dynamic 2D sheets remains a great challenge. Static and dynamic sheets formed from selective self-assembly of geometric macrocycle isomers based on anthracene units are presented. The self-assembly of the cis isomer generates static planar sheets, whereas the trans isomer forms dynamic rolled sheets which are reversibly unrolled upon stimulation by a thermal signal. Furthermore, the mixed solution of the two isomers exhibits self-sorting behavior, generating the coexistence of the two independent self-assembled structures, the planar sheets and the folded scrolls. The self-sorted supramolecular objects with considerable shape and size differences are able to be readily separated, one isomer from the other.

  13. Structures of cage, prism, and book isomers of water hexamer from broadband rotational spectroscopy.

    PubMed

    Pérez, Cristóbal; Muckle, Matt T; Zaleski, Daniel P; Seifert, Nathan A; Temelso, Berhane; Shields, George C; Kisiel, Zbigniew; Pate, Brooks H

    2012-05-18

    Theory predicts the water hexamer to be the smallest water cluster with a three-dimensional hydrogen-bonding network as its minimum energy structure. There are several possible low-energy isomers, and calculations with different methods and basis sets assign them different relative stabilities. Previous experimental work has provided evidence for the cage, book, and cyclic isomers, but no experiment has identified multiple coexisting structures. Here, we report that broadband rotational spectroscopy in a pulsed supersonic expansion unambiguously identifies all three isomers; we determined their oxygen framework structures by means of oxygen-18-substituted water (H(2)(18)O). Relative isomer populations at different expansion conditions establish that the cage isomer is the minimum energy structure. Rotational spectra consistent with predicted heptamer and nonamer structures have also been identified.

  14. An inconvenient influence of iridium(III) isomer on OLED efficiency.

    PubMed

    Baranoff, Etienne; Bolink, Henk J; De Angelis, Filippo; Fantacci, Simona; Di Censo, Davide; Djellab, Karim; Grätzel, Michael; Nazeeruddin, Md Khaja

    2010-10-14

    The recently reported heteroleptic cyclometallated iridium(III) complex [Ir(2-phenylpyridine)(2)(2-carboxy-4-dimethylaminopyridine)] N984 and its isomer N984b have been studied more in detail. While photo- and electrochemical properties are very similar, DFT/TDDFT calculations show that the two isomers have different HOMO orbital characteristics. As a consequence, solution processed OLEDs made using a mixture of N984 and isomer N984b similar to vacuum processed devices show that the isomer has a dramatic detrimental effect on the performances of the device. In addition, commonly used thermogravimetric analysis is not suitable for showing the isomerization process. The isomer could impact performances of vacuum processed OLEDs using heteroleptic cyclometallated iridium(III) complexes as dopant.

  15. Lipid and Glycolipid Isomer Analyses Using Ultra-High Resolution Ion Mobility Spectrometry Separations

    SciTech Connect

    Wojcik, Roza; Webb, Ian; Deng, Liulin; Garimella, Sandilya; Prost, Spencer; Ibrahim, Yehia; Baker, Erin; Smith, Richard

    2017-01-01

    Understanding the biological mechanisms related to lipids and glycolipids is challenging due to the vast number of possible isomers. Mass spectrometry (MS) measurements are currently the dominant approach for studying and providing detailed information on lipid and glycolipid structures. However, difficulties in distinguishing many structural isomers (e.g. distinct acyl chain positions, double bond locations, as well as glycan isomers) inhibit the understanding of their biological roles. Here we utilized ultra-high resolution ion mobility spectrometry (IMS) separations based upon the use of traveling waves in a serpentine long path length multi-pass Structures for Lossless Manipulations (SLIM) to enhance isomer resolution. The multi-pass arrangement allowed separations ranging from ~16 m (1 pass) to ~470 m (32 passes) to be investigated for the distinction of lipids and glycolipids with extremely small structural differences. These ultra-high resolution SLIM IMS-MS analyses provide a foundation for exploring and better understanding isomer specific biological and disease processes.

  16. Odd tensor electric transitions in high-spin Sn-isomers and generalized seniority

    NASA Astrophysics Data System (ADS)

    Maheshwari, Bhoomika; Jain, Ashok Kumar

    2016-02-01

    The similar behavior of the B (E 1) values of the recently observed 13- odd tensor E1 isomers and the B (E 2) values of the 10+ and 15- even tensor E2 isomers in the Sn-isotopes has been understood in terms of the generalized seniority for multi-j orbits by using the quasi-spin scheme. This simple approach proves to be quite successful in explaining the measured transition probabilities and the corresponding half-lives in the high-spin isomers of the semi-magic Sn-isotopes. Hence, we show for the first time the occurrence of seniority isomers in the 13- Sn-isomers, which decay by odd-tensor E1 transitions to the same seniority states.

  17. Table of superdeformed nuclear bands and fission isomers

    SciTech Connect

    Firestone, R.B.; Singh, B.

    1994-06-01

    A minimum in the second potential well of deformed nuclei was predicted and the associated shell gaps are illustrated in the harmonic oscillator potential shell energy surface calculations shown in this report. A strong superdeformed minimum in {sup 152}Dy was predicted for {beta}{sub 2}-0.65. Subsequently, a discrete set of {gamma}-ray transitions in {sup 152}DY was observed and, assigned to the predicted superdeformed band. Extensive research at several laboratories has since focused on searching for other mass regions of large deformation. A new generation of {gamma}-ray detector arrays is already producing a wealth of information about the mechanisms for feeding and deexciting superdeformed bands. These bands have been found in three distinct regions near A=l30, 150, and 190. This research extends upon previous work in the actinide region near A=240 where fission isomers were identified and also associated with the second potential well. Quadrupole moment measurements for selected cases in each mass region are consistent with assigning the bands to excitations in the second local minimum. As part of our committment to maintain nuclear structure data as current as possible in the Evaluated Nuclear Structure Reference File (ENSDF) and the Table of Isotopes, we have updated the information on superdeformed nuclear bands. As of April 1994, we have complied data from 86 superdeformed bands and 46 fission isomers identified in 73 nuclides for this report. For each nuclide there is a complete level table listing both normal and superdeformed band assignments; level energy, spin, parity, half-life, magneto moments, decay branchings; and the energies, final levels, relative intensities, multipolarities, and mixing ratios for transitions deexciting each level. Mass excess, decay energies, and proton and neutron separation energies are also provided from the evaluation of Audi and Wapstra.

  18. Gaussian and linear deconvolution of LC-MS/MS chromatograms of the eight aminobutyric acid isomers.

    PubMed

    Vemula, Harika; Kitase, Yukiko; Ayon, Navid J; Bonewald, Lynda; Gutheil, William G

    2017-01-01

    Isomeric molecules present a challenge for analytical resolution and quantification, even with MS-based detection. The eight aminobutyric acid (ABA) isomers are of interest for their various biological activities, particularly γ-aminobutyric acid (GABA) and the d- and l-isomers of β-aminoisobutyric acid (β-AIBA; BAIBA). This study aimed to investigate LC-MS/MS-based resolution of these ABA isomers as their Marfey's (Mar) reagent derivatives. HPLC was able to separate three Mar-ABA isomers l-β-ABA (l-BABA), and l- and d-α-ABA (AABA) completely, with three isomers (GABA, and d/l-BAIBA) in one chromatographic cluster, and two isomers (α-AIBA (AAIBA) and d-BABA) in a second cluster. Partially separated cluster components were deconvoluted using Gaussian peak fitting except for GABA and d-BAIBA. MS/MS detection of Marfey's derivatized ABA isomers provided six MS/MS fragments, with substantially different intensity profiles between structural isomers. This allowed linear deconvolution of ABA isomer peaks. Combining HPLC separation with linear and Gaussian deconvolution allowed resolution of all eight ABA isomers. Application to human serum found a substantial level of l-AABA (13 μM), an intermediate level of l-BAIBA (0.8 μM), and low but detectable levels (<0.2 μM) of GABA, l-BABA, AAIBA, d-BAIBA, and d-AABA. This approach should be useful for LC-MS/MS deconvolution of other challenging groups of isomeric molecules.

  19. Structural and dynamic effects of cholesterol at preferred sites of interaction with rhodopsin identified from microsecond length molecular dynamics simulations

    PubMed Central

    Khelashvili, George; Grossfield, Alan; Feller, Scott E.; Pitman, Michael C.; Weinstein, Harel

    2014-01-01

    An unresolved question about GPCR function is the role of membrane components in receptor stability and activation. In particular, cholesterol is known to affect the function of membrane proteins, but the details of its effect on GPCRs are still elusive. Here, we describe how cholesterol modulates the behavior of the TM1-TM2-TM7-helix 8(H8) functional network that comprises the highly conserved NPxxY(x)5,6F motif, through specific interactions with the receptor. The inferences are based on the analysis of microsecond length molecular dynamics (MD) simulations of rhodopsin in an explicit membrane environment. Three regions on the rhodopsin exhibit the highest cholesterol density throughout the trajectory: the extracellular end of TM7, a location resembling the high-density sterol area from the electron microscopy data; the intracellular parts of TM1, TM2, and TM4, a region suggested as the cholesterol binding site in the recent X-ray crystallography data on β2-adrenergic GPCR; and the intracellular ends of TM2-TM3, a location that was categorized as the high cholesterol density area in multiple independent 100 ns MD simulations of the same system. We found that cholesterol primarily affects specific local perturbations of the helical TM domains such as the kinks in TM1, TM2, and TM7. These local distortions, in turn, relate to rigid-body motions of the TMs in the TM1-TM2-TM7-H8 bundle. The specificity of the effects stems from the nonuniform distribution of cholesterol around the protein. Through correlation analysis we connect local effects of cholesterol on structural perturbations with a regulatory role of cholesterol in the structural rearrangements involved in GPCR function. PMID:19173312

  20. Characterization of neutron emission from mega-ampere deuterium gas puff Z-pinch at microsecond implosion times

    NASA Astrophysics Data System (ADS)

    Klir, D.; Shishlov, A. V.; Kokshenev, V. A.; Kubes, P.; Labetsky, A. Yu; Rezac, K.; Cikhardt, J.; Fursov, F. I.; Kovalchuk, B. M.; Kravarik, J.; Kurmaev, N. E.; Ratakhin, N. A.; Sila, O.; Stodulka, J.

    2013-08-01

    Experiments with deuterium (D2) triple shell gas puffs were carried out on the GIT-12 generator at a 3 MA current level and microsecond implosion times. The outer, middle and inner nozzle diameters were 160 mm, 80 mm and 30 mm, respectively. The influence of the mass of deuterium shells on neutron emission times, neutron yields and neutron energy spectra was studied. The injected linear mass of deuterium varied between 50 and 255 µg cm-1. Gas puffs imploded onto the axis before the peak of generator current at 700-1100 ns. Most of the neutrons were emitted during the second neutron pulse after the development of instabilities. Despite higher currents, heavier gas puffs produced lower neutron yields. Optimal mass and a short time delay between the valve opening and the generator triggering were more important than the better coincidence of stagnation with peak current. The peak neutron yield from D(d, n)3He reactions reached 3 × 1011 at 2.8 MA current, 90 µg cm-1 injected linear mass and 37 mm anode-cathode gap. In the case of lower mass shots, a large number of 10 MeV neutrons were produced either by secondary DT reactions or by DD reactions of deuterons with energies above 7 MeV. The average neutron yield ratio Y>10 MeV/Y2.5 MeV reached (6 ± 3) × 10-4. Such a result can be explained by a power law distribution for deuterons as \\rmd N_d/\\rmd E_d\\propto E_d^{-3} . The optimization of a D2 gas puff Z-pinch and similarities to a plasma focus and its drive parameter are described.

  1. High longitudinal relaxivity of ultra-small gadolinium oxide prepared by microsecond laser ablation in diethylene glycol

    SciTech Connect

    Luo Ningqi; Xiao Jun; Hu Wenyong; Chen Dihu; Tian Xiumei; Yang Chuan; Li Li

    2013-04-28

    Ultra-small gadolinium oxide (Gd{sub 2}O{sub 3}) can be used as T{sub 1}-weighted Magnetic Resonance Imaging (MRI) contrast agent own to its high longitudinal relaxivity (r{sub 1}) and has attracted intensive attention in these years. In this paper, ultra-small Gd{sub 2}O{sub 3} nanoparticles of 3.8 nm in diameter have been successfully synthesized by a microsecond laser ablating a gadolinium (Gd) target in diethylene glycol (DEG). The growth inhibition effect induced by the large viscosity of DEG makes it possible to synthesize ultra-small Gd{sub 2}O{sub 3} by laser ablation in DEG. The r{sub 1} value and T{sub 1}-weighted MR images are measured by a 3.0 T MRI spectroscope. The results show these nanoparticles with a high r{sub 1} value of 9.76 s{sup -1} mM{sup -1} to be good MRI contrast agents. We propose an explanation for the high r{sub 1} value of ultra-small Gd{sub 2}O{sub 3} by considering the decreasing factor (surface to volume ratio of the nanoparticles, S/V) and the increasing factor (water hydration number of the Gd{sup 3+} on Gd{sub 2}O{sub 3} surface, q), which offer a new look into the relaxivity studies of MRI contrast agents. Our research provides a new approach to preparing ultra-small Gd{sub 2}O{sub 3} of high r{sub 1} value by laser ablation in DEG and develops the understanding of high relaxivity of ultra-small Gd{sub 2}O{sub 3} MRI contrast agents.

  2. Experimental studies of a microsecond plasma opening switch in the positive polarity regime with inductive load/extraction ion diode

    NASA Astrophysics Data System (ADS)

    Bystritskii, V. M.; Lisitsyn, I. V.; Sinebryukhov, V. A.; Volkov, S. N.; Krasik, Ya. E.

    1992-06-01

    Systematic studies of the microsecond plasma opening switch (MPOS) operation in the positive polarity of its inner electrode with an inductive load/B-applied ion diode of the extraction type at a level of 0.3 TW of dissipated power were performed at the DOUBLE generator (300 kA, 480 kV, 1 μs). The detailed measurements of ion flow parameters in the conductive phase of the MPOS showed the considerable enhancement of the ion current amplitude over the thermal flow limit (3-10 times) which is coupled with a significant decrease of electron conductivity in the MPOS across its self-magnetic field. The positive polarity MPOS operation proved to be more critical to the stored current amplitudes and geometry of the electrodes in comparison with the negative polarity case. This fact resulted in limitations of satisfactory performance of the MPOS involving short high-voltage pulse duration, low stored current amplitudes, and a narrow region of acceptable electrode diameters. The variation of the diode anode-cathode (AC) gap provided a sensitive control of the MPOS + magnetically insulated diode (MID) system, which displayed very strong coupling, resulting in clamping of the output voltage in a wide region of diode impedances. The early long-duration (<300 ns) high-voltage (50-200 kV) prepulse improves plasma production at the anode of the MID prior to the application of the main pulse. The optimal performance of the MPOS+MID system was realized at the level of ZMPOS/ZMID = 2.5. The energy of the extracted high-power ion beam made up 3.5 kJ, its power being 120 GW with 40% efficiency of energy transfer from MPOS to the MID.

  3. Examination of isomer specific bioaccumulation parameters and potential in vivo hepatic metabolites of syn- and anti-Dechlorane Plus isomers in juvenile rainbow trout (Oncorhynchus mykiss).

    PubMed

    Tomy, Gregg T; Thomas, Caden R; Zidane, Thane M; Murison, Kathryn E; Pleskach, Kerri; Hare, Jonathon; Arsenault, Gilles; Marvin, Chris H; Sverko, Ed

    2008-08-01

    Juvenile rainbow trout (Oncorhynchus mykiss) were exposed in the laboratory to elevated doses of syn- and anti-isomers of Dechlorane Plus (DP) via their diet for 49 days (uptake phase), followed by 112 days of untreated food (depuration phase) to examine bioaccumulation parameters and possible metabolic products. Three groups of 60 fish were used in the study. Two groups were exposed separately to food fortified with known concentrations of syn- (0.79 +/- 0.03 microg/g, lipid weight) and anti-DP (1.17 +/- 0.12 microg/g, lipid weight) while a third control group was fed unfortified food. Neither isomer reached steady-state after 49 days of exposure. Only the syn-isomer accumulated linearly in the fish (whole-body minus liver) during the dosing phase with a calculated uptake rate constant of 0.045 +/- 0.005 (arithmetic mean +/- 1 x standard error) nmoles per day. A similar uptake rate was also observed for this isomer in the liver. The elimination of both isomers from the whole fish (minus liver) obeyed first order depuration kinetics (syn-: r2 = 0.6427, p < 0.001, anti-: r2 = 0.5350, p < 0.005) with calculated half-lives (t1/2) of 53.3 +/- 13.1 (syn-) and 30.4 +/- 5.7 (anti-) days. Elimination of the isomers from the liver was difficult to interpret because of suspected enterohepatic circulation and redistribution of the isomers in the liver during clearance from other tissues. The biomagnification factor (BMF, determined in whole fish minus liver) of the syn-isomer (5.2) was greater than the anti-isomer (1.9) suggesting that the former isomer is more bioavailable. A suite of metabolites were screened for in the liver including dechlorinated, hydroxylated, methoxylated and methyl sulfone degradates. Even with the purposely high dose used in the uptake phase, none of these degradates could be detected in the extracts. This suggests that if metabolites of DP are detected in fish from aquatic food webs their presence is likely not from in vivo biotransformation of the

  4. INTERACTION OF LASER RADIATION WITH MATTER. LASER PLASMA: Excitation of nuclear isomers by X rays from laser plasma

    NASA Astrophysics Data System (ADS)

    Andreev, Aleksandr A.; Platonov, Konstantin Yu; Rozhdestvenskii, Yu V.; Karpeshin, F.; Trzhaskovskaya, M. B.

    2010-06-01

    The possibility of obtaining isomer nuclei is studied by the example of the molybdenum isomer 93Mo upon irradiation of a niobium 93Nb target by ~50-J, 100-fs laser pulses. It is shown that the modern laser technique allows production of isomer nuclei by accelerated protons and radiative de-excitation of isomer nuclear states by thermal or line X-rays from laser plasma.

  5. Matrix Isolation and Computational Study of [2C, 2N, x] (X=S, Se) Isomers

    NASA Astrophysics Data System (ADS)

    Voros, Tamas; Tarczay, Gyorgy

    2015-06-01

    The [2C, 2N, S] and the [2C, 2N, Se] systems were investigated by quantum chemical computations and matrix isolation IR spectroscopy. For both systems nine isomers were computationally investigated, for which harmonic and anharmonic vibrational wavenumbers and infrared (IR) intensities were calculated using the CCSD(T)/aug-cc-pVTZ level of theory. The results show that each of the isomers have two or more detectable bands in the mid IR region, which have one or two orders of magnitude larger intensity compared to the IR intensity of the most intense bands of the most stable NCSCN and NCSeCN isomers'. It follows that if the most stable isomers can be detected, then the other previously unobserved isomers generated from NCSCN or NCSeCN should also be detectable with IR spectroscopy. UV spectra were also computed for each isomer at the TD-DFT B3LYP/aug-cc-pVTZ level of theory. These computations showed that the most stable isomers (NCSCN and NCSeCN) can absorb the UV radiation around 250 nm, and the irradiation may promote photoisomerization. This means that if the initial isomers are irradiated by narrow-band UV radiation, new isomers may be generated, which likely decompose by irradiating broad-band UV radiation. The two most stable isomers, sulphur dicyanide (NCSCN) and selenium dicyanide (NCSeCN), were prepared following literature methods. The matrix isolation IR spectra of these molecules in Ar and Kr were measured for the first time. As a result of a selective 254 nm-irradiation of the deposited matrices some new bands appeared in the IR spectra, while the intensity of the bands of NCSCN or NCSeCN were decreased at the same time. Irradiation of the matrices with broad-band UV light decreased the intensity of the bands corresponding to the deposited isomers and some of the bands appeared on the 254 nm-irradiation. On the basis of the analysis of the formation rates of the different bands upon 254 nm photolysis and by comparison with the results of the quantum

  6. 40 CFR 180.157 - Methyl 3-[(dimethoxyphos-phinyl) oxy]butenoate, alpha and beta isomers; tolerances for residues.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... isomers; tolerances for residues. 180.157 Section 180.157 Protection of Environment ENVIRONMENTAL... FOOD Specific Tolerances § 180.157 Methyl 3- butenoate, alpha and beta isomers; tolerances for residues... and beta isomers, in or on the following raw agricultural commodities: Commodity Parts per...

  7. 40 CFR 180.157 - Methyl 3-[(dimethoxyphos-phinyl) oxy]butenoate, alpha and beta isomers; tolerances for residues.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... isomers; tolerances for residues. 180.157 Section 180.157 Protection of Environment ENVIRONMENTAL... FOOD Specific Tolerances § 180.157 Methyl 3- butenoate, alpha and beta isomers; tolerances for residues... and beta isomers, in or on the following raw agricultural commodities: Commodity Parts per...

  8. 40 CFR 180.449 - Avermectin B1 and its delta-8,9-isomer; tolerances for residues.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Avermectin B1 and its delta-8,9-isomer... Tolerances § 180.449 Avermectin B1 and its delta-8,9-isomer; tolerances for residues. (a) General. Tolerances... delta-8,9-isomer in or on the following commodities: Commodity Parts per million Almond, hulls...

  9. Structural-based differences in ecotoxicity of benzoquinoline isomers to the zebra mussel (Dreissena polymorpha)

    SciTech Connect

    Kraak, M.H.S.; Wijnands, P.; Govers, H.A.J.; Admiraal, W.; Voogt, P. de

    1997-10-01

    Effects of four benzoquinoline isomers on the filtration rate of the zebra mussel (Dreissena polymorpha) were analyzed, to study the effect of minor differences in chemical structure on adverse biological effects. Filtration rates were measured after 48 h of exposure to different concentrations of acridine, phenanthridine, benzo[f]quinoline, and benzo[h]quinoline in the water. The 50% effective concentration (EC50) values for filtration rate of the four isomers differed significantly. Effects increased in the order benzo[f], -[h], -[b], and -[c]quinoline, and the difference between the most toxic isomer and the least toxic isomer amounted to a factor of 30. Attempts were made to relate these differences in toxicity to the structure of the isomers. Size- or topology-related molecular descriptors provided insufficient resolution to distinguish between the benzoquinoline isomers, and none of the electronic descriptors separately provided a significant correlation with the observed effects. In an alternative approach, molecular shape, accessibility, and minimum agent-macromolecule distance were used to represent repulsive and attractive forces between the benzoquinoline isomers and biological membranes. This approach could tentatively explain the observed effects and is supported by a high correlation between the EC50 data and the reversed-phase C18-HPLC behavior of the benzoquinolines (k{sub 0}), which is likely to be governed by similar processes.

  10. Decay and Fission Hindrance of Two- and Four-Quasiparticle K Isomers in 254Rf

    NASA Astrophysics Data System (ADS)

    David, H. M.; Chen, J.; Seweryniak, D.; Kondev, F. G.; Gates, J. M.; Gregorich, K. E.; Ahmad, I.; Albers, M.; Alcorta, M.; Back, B. B.; Baartman, B.; Bertone, P. F.; Bernstein, L. A.; Campbell, C. M.; Carpenter, M. P.; Chiara, C. J.; Clark, R. M.; Cromaz, M.; Doherty, D. T.; Dracoulis, G. D.; Esker, N. E.; Fallon, P.; Gothe, O. R.; Greene, J. P.; Greenlees, P. T.; Hartley, D. J.; Hauschild, K.; Hoffman, C. R.; Hota, S. S.; Janssens, R. V. F.; Khoo, T. L.; Konki, J.; Kwarsick, J. T.; Lauritsen, T.; Macchiavelli, A. O.; Mudder, P. R.; Nair, C.; Qiu, Y.; Rissanen, J.; Rogers, A. M.; Ruotsalainen, P.; Savard, G.; Stolze, S.; Wiens, A.; Zhu, S.

    2015-09-01

    Two isomers decaying by electromagnetic transitions with half-lives of 4.7(1.1) and 247 (73 ) μ s have been discovered in the heavy 254Rf nucleus. The observation of the shorter-lived isomer was made possible by a novel application of a digital data acquisition system. The isomers were interpreted as the Kπ=8- , ν2(7 /2+[624 ],9 /2-[734 ]) two-quasineutron and the Kπ=1 6+, 8-ν2(7 /2+[624 ],9 /2-[734 ])⊗8-π2(7 /2-[514 ],9 /2+[624 ]) four-quasiparticle configurations, respectively. Surprisingly, the lifetime of the two-quasiparticle isomer is more than 4 orders of magnitude shorter than what has been observed for analogous isomers in the lighter N =150 isotones. The four-quasiparticle isomer is longer lived than the 254Rf ground state that decays exclusively by spontaneous fission with a half-life of 23.2 (1.1 ) μ s . The absence of sizable fission branches from either of the isomers implies unprecedented fission hindrance relative to the ground state.

  11. Gas-phase Ion Isomer Analysis Reveals the Mechanism of Peptide Sequence Scrambling

    PubMed Central

    Jia, Chenxi; Wu, Zhe; Lietz, Christopher B.; Liang, Zhidan; Cui, Qiang; Li, Lingjun

    2014-01-01

    Peptide sequence scrambling during mass spectrometry-based gas-phase fragmentation analysis causes misidentification of peptides and proteins. Thus, there is a need to develop an efficient approach to probing the gas-phase fragment ion isomers related to sequence scrambling and the underlying fragmentation mechanism, which will facilitate the development of bioinformatics algorithm for proteomics research. Herein, we report on the first use of electron transfer dissociation (ETD)-produced diagnostic fragment ions to probe the components of gas-phase peptide fragment ion isomers. In combination with ion mobility spectrometry (IMS) and formaldehyde labeling, this novel strategy enables qualitative and quantitative analysis of b-type fragment ion isomers. ETD fragmentation produced diagnostic fragment ions indicative of the precursor ion isomer components, and subsequent IMS analysis of b ion isomers provided their quantitative and structural information. The isomer components of three representative b ions (b9, b10, and b33 from three different peptides) were accurately profiled by this method. IMS analysis of the b9 ion isomers exhibited dynamic conversion among these structures. Furthermore, molecular dynamics simulation predicted theoretical drift time values which were in good agreement with experimentally measured values. Our results strongly support the mechanism of peptide sequence scrambling via b ion cyclization, and provide the first experimental evidence to support that the conversion from molecular precursor ion to cyclic b ion (M→cb) pathway is less energetically (or kinetically) favored. PMID:24313304

  12. Gas-phase ion isomer analysis reveals the mechanism of peptide sequence scrambling.

    PubMed

    Jia, Chenxi; Wu, Zhe; Lietz, Christopher B; Liang, Zhidan; Cui, Qiang; Li, Lingjun

    2014-03-18

    Peptide sequence scrambling during mass spectrometry-based gas-phase fragmentation analysis causes misidentification of peptides and proteins. Thus, there is a need to develop an efficient approach to probing the gas-phase fragment ion isomers related to sequence scrambling and the underlying fragmentation mechanism, which will facilitate the development of bioinformatics algorithm for proteomics research. Herein, we report on the first use of electron transfer dissociation (ETD)-produced diagnostic fragment ions to probe the components of gas-phase peptide fragment ion isomers. In combination with ion mobility spectrometry (IMS) and formaldehyde labeling, this novel strategy enables qualitative and quantitative analysis of b-type fragment ion isomers. ETD fragmentation produced diagnostic fragment ions indicative of the precursor ion isomer components, and subsequent IMS analysis of b ion isomers provided their quantitative and structural information. The isomer components of three representative b ions (b9, b10, and b33 from three different peptides) were accurately profiled by this method. IMS analysis of the b9 ion isomers exhibited dynamic conversion among these structures. Furthermore, molecular dynamics simulation predicted theoretical drift time values, which were in good agreement with experimentally measured values. Our results strongly support the mechanism of peptide sequence scrambling via b ion cyclization, and provide the first experimental evidence to support that the conversion from molecular precursor ion to cyclic b ion (M → (c)b) pathway is less energetically (or kinetically) favored.

  13. Search for a 2-quasiparticle high-K isomer in {sup 256}Rf

    SciTech Connect

    Robinson, A. P.; Jenkins, D. G.; Marley, P.; Khoo, T. L.; Seweryniak, D.; Ahmad, I.; Back, B. B.; Carpenter, M. P.; Davids, C. N.; Greene, J.; Janssens, R. V. F.; Kondev, F. G.; Lauritsen, T.; Lister, C. J.; McCutchan, E.; Peterson, D.; Stefanescu, I.; Zhu, S.; Asai, M.; Chowdhury, P.

    2011-06-15

    The energies of 2-quasiparticle (2-qp) states in heavy shell-stabilized nuclei provide information on the single-particle states that are responsible for the stability of superheavy nuclei. We have calculated the energies of 2-qp states in {sup 256}Rf, which suggest that a long-lived, low-energy 8{sup -} isomer should exist. A search was conducted for this isomer through a calorimetric conversion electron signal, sandwiched in time between implantation of a {sup 256}Rf nucleus and its fission decay, all within the same pixel of a double-sided Si strip detector. A 17(5)-{mu}s isomer was identified. However, its low population, {approx}5(2)% that of the ground state instead of the expected {approx}30%, suggests that it is more likely a 4-qp isomer. Possible reasons for the absence of an electromagnetic signature of a 2-qp isomer decay are discussed. These include the favored possibility that the isomer decays by fission, with a half-life indistinguishably close to that of the ground state. Another possibility, that there is no 2-qp isomer at all, would imply an abrupt termination of axially symmetric deformed shapes at Z=104, which describes nuclei with Z=92-103 very well.

  14. Search for a 2-quasiparticle high-K isomer in {sup 256}Rf.

    SciTech Connect

    Robinson, A. P.; Khoo, T. L.; Seweryniak, D.; Ahmad, I.; Asai, M.; Back, B. B.; Carpenter, M. P.; Davids, C. N.; Greene, J.; Janssens, R. V. F.; Kondev, F. G.; Lauritsen, T.; Lister, C. J.; McCutchan, E.; Peterson, D.; Zhu, S.

    2011-06-13

    The energies of 2-quasiparticle (2-qp) states in heavy shell-stabilized nuclei provide information on the single-particle states that are responsible for the stability of superheavy nuclei. We have calculated the energies of 2-qp states in {sup 256}Rf, which suggest that a long-lived, low-energy 8{sup -} isomer should exist. A search was conducted for this isomer through a calorimetric conversion electron signal, sandwiched in time between implantation of a {sup 256}Rf nucleus and its fission decay, all within the same pixel of a double-sided Si strip detector. A 17(5)-{micro}s isomer was identified. However, its low population, {approx}5(2)% that of the ground state instead of the expected {approx}30%, suggests that it is more likely a 4-qp isomer. Possible reasons for the absence of an electromagnetic signature of a 2-qp isomer decay are discussed. These include the favored possibility that the isomer decays by fission, with a half-life indistinguishably close to that of the ground state. Another possibility, that there is no 2-qp isomer at all, would imply an abrupt termination of axially symmetric deformed shapes at Z = 104, which describes nuclei with Z = 92-103 very well.

  15. Utilization of Lactate Isomers by Propionibacterium freudenreichii subsp. shermanii: Regulatory Role for Intracellular Pyruvate

    PubMed Central

    Crow, Vaughan L.

    1986-01-01

    Five strains of Propionibacterium freudenreichii subsp. shermanii utilized the l-(+) isomer of lactate at a faster rate than they did the d-(−) isomer when grown with a mixture of lactate isomers under a variety of conditions. ATCC 9614, grown anaerobically in defined medium containing 160 mM dl-lactate, utilized only 4 and 15% of the d-(−)-lactate by the time 50 and 90%, respectively, of the l-(+)-lactate was used. The intracellular pyruvate concentration was high (>100 mM) in the initial stages of lactate utilization, when either dl-lactate or the l-(+) isomer was the starting substrate. The concentration of this intermediate dropped during dl-lactate fermentation such that when only d-(−)-lactate remained, the concentration was <20 mM. When only the d-(−) isomer was initially present, a similar relatively low concentration of intracellular pyruvate was present, even at the start of lactate utilization. The NAD+-independent lactate dehydrogenase activities in extracts showed different kinetic properties with regard to pyruvate inhibition, depending upon the lactate isomer present. Pyruvate gave a competitive inhibitor pattern with l-(+)-lactate and a mixed-type inhibitor pattern with d-(−)-lactate. It is suggested that these properties of the lactate dehydrogenases and the intracellular pyruvate concentrations explain the preferential use of the l-(+) isomer. PMID:16347134

  16. Isomers/enantiomers of perfluorocarboxylic acids: Method development and detection in environmental samples.

    PubMed

    Naile, Jonathan E; Garrison, A Wayne; Avants, Jimmy K; Washington, John W

    2016-02-01

    Perfluoroalkyl substances are globally distributed in both urban and remote settings, and routinely are detected in wildlife, humans, and the environment. One of the most prominent and routinely detected perfluoroalkyl substances is perfluorooctanoic acid (PFOA), which has been shown to be toxic to both humans and animals. PFOA exists as both linear and branched isomers; some of the branched isomers are chiral. A novel GC-NCI-MS method was developed to allow for isomer/enantiomer separation, which was achieved using two columns working in tandem; a 30-m DB-5MS column and a 30-m BGB-172 Analytik column. Samples were derivatized with diazomethane to form methyl esters of the PFOA isomers. In standards, at least eight PFOA isomers were detected, of which at least four were enantiomers of chiral isomers; one chiral isomer (P3) was sufficiently separated to allow for enantiomer-fraction calculations. Soil, sediment and plant samples from contaminated locations in Alabama and Georgia were analyzed. P3 was observed in most of these environmental samples, and was non-racemic in at least one sediment, suggesting the possibility of chirally selective generation from precursors or enantioselective sorption. In addition, the ratio of P3/linear PFOA was inversely related to distance from source, which we suggest might reflect a higher sorption affinity for the P3 over the linear isomer. This method focuses on PFOA, but preliminary results suggest that it should be broadly applicable to other chiral and achiral perfluorocarboxylic acids (PFCAs); e.g., we detected several other homologous PFCA isomers in our PFCA standards and some environmental samples.

  17. [Identification of Six Isomers of Dimethylbenzoic Acid by Using Terahertz Time-Domain Spectroscopy Technique].

    PubMed

    Liu, Jian-wei; Shen, Jing-ling; Zhang, Bo

    2015-11-01

    In this paper, the absorption spectra of 6 isomers of dimethylbenzoic acid, which were widely used in chemical and pharmaceutical production as intermediate substance, were measured by using the terahertz time-domain spectroscopy (THz-TDS) system in the range 0.2-2.2 THz at room temperature. The experimental results show that the six measured isomers present apparent different spectral response. However, the results of using infrared spectroscopy indicates that different isomers show high similarity in absorption spectra in the range 1450-1700 cm⁻¹. The vibrational frequencies are calculated by using the density functional theory (DFT), and identification of vibrational modes are given. It is clear that the absorption peaks of the 6 isomers in the range 1450-1700 cm⁻¹ come from the stretching vibration of benzene ring and C==O, while the absorption peaks in the terahertz range are caused by the relative wagging of benzene ring and all the chains out of plane, which lead to the different absorption characteristics of the 6 isomers in the range 0.2-2.2 THz. The results suggest that the difference and similarity of the absorption spectra observed in the two different frequency range are resulted from the difference and similarity of the molecular structures of the six isomers. By using the different absorption characteristics, we can identify the six isomers of dimethylbenzoic acid effectively. Our study indicates that it is feasible to distinguish the isomers by using terahertz and infrared spectroscopy technique. It provides an effective way to identify different isomers and test the purity of the intermediate substance in the process of production quickly and accurately.

  18. Detailed Chemical Kinetic Reaction Mechanisms for Autoignition of Isomers of Heptane Under Rapid Compression

    SciTech Connect

    Westbrook, C K; Pitz, W J; Boercker, J E; Curran, H J; Griffiths, J F; Mohamed, C; Ribaucour, M

    2001-12-17

    Detailed chemical kinetic reaction mechanisms are developed for combustion of all nine isomers of heptane (C{sub 7}H{sub 16}), and these mechanisms are tested by simulating autoignition of each isomer under rapid compression machine conditions. The reaction mechanisms focus on the manner in which the molecular structure of each isomer determines the rates and product distributions of possible classes of reactions. The reaction pathways emphasize the importance of alkylperoxy radical isomerizations and addition reactions of molecular oxygen to alkyl and hydroperoxyalkyl radicals. A new reaction group has been added to past models, in which hydroperoxyalkyl radicals that originated with abstraction of an H atom from a tertiary site in the parent heptane molecule are assigned new reaction sequences involving additional internal H atom abstractions not previously allowed. This process accelerates autoignition in fuels with tertiary C-H bonds in the parent fuel. In addition, the rates of hydroperoxyalkylperoxy radical isomerization reactions have all been reduced so that they are now equal to rates of analogous alkylperoxy radical isomerizations, significantly improving agreement between computed and experimental ignition delay times in the rapid compression machine. Computed ignition delay times agree well with experimental results in the few cases where experiments have been carried out for specific heptane isomers, and predictive model calculations are reported for the remaining isomers. The computed results fall into three general groups; the first consists of the most reactive isomers, including n-heptane, 2-methyl hexane and 3-methyl hexane. The second group consists of the least reactive isomers, including 2,2-dimethyl pentane, 3,3-dimethyl pentane, 2,3-dimethyl pentane, 2,4-dimethyl pentane and 2,2,3-trimethyl butane. The remaining isomer, 3-ethyl pentane, was observed computationally to have an intermediate level of reactivity. These observations are generally

  19. Isomer Shift and Magnetic Moment of the Long-Lived 1 /2+ Isomer in 30,79Zn49: Signature of Shape Coexistence near 78Ni

    NASA Astrophysics Data System (ADS)

    Yang, X. F.; Wraith, C.; Xie, L.; Babcock, C.; Billowes, J.; Bissell, M. L.; Blaum, K.; Cheal, B.; Flanagan, K. T.; Garcia Ruiz, R. F.; Gins, W.; Gorges, C.; Grob, L. K.; Heylen, H.; Kaufmann, S.; Kowalska, M.; Kraemer, J.; Malbrunot-Ettenauer, S.; Neugart, R.; Neyens, G.; Nörtershäuser, W.; Papuga, J.; Sánchez, R.; Yordanov, D. T.

    2016-05-01

    Collinear laser spectroscopy is performed on the 30,79Zn49 isotope at ISOLDE-CERN. The existence of a long-lived isomer with a few hundred milliseconds half-life is confirmed, and the nuclear spins and moments of the ground and isomeric states in 79Zn as well as the isomer shift are measured. From the observed hyperfine structures, spins I =9 /2 and I =1 /2 are firmly assigned to the ground and isomeric states. The magnetic moment μ (79Zn)=-1.1866 (10 )μN , confirms the spin-parity 9 /2+ with a ν g9/2 -1 shell-model configuration, in excellent agreement with the prediction from large scale shell-model theories. The magnetic moment μ (Znm79)=-1.0180 (12 )μN supports a positive parity for the isomer, with a wave function dominated by a 2 h -1 p neutron excitation across the N =50 shell gap. The large isomer shift reveals an increase of the intruder isomer mean square charge radius with respect to that of the ground state, δ ⟨rc2⟩79 ,79 m=+0.204 (6 ) fm2 , providing first evidence of shape coexistence.

  20. Isolation and spectral characterization of thermally generated multi-Z-isomers of lycopene and the theoretically preferred pathway to di-Z-isomers.

    PubMed

    Honda, Masaki; Kudo, Tatsuya; Kuwa, Takahiro; Higashiura, Takuma; Fukaya, Tetsuya; Inoue, Yoshinori; Kitamura, Chitoshi; Takehara, Munenori

    2017-02-01

    Lycopene has a large number of geometric isomers caused by E/Z isomerization at arbitrary sites within the 11 conjugated double bonds, offering varying characteristics related to features such as antioxidant capacity and bioavailability. However, the geometric structures of only a few lycopene Z-isomers have been thoroughly identified from natural sources. In this study, seven multi-Z-isomers of lycopene, (9Z,13'Z)-, (5Z,13Z,9'Z)-, (9Z,9'Z)-, (5Z,13'Z)-, (5Z,9'Z)-, (5Z,9Z,5'Z)-, and (5Z,9Z)-lycopene, were obtained from tomato samples by thermal isomerization, and then isolated by elaborate chromatography, and fully assigned using proton nuclear magnetic resonance. Moreover, the theoretically preferred pathway from (all-E)-lycopene to di-Z-isomers was examined with a computational approach using a Gaussian program. Fine-tuning of the HPLC separation conditions led to the discovery of novel multi-Z-isomers, and whose formation was supported by advanced theoretical calculations.

  1. Isomer Shift and Magnetic Moment of the Long-Lived 1/2^{+} Isomer in _{30}^{79}Zn_{49}: Signature of Shape Coexistence near ^{78}Ni.

    PubMed

    Yang, X F; Wraith, C; Xie, L; Babcock, C; Billowes, J; Bissell, M L; Blaum, K; Cheal, B; Flanagan, K T; Garcia Ruiz, R F; Gins, W; Gorges, C; Grob, L K; Heylen, H; Kaufmann, S; Kowalska, M; Kraemer, J; Malbrunot-Ettenauer, S; Neugart, R; Neyens, G; Nörtershäuser, W; Papuga, J; Sánchez, R; Yordanov, D T

    2016-05-06

    Collinear laser spectroscopy is performed on the _{30}^{79}Zn_{49} isotope at ISOLDE-CERN. The existence of a long-lived isomer with a few hundred milliseconds half-life is confirmed, and the nuclear spins and moments of the ground and isomeric states in ^{79}Zn as well as the isomer shift are measured. From the observed hyperfine structures, spins I=9/2 and I=1/2 are firmly assigned to the ground and isomeric states. The magnetic moment μ (^{79}Zn)=-1.1866(10)μ_{N}, confirms the spin-parity 9/2^{+} with a νg_{9/2}^{-1} shell-model configuration, in excellent agreement with the prediction from large scale shell-model theories. The magnetic moment μ (^{79m}Zn)=-1.0180(12)μ_{N} supports a positive parity for the isomer, with a wave function dominated by a 2h-1p neutron excitation across the N=50 shell gap. The large isomer shift reveals an increase of the intruder isomer mean square charge radius with respect to that of the ground state, δ⟨r_{c}^{2}⟩^{79,79m}=+0.204(6)  fm^{2}, providing first evidence of shape coexistence.

  2. Ab initio quantum chemical investigation of several isomers of anionic Si 6

    NASA Astrophysics Data System (ADS)

    Takahashi, Masae; Kawazoe, Yoshiyuki

    2006-02-01

    Eight isomers (planar hexagon, benzvalene, Dewar benzene, triangular prismane, bicyclopropenyl, octahedron, chair form, and twist boat form) of Si 6, Si62-, Si64-, and Si66-, have been searched for by the MP2 and B3LYP electronic structure calculations. Totally 14 isomers were found: two Si 6, six Si62-, five Si64-, and one Si66-. Two of them are different from the eight isomers: deformed triangle Si62-; pentagonal pyramidal Si64-. We discovered that the predicted stable shapes of Si62-, Si64-, and Si66- are octahedral, pentagonal pyramidal, and hexagonal, respectively, which agrees well with Wade rule.

  3. Controlling the Excited-State Dynamics of Nuclear Spin Isomers Using the Dynamic Stark Effect.

    PubMed

    Waldl, Maria; Oppel, Markus; González, Leticia

    2016-07-14

    Stark control of chemical reactions uses intense laser pulses to distort the potential energy surfaces of a molecule, thus opening new chemical pathways. We use the concept of Stark shifts to convert a local minimum into a local maximum of the potential energy surface, triggering constructive and destructive wave-packet interferences, which then induce different dynamics on nuclear spin isomers in the electronically excited state of a quinodimethane derivative. Model quantum-dynamical simulations on reduced dimensionality using optimized ultrashort laser pulses demonstrate a difference of the excited-state dynamics of two sets of nuclear spin isomers, which ultimately can be used to discriminate between these isomers.

  4. Theoretical studies of possible toroidal high-spin isomers in the light-mass region

    DOE PAGES

    Staszczak, A.; Wong, Cheuk-Yin

    2016-05-11

    We review our theoretical knowledge of possible toroidal high-spin isomers in the light mass region in 28≤A≤52 obtained previously in cranked Skyrme-Hartree-Fock calculations. We report additional toroidal high-spin isomers in 56Ni with I=114ℏ and 140ℏ, which follow the same (multi-particle) (multi-hole) systematics as other toroidal high-spin isomers. We examine the production of these exotic nuclei by fusion of various projectiles on 20Ne or 28Si as an active target in time-projection-chamber (TPC) experiments.

  5. Identification of a new isomer from a reversible isomerization of ceftriaxone in aqueous solution.

    PubMed

    Tian, Ye; Lu, Li; Chang, Yan; Zhang, Dou-sheng; Li, Jin; Feng, Yan-Chun; Hu, Chang-Qin

    2015-01-01

    A reversible isomerization of ceftriaxone in aqueous solution was observed, and the structure of the isomer was determined by mass spectrometry and various 1D and 2D NMR techniques. The mechanism of isomerization was also discussed. Finally, molecular docking simulations were performed and the antimicrobial activities of the isomers were measured. This showed that the biological activity of ceftriaxone was stronger than that of its isomer. The results reported in this article may be important to quality control requirements and to the stability of ceftriaxone products.

  6. Theoretical studies of possible toroidal high-spin isomers in the light-mass region

    SciTech Connect

    Staszczak, A.; Wong, Cheuk-Yin

    2016-05-11

    We review our theoretical knowledge of possible toroidal high-spin isomers in the light mass region in 28≤A≤52 obtained previously in cranked Skyrme-Hartree-Fock calculations. We report additional toroidal high-spin isomers in 56Ni with I=114ℏ and 140ℏ, which follow the same (multi-particle) (multi-hole) systematics as other toroidal high-spin isomers. We examine the production of these exotic nuclei by fusion of various projectiles on 20Ne or 28Si as an active target in time-projection-chamber (TPC) experiments.

  7. Pulpal Effects of Enamel Ablation With a Microsecond Pulsed λ=9.3-μm CO2 Laser

    PubMed Central

    Staninec, Michal; Darling, Cynthia L.; Goodis, Harold E.; Pierre, Daniel; Cox, Darren P.; Fan, Kenneth; Larson, Michael; Parisi, Renaldo; Hsu, Dennis; Manesh, Saman K.; Ho, Chi; Hosseini, Mehran; Fried, Daniel

    2011-01-01

    Background and Objectives In vitro studies have shown that CO2 lasers operating at the highly absorbed 9.3 and 9.6-μm wavelengths with a pulse duration in the range of 10–20-microsecond are well suited for the efficient ablation of enamel and dentin with minimal peripheral thermal damage. Even though these CO2 lasers are highly promising, they have yet to receive FDA approval. Clinical studies are necessary to determine if excessive heat deposition in the tooth may have any detrimental pulpal effects, particularly at higher ablative fluencies. The purpose of this study was to evaluate the pulpal safety of laser irradiation of tooth occlusal surfaces under the conditions required for small conservative preparations confined to enamel. Study Design/Materials and Methods Test subjects requiring removal of third molar teeth were recruited and teeth scheduled for extraction were irradiated using a pulsed CO2 laser at a wavelength of 9.3 μm operating at 25 or 50 Hz using a incident fluence of 20 J/cm2 for a total of 3,000 laser pulses (36 J) for both rates with water cooling. Two control groups were used, one with no treatment and one with a small cut made with a conventional high-speed hand-piece. No anesthetic was used for any of the procedures and tooth vitality was evaluated prior to treatment by heat, cold and electrical testing. Short term effects were observed on teeth extracted within 72 hours after treatment and long term effects were observed on teeth extracted 90 days after treatment. The pulps of the teeth were fixed with formalin immediately after extraction and subjected to histological examination. Additionally, micro-thermocouple measurements were used to estimate the potential temperature rise in the pulp chamber of extracted teeth employing the same irradiation conditions used in vivo. Results Pulpal thermocouple measurements showed the internal temperature rise in the tooth was within safe limits, 3.3±4°C without water cooling versus 1.7±6

  8. Polymerization of the cis- and trans-isomers of bis(triethoxysilyl)-2-butene and comparison of their structural properties

    SciTech Connect

    Shaltout, R.M.; Loy, D.A.; Carpenter, J.P.; Dorhout, K.; Shea, K.J.

    1998-09-01

    The cis and trans isomers of bis-(triethoxysilyl)-2-butene were polymerized by the sol-gel method under various conditions. The trans isomer formed gels under all conditions. The cis isomer formed gels only under basic conditions. Under acidic conditions it formed soluble resins of molecular weight ranging from 88,000 to 180,000 Daltons. Solid state and solution {sup 29}Si NMR revealed that the trans isomer formed condensed gels, and that the resins formed by the cis isomer contained cyclic monomers and/or ordered oligomers.

  9. The CBM RICH detector

    NASA Astrophysics Data System (ADS)

    Adamczewski-Musch, J.; Akishin, P.; Becker, K.-H.; Belogurov, S.; Bendarouach, J.; Boldyreva, N.; Chernogorov, A.; Deveaux, C.; Dobyrn, V.; Dürr, M.; Eschke, J.; Förtsch, J.; Heep, J.; Höohne, C.; Kampert, K.-H.; Kochenda, L.; Kopfer, J.; Kravtsov, P.; Kres, I.; Lebedev, S.; Lebedeva, E.; Leonova, E.; Linev, S.; Mahmoud, T.; Michel, J.; Miftakhov, N.; Niebur, W.; Ovcharenko, E.; Pauly, C.; Pfeifer, D.; Querchfeld, S.; Rautenberg, J.; Reinecke, S.; Riabov, Y.; Roshchin, E.; Samsonov, V.; Tarasenkova, O.; Traxler, M.; Ugur, C.; Vznuzdaev, E.; Vznuzdaev, M.

    2016-05-01

    The CBM RICH detector will use CO2 as radiator gas, focussing glass mirrors with Al+MgF2 reflective and protective coating and Hamamatsu H12700 MAPMTs as photon detectors. The detector will serve for electron to pion separation up to momenta of 8 GeV/c and thus enable in CBM the measurement of electromagnetic radiation from the early and dense fireball in A+A collisions at SIS 100. In this article, the current status of the CBM RICH development will be presented including new measurements of the radiation hardness of the H12700 MAPMT and WLS coatings with p-terphenyl, the new concept for the readout electronics, and optimizations ongoing with respect to the mirror mount structure and overall geometry. Prior to the usage in CBM, part of the already ordered MAPMTs will be used to upgrade the HADES RICH detector for a new measurement campaign at SIS 18 from 2018-2020.

  10. Comparative pharmacological activity of optical isomers of phenibut.

    PubMed

    Dambrova, Maija; Zvejniece, Liga; Liepinsh, Edgars; Cirule, Helena; Zharkova, Olga; Veinberg, Grigory; Kalvinsh, Ivars

    2008-03-31

    Phenibut (3-phenyl-4-aminobutyric acid) is a GABA (gamma-aminobutyric acid)-mimetic psychotropic drug which is clinically used in its racemic form. The aim of the present study was to compare the effects of racemic phenibut and its optical isomers in pharmacological tests and GABAB receptor binding studies. In pharmacological tests of locomotor activity, antidepressant and pain effects, S-phenibut was inactive in doses up to 500 mg/kg. In contrast, R-phenibut turned out to be two times more potent than racemic phenibut in most of the tests. In the forced swimming test, at a dose of 100 mg/kg only R-phenibut significantly decreased immobility time. Both R-phenibut and racemic phenibut showed analgesic activity in the tail-flick test with R-phenibut being slightly more active. An GABAB receptor-selective antagonist (3-aminopropyl)(diethoxymethyl)phosphinic acid (CGP35348) inhibited the antidepressant and antinociceptive effects of R-phenibut, as well as locomotor depressing activity of R-phenibut in open field test in vivo. The radioligand binding experiments using a selective GABAB receptor antagonist [3H]CGP54626 revealed that affinity constants for racemic phenibut, R-phenibut and reference GABA-mimetic baclofen were 177+/-2, 92+/-3, 6.0+/-1 microM, respectively. We conclude that the pharmacological activity of racemic phenibut relies on R-phenibut and this correlates to the binding affinity of enantiomers of phenibut to the GABAB receptor.

  11. Quantification of Triacylglycerol Positional Isomers in Rat Milk.

    PubMed

    Watanabe, Natsuko; Nagai, Toshiharu; Mizobe, Hoyo; Yoshinaga, Kazuaki; Yoshida, Akihiko; Kitamura, Yohei; Shimizu, Takashi; Beppu, Fumiaki; Gotoh, Naohiro

    2016-12-01

    The absolute amount of triacylglycerol (TAG) positional isomers was analyzed in rat milk fat, a representative of non-ruminant milk fat, using a HPLC-UV-atmospheric pressure chemical ionization-MS/MS system equipped with an octacosyl silylation column or polymeric ODS column. TAGs consisting of two oleic acids (O) and one palmitic acid (P) were the most abundant. In particular, β-OPO, a TAG binding P at the β-position (sn-2) and two Os at the α-positions (sn-1/3), was prominent. The β-OPO content decreased over time, while a TAG consisting of two Ps and one capric acid, a medium-chain fatty acid, increased. TAGs consisting of two Ps and one docosahexaenoic acid were present in small amounts and decreased with time. These results indicated that the recombination of fatty acids in TAGs in milk fat occurs in the mother, and is thought to depend on the infant's stage of growth, in response to their nutritional needs. It was also demonstrated that medium-chain fatty acids were mainly located at the α-position (sn-3), while Ps were mainly located at the β-position (sn-2). Therefore, the combination and binding positions of fatty acids of TAG are considered very important in infant nutrition.

  12. Actual ratio of triacylglycerol positional isomers in milk and cheese.

    PubMed

    Gotoh, Naohiro; Matsumoto, Yumiko; Nagai, Toshiharu; Mizobe, Hoyo; Yoshinaga, Kazuaki; Kojima, Koichi; Kuroda, Ikuma; Kitamura, Yohei; Shimizu, Takashi; Ishida, Hiroki; Wada, Shun

    2012-01-01

    Actual ratios of triacylglycerol (TAG) positional isomers in human, rat, and cow milk fat and cow, buffalo, goat, and sheep cheese fat were analyzed using HPLC-UV-atmospheric pressure chemical ionization-MS/MS system equipped with an octacosyl silylation column or polymeric ODS column. We substituted cheese fats for milk fats in parts of our study because milks from ruminants, with the exception of cows, are difficult to get in Japan. The actual ratio of β-PPC (the TAG consisting of two palmitic acids (P) and one capric acid (C), with the palmitic acid located at the β position) and β-PCP in human milk was different from those in ruminants, with more than half of the medium-chain fatty acids located at the β position even though other fats possessed it mainly at the α position. Palmitic acid was mainly located at the β position for human milk and rat milk; however, the location in ruminant cheese fat was mainly at the α position. The location of fatty acids is thought to be very important for infant nutrition. Particularly, the location of palmitic acid in case of human milk and of medium-chain fatty acids in case of ruminant milk was very characteristic and is considered to be very important to the fatty acids in milk fat.

  13. Electron and Positron Scattering from C3H6 Isomers

    NASA Astrophysics Data System (ADS)

    Makochekanwa, Casten; Sueoka, Osamu; Kimura, Mineo; Hoshino, Masamitsu; Tanaka, Takahiro; Kitajima, Masashi; Tanaka, Hiroshi

    2004-09-01

    Hydrocarbons play an important role in high temperature plasmas in Tokamak fusion devices in plasma processing and many other fields [1]. In this paper we report experiments for 0.4-1000 eV electron and 0.2-1000 eV positron total cross sections (TCS) measured using a linear time-of-flight apparatus [2], and electron differential cross sections (DCS) for elastic, vibrational and electronic excitations covering the ranges 1.5 to 100 eV and 15 deg to 130 deg, measured using the crossed beam and relative flow method [3]. The continuum multiple scattering (CMS) [4] calculations have also been performed for the theoretical analysis of the observed features in our cross sections. We observe the isomer effect in both electron and positron TCSs and DCSs. The presence of a dipole moment in propene molecules shows up in enhanced forward scattering in DCSs, leading to larger TCSs and integral cross sections compared to cyclopropane at energies less than 20 eV. However, both electron and positron TCSs for these two molecules nearly equal each other above 100 eV, i.e. the molecular size effect. [1] W. L. Moragn, Adv. At. Mol. Opt. Phys. 43, 79 (2000). [2] O. Sueoka, S. Mori and A. Hamada, J. Phys. B 27, 1453 (1994). [3] H. Tanaka, L. Boesten, D. Matsunaga and T. Kudo, J. Phys. B 21, 1255 (1988). [4] M. Kimura and H. Sato, Comments At. Mol. Phys. 26, 333 (1991).

  14. Search for superradiant emission states in nuclear isomer crystals

    SciTech Connect

    Rundberg, R.S.; Wilhelmy, J.B.; Taylor, R.D.; Solem, J.C.; Fowler, M.M.; Miller, G.G.; Baldwin, G.

    1998-01-01

    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). The objective was to verify the stimulated emission of gamma rays from {sup 125m}Te, as claimed by Russian scientists. The reported cross section for stimulated emission was sufficiently large to allow gain in a single-pass gamma-ray laser. The stimulated emission of gamma rays from a nuclear isomer is expected to result in collinear photons and, therefore, should be observable as a sum peak in the gamma-ray spectrum. Skorobogatov and Dzevitskii reported an increase of an order of magnitude in the sum peak (218.56 keV) when a sample of beryllium telluride containing {sup 125m}Te was cooled from room temperature to near-liquid-helium temperatures. The authors have repeated their experiment and have observed no increase in the sum peak above accidental summing. The upper limit for the stimulated-emission cross section based on the three-standard-deviation statistical error is 6.8 x 10 {sup {minus}21} cm{sup 2}. This result is one order of magnitude lower than the cross section reported by Skorobogatov and Dzevitskii. The cross section would not allow gain in a single-pass gamma-ray laser. Their results support the position of Baldwin and Solem rather than that of Kamenov.

  15. Hydrogen rich gas generator

    NASA Technical Reports Server (NTRS)

    Houseman, J.; Rupe, J. H.; Kushida, R. O. (Inventor)

    1976-01-01

    A process and apparatus is described for producing a hydrogen rich gas by injecting air and hydrocarbon fuel at one end of a cylindrically shaped chamber to form a mixture and igniting the mixture to provide hot combustion gases by partial oxidation of the hydrocarbon fuel. The combustion gases move away from the ignition region to another region where water is injected to be turned into steam by the hot combustion gases. The steam which is formed mixes with the hot gases to yield a uniform hot gas whereby a steam reforming reaction with the hydrocarbon fuel takes place to produce a hydrogen rich gas.

  16. The space-angular characteristics of a microsecond solid laser on the basis of a nano-porous glass polymer composite activated with dyes

    NASA Astrophysics Data System (ADS)

    Tarkovsky, V.; Anufrik, S.; Koldunov, M.; Manenkov, A.

    2007-06-01

    The optimum conditions of excitation in a two-spool laser are determined, in which the pumping of a solid laser on the basis of nanoporous glass - polymer composite with the inserted dyes is made by a laser on dyes emission with a lamp pumping of microsecond duration, which provides overlapping of a broad spectral range with laser momentums with energy up to 500 mJ at the duration of 1 mcs and the divergence of 1 millirad and the increase of the radiance in 140-700 times.

  17. AN ISOMER PREDICTION MODEL FOR PCNS, PCDD/FS, AND PCBS FROM MUNICIPAL WASTE INCINERATORS

    EPA Science Inventory

    Isomer patterns of polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated biphenyls (PCBs) from municipal waste incinerators (MWIs) were predicted by a model based on dechlorination kinetics from the most-chlorinated species. Successfu...

  18. Low-energy electron scattering from C{sub 4}H{sub 9}OH isomers

    SciTech Connect

    Bettega, M. H. F.; Winstead, C.; McKoy, V.

    2010-12-15

    We present differential, integral, and momentum-transfer cross sections for elastic scattering of low-energy electrons by three butanol isomers, isobutanol, t-butanol, and 2-butanol. Our results were calculated with the Schwinger multichannel method in the static-exchange plus polarization approximation for collision energies from 1 to 50 eV. The present results are compared with previous calculations and measurements for the remaining C{sub 4}H{sub 9}OH isomer, n-butanol [Khakoo et al., Phys. Rev. A 78, 062714 (2008)]. Distinctive behavior is observed in the differential cross sections at collision energies between 5 and 10 eV. In particular, whereas n-butanol exhibits an f-wave scattering pattern, the other isomers exhibit d-wave behavior. A similar pattern is found in the related alkanes when comparing straight-chain versus branched isomers. We discuss the possible connection of this behavior to shape resonances that influence the scattering.

  19. Differential Effect of Amphetamine Optical Isomers on Bender Gestalt Performance of the Minimally Brain Dysfunctioned

    ERIC Educational Resources Information Center

    Arnold, L. Eugene; And Others

    1978-01-01

    The differential effect of amphetamine optical isomers on Bender Gestalt performance was examined in 31 hyperkinetic minimally brain dysfunctioned children between the ages of 4 and 12 years, using a double-blind Latin-square crossover comparison. (Author)

  20. Identification of Geometrical Isomers of the Cobalt(III)-Iminodiacetate System.

    ERIC Educational Resources Information Center

    Lawrance, Geoffrey A.; Rix, Colin J.

    1979-01-01

    In this experiment, students prepare, isolate, and characterize two geometrical isomers of a metal coordination compound. This experiment provides a good introduction to the techniques of modern coordination chemistry. (BB)

  1. Structural isomers of C2N(+) - A selected-ion flow tube study

    NASA Technical Reports Server (NTRS)

    Knight, J. S.; Petrie, S. A. H.; Freeman, C. G.; Mcewan, M. J.; Mclean, A. D.

    1988-01-01

    Reactivities of the structural isomers CCN(+) and CNC(+) were examined in a selected-ion flow tube at 300 + or - 5 K. The less reactive CNC(+) isomer was identified as the product of the reactions of C(+) + HCN and C(+) + C2N2; in these reactions only CNC(+) can be produced because of energy constraints. Rate coefficients and branching ratios are reported for the reactions of each isomer with H2, CH4, NH3, H2O, C2H2, HCN, N2, O2, N2O, and CO2. Ab initio calculations are presented for CCN(+) and CNC(+); a saddle point for the reaction CCN(+) yielding CNC(+) is calculated to be 195 kJ/mol above CNC(+). The results provide evidence that the more reactive CCN(+) isomer is unlikely to be present in measurable densities in interstellar clouds.

  2. Differential adsorption of complex organic molecule isomers on interstellar ice surfaces

    NASA Astrophysics Data System (ADS)

    Bertin, M.; Michaut, X.; Lattelais, M.; Mokrane, H.; Pauzat, F.; Pilmé, J.; Minot, C.; Ellinger, Y.; Romanzin, C.; Jeseck, P.; Fillion, J.-H.; Chaabouni, H.; Congiu, E.; Dulieu, F.; Baouche, S.; Lemaire, J.-L.

    2012-02-01

    We present a combined theoretical and experimental study of the adsorption of two pairs of organic isomers, (i) acetic acid AA (CH3COOH) and methyl formate MF (HCOOCH3), and (ii) ethanol EtOH (CH3CH2OH) and dimethyl ether DME (CH3OCH3), onto crystalline water ice surfaces at low temperatures. Both approaches show that, for each pair, the most stable isomer from a thermodynamical point of view, i.e. AA and EtOH, is also the one which is the more tightly bound to the water ice surface compared to the less stable isomers (MF and DME). This finding, which can be explained by the ability of AA or EtOH to efficiently interact with the ice surface via hydrogen bondings, may have important consequences in an astrophysical context, since it could explain why the most stable isomer is not the most abundant observed in the interstellar gas phase.

  3. New isomer in 96Y marking the onset of deformation at N = 57

    NASA Astrophysics Data System (ADS)

    Iskra, Ł. W.; Fornal, B.; Leoni, S.; Bocchi, G.; Petrovici, A.; Porzio, C.; Blanc, A.; De France, G.; Jentschel, M.; Köster, U.; Mutti, P.; Régis, J.-M.; Simpson, G.; Soldner, T.; Ur, C. A.; Urban, W.; Bazzacco, D.; Benzoni, G.; Bottoni, S.; Bruce, A.; Cieplicka-Oryńczak, N.; Crespi, F. C. L.; Fraile, L. M.; Korten, W.; Kröll, T.; Lalkovski, S.; Márginean, N.; Michelagnoli, C.; Melon, B.; Mengoni, D.; Million, B.; Nannini, A.; Napoli, D.; Podolyák, Zs.; Regan, P. H.; Szpak, B.

    2017-01-01

    The level scheme of 96Y was significantly extended and a new 201 ns isomer was located at 1655 keV excitation energy, with spin-parity assignment of 5± or 6‑. The isomer decays to spherical low-spin structure by transitions with large hindrance and is fed by a short cascade which resembles the beginning of a rotational band. This is in analogy with the feeding and decay pattern of the 4‑ isomer in 98Y, here confirmed, by lifetime analysis, as a bandhead of a rotational structure with sizable deformation. It is suggested that the new isomer in 96Y arises from a shape change between deformed and spherical configurations, which indicates the appearance of deformation already at N = 57 in the yttrium chain. The experimental findings for 96Y are strengthened by theoretical calculations based on the complex Excited Vampir model.

  4. Optical isomer separation of single-chirality carbon nanotubes using gel column chromatography.

    PubMed

    Liu, Huaping; Tanaka, Takeshi; Kataura, Hiromichi

    2014-11-12

    We report a gel column chromatography method for easily separating the optical isomers (i.e., left- and right-handed structures) of single-chirality carbon nanotubes. This method uses the difference in the interactions of the two isomers of a chiral single-wall carbon nanotube (SWCNT) with an allyl dextran-based gel, which result from the selective interaction of the chiral moieties of the gel with the isomers. Using this technique, we sorted optical isomers of nine distinct (n, m) single-chirality species from HiPco SWCNTs, which is the maximum number of isolable species of SWCNTs reported to date. Because of its advantages of technical simplicity, low cost, and high efficiency, gel column chromatography allows researchers to prepare macroscopic ensembles of single-structure SWCNTs and enables the complete discovery of intrinsic properties of SWCNTs and advances their application.

  5. Thinking about "Rich" Tasks

    ERIC Educational Resources Information Center

    Box, Lorna; Watson, Anne

    2010-01-01

    This article presents an e-mail conversation between two teachers discussing how to have a "rich task" lesson in which they get to the heart of mathematical modeling and in which students are motivated into working on mathematics. One teacher emphasizes that the power of maths is in developing mathematical descriptions of situations by…

  6. From Rags to Riches

    ERIC Educational Resources Information Center

    Sweet, Colleen

    2008-01-01

    In this article, the author presents the "Rags to Riches" design project she introduced to her students. She assigned each of her students one item from an array to thrift store goods which included old scarves, sweaters, jackets, and even evening gowns. The design problem was to imagine what a clothing tag might look like if the assigned item…

  7. Isomer Tagging with a Dual Multi-Wire Proportional Counter and a Differential Plunger

    SciTech Connect

    Cullen, D. M.; Mason, P. J. R.; Khan, S.; Kishada, A. M.; Varley, B. J.; Rigby, S. V.; Scholey, C.; Greenlees, P.; Rahkila, P.; Jones, P. M.; Julin, R.; Juutinen, S.; Leino, M.; Leppaenen, A. P.; Nyman, M.; Uusitalo, J.; Grahn, T.; Pakarinen, J.; Nieminen, P.

    2008-05-12

    This report details the status of an experimental research programme which has studied isomeric states in the mass 130-160 region of the nuclear chart. Several new isomers have been established and characterised near the proton drip line using a recoil isomer tagging technique at the University of Jyvaeskylae, Finland. The latest experiments have been performed with a modified setup where the standard GREAT focal-plane double-sided silicon-strip detector was changed to a dual multi-wire proportional-counter arrangement. This new setup has improved capability for short-lived isomer studies where large focal-plane rates can be tolerated. The results of key recent experiments for nuclei situated above ({sup 153}Yb, {sup 152}Tm) and below ({sup 144}Ho, {sup 142}Tb) the N = 82 shell gap were presented. These studies have charted the evolution of isomeric states across the neutron shell from K-Isomers at N = 74, to shape isomers at N = 77 and shell-model isomers at N = 82, 83. The excitation energies for some of the lowest-lying excited states in these isomeric nuclei show behaviour which is characteristic of an X(5) symmetry falling midway between the limits expected for pure vibrational and rotational behaviour. The future prospects for studies of these nuclei were discussed using an isomer-tagged differential-plunger setup. This technique will be capable of establishing the deformation of the states above the isomers and will aid in determining whether their behaviour is indeed well described by the X(5) symmetry limit.

  8. Laser-optical studies of the spontaneous-fission isomer /sup 240m/Am

    SciTech Connect

    Beene, J.R.; Bemis, C.E. Jr.; Kramer, S.D.; Young, J.P.

    1982-01-01

    Improved optical pumping experiments on the /sup 240m/Am fission isomer have been performed using the Laser Induced Nuclear Polarization (LINUP) technique. Results of these experiments are discussed in terms of the constraints they place on the spectroscopic properties of /sup 240m/Am. In addition, a quantitative analysis of the isomer shift in terms of nuclear shape is undertaken making use of recent muonic x-ray data on /sup 241/Am and /sup 243/Am.

  9. Isomer-specific biotransformation of perfluorooctane sulfonamide in Sprague-Dawley rats.

    PubMed

    Ross, Matthew S; Wong, Charles S; Martin, Jonathan W

    2012-03-20

    Great variability exists in perfluorooctane sulfonate (PFOS) isomer patterns in human and wildlife samples, including unexpectedly high percentages (e.g., >40%) of branched isomers in human sera. Previous in vitro tests showed that branched PFOS-precursors were biotransformed faster than the corresponding linear isomer. Thus, high percentages of branched PFOS may be a biomarker of PFOS-precursor exposure in humans. We evaluated this hypothesis by examining the isomer-specific fate of perfluorooctane sulfonamide (PFOSA), a known PFOS-precursor, in male Sprague-Dawley rats exposed to commercial PFOSA via food for 77 days (83.0 ± 20.4 ng kg(-1) day(-1)), followed by 27 days of depuration. Elimination half-lives of the two major branched PFOSA isomers (2.5 ± 1.0 days and 3.7 ± 1.2 days) were quicker than for linear PFOSA (5.9 ± 4.6 days), resulting in a depletion of branched PFOSA isomers in blood and tissues relative to the dose. A corresponding increase in the total branched isomer content of PFOS, the ultimate metabolite, in rat serum was not observed. However, a significant enrichment of 5m-PFOS and a significant depletion of 1m-PFOS were observed, relative to authentic electrochemical PFOS. The data cannot be directly extrapolated to humans, due to known differences in the toxicokinetics of PFOS in rodents and humans. However, the results confirm that in vivo exposure to commercially relevant PFOS-precursors can result in a distinct PFOS isomer profile that may be useful as a biomarker of exposure source.

  10. Theoretical 57Fe Mössbauer spectroscopy: isomer shifts of [Fe]-hydrogenase intermediates.

    PubMed

    Hedegård, Erik Donovan; Knecht, Stefan; Ryde, Ulf; Kongsted, Jacob; Saue, Trond

    2014-03-14

    Mössbauer spectroscopy is an indispensable spectroscopic technique and analytical tool in iron coordination chemistry. The linear correlation between the electron density at the nucleus ("contact density") and experimental isomer shifts has been used to link calculated contact densities to experimental isomer shifts. Here we have investigated relativistic methods of systematically increasing sophistication, including the eXact 2-Component (X2C) Hamiltonian and a finite-nucleus model, for the calculation of isomer shifts of iron compounds. While being of similar accuracy as the full four-component treatment, X2C calculations are far more efficient. We find that effects of spin-orbit coupling can safely be neglected, leading to further speedup. Linear correlation plots using effective densities rather than contact densities versus experimental isomer shift lead to a correlation constant a = -0.294 a0(-3) mm s(-1) (PBE functional) which is close to an experimentally derived value. Isomer shifts of similar quality can thus be obtained both with and without fitting, which is not the case if one pursues a priori a non-relativistic model approach. As an application for a biologically relevant system, we have studied three recently proposed [Fe]-hydrogenase intermediates. The structures of these intermediates were extracted from QM/MM calculations using large QM regions surrounded by the full enzyme and a solvation shell of water molecules. We show that a comparison between calculated and experimentally observed isomer shifts can be used to discriminate between different intermediates, whereas calculated atomic charges do not necessarily correlate with Mössbauer isomer shifts. Detailed analysis reveals that the difference in isomer shifts between two intermediates is due to an overlap effect.

  11. Superprolate shape of the spontaneous-fission isomer /sup 240/Am/sup m/

    SciTech Connect

    Pauling, L.

    1980-10-01

    A superprolate structure for nuclei with Aapprox.240 proposed in 1965 on the basis of the polyspheron theory leads to the value 0.66 for the deformation parameter ..beta... This value agrees well with a recently reported experimental value, 0.66 +- 0.04 for the spontaneous-fission isomer /sup 240/Am/sup m/, obtained by Bemis et al. from their measurement of the optical isomer shift. This agreement provides additional support for the proposed superprolate structure.

  12. Energy spectrum of isomer no. 3 of C82 fullerene of C 2 symmetry

    NASA Astrophysics Data System (ADS)

    Kareev, I. E.; Bubnov, V. P.; Kotov, A. I.; Lobanov, B. V.; Murzashev, A. I.; Rumyantsev, I. A.

    2017-01-01

    The energy spectrum of C82 fullerene (isomer no. 3 of C 2 symmetry) is calculated within the Hubbard model in the approximation of static fluctuations. Based on the energy spectrum, optical absorption spectra of this isomer in neutral and anionic states with one, two, three, and four additional electrons are simulated. The calculated optical spectra in neutral and monoanionic states are compared with known experimental spectra.

  13. Isomer Studies for Nuclei near the Proton Drip Line in the Mass 130-160 Region

    SciTech Connect

    Cullen, D. M.; Mason, P. J. R.; Khan, S.; Kishada, A. M.; Varley, B. J.; Rigby, S. V.; Scholey, C.; Greenlees, P.; Rahkila, P.; Jones, P. M.; Julin, R.; Juutinen, S.; Leino, M.; Leppaenen, A. P.; Nyman, M.; Uusitalo, J.; Grahn, T.; Nieminen, P.; Pakarinen, J.

    2007-11-30

    This report details the status of an experimental research programme which has studied isomeric states in the mass 130-160 region of the nuclear chart. Several new isomers have been established and characterised near the proton drip line using a recoil isomer tagging technique at the University of Jyvaeskylae, Finland. The latest experiments have been performed with a modified setup where the standard GREAT focal-plane double-sided silicon-strip detector was changed to a dual multi-wire proportional-counter arrangement. This new setup has improved capability for short-lived isomer studies where high focal-plane rates can be tolerated. The results of key recent experiments for nuclei situated above ({sup 153}Yb,{sup 152}Tm) and below ({sup 136}Pm,{sup 142}Tb) the N = 82 shell gap were presented along with an interpretation for the isomers. Finally, the future prospects of the technique, using an isomer-tagged differential-plunger setup, were discussed. This technique will be capable of establishing the deformation of the states above the isomers and will aid in the process of assigning underlying single-particle configurations to the isomeric states.

  14. Roles of the tyrosine isomers meta-tyrosine and ortho-tyrosine in oxidative stress.

    PubMed

    Ipson, Brett R; Fisher, Alfred L

    2016-05-01

    The damage to cellular components by reactive oxygen species, termed oxidative stress, both increases with age and likely contributes to age-related diseases including Alzheimer's disease, atherosclerosis, diabetes, and cataract formation. In the setting of oxidative stress, hydroxyl radicals can oxidize the benzyl ring of the amino acid phenylalanine, which then produces the abnormal tyrosine isomers meta-tyrosine or ortho-tyrosine. While elevations in m-tyrosine and o-tyrosine concentrations have been used as a biological marker of oxidative stress, there is emerging evidence from bacterial, plant, and mammalian studies demonstrating that these isomers, particularly m-tyrosine, directly produce adverse effects to cells and tissues. These new findings suggest that the abnormal tyrosine isomers could in fact represent mediators of the effects of oxidative stress. Consequently the accumulation of m- and o-tyrosine may disrupt cellular homeostasis and contribute to disease pathogenesis, and as result, effective defenses against oxidative stress can encompass not only the elimination of reactive oxygen species but also the metabolism and ultimately the removal of the abnormal tyrosine isomers from the cellular amino acid pool. Future research in this area is needed to clarify the biologic mechanisms by which the tyrosine isomers damage cells and disrupt the function of tissues and organs and to identify the metabolic pathways involved in removing the accumulated isomers after exposure to oxidative stress.

  15. Surfactant mediated enhanced biodegradation of hexachlorocyclohexane (HCH) isomers by Sphingomonas sp. NM05.

    PubMed

    Manickam, Natesan; Bajaj, Abhay; Saini, Harvinder S; Shanker, Rishi

    2012-09-01

    Environmental biodegradation of several chlorinated pesticides is limited by their low solubility and sorption to soil surfaces. To mitigate this problem we quantified the effect of three biosurfactant viz., rhamnolipid, sophorolipid and trehalose-containing lipid on the dissolution, bioavailability, and biodegradation of HCH-isomers in liquid culture and in contaminated soil. The effect of biosurfactants was evaluated through the critical micelle concentration (CMC) value as determined for each isomer. The surfactant increased the solubilization of HCH isomers by 3-9 folds with rhamnolipid and sophorolipid being more effective and showing maximum solubilization of HCH isomers at 40 μg/mL, compared to trehalose-containing lipid showing peak solubilization at 60 μg/mL. The degradation of HCH isomers by Sphingomonas sp. NM05 in surfactant-amended liquid mineral salts medium showed 30% enhancement in 2 days as compared to degradation in 10 days in the absence of surfactant. HCH-spiked soil slurry incubated with surfactant also showed around 30-50% enhanced degradation of HCH which was comparable to the corresponding batch culture experiments. Among the three surfactants, sophorolipid offered highest solubilization and enhanced degradation of HCH isomers both in liquid medium and soil culture. The results of this study suggest the effectiveness of surfactants in improving HCH degradation by increased bioaccessibility.

  16. 241Am (n,gamma) isomer ratio measurement

    SciTech Connect

    Bond, Evelyn M; Vieira, David J; Moody, Walter A; Slemmons, Alice K

    2011-01-05

    The objective of this project is to improve the accuracy of the {sup 242}Cm/{sup 241}Am radiochemistry ratio. We have performed an activation experiment to measure the {sup 241}Am(n,{gamma}) cross section leading to either the ground state of {sup 242g}Am (t{sub 1/2} = 16 hr) which decays to {sup 242}Cm (t{sub 1/2} = 163 d) or the long-lived isomer {sup 242m}Am (t{sub 1/2} = 141 yr). This experiment will develop a new set of americium cross section evaluations that can be used with a measured {sup 242}Cm/{sup 241}Am radiochemical measurement for nuclear forensic purposes. This measurement is necessary to interpret the {sup 242}Cm/{sup 241}Am ratio because a good measurement of this neutron capture isomer ratio for {sup 241}Am does not exist. The targets were prepared in 2007 from {sup 241}Am purified from LANL stocks. Gold was added to the purified {sup 241}Am as an internal neutron fluence monitor. These targets were placed into a holder, packaged, and shipped to Forschungszentrum Karlsruhe, where they were irradiated at their Van de Graff facility in February 2008. One target was irradiated with {approx}25 keV quasimonoenergetic neutrons produced by the {sup 7}Li(p,n) reaction for 3 days and a second target was also irradiated for 3 days with {approx}500 keV neutrons. Because it will be necessary to separate the {sup 242}Cm from the {sup 241}Am in order to measure the amount of {sup 242}Cm by alpha spectrometry, research into methods for americium/curium separations were conducted concurrently. We found that anion exchange chromatography in methanol/nitric acid solutions produced good separations that could be completed in one day resulting in a sample with no residue. The samples were returned from Germany in July 2009 and were counted by gamma spectrometry. Chemical separations have commenced on the blank sample. Each sample will be spiked with {sup 244}Cm, dissolved and digested in nitric acid solutions. One third of each sample will be processed at a time

  17. Neutron-Rich Isotopes from 208Pb at 86 MeV/u

    NASA Astrophysics Data System (ADS)

    Tarasov, O. B.; Portillo, M.; Amthor, A. M.; Baumann, T.; Bazin, D.; Folden, C.; Ginter, T.; Hausmann, M.; Morrissey, D. J.; Pereira, J.; Sherrill, B. M.; Thoennessen, M.; Nociforo, C.

    2008-10-01

    An experiment to measure production yields from a beam of ^208Pb (86 MeV/u) on Be and Ni-targets has recently been performed. The A1900 fragment-separator [1] was used to analyze products from projectile fragmentation and abrasion-fission [2]. Isotopic identification of nuclides having A˜200 has been achieved, demonstrating that adequate A,Z,Q resolution at this energy region is possible when using silicon detectors. The verification of PID is done via detection of multiple charge state distributions of the primary beam, as well as γ-decay of known isomers with half-lives in the microsecond range. The results demonstrate that experiments with heavy nuclei are possible at the NSCL using beams of A>200. Production cross-sections have been extracted from the data that can help improve the accuracy of production models such as Abrasion-Ablation and Abrasion-Fission used in the LISE++ code [3]. The data reveal the existence of previously unreported isomeric transitions and further analysis is ongoing that may also lead to the observation of new isotopes. References: [1] D.J.Morrissey et al., Nucl. Instrum. Meth. B204 (2003) 90--96. [2] O.B. Tarasov, Tech. Rep. MSUCL1300, NSCL, Michigan St.Univ., 2005. [3] O.B. Tarasov, D. Bazin, Nucl. Phys. A 746 (2004) 411; www.nscl.msu.edu/lise .

  18. Quantification of Structural Isomers via Mode-Selective Irmpd

    NASA Astrophysics Data System (ADS)

    Polfer, Nicolas C.

    2016-06-01

    Mixtures of structural isomers can pose a challenge for vibrational ion spectroscopy. In cases where particular structures display diagnostic vibrations, these structures can be selectively "burned away". In ion traps, the ion population can be subjected to multiple laser shots, in order to fully deplete a particular structure, in effect allowing a quantification of this structure. Protonated para-amino benzoic acid (PABA) serves as an illustrative example. PABA is known to preferentially exist in the N-protonated (N-prot) form in solution, but in the gas phase it is energetically favorable in the O-protonated (O-prot) form. As shown in Figure 1, the N-prot structure can be kinetically trapped in the gas phase when sprayed from non-protic solvent, whereas the O-prot structure is obtained when sprayed from protic solvents, analogous to results by others [1,2]. y parking the light source on the diagnostic 3440 wn mode, the percentage of the O-prot structure can be determined, and by default the remainder is assumed to adopt the N-prot structure. It will be shown that the relative percentages of O-prot vs N-prot are highly dependent on the solvent mixture, going from close to 0% O-prot in non-protic solvents, to 99% in protic solvents. Surprisingly, water behaves much more like a non-protic solvent than methanol. It is observed that the capillary temperature, which aids droplet desolvation by black-body radiation in the ESI source, is critical to promote the appearance of O-prot structures. These results are consistent with the picture that a protic bridge mechanism is at play to facilitate proton transfer, and thus allow conversion from N-prot to O-prot, but that this mechanism is subject to appreciable kinetic barriers on the timescale of solvent evaporation. 1. J. Phys. Chem. A 2011, 115, 7625. 2. Anal. Chem. 2012, 84, 7857.

  19. Tuneable microsecond-pulsed glow discharge design for the simultaneous acquisition of elemental and molecular chemical information using a time-of-flight mass spectrometer.

    PubMed

    Solà-Vázquez, Auristela; Martín, Antonio; Costa-Fernández, José M; Pereiro, Rosario; Sanz-Medel, Alfredo

    2009-04-01

    A microsecond-pulsed direct current glow discharge (GD) was interfaced and synchronized to a time-of-flight mass spectrometer MS(TOF) for time-gated generation and detection of elemental, structural, and molecular ions. In this way, sequential collection of the mass spectra at different temporal regimes occurring during the GD pulse cycle is allowed. The capabilities of this setup were explored using bromochloromethane as model analyte. A simple GD chamber, developed in our laboratory and characterized by a low plasma volume minimizing dilution of the sample but showing great robustness to the entrance of organic compounds in the microsecond-pulsed plasma, has been used. An exhaustive analytical characterization of the GD-MS(TOF) prototype has been performed. Calibration curves for bromochloromethane observed at the different time regimes of the GD pulse cycle (that is, for elemental, fragment, and molecular ions from the analyte) showed very good linearity for the measurement of the different involved ions, with precisions in the range of 7-13% (relative standard deviation). Actual detection limits obtained for bromochloromethane were in the range of 1-3 microg/L for elements monitoring in the GD pulse "prepeak", in the range of 11-13 microg/L when monitoring analyte fragments in the plateau, and about 238 microg/L when measuring the molecular peak in the afterpeak regime.

  20. Definition of "positional isomer" as it pertains to the control of schedule I controlled substances. Final rule.

    PubMed

    2007-12-03

    On May 25, 2006, DEA published a Notice of Proposed Rulemaking which proposed the addition of a specific definition for the term "positional isomer" to allow for the systematic determination of which isomers of schedule I substances would be considered to be "positional," and therefore, subject to schedule I control. This rulemaking finalizes that definition. The Controlled Substances Act (CSA) and its implementing regulations specify which hallucinogenic substances are considered schedule I controlled substances. The CSA states that all salts, isomers, and salts of isomers of these substances are also schedule I controlled substances. In non-technical terms, an isomer of a substance is a different compound, but a compound which has the same number and kind of atoms. The terms "optical isomer" and "geometric isomer" are specific scientific terms and it is easy to determine whether one substance is an optical or geometric isomer of another. The term "positional isomer," however, is subject to scientific interpretation. The addition of a definition for the term "positional isomer" will assist legitimate research[ers] and industry in determining the control status of materials that are "positional isomers" of schedule I hallucinogens. While the DEA will remain the authority for ultimately determining the control status of a given material, providing a specific definition for "positional isomer" will ensure consistent criteria are utilized in making these determinations. This rule does not change existing laws, regulations, policies, processes, and procedures regarding the determination of control status for schedule I hallucinogenic substances. This rule merely makes available to the public the longstanding definition of "positional isomer" which DEA has used when making these scheduling determinations. This rule is relevant only to specialized forensic or research chemists. Most of these individuals are existing DEA registrants who are authorized by the DEA to handle

  1. The CBM RICH project

    NASA Astrophysics Data System (ADS)

    Adamczewski-Musch, J.; Akishin, P.; Becker, K.-H.; Belogurov, S.; Bendarouach, J.; Boldyreva, N.; Chernogorov, A.; Deveaux, C.; Dobyrn, V.; Dürr, M.; Eschke, J.; Förtsch, J.; Heep, J.; Höhne, C.; Kampert, K.-H.; Kochenda, L.; Kopfer, J.; Kravtsov, P.; Kres, I.; Lebedev, S.; Lebedeva, E.; Leonova, E.; Linev, S.; Mahmoud, T.; Michel, J.; Miftakhov, N.; Niebur, W.; Ovcharenko, E.; Patel, V.; Pauly, C.; Pfeifer, D.; Querchfeld, S.; Rautenberg, J.; Reinecke, S.; Riabov, Y.; Roshchin, E.; Samsonov, V.; Tarasenkova, O.; Traxler, M.; Ugur, C.; Vznuzdaev, E.; Vznuzdaev, M.

    2017-02-01

    The CBM RICH detector is an integral component of the future CBM experiment at FAIR, providing efficient electron identification and pion suppression necessary for the measurement of rare dileptonic probes in heavy ion collisions. The RICH design is based on CO2 gas as radiator, a segmented spherical glass focussing mirror with Al+MgF2 reflective coating, and Multianode Photomultipliers for efficient Cherenkov photon detection. Hamamatsu H12700 MAPMTs have recently been selected as photon sensors, following an extensive sensor evaluation, including irradiation tests to ensure sufficient radiation hardness of the MAPMTs. A brief overview of the detector design and concept is given, results on the radiation hardness of the photon sensors are shown, and the development of a FPGA-TDC based readout chain is discussed.

  2. Feeding of Rh and Ag isomers in fast-neutron-induced reactions

    DOE PAGES

    Fotiades, Nikolaos; Devlin, Matthew James; Nelson, Ronald Owen; ...

    2016-10-17

    In (n,n') reactions on stable Ir and Au isotopes in the mass A=190 region, the experimentally established feeding of the isomers relative to the feeding of the corresponding ground states increases with increasing neutron energy, up to the neutron energy where the (n,2n) reaction channel opens up, and then decreases. In order to check for similar behavior in the mass A=100 region, the feeding of isomers and ground states in fast-neutron-induced reactions on stable isotopes in this mass region was studied. This is of especial interest for Rh which can be used as a radiochemical detector. Here, excited states weremore » studied using the (n,n'γ), (n,2nγ), and (n,3nγ) reactions on 103Rh and 109Ag. A germanium detector array for γ-ray detection and the broad-spectrum pulsed neutron source of the Los Alamos Neutron Science Center's Weapons Neutron Research facility were used for the measurement. The energy of the incident neutrons was determined using the time-of-flight technique. Absolute partial γ-ray cross sections were measured for 57 transitions feeding isomers and ground states in 101,102,103Rh and 107,108,109Ag. The feeding of the isomers was found to be very similar in the corresponding reaction channels and it is compared to the feeding determined for the ground states. In conclusion, the opening of reaction channels at higher neutron energies removes angular momentum from the residual nucleus and reduces the population of the higher-spin isomers relative to the feeding of the lower-spin ground states. Similar behavior was observed in the mass A=190 region in the feeding of higher-spin isomers, but the reverse behavior was observed in 176Lu with a lower-spin isomer and a higher-spin ground state.« less

  3. Accurate ab initio Quartic Force Fields of Cyclic and Bent HC2N Isomers

    NASA Technical Reports Server (NTRS)

    Inostroza, Natalia; Huang, Xinchuan; Lee, Timothy J.

    2012-01-01

    Highly correlated ab initio quartic force field (QFFs) are used to calculate the equilibrium structures and predict the spectroscopic parameters of three HC2N isomers. Specifically, the ground state quasilinear triplet and the lowest cyclic and bent singlet isomers are included in the present study. Extensive treatment of correlation effects were included using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted CCSD(T). Dunning s correlation-consistent basis sets cc-pVXZ, X=3,4,5, were used, and a three-point formula for extrapolation to the one-particle basis set limit was used. Core-correlation and scalar relativistic corrections were also included to yield highly accurate QFFs. The QFFs were used together with second-order perturbation theory (with proper treatment of Fermi resonances) and variational methods to solve the nuclear Schr dinger equation. The quasilinear nature of the triplet isomer is problematic, and it is concluded that a QFF is not adequate to describe properly all of the fundamental vibrational frequencies and spectroscopic constants (though some constants not dependent on the bending motion are well reproduced by perturbation theory). On the other hand, this procedure (a QFF together with either perturbation theory or variational methods) leads to highly accurate fundamental vibrational frequencies and spectroscopic constants for the cyclic and bent singlet isomers of HC2N. All three isomers possess significant dipole moments, 3.05D, 3.06D, and 1.71D, for the quasilinear triplet, the cyclic singlet, and the bent singlet isomers, respectively. It is concluded that the spectroscopic constants determined for the cyclic and bent singlet isomers are the most accurate available, and it is hoped that these will be useful in the interpretation of high-resolution astronomical observations or laboratory experiments.

  4. Isomers of perfluorooctanesulfonate (PFOS) in cord serum and birth outcomes in China: Guangzhou Birth Cohort Study.

    PubMed

    Li, Meng; Zeng, Xiao-Wen; Qian, Zhengmin Min; Vaughn, Michael G; Sauvé, Sébastien; Paul, Gunther; Lin, Shao; Lu, Long; Hu, Li-Wen; Yang, Bo-Yi; Zhou, Yang; Qin, Xiao-Di; Xu, Shu-Li; Bao, Wen-Wen; Zhang, Ya-Zhi; Yuan, Ping; Wang, Jia; Zhang, Chuan; Tian, Yan-Peng; Nian, Min; Xiao, Xiang; Fu, Chuanxi; Dong, Guang-Hui

    2017-03-12

    Prior investigations on the associations of polyfluoroalkyl substances (PFASs) with fetal growth are mixed. Moreover, little research has accrued pertaining to the association between isomers of PFASs with gestational age and birth weight. To address this gap and present novel information, we conducted a study including 321 pairs of mothers and their infants recruited from Guangzhou, China. High performance liquid chromatography-mass spectrometry was utilized to analyze isomers of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA) along with other PFAS levels in cord serum samples. Mothers' and infants' characteristics were gathered from medical records. The resulting data revealed that higher PFOS, PFOA and isomers of PFOS were associated with lower birth weight. Per ln-unit (ng/mL) increase in cord serum total branched PFOS isomers was associated with a 126.3g (95% CI: -195.9, -56.8) reduction in the weight of infants at birth, while an ln-unit (ng/mL) increase of serum linear PFOS isomers (n-PFOS) was associated with a 57.2g (95% CI: -103.1, -11.3) reduction in the weight of infants at birth upon the subsequent adjustment for potential confounding variables. Notably, the association between cord PFAS level and birth weight was more pronounced in male infants. Furthermore, a positive association among branched PFOS isomers (1m-PFOS and 3+4+5m-PFOS) and gestational age was found. No associations could be found among other PFASs in conjunction with gestational age or birth weight. In conclusion, this investigation suggests that higher PFAS concentrations are associated with lower birth weight, and branched PFOS isomers show greater impact on infant birth weight than linear PFOS.

  5. Feeding of Rh and Ag isomers in fast-neutron-induced reactions

    NASA Astrophysics Data System (ADS)

    Fotiades, N.; Devlin, M.; Nelson, R. O.; Kawano, T.; Carroll, J. J.

    2016-10-01

    Background: In (n ,n' ) reactions on stable Ir and Au isotopes in the mass A =190 region, the experimentally established feeding of the isomers relative to the feeding of the corresponding ground states increases with increasing neutron energy, up to the neutron energy where the (n ,2 n ) reaction channel opens up, and then decreases. Purpose: In order to check for similar behavior in the mass A =100 region, the feeding of isomers and ground states in fast-neutron-induced reactions on stable isotopes in this mass region was studied. This is of especial interest for Rh which can be used as a radiochemical detector. Methods: Excited states were studied using the (n ,n'γ ), (n ,2 n γ ), and (n ,3 n γ ) reactions on 103Rh and 109Ag. A germanium detector array for γ -ray detection and the broad-spectrum pulsed neutron source of the Los Alamos Neutron Science Center's Weapons Neutron Research facility were used for the measurement. The energy of the incident neutrons was determined using the time-of-flight technique. Results: Absolute partial γ -ray cross sections were measured for 57 transitions feeding isomers and ground states in 101,102,103Rh and 107,108,109Ag. The feeding of the isomers was found to be very similar in the corresponding reaction channels and it is compared to the feeding determined for the ground states. Conclusions: The opening of reaction channels at higher neutron energies removes angular momentum from the residual nucleus and reduces the population of the higher-spin isomers relative to the feeding of the lower-spin ground states. Similar behavior was observed in the mass A =190 region in the feeding of higher-spin isomers, but the reverse behavior was observed in 176Lu with a lower-spin isomer and a higher-spin ground state.

  6. Feeding of Rh and Ag isomers in fast-neutron-induced reactions

    SciTech Connect

    Fotiades, Nikolaos; Devlin, Matthew James; Nelson, Ronald Owen; Kawano, T.; Carroll, J. J.

    2016-10-17

    In (n,n') reactions on stable Ir and Au isotopes in the mass A=190 region, the experimentally established feeding of the isomers relative to the feeding of the corresponding ground states increases with increasing neutron energy, up to the neutron energy where the (n,2n) reaction channel opens up, and then decreases. In order to check for similar behavior in the mass A=100 region, the feeding of isomers and ground states in fast-neutron-induced reactions on stable isotopes in this mass region was studied. This is of especial interest for Rh which can be used as a radiochemical detector. Here, excited states were studied using the (n,n'γ), (n,2nγ), and (n,3nγ) reactions on 103Rh and 109Ag. A germanium detector array for γ-ray detection and the broad-spectrum pulsed neutron source of the Los Alamos Neutron Science Center's Weapons Neutron Research facility were used for the measurement. The energy of the incident neutrons was determined using the time-of-flight technique. Absolute partial γ-ray cross sections were measured for 57 transitions feeding isomers and ground states in 101,102,103Rh and 107,108,109Ag. The feeding of the isomers was found to be very similar in the corresponding reaction channels and it is compared to the feeding determined for the ground states. In conclusion, the opening of reaction channels at higher neutron energies removes angular momentum from the residual nucleus and reduces the population of the higher-spin isomers relative to the feeding of the lower-spin ground states. Similar behavior was observed in the mass A=190 region in the feeding of higher-spin isomers, but the reverse behavior was observed in 176Lu with a lower-spin isomer and a higher-spin ground state.

  7. Accurate ab initio quartic force fields of cyclic and bent HC2N isomers.

    PubMed

    Inostroza, Natalia; Huang, Xinchuan; Lee, Timothy J

    2011-12-28

    Highly correlated ab initio quartic force fields (QFFs) are used to calculate the equilibrium structures and predict the spectroscopic parameters of three HC(2)N isomers. Specifically, the ground state quasilinear triplet and the lowest cyclic and bent singlet isomers are included in the present study. Extensive treatment of correlation effects were included using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted as CCSD(T). Dunning's correlation-consistent basis sets cc-pVXZ, X = 3,4,5, were used, and a three-point formula for extrapolation to the one-particle basis set limit was used. Core-correlation and scalar relativistic corrections were also included to yield highly accurate QFFs. The QFFs were used together with second-order perturbation theory (PT) (with proper treatment of Fermi resonances) and variational methods to solve the nuclear Schrödinger equation. The quasilinear nature of the triplet isomer is problematic, and it is concluded that a QFF is not adequate to describe properly all of the fundamental vibrational frequencies and spectroscopic constants (though some constants not dependent on the bending motion are well reproduced by PT). On the other hand, this procedure (a QFF together with either PT or variational methods) leads to highly accurate fundamental vibrational frequencies and spectroscopic constants for the cyclic and bent singlet isomers of HC(2)N. All three isomers possess significant dipole moments, 3.05 D, 3.06 D, and 1.71 D, for the quasilinear triplet, the cyclic singlet, and the bent singlet isomers, respectively. It is concluded that the spectroscopic constants determined for the cyclic and bent singlet isomers are the most accurate available, and it is hoped that these will be useful in the interpretation of high-resolution astronomical observations or laboratory experiments.

  8. Nucleation and stabilization of carbon-rich structures in interstellar media

    SciTech Connect

    Patra, N.; Král, P.; Sadeghpour, H. R. E-mail: pkral@uic.edu

    2014-04-10

    We study the conditions under which carbon clusters of different sizes form and stabilize. We describe the approach to equilibrium by simulating tenuous carbon gas dynamics to long times. First, we use reactive molecular dynamics simulations to describe the nucleation of long chains, large clusters, and complex cage structures in carbon- and hydrogen-rich interstellar gas phases. We study how temperature, particle density, the presence of hydrogen, and carbon inflow affect the nucleation of molecular moieties with different characteristics, in accordance with astrophysical conditions. We extend the simulations to densities that are orders of magnitude lower than current laboratory densities, to temperatures that are relevant to circumstellar environments of planetary nebulae, and microsecond formation times. We correlate cluster size distributions from the simulations with thermodynamic equilibrium at low temperatures and gas densities, where entropy plays a significant role.

  9. Isomers of fluoroamphetamines detected in forensic cases in Denmark.

    PubMed

    Johansen, Sys Stybe; Hansen, Tina Maria

    2012-07-01

    A study was performed on the detection, separation and quantification of isomers from the new designer drugs named fluoroamphetamines (FAs) in forensic cases in eastern Denmark. The drugs were detected in whole blood extracts by ultraperformance liquid chromatography with time of flight mass spectrometer (UPLC-TOF-MS) and thereafter verified and quantified by UPLC tandem mass spectrometer (MS/MS). The quantitative method involved liquid–liquid extraction of FAs from whole blood, evaporation of organic solvent, and reconstitution with a mobile phase mixture. Identification of the FAs was achieved by the retention time, multiple reaction monitoring (MRM) traces [154 > 109 (quantifier); 154 > 137], and ion ratio of the two transitions. For all FAs, LOQ was 0.002 mg/kg with linear ranges from 0.002 to 1.0 mg/kg whole blood. Since 2008, a total of 15 forensic investigations, mainly driving under the influence of drugs (DUID) cases, involving 4-fluoroamphetamine (4-FA) have been observed with whole blood concentrations ranging from 0.006 to 0.58 mg/kg. One autopsy case involved 4-FA; however, it was determined to be a combined intoxication. In 2010, ortho-fluoroamphetamine (2-FA) was discovered in forensic samples by the same UPLC/MS/MS method and MRM functions because of variation in retention time and ion ratio. Up to now, three eastern Danish DUID cases have involved 2-FA. The whole blood concentrations of 2-FA were 0.028, 0.041 and 0.37 mg/kg, respectively. Thirteen cases with 4-FA and the three cases with 2-FA also contained amphetamine, but no correlation was observed between the amount of FA and amphetamine. So far, 3-FA has not been observed in any cases, and although it co-elutes with 4-FA, 3-FA will be identified by its variation in ion ratio. To our knowledge, this study has confirmed 2-FA in blood from DUID cases for the first time, and provides typical whole blood concentrations of FAs in forensic cases.

  10. 40 CFR 180.449 - Avermectin B1 and its delta-8,9-isomer; tolerances for residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Avermectin B1 and its delta-8,9-isomer... Tolerances § 180.449 Avermectin B1 and its delta-8,9-isomer; tolerances for residues. (a) General. Tolerances... (5-O-demethyl-25-de(1-methylpropyl)-25-(1-methylethyl) avermectin A1) and its delta-8,9-isomer in...

  11. 40 CFR 180.449 - Avermectin B1 and its delta-8,9-isomer; tolerances for residues.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Avermectin B1 and its delta-8,9-isomer... Tolerances § 180.449 Avermectin B1 and its delta-8,9-isomer; tolerances for residues. (a) General. Tolerances... (5-O-demethyl-25-de(1-methylpropyl)-25-(1-methylethyl) avermectin A1) and its delta-8,9-isomer in...

  12. 40 CFR 180.449 - Avermectin B1 and its delta-8,9-isomer; tolerances for residues.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Avermectin B1 and its delta-8,9-isomer... Tolerances § 180.449 Avermectin B1 and its delta-8,9-isomer; tolerances for residues. (a) General. Tolerances... following table is to be determined by measuring only avermectin B1 and its delta-8,9-isomer in or on...

  13. Impact of the electron environment on the lifetime of the {sup 229}Th{sup m} low-lying isomer

    SciTech Connect

    Karpeshin, F. F.; Trzhaskovskaya, M. B.

    2007-11-15

    The question of the lifetime of the {sup 229}Th{sup m} low-lying isomer is considered in light of current experimental research. A strong effect of the electron shell on lifetime is demonstrated, depending on the energy of the isomer. Calculations are performed within the framework of the multiconfiguration Dirac-Fock method. The calculated lifetime ranges from around 1 min down to 10{sup -5} s. Prospects for further experimental research of the isomer are discussed.

  14. Data Rich, Information Poor

    SciTech Connect

    Kaplan, P.G.; Rautman, C.A.

    1998-11-09

    Surviving in a data-rich environment means understanding the difference between data and information. This paper reviews an environmental case study that illustrates that understanding and shows its importance. In this study, a decision problem was stated in terms of au economic-objective fimction. The function contains a term that defines the stochastic relationship between the decision and the information obtained during field chamctetition for an environmental contaminant. Data is defied as samples drawn or experimental realizations of a mudom fimction. Information is defined as the quantitative change in the value of the objective fiction as a result of the sample.

  15. Elucidation of Drug Metabolite Structural Isomers Using Molecular Modeling Coupled with Ion Mobility Mass Spectrometry.

    PubMed

    Reading, Eamonn; Munoz-Muriedas, Jordi; Roberts, Andrew D; Dear, Gordon J; Robinson, Carol V; Beaumont, Claire

    2016-02-16

    Ion mobility-mass spectrometry (IM-MS) in combination with molecular modeling offers the potential for small molecule structural isomer identification by measurement of their gas phase collision cross sections (CCSs). Successful application of this approach to drug metabolite identification would facilitate resource reduction, including animal usage, and may benefit other areas of pharmaceutical structural characterization including impurity profiling and degradation chemistry. However, the conformational behavior of drug molecules and their metabolites in the gas phase is poorly understood. Here the gas phase conformational space of drug and drug-like molecules has been investigated as well as the influence of protonation and adduct formation on the conformations of drug metabolite structural isomers. The use of CCSs, measured from IM-MS and molecular modeling information, for the structural identification of drug metabolites has also been critically assessed. Detection of structural isomers of drug metabolites using IM-MS is demonstrated and, in addition, a molecular modeling approach has been developed offering rapid conformational searching and energy assessment of candidate structures which agree with experimental CCSs. Here it is illustrated that isomers must possess markedly dissimilar CCS values for structural differentiation, the existence and extent of CCS differences being ionization state and molecule dependent. The results present that IM-MS and molecular modeling can inform on the identity of drug metabolites and highlight the limitations of this approach in differentiating structural isomers.

  16. Classification of polychlorinated biphenyl residues: isomers vs. homologue concentrations in modeling aroclors and polychlorinated biphenyl residues

    SciTech Connect

    Stalling, D.L.; Schwartz, T.R.; Dunn, W.J. III; Wold, S.

    1987-07-15

    SIMCA (soft independent modeling by class analogy), a principal components chemometric modeling program, was used to examine complex mixtures of polychlorinated biphenyl residues (PCBs) in fish and turtles. Individual PCB isomers were measured by electron capture capillary gas chromatography. The authors calculated PCB (Cl/sub 1-10/) congener concentrations by summing 105 isomer concentrations into homologue subgroups. Information theory was used to estimate the maximum information content of the two data sets. The authors compared the results from principal components modeling of samples and Aroclors by using both isomer and Cl/sub 1-10/ homologue concentrations. Modeling of normalized data from Aroclors or their mixtures gave similar sample score plots for both data sets. However, modeling environmental sample congener concentrations gave erroneous classification results when compared to results from modeling isomer data. Although the Cl/sub 1-10/ sums accurately reflect the concentration of PCBs in the sample, calculations to determine PCB profiles as Aroclor mixtures should be made by using individual PCB isomers.

  17. Incorporation profiles of conjugated linoleic acid isomers in cell membranes and their positional distribution in phospholipids

    PubMed Central

    Subbaiah, Papasani V.; Gould, Ian G.; Lal, Samanta; Aizezi, Buzulagu

    2010-01-01

    Although the conjugated linoleic acids (CLA) have several isomer-specific biological effects including anti-carcinogenic and anti-adipogenic effects, their mechanisms of action remain unclear. To determine their potential effects on membrane structure and function, we studied the incorporation profiles of four CLA isomers (trans-10 cis-12 (A), trans-9 trans-11 (B), cis-9 trans-11 (C), and cis-9 cis-11 (D)) in CHO and HepG2 cells. All four isomers were incorporated into cellular lipids as efficiently as linoleic acid (LA), with the majority of the incorporated CLA present in membrane rafts. Of the four isomers, only CLA-A increased the cholesterol content of the raft fraction. Over 50% of the incorporated CLAs were recovered in phosphatidylcholine of CHO cells, but in HepG2 the neutral lipids contained the majority of CLA. The desaturation index (18:1/18:0 and 16:1/16:0) was reduced by CLA-A, but increased by CLA-B, the effects being apparent mostly in raft lipids. The Δ9 desaturase activity was inhibited by CLAs A and C. Unlike LA, which was mostly found in the sn-2 position of phospholipids, most CLAs were also incorporated significantly into the sn-1 position in both cell types. These studies show that the incorporation profiles of CLA isomers differ significantly from that of LA, and this could lead to alterations in membrane function, especially in the raft-associated proteins. PMID:20920595

  18. Perfluorinated acid isomer profiling in water and quantitative assessment of manufacturing source.

    PubMed

    Benskin, Jonathan P; Yeung, Leo W Y; Yamashita, Nobuyoshi; Taniyasu, Sachi; Lam, Paul K S; Martin, Jonathan W

    2010-12-01

    A method for isomer profiling of perfluorinated compounds (PFCs) in water was developed and applied to quantitatively assess the contributions from electrochemical (ECF) and telomer manufacturing processes around source regions of North America, Asia, and Europe. With the exception of 3 sites in Japan, over 80% of total perfluorooctanoate (PFOA, C(7)F(15)COO(-)) was from ECF, with the balance attributable to strictly linear (presumably telomer) manufacturing source(s). Comparing PFOA isomer profiles in samples from China, with PFOA obtained from a local Chinese manufacturer, indicated <3% difference in overall branched isomer content; thus, exclusive contribution from local ECF production cannot be ruled out. In Tokyo Bay, ECF, linear-telomer, and isopropyl-telomer sources contributed to 33%, 53%, and 14% of total PFOA, respectively. Perfluorooctane sulfonate (PFOS, C(8)F(17)SO(3)(-)) isomer profiles were enriched in branched content (i.e., >50% branched) in the Mississippi River but in all other locations were similar or only slightly enriched in branched content relative to historical ECF PFOS. Isomer profiles of other PFCs are also reported. Overall, these data suggest that, with the exception of Tokyo Bay, ECF manufacturing has contributed to the bulk of contamination around these source regions, but other sources are significant, and remote sites should be monitored.

  19. Geometric isomerism in the OCS-CS2 complex: observation of a cross-shaped isomer.

    PubMed

    Norooz Oliaee, J; Mivehvar, F; Dehghany, M; Moazzen-Ahmadi, N

    2010-07-15

    Infrared spectra of the OCS-CS(2) van der Waals complex were studied in a pulsed supersonic slit-jet using a tunable diode laser probe. Spectra were recorded in the region of nu(1) fundamental of OCS. Two bands were observed and analyzed, one band corresponding to a previously observed planar isomer and another due to a new isomer which has a nonplanar cross-shaped structure. The intermolecular (center of mass) separation of the planar isomer is 3.87017(2) A. The structure of this isomer has been determined previously from its rotational spectrum. The cross-shaped isomer was observed here for the first time, and its structure was determined with the help of isotopic substitution. Two structural parameters, the intermolecular distance (R) and an angle (phi), are necessary to completely define the structure. These were determined to be R 3.5553(8) A and phi = 104.82(22) degrees which are in fair agreement with the theoretical predictions.

  20. Isomer profiles of perfluoroalkyl substances in water and soil surrounding a chinese fluorochemical manufacturing park.

    PubMed

    Jin, Hangbiao; Zhang, Yifeng; Zhu, Lingyan; Martin, Jonathan W

    2015-04-21

    Despite that China is the largest global manufacturer of perfluoroalkyl substances (PFASs), the manufacturing methods and isomer purity of these chemicals are generally unknown. Here, sampling was conducted around a major fluorochemical manufacturing park in China in 2012, including soil and water collection inside the park, including from a wastewater treatment plant (WWTP), as well as in surrounding rivers and soil (∼15 km radius). Perfluoroalkyl sulfonates (PFSAs) were lower than perfluoroalkyl carboxylates (PFCAs) in all samples, and short-chain (C4-C6) PFCAs were predominant. Perfluoroalkyl phosphonates and phosphate diesters were occasionally detected, but at low detection frequency. Branched isomers of perfluorobutanesulfonate (PFBS) are reported for the first time, accounting for 15-27% of total PFBS in water. An enrichment of isopropyl-PFOA (28%) was found in WWTP influent, suggesting its manufacturing primarily by isopropyl telomerization. More numerous branched isomers were observed for the longer C9-C13 PFCAs (e.g., C12 PFCA had 16 branched isomers), including high proportions of one major branched isomer (likely isopropyl), possibly as impurities from isopropyl-PFOA manufacturing. Overall, short-chain perfluorinated acids were the predominant PFASs being released, but PFOA was still a major chemical in use at this site, primarily from isopropyl telomerization.

  1. Natural and bioremediated selective degradation of polycyclic aromatic alkyl isomers in oil-contaminated soils

    SciTech Connect

    Sauer, T.C.; McCarthy, K.; Uhler, A.; Porta, A.

    1995-12-31

    In studies where 2- to 6-ring polycyclic aromatic hydrocarbons (PAHs) are determined as part of characterizing released oil constituents in environmental samples, the changes in composition of PAHs from weathering (e.g., evaporation, dissolution) and biodegradation are most often represented by PAH alkyl homologue distributions. Concentrations of PAH alkyl groups are the sum of individual PAH isomers of similar carbon number; such as for C2-naphthalenes, the C2 alkyl group consists of dimethyl and ethyl substitutions on the parent naphthalene. In weathering and degradation studies, the changes in relative concentration of the individual isomers within an alkyl group are rarely reported. In a field study of oiled soils, the authors looked at the selective losses, for a period of a year, of individual PAH alkyl isomers that occur both naturally by weathering processes and through the use of bioremediation technology. Results showed that decreases in alkyl group concentrations were not always represented by similar losses of each isomer in the alkyl group, but were often due to the preferential or selective loss of certain isomers in the group.

  2. Generation of viroid conformational isomers that are stable to incubation with magnesium ions and in a nuclear extract from tomato plants.

    PubMed Central

    Pace, U; Branch, A D; Robertson, H D

    1992-01-01

    We identified conditions for heating and quick cooling viroid RNAs in the presence of salt which lead to the production of conformational isomers stable to incubation for at least 45 minutes at 30 degrees in the presence of magnesium ions. Elution in 0.3 M NaCl allowed the purification of an electrophoretically slow form of an in vitro transcript carrying a complete copy of the potato spindle tuber viroid RNA sequence. Slow forms of this transcript and of kinase-labeled linear viroid RNA persisted for longer than 20 minutes when incubated with a protein-rich extract prepared from the nuclei of uninfected tomato plants, although both were slowly cleaved by a nuclease present in this extract. The fast form of the transcript was highly resistant to this tomato ribonuclease. The slow form of the transcript was much more susceptible to cleavage by RNase T1 than the fast form of this RNA, suggesting that the reduced gel mobility of the slow forms results from their relatively open structure. The ability to purify viroid conformational isomers from polyacrylamide gels will facilitate biochemical studies aimed at identifying host components interacting with RNAs of the viroid replication complex, which may not all be present in the most thermodynamically favored rodlike structure of mature viroids. Images PMID:1282703

  3. Identification of the isomer of methionine sulfoximine that extends the lifespan of the SOD1 G93A mouse.

    PubMed

    Brusilow, William S A

    2017-04-24

    In previous studies methionine sulfoximine (MSO) significantly extended the lifespan of the SOD1 G93A mouse model for ALS. Those studies used commercially available MSO, which is a racemic mixture of the LS and LR diastereomers, leaving unanswered the question of which isomer was responsible for the therapeutic effects. In this study we tested both purified isomers and showed that the LS isomer, a well-characterized inhibitor of glutamine synthetase, extends the lifespan of these mice, but the LR isomer, which has no known activity, does not.

  4. [C72]—Fullerene: Enumeration of Substitution Isomers Based on the Vertex, Edge and Facial Differentiation

    NASA Astrophysics Data System (ADS)

    Smolyakov, V. M.; Sokolov, D. V.; Nilov, D. Yu.; Grebeshkov, V. V.; Bolshakov, V. V.

    2010-11-01

    The paper discusses substitution isomers [C72]—fullerene by vertices, edges and faces. The derivation of isomers is based on the Polya theorem [1]. Formulas of symmetry Z, generating functions for identification of the number of substitution isomers of [C72]—fullerene, distribution of isomers over families ρ(m) and depending on number m of places of substitution is established. Based on the models [2-5] an addictive assessment scheme of the properties of gaseous carbon clusters [C60]-[C100] is obtained, and calculations of gaseous carbon clusters ΔfH° 298к, S° 298к not studied experimentally yet, are carried out.

  5. Search for the isomers of C2H3NO and C2H3NS in the Interstellar Medium

    NASA Astrophysics Data System (ADS)

    Etim, Emmanuel; Chakrabarti, Sandip Kumar; Das, Ankan; Gorai, Prasanta; Arunan, Elangannan

    2016-07-01

    With about 40% of all the known interstellar and circumstellar molecules having their isomeric analogues as known astromolecules, isomerism remains one of the leading themes in interstellar chemistry. In this regard, the recent detection of methyl isocyanate (with a number of isomeric analogues) in the Sgr B2(N) giant molecular cloud opens a new window for the possible astronomical detection of other C_2H_3NO isomers. The present work looks at the possibility of detecting other isomers of methyl isocyanate by considering different factors such as thermodynamic stability of the different isomers with respect to the Energy, Stability and Abundance (ESA) relationship, effect of interstellar hydrogen bonding with respect to the formation these isomers on the surface of the interstellar dust grains, possible formation routes for these isomers, spectroscopic parameters for potential astromolecules among these isomers, chemical modeling among other studies. The same studies are repeated for the C_2H_3NS isomers which are the isoelectroninc analogues of the C_2H_3NO isomers taking into account the unique chemistry of S and O-containing interstellar molecular species. Among the C_2H_3NS isomers, methyl isothiocyanate remains the most potential candidate for astronomical observation.

  6. Isomer-specific accumulation of perfluorooctane sulfonate in the liver of chicken embryos exposed in ovo to a technical mixture.

    PubMed

    O'Brien, Jason M; Kennedy, Sean W; Chu, Shaogang; Letcher, Robert J

    2011-01-01

    Prior to its recent phaseout, perfluorooctane sulfonate (PFOS) was produced by electrochemical fluorination processes, which yielded technical mixtures composed of linear isomer (∼65-79%) and several branched isomers (∼21-35%). Because PFOS can biomagnify in wildlife, birds that occupy higher trophic levels are at increased risk of exposure. We hypothesized that the pharmacokinetic properties of PFOS are isomer-specific in developing chicken (Gallus gallus domesticus) embryos exposed to technical grade PFOS (T-PFOS). In the present study, T-PFOS was composed of 62.7% linear isomer (L-PFOS), and 37.3% branched isomer, including six mono(trifluoromethyl)-branched isomers and four bis(trifluoromethyl)-branched isomers. Concentrations of 0.1, 5, or 100 µg/g of T-PFOS were injected into the air cell of chicken eggs prior to incubation. After pipping, compared with T-PFOS, the PFOS isomer profile in embryonic liver tissue for the 0.1 µg/g dose group showed 21% enrichment in the proportion of L-PFOS with a corresponding decrease in the proportion of branched isomers. Not all branched isomers were discriminated against at equal rates. The proportion of two mono(trifluoromethyl)-branched isomers and three bis(trifluoromethyl)-branched isomers decreased to a greater degree than other branched isomers. In contrast, the mono-branched isomer, P6MHpS, was overrepresented in the low-dose group. In the higher dose groups, L-PFOS was still enriched but only by approximately 10%, which indicated a dose-dependent change in isomer composition relative to T-PFOS. These results show that accumulation of PFOS in chicken embryo livers is dependent on the presence and position of branches on the alkyl backbone. This supports the hypothesis that the pharmacokinetics of PFOS are isomer-specific in biota, and may help explain why wildlife PFOS burdens are dominated by L-PFOS relative to T-PFOS mixtures.

  7. Advances in research on cis-9, trans-11 conjugated linoleic acid: a major functional conjugated linoleic acid isomer.

    PubMed

    Wang, Tao; Lee, Hong Gu

    2015-01-01

    Conjugated linoleic acid (CLA) consists of a group of positional and geometric conjugated isomers of linoleic acid. Since the identification of CLA as a factor that can inhibit mutagenesis and carcinogenesis, thousands of studies have been conducted in the last several decades. Among the many isomers discovered, cis-9, trans-11 CLA is the most intensively studied because of its multiple, isomer-specific effects in humans and animals. This paper provides an overview of the available data on cis-9, trans-11 CLA, including its isomer-specific effects, biosynthesis, in vivo/in vitro research models, quantification, and the factors influencing its content in ruminant products.

  8. Linear and branched perfluorooctane sulfonate (PFOS) isomer patterns differ among several tissues and blood of polar bears.

    PubMed

    Greaves, Alana K; Letcher, Robert J

    2013-09-01

    Perfluorooctane sulfonate (PFOS) is a globally distributed persistent organic pollutant that has been found to bioaccumulate and biomagnify in aquatic food webs. Although principally in its linear isomeric configuration, 21-35% of the PFOS manufactured via electrochemical fluorination is produced as a branched structural isomer. PFOS isomer patterns were investigated in multiple tissues of polar bears (Ursus maritimus) from East Greenland. The liver (n = 9), blood (n = 19), brain (n = 16), muscle (n = 5), and adipose (n = 5) were analyzed for linear PFOS (n-PFOS), as well as multiple mono- and di-trifluoromethyl-substituted branched isomers. n-PFOS accounted for 93.0 ± 0.5% of Σ-PFOS isomer concentrations in the liver, whereas the proportion was significantly lower (p<0.05) in the blood (85.4 ± 0.5%). Branched isomers were quantifiable in the liver and blood, but not in the brain, muscle, or adipose. In both the liver and blood, 6-perfluoromethylheptane sulfonate (P6MHpS) was the dominant branched isomer (2.61 ± 0.10%, and 3.26 ± 0.13% of Σ-PFOS concentrations, respectively). No di-trifluoromethyl-substituted isomers were detectable in any of the tissues analyzed. These tissue-specific isomer patterns suggest isomer-specific pharmacokinetics, perhaps due to differences in protein affinities, and thus differences in protein interactions, as well transport, absorption, and/or metabolism in the body.

  9. Studies of multi-quasiparticle k-isomers in rare-earth and trans-fermium nuclei.

    SciTech Connect

    Kondev, F. G.; Dracoulis, G. D.; Khoo, T. L.; Lane, G. J.; Byrne, A. P.; Kibedi, T.; Ahmad, I.; Carpenter, M. P.; Janssens, R. V. F.; Lauritzen, T.; Lister, C. J.; Seweryniak, D.; Zhu, S.; Chowdhury, P.; Tandel, S. K.; Australian National Univ.; Univ. of Massachusetts Lowell

    2007-01-01

    Nuclear K-isomers play an important role in understanding the structure of deformed axially symmetric nuclei. Examples are presented of recent studies in the rare-earth region (A {approx} 180) using deep-inelastic and multi-nucleon transfer reactions, and in the trans-fermium region (A {approx} 250) using fusion-evaporation reactions. A specific two-level mixing scenario is invoked to explain the unusual decay of the K{sup {pi}} = 13{sup +} isomer in {sup 174}Lu. The identification of 2- and 4-quasiparticle isomers in {sup 254}No is discussed and predictions of similar isomers in neighboring No and Rf nuclei are presented.

  10. Fast photon detection for the COMPASS RICH detector

    NASA Astrophysics Data System (ADS)

    Abbon, P.; Alekseev, M.; Angerer, H.; Apollonio, M.; Birsa, R.; Bordalo, P.; Bradainante, F.; Bressan, A.; Busso, L.; Chiosso, M.; Ciliberti, P.; Colantoni, M. L.; Costa, S.; Dalla Torre, S.; Dafni, T.; Delagnes, E.; Deschamps, H.; Diaz, V.; Dibiase, N.; Duic, V.; Eyrich, W.; Faso, D.; Ferrero, A.; Finger, M.; Finger, M.; Fischer, H.; Gerassimov, S.; Giorgi, M.; Gobbo, B.; Hagemann, R.; von Harrach, D.; Heinsius, F. H.; Joosten, R.; Ketzer, B.; Königsmann, K.; Kolosov, V. N.; Konorov, I.; Kramer, D.; Kunne, F.; Lehmann, A.; Levorato, S.; Maggiora, A.; Magnon, A.; Mann, A.; Martin, A.; Menon, G.; Mutter, A.; Nähle, O.; Nerling, F.; Neyret, D.; Pagano, P.; Panebianco, S.; Panzieri, D.; Paul, S.; Pesaro, G.; Polak, J.; Rebourgeard, P.; Robinet, F.; Rocco, E.; Schiavon, P.; Schill, C.; Schröder, W.; Silva, L.; Slunecka, M.; Sozzi, F.; Steiger, L.; Sulc, M.; Svec, M.; Tessarotto, F.; Teufel, A.; Wollny, H.

    2007-10-01

    Particle identification at high rates is a central aspect of many present and future experiments in high-energy particle physics. The COMPASS experiment at the SPS accelerator at CERN uses a large scale Ring Imaging CHerenkov detector (RICH) to identify pions, kaons and protons in a wide momentum range. For the data taking in 2006, the COMPASS RICH has been upgraded in the central photon detection area (25% of the surface) with a new technology to detect Cherenkov photons at very high count rates of several 10s per channel and a new dead-time free read-out system, which allows trigger rates up to 100 kHz. The Cherenkov photons are detected by an array of 576 visible and ultra-violet sensitive multi-anode photomultipliers with 16 channels each. Lens telescopes of fused silica lenses have been designed and built to focus the Cherenkov photons onto the individual photomultipliers. The read-out electronics of the PMTs is based on the MAD4 amplifier-discriminator chip and the dead-time free high resolution F1-TDC. The 120 ps time resolution of the digital card guarantees negligible background from uncorrelated physical events. In the outer part of the detector, where the particle rates are lower, the present multi-wire proportional chambers (MWPC) with Cesium Iodide photo-cathodes have been upgraded with a new read-out electronic system based on the APV preamplifier and shaper ASIC with analog pipeline and sampling ADCs. The project was fully designed and implemented in the period November 2004 until May 2006. The upgraded detector showed an excellent performance during the 2006 data taking: the number of detected Cherenkov photons per ring was increased from 14 to above 60 at saturation. The time resolution was improved from about 3 microseconds to about one nanosecond which allows an excellent suppression of the background photons from uncorrelated events.

  11. Effect of the Initial Load Parameters on the K-shell Output of Al Planar Wire Arrays Operating in the Microsecond Implosion Regime

    SciTech Connect

    Shishlov, A.; Chaikovsky, S.; Fedunin, A.; Fursov, F.; Kokshenev, V.; Kurmaev, N.; Labetsky, A.; Oreshkin, V.; Rousskikh, A.; Labetskaya, N.

    2009-01-21

    A set of microsecond implosion experiments was carried on the GIT-12 generator to study the radiative performance of Al planar wire arrays. The load parameters such as a wire diameter, a gap between the wires, the number of wires, and the total planar wire mass and width were varied during the experiments, however the implosion time and the peak implosion current were almost the same for all load configurations. This ensured equal energy deposition to the plasma due to kinetic mechanisms for all load configurations. Two implosion regimes with the implosion times of 1050 ns and 850 ns were investigated. The experimental data on the K-shell radiation yield and power at varying load parameters are presented.

  12. A 10 kHz Sub-microsecond High-voltage Pulse Generator using SI Thyristor for Micro-plasma Jets Generation

    NASA Astrophysics Data System (ADS)

    Jia, Li; Sakai, Natsuko; Watanabe, Masato; Hotta, Eiki

    Employing an inductive energy storage system, a stable and high-repetitive sub-microsecond pulse generator is developed for generation of micro-plasma jets. Its operation is based on the current interruption by an SI Thyristor, coupled with MOSFETs connected in series. While being operated without loads, the pulse generator can reliably generate high-voltage pulses of ∼20 kV with pulse duration of about 400 ns at the repetition rate up to 10 kHz. At the operating frequency of 1 kHz, a maximal energy transfer efficiency of ∼57 % has been obtained with 3 kΩ resistor as a dummy load. Driven by this pulse generator, a 6 mm long N2 plasma plume at atmospheric pressure was successfully produced.

  13. Photographic studies of laser-induced bubble formation in absorbing liquids and on submerged targets: implications for drug delivery with microsecond laser pulses

    NASA Astrophysics Data System (ADS)

    Shangguan, HanQun; Casperson, Lee W.; Paisley, Dennis L.; Prahl, Scott A.

    1998-08-01

    Pulsed laser ablation of blood clots in a fluid-filled blood vessel is accompanied by an explosive evaporation process. The resulting vapor bubble rapidly expands and collapses to disrupt the thrombus (blood clot). The hydrodynamic pressures following the bubble expansion and collapse can also be used as a driving force to deliver clot-dissolving agents into thrombus for enhancement of laser thrombolysis. Thus, the laser-induced bubble formation plays an important role in the thrombus removal process. We investigate the effects of boundary configurations and materials on bubble formation with time-resolved flash photography and high- speed photography. Potential applications in drug delivery using microsecond laser pulses are then discussed.

  14. Chemical profiling of the cytotoxic triterpenoid-concentrating fraction and characterization of ergostane stereo-isomer ingredients from Antrodia camphorata.

    PubMed

    Du, Ying-Chi; Wu, Tung-Ying; Chang, Fang-Rong; Lin, Wan-Yu; Hsu, Yu-Ming; Cheng, Fu-Ting; Lu, Chi-Yu; Yen, Ming-Hong; Tsui, Ya-Ting; Chen, Hsuan-Lun; Hou, Ming-Feng; Lu, Mei-Chin; Wu, Yang-Chang

    2012-01-25

    Antrodia camphorata (AC), also known as Antrodia cinnamomea, an endemic species in Taiwan, is one of the treasured medicinal mushrooms. AC is traditionally used for its chemopreventive biofunctions. In this investigation, we report a convenient method for concentrating the antiproliferative active triterpenoid-rich fraction (FEA), from ethanolic extract of AC (EEAC). A series of stereo-isomers of zhankuic acids (1-8) from the FEA was purified by HPLC using an efficient acidic solvent system. The structures of compounds 1-8 were elucidated based on spectroscopic data analysis, and the absolute configuration of α-chiral carboxylic acid at C-25 in the structures was assigned based on reaction with (R)- and (S)-1-(9-anthryl)-2,2,2-trifluoroethanol. Major ingredients of FEA (eight ergostanes 1-8 and two lanostanes 9-10) were further characterised by high-performance liquid chromatography-photodiode array detection/mass spectrometry (HPLC-PDA/MS). Compounds 1-8 and their pair mixture forms (antcin K, antcin C, zhankuic acid C, and zhankuic acid A) were subjected to anti-proliferative assay against three human leukemia cell lines. Among them, the derivatives with carbonyl group at C-3 showed cytotoxicity with IC(50) values ranging from 16.44 to 77.04 μg/ml.

  15. Bioaugmentation with a consortium of bacterial nitrophenol-degraders for remediation of soil contaminated with three nitrophenol isomers.

    PubMed

    Chi, Xiang-Qun; Zhang, Jun-Jie; Zhao, Shuo; Zhou, Ning-Yi

    2013-01-01

    A consortium consisting of para-nitrophenol utilizer Pseudomonas sp. strain WBC-3, meta-nitrophenol utilizer Cupriavidus necator JMP134 and ortho-nitrophenol utilizer Alcaligenes sp. strain NyZ215 was inoculated into soil contaminated with three nitrophenol isomers for bioaugmentation. Accelerated removal of all nitrophenols was achieved in inoculated soils compared to un-inoculated soils, with complete removal of nitrophenols in inoculated soils occurring between 2 and 16 days. Real-time polymerase chain reaction (PCR) targeting nitrophenol-degradation functional genes indicated that the three strains survived and were stable over the course of the incubation period. The abundance of total indigenous bacteria (measured by 16S rRNA gene real-time PCR) was slightly negatively impacted by the nitrophenol contamination. Denaturing gradient gel electrophoresis profiles of total and group-specific indigenous community suggested a dynamic change in species richness occurred during the bioaugmentation process. Furthermore, Pareto-Lorenz curves and Community organization parameters indicated that the bioaugmentation process had little impact on species evenness within the microbial community.

  16. [GC-FTIR analysis of structural isomers from hydrogenation products of p-phenylphenol].

    PubMed

    Xin, Jun-Na; Xu, Qiang; Zhang, Hua; Yang, Xi-Chuan; Lü, Lian-Hai

    2008-04-01

    The hydrogenation of p-phenylphenol is a consecutive and parallel complex reaction. Owing to the difference in the hydrogenation ability of the two benzene rings in pphenylphenol, the hydrogenation products contained several structural isomers, which can not be identified by normal analytical method. However, the reaction mixture was effectively separated and identified by GC-FTIR technique. According to the characteristic wave numbers of benzene ring substituted at different positions, the main product was confirmed to be p-cyclohexylphenol, and the two typical by-products were p-phenylcyclohexanol and p-cyclohexylcyclohexanol, respectively. Each product has several stereo-isomers. GC-MS, melting point measurement and NMR proved the accuracy of GC-FTIR results, indicating that GC-IR is an useful and rapid method for analyzing structural isomers of organic compounds.

  17. Reduction of MTT to Purple Formazan by Vitamin E Isomers in the Absence of Cells.

    PubMed

    Lim, Su-Wen; Loh, Hwei-San; Ting, Kang-Nee; Bradshaw, Tracey Dawn; Allaudin, Zeenathul Nazariah

    2015-04-01

    The yellow tetrazolium salt 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide (MTT) is widely used to determine cell viability in cell proliferation and cytotoxic assays. MTT is reduced by metabolically active cells to form an insoluble purple formazan product that is quantifiable by spectrophotometry. It is the most common and direct assay for cell viability. However, in this present study, we demonstrated that the vitamin E isomers α-β-γ-δ-tocotrienols and α-tocopherol were able to reduce MTT into a formazan product, despite the absence of living cells. For comparison, a second method for determining cell viability, which is the neutral red uptake assay, was used in parallel with the MTT assay. The results showed that neutral red did not interact with the vitamin E isomers. Our findings suggest that the MTT assay is not suitable for studying the proliferative effects of vitamin E isomers on cell growth.

  18. Isomer discrimination of polycyclic aromatic hydrocarbons in the Murchison meteorite by resonant ionization.

    PubMed

    Callahan, Michael P; Abo-Riziq, Ali; Crews, Bridgit; Grace, Louis; de Vries, Mattanjah S

    2008-12-15

    We have used two-color resonant two-photon ionization (2C-R2PI) mass spectrometry to discriminate between isomers of polycyclic aromatic hydrocarbons in the Murchison meteorite. We measured the 2C-R2PI spectra of chrysene and triphenylene seeded in a supersonic jet by laser desorption. Since each isomer differs in its R2PI spectrum, we can distinguish between isomers using wavelength dependent ionization and mass spectrometry. We found both chrysene and triphenylene in sublimates from carbonaceous residue obtained by acid demineralization of the Murchison meteorite. Their R2PI mass spectra show only the molecular ion, even though these samples contain a complex inventory of organic molecules.

  19. Visualizing the Role of Molecular Orbitals in Charge Transport through Individual Diarylethene Isomers

    PubMed Central

    2016-01-01

    Diarylethene molecules are prototype molecular switches with their two isomeric forms exhibiting strikingly different conductance, while maintaining similar length. We employed low-temperature scanning tunneling microscopy (STM) to resolve the energy and the spatial extend of the molecular orbitals of the open and closed isomers when lying on a Au(111) surface. We find an intriguing difference in the extension of the respective HOMOs and a peculiar energy splitting of the formerly degenerate LUMO of the open isomer. We then lift the two isomers with the tip of the STM and measure the current through the individual molecules. By a simple analytical model of the transport, we show that the previously determined orbital characteristics are essential ingredients for the complete understanding of the transport properties. We also succeeded in switching the suspended molecules by the current, while switching the ones which are in direct contact to the surface occurs nonlocally with the help of the electric field of the tip. PMID:27775886

  20. Isomer Specific Microwave Spectrum of - and - Phenylvinylnitrile. Implementing a New Multi-Resonant Spectral Analysis Tool.

    NASA Astrophysics Data System (ADS)

    Hernandez-Castillo, Alicia O.; Hays, Brian M.; Abeysekera, Chamara; Zwier, Timothy S.

    2016-06-01

    There are many circumstances in modern microwave spectroscopy where the observed spectra contain contributions from many distinct sub-populations, creating a complicated spectrum with interleaved transitions due to its components making spectral assignment challenging. A new method, exploiting multi resonance effects with broadband CP-FTMW was developed and implemented to differentiate the structural isomers: (E)- and (Z)-phenylvinylnitrile. This method will output an exclusive set of isomer-specific transitions reducing the spectral assignment time. Details of the method implementation and structural analysis of the two-isomer mixture will be discussed. The application of the method to other circumstances where selective modulation of the transitions due to a single set of connected transitions is vital for complex spectral assignment, will also be considered.

  1. Curcumin promotes fibril formation in F isomer of human serum albumin via amorphous aggregation.

    PubMed

    Mothi, Nivin; Muthu, Shivani A; Kale, Avinash; Ahmad, Basir

    2015-12-01

    We here describe the amyloid fibrils promoting behavior of curcumin, which ability to inhibit amyloid fibrillization of several globular proteins is well documented. Transmission electron microscopy (TEM), 90° light scattering (RLS), thioflavine T (ThT) and Congo red (CR) binding studies demonstrated that both F (pH3.4) and E (pH1.8) isomers of human serum albumin (HSA) in the absence and presence of curcumin initially converted into amorphous aggregates. Interestingly, only the sample containing F isomer preincubated with curcumin formed fibrils on incubation for longer period. We also found that curcumin strongly bind to the F isomer, alter its secondary, tertiary structures and thermal stability. We conclude that the conversion of intermediate states into amorphous aggregate to fibrils is dictated by its conformation. This study provides unique insights into ligand-controlled HSA aggregation pathway and should provide a useful model system to study both amorphous and the fibrillar aggregation of multidomain proteins.

  2. Effects of pentanol isomers on the phase behavior of phospholipid bilayer membranes.

    PubMed

    Griffin, Kathryn L; Cheng, Chih-Yin; Smith, Eric A; Dea, Phoebe K

    2010-11-01

    Differential scanning calorimetry (DSC) was used to analyze the thermotropic phase behavior of dipalmitoylphosphatidylcholine (DPPC) bilayers in the presence of pentanol isomers. The concentration of each pentanol isomer needed to induce the interdigitated phase was determined by the appearance of a biphasic effect in the main transition temperatures, the onset of a hysteresis associated with the main transition from the gel-to-liquid crystalline phase, and the disappearance of the pretransition. Lower threshold concentrations were found to correlate with isomers of greater alkyl chain length while branching of the alkyl chain was found to increase biphasic behavior. The addition of a methyl group to butanol systems drastically decreased threshold concentrations. However, as demonstrated in the DPPC/neopentanol system, branching of the alkyl chain away from the -OH group lowers the threshold concentration while maintaining a biphasic effect.

  3. On the nature of the 17 μs isomer of the 133Sb valence nucleus

    NASA Astrophysics Data System (ADS)

    Genevey, J.; Pinston, J. A.; Faust, H.; Foin, C.; Oberstedt, S.; Weiss, B.

    The decay of the 17 μs isomer of 133Sb was re-investigated experimentally. It was produced by thermal neutron induced fission of 241Pu. Its detection is based on time correlation between fission fragments selected by the LOHENGRIN spectrometer at ILL (Grenoble), and the γ-rays, and conversion electrons from the isomer. The interpretation of the level scheme is based on shell model calculations, where empirical two-body matrix elements were employed. The good agreement between theory and experiment suggests that the isomer is the 21/2+ member of the 2p-1h πg7/2ν(f7/2h11/2-1) configuration.

  4. Theoretical investigation of the 67Zn Mössbauer isomer shifts in the zinc chalcogenides

    NASA Astrophysics Data System (ADS)

    Svane, A.; Antoncik, E.

    1986-06-01

    The band structures of the zinc chalcogenides ZnO, ZnS, ZnSe, and ZnTe having the sphalerite crystal structure are calculated. The first-principles linear muffin-tin-orbital-atomic sphere approximation method is employed, in which all solid-state and scalar relativistic effects are taken into account, including the self-consistency of the crystal potential and the charge density. The corresponding electronic configurations are discussed, and the electron contact densities at the zinc nucleus are obtained and compared to experimental isomer-shift data with good agreement. The estimated static charge transfers of the zinc chalcogenides are demonstrated to correlate neatly with the isomer shift. For the first time an accurate value of the calibration constant for the 67Zn isomer transition is derived: ΔR/R=(7.0+/-1.0)×10-4.

  5. Identification of μs-isomers produced in the fragmentation of a 112Sn beam

    NASA Astrophysics Data System (ADS)

    Grzywacz, R.; Anne, R.; Auger, G.; Bazin, D.; Borcea, C.; Borrel, V.; Corre, J. M.; Dörfler, T.; Fomichov, A.; Gaelens, M.; Guillemaud-Mueller, D.; Hue, R.; Huyse, M.; Janas, Z.; Keller, H.; Lewitowicz, M.; Lukyanov, S.; Mueller, A. C.; Penionzhkevich, Yu.; Pfützner, M.; Pougheon, F.; Rykaczewski, K.; Saint-Laurent, M. G.; Schmidt, K.; Schmidt-Ott, W.-D.; Sorlin, O.; Szerypo, J.; Tarasov, O.; Wauters, J.; Żylicz, J.

    1995-02-01

    Decays of over forty short-lived ( T {1}/{2} from ≈ 50 ns to 70 μs) isomeric states including a new isomer 66mAs produced in the fragmentation of a 112Sn beam (58 A·MeV, 63 A·MeV) on a natNi target were observed at the final focus of the LISE3 spectrometer at GANIL. Their detection, based on the slow (≈ 10 μs) time correlation of identified ions with the characteristic γ-radiation, represents a novel method to search for new isomers and can be used for unambiguous isotope identification for projectile fragment separator experiments. Isomeric yields and isomer-to-total production ratios were determined.

  6. Synthesis and isolation of one isomer of C{sub 60}H{sub 6}

    SciTech Connect

    Meier, M.S.; Weedon, B.R.; Spielmann, H.P.

    1996-11-20

    A reaction is reported that produces C{sub 60}H{sub 6} with essentially no contamination by adjacent oxidation states. The compound is formed as one dominant isomer and one minor isomer, and the assignment is reported of the structure of the major isomer through a comparison of its C-H coupled {sup 13}C NMR spectrum with that of 1, 2-C{sub 60}H{sub 2}. Isolation of the major C{sub 60}H{sub 6} band was accomplished by HPLC using a preparative Buckyclutcher column and an automated injector/fraction collector. Analysis of the fraction containing 1 (a cranberry-colored solution when concentrated) by Buckyclutcher and C{sub 18} HPCL in several different solvent systems has failed to produce evidence of more than one component. The typical isolated yield is 35%. 15 refs., 3 figs.

  7. Reduction of MTT to Purple Formazan by Vitamin E Isomers in the Absence of Cells

    PubMed Central

    Lim, Su-Wen; Loh, Hwei-San; Ting, Kang-Nee; Bradshaw, Tracey Dawn; Allaudin, Zeenathul Nazariah

    2015-01-01

    The yellow tetrazolium salt 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide (MTT) is widely used to determine cell viability in cell proliferation and cytotoxic assays. MTT is reduced by metabolically active cells to form an insoluble purple formazan product that is quantifiable by spectrophotometry. It is the most common and direct assay for cell viability. However, in this present study, we demonstrated that the vitamin E isomers α-β-γ-δ-tocotrienols and α-tocopherol were able to reduce MTT into a formazan product, despite the absence of living cells. For comparison, a second method for determining cell viability, which is the neutral red uptake assay, was used in parallel with the MTT assay. The results showed that neutral red did not interact with the vitamin E isomers. Our findings suggest that the MTT assay is not suitable for studying the proliferative effects of vitamin E isomers on cell growth. PMID:26868595

  8. An all-solid-state microsecond-range quasi-square pulse generator based on fractional-turn ratio saturable pulse transformer and anti-resonance network

    NASA Astrophysics Data System (ADS)

    Chen, Rong; Yang, Jianhua; Cheng, Xinbing; Pan, Zilong

    2017-03-01

    High voltage pulse generators are widely applied in a number of fields. Defense and industrial applications stimulated intense interests in the area of pulsed power technology towards the system with high power, high repetition rate, solid state characteristics, and compact structure. An all-solid-state microsecond-range quasi-square pulse generator based on a fractional-turn ratio saturable pulse transformer and anti-resonance network is proposed in this paper. This generator consists of a charging system, a step-up system, and a modulating system. In this generator, the fractional-turn ratio saturable pulse transformer is the key component since it acts as a step-up transformer and a main switch during the working process. Demonstrative experiments show that if the primary storage capacitors are charged to 400 V, a quasi-square pulse with amplitude of about 29 kV can be achieved on a 3500 Ω resistive load, as well as the pulse duration (full width at half maximum) of about 1.3 μs. Preliminary repetition rate experiments are also carried out, which indicate that this pulse generator could work stably with the repetition rates of 30 Hz and 50 Hz. It can be concluded that this kind of all-solid-state microsecond-range quasi-square pulse generator can not only lower both the operating voltage of the primary windings and the saturable inductance of the secondary windings, thus ideally realizing the magnetic switch function of the fractional-turn ratio saturable pulse transformer, but also achieve a quasi-square pulse with high quality and fixed flat top after the modulation of a two-section anti-resonance network. This generator can be applied in areas of large power microwave sources, sterilization, disinfection, and wastewater treatment.

  9. An all-solid-state microsecond-range quasi-square pulse generator based on fractional-turn ratio saturable pulse transformer and anti-resonance network.

    PubMed

    Chen, Rong; Yang, Jianhua; Cheng, Xinbing; Pan, Zilong

    2017-03-01

    High voltage pulse generators are widely applied in a number of fields. Defense and industrial applications stimulated intense interests in the area of pulsed power technology towards the system with high power, high repetition rate, solid state characteristics, and compact structure. An all-solid-state microsecond-range quasi-square pulse generator based on a fractional-turn ratio saturable pulse transformer and anti-resonance network is proposed in this paper. This generator consists of a charging system, a step-up system, and a modulating system. In this generator, the fractional-turn ratio saturable pulse transformer is the key component since it acts as a step-up transformer and a main switch during the working process. Demonstrative experiments show that if the primary storage capacitors are charged to 400 V, a quasi-square pulse with amplitude of about 29 kV can be achieved on a 3500 Ω resistive load, as well as the pulse duration (full width at half maximum) of about 1.3 μs. Preliminary repetition rate experiments are also carried out, which indicate that this pulse generator could work stably with the repetition rates of 30 Hz and 50 Hz. It can be concluded that this kind of all-solid-state microsecond-range quasi-square pulse generator can not only lower both the operating voltage of the primary windings and the saturable inductance of the secondary windings, thus ideally realizing the magnetic switch function of the fractional-turn ratio saturable pulse transformer, but also achieve a quasi-square pulse with high quality and fixed flat top after the modulation of a two-section anti-resonance network. This generator can be applied in areas of large power microwave sources, sterilization, disinfection, and wastewater treatment.

  10. New isomers and medium-spin structure of the {sup 95}Y nucleus

    SciTech Connect

    Urban, W.; Sieja, K.; Simpson, G. S.; Rzaca-Urban, T.; Zlomaniec, A.; Lukasiewicz, M.; Smith, A. G.; Durell, J. L.; Smith, J. F.; Varley, B. J.; Nowacki, F.; Ahmad, I.

    2009-04-15

    Excited states in {sup 95}Y, populated following the spontaneous fission of {sup 248}Cm and {sup 252}Cf and following fission of {sup 235}U induced by thermal neutrons, were studied by means of {gamma} spectroscopy using the EUROGAM2 and GAMMASPHERE multidetector Ge arrays and the LOHENGRIN fission-fragment separator, respectively. We have found a new (17/2{sup -}) isomer in {sup 95}Y at 3142.2 keV with a half-life of T{sub 1/2}=14.9(5) ns. Another isomer was identified in {sup 95}Y at 5022.1 keV and it was assigned a spin-parity (27/2{sup -}). For this isomer a half-life of T{sub 1/2}=65(4) ns was determined and four decay branches were found, including an E3 decay. A new E3 decay branch was also found for the known, 1087.5-keV isomer in {sup 95}Y, for which we measured a half-life of 51.2(9) {mu}s. The B(E3) and B(E1) transition rates, of 2.0 and 3.8x10{sup -7} W.u., respectively, observed in {sup 95}Y are significantly lower than in the neighboring {sup 96}Zr core, suggesting that octupole correlations in this region are mainly due to the coupling of proton {delta}j=3 orbitals. Shell-model calculations indicate that the (27/2{sup -}) isomer in {sup 95}Y corresponds to the {pi}g{sub 9/2}{nu}(g{sub 7/2}h{sub 11/2}) maximally aligned configuration and that all three isomers in {sup 95}Y decay, primarily, by M2 transitions between proton g{sub 9/2} and f{sub 5/2} orbitals.

  11. Experimental investigation of the low temperature oxidation of the five isomers of hexane.

    PubMed

    Wang, Zhandong; Herbinet, Olivier; Cheng, Zhanjun; Husson, Benoit; Fournet, René; Qi, Fei; Battin-Leclerc, Frédérique

    2014-07-31

    The low-temperature oxidation of the five hexane isomers (n-hexane, 2-methyl-pentane, 3-methyl-pentane, 2,2-dimethylbutane, and 2,3-dimethylbutane) was studied in a jet-stirred reactor (JSR) at atmospheric pressure under stoichiometric conditions between 550 and 1000 K. The evolution of reactant and product mole fraction profiles were recorded as a function of the temperature using two analytical methods: gas chromatography and synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). Experimental data obtained with both methods were in good agreement for the five fuels. These data were used to compare the reactivity and the nature of the reaction products and their distribution. At low temperature (below 800 K), n-hexane was the most reactive isomer. The two methyl-pentane isomers have about the same reactivity, which was lower than that of n-hexane. 2,2-Dimethylbutane was less reactive than the two methyl-pentane isomers, and 2,3-dimethylbutane was the least reactive isomer. These observations are in good agreement with research octane numbers given in the literature. Cyclic ethers with rings including 3, 4, 5, and 6 atoms have been identified and quantified for the five fuels. While the cyclic ether distribution was notably more detailed than in other literature of JSR studies of branched alkane oxidation, some oxiranes were missing among the cyclic ethers expected from methyl-pentanes. Using SVUV-PIMS, the formation of C2-C3 monocarboxylic acids, ketohydroperoxides, and species with two carbonyl groups have also been observed, supporting their possible formation from branched reactants. This is in line with what was previously experimentally demonstrated from linear fuels. Possible structures and ways of decomposition of the most probable ketohydroperoxides were discussed. Above 800 K, all five isomers have about the same reactivity, with a larger formation from branched alkanes of some unsaturated species, such as allene and propyne, which

  12. Trophic magnification and isomer fractionation of perfluoroalkyl substances in the food web of Taihu Lake, China.

    PubMed

    Fang, Shuhong; Chen, Xinwei; Zhao, Shuyan; Zhang, Yifeng; Jiang, Weiwei; Yang, Liping; Zhu, Lingyan

    2014-02-18

    Biomagnification of perfluoroalkyl substances (PFASs) are well studied in marine food webs, but related information in fresh water ecosystem and knowledge on fractionation of their isomers along the food web are limited. The distribution, bioaccumulation, magnification, and isomer fractionation of PFASs were investigated in a food web of Taihu Lake, China. Perfluorooctanesulfonate (PFOS) and perfluorocarboxylates (PFCAs) with longer carbon chain lengths, such as perfluorodecanoate (PFDA) and perfluoroundecanoate (PFUnA), were predominant in organisms, while perfluorohexanoate (PFHxA) and perfluorooctanoate (∑PFOA) contributed more in the water phase. The consistent profile signature of PFOA isomers in water phase with 3M electrochemical fluorination (ECF) products suggests that ECF production of PFOA still exists in China. Linear proportions of PFOA, PFOS and perfluorooctane sulfonamide (PFOSA) in the biota were in the range of 91.9-100%, 78.6-95.5%, and 72.2-95.5%, respectively, indicating preferential bioaccumulation of linear isomers in biota. Trophic magnification factors (TMFs) were estimated for PFDA (2.43), perfluorododecanoate (PFDoA) (2.68) and PFOS (3.46) when all biota were included, suggesting that PFOS and long-chained PFCAs are biomagnified in the fresh water food web. The TMF of PFOS isomers descended in the order: n-PFOS (3.86) > 3+5m-PFOS (3.35) > 4m-PFOS (3.32) > 1m-PFOS (2.92) > m2-PFOS (2.67) > iso-PFOS (2.59), which is roughly identical to their elution order on a FluoroSep-RP Octyl column, suggesting that hydrophobicity may be an important contributor for isomer discrimination in biota.

  13. Terahertz Spectroscopy and Solid-State Density Functional Theory Calculations of Cyanobenzaldehyde Isomers.

    PubMed

    Dash, Jyotirmayee; Ray, Shaumik; Nallappan, Kathirvel; Kaware, Vaibhav; Basutkar, Nitin; Gonnade, Rajesh G; Ambade, Ashootosh V; Joshi, Kavita; Pesala, Bala

    2015-07-23

    Spectral signatures in the terahertz (THz) frequency region are mainly due to bulk vibrations of the molecules. These resonances are highly sensitive to the relative position of atoms in a molecule as well as the crystal packing arrangement. To understand the variation of THz resonances, THz spectra (2-10 THz) of three structural isomers: 2-, 3-, and 4-cyanobenzaldehyde have been studied. THz spectra obtained from Fourier transform infrared (FTIR) spectrometry of these isomers show that the resonances are distinctly different especially below 5 THz. For understanding the intermolecular interactions due to hydrogen bonds, four molecule cluster simulations of each of the isomers have been carried out using the B3LYP density functional with the 6-31G(d,p) basis set in Gaussian09 software and the compliance constants are obtained. However, to understand the exact reason behind the observed resonances, simulation of each isomer considering the full crystal structure is essential. The crystal structure of each isomer has been determined using X-ray diffraction (XRD) analysis for carrying out crystal structure simulations. Density functional theory (DFT) simulations using CRYSTAL14 software, utilizing the hybrid density functional B3LYP, have been carried out to understand the vibrational modes. The bond lengths and bond angles from the optimized structures are compared with the XRD results in terms of root-mean-square-deviation (RMSD) values. Very low RMSD values confirm the overall accuracy of the results. The simulations are able to predict most of the spectral features exhibited by the isomers. The results show that low frequency modes (<3 THz) are mediated through hydrogen bonds and are dominated by intermolecular vibrations.

  14. Quantitative Analysis of the Distribution of cis-Eicosenoic Acid Positional Isomers in Marine Fishes from the Indian Ocean.

    PubMed

    Senarath, Samanthika; Yoshinaga, Kazuaki; Nagai, Toshiharu; Yoshida, Akihiko; Beppu, Fumiaki; Jayasinghe, Chamila; Devadawson, Chandravathany; Gotoh, Naohiro

    2017-02-01

    This study investigated the occurrence and distribution of cis-eicosenoic acid (c-20:1) positional isomers in fishes from the Indian Ocean and compared to those from the Pacific and Atlantic Ocean. Lipids were extracted from the edible part of the fish and then methylated. The eicosenoic acid methyl ester fraction was separated from total fatty acid methyl esters by reversed-phase HPLC and quantitatively analyzed using a GC-FID fitted with the SLB-IL111 highly polar GC column. c14-20:1 was used as an internal standard. The results indicated that the highest levels of c-20:1 positional isomers were found in fishes from the Pacific Ocean (saury, 166.95±12.4 mg/g of oil), followed by the Atlantic Ocean (capelin, 162.7±3.5 mg/g of oil), and lastly in fishes from the Indian Ocean (goatfish, 34.39 mg/g of oil). With only a few exceptions, the most abundant 20:1 positional isomer found in fishes of the Indian and Atlantic Ocean was the c11-20:1 isomer (>50%) followed by the c13-20:1 isomer (<25%). Unusually, the c7-20:1 isomer was predominantly found in a few fishes such as the tooth ponyfish, longface emperor, and commerson's sole. The c9, c5, and c15-20:1 isomers were the least occurring in fishes from the Indian and Atlantic Ocean. In contrast, the c9-20:1 isomer was the principal isomer identified in fishes from the Pacific Ocean. The results revealed that the content and distribution of c-20:1 positional isomers varied among fishes in different oceans. The data presented in the current study are the first to report on the distribution of c-20:1 positional isomers in fishes from the Indian Ocean.

  15. NMR study on iridium(III) complexes for identifying disulfonate substituted bathophenanthroline regio-isomers.

    PubMed

    Liu, Chenchen; Yu, Linpo; Liu, Yang; Li, Fang; Zhou, Ming

    2011-12-01

    A series of novel biscyclometalated iridium (III) complexes with an ancillary disulfonated bathophenanthroline (DSBP(2-)) ligand, Ir(L)(2)DSBPNa, L = 2-phenylpyridine (ppy), 2,4-difluorophenylpyridine (fppy), and 1-phenylisoquinoline (piq) were found to have two isomeric forms. The chemical structures of the isomers were determined by the one- and two-dimensional (1)H and (13)C NMR studies. The isomeric state was proved to have originated from the disulfonate-related regio-isomer of the DSBP(2-) ligand.

  16. Isomer ratio measurements as a probe of the dynamics of breakup and incomplete fusion

    SciTech Connect

    Gasques, L. R.; Dasgupta, M.; Hinde, D. J.; Peatey, T.; Diaz-Torres, A.; Newton, J. O.

    2006-12-15

    The incomplete fusion mechanism following breakup of {sup 6,7}Li and {sup 9}Be projectiles incident on targets of {sup 209}Bi and {sup 208}Pb is investigated through isomer ratio measurements for the {sup 212}At and {sup 211}Po products. The phenomenological analysis presented in this paper indicates that incomplete fusion brings relatively more angular momentum into the system than equivalent reactions with a direct beam of the fused fragment. This is attributed to the trajectories of breakup fragments. Calculations with a 3D classical trajectory model support this. Isomer ratio measurements for incomplete fusion reactions can provide a test of new theoretical models of breakup and fusion.

  17. Laminar burning velocities and flame instabilities of butanol isomers-air mixtures

    SciTech Connect

    Gu, Xiaolei; Huang, Zuohua; Wu, Si; Li, Qianqian

    2010-12-15

    Laminar burning velocities and flame instabilities of the butanol-air premixed flames and its isomers are investigated using the spherically expanding flame with central ignition at initial temperature of 428 K and initial pressures of 0.10 MPa, 0.25 MPa, 0.50 MPa and 0.75 MPa. Laminar burning velocities and sensitivity factor of n-butanol-air mixtures are computed using a newly developed kinetic mechanism. Unstretched laminar burning velocity, adiabatic temperature, Lewis number, Markstein length, critical flame radius and Peclet number are obtained over a wide range of equivalence ratios. Effect of molecular structure on laminar burning velocity of the isomers of butanol is analyzed from the aspect of C-H bond dissociation energy. Study indicates that although adiabatic flame temperatures of the isomers of butanol are the same, laminar burning velocities give an obvious difference among the isomers of butanol. This indicates that molecular structure has a large influence on laminar burning velocities of the isomers of butanol. Branching (-CH3) will decrease laminar burning velocity. Hydroxyl functional group (-OH) attaching to the terminal carbon atoms gives higher laminar burning velocity compared to that attaching to the inner carbon atoms. Calculated dissociation bond energies show that terminal C-H bonds have larger bond energies than that of inner C-H bonds. n-Butanol, no branching and with hydroxyl functional group (-OH) attaching to the terminal carbon atom, gives the largest laminar burning velocity. tert-Butanol, with highly branching and hydroxyl functional group (-OH) attaching to the inner carbon atom, gives the lowest laminar burning velocity. Laminar burning velocities of iso-butanol and sec-butanol are between those of n-butanol and tert-butanol. The instant of transition to cellularity is experimentally determined for the isomers of butanol and subsequently interpreted on the basis of hydrodynamic and diffusion-thermal instabilities. Little effect

  18. Laboratory data base for isomer-specific determination of polychlorinated biphenyls

    SciTech Connect

    Schwartz, T.R.; Campbell, R.D.; Stalling, D.L.; Little, R.L.; Petty, J.D.; Hogan, J.W.; Kaiser, E.M.

    1984-07-01

    A computer-assisted technique for quantitative determination of polychlorinated biphenyl isomers is described. PCB isomers were identified by use of a retention index system with n-alkyl trichloroacetates as retention index marker compounds. A laboratory data base system was developed to aid in editing and quantitation of data generated from capillary gas chromatographic data. Data base management was provided by computer programs written in DSM-11 (Digital Standard MUMPS) for the PDP-11 family of computers. 13 references, 4 figures, 2 tables.

  19. New decay scheme of the 85Sb 51 136 6- isomer

    NASA Astrophysics Data System (ADS)

    Lozeva, R.; Odahara, A.; Moon, C.-B.; Nishimura, S.; Doornenbal, P.; Naïdja, H.; Nowacki, F.; Söderström, P.-A.; Sumikama, T.; Lorusso, G.; Wu, J.; Xu, Z. Y.; Baba, H.; Browne, F.; Daido, R.; Daugas, J.-M.; Didierjean, F.; Fang, Y.; Isobe, T.; Kojouharov, I.; Kurz, N.; Patel, Z.; Rice, S.; Sakurai, H.; Schaffner, H.; Sinclair, L.; Watanabe, H.; Yagi, A.; Yokoyama, R.; Kubo, T.; Inabe, N.; Suzuki, H.; Fukuda, N.; Kameda, D.; Takeda, H.; Ahn, D. S.; Murai, D.; Bello Garrote, F. L.; Ideguchi, E.; Ishigaki, T.; Jung, H. S.; Komatsubara, T.; Kwon, Y. K.; Morimoto, S.; Niikura, M.; Nishibata, H.; Nishizuka, I.; Shimoda, T.; Tshoo, K.

    2015-08-01

    We report new data on the 136Sb6- yrast isomer with T1 /2=489 (40 ) μ s and π g7/2 1×ν f7/2 3 configuration, populated in the projectile fission of 238U on a 9Be target. The analysis confirms the lifetime, providing a good accuracy measurement. In addition, the decay of the isomer to the ground state is newly suggested. Our result for the isomeric decay scheme is in a good agreement with shell-model calculations.

  20. Conversion-electron experiment to characterize the decay of the Np-237 shape isomer

    NASA Astrophysics Data System (ADS)

    Henry, E. A.; Becker, J. A.; Bauer, R. W.; Gardner, D. G.; Decman, D. J.

    1988-01-01

    Nuclear isomerism plays a key role in current conceptual designs of a gamma-ray laser. Conversion electrons from the decay of low-lying levels of Np-237 have been measured to detect the population of these levels by gamma-ray decay of the Np-237 shape isomer. Analysis of the 208-keV transition L conversion-electron peak gives an upper limit of about 17 micro-b for the population of the 3/2(-) 267-keV level in Np-237 from the shape isomer decay. Model calculations are compared with the measured limit, and experimental improvements are suggested.

  1. Separation of cis and trans Isomers of Polyproline by FAIMS Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Creese, Andrew J.; Cooper, Helen J.

    2016-12-01

    High field asymmetric waveform ion mobility spectrometry (FAIMS) is well-established as a tool for separating peptide isomers (sequence inversions and post-translationally modified localization variants). Here, we demonstrate the FAIMS is able to differentiate cis and trans isomers of polyproline. Polyproline assumes an all- cis conformation—the PPI helix—in 1-propanol, and an all- trans conformation—the PPII helix—in aqueous solutions. Differentiation of these conformers may be achieved both through use of a cylindrical FAIMS device and a miniaturized ultrahigh field planar FAIMS device.

  2. Pressure dependence of the isomer shifts in Gd2Fe17: An ab initio calculation

    NASA Astrophysics Data System (ADS)

    Komelj, M.; Grotheer, O.; Fähnle, M.

    1999-05-01

    The geometrical and chemical effects of interstitial doping on the average isomer shifts in the systems Gd2Fe17C3 and Gd2Fe17N3 are studied within the framework of the local density approximation using the linear-muffin-tin-orbital method in the atomic-sphere approximation. The sensitivity of the results on the details of the calculation is discussed. It is shown that it is not possible to extract reliable information on the geometrical effect of volume expansion upon interstitial doping of such system on the average isomer shifts by experiments on non-doped samples under compression.

  3. Effectiveness of Iron Ethylenediamine-N,N'-bis(hydroxyphenylacetic) Acid (o,o-EDDHA/Fe(3+)) Formulations with Different Ratios of Meso and d,l-Racemic Isomers as Iron Fertilizers.

    PubMed

    Alcañiz, Sara; Jordá, Juana D; Cerdán, Mar

    2017-01-18

    Two o,o-EDDHA/Fe(3+) formulations (meso, 93.5% w/w of meso isomer; and d,l-racemic, 91.3% w/w of d,l-racemic mixture) were prepared, and their efficacy to avoid or to relieve iron deficiency in Fe-sufficient and Fe-deficient tomato plants grown on hydroponic solution was compared with that of the current o,o-EDDHA/Fe(3+) formulations (50% of meso and d,l-racemic isomers). The effectiveness of the three o,o-EDDHA/Fe(3+) formulations was different depending on the iron nutritional status of plants. The three o,o-EDDHA/Fe(3+) formulations tested were effective in preventing iron chlorosis in healthy plants. However, the higher the meso concentration in the formulations, the higher the effectiveness in the recovery of iron chlorotic plants from iron deficiency. Accordingly, o,o-EDDHA/Fe(3+) formulations rich in meso isomer are recommended in hydroponic systems.

  4. Highly enantioselective and anti-diastereoselective catalytic intermolecular glyoxylate-ene reactions: effect of the geometrical isomers of alkenes.

    PubMed

    Zhang, Xiang; Wang, Min; Ding, Ran; Xu, Yun-He; Loh, Teck-Peng

    2015-06-05

    An efficient method for the synthesis of homoallylic alcohols with high enantioselectivities and anti-diastereoselectivities via an In(III)-catalyzed intermolecular glyoxylate-ene reaction has been developed. The geometrical isomers of alkenes were shown to have different reactivities. Only the isomers of the alkenes having a proton β-cis to the substituent reacted in this catalytic system.

  5. SEPARATION OF ISOMERS OF NONYLPHENOL AND SELECT NONPHENYL POLYETHOXYLATES BY HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY ON A GRAPHITIC CARBON COLUMN

    EPA Science Inventory

    p-Nonylphenol (NP) is ubiquitous degradation product of nonylphenol polyethoxylate (NPE) surfactants and has been reported to be an endocrine disrupter. It is composed of numerous structural isomers resulting from ;the various branching patterns of the C-9 group. Twenty-two isome...

  6. Energetics of the S2 State Spin Isomers of the Oxygen-Evolving Complex of Photosystem II.

    PubMed

    Vinyard, David J; Khan, Sahr; Askerka, Mikhail; Batista, Victor S; Brudvig, Gary W

    2017-02-09

    The S2 redox intermediate of the oxygen-evolving complex in photosystem II is present as two spin isomers. The S = 1/2 isomer gives rise to a multiline electron paramagnetic resonance (EPR) signal at g = 2.0, whereas the S = 5/2 isomer exhibits a broad EPR signal at g = 4.1. The electronic structures of these isomers are known, but their role in the catalytic cycle of water oxidation remains unclear. We show that formation of the S = 1/2 state from the S = 5/2 state is exergonic at temperatures above 160 K. However, the S = 1/2 isomer decays to S1 more slowly than the S = 5/2 isomer. These differences support the hypotheses that the S3 state is formed via the S2 state S = 5/2 isomer and that the stabilized S2 state S = 1/2 isomer plays a role in minimizing S2QA(-) decay under light-limiting conditions.

  7. Analysis of 2,4,6-nonatrienal geometrical isomers from male flea beetles, Epitrix hirtipennis and E. fuscula

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Geometrical isomers of 2,4,6-nonatrienal have been reported from a variety of food- and insect-related sources. It was discovered recently that the eggplant flea beetle, Epitrix fuscula, uses the (2E,4E,6Z) and (2E,4E,6E) isomers as components of its male-produced aggregation pheromone. Here, we l...

  8. Metabolism of a- and y-hexabromocyclododecane and enantioselective fractions of a-, ß-, y-isomers in mice

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Commercial HBCD is a mixture of three major isomers, a, ß, and ', with the '-diastereoisomer predominating (>70%). Thus, the prevalence of the a-isomer as an environmental contaminant must be explained by either different pharmacokinetics, or by isomerization of the '-diastereoisomer. a- and '-[14...

  9. Energetics of the S2 state spin isomers of the oxygen-evolving complex of Photosystem II

    DOE PAGES

    Vinyard, David J.; Khan, Sahr; Askerka, Mikhail; ...

    2017-01-12

    Here, the S2 redox intermediate of the oxygen-evolving complex in Photosystem II is present as two spin isomers. The S = 1/2 isomer gives rise to a multiline EPR signal at g = 2, while the S = 5/2 isomer exhibits a broad EPR signal at g = 4.1. The electronic structures of these isomers are known, but their role in the catalytic cycle of water oxidation remains unclear. We show that formation of the S = 1/2 state from the S = 5/2 state is exergonic at temperatures above 160 K. However, the S = 1/2 isomer decays tomore » S1 more slowly than the S = 5/2 isomer. These differences support the hypotheses that the S3 state is formed via the S2 state S = 5/2 isomer and that the stabilized S2 state S = 1/2 isomer plays a role in minimizing S2QA- decay in light-limiting conditions.« less

  10. Yrast 6+ Seniority Isomers of 136,138Sn

    NASA Astrophysics Data System (ADS)

    Simpson, G. S.; Gey, G.; Jungclaus, A.; Taprogge, J.; Nishimura, S.; Sieja, K.; Doornenbal, P.; Lorusso, G.; Söderström, P.-A.; Sumikama, T.; Xu, Z. Y.; Baba, H.; Browne, F.; Fukuda, N.; Inabe, N.; Isobe, T.; Jung, H. S.; Kameda, D.; Kim, G. D.; Kim, Y.-K.; Kojouharov, I.; Kubo, T.; Kurz, N.; Kwon, Y. K.; Li, Z.; Sakurai, H.; Schaffner, H.; Shimizu, Y.; Suzuki, H.; Takeda, H.; Vajta, Z.; Watanabe, H.; Wu, J.; Yagi, A.; Yoshinaga, K.; Bönig, S.; Daugas, J.-M.; Drouet, F.; Gernhäuser, R.; Ilieva, S.; Kröll, T.; Montaner-Pizá, A.; Moschner, K.; Mücher, D.; Naïdja, H.; Nishibata, H.; Nowacki, F.; Odahara, A.; Orlandi, R.; Steiger, K.; Wendt, A.

    2014-09-01

    Delayed γ-ray cascades, originating from the decay of (6+) isomeric states, in the very neutron-rich, semimagic isotopes 136,138Sn have been observed following the projectile fission of a 238U beam at RIBF, RIKEN. The wave functions of these isomeric states are proposed to be predominantly a fully aligned pair of f7/2 neutrons. Shell-model calculations, performed using a realistic effective interaction, reproduce well the energies of the excited states of these nuclei and the measured transition rates, with the exception of the B(E2;6+→4+) rate of 136Sn, which deviates from a simple seniority scheme. Empirically reducing the νf7/22 orbit matrix elements produces a 41+ state with almost equal seniority 2 and 4 components, correctly reproducing the experimental B(E2;6+→4+) rate of 136Sn. These data provide a key benchmark for shell-model interactions far from stability.

  11. Structural, electronic, and magnetic properties of two isomers of C40 O10 with cage-like structure.

    PubMed

    Liu, Feng-Ling; Wang, Chen-Hui

    2008-02-01

    Bonding, vibrational and magnetic properties of two isomers of cage-like molecule C40 O10 are studied by using hybrid DFT calculations at the B3LYP/6-31G* level of theory. Infrared- and Raman-active vibrational frequencies of two isomers of C40 O10 are assigned. Three 13C and one 17O nuclear magnetic resonance (NMR) spectral signals of each isomer are characterized. Heat of formation of each isomer is estimated. Compared the stability of the two isomers of C40 O10 with that of C60, only from the thermodynamic points of view, they are more stable than C60. Thus, we believe that they have sufficient stability to allow their experimental preparation. We proposed their synthesized route in this paper.

  12. Mechanistic evaluation of polychlorinated dibenzo-p-dioxin, dibenzofuran and naphthalene isomer fingerprints in microwave pyrolysis of biomass.

    PubMed

    Gao, Qiuju; Cieplik, Mariusz K; Budarin, Vitaliy L; Gronnow, Mark; Jansson, Stina

    2016-05-01

    Isomer distribution patterns of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and naphthalenes (PCNs) were investigated in microwave-assisted pyrolysis (MAP) products of woody biomass. The feedstocks included bark and impregnated wood. The results indicated that isomer distributions in MAP are more selective compared to those reported from wood burning and waste incineration. Favored formation of 4-MoCDF and highly selective chlorine substitution at the 2,4-position observed during MAP suggested a preferred formation pathway of PCDFs involving (chloro)phenol precursors followed by subsequent chlorination. The PCDD distribution was dominated by isomers typically formed from chlorophenol condensation at relatively low temperature. The PCN isomer distributions showed a tendency for sequential chlorination from non-substituted naphthalene at successive positions. The presence of isomers such as 1-MoCDD, 4-MoCDF, 1,2,3-TriCN with low thermodynamic stability indicates that kinetic factors may be important in the MAP process.

  13. Design Study of Triggered Isomer Heat Exchanger-Combustion Hybrid Jet Engine for High Altitude Flight

    DTIC Science & Technology

    2007-11-02

    Lift (lbf) l Nozzle length (ft) lbf Pounds force lbm Pounds mass LPC π Low pressure compressor pressure ratio Lu Lutetium M Mach number m0 Mass...sponsoring an international group of physicists to research an exciting new process for extracting energy from isomers of Lutetium (Lu), Hafnium (Hf), and

  14. 57Fe quadrupole splitting and isomer shift in various oxyhemoglobins: study using Mössbauer spectroscopy

    NASA Astrophysics Data System (ADS)

    Oshtrakh, M. I.; Berkovsky, A. L.; Kumar, A.; Kundu, S.; Vinogradov, A. V.; Konstantinova, T. S.; Semionkin, V. A.

    2010-04-01

    A comparative study of normal human, rabbit and pig oxyhemoglobins and oxyhemoglobin from patients with chronic myeloleukemia and multiple myeloma using Mössbauer spectroscopy with a high velocity resolution demonstrated small variations of the 57Fe quadrupole splitting and isomer shift. These variations may be a result of small structural differences in the heme iron stereochemistry of various hemoglobins.

  15. Positional isomers of cyanostilbene: two-component molecular assembly and multiple-stimuli responsive luminescence

    PubMed Central

    Fan, Guoling; Yan, Dongpeng

    2014-01-01

    An understanding of the aggregates and properties of positional isomers can not only uncover how a slight difference in molecular structure alter crystal packing and bulk solid-state properties, but also plays an important role in developing new types of molecule-based functional materials. Herein, we report a study of the molecular packing and static/dynamic luminescence properties of three cyanostilbene (CS)-based isomers (CS1, CS2, CS3) within their single- and two-component molecular solids. Changing the positions of the cyano substitutents in the CS isomers has a marked influence on their packing modes and luminescent properties. Moreover, two-component CS-based materials have been constructed, which exhibit tunable conformations and packing fashions, as well as fluorescence properties, which differ from the pristine CS solids. The CS-based two-component molecular materials show solvent-responsive luminescence due to the dynamic disassembly of the samples. Moreover, it was found that the system based on CS2 and octafluoronaphthalene shows reversible photochromic fluorescence upon alternating light illumination and grinding. Such co-assembly procedures provide a facile way to fabricate patterned luminescent film materials. Therefore, this work not only affords new insight into the relationship between isomers and luminescence from molecular and supramolecular perspectives, but provides an effective strategy to develop multiple-stimuli-responsive luminescent materials. PMID:24816686

  16. Isomer production ratios and the angular momentum distribution of fission fragments

    NASA Astrophysics Data System (ADS)

    Stetcu, I.; Talou, P.; Kawano, T.; Jandel, M.

    2013-10-01

    Latest generation fission experiments provide an excellent testing ground for theoretical models. In this contribution we compare the measurements for 235U(nth,f), obtained with the Detector for Advanced Neutron Capture Experiments (DANCE) calorimeter at Los Alamos Neutron Science Center (LANSCE), with our full-scale simulation of the primary fragment de-excitation, using the recently developed cgmf code, based on a Monte Carlo implementation of the Hauser-Feshbach theoretical model. We compute the isomer ratios as a function of the initial angular momentum of the fission fragments, for which no direct information exists. Comparison with the available experimental data allows us to determine the initial spin distribution. We also study the dependence of the isomer ratio on the knowledge of the low-lying discrete spectrum input for nuclear fission reactions, finding a high degree of sensitivity. Finally, in the same Hauser-Feshbach approach, we calculate the isomer production ratio for thermal neutron capture on stable isotopes, where the initial conditions (spin, excitation energy, etc.) are well understood. We find that with the current parameters involved in Hauser-Feshbach calculations, we obtain up to a factor of 2 deviation from the measured isomer ratios.

  17. Positional isomers of cyanostilbene: two-component molecular assembly and multiple-stimuli responsive luminescence

    NASA Astrophysics Data System (ADS)

    Fan, Guoling; Yan, Dongpeng

    2014-05-01

    An understanding of the aggregates and properties of positional isomers can not only uncover how a slight difference in molecular structure alter crystal packing and bulk solid-state properties, but also plays an important role in developing new types of molecule-based functional materials. Herein, we report a study of the molecular packing and static/dynamic luminescence properties of three cyanostilbene (CS)-based isomers (CS1, CS2, CS3) within their single- and two-component molecular solids. Changing the positions of the cyano substitutents in the CS isomers has a marked influence on their packing modes and luminescent properties. Moreover, two-component CS-based materials have been constructed, which exhibit tunable conformations and packing fashions, as well as fluorescence properties, which differ from the pristine CS solids. The CS-based two-component molecular materials show solvent-responsive luminescence due to the dynamic disassembly of the samples. Moreover, it was found that the system based on CS2 and octafluoronaphthalene shows reversible photochromic fluorescence upon alternating light illumination and grinding. Such co-assembly procedures provide a facile way to fabricate patterned luminescent film materials. Therefore, this work not only affords new insight into the relationship between isomers and luminescence from molecular and supramolecular perspectives, but provides an effective strategy to develop multiple-stimuli-responsive luminescent materials.

  18. Clusterization in the shape isomers of the {sup 56}Ni nucleus

    SciTech Connect

    Darai, J.; Cseh, J.; Antonenko, N. V.; Jolos, R. V.; Royer, G.; Algora, A.; Hess, P. O.; Scheid, W.

    2011-08-15

    The interrelation of the quadrupole deformation and clusterization is investigated in the example of the {sup 56}Ni nucleus. The shape isomers, including superdeformed and hyperdeformed states, are obtained as stability regions of the quasidynamical U(3) symmetry based on a Nilsson calculation. Their possible binary clusterizations are investigated by considering both the consequences of the Pauli exclusion principle and the energetic preference.

  19. Improved synthesis and characterization of saturated branched-chain fatty acid isomers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The development of viable technologies for producing green products from renewable fats and oils is highly desirable since such materials can serve as replacements for non-renewable and poorly biodegradable petroleum-based products. Mixtures of saturated branched-chain fatty acid isomers (sbc-FAs),...

  20. Photocontrolled nitric oxide release from two nitrosylruthenium isomer complexes and their potential biomedical applications

    NASA Astrophysics Data System (ADS)

    Liu, Jiao; Duan, Qingqing; Wang, Jianru; Song, Zhen; Qiao, Xiaoyan; Wang, Hongfei

    2015-01-01

    Nitric oxide (NO) has key regulatory roles in various biological and medical processes. The control of its local concentration, which is crucial for obtaining the desired effect, can be achieved with exogenous NO donors. Release of NO from metal-nitrosyl complexes upon exposure to light is a strategy that could allow for the site-specific delivery of the reactive species NO to physiological targets. The photodissociation of NO from two nitrosylruthenium(II) isomer complexes {cis- and trans-[Ru(OAc)2NO]} was demonstrated by matrix-assisted laser desorption ionization time-of-flight mass spectrometry spectra, and electron paramagnetic resonance spectra further prove the photoinduced NO release by spin trapping of NO free radicals upon photoirradiation. Real-time NO release was quantitatively measured by electrochemistry with an NO-specific electrode. The quantitative control of NO release from [Ru(OAc)2NO] in aqueous solutions was done by photoirradiation at different wavelengths. Both isomers show photoinduced damage on plasmid DNA, but the trans isomer has higher cytotoxicity and photocytotoxicity activity against the HeLa tumor cell line than that of the cis isomer. Nitrosylruthenium(II) complex, with 8-quinolinol derivatives as ligands, has a great potential as a photoactivated NO donor reagent for biomedical applications.

  1. Using One's Hands for Naming Optical Isomers and Other Stereochemical Positions.

    ERIC Educational Resources Information Center

    Mezl, Vasek A.

    1996-01-01

    Presents a method that allows students to use their hands to obtain the stereochemistry of chiral centers without redrawing the structure. Discusses the use of the model in: determining the configurations of amino acids, determining if sugars are D or L isomers, the sequence rule procedure, prochirality, naming the sides of trigonal carbons, and…

  2. Prospects for measuring the 229Th isomer energy using a metallic magnetic microcalorimeter☆

    PubMed Central

    Kazakov, G.A.; Schauer, V.; Schwestka, J.; Stellmer, S.P.; Sterba, J.H.; Fleischmann, A.; Gastaldo, L.; Pabinger, A.; Enss, C.; Schumm, T.

    2014-01-01

    The Thorium-229 isotope features a nuclear isomer state with an extremely low energy. The currently most accepted energy value, 7.8±0.5 eV, was obtained from an indirect measurement using a NASA x-ray microcalorimeter with an instrumental resolution 26 eV. We study, how state-of-the-art magnetic metallic microcalorimeters with an energy resolution down to a few eV can be used to measure the isomer energy. In particular, resolving the 29.18 keV doublet in the γ-spectrum following the α-decay of Uranium-233, corresponding to the decay into the ground and isomer state, allows to measure the isomer transition energy without additional theoretical input parameters, and increase the energy accuracy. We study the possibility of resolving the 29.18 keV line as a doublet and the dependence of the attainable precision of the energy measurement on the signal and background count rates and the instrumental resolution. PMID:25844000

  3. Prospects for measuring the 229Th isomer energy using a metallic magnetic microcalorimeter

    NASA Astrophysics Data System (ADS)

    Kazakov, G. A.; Schauer, V.; Schwestka, J.; Stellmer, S. P.; Sterba, J. H.; Fleischmann, A.; Gastaldo, L.; Pabinger, A.; Enss, C.; Schumm, T.

    2014-01-01

    The Thorium-229 isotope features a nuclear isomer state with an extremely low energy. The currently most accepted energy value, 7.8±0.5 eV, was obtained from an indirect measurement using a NASA x-ray microcalorimeter with an instrumental resolution 26 eV. We study, how state-of-the-art magnetic metallic microcalorimeters with an energy resolution down to a few eV can be used to measure the isomer energy. In particular, resolving the 29.18 keV doublet in the γ-spectrum following the α-decay of Uranium-233, corresponding to the decay into the ground and isomer state, allows to measure the isomer transition energy without additional theoretical input parameters, and increase the energy accuracy. We study the possibility of resolving the 29.18 keV line as a doublet and the dependence of the attainable precision of the energy measurement on the signal and background count rates and the instrumental resolution.

  4. Prospects for measuring the (229)Th isomer energy using a metallic magnetic microcalorimeter.

    PubMed

    Kazakov, G A; Schauer, V; Schwestka, J; Stellmer, S P; Sterba, J H; Fleischmann, A; Gastaldo, L; Pabinger, A; Enss, C; Schumm, T

    2014-01-21

    The Thorium-229 isotope features a nuclear isomer state with an extremely low energy. The currently most accepted energy value, 7.8±0.5 eV, was obtained from an indirect measurement using a NASA x-ray microcalorimeter with an instrumental resolution 26 eV. We study, how state-of-the-art magnetic metallic microcalorimeters with an energy resolution down to a few eV can be used to measure the isomer energy. In particular, resolving the 29.18 keV doublet in the γ-spectrum following the α-decay of Uranium-233, corresponding to the decay into the ground and isomer state, allows to measure the isomer transition energy without additional theoretical input parameters, and increase the energy accuracy. We study the possibility of resolving the 29.18 keV line as a doublet and the dependence of the attainable precision of the energy measurement on the signal and background count rates and the instrumental resolution.

  5. Toward the laboratory identification of [O,N,S,S] isomers: Implications for biological NO chemistry

    NASA Astrophysics Data System (ADS)

    Ayari, Tarek; Jaidane, Nejm-Eddine; Al Mogren, Muneerah Mogren; Francisco, Joseph S.; Hochlaf, Majdi

    2016-06-01

    Benchmark ab initio calculations are performed to investigate the stable isomers of [O,N,S,S]. These computations are carried out using coupled cluster (RCCSD(T)) and explicitly correlated coupled cluster methods (RCCSD(T)-F12). In addition to the already known cis isomer of SSNO, nine other stable forms are predicted. The most stable isomer is cis-OSNS. Nine structures are chain bent-bent with relatively large dipole moments which make them detectable, as cis-SSNO, by infrared, far-infrared, and microwave spectroscopies. We found also a C2v isomer (NS2O). Since these species are strongly suggested to play an important role as intermediates during the bioactive reaction products of the NO/H2S interaction, the rotational and vibrational spectroscopic parameters are presented to help aid the in vivo identification and assignment of these spectra. Results from this work show that [O,N,S,S] may play key roles during nitric oxide transport and deliver in biological media, as well as, provide an explanation for the weak characteristic of disulfide bridges within proteins.

  6. Optical Spectroscopy of an Atomic Nucleus: Progress toward Direct Observation of the 229Th Isomer Transition

    DTIC Science & Technology

    2011-09-28

    3.1. Acquisition of 229Th Thorium is an actinide element , and the most abundant isotope is 232Th with a half life of 1.41010 years [1]. In contrast...isomer u·ansition Sb. GRANT NUMBER Sc. PROGRAM ELEMENT NUMBER 1D10BP 6. AUTHORS Sd. PROJECT NUMBER Wade G . Rellergett, Scott T . Sullivan, David

  7. Infrared spectroscopy of the acetyl cation and its protonated ketene isomer

    SciTech Connect

    Mosley, J. D.; Young, J. W.; Duncan, M. A.

    2014-07-14

    [C{sub 2},H{sub 3},O]{sup +} ions are generated with a pulsed discharge in a supersonic expansion containing methyl acetate or acetone. These ions are mass selected and their infrared spectra are recorded via laser photodissociation and the method of argon tagging. Computational chemistry is employed to investigate structural isomers and their spectra. The acetyl cation (CH{sub 3}CO{sup +}) is the global minimum and protonated ketene (CH{sub 2}COH{sup +}) is the next lowest energy isomer (+176.2 kJ/mol). When methyl acetate is employed as the precursor, the infrared spectrum reveals that only the acetyl cation is formed. Partially resolved rotational structure reveals rotation about the C{sub 3} axis. When acetone is used as the precursor, acetyl is still the most abundant cation, but there is also a minor component of protonated ketene. Computations reveal a significant barrier to interconversion between the two isomers (+221 kJ/mol), indicating that protonated ketene must be obtained via kinetic trapping. Both isomers may be present in interstellar environments, and their implications for astrochemistry are discussed.

  8. Excitation of the {sup 229m}Th nuclear isomer via resonance conversion in ionized atoms

    SciTech Connect

    Karpeshin, F. F.; Trzhaskovskaya, M. B.

    2015-09-15

    Pressing problems concerning the optical pumping of the 7.6-eV {sup 229m}Th nuclear isomer, which is a candidate for a new nuclear optical reference point for frequencies, are examined. Physics behind the mechanism of the two-photon optical pumping of the isomer is considered. It is shown that, irrespective of the pumping scheme, a dominant contribution comes, in accord with what was proven earlier for the 3.5-eV isomer, from the resonance 8s–7s transition. Details of an optimum experimental scheme are discussed. It is shown that, after isomer excitation, the atom involved remains with a high probability in an excited state at an energy of about 0.5 eV rather than in the ground state, the required energy of the two photons being equal to the energy of the nuclear level plus the energy of the lowest 7s state of the atom. The estimated pumping time is about 1.5 s in the case where the field strength of each laser is 1 V/cm.

  9. Isomer residual ratio of odd-odd isotope {sup 180}Ta in supernova nucleosynthsis

    SciTech Connect

    Hayakawa, Takehito; Kajino, Toshitaka; Chiba, Satoshi; Mathews, Grant

    2010-06-01

    The nucleosynthesis of {sup 180}Ta has remained an unsolved problem and as its origin many nucleosynthesis mechanisms have been proposed. This isotope has the unique feature that the naturally occurring abundance of {sup 180}Ta is actually a meta-stable isomer (half-life of >=10{sup 15} yr), while the ground state is a 1{sup +} unstable state which beta-decays with a half-life of only 8.15 hr. We have made a new time-dependent calculation of {sup 180}Ta meta-stable isomer residual ratio after supernova neutrino-induced reactions. This residual isomer ratio is crucial for understanding the production and survival of this naturally occurring rare isotope. We have constructed a new model under temperature evolution after type II supernova explosion. We include the explicit linking between the isomer and all known excited states and found that the residual ratio is insensitive to astrophysical parameters such as neutrino energy spectrum, explosion energy, decay time constant. We find that the explicit time evolution of the synthesis of {sup 180}Ta avoids the overproduction relative to {sup 138}La for a neutrino process neutrino temperature of 4 MeV.

  10. Structural Isomer Identification via NMR: A Nuclear Magnetic Resonance Experiment for Organic, Analytical, or Physical Chemistry.

    ERIC Educational Resources Information Center

    Szafran, Zvi

    1985-01-01

    Background information, procedures used, and typical results obtained are provided for an experiment that examines the ability of nuclear magnetic resonance (NMR) to distinguish between structural isomers via resonance multiplicities and chemical shifts. Reasons for incorporating the experiment into organic, analytical, or physical chemistry…

  11. Magnetite-platinum nanoparticles-modified glassy carbon electrode as electrochemical detector for nitrophenol isomers.

    PubMed

    Gerent, Giles G; Spinelli, Almir

    2017-05-15

    A glassy carbon electrode was modified with magnetite and platinum nanoparticles stabilized with 3-n-propyl-4-picoline silsesquioxane chloride. This chemically-modified electrode is proposed for the first time for the individual or simultaneous electrochemical detection of nitrophenol isomers. Nanoparticles act as catalysts and also increase the surface area. The polymer stabilizes the particles and provides the electrochemical separation of isomers. Under optimized conditions, the reduction peak currents, obtained by differential-pulse voltammetry, of 2-, 3-, and 4-nitrophenol increased linearly with increases in their concentration in the range of 0.1-1.5μmolL(-1). In individual analysis, the detection limits were 33.7nmolL(-1), 45.3nmolL(-1) and 48.2nmolL(-1), respectively. Also, simultaneous analysis was possible for 2-, and 4-nitrophenol. In this case, the separation of the peak potentials was 0.138V and the detection limits were 69.6nmolL(-1) and 58.0nmolL(-1), respectively. These analytical figures of merit evidence the outstanding performance of the modified electrode, which was also successfully applied to the individual determination of isomers in environmental and biological samples. The magnetite and platinum nanoparticles modified glassy carbon electrode was able to detect nitrophenol isomers at the ppm level in rain water and human urine samples.

  12. Differentiation of hydroxyproline isomers and isobars in peptides by tandem mass spectrometry.

    PubMed

    Kassel, D B; Biemann, K

    1990-08-01

    The isomeric 3- and 4-hydroxyprolines are isobaric with the isomers leucine and isoleucine, and all four have, therefore, the same "residue mass" of 113. Secondary fragmentation processes were found that differentiate the hydroxyproline isomers from each other and from the leucines. Variants of synthetic bradykinin containing one or two hydroxyproline moieties were prepared by using manual Edman degradation and/or enzymatic methods. The tandem mass spectra of these peptides were recorded. The C-terminal wn fragment ions allow the differentiation of 4-hydroxyproline from the 3-isomer and isoleucine, while the N-terminal an ions containing 4-hydroxyproline undergo H2O elimination to differentiate this amino acid from the 3-isomer and leucine. Lys-C digestion of a mussel adhesive protein produced a set of decapeptides varying in the degree of hydroxylation of proline and tyrosine. Heterogeneity with respect to 3-hydroxyproline and 4-hydroxyproline at a certain position in these peptides was assessed by tandem mass spectrometry based on the wn ion series in the CID spectra of these Lys-C peptides. Some N-terminal ions further allow for the differentiation of these two isomeric species.

  13. Ultrafast time-resolved absorption spectroscopy of geometric isomers of xanthophylls

    NASA Astrophysics Data System (ADS)

    Niedzwiedzki, Dariusz M.; Enriquez, Miriam M.; LaFountain, Amy M.; Frank, Harry A.

    2010-07-01

    This paper presents an ultrafast optical spectroscopic investigation of the excited state energies, lifetimes and spectra of specific geometric isomers of neoxanthin, violaxanthin, lutein, and zeaxanthin. All- trans- and 15,15'- cis-β-carotene were also examined. The spectroscopy was done on molecules purified by HPLC frozen immediately to inhibit isomerization. The spectra were taken at 77 K to maintain the configurations and to provide better spectral resolution than seen at room temperature. The kinetics reveal that for all of the molecules except neoxanthin, the S 1 state lifetime of the cis isomers is shorter than that of the all- trans isomers. The S 1 excited state energies of all the isomers were determined by recording S 1 → S 2 transient absorption spectra. The results obtained in this manner at cryogenic temperatures provide an unprecedented level of precision in the measurement of the S 1 energies of these xanthophylls, which are critical components in light-harvesting pigment-protein complexes of green plants.

  14. Lactones 42. Stereoselective enzymatic/microbial synthesis of optically active isomers of whisky lactone.

    PubMed

    Boratyński, Filip; Smuga, Małgorzata; Wawrzeńczyk, Czesław

    2013-11-01

    Two different methods, enzyme-mediated reactions and biotrasformations with microorganisms, were applied to obtain optically pure cis- and trans-isomers of whisky lactone 4a and 4b. In the first method, eight alcohol dehydrogenases were investigated as biocatalysts to enantioselective oxidation of racemic erythro- and threo-3-methyloctane-1,4-diols (1a and 1b). Oxidation processes with three of them, alcohol dehydrogenases isolated from horse liver (HLADH) as well as recombinant from Escherichia coli and primary alcohol dehydrogenase (PADH I), were characterized by the highest degree of conversion with moderate enantioselectivity (ee=27-82%) of the reaction. In all enzymatic reactions enantiomerically enriched not naturally occurring isomers of trans-(-)-(4R,5S)-4b or cis-(+)-(4R,5R)-4a were formed preferentially. In the second strategy, based on microbial lactonization of γ-oxoacids, naturally occurring opposite isomers of whisky lactones were obtained. Trans-(+)-(4S,5R)-isomer (ee=99%) of whisky lactone 4b was stereoselectively formed as the only product of biotransformations of 3-methyl-4-oxooctanoic acid (5) catalyzed by Didimospheria igniaria KCH6651, Laetiporus sulphurens AM525, Chaetomium sp.1 KCH6670 and Saccharomyces cerevisiae AM464. Biotransformation of γ-oxoacid 5, in the culture of Beauveria bassiana AM278 and Pycnidiella resinae KCH50 afforded a mixtures of trans-(+)-(4S,5R)-4b with enantiomeric excess ee=99% and cis-(-)-(4S,5S)-4a with enantiomeric excesses ee=77% and ee=45% respectively.

  15. Lipid and Glycolipid Isomer Analyses Using Ultra-High Resolution Ion Mobility Spectrometry Separations

    PubMed Central

    Wojcik, Roza; Webb, Ian K.; Deng, Liulin; Garimella, Sandilya V. B.; Prost, Spencer A.; Ibrahim, Yehia M.; Baker, Erin S.; Smith, Richard D.

    2017-01-01

    Understanding the biological roles and mechanisms of lipids and glycolipids is challenging due to the vast number of possible isomers that may exist. Mass spectrometry (MS) measurements are currently the dominant approach for studying and providing detailed information on lipid and glycolipid presence and changes. However, difficulties in distinguishing the many structural isomers, due to the distinct lipid acyl chain positions, double bond locations or specific glycan types, inhibit the delineation and assignment of their biological roles. Here we utilized ultra-high resolution ion mobility spectrometry (IMS) separations by applying traveling waves in a serpentine multi-pass Structures for Lossless Ion Manipulations (SLIM) platform to enhance the separation of selected lipid and glycolipid isomers. The multi-pass arrangement allowed the investigation of paths ranging from ~16 m (one pass) to ~60 m (four passes) for the distinction of lipids and glycolipids with extremely small structural differences. These ultra-high resolution SLIM IMS-MS analyses provide a foundation for exploring and better understanding isomer-specific biological activities and disease processes. PMID:28106768

  16. Infrared Spectra of (CO2)2-OCS Complex: Infrared Observation of Two Distinct Barrel-Shaped Isomers

    NASA Astrophysics Data System (ADS)

    Norooz Oliaee, J.; Dehghany, M.; Mivehvar, F.; Moazzen-Ahmadi, N.; McKellar, A. R. W.

    2010-06-01

    Spectra of (CO2)2-OCS complex in the region of the OCS ν 1 fundamental (˜ 2062 cm-1) are observed using a tunable diode laser to probe a pulsed supersonic slit jet expansion. A previous microwave study of the complex by Peebles and Kuczkowskia gave a distorted triangular cylinder. The geometerical disposition of the three dimer faces of this trimer are quite similar to the slipped CO2 dimer, the lowest energy form of OCS-CO2 (isomer a), also observed and analyzed in the microwave region, and the higher energy form of OCS-CO2 (isomer b), first observed by our group in the infrared region. Here we report the observation and analysis of two infrared bands, corresponding to two distinct isomers of the (CO2)2-OCS complex. A band around 2058.8 cm-1 was assigned to isomer I, which is the same as that studied previously by microwave spectroscopy. A second band around 2051.7 cm-1 was assigned to a higher energy isomer of the complex, isomer II, has not been observed previously, but expected on the basis of ab initio calculations. Approximate structural parameters for this new isomer were obtained by means of isotopic substitution. In contrast to isomer I, the geometerical disposition of the faces containing OCS and CO2 in isomer II are similar to isomer b of the OCS-CO2 complex. S. A. Peebles and R. L. Kuczkowski, J. Chem. Phys. 109, 5277 (1998). S. E. Novick, R. D. Suenram, and F. J. Lovas, J. Chem. Phys. 88, 687 (1988). M. Dehghany, J. Nooroz Oliaee, M. Afshari, N. Moazzen-Ahmadi, and A. R. W. McKellar, J. Chem. Phys. 130, 224310 (2009). H. Valdés and J. A. Sordo, Int. J. Comput. Chem. 23, 444 (2002).

  17. Branched perfluorooctane sulfonate isomer quantification and characterization in blood serum samples by HPLC/ESI-MS(/MS).

    PubMed

    Riddell, Nicole; Arsenault, Gilles; Benskin, Jonathan P; Chittim, Brock; Martin, Jonathan W; McAlees, Alan; McCrindle, Robert

    2009-10-15

    Perfluorooctane sulfonate (PFOS) is a global contaminant and is currently among the most prominent contaminants in human blood and wildlife samples. Although "total PFOS" (SigmaPFOS) analytical methods continue to be the most commonly used for quantification, recent analytical method developments have made it possible to resolve the various isomers of PFOS by HPLC-MS/MS. Characterized technical PFOS standards (i.e., containing a mixture of PFOS isomers) are now available that enable isomer specific quantification of PFOS, however the advantages of such an analysis have notyet been examined systematically. Herein, PFOS isomers have been individually quantified for the first time in real samples and the results are compared to a traditional SigmaPFOS method; the influence of analytical standards and isomer specific electrospray and MS/ MS behavior were also investigated. The two human serum standard reference materials chosen for analysis contained dramaticallydifferent PFOS isomer profiles (approximately 30-50% total branched isomers) emphasizing that isomer patterns should not be ignored and may provide useful information on exposure sources (i.e., direct exposure to PFOS vs indirect exposure from PFOS-precursors). Depending on the sample and the particular MS/MS transition chosen for SigmaPFOS analysis (i.e., 499-->80 or 499-->99), SigmaPFOS concentrations may be over- or underestimated compared to the isomer specific analysis. Differences in the extent of in-source fragmentation and MS/MS dissociation contributed to the systematic analytical bias. It was also shown that SigmaPFOS data are prone to interlaboratory variation due to various choices of PFOS standards and instrumental conditions used. In the future, for either SigmaPFOS or isomer specific PFOS analyses, we suggest that accuracy can be maximized and interlaboratory discrepancies minimized by using a common chemically pure technical PFOS standard characterized by 19F NMR.

  18. Evaluation of Enhanced Comprehensive 2-D Gas Chromatography-Time-Of-Flight Mass Spectrometry for the Separation of Recalcitrant Polychlorinated Biphenyl Isomers

    EPA Science Inventory

    The separation of some recalcitrant polychlorinated biphenyl (PCB) isomers in extracts from environmental compartments has been a daunting task for environmental chemists. Summed quantitation values for coeluting PCB isomers are often reported. This composite data obscures the ac...

  19. Probing ground and low-lying excited states for HIO2 isomers

    NASA Astrophysics Data System (ADS)

    de Souza, Gabriel L. C.; Brown, Alex

    2014-12-01

    We present a computational study on HIO2 molecules. Ground state properties such as equilibrium structures, relative energetics, vibrational frequencies, and infrared intensities were obtained for all the isomers at the coupled-cluster with single and double excitations as well as perturbative inclusion of triples (CCSD(T)) level of theory with the aug-cc-pVTZ-PP basis set and ECP-28-PP effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. The HOIO structure is confirmed as the lowest energy isomer. The relative energies are shown to be HOIO < HOOI < HI(O)O. The HO(O)I isomer is only stable at the density functional theory (DFT) level of theory. The transition states determined show interconversion of the isomers is possible. In order to facilitate future experimental identification, vibrational frequencies are also determined for all corresponding deuterated species. Vertical excitation energies for the three lowest-lying singlet and triplet excited states were determined using the configuration interaction singles, time-dependent density functional theory (TD-DFT)/B3LYP, TD-DFT/G96PW91, and equation of motion-CCSD approaches with the LANL2DZ basis set plus effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. It is shown that HOIO and HOOI isomers have excited states accessible at solar wavelengths (<4.0 eV) but these states have very small oscillator strengths (<2 × 10-3).

  20. Portable, Battery Operated Capillary Electrophoresis with Optical Isomer Resolution Integrated with Ionization Source for Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Moini, Mehdi; Rollman, Christopher M.

    2016-03-01

    We introduce a battery operated capillary electrophoresis electrospray ionization (CE/ESI) source for mass spectrometry with optical isomer separation capability. The source fits in front of low or high resolution mass spectrometers similar to a nanospray source with about the same weight and size. The source has two high voltage power supplies (±25 kV HVPS) capable of operating in forward or reverse polarity modes and powered by a 12 V rechargeable lithium ion battery with operation time of ~10 h. In ultrafast CE mode, in which short narrow capillaries (≤15 μm i.d., 15-25 cm long) and field gradients ≥1000 V/cm are used, peak widths at the base are <1 s wide. Under these conditions, the source provides high resolution separation, including optical isomer resolution in ~1 min. Using a low resolution mass spectrometer (LTQ Velos) with a scan time of 0.07 s/scan, baseline separation of amino acids and their optical isomers were achieved in ~1 min. Moreover, bovine serum albumin (BSA) was analyzed in ~1 min with 56% coverage using the data-dependent MS/MS. Using a high resolution mass spectrometer (Thermo Orbitrap Elite) with 15,000 resolution, the fastest scan time achieved was 0.15 s, which was adequate for CE-MS analysis when optical isomer separation is not required or when the optical isomers were well separated. Figures of merit including a detection limit of 2 fmol and linear dynamic range of two orders of magnitude were achieved for amino acids.

  1. Probing ground and low-lying excited states for HIO2 isomers.

    PubMed

    de Souza, Gabriel L C; Brown, Alex

    2014-12-21

    We present a computational study on HIO2 molecules. Ground state properties such as equilibrium structures, relative energetics, vibrational frequencies, and infrared intensities were obtained for all the isomers at the coupled-cluster with single and double excitations as well as perturbative inclusion of triples (CCSD(T)) level of theory with the aug-cc-pVTZ-PP basis set and ECP-28-PP effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. The HOIO structure is confirmed as the lowest energy isomer. The relative energies are shown to be HOIO < HOOI < HI(O)O. The HO(O)I isomer is only stable at the density functional theory (DFT) level of theory. The transition states determined show interconversion of the isomers is possible. In order to facilitate future experimental identification, vibrational frequencies are also determined for all corresponding deuterated species. Vertical excitation energies for the three lowest-lying singlet and triplet excited states were determined using the configuration interaction singles, time-dependent density functional theory (TD-DFT)/B3LYP, TD-DFT/G96PW91, and equation of motion-CCSD approaches with the LANL2DZ basis set plus effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. It is shown that HOIO and HOOI isomers have excited states accessible at solar wavelengths (<4.0 eV) but these states have very small oscillator strengths (<2 × 10(-3)).

  2. Retinal isomer ratio in dark-adapted purple membrane and bacteriorhodopsin monomers.

    PubMed

    Scherrer, P; Mathew, M K; Sperling, W; Stoeckenius, W

    1989-01-24

    On the basis of data obtained by spectroscopic analysis and chromatography of retinal extracts, a consensus has been adopted that dark-adapted purple membrane (pm) contains 13-cis- and all-trans-retinal in equal amounts, whereas the light-adapted membrane contains all-trans-retinal only. We have developed an improved extraction technique which extracts up to 70% of the retinal in pm within 4 min. In the extracts from dark-adapted pm at room temperature, we consistently find 66-67% 13-cis-retinal and 33-34% all-trans-retinal, and more than 98.5% all-trans isomer in light-adapted samples. The spectrum obtained by reconstitution of bacterioopsin with 13-cis-retinal at 2 degrees C (to minimize isomerization) shows an absorbance maximum at 554 nm and agrees well with the spectrum for the 13-cis component calculated from the dark-adapted and light-adapted bR spectra with our extraction data. The ratio of 13-cis:all-trans isomer in dark-adapted pm is 2:1 and nearly constant between 0 and 38 degrees C but begins to decrease distinctly above 40 degrees C, and more rapidly near 70 degrees C, reaching 0.75 at 90 degrees C. The van't Hoff plot of the isomer ratio shows a nonlinear temperature dependence above 40 degrees C, indicating a more complex system than a simple thermal 13-cis/all-trans isomer equilibrium. We attribute the broadening, absorbance decrease, and blut shift of the visible absorption band with increasing temperature to the appearance of at least one and possibly two or three new chromophores which contain, mainly or exclusively, the all-trans isomer.(ABSTRACT TRUNCATED AT 250 WORDS)

  3. Conformational preferences and synthesis of isomers Z and E of oxazole-dehydrophenylalanine.

    PubMed

    Staś, Monika; Bujak, Maciej; Broda, Małgorzata A; Siodłak, Dawid

    2016-05-01

    Dehydrophenylalanine, ΔPhe, is the most commonly studied α,β-dehydroamino acid. In nature, further modifications of the α,β-dehydroamino acids were found, for example, replacement of the C-terminal amide group by oxazole ring. The conformational properties of oxazole-dehydrophenylalanine residue (ΔPhe-Ozl), both isomers Z and E, were investigated. To determine all possible conformations, theoretical calculations were performed using Ac-(Z/E)-ΔPhe-Ozl(4-Me) model compounds at M06-2X/6-31++G(d,p) level of theory. Ac-(Z/E)-ΔPhe-Ozl-4-COOEt compounds were synthesized and the conformational preferences of each isomer, Z and E, were investigated using FTIR and NMR-NOE in solutions of increasing polarity (CHCl3 , DMSO-d6). The solid-state low-temperature structures of Ac-(Z)-ΔPhe-Ozl-4-COOEt and its intermediate analog Ac-(Z)-ΔPhe-Ozn(4-OH)-4-COOEt were also determined. In a weakly polar environment, the ΔPhe-Ozl residue has a tendency to adopt the conformation β2 with the calculated φ and ψ angles of -127° and 0° for the isomer Z and -170° and 26° for the isomer E. The increase of environment polarity favors the helical conformation α and the beta-turn like conformation β, but the conformation β2 seems to be still accessible. The (E)-ΔPhe-Ozl residue can be obtained from the isomer Z in photoisomerization reaction. However, hydroxyl-oxazoline-dehydrophenylalanine ΔPhe-Ozn(4-OH) decomposes in such conditions. Alternatively, (E)-ΔPhe-NH2 can be applied as a substrate in the Hantzsch reaction. © 2016 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 106: 283-294, 2016.

  4. Glass transition dynamics and boiling temperatures of molecular liquids and their isomers.

    PubMed

    Wang, Li-Min; Richert, Ranko

    2007-03-29

    The relation between a dynamic and a thermodynamic temperature, glass transition Tg and boiling point Tb, is investigated for various glass-forming liquids, with emphasis on monohydroxy alcohols. As is well known, Tb and Tg are positively correlated across a large variety of liquids. However, we found that the same quantities show a negative correlation within an isomeric series, i.e., Tb decreases with increasing Tg for different isomers of the same chemical formula. For the alcohol series, CnH2n+1OH with 3 < or = n < or = 10, a master curve of the negative Tg - Tb correlation is obtained if the temperatures are normalized to the respective values of the n-alkanols. This Tg - Tb dependence of isomeric liquids is linked to entropic effects and responsible for much of the scatter of the correlation observed for a large number of molecular organic glass-formers with 45 < Tg < 250 K. Dielectric relaxation is measured for three groups of isomers: (a) 3-methoxyl-1-butanol and 2-iso-propoxyethanol, (b) 1,4-, 1,2-, and 2,4-pentanediol, and (c) di-n- and di-iso-butyl phthalate. Two key parameters of the dynamics, fragility m and stretching exponent beta, are found to be indistinguishable within isomers of moderately different Tgs. Larger fragility differences are readily expected with pronounced structural change, but no systematic trend is observed within an isomer series. The results provide a useful tool for assessing Tg, m, and beta for marginal glass formers on the basis of their isomers.

  5. Portable, Battery Operated Capillary Electrophoresis with Optical Isomer Resolution Integrated with Ionization Source for Mass Spectrometry.

    PubMed

    Moini, Mehdi; Rollman, Christopher M

    2016-03-01

    We introduce a battery operated capillary electrophoresis electrospray ionization (CE/ESI) source for mass spectrometry with optical isomer separation capability. The source fits in front of low or high resolution mass spectrometers similar to a nanospray source with about the same weight and size. The source has two high voltage power supplies (±25 kV HVPS) capable of operating in forward or reverse polarity modes and powered by a 12 V rechargeable lithium ion battery with operation time of ~10 h. In ultrafast CE mode, in which short narrow capillaries (≤15 μm i.d., 15-25 cm long) and field gradients ≥1000 V/cm are used, peak widths at the base are <1 s wide. Under these conditions, the source provides high resolution separation, including optical isomer resolution in ~1 min. Using a low resolution mass spectrometer (LTQ Velos) with a scan time of 0.07 s/scan, baseline separation of amino acids and their optical isomers were achieved in ~1 min. Moreover, bovine serum albumin (BSA) was analyzed in ~1 min with 56% coverage using the data-dependent MS/MS. Using a high resolution mass spectrometer (Thermo Orbitrap Elite) with 15,000 resolution, the fastest scan time achieved was 0.15 s, which was adequate for CE-MS analysis when optical isomer separation is not required or when the optical isomers were well separated. Figures of merit including a detection limit of 2 fmol and linear dynamic range of two orders of magnitude were achieved for amino acids.

  6. Probing ground and low-lying excited states for HIO{sub 2} isomers

    SciTech Connect

    Souza, Gabriel L. C. de; Brown, Alex

    2014-12-21

    We present a computational study on HIO{sub 2} molecules. Ground state properties such as equilibrium structures, relative energetics, vibrational frequencies, and infrared intensities were obtained for all the isomers at the coupled-cluster with single and double excitations as well as perturbative inclusion of triples (CCSD(T)) level of theory with the aug-cc-pVTZ-PP basis set and ECP-28-PP effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. The HOIO structure is confirmed as the lowest energy isomer. The relative energies are shown to be HOIO < HOOI < HI(O)O. The HO(O)I isomer is only stable at the density functional theory (DFT) level of theory. The transition states determined show interconversion of the isomers is possible. In order to facilitate future experimental identification, vibrational frequencies are also determined for all corresponding deuterated species. Vertical excitation energies for the three lowest-lying singlet and triplet excited states were determined using the configuration interaction singles, time-dependent density functional theory (TD-DFT)/B3LYP, TD-DFT/G96PW91, and equation of motion-CCSD approaches with the LANL2DZ basis set plus effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. It is shown that HOIO and HOOI isomers have excited states accessible at solar wavelengths (<4.0 eV) but these states have very small oscillator strengths (<2 × 10{sup −3})

  7. Vitamin E and cancer: An insight into the anticancer activities of vitamin E isomers and analogs.

    PubMed

    Constantinou, Constantina; Papas, Andreas; Constantinou, Andreas I

    2008-08-15

    Current observations in the literature suggest that vitamin E may be a suitable candidate for the adjuvant treatment of cancer. Even though historically most research focused on alpha-tocopherol, more recent evidence suggests that the other isomers of vitamin E (beta-, gamma- and delta-tocopherols and alpha-, beta-, gamma- and delta-tocotrienols) differ in their proapoptotic potencies. The main focus of this communication is the current understanding of the molecular mechanisms regulated by vitamin E isomers and their analogs during the induction of apoptosis. This review highlights that the mitochondria are the major target for the induction of apoptosis by vitamin E isomers and analogs and that the various signaling pathways regulated by these agents are likely to contribute towards maximizing the intrinsic pathway of apoptosis triggered initially by the mitochondria. Overall, the presentation of recent studies from the literature in this communication allows the drawing of the following important conclusions: (i) no direct link exists between the antioxidant activity of each isomer/derivative and proapoptotic potency, (ii) tocotrienols are more effective proapoptotic agents than tocopherols, (iii) synthetic modifications of the naturally occurring compounds may improve their apoptotic potency and (iv) vitamin E isomers and derivatives regulate caspase-independent pathways of apoptosis. The latter combined with the evidence presented in this review regarding the additive or synergistic anticarcinogenic effects obtained when vitamin E analogs are used in combination with other cancer chemotherapeutic agents, supports further research to design the most promising vitamin E derivatives and clinically test them in adjuvant chemotherapeutic treatments.

  8. The Metal-Rich Universe

    NASA Astrophysics Data System (ADS)

    Israelian, Garik; Meynet, Georges

    2012-10-01

    Preface; Part I. Abundances in the Galaxy: Field Stars: 1. Metal-rich stars and stellar populations: A brief history and new results; 2. The metal-rich nature of stars with planets; 3. Solar chemical peculiarities; 4. Kinematics of metal-rich stars with and without planets; 5. Elemental abundance trends in the metal-rich thin and thick disks; 6. Metal-rich massive stars - how metal-rich are they?; 7. Hercules stream stars and the metal-rich thick disk; 8. Abundance survey of the galactic thick disk; Part II. Abundances in the Galaxy: Galactic Stars in Clusters, Bulges and Centre: 9. Galactic open clusters with super solar metallicities; 10. Old and very metal-rich open clusters in the BOCCE project; 11. Massive stars vs. nebular abundances in the Orion nebula; 12. Abundance surveys of metal-rich bulge stars; 13. Metal abundances in the galactic center; 14. Light elements in the galactic bulge; 15. Metallicity and ages of selected G-K giants; Part III. Observations - Abundances in Extragalactic Contexts: 16. Stellar abundances of early-type galaxies and galactic spheroids: Evidence for metal-rich stars; 17. Measuring chemical abundances in extragalactic metal-rich HII regions; 18. On the maximum oxygen abundance in metal-rich spiral galaxies; 19. Starbursts and their contribution to metal enrichment; 20. High metallicities at high redshifts; 21. Evolution of dust and elemental abundances in quasar DLAs and GRB afterglows as a function of cosmic time; 22. Dust, metals and diffuse interstellar bands in damped Lyman Alpha systems; 23. Tracing metallicities in the Universe with the James Webb Space Telescope; Part IV. Stellar Populations and Mass Functions: 24. The stellar initial mass function of metal-rich populations; 25. IMF effects on the metallicity and colour evolution of disk galaxies; 26. The metallicity of circumnuclear star forming regions; 27. The stellar population of bulges; 28. The metallicity distribution of the stars in elliptical galaxies; 29. Wolf

  9. Measurement of internal movements of the Escherichia coli ribosome using Forster resonance energy transfer and microsecond, continuous-flow turbulent mixing in micro-fabricated devices

    NASA Astrophysics Data System (ADS)

    Majumdar, Zigurts Krishna

    We have studied internal movements of the Eschericia coli ribosome with Forster Resonance Energy Transfer (FRET) using multiple donor-acceptor pairs labeled at specific ribosomal protein residues. We have developed a novel methodology that allows a more quantitative interpretation of distance data from FRET measurements, accounting for specific effects when using fluorescent probes, such as: non-stoichiometric labeling when biochemical separation is not possible, quantification of static and dynamic quenching, changes in extinction coefficients, effects of the orientation factor and the presence of random and systematic errors. From the obtained distance data, 13 donor-acceptor positions (from 18 independent FRET pairs) are used to model internal movements within the 30S subunit upon 70S association. These measurements are also applied to monitoring inter-subunit movements in functional states of the ribosome that are associated with the translocation cycle of the ribosome. This work reveals internal movements of the ribosome observed for the first time in solution, and presents in vitro evidence for large concerted inter-subunit motions associated with ribosome translocation. The second half of this thesis is independent of the above. We present the design, construction and implementation of micro-fabricated, continuous-flow, turbulent mixing devices that can mix two or three fluids to complete homogeneity on the molecular scale in the microsecond range. The prototypical designs are compact, portable, simple to fabricate and consume smaller sample volumes than current technology. We characterize the turbulent mixing process in microfluidic channels with fluorescence intensity and lifetime imaging and show that both the dependence of mixing times and pressure drop on the flow velocity and Reynolds number agree well with theoretical expectations for turbulent pipe flow. The novelties in this work are: the new methods of fabrication which enable production of three

  10. Detection, identification, and quantification of hydroxylated bis(2-ethylhexyl)-tetrabromophthalate isomers in house dust.

    PubMed

    Peng, Hui; Saunders, David M V; Sun, Jianxian; Codling, Garry; Wiseman, Steve; Jones, Paul D; Giesy, John P

    2015-03-03

    Ultra-High Resolution LC/mass spectrometry (LC-UHRMS; Thermo Fisher Q-Exactive) was used to identify two novel isomers of hydroxylated bis(2-ethylhexyl)-tetrabromophthalate (OH-TBPH) which were unexpectedly observed in a commercial standard of TBPH. By combining ultra-high resolution (UHR) mass spectra (MS(1)), mass errors to theoretical [TBPH-Br+O](-) were 2.1 and 1.0 ppm for the two isomers, UHR-MS(2) spectra and NMR analysis; the structures of the two compounds were identified as hydroxylated TBPH with a hydroxyl group on the aromatic ring. Relatively great proportions of the two isomers of OH-TBPH were detected in two technical products, Firemaster 550 (FM-550; 0.1% and 6.2%, respectively) and Firemaster BZ 54 (BZ-54; 0.1% and 7.9%), compared to a commercial standard (0.4% and 0.9%). To simultaneously analyze OH-TBPH isomers and TBPH in samples of dust, a method based on LC-UHRMS was developed to quantify the two compounds, using negative and positive ion modes, respectively. The instrumental limit of detection for TBPH was 0.01 μg/L, which was 200-300 times better than traditional methods (2.5 μg/L) based on gas chromatography-mass spectrometry. The analytical method combined with a Florisil cleanup was successfully applied to analyze TBPH and OH-TBPH in 23 indoor dust samples from Saskatoon, Saskatchewan, Canada. Two OH-TBPH isomers, OH-TBPH1 and OH-TBPH2, were detected in 52% and 91% of dust samples, respectively. Concentrations of OH-TBPH2 (0.35 ± 1.0 ng/g) were 10-fold greater than those of OH-TBPH1 (0.04 ± 0.88 ng/g) in dust, which was similar to profiles in FM-550 and BZ-54. TBPH was also detected in 100% of dust samples with a mean concentration of 733 ± 0.87 ng/g. A significant (p < 0.001) log-linear relationship was observed between TBPH and OH-TBPH isomers, further supporting the hypothesis of a common source of emission. Relatively small proportions of OH-TBPH isomers were detected in dust (0.01% ± 0.67 OH-TBPH1 and 0.1% ± 0.60 OH-TBPH2

  11. Trolox equivalent antioxidant capacity of different geometrical isomers of alpha-carotene, beta-carotene, lycopene, and zeaxanthin.

    PubMed

    Böhm, Volker; Puspitasari-Nienaber, Ni Luh; Ferruzzi, Mario G; Schwartz, Steven J

    2002-01-02

    Isomerization of carotenoids, which is often encountered in food processing under the influence of temperature and light, may play a role in the observed protective effects of this group of secondary plant products. Investigation of in vitro antioxidant activity of prominent carotenoid geometrical isomers was undertaken in light of recent reports illustrating a large percentage of carotenoid (Z)-isomers in biological fluids and tissues. Alpha-carotene, beta-carotene, lycopene, and zeaxanthin were isolated from foods or supplements and subsequently photoisomerized with iodine as a catalyst. Major Z-isomers of each carotenoid were fractionated by semipreparative C(30) HPLC. In vitro antioxidant activity of all isomers collected was measured photometrically using the Trolox equivalent antioxidant capacity (TEAC) assay. TEAC values of 17 geometrical isomers investigated ranged from 0.5 to 3.1 mmol/L. Three unidentified (Z)-isomers of lycopene showed the highest antioxidant activity, being significantly higher than the result for (all-E)-lycopene, which had approximately two times the activity of (all-E)-beta-carotene. On the other hand, (9Z)-zeaxanthin had a more than 80% lower TEAC value compared to that of (all-E)-lycopene. These results allow for the in vivo relevance of (Z)-isomers of carotenoids to be considered.

  12. Perfluorooctane sulfonate toxicity, isomer-specific accumulation, and maternal transfer in zebrafish (Danio rerio) and rainbow trout (Oncorhynchus mykiss).

    PubMed

    Sharpe, Rainie L; Benskin, Jonathan P; Laarman, Anne H; Macleod, Sherri L; Martin, Jonathan W; Wong, Charles S; Goss, Greg G

    2010-09-01

    Perfluorooctane sulfonate (PFOS; C(8)F(17)SO(3) (-)) bioaccumulation and toxicity have been demonstrated in both aquatic and terrestrial organisms. The majority of investigations have examined total PFOS concentrations in wildlife and in toxicity testing, but isomer-specific monitoring studies are less common, and no laboratory-based study of PFOS isomer accumulation in fish has been reported. The present study examined accumulation and maternal transfer of PFOS isomers in zebrafish and tissue-specific accumulation of PFOS isomers in trout parr. A median lethal dose (LC50) of 22.2 and 2.5 mg/L was calculated for adult zebrafish and trout parr, respectively. A two-week PFOS exposure resulted in tissue-specific PFOS accumulation in trout, with maximum concentrations identified in the liver tissue (>50 microg/g). Prior exposure to PFOS as alevin did not affect the accumulation of PFOS in tissues later in life. In both species, accumulation of branched PFOS isomers generally occurred to a lesser extent than linear PFOS, which may explain the relative deficiency of branched PFOS isomers in some aquatic species in the field. Analysis of exposed trout tissues indicated that isomer discrimination may occur at the level of elimination or uptake and elimination processes in the kidney or gill, respectively. When zebrafish underwent a reproductive cycle in the presence of PFOS, approximately 10% (wt) of the adult PFOS body burden was transferred to the developing embryos, resulting in a higher total PFOS concentration in eggs (116 +/- 13.3 microg/g) than in the parent fish (72.1 +/- 7.6 microg/g). The isomer profile in eggs was not significantly different from that of adults, suggesting that the maternal transfer of branched and linear PFOS isomers in fish is largely nonisomer specific.

  13. Biochemical Characterization of Inducible 'Reductase' Component of Benzoate Dioxygenase and Phthalate Isomer Dioxygenases from Pseudomonas aeruginosa strain PP4.

    PubMed

    Karandikar, Rohini; Badri, Abinaya; Phale, Prashant S

    2015-09-01

    The first step involved in the degradation of phthalate isomers (phthalate, isophthalate and terephthalate) is the double hydroxylation by respective aromatic-ring hydroxylating dioxygenases. These are two component enzymes consisting of 'oxygenase' and 'reductase' components. Soil isolate Pseudomonas aeruginosa strain PP4 degrades phthalate isomers via protocatechuate and benzoate via catechol 'ortho' ring cleavage pathway. Metabolic studies suggest that strain PP4 has carbon source-specific inducible phthalate isomer dioxygenase and benzoate dioxygenase. Thus, it was of interest to study the properties of reductase components of these enzymes. Reductase activity from phthalate isomer-grown cells was 3-5-folds higher than benzoate grown cells. In-gel activity staining profile showed a reductase activity band of R f 0.56 for phthalate isomer-grown cells as compared to R f 0.73 from benzoate-grown cells. Partially purified reductase components from phthalate isomer grown cells showed K m in the range of 30-40 μM and V max = 34-48 μmol min(-1) mg(-1). However, reductase from benzoate grown cells showed K m = 49 μM and V max = 10 μmol min(-1) mg(-1). Strikingly similar molecular and kinetic properties of reductase component from phthalate isomer-grown cells suggest that probably the same reductase component is employed in three phthalate isomer dioxygenases. However, reductase component is different, with respect to kinetic properties and zymogram analysis, from benzoate-grown cells when compared to that from phthalate isomer grown cells of PP4.

  14. High-K isomers in {sup 176}W and mechanisms of K-violation

    SciTech Connect

    Crowell, B.; Janssens, R.V.F.; Blumenthal, D.J.

    1995-08-01

    K-isomers are states in deformed nuclei whose {gamma}-decay is hindered by selection rules involving K, the projection of the angular momentum along the axis of symmetry of the nucleus. Previous work with the Argonne Notre Dame BGO Array delineated the existence of two K-isomers in {sup 176}W, one of which had a very unusual pattern of decay. A short description of this work was published as a letter, and a more complete account is being readied for submission. These results provided evidence that quantum-mechanical fluctuations in the nuclear shape may be responsible for some of the observed K-violating transitions. In addition, hints were present in the data of the existence of another K-isomer with an even higher in. An experiment was performed in September 1994 to observe this isomer, using the reaction {sup 50}Ti({sup 130}Te,4n), and a technique in which recoiling {sup 176}W nuclei were created 17-cm upstream of the center of the array and caught on a Pb catcher foil at the center. Intense ({approximately} 3 pnA) beams of {sup 130}Te were supplied by the ECR source using a new sputtering technique. The recoil-shadow geometry was highly successful at removing the background from non-isomeric decays, allowing the weakly populated K-isomers to be detected cleanly. In addition, the availability of pulsed beams from ATLAS and the timing data from the BGO array provided a second technique for isolating the decays of interest, by selecting events in which a given number of BGO detectors fired between beam pulses. This method was used in the previous experiment, and was also applied in this experiment as a second level of selection. As a result, gamma-ray transitions were detected in the present experiment with intensities as small as {approximately} 0.02 % of the {sup 176}W reaction channel. The existence of the new isomer was confirmed, and a partial level-scheme was constructed.

  15. Differential adsorption of complex organic molecules isomers at interstellar ice surfaces

    NASA Astrophysics Data System (ADS)

    Lattelais, M.; Bertin, M.; Mokrane, H.; Romanzin, C.; Michaut, X.; Jeseck, P.; Fillion, J.-H.; Chaabouni, H.; Congiu, E.; Dulieu, F.; Baouche, S.; Lemaire, J.-L.; Pauzat, , F.; Pilmé, J.; Minot, C.; Ellinger, Y.

    2011-08-01

    Context. Over 20 of the ~150 different species detected in the interstellar and circumstellar media have also been identified in icy environments. For most of the species observed so far in the interstellar medium (ISM), the most abundant isomer of a given generic chemical formula is the most stable one (minimum energy principle - MEP) with few exceptions such as, for example, CH3COOH/HCOOCH3 and CH3CH2OH/CH3OCH3, whose formation is thought to occur on the icy mantles of interstellar grains. Aims: We investigate whether differences found in the compositions of molecular ices and the surrounding gas phase could originate from differences between the adsorption of one isomer from that of another at the ice surface. Methods: We performed a coherent and concerted theoretical/experimental study of the adsorption energies of the four molecules mentioned above, i.e. acetic acid (AA)/methyl formate (MF) and ethanol (EtOH)/dimethyl ether (DME) on the surface of water ice at low temperature. The question was first addressed theoretically at LCT using solid state periodic density functional theory (DFT) to represent the organized solid support. The experimental determination of the ice/molecule interaction energies was then carried out independently by two teams at LPMAA and LERMA/LAMAp using temperature programmed desorption (TPD) under an ultra-high vacuum (UHV) between 70 and 160 K. Results: For each pair of isomers, theory and experiments both agree that the most stable isomer (AA or EtOH) interacts more efficiently with the water ice than the higher energy isomer (MF or DME). This differential adsorption can be clearly seen in the different desorption temperatures of the isomers. It is not related to their intrinsic stability but instead to both AA and EtOH producing more and stronger hydrogen bonds with the ice surface. Conclusions: We show that hydrogen bonding may play an important role in the release of organic species from grains and propose that, depending on the

  16. NMR Method for Characterizing Microsecond-to-Millisecond Chemical Exchanges Utilizing Differential Multiple-Quantum Relaxation in High Molecular Weight Proteins.

    PubMed

    Toyama, Yuki; Osawa, Masanori; Yokogawa, Mariko; Shimada, Ichio

    2016-02-24

    Chemical exchange processes of proteins on the order of microseconds (μs) to milliseconds (ms) play critical roles in biological functions. Developments in methyl-transverse relaxation optimized spectroscopy (methyl-TROSY), which observes the slowly relaxing multiple quantum (MQ) coherences, have enabled the studies of biologically important large proteins. However, the analyses of μs to ms chemical exchange processes based on the methyl-TROSY principle are still challenging, because the interpretation of the chemical exchange contributions to the MQ relaxation profiles is complicated, as significant chemical shift differences occur in both (1)H and (13)C nuclei. Here, we report a new methyl-based NMR method for characterizing chemical exchanges, utilizing differential MQ relaxation rates and a heteronuclear double resonance pulse technique. The method enables quantitative evaluations of the chemical exchange processes, in which significant chemical shift differences exist in both the (1)H and (13)C nuclei. The versatility of the method is demonstrated with the application to KirBac1.1, with an apparent molecular mass of 200 kDa.

  17. High-power QCW microsecond-pulse solid-state sodium beacon laser with spiking suppression and D2b re-pumping.

    PubMed

    Bian, Qi; Bo, Yong; Zuo, Jun-wei; Guo, Chuan; Xu, Chang; Tu, Wei; Shen, Yu; Zong, Nan; Yuan, Lei; Gao, Hong-wei; Peng, Qin-jun; Chen, Hong-bin; Feng, Lu; Jin, Kai; Wei, Kai; Cui, Da-fu; Xue, Sui-jian; Zhang, Yu-dong; Xu, Zu-yan

    2016-04-15

    A 65 W quasi-continuous-wave microsecond-pulse solid-state sodium beacon laser tuned to the sodium D2a line has been developed with a linewidth of 0.3 GHz, beam quality of M2=1.38, and pulse width of 120 μs at a repetition rate of 500 Hz by sum-frequency mixing 1319 and 1064 nm diode-pumped Nd:YAG master-oscillator power-amplifier systems. The laser wavelength stability is less than ±0.15 GHz through feedback controlling. The laser spiking due to relaxation oscillations is suppressed by inserting frequency doublers in both 1319 and 1064 nm oscillators. Sodium D2b re-pumping is accomplished by tuning the frequency of the electro-optic modulator with the right D2a-D2b offset. A bright sodium laser guide star with a photon return of 1820 photons/cm2/s was achieved with the laser system when a 32 W circular polarized beam was projected to the sky during our field test at the Xinglong Observatory.

  18. EFFECT OF LASER LIGHT ON MATTER. LASER PLASMAS: Compression of hollow gaseous envelopes at a microsecond plasma generator of x radiation

    NASA Astrophysics Data System (ADS)

    Bartnik, A.; Karpinski, L.; Ivanenkov, G. V.; Pikuz, S. A.; Shelkovenko, T. A.

    1993-11-01

    Experiments with electric discharges across hollow gaseous envelopes have been carried out on a microsecond plasma generator of x radiation (200 kA, 40 kV, 1.5 μs, Ne-Ar mixture). The diagnostic complex made it possible to carry out time- and space-resolved observations in the visible range by means of streak and framing cameras. In the vacuum-UV range, a spectrograph with a transparent grating and a vacuum x-ray diode were used. In the soft x-ray range, a crystal spectrograph with convex and spherically bent crystals, a crystal x-ray microscope, pinhole cameras, and p-i-n diodes were used. The spectral range 0.3-1.5 nm contains lines of He- and H-like Ne and of He-like Ar. These ions are used for x-ray-spectral estimates of the electron temperatures and the densities of the plasma of the hot spots. These estimates lie in the ranges 1-1.3 keV and (0.5-1) · 1022 cm-3. At the optimum nozzle diameter in terms of the x-ray yield, a kink instability and the formation of hot spots are observed simultaneously. Suppressing the kink instability increases the radiation yield. Emission from the plasma column in Kα lines of argon has been observed.

  19. Synthesis of the E and Z isomers of the antiestrogen tamoxifen and its metabolite, hydroxytamoxifen, in tritium-labeled form

    SciTech Connect

    Robertson, D.W.; Katzenellenbogen, J.A.

    1982-06-04

    Both isomers of the potent antiestrogen tamoxifen (1,2-diphenyl-1-(4-(2-(dimethylamino)ethoxy)phenyl)-1-butene: E isomer = ICI-47699; Z isomer = ICI-46474, Nolvadex) and its metabolite, hydroxytamoxifen (1-(4-(2-(dimethylamino)ethoxy)phenyl)-1-(4-hydroxyphenyl)-2-phenyl-1-butene), have been synthesized in a high specific activity, tritium-labeled form by catalytic tritium-halogen exchange performed on brominated precursors. The synthesis of another precursor to labeled tamoxifen which would enable the incorporation of three tritium atoms into the molecule by tritium-halogen exchange is reported.

  20. Molecular orbital (MSXα) calculations of s-electron densities of tetrahedrally coordinated ferric iron: Comparison with experimental isomer shifts

    NASA Astrophysics Data System (ADS)

    Tang Kai, A.; Annersten, H.; Ericsson, T.

    1980-04-01

    The MSXα method has been used to calculate the s-electron densities at the nucleus for tetrahedrally coordinated ferric iron, (FeO4)5-, comparing the observed increase in isomer shift values with increasing Fe-O separation. The results give an isomer shift calibration constant of -0.3 (a.u. mm×s-1) assuming a constant ratio for the iron and oxygen sphere radii for the different polyhedra sizes. It is suggested that increasing bonding distances in tetrahedral coordination polyhedra are the dominant factors determining the value of the isomer shifts in Fe-Mg-silicates.

  1. Identification of (2-aminopropyl)benzofuran (APB) phenyl ring positional isomers in internet purchased products.

    PubMed

    Stanczuk, Andrzej; Morris, Noreen; Gardner, Elizabeth A; Kavanagh, Pierce

    2013-04-01

    5-(2-Aminopropyl)benzofuran (5-APB), a 'research chemical' that was first reported by UK authorities to the European Monitoring Centre for Drugs and Drug Addiction (EMCDDA) in 2010, is anecdotally reported to produce a combination of stimulant and entactogenic effects. More recently, in 2011, 6-(2-aminopropyl)benzofuran (6-APB) was identified by Hungarian authorities. To confirm positional isomer identity in Internet purchased products, 4- 5- 6- and 7-APBs were synthesized and found to be separable by gas chromatography (as heptafluorobutyramide derivatives) and liquid chromatography. The analyses of products purchased from online vendors of 'research chemicals' identified the presence of 5- or 6-APBs. These findings were further confirmed by liquid chromatography-mass spectrometry and (1) H nuclear magnetic resonance spectroscopy. In products containing 6-APB, the 4- positional isomer was also identified and this may have arisen during the manufacturing process.

  2. Deformation increase of high-spin core-excited isomers in the astatine nuclei

    SciTech Connect

    Scheveneels, G.; Hardeman, F.; Neyens, G.; Coussement, R. )

    1991-06-01

    Quadrupole moments of six high-spin isomers in the At isotopes have been measured with the level-mixing-spectroscopy method: {sup 208}At(16{sup {minus}}), {sup 209}At(29/2{sup +}), {sup 210}At(19{sup +},15{sup {minus}}), {sup 211}At(39/2{sup {minus}},29/2{sup +}). The results show that level mixing spectroscopy is a promising technique to determine quadrupole moments of isomers that are difficult to measure by other in-beam hyperfine interaction methods. A large increase of the quadrupole moment is observed if neutrons are excited across or removed from the {ital N}=126 shell closure. This behavior is explained in terms of an enhanced core softness for fewer core neutrons; the aligned valence particles, moving in equatorial orbits, then easily polarize the core towards oblate deformation.

  3. High-K isomers in transactinide nuclei close to N = 162

    SciTech Connect

    Prassa, V. Nikšić, T.; Vretenar, D.; Lu, Bing-Nan; Ackermann, D.

    2015-10-15

    Transactinide nuclei around neutron number N = 162 display axially deformed equilibrium shapes, as shown in our previous analysis [1] of constrained mean-field energy surfaces and collective excitation spectra. In the present study we are particularly interested in the occurrence of high-K isomers in the axially deformed isotopes of Rf (Z = 104), Sg (Z = 106), Hs (Z = 108), and Ds (Z = 110), with neutron number N = 160 − 166 and the effect of the N=162 closure on the structure and distribution of two-quasiparticle (2qp) states. The evolution of high-K isomers is analysed in a self-consistent axially-symmetric relativistic Hartree-Bogoliubov calculation using the blocking approximation with time-reversal symmetry breaking.

  4. Large-scale shell model study of the newly found isomer in 136La

    NASA Astrophysics Data System (ADS)

    Teruya, E.; Yoshinaga, N.; Higashiyama, K.; Nishibata, H.; Odahara, A.; Shimoda, T.

    2016-07-01

    The doubly-odd nucleus 136La is theoretically studied in terms of a large-scale shell model. The energy spectrum and transition rates are calculated and compared with the most updated experimental data. The isomerism is investigated for the first 14+ state, which was found to be an isomer in the previous study [Phys. Rev. C 91, 054305 (2015), 10.1103/PhysRevC.91.054305]. It is found that the 14+ state becomes an isomer due to a band crossing of two bands with completely different configurations. The yrast band with the (ν h11/2 -1⊗π h11 /2 ) configuration is investigated, revealing a staggering nature in M 1 transition rates.

  5. Interactions between major chlorogenic acid isomers and chemical changes in coffee brew that affect antioxidant activities.

    PubMed

    Liang, Ningjian; Xue, Wei; Kennepohl, Pierre; Kitts, David D

    2016-12-15

    Coffee bean source and roasting conditions significantly (p<0.05) affected the content of chlorogenic acid (CGA) isomers, several indices of browning and subsequent antioxidant values. Principal component analysis was used to interpret the correlations between physiochemical and antioxidant parameters of coffee. CGA isomer content was positively correlated (p<0.001) to capacity of coffee to reduce nitric oxide and scavenge Frémy's salt. Indices of browning in roasted coffee were positively correlated (p<0.001) to ABTS and TEMPO radical scavenging capacity, respectively. Only the CGA content of coffee corresponded to intracellular antioxidant capacity measured in Caco-2 intestinal cells. This study concluded that the intracellular antioxidant capacity that best describes potential health benefits of coffee positively corresponds best with CGA content.

  6. Electronic single-molecule identification of carbohydrate isomers by recognition tunnelling

    PubMed Central

    Im, JongOne; Biswas, Sovan; Liu, Hao; Zhao, Yanan; Sen, Suman; Biswas, Sudipta; Ashcroft, Brian; Borges, Chad; Wang, Xu; Lindsay, Stuart; Zhang, Peiming

    2016-01-01

    Carbohydrates are one of the four main building blocks of life, and are categorized as monosaccharides (sugars), oligosaccharides and polysaccharides. Each sugar can exist in two alternative anomers (in which a hydroxy group at C-1 takes different orientations) and each pair of sugars can form different epimers (isomers around the stereocentres connecting the sugars). This leads to a vast combinatorial complexity, intractable to mass spectrometry and requiring large amounts of sample for NMR characterization. Combining measurements of collision cross section with mass spectrometry (IM–MS) helps, but many isomers are still difficult to separate. Here, we show that recognition tunnelling (RT) can classify many anomers and epimers via the current fluctuations they produce when captured in a tunnel junction functionalized with recognition molecules. Most importantly, RT is a nanoscale technique utilizing sub-picomole quantities of analyte. If integrated into a nanopore, RT would provide a unique approach to sequencing linear polysaccharides. PMID:28000682

  7. New shape isomer in the self-conjugate nucleus 72Kr.

    PubMed

    Bouchez, E; Matea, I; Korten, W; Becker, F; Blank, B; Borcea, C; Buta, A; Emsallem, A; de France, G; Genevey, J; Hannachi, F; Hauschild, K; Hürstel, A; Le Coz, Y; Lewitowicz, M; Lucas, R; Negoita, F; de Oliveira Santos, F; Pantelica, D; Pinston, J; Rahkila, P; Rejmund, M; Stanoiu, M; Theisen, Ch

    2003-02-28

    A new isomeric 0(+) state was identified as the first excited state in the self-conjugate (N=Z) nucleus 72Kr. By combining for the first time conversion-electron and gamma-ray spectroscopy with the production of metastable states in high-energy fragmentation, the electric-monopole decay of the new isomer to the ground state was established. The new 0(+) state is understood as the band head of the known prolate rotational structure, which strongly supports the interpretation that 72Kr is one of the rare nuclei having an oblate-deformed ground state. This observation gives in fact the first evidence for a shape isomer in a N=Z nucleus.

  8. Electronic single-molecule identification of carbohydrate isomers by recognition tunnelling

    NASA Astrophysics Data System (ADS)

    Im, Jongone; Biswas, Sovan; Liu, Hao; Zhao, Yanan; Sen, Suman; Biswas, Sudipta; Ashcroft, Brian; Borges, Chad; Wang, Xu; Lindsay, Stuart; Zhang, Peiming

    2016-12-01

    Carbohydrates are one of the four main building blocks of life, and are categorized as monosaccharides (sugars), oligosaccharides and polysaccharides. Each sugar can exist in two alternative anomers (in which a hydroxy group at C-1 takes different orientations) and each pair of sugars can form different epimers (isomers around the stereocentres connecting the sugars). This leads to a vast combinatorial complexity, intractable to mass spectrometry and requiring large amounts of sample for NMR characterization. Combining measurements of collision cross section with mass spectrometry (IM-MS) helps, but many isomers are still difficult to separate. Here, we show that recognition tunnelling (RT) can classify many anomers and epimers via the current fluctuations they produce when captured in a tunnel junction functionalized with recognition molecules. Most importantly, RT is a nanoscale technique utilizing sub-picomole quantities of analyte. If integrated into a nanopore, RT would provide a unique approach to sequencing linear polysaccharides.

  9. Preferential Isomer Formation Observed in H3+ + CO by Crossed Beam Imaging

    PubMed Central

    2016-01-01

    The proton transfer reaction H3+ + CO is one of the cornerstone chemical processes in the interstellar medium. Here, the dynamics of this reaction have been investigated using crossed beam velocity map imaging. Formyl product cations are found to be predominantly scattered into the forward direction irrespective of the collision energy. In this process, a high amount of energy is transferred to internal product excitation. By fitting a sum of two distribution functions to the measured internal energy distributions, the product isomer ratio is extracted. A small HOC+ fraction is obtained at a collision energy of 1.8 eV, characterized by an upper limit of 24% with a confidence level of 84%. At lower collision energies, the data indicate purely HCO+ formation. Such low values are unexpected given the previously predicted efficient formation of both HCO+ and HOC+ isomers for thermal conditions. This is discussed in light of the direct reaction dynamics that are observed. PMID:27352138

  10. Ab initio kinetics for isomerization reaction of normal-chain hexadiene isomers

    NASA Astrophysics Data System (ADS)

    Yang, Feiyu; Deng, Fuquan; Pan, Youshun; Tian, Zemin; Zhang, Yingjia; Huang, Zuohua

    2016-10-01

    The ground-state potential energy surface (PES) of isomerization philosophy of ten normal-chain hexadiene isomers is computed by density functional methods using the geometries optimized at B3LYP/6-311++G (d, p) level of theory. These detailed reaction pathways are used to calculate the rate constants for the unimolecular isomerization reactions by transition state theory (TST) in the temperature range of 500-2500 K. Difference of rate constant between each hexadiene isomer is interpreted through the PES and Ḣ atom transfer, and only 2,4-hexadiene readily fulfills cis-cis to trans-trans conformation conversion. All the conversions are kinetically interpreted from the PES and ST geometry.

  11. Identification of an {alpha}-decaying (9{sup -}) isomer in {sup 216}Fr

    SciTech Connect

    Kurcewicz, J.; Karny, M.; Korgul, A.; Kurcewicz, W.; Kurpeta, J.; Lewandowski, S.; Majorkiewicz, P.; Plochocki, A.; Wojtasiewicz, A.; Czarnacki, W.; Kasztelan, M.; Kisielinski, M.; Penttilae, H.; Roussiere, B.; Steczkiewicz, O.

    2007-11-15

    The {alpha} decay of the trans-lead isotopes {sup 212}At, {sup 216}Fr, and {sup 220}Ac was investigated by using mass-separated sources and analog as well as digital signal processing. By measuring {alpha}-{alpha} time correlations evidence was obtained for the occurrence of an {alpha}-decaying (9{sup -}) isomer in {sup 216}Fr. The {alpha}-decay energy and half-life amount to 9000(5) keV and 850(30) ns, respectively. The excitation energy of the isomer is compared with shell-model predictions for the high-spin members of the {pi}(h{sub 9/2}){nu}(g{sub 9/2}) multiplet, and the relevance of the new data concerning the search for reflection asymmetry is presented.

  12. Thermochemical stabilities and vibrational spectra of isomers of the chlorine oxide dimer

    NASA Technical Reports Server (NTRS)

    Mcgrath, M. P.; Clemitshaw, K. C.; Rowland, F. S.; Hehre, W. J.

    1988-01-01

    Molecular orbital calculations were performed to determine the relative thermochemical stabilities and IR vibrational spectra of isomers of the ClO dimer. Two straight-chain isomers (ClOOCl and ClOClO) and one branched species (ClClO2) were identified as energy minima on the Cl2O2 potential surface. It is shown that ClOOCl and ClClO2 are comparable in terms of stability, while ClOClO is about 11 kcal/mol higher in energy. The IR spectra obtained by Molina and Molina (1987) as a result of the reaction of chlorine atoms with ClO precursors are consistent with the production of the two most stable forms of Cl2O2.

  13. Exclusive accumulation of Z-isomers of monolignols and their glucosides in bark of Fagus grandifolia

    NASA Technical Reports Server (NTRS)

    Lewis, N. G.; Inciong, E. J.; Ohashi, H.; Towers, G. H.; Yamamoto, E.

    1988-01-01

    In addition to Z-coniferyl and Z-sinapyl alcohols, bark extracts of Fagus grandifolia also contain significant amounts of the glucosides, Z-coniferin, Z-isoconiferin (previously called faguside) and Z-syringin. The corresponding E-isomers of these glucosides do not accumulate to a detectable level. The accumulation of the Z-isomers suggests that either they are not lignin precursors or that they are reservoirs of monolignols for subsequent lignin biosynthesis; it is not possible to distinguish between these alternatives. The co-occurrence of Z-coniferin and Z-isoconiferin demonstrate that glucosylation of monolignols can occur at either the phenolic or the allylic hydroxyl groups.

  14. Adsorptive process design for the separation of hexane isomers using zeolites.

    PubMed

    Luna-Triguero, A; Gómez-Álvarez, P; Calero, S

    2017-02-15

    The product of catalytic isomerization is a mixture of linear and branched hydrocarbons that are in thermodynamic equilibrium, and their separation becomes necessary in the petrochemical industry. Zeolite 5A is usually industrially used to sieve alkane isomers, but its pore size allows only the separation of linear alkanes from the monobranched and dibranched alkanes by a kinetic mechanism. A more efficient approach to improve the average research octane number would be to adsorptively separate the di-methyl alkanes as products and recycle both the linear and mono-methyl alkanes to the isomerization reactor. Since the microscopic processes of adsorbates in zeolites are generally difficult or impossible to determine by experiments, especially in the case of mixtures, molecular simulation represents an attractive alternative. In this computational study, we propose a conceptual separation process for hexane isomers consisting of several adsorptive steps. Different zeolite topologies were examined for their ability to conduct this separation based on adsorption equilibrium and kinetics.

  15. Isomer production in intermediate-energy deuteron-induced reactions on a gold target

    NASA Astrophysics Data System (ADS)

    Balabekyan, A. R.; Karapetyan, G. S.; Demekhina, N. A.; Drnoyan, D. R.; Zhemenik, V. I.; Adam, J.; Zavorka, L.; Solnyshkin, A. A.; Tsoupko-Sitnikov, V. M.; Guimarães, V.; Deppman, A.

    2016-05-01

    Residual nuclei formed at ground and isomeric states from the interaction of 4.4 GeV deuteron with a gold target have been measured and investigated by the induced-activity method. Eight isomeric and ground-state pairs of target residues in the mass range of 44 isomer ratios were obtained from the cross-section production. From the isomer ratio data of the formed 196Au and 197Hg nuclei, the average intrinsic angular momentum of the composite system was estimated by means of a simple statistical model based on the formalism developed by Huizenga and Vandenbosch.

  16. Isomer-specific product formation in the proton transfer reaction of HOCO+ with CO

    NASA Astrophysics Data System (ADS)

    Carrascosa, Eduardo; Stei, Martin; Kainz, Martin A.; Wester, Roland

    2015-12-01

    The proton transfer reaction HOCO++CO → HCO+/HOC+ has been studied using crossed-beam velocity map imaging. Angular and energy differential cross sections were obtained for collision energies from 0.3 to 2.3 eV. Scattering in forward direction together with a prominent scattering angle-dependent internal excitation is found at all collision energies. The exothermic HCO+ product appears to be very dominant even at energies above the energy threshold for the formation of metastable HOC+ ion. To determine the HOC+ contribution for different angular ranges, a model has been developed. We obtain an upper limit for the HOC+ product isomer fraction of <2%. In theoretical calculations, we find the CO2-catalysed isomerisation channel to be energetically accessible. However, it may not have a strong impact on the isomer ratio. Chemical dynamics simulations are needed to shed more light on this question.

  17. Experimental and computational investigation of the thermochemistry of the six isomers of dichloroaniline.

    PubMed

    Ribeiro da Silva, Manuel A V; Amaral, Luísa M P F; Gomes, José R B

    2006-07-27

    The standard (p(o) = 0.1 MPa) molar enthalpies of formation of 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dichloroanilines were derived from the standard molar energies of combustion, in oxygen, to yield CO(2)(g), N(2)(g) and HCl.600H(2)O(l), at T = 298.15 K, measured by rotating bomb combustion calorimetry. The Calvet high-temperature vacuum sublimation technique was used to measure the enthalpies of sublimation of the six isomers. These two thermodynamic parameters yielded the standard molar enthalpies of formation of the six isomers of dichloroaniline, in the gaseous phase, at T = 298.15 K. The gas-phase enthalpies of formation were also estimated by G3MP2B3 calculations, which were further extended to the computation of gas-phase acidities, proton affinities, and ionization enthalpies.

  18. Determination of ortho-cresyl phosphate isomers of tricresyl phosphate used in aircraft turbine engine oils by gas chromatography and mass spectrometry.

    PubMed

    De Nola, G; Kibby, J; Mazurek, W

    2008-07-25

    Tricresyl phosphate (TCP) is used as an anti-wear additive in aircraft turbine engine oil. Concerns about its toxicity are largely based on the tri-o-cresyl phosphate isomer content. However, the presence of other and more toxic isomers has been previously suggested. In this work, the structural isomers of TCP have been determined by two methods (experimental and semi-theoretical). First, the TCP isomers were separated by gas chromatography (GC) and identified by mass spectrometry (MS). Second, after base cleavage of TCP, GC was used to quantify the cresol precursors. These results were used to calculate the TCP isomer distribution based on the assumption of a statistical distribution of the TCP isomers. The results from the two determinations showed reasonable agreement for three of the four oils studied. The o-cresyl isomers were found to be present almost exclusively as the more toxic mono-o-cresyl isomers in the concentration range 13-150 mg/L. The ability to analyse for the mono-o-cresyl isomers allows the toxicity of TCP to be based on the latter isomers rather than on the less toxic tri-o-cresyl phosphate isomer.

  19. Two new antioxidant malonated caffeoylquinic acid isomers in fruits of wild eggplant relatives.

    PubMed

    Ma, Chunhui; Dastmalchi, Keyvan; Whitaker, Bruce D; Kennelly, Edward J

    2011-09-14

    Fruits of the cultivated eggplant species Solanum melongena and its wild relative Solanum incanum have a high content of hydroxycinnamic acid conjugates, which are implicated in the human health benefits of various fruits and vegetables. Monocaffeoylquinic acid esters, in particular 5-O-(E)-caffeoylquinic acid, are usually predominant in solanaceous fruits and tubers. Two closely related caffeoylquinic acid derivatives with longer C(18) HPLC retention times than those of monocaffeoylquinic acids are minor constituents in cultivated eggplant fruit. In a prior study, the two compounds were tentatively identified as 3-O-acetyl- and 4-O-acetyl-5-O-(E)-caffeoylquinic acids and composed ≤2% of the total hydroxycinnamic acid conjugates in fruit of most S. melongena accessions. It was recently found that the pair of these caffeoylquinic acid derivatives can compose 15-25% of the total hydroxycinnamic acid conjugates in fruits of S. incanum and wild S. melongena. This facilitated C(18) HPLC isolation and structural elucidation using (1)H and (13)C NMR techniques and HR-ToF-MS. The isomeric compounds were identified as 3-O-malonyl-5-O-(E)-caffeoylquinic acid (isomer 1) and 4-O-(E)-caffeoyl-5-O-malonylquinic acid (isomer 2). Both exhibited free radical scavenging activity, albeit about 4-fold lower than that of the flavonol quercetin dihydrate. By contrast, the iron chelation activities of isomers 1 and 2, respectively, were about 3- and 6-fold greater than that of quercetin dihydrate. Reports of malonylhydroxycinnamoylquinic acids are rare, and only a few of these compounds have been structurally elucidated using both NMR and MS techniques. To the authors' knowledge, these two malonylcaffeoylquinic acid isomers have not previously been reported.

  20. Low and High Temperature Combustion Chemistry of Butanol Isomers in Premixed Flames and Autoignition Systems

    SciTech Connect

    Sarathy, S M; Pitz, W J; Westbrook, C K; Mehl, M; Yasunaga, K; Curran, H J; Tsujimura, T; Osswald, P; Kohse-Hoinghaus, K

    2010-12-12

    Butanol is a fuel that has been proposed as a bio-derived alternative to conventional petroleum derived fuels. The structural isomer in traditional 'bio-butanol' fuel is n-butanol, but newer conversion technologies produce iso-butanol as a fuel. In order to better understand the combustion chemistry of bio-butanol, this study presents a comprehensive chemical kinetic model for all the four isomers of butanol (e.g., 1-, 2-, iso- and tert-butanol). The proposed model includes detailed high temperature and low temperature reaction pathways. In this study, the primary experimental validation target for the model is premixed flat low-pressure flame species profiles obtained using molecular beam mass spectrometry (MBMS). The model is also validated against previously published data for premixed flame velocity and n-butanol rapid compression machine and shock tube ignition delay. The agreement with these data sets is reasonably good. The dominant reaction pathways at the various pressures and temperatures studied are elucidated. At low temperature conditions, we found that the reaction of alphahydroxybutyl with O{sub 2} was important in controlling the reactivity of the system, and for correctly predicting C{sub 4} aldehyde profiles in low pressure premixed flames. Enol-keto isomerization reactions assisted by HO{sub 2} were also found to be important in converting enols to aldehydes and ketones in the low pressure premixed flames. In the paper, we describe how the structural features of the four different butanol isomers lead to differences in the combustion properties of each isomer.

  1. Optical isomers of a new 2-nitroimidazole nucleoside analog (PR-350 series): Radiosensitization efficiency and toxicity

    SciTech Connect

    Oya, Natsuo; Sasai, Keisuke; Shibata, Toru

    1995-08-30

    A new 2-nitroimidazole nucleoside radiosensitizer, PR-350 (1-[1{prime},3{prime},4{prime}-trihydroxy-2{prime}-butoxy]-methyl-2-nitroimidazole), has been reported to be as efficient as and less toxic than etanidazole. This compound is racemic, and it was recently optically resolved into two isomers, PR-68 (2{prime}R,3{prime}S type) and PR-69 (2{prime}S,3{prime}R type). The other two isomers, PR-28 (2{prime}S,3{prime}S type) and PR-44 (2{prime}R,3{prime}R type), were asymmetrically synthesized. In the present study, we investigated the properties, sensitizing activity, and toxicity of PR-350 and the four optical isomers in comparison with those of other 2-nitroimidazole hypoxic cell radiosensitizers, etanidazole, KU-2285, KIN-804, and RP-170. Because PR-350 and PR-28 can be industrially synthesized, we evaluated whether either of these two drugs are suitable for further investigation. In vivo radiosensitizing activity differed among the four optical isomers, which appeared to be due, at least in part, to differences in lipophilicity. Although PR-28 was the least toxic, its low sensitization efficiency does not warrant clinical trials. Among the PR compounds, PR-68 appears to be most efficient, but optical resolution of PR-68 from PR-350 is expensive, and asymmetrical synthesis of PR-68 is not established. Therefore, PR-350 seems to be most suitable for further investigation among the PR-350 series compounds, considering its higher efficiency compared with PR-28 and PR-44, and established synthesis. 28 refs., 7 figs., 1 tab.

  2. Half-life and excitation energy of the Iπ=13/2+ isomer in Ra209

    NASA Astrophysics Data System (ADS)

    Hauschild, K.; Lopez-Martens, A.; Yeremin, A. V.; Dorvaux, O.; Belozerov, A. V.; Chelnokov, M. L.; Chepigin, V. I.; Gall, B.; Gorshkov, V. A.; Guttormsen, M.; Jones, P.; Kabachenko, A. P.; Khouaja, A.; Larsen, A. C.; Malyshev, O. N.; Minkova, A.; Nyhus, H. T.; Oganessian, Yu. Ts.; Pantelica, D.; Popeko, A. G.; Rotaru, F.; Saro, S.; Shutov, A. V.; Siem, S.; Svirikhin, A. I.; Syed, N. U. H.

    2008-04-01

    An isomeric state in Ra209 has been observed for the first time, using the GABRIELA setup at the focal plane of VASSILISSA, to decay to the ground state of Ra209 via a cascade of 238-keV (M2) and 644-keV transitions. The half-life of the isomer has been measured to be 117(5)μs and from systematics is assigned as a neutron i13/2-1 excitation.

  3. Ignition of Isomers of Pentane: An Experimental and Kinetic Modeling Study

    DTIC Science & Technology

    2000-08-04

    diesel engines [26,27], and ignition under homogeneous charge compres- sion ignition ( HCCI ) conditions [26,28]. Kinetic modeling shows that the isomers of...Introduction Hydrocarbon ignition is important in many prac- tical combustion systems, including internal com- bustion engines , detonations, pulse combustors...tem- peratures are similar to those in automotive engines during diesel ignition and end-gas autoignition in spark-ignition engines . The RCM provides

  4. Discrimination of nuclear spin isomers exploiting the excited state dynamics of a quinodimethane derivative

    SciTech Connect

    Obaid, Rana; Kinzel, Daniel; Oppel, Markus González, Leticia

    2014-10-28

    Despite the concept of nuclear spin isomers (NSIs) exists since the early days of quantum mechanics, only few approaches have been suggested to separate different NSIs. Here, a method is proposed to discriminate different NSIs of a quinodimethane derivative using its electronic excited state dynamics. After electronic excitation by a laser field with femtosecond time duration, a difference in the behavior of several quantum mechanical operators can be observed. A pump-probe experimental approach for separating these different NSIs is then proposed.

  5. Discrimination of nuclear spin isomers exploiting the excited state dynamics of a quinodimethane derivative.

    PubMed

    Obaid, Rana; Kinzel, Daniel; Oppel, Markus; González, Leticia

    2014-10-28

    Despite the concept of nuclear spin isomers (NSIs) exists since the early days of quantum mechanics, only few approaches have been suggested to separate different NSIs. Here, a method is proposed to discriminate different NSIs of a quinodimethane derivative using its electronic excited state dynamics. After electronic excitation by a laser field with femtosecond time duration, a difference in the behavior of several quantum mechanical operators can be observed. A pump-probe experimental approach for separating these different NSIs is then proposed.

  6. Efficient algorithms to enumerate isomers and diamutamers with more than one type of substituent

    PubMed

    van Almsick M; Dolhaine; Honig

    2000-07-01

    In this paper we describe numeric as well as symbolic algorithms for the enumeration of substitutional isomers with an unlimited number of different achiral substituents. We consider three different scenarios: first, the enumeration of diamutamers with a given set of ligand types and ligand multiplicity, second, the enumeration of diamutamer libraries with a given ligand assortment pattern, and, third, the enumerations of libraries with diamutamers exhibiting a limited number of ligands.

  7. High-spin isomers in some of the heaviest nuclei: Spectra, decays, and population

    SciTech Connect

    Adamian, G. G.; Antonenko, N. V.; Scheid, W.

    2010-02-15

    The isotopic dependence of two-quasiparticle isomeric states in Fm and No is treated for future experiments. The population of the isomeric states in evaporation residues is considered. In several even isotopes of Rf, Sg, Hs, and Ds, the K isomers and their decay modes are predicted. An alpha-decay chain through the isomeric states of superheavy nuclei is demonstrated for the first time and proposed for the experimental verification.

  8. Urinary Coproporphyrin Isomers I and III in Lead Workers and a Control Group

    PubMed Central

    Mehani, Shawkia

    1966-01-01

    The excretory pattern of coproporphyrin I and III isomers has been studied in urine from nine health subjects and 10 lead-exposed workers with no clinical evidence of lead poisoning. In normal urine it was found that coproporphyrin I exceeded coproporphyrin III, whereas in lead workers coproporphyrin III predominated, although this was accompanied by an increase in the absolute amount of coproporphyrin I, indicating active haemopoiesis in lead absorption. PMID:5929684

  9. Separation and identification of Taxifolin 3-O-glucoside isomers from Chamaecyparis obtusa (Cupressaceae).

    PubMed

    Sakushima, Akiyo; Ohno, Kosei; Coskun, Makusut; Seki, Koh-Ichi; Ohkura, Kazue

    2002-12-01

    Taxifolin 3-O-glucoside isomers, [(2R, 3R)-, (2R, 3S)-, (2S, 3R)- and (2S, 3S)-] were isolated from leaves of Chamaecyparis obtuse (Cupressaceae). Their structures were elucidated on the basis of UV, MS, CD, 1H- and 13C-NMR spectral data, including 2D shift correlation. It was found that the compounds could be distinguished by the use of 1H- and 13C-NMR spectral data.

  10. Catalytic Oxidative Dehydration of Butanol Isomers: 1-Butanol, 2-Butanol, and Isobutanol

    DTIC Science & Technology

    2011-09-01

    the literature (9–12). In one such process, ethane auto- thermally decomposes to form ethylene (9). This process also converts heavier paraffins...production enables the reaction to perform auto- thermally . As a result, the catalytic reaction initiates at a temperature as low as 240 °C, and the catalyst...There was minimal thermal cracking along the carbon backbone since 88– 99% of the olefins produced were butene isomers. Then the degree of

  11. Investigation of HNCO isomer formation in ice mantles by UV and thermal processing: An experimental approach

    SciTech Connect

    Jiménez-Escobar, A.; Giuliano, B. M.; Caro, G. M. Muñoz; Cernicharo, J.; Marcelino, N.

    2014-06-10

    Current gas-phase models do not account for the abundances of HNCO isomers detected in various environments, suggesting their formation in icy grain mantles. We attempted to study a formation channel of HNCO and its possible isomers by vacuum-UV photoprocessing of interstellar ice analogs containing H{sub 2}O, NH{sub 3}, CO, HCN, CH{sub 3}OH, CH{sub 4}, and N{sub 2} followed by warm-up under astrophysically relevant conditions. Only the H{sub 2}O:NH{sub 3}:CO and H{sub 2}O:HCN ice mixtures led to the production of HNCO species. The possible isomerization of HNCO to its higher energy tautomers following irradiation or due to ice warm-up has been scrutinized. The photochemistry and thermal chemistry of H{sub 2}O:NH{sub 3}:CO and H{sub 2}O:HCN ices were simulated using the Interstellar Astrochemistry Chamber, a state-of-the-art ultra-high-vacuum setup. The ice was monitored in situ by Fourier transform mid-infrared spectroscopy in transmittance. A quadrupole mass spectrometer detected the desorption of the molecules in the gas phase. UV photoprocessing of H{sub 2}O:NH{sub 3}:CO and H{sub 2}O:HCN ices lead to the formation of OCN{sup –} as a main product in the solid state and a minor amount of HNCO. The second isomer HOCN has been tentatively identified. Despite its low efficiency, the formation of HNCO and the HOCN isomers by UV photoprocessing of realistic simulated ice mantles might explain the observed abundances of these species in photodissociation regions, hot cores, and dark clouds.

  12. PARTICLE-HOLE NATURE OF THE LIGHT HIGH-SPIN TOROIDAL ISOMERS

    SciTech Connect

    Staszczak, A.; Wong, Cheuk-Yin

    2015-01-01

    Nuclei under non-collective rotation with a large angular momentum above some threshold can assume a toroidal shape. In our previous work, we showed by using cranked Skyrme Hartree Fock approach that even even, N = Z, high-K, toroidal isomeric states may have general occurrences for light nuclei with 28 < A < 52. We present here some additional results and systematics on the particle-hole nature of these high-spin toroidal isomers.

  13. Isomer differentiation of poly aromatic hydrocarbons by means of cryotrapping GC-FTIR

    NASA Astrophysics Data System (ADS)

    Vredenbregt, Marjo J.; Visser, Tom

    1994-01-01

    The usefulness of cryotrapping GC-FTIR to detect and identify polycyclic aromatic hydrocarbons (PAHs) in soil extracts has been studied. Specific attention was given to the differentiation and identification of molecular isomers in order to confirm and complement the results of HPLC/fluorescence analysis of these samples. The technique was found to be very useful for this purpose. Detection limits in the range 0.25 - 1 ng/(mu) l injected have been determined.

  14. Effect of flupenthixol and butaclamol isomers on prolactin secretion in rats.

    PubMed

    Meltzer, H Y; Paul, S M; Fang, V S

    1977-01-31

    Cis (alpha)-flupenthixol and (+)-butaclamol are effective anti-psychotic agents but trans (beta)-flupenthixol and (-)-butaclamol are not. alpha-Flupenthixol was found to be 245 times more active in elevating rat plasma prolactin than the beta-isomer. The discrepancy between (+)-butaclamol and (-)-butaclamol was even greater. These results support the hypothesis that the dopamine receptors that mediate the effects of dopamine on prolactin secretion are similar to those that mediate the anti-psychotic effect of neuroleptic drugs.

  15. Infrared spectroscopy of the methanol cation and its methylene-oxonium isomer

    SciTech Connect

    Mosley, J. D.; Young, J. W.; Duncan, M. A. E-mail: maduncan@uga.edu; Huang, M.; McCoy, A. B. E-mail: maduncan@uga.edu

    2015-03-21

    The carbenium ion with nominal formula [C,H{sub 4},O]{sup +} is produced from methanol or ethylene glycol in a pulsed-discharge supersonic expansion source. The ion is mass selected, and its infrared spectrum is measured from 2000 to 4000 cm{sup −1} using laser photodissociation spectroscopy and the method of rare gas atom tagging. Computational chemistry predicts two isomers, the methanol and methylene-oxonium cations. Predicted vibrational spectra based on scaled harmonic and reduced dimensional treatments are compared to the experimental spectra. The methanol cation is the only isomer produced when methanol is used as a precursor. When ethylene glycol is used as the precursor, methylene-oxonium is produced in addition to the methanol cation. Theoretical results at the CCSD(T)/cc-pVTZ level show that methylene-oxonium is lower in energy than methanol cation by 6.4 kcal/mol, and is in fact the global minimum isomer on the [C,H{sub 4},O]{sup +} potential surface. Methanol cation is trapped behind an isomerization barrier in our source, providing a convenient method to produce and characterize this transient species. Analysis of the spectrum of the methanol cation provides evidence for strong CH stretch vibration/torsion coupling in this molecular ion.

  16. Levels and temporal trends of HCH isomers in ringed seals from West and East Greenland.

    PubMed

    Rigét, Frank; Vorkamp, Katrin; Dietz, Rune; Muir, Derek C G

    2008-08-01

    Levels and temporal trends of the hexachlorocyclohexane isomers alpha-, beta- and gamma-HCH were analysed in blubber of juvenile ringed seals from West Greenland (1994 to 2006) and juvenile and adult ringed seals from East Greenland (1986 to 2006). No significant differences in the concentration levels in the juvenile seals were found between East and West Greenland for any of the three isomers. alpha-HCH concentrations were not significantly different between juvenile and adult ringed seals from East Greenland, whereas beta- and gamma-HCH concentrations were significantly higher in adult ringed seals. alpha- and beta-HCH in Greenland ringed seals were approximately a factor two lower than in the Canadian Arctic, and alpha-HCH was a factor 2-3 higher than in ringed seals from an area east of Svalbard, Norway. Annual decreases in ringed seals from Greenland during the study periods were detected to be 9.1-11.7%, 1.4-3.9% and 6.0-6.4% for alpha-, beta- and gamma-HCH, respectively, being quite similar in both East and West Greenland. Similar levels and trends in East and West Greenland support the general understanding of the pathways of HCH isomers to and in the Arctic.

  17. The Immunomodulatory Activity of Jacaric Acid, a Conjugated Linolenic Acid Isomer, on Murine Peritoneal Macrophages

    PubMed Central

    Liu, Wai Nam; Leung, Kwok Nam

    2015-01-01

    This study aims at demonstrating the immunomodulatory property of jacaric acid, a conjugated linolenic acid (CLNA) isomer that is present in jacaranda seed oil, on murine peritoneal macrophages. Our results showed that jacaric acid exhibited no significant cytotoxicity on the thioglycollate-elicited murine peritoneal macrophages as revealed by the neutral red uptake assay, but markedly increased their cytostatic activity on the T-cell lymphoma MBL-2 cells as measured by the fluorometric CyQuant® NF Cell Proliferation Assay Kit. Flow cytometric analysis indicated that jacaric acid could enhance the endocytic activity of macrophages and elevated their intracellular production of superoxide anion. Moreover, jacaric acid-treated macrophages showed an increase in the production of nitric oxide which was accompanied by an increase in the expression level of inducible nitric oxide synthase protein. In addition, the secretion of several pro-inflammatory cytokines, including interferon-γ, interleukin-1β and tumor necrosis factor-α, was up-regulated. Collectively, our results indicated that the naturally-occurring CLNA isomer, jacaric acid, could exhibit immunomodulating activity on the murine peritoneal macrophages in vitro, suggesting that this CLNA isomer may act as an immunopotentiator which can be exploited for the treatment of some immunological disorders with minimal toxicity and fewer side effects. PMID:26629697

  18. Partition function and astronomical observation of interstellar isomers: Is there a link?

    NASA Astrophysics Data System (ADS)

    Etim, Emmanuel E.; Arunan, Elangannan

    2017-02-01

    The unsuccessful astronomical searches for some important astrophysical and astrobiological molecules have been linked to the large partition function of these molecules. This letter reports an extensive investigation of the relationship between partition function and astronomical observation of interstellar isomers using high level quantum chemical calculations. 120 molecules from 30 different isomeric groups have been considered. Partition function and thermodynamic stabilities are determined for each set of isomeric species. From the results, there is no direct correlation between partition function and astronomical observation of the same isomeric species. Though interstellar formations processes are generally controlled by factors like kinetics, thermodynamics, formation and destruction pathways. However, the observation of the isomers seems to correlate well with thermodynamics. For instance, in all the groups considered, the astronomically detected isomers are the thermodynamically most stable molecules in their respective isomeric groups. The implications of these results in accounting for the limited number of known cyclic interstellar molecules, unsuccessful searches for amino acid and the possible molecules for astronomical observations are discussed.

  19. Atmospheric polycyclic aromatic hydrocarbons and isomer ratios as tracers of biomass burning emissions in Northern India.

    PubMed

    Rajput, Prashant; Sarin, M M; Sharma, Deepti; Singh, Darshan

    2014-04-01

    Emission from large-scale post-harvest agricultural-waste burning (paddy-residue burning during October-November and wheat-residue burning in April-May) is a conspicuous feature in northern India. The poor and open burning of agricultural residue result in massive emission of carbonaceous aerosols and organic pollutants to the atmosphere. In this context, concentrations of atmospheric polycyclic aromatic hydrocarbons (PAHs) and their isomer ratios have been studied for a 2-year period from a source region (Patiala: 30.2°N; 76.3°E) of two distinct biomass burning emissions. The concentrations of 4-6 ring PAHs are considerably higher compared to 2-3 ring PAHs in the ambient particulate matter (PM2.5). The crossplots of PAH isomer ratios, fluoranthene / (fluoranthene + pyrene) and indeno[1,2,3-cd]pyrene/(indeno[1,2,3-cd]pyrene + benzo[g,h,i]perylene) for two biomass burning emissions, exhibit distinctly different source characteristics compared to those for fossil-fuel combustion sources in south and south-east Asia. The PAH isomer ratios studied from different geographical locations in northern India also exhibit similar characteristics on the crossplot, suggesting their usefulness as diagnostic tracers of biomass burning emissions.

  20. Searching for exotic particle emission in the decay of trapped Rb isomers

    NASA Astrophysics Data System (ADS)

    Kong, Tao; Gorelov, Alexander; Wiebe, Tegan; Pearson, Matthew; Behr, John

    2009-05-01

    During the decay of nuclear isomers, the momentum of the recoil nucleus will change if any massive particle is emitted instead of a Gamma photon. The Rb isomer transitions are sensitive to a mass range between 20 to 550 keV/c2. This range covers masses for pseudoscalar axions which were proposed to solve the strong CP problem and for scalar particles. In our experiment, trapped metastable Rb isomers will be used to search for these particles. To measure the recoiling momentum, the daughter Rb atoms are photo-ionized. The resulting electrons and photo-ions are detected in a ``MOTRIMS'' setup, where charged particles are guided onto time and position sensitive detectors by means of electric fields. The photo-ionization involves firstly the excitation from 5S state to 5D state by Doppler-free two-photon transitions using an MBR-110 laser at 778 nm, and then ionization to the continuum by a broadband Fibre laser at 1064 nm.