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Sample records for 2h nqr parameters

  1. Asymmetry parameter studies for systems containing the 35Cl nucleus from Zeeman NQR data

    NASA Astrophysics Data System (ADS)

    Raman, K. V.

    1995-02-01

    A review of Zeeman nuclear quadrupole resonance (NQR) work on systems containing the 35Cl nucleus is presented. In the case of the 35cl nucleus with spin I = {3}/{2}, owing to the existence of ± m degeneracy in the absence of a magnetic field (Kramer's degeneracy), there exists only one pure NQR frequency which is related to the two electric field gradient (EFG) parameters, η and e2qQ, by the formula, v = ( {e 2qQ }/{2h})(1 + ( {η 2}/{3})) {1}/{2}. Hence it is necessary to study the Zeeman effect to obtain both these parameters. Zeeman NQR studies have been carried out by many workers using single crystals and powder specimens, and these are discussed here. The computer simulation method for powder η values is also presented in this paper. The numerical computation program for an IBM 370-158 computer used to simulate the powder Zeeman spectrum is also discussed briefly. The paper also presents two-dimensional Zeeman NQR and Zeeman perturbed spin-echo envelope modulation (ZSEEM) studies on 35Cl systems. Very recently, two-dimensional NQR experiments based on the principle of nutation spectroscopy have been carried out with zero applied magnetic field on {3}/{2} spin nuclei. This method is also discussed in this review. The relationship between the asymmetry parameter (η) and bond properties is also discussed.

  2. A systematic study on hydrogen bond interactions in sulfabenzamide: DFT calculations of the N-14, O-17, and H-2 NQR parameters.

    PubMed

    Nozad, Ahmad G; Najafi, Hamidreza; Meftah, Sakineh; Aghazadeh, Mustafa

    2009-02-01

    A systematic computational study was carried out to characterize the hydrogen bond, HB, interactions of sulfabenzamide crystal structure by DFT calculations of electric field gradient, EFG, tensors at the sites of 14N, 17O, and 2H nuclei. The computations were performed with the B3LYP and B3PW91 DFT methods and 6-311+G and 6-311++G* standard basis sets using the Gaussian 98 package. To perform the calculations, a hydrogen-bonded heptameric cluster of sulfabenzamide was created by X-ray coordinates where the hydrogen atom positions were optimized and the EFG tensors were calculated for the target molecule. Additional optimization and EFG calculations were also performed for crystalline monomer and an isolated gas-phase sulfabenzamide. The calculated EFG tensors were converted to the experimentally measurable nuclear quadrupole resonance, NQR, parameters: quadrupole coupling constant, C(Q), and asymmetry parameter, eta(Q). The results reveal that the geometrical and NQR parameters of the optimized isolated gas-phase and crystalline phase are different. In addition, the difference between the calculated NQR parameters of the monomer and the target molecule shows how much H-bonding interactions affect the EFG tensors of each nucleus. The evaluated NQR parameters reveal that due to the contribution of the target molecule to N-H...O and C-H...O hydrogen bond interactions, the EFG tensors at the sites of N1, O3 and H1 undergo significant changes from monomer to the target molecule in cluster. These features reveal the major role of N-H...O type intermolecular HBs in cluster model of sulfabenzamide which the presence of these interactions can lead to polymorphism directly related to the drug activity and related properties.

  3. 14 N NQR spectrum of sildenafil citrate

    NASA Astrophysics Data System (ADS)

    Stephenson, David; Singh, Nadia

    2015-04-01

    The 14N nuclear quadrupole resonance (NQR) spectrum of sildenafil citrate tablets has been recorded allowing the quadrupole coupling constants and asymmetry parameters of all six unique nitrogen atoms in its structure to be determined. A density function calculation gives results that are largely in agreement with the experimental values.

  4. NQR Characteristics of an RDX Plastic Explosives Simulant.

    PubMed

    Turecek, J; Schwitter, B; Miljak, D; Stancl, M

    2012-12-01

    For reliable detection of explosives, a combination of methods integrated within a single measurement platform may increase detection performance. However, the efficient field testing of such measurement platforms requires the use of inexplosive simulants that are detectable by a wide range of methods. Physical parameters such as simulant density, elemental composition and crystalline structure must closely match those of the target explosive. The highly discriminating bulk detection characteristics of nuclear quadrupole resonance (NQR) especially constrain simulant design. This paper describes the development of an inexplosive RDX simulant suited to a wide range of measurement methods, including NQR. Measurements are presented that confirm an RDX NQR response from the simulant. The potential use of the simulant for field testing a prototype handheld NQR-based RDX detector is analyzed. Only modest changes in prototype operation during field testing would be required to account for the use of simulant rather than real explosive. PMID:23204647

  5. Electron swarm parameters in pure C2H2 and in C2H2-Ar mixtures and electron collision cross sections for the C2H2 molecule

    NASA Astrophysics Data System (ADS)

    Nakamura, Yoshiharu

    2010-09-01

    Electron swarm parameters (the drift velocity and the longitudinal diffusion coefficient) were measured in pure C2H2 and also in C2H2-Ar mixtures containing 0.517% and 5.06% acetylene over wide E/N ranges. These swarm parameters were analysed using a Boltzmann equation analysis and a set of electron collision cross sections for the C2H2 molecule was derived so that it was consistent with the present swarm data and published ionization coefficient. The present result suggested the presence of a Ramsauer-Townsend minimum in the elastic momentum transfer cross section at 0.08 eV and prominent threshold and resonance peaks in the ν4/ν5 vibrational excitation cross section. The present cross section set was also confirmed to be consistent with the published experimental total cross section of C2H2.

  6. Optimization of intermolecular potential parameters for the CO2/H2O mixture.

    PubMed

    Orozco, Gustavo A; Economou, Ioannis G; Panagiotopoulos, Athanassios Z

    2014-10-01

    Monte Carlo simulations in the Gibbs ensemble were used to obtain optimized intermolecular potential parameters to describe the phase behavior of the mixture CO2/H2O, over a range of temperatures and pressures relevant for carbon capture and sequestration processes. Commonly used fixed-point-charge force fields that include Lennard-Jones 12-6 (LJ) or exponential-6 (Exp-6) terms were used to describe CO2 and H2O intermolecular interactions. For force fields based on the LJ functional form, changes of the unlike interactions produced higher variations in the H2O-rich phase than in the CO2-rich phase. A major finding of the present study is that for these potentials, no combination of unlike interaction parameters is able to adequately represent properties of both phases. Changes to the partial charges of H2O were found to produce significant variations in both phases and are able to fit experimental data in both phases, at the cost of inaccuracies for the pure H2O properties. By contrast, for the Exp-6 case, optimization of a single parameter, the oxygen-oxygen unlike-pair interaction, was found sufficient to give accurate predictions of the solubilities in both phases while preserving accuracy in the pure component properties. These models are thus recommended for future molecular simulation studies of CO2/H2O mixtures. PMID:25198539

  7. Explosives detection by nuclear quadrupole resonance (NQR)

    NASA Astrophysics Data System (ADS)

    Garroway, Allen N.; Buess, Michael L.; Yesinowski, James P.; Miller, Joel B.; Krauss, Ronald A.

    1994-10-01

    Pure nuclear quadrupole resonance (NQR) of 14N nuclei is quite promising as a method for detecting explosives such as RDX and contraband narcotics such as cocaine and heroin in quantities of interest. Pure NQR is conducted without an external applied magnetic field, so potential concerns about damage to magnetically encoded data or exposure of personnel to large magnetic fields are not relevant. Because NQR frequencies of different compounds are quite distinct, we do not encounter false alarms from the NQR signals of other benign materials. We have constructed a laboratory prototype NQR explosives detector which interrogates a volume of 300 liters (10 ft3). This paper presents abbreviated results from a demonstration of the laboratory prototype NQR explosives detector conducted at the Federal Aviation Administration Technical Center in May 1994 on RDX-based explosives.

  8. Determination of orientational order parameters from 2H NMR spectra of magnetically partially oriented lipid bilayers.

    PubMed Central

    Schäfer, H; Mädler, B; Sternin, E

    1998-01-01

    The partial orientation of multilamellar vesicles (MLVs) in high magnetic fields is known to affect the shape of 2H NMR spectra. There are numerical methods for extracting either the orientational order parameters of lipid molecules for a random distribution of domain orientations in the sample, or the distribution of orientations for a known set of spectral anisotropies. A first attempt at determining the orientational order parameters in the presence of an unknown nonrandom distribution of orientations is presented. The numerical method is based on the Tikhonov regularization algorithm. It is tested using simulated partially oriented spectra. An experimental spectrum of a phospholipid-ether mixture in water is analyzed as an example. The experimental spectrum is consistent with an ellipsoidal shape of MLVs with a ratio of semiaxes of approximately 3.4. PMID:9533713

  9. Mixed H(2)/H(sub infinity): Control with output feedback compensators using parameter optimization

    NASA Technical Reports Server (NTRS)

    Schoemig, Ewald; Ly, Uy-Loi

    1992-01-01

    Among the many possible norm-based optimization methods, the concept of H-infinity optimal control has gained enormous attention in the past few years. Here the H-infinity framework, based on the Small Gain Theorem and the Youla Parameterization, effectively treats system uncertainties in the control law synthesis. A design approach involving a mixed H(sub 2)/H-infinity norm strives to combine the advantages of both methods. This advantage motivates researchers toward finding solutions to the mixed H(sub 2)/H-infinity control problem. The approach developed in this research is based on a finite time cost functional that depicts an H-infinity bound control problem in a H(sub 2)-optimization setting. The goal is to define a time-domain cost function that optimizes the H(sub 2)-norm of a system with an H-infinity-constraint function.

  10. First line shape analysis and spectroscopic parameters for the ν11 band of 12C2H4

    NASA Astrophysics Data System (ADS)

    Es-sebbar, Et-touhami; Mantzaras, John; Benilan, Yves; Farooq, Aamir

    2016-11-01

    An accurate knowledge of line intensities, collisional broadening coefficients and narrowing parameters is necessary for the interpretation of high-resolution infrared spectra of the Earth and other planetary atmospheres. One of the most promising spectral domains for 12C2H4 monitoring in such environments is located near the 3.36 μm window, through its ν11 C-H stretching mode. In this paper, we report an extensive study in which we precisely determine spectroscopic parameters of 12C2H4 ν11 band at 297±1 K, using a narrow Difference-Frequency-Generation (DFG) laser with 10-4 cm-1 resolution. Absorption measurements were performed in the 2975-2980 cm-1 spectral window to investigate 32 lines corresponding to J'Ka',Kc'←JKa,Kc, where, 5≤J≤7; 0≤Ka≤6 and 1≤Kc≤14. Spectroscopic parameters are retrieved using either Voigt or appropriate Galatry profile to simulate the measured 12C2H4 line shape. Line intensities along with self-broadening coefficients are reported for all lines. Narrowing coefficients for each isolated line are also derived. To our knowledge, the current study reports the first extensive spectroscopic parameter measurements of the 12C2H4 ν11 band in the 2975-2980 cm-1 range.

  11. A theoretical study of 17O, 14N and 2H nuclear quadrupole coupling tensors in the real crystalline structure of acetaminophen

    NASA Astrophysics Data System (ADS)

    Behzadi, Hadi; Esrafili, Mehdi D.; Hadipour, Nasser L.

    2007-03-01

    A systematic computational investigation was carried out to characterize the 17O, 14N and 2H electric field gradient, EFG, tensors in the acetaminophen real crystalline structure. To include the hydrogen bonding effects in the calculations, the most probable interacting molecules with the target molecule in the crystalline phase were considered through the various molecular clusters. The calculations were performed with the B3LYP method and 6-311++G ∗∗ and 6-311+G ∗ standard basis sets using the Gaussian 98 suite of programs. Calculated EFG tensors were used to evaluate the 17O, 14N, and 2H nuclear quadrupole resonance, NQR, parameters in acetaminophen crystalline structure, which are in good agreement with the available experimental data. The difference between the calculated NQR parameters of the monomer and molecular clusters shows how much hydrogen bonding interactions affect the EFG tensors of each nucleus. These results indicate that both O-H⋯O and N-H⋯O hydrogen bonding have major influence on the NQR parameters. Moreover, the quantum chemical calculation indicated that the intermolecular hydrogen bonding interactions play an essential role in determining the relative orientation of quadrupole coupling principal components in the molecular frame axes.

  12. A theoretical study on the characteristics of the intermolecular interactions in the active site of human androsterone sulphotransferase: DFT calculations of NQR and NMR parameters and QTAIM analysis.

    PubMed

    Astani, Elahe K; Heshmati, Emran; Chen, Chun-Jung; Hadipour, Nasser L

    2016-07-01

    A theoretical study at the level of density functional theory (DFT) was performed to characterize noncovalent intermolecular interactions, especially hydrogen bond interactions, in the active site of enzyme human androsterone sulphotransferase (SULT2A1/ADT). Geometry optimization, interaction energy, (2)H, (14)N, and (17)O electric field gradient (EFG) tensors, (1)H, (13)C, (17)O, and (15)N chemical shielding (CS) tensors, Natural Bonding Orbital (NBO) analysis, and quantum theory of atoms in molecules (QTAIM) analysis of this active site were investigated. It was found that androsterone (ADT) is able to form hydrogen bonds with residues Ser80, Ile82, and His99 of the active site. The interaction energy calculations and NBO analysis revealed that the ADT molecule forms the strongest hydrogen bond with Ser80. Results revealed that ADT interacts with the other residues through electrostatic and Van der Waals interactions. Results showed that these hydrogen bonds influence on the calculated (2)H, (14)N, and (17)O quadrupole coupling constants (QCCs), as well as (1)H, (13)C, (17)O, and (15)N CS tensors. The magnitude of the QCC and CS changes at each nucleus depends directly on its amount of contribution to the hydrogen bond interaction. PMID:27337388

  13. NQR investigation and characterization of cocrystals and crystal polymorphs

    NASA Astrophysics Data System (ADS)

    Seliger, Janez; Žagar, Veselko; Asaji, Tetsuo

    2013-05-01

    The application of 14N NQR to the study of cocrystals and crystal polymorphs is reviewed. In ferroelectric and antiferroelectric organic cocrystals 14N NQR is used to determine proton position in an N-H...O hydrogen bond and proton displacement below TC. In cocrystal isonicitinamide - oxalic acid (2:1) 14N NQR is used to distinguish between two polymorphs and to determine the type of the hydrogen bond (N-...H-O). The difference in the 14N NQR spectra of cocrystal formers and cocrystal is investigated in case of carbamazepine, saccharin and carbamazepine - saccharin (1:1). The experimental resolution allows an unambiguous distinction between the 14N NQR spectrum of the cocrystal and the 14N NQR spectra of the cocrystal formers. The possibility of application of NQR and double resonance for the determination of the inhomogeneity of the sample and for the study of the life time of an unstable polymorph is discussed.

  14. A miniaturized NQR spectrometer for a multi-channel NQR-based detection device.

    PubMed

    Beguš, Samo; Jazbinšek, Vojko; Pirnat, Janez; Trontelj, Zvonko

    2014-10-01

    A low frequency (0.5-5 MHz) battery operated sensitive pulsed NQR spectrometer with a transmitter power up to 5 W and a total mass of about 3 kg aimed at detecting (14)N NQR signals, predominantly of illicit materials, was designed and assembled. This spectrometer uses a standard software defined radio (SDR) platform for the data acquisition unit. Signal processing is done with the LabView Virtual instrument on a personal computer. We successfully tested the spectrometer by measuring (14)N NQR signals from aminotetrazole monohydrate (ATMH), potassium nitrate (PN), paracetamol (PCM) and trinitrotoluene (TNT). Such a spectrometer is a feasible component of a portable single or multichannel (14)N NQR based detection device. PMID:25233110

  15. A miniaturized NQR spectrometer for a multi-channel NQR-based detection device.

    PubMed

    Beguš, Samo; Jazbinšek, Vojko; Pirnat, Janez; Trontelj, Zvonko

    2014-10-01

    A low frequency (0.5-5 MHz) battery operated sensitive pulsed NQR spectrometer with a transmitter power up to 5 W and a total mass of about 3 kg aimed at detecting (14)N NQR signals, predominantly of illicit materials, was designed and assembled. This spectrometer uses a standard software defined radio (SDR) platform for the data acquisition unit. Signal processing is done with the LabView Virtual instrument on a personal computer. We successfully tested the spectrometer by measuring (14)N NQR signals from aminotetrazole monohydrate (ATMH), potassium nitrate (PN), paracetamol (PCM) and trinitrotoluene (TNT). Such a spectrometer is a feasible component of a portable single or multichannel (14)N NQR based detection device.

  16. A miniaturized NQR spectrometer for a multi-channel NQR-based detection device

    NASA Astrophysics Data System (ADS)

    Beguš, Samo; Jazbinšek, Vojko; Pirnat, Janez; Trontelj, Zvonko

    2014-10-01

    A low frequency (0.5-5 MHz) battery operated sensitive pulsed NQR spectrometer with a transmitter power up to 5 W and a total mass of about 3 kg aimed at detecting 14N NQR signals, predominantly of illicit materials, was designed and assembled. This spectrometer uses a standard software defined radio (SDR) platform for the data acquisition unit. Signal processing is done with the LabView Virtual instrument on a personal computer. We successfully tested the spectrometer by measuring 14N NQR signals from aminotetrazole monohydrate (ATMH), potassium nitrate (PN), paracetamol (PCM) and trinitrotoluene (TNT). Such a spectrometer is a feasible component of a portable single or multichannel 14N NQR based detection device.

  17. Spin 3/2 Zeeman perturbed NQR in the presence of slow sample rotation.

    PubMed

    Panguluri, R P; Suits, B H

    2006-09-01

    Theoretical and experimental results are presented for the case of Zeeman perturbed nuclear quadrupole resonance (NQR) using spin-3/2 nuclei with a small Zeeman interaction, gammaB0, while the sample is very slowly rotated. It is found that the decay envelope for a simple two-pulse echo measurement can be strongly affected even though the sample may rotate only a few degrees or less during the course of the measurement. To lowest order the decay envelope can be described using a one dimensional function of the product of gammaB0, the rotation rate, and the square of the pulse spacing. Aside from an indirect and weak dependence on the quadrupole asymmetry parameter, eta, the result is independent of the NQR frequency. Identical results are expected for a stationary sample in a small rotating magnetic field. The effect seen here may be used to advantage to measure rotational motion, for example of particles in fluids, or may be an additional complication for some Zeeman perturbed NQR measurements, including some NQR detection and imaging methods.

  18. NQR detection of explosive simulants using RF atomic magnetometers

    NASA Astrophysics Data System (ADS)

    Monti, Mark C.; Alexson, Dimitri A.; Okamitsu, Jeffrey K.

    2016-05-01

    Nuclear Quadrupole Resonance (NQR) is a highly selective spectroscopic method that can be used to detect and identify a number of chemicals of interest to the defense, national security, and law enforcement community. In the past, there have been several documented attempts to utilize NQR to detect nitrogen bearing explosives using induction sensors to detect the NQR RF signatures. We present here our work on the NQR detection of explosive simulants using optically pumped RF atomic magnetometers. RF atomic magnetometers can provide an order of magnitude (or more) improvement in sensitivity versus induction sensors and can enable mitigation of RF interference, which has classically has been a problem for conventional NQR using induction sensors. We present the theory of operation of optically pumped RF atomic magnetometers along with the result of laboratory work on the detection of explosive simulant material. An outline of ongoing work will also be presented along with a path for a fieldable detection system.

  19. Weakly coordinating anions: crystallographic and NQR studies of halogen-metal bonding in silver, thallium, sodium, and potassium halomethanesulfonates.

    PubMed

    Wulfsberg, Gary; Parks, Katherine D; Rutherford, Richard; Jackson, Debra Jones; Jones, Frank E; Derrick, Dana; Ilsley, William; Strauss, Steven H; Miller, Susie M; Anderson, Oren P; Babushkina, T A; Gushchin, S I; Kravchenko, E A; Morgunov, V G

    2002-04-22

    35Cl, (79,81)Br, and (127)I NQR (nuclear quadrupole resonance) spectroscopy in conjunction with X-ray crystallography is potentially one of the best ways of characterizing secondary bonding of metal cations such as Ag(+) to halogen donor atoms on the surfaces of very weakly coordinating anions. We have determined the X-ray crystal structure of Ag(O(3)SCH(2)Cl) (a = 13.241(3) A; b = 7.544(2) A; c = 4.925(2) A; orthorhombic; space group Pnma; Z = 4) and compared it with the known structure of Ag(O(3)SCH(2)Br) (Charbonnier, F.; Faure, R.; Loiseleur, H. Acta Crystallogr., Sect. B 1978, 34, 3598-3601). The halogen atom in each is apical (three-coordinate), being weakly coordinated to two silver ions. (127)I NQR studies on Ag(O(3)SCH(2)I) show the expected NQR consequences of three-coordination of iodine: substantially reduced NQR frequencies nu(1) and nu(2) and a fairly small NQR asymmetry parameter eta. The reduction of the halogen NQR frequency of the coordinating halogen atom in Ag(O(3)SCH(2)X) becomes more substantial in the series X = Cl < Br < I, indicating that the coordination to Ag(+) strengthens in this series, as expected from hard-soft acid-base principles. The numbers of electrons donated by the organic iodine atom to Ag(+) have been estimated; these indicate that the bonding to the cation is weak but not insignificant. We have not found any evidence for the bonding of these organohalogen atoms to another soft-acid metal ion, thallium. A scheme for recycling of thallium halide wastes is included.

  20. Crystallization and preliminary analysis of the NqrA and NqrC subunits of the Na+-translocating NADH:ubiquinone oxidoreductase from Vibrio cholerae

    PubMed Central

    Vohl, Georg; Nedielkov, Ruslan; Claussen, Björn; Casutt, Marco S.; Vorburger, Thomas; Diederichs, Kay; Möller, Heiko M.; Steuber, Julia; Fritz, Günter

    2014-01-01

    The Na+-translocating NADH:ubiquinone oxidoreductase (Na+-NQR) from Vibrio cholerae is a membrane protein complex consisting of six different subunits NqrA–NqrF. The major domains of the NqrA and NqrC subunits were heterologously expressed in Escherichia coli and crystallized. The structure of NqrA1–377 was solved in space groups C2221 and P21 by SAD phasing and molecular replacement at 1.9 and 2.1 Å resolution, respectively. NqrC devoid of the transmembrane helix was co-expressed with ApbE to insert the flavin mononucleotide group covalently attached to Thr225. The structure was determined by molecular replacement using apo-NqrC of Parabacteroides distasonis as search model at 1.8 Å resolution. PMID:25005105

  1. Crystallization and preliminary analysis of the NqrA and NqrC subunits of the Na+-translocating NADH:ubiquinone oxidoreductase from Vibrio cholerae.

    PubMed

    Vohl, Georg; Nedielkov, Ruslan; Claussen, Björn; Casutt, Marco S; Vorburger, Thomas; Diederichs, Kay; Möller, Heiko M; Steuber, Julia; Fritz, Günter

    2014-07-01

    The Na+-translocating NADH:ubiquinone oxidoreductase (Na+-NQR) from Vibrio cholerae is a membrane protein complex consisting of six different subunits NqrA-NqrF. The major domains of the NqrA and NqrC subunits were heterologously expressed in Escherichia coli and crystallized. The structure of NqrA1-377 was solved in space groups C222₁ and P2₁ by SAD phasing and molecular replacement at 1.9 and 2.1 Å resolution, respectively. NqrC devoid of the transmembrane helix was co-expressed with ApbE to insert the flavin mononucleotide group covalently attached to Thr225. The structure was determined by molecular replacement using apo-NqrC of Parabacteroides distasonis as search model at 1.8 Å resolution.

  2. Spontaneous piezoelectric effect as order parameter in (NH4)2CuBr4·2H2O crystal

    NASA Astrophysics Data System (ADS)

    Tylczyński, Z.; Wiesner, M.; Trzaskowska, A.

    2016-11-01

    Temperature change of piezoelectric properties of (NH4)2CuBr4·2H2O crystal in the low-temperature ferroelastoelectric phase is studied. The macroscopic order parameter is proved to be the h36 component of the spontaneous piezoelectric tensor. The critical exponent related with the phase transition is α=0.60±0.05.

  3. Frequency selective detection of nuclear quadrupole resonance (NQR) spin echoes

    NASA Astrophysics Data System (ADS)

    Somasundaram, Samuel D.; Jakobsson, Andreas; Smith, John A. S.; Althoefer, Kaspar A.

    2006-05-01

    Nuclear Quadrupole Resonance (NQR) is a radio frequency (RF) technique that can be used to detect the presence of quadrupolar nuclei, such as the 14N nucleus prevalent in many explosives and narcotics. The technique has been hampered by low signal-to-noise ratios and is further aggravated by the presence of RF interference (RFI). To ensure accurate detection, proposed detectors should exploit the rich form of the NQR signal. Furthermore, the detectors should also be robust to any remaining residual interference, left after suitable RFI mitigation has been employed. In this paper, we propose a new NQR data model, particularly for the realistic case where multiple pulse sequences are used to generate trains of spin echoes. Furthermore, we refine two recently proposed approximative maximum likelihood (AML) detectors, enabling the algorithm to optimally exploit the data model of the entire echo train and also incorporate knowledge of the temperature dependent spin-echo decay time. The AML-based detectors ensure accurate detection and robustness against residual RFI, even when the temperature of the sample is not precisely known, by exploiting the dependencies of the NQR resonant lines on temperature. Further robustness against residual interference is gained as the proposed detector is frequency selective; exploiting only those regions of the spectrum where the NQR signal is expected. Extensive numerical evaluations based on both simulated and measured NQR data indicate that the proposed Frequency selective Echo Train AML (FETAML) detector offers a significant improvement as compared to other existing detectors.

  4. A new approach to mixed H2/H infinity controller synthesis using gradient-based parameter optimization methods

    NASA Technical Reports Server (NTRS)

    Ly, Uy-Loi; Schoemig, Ewald

    1993-01-01

    In the past few years, the mixed H(sub 2)/H-infinity control problem has been the object of much research interest since it allows the incorporation of robust stability into the LQG framework. The general mixed H(sub 2)/H-infinity design problem has yet to be solved analytically. Numerous schemes have considered upper bounds for the H(sub 2)-performance criterion and/or imposed restrictive constraints on the class of systems under investigation. Furthermore, many modern control applications rely on dynamic models obtained from finite-element analysis and thus involve high-order plant models. Hence the capability to design low-order (fixed-order) controllers is of great importance. In this research a new design method was developed that optimizes the exact H(sub 2)-norm of a certain subsystem subject to robust stability in terms of H-infinity constraints and a minimal number of system assumptions. The derived algorithm is based on a differentiable scalar time-domain penalty function to represent the H-infinity constraints in the overall optimization. The scheme is capable of handling multiple plant conditions and hence multiple performance criteria and H-infinity constraints and incorporates additional constraints such as fixed-order and/or fixed structure controllers. The defined penalty function is applicable to any constraint that is expressible in form of a real symmetric matrix-inequity.

  5. Electron density distribution in cladribine (2-chloro-2‧-deoxyadenosine) - A drug against leukemia and multiple sclerosis - Studied by multinuclear NQR spectroscopy and DFT calculations

    NASA Astrophysics Data System (ADS)

    Latosińska, J. N.; Latosińska, M.; Seliger, J.; Žagar, V.; Kazimierczuk, Z.

    2009-07-01

    2-Chloro-2'-deoxyadenosine (Cladribine) chemotherapeutic drug has been studied experimentally in solid state by 35Cl NQR and NMR-NQR double resonance and theoretically by the Density Functional Theory. Fifteen resonance frequencies on 14N have been detected and assigned to particular nitrogen sites in the 2-CdA molecule. The effects of tautomerism, regioisomerism, conformations and molecular aggregations, related to intermolecular hydrogen bond formation, on the NQR parameters have been analysed within the DFT and AIM ( Atoms in Molecules) formalism. The properties of the whole molecule, the so-called global reactivity descriptors, have been calculated for a comparison of both syn and anti conformations of 2-CdA molecule to check the effect of crystal packing on molecular conformation.

  6. Effect of hydrogen ratio on plasma parameters of N{sub 2}-H{sub 2} gas mixture glow discharge

    SciTech Connect

    El-Brulsy, R. A.; Abd Al-Halim, M. A.; Abu-Hashem, A.; Rashed, U. M.; Hassouba, M. A.

    2012-05-15

    A dc plane glow discharge in a nitrogen-hydrogen (N{sub 2}-H{sub 2}) gas mixture has been operated at discharge currents of 10 and 20 mA. The electron energy distribution function (EEDF) at different hydrogen concentrations is measured. A Maxwellian EEDF is found in the positive column region, while in both cathode fall and negative glow regions, a non-Maxwellian one is observed. Langmuir electric probes are used at different axial positions, gas pressures, and hydrogen concentrations to measure the electron temperature and plasma density. The electron temperature is found to increase with increasing H{sub 2} concentration and decrease with increasing both the axial distance from the cathode and the mixture pressure. At first, with increasing distance from the cathode, the ion density decreases, while the electron density increases; then, as the anode is further approached, they remain nearly constant. At different H{sub 2} concentrations, the electron and ion densities decrease with increasing the mixture pressure. Both the electron and ion densities slightly decrease with increasing H{sub 2} concentration.

  7. Numerical simulation of NQR/NMR: Applications in quantum computing.

    PubMed

    Possa, Denimar; Gaudio, Anderson C; Freitas, Jair C C

    2011-04-01

    A numerical simulation program able to simulate nuclear quadrupole resonance (NQR) as well as nuclear magnetic resonance (NMR) experiments is presented, written using the Mathematica package, aiming especially applications in quantum computing. The program makes use of the interaction picture to compute the effect of the relevant nuclear spin interactions, without any assumption about the relative size of each interaction. This makes the program flexible and versatile, being useful in a wide range of experimental situations, going from NQR (at zero or under small applied magnetic field) to high-field NMR experiments. Some conditions specifically required for quantum computing applications are implemented in the program, such as the possibility of use of elliptically polarized radiofrequency and the inclusion of first- and second-order terms in the average Hamiltonian expansion. A number of examples dealing with simple NQR and quadrupole-perturbed NMR experiments are presented, along with the proposal of experiments to create quantum pseudopure states and logic gates using NQR. The program and the various application examples are freely available through the link http://www.profanderson.net/files/nmr_nqr.php.

  8. Signal processing for NQR discrimination of buried land mines

    NASA Astrophysics Data System (ADS)

    Tantum, Stacy L.; Collins, Leslie M.; Carin, Lawrence; Gorodnitsky, Irina; Hibbs, Andrew D.; Walsh, David O.; Barrall, Geoffrey A.; Gregory, David M.; Matthews, Robert; Vierkotter, Stephie A.

    1999-08-01

    Nuclear quadrupole resonance (NQR) is a technique that discriminates mines from clutter by exploiting unique properties of explosives, rather than the attributes of the mine that exist in many forms of anthropic clutter. After exciting the explosive with a properly designed electromagnetic-induction (EMI) system, one attempts to sense late-time spin echoes, which are characterized by radiation at particular frequencies. It is this narrow-band radiation that indicates the presence of explosives, since this effect is not seen in most clutter, both natural and anthropic. However, this problem is complicated by several issues. First, the late-time radiation if often very weak, particularly for TNT, and therefore the signal-to-noise ratio must be high for extracting the NQR response. Further, the frequency at which the explosive radiates is often a strong function of the background environment, and therefore in practice the NQR radiation frequency is not known a priori. Finally, at the frequencies of interest, there is a significant amount of background radiation, which induces radio frequency interference (RFI). In this paper we discuss several signal processing tools we have developed to enhance the utility of NQR explosives detection. In particular, with regard to the RFI, we exposure least-mean-squares algorithms which have proven well suited to extracting background interference. Algorithm performance is assessed through consideration of actual measured data. With regard to the detection of the NQR electromagnetic echo, we consider a Bayesian discrimination algorithm. The performance of the Bayesian algorithm is presented, again using measured NQR data.

  9. Detection of {sup 14}N and {sup 35}Cl in cocaine base and hydrochloride using NQR, NMR, and SQUID techniques

    SciTech Connect

    Yesinowski, J.P.; Buess, M.L.; Garroway, A.N.; Ziegeweid, M.; Pines, A. |

    1995-07-01

    Results from {sup 14}N pure NQR of cocaine in the free base form (cocaine base) yield a nuclear quadrupole coupling constant (NQCC) e{sup 2}Qq/h of 5.0229 ({+-}0.0001) MHz and an asymmetry parameter {eta} of 0.0395 ({+-}0.0001) at 295 K, with corresponding values of 5.0460 ({+-}0.0013) MHz and 0.0353 ({+-}0.0008) at 77 K. Both pure NQR (at 295-77 K) and a superconducting quantum interference device (SQUID) detector (at 4.2 K) were used to measure the very low (<1 MHz) {sup 14}N transition frequencies in cocaine hydrochloride; at 295 K the NQCC is 1.1780 ({+-}0.0014) MHz and the asymmetry parameter is 0.2632 ({+-}0.0034). Stepping the carrier frequency enables one to obtain a powder pattern without the severe intensity distortions that otherwise arise from finite pulse power. A powder pattern simulation using an NQCC value of 5.027 MHz and an asymmetry parameter {eta} of 0.2 agrees reasonably well with the experimental stepped-frequency spectrum. The use of pure NQR for providing nondestructive, quantitative, and highly specific detection of crystalline compounds is discussed, as are experimental strategies. 31 refs., 8 figs., 1 tab.

  10. Solid-state NMR/NQR and first-principles study of two niobium halide cluster compounds.

    PubMed

    Perić, Berislav; Gautier, Régis; Pickard, Chris J; Bosiočić, Marko; Grbić, Mihael S; Požek, Miroslav

    2014-01-01

    Two hexanuclear niobium halide cluster compounds with a [Nb6X12](2+) (X=Cl, Br) diamagnetic cluster core, have been studied by a combination of experimental solid-state NMR/NQR techniques and PAW/GIPAW calculations. For niobium sites the NMR parameters were determined by using variable Bo field static broadband NMR measurements and additional NQR measurements. It was found that they possess large positive chemical shifts, contrary to majority of niobium compounds studied so far by solid-state NMR, but in accordance with chemical shifts of (95)Mo nuclei in structurally related compounds containing [Mo6Br8](4+) cluster cores. Experimentally determined δiso((93)Nb) values are in the range from 2,400 to 3,000 ppm. A detailed analysis of geometrical relations between computed electric field gradient (EFG) and chemical shift (CS) tensors with respect to structural features of cluster units was carried out. These tensors on niobium sites are almost axially symmetric with parallel orientation of the largest EFG and the smallest CS principal axes (Vzz and δ33) coinciding with the molecular four-fold axis of the [Nb6X12](2+) unit. Bridging halogen sites are characterized by large asymmetry of EFG and CS tensors, the largest EFG principal axis (Vzz) is perpendicular to the X-Nb bonds, while intermediate EFG principal axis (Vyy) and the largest CS principal axis (δ11) are oriented in the radial direction with respect to the center of the cluster unit. For more symmetrical bromide compound the PAW predictions for EFG parameters are in better correspondence with the NMR/NQR measurements than in the less symmetrical chlorine compound. Theoretically predicted NMR parameters of bridging halogen sites were checked by (79/81)Br NQR and (35)Cl solid-state NMR measurements.

  11. Electronic structure and biological activity of chosen DDT-type insecticides studied by 35Cl-NQR.

    PubMed

    Jadzyn, Maciej; Nogaj, Bolesław

    2009-02-01

    A correlation between the electronic structure and biological activity of chosen dichlorodiphenyltrichloroethane (DDT)-type insecticides: 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane, 1,1-dichloro-2,2-bis(4-chlorophenyl)ethane, 2,2-bis(p-chlorophenyl)-1,1-dichloroethylene, 2,2-bis(4-chlorophenyl)ethanoic acid and 4,4'-dichlorobenzophenone (used in agriculture) has been analysed on the basis of the (35)Cl-nuclear quadrupole resonance (NQR) spectroscopy. The (35)Cl-NQR resonance frequencies measured at 77 K have been correlated with the lethal dose (LD(50)) parameter that characterises the biological activity of these insecticides.

  12. NqrM (DUF539) Protein Is Required for Maturation of Bacterial Na+-Translocating NADH:Quinone Oxidoreductase

    PubMed Central

    Kostyrko, Vitaly A.; Bertsova, Yulia V.; Serebryakova, Marina V.; Baykov, Alexander A.

    2015-01-01

    ABSTRACT Na+-translocating NADH:quinone oxidoreductase (Na+-NQR) catalyzes electron transfer from NADH to ubiquinone in the bacterial respiratory chain, coupled with Na+ translocation across the membrane. Na+-NQR maturation involves covalent attachment of flavin mononucleotide (FMN) residues, catalyzed by flavin transferase encoded by the nqr-associated apbE gene. Analysis of complete bacterial genomes has revealed another putative gene (duf539, here renamed nqrM) that usually follows the apbE gene and is present only in Na+-NQR-containing bacteria. Expression of the Vibrio harveyi nqr operon alone or with the associated apbE gene in Escherichia coli, which lacks its own Na+-NQR, resulted in an enzyme incapable of Na+-dependent NADH or reduced nicotinamide hypoxanthine dinucleotide (dNADH) oxidation. However, fully functional Na+-NQR was restored when these genes were coexpressed with the V. harveyi nqrM gene. Furthermore, nqrM lesions in Klebsiella pneumoniae and V. harveyi prevented production of functional Na+-NQR, which could be recovered by an nqrM-containing plasmid. The Na+-NQR complex isolated from the nqrM-deficient strain of V. harveyi lacks several subunits, indicating that nqrM is necessary for Na+-NQR assembly. The protein product of the nqrM gene, NqrM, contains a single putative transmembrane α-helix and four conserved Cys residues. Mutating one of these residues (Cys33 in V. harveyi NqrM) to Ser completely prevented Na+-NQR maturation, whereas mutating any other Cys residue only decreased the yield of the mature protein. These findings identify NqrM as the second specific maturation factor of Na+-NQR in proteobacteria, which is presumably involved in the delivery of Fe to form the (Cys)4[Fe] center between subunits NqrD and NqrE. IMPORTANCE Na+-translocating NADH:quinone oxidoreductase complex (Na+-NQR) is a unique primary Na+ pump believed to enhance the vitality of many bacteria, including important pathogens such as Vibrio cholerae, Vibrio

  13. Generation of 4-hydroxy-2,5-dimethyl-3(2H)-furanone from rhamnose as affected by reaction parameters: experimental design approach.

    PubMed

    Illmann, Silke; Davidek, Tomas; Gouézec, Elisabeth; Rytz, Andreas; Schuchmann, Heike P; Blank, Imre

    2009-04-01

    The formation of 4-hydroxy-2,5-dimethyl-3(2H)-furanone (HDMF) was studied in aqueous model systems containing L-rhamnose and L-lysine. The approach consisted in systematically varying four reaction parameters (rhamnose concentration, rhamnose to lysine ratio, pH, and phosphate concentration) at 3 levels. A fractional factorial design was used to reduce the number of trials. The degradation of rhamnose was followed by high performance anion exchange chromatography and the formation of HDMF by solid phase extraction in combination with GC/MS. The study permitted the identification of critical reaction parameters that affect the formation of HDMF from rhamnose in aqueous systems. Although all studied parameters have some impact on the HDMF formation and rhamnose degradation kinetics, the effect of phosphate is by far the most important, followed by concentration of precursors and pH. The experimental design approach permitted us, with a limited number of experiments, to accurately model the effects of the four investigated reaction parameters on the kinetics of rhamnose degradation and HDMF formation (R(2)>0.93). Overall, the results indicate that rhamnose can be an excellent precursor of HDMF (yield >40 mol%), if the reaction conditions are well mastered. PMID:19256512

  14. NMR and NQR study of the thermodynamically stable quasicrystals

    SciTech Connect

    Shastri, A.

    1995-02-10

    {sup 27}Al and {sup 61,65}Cu NMR measurements are reported for powder samples of stable AlCuFe and AlCuRu icosahedral quasicrystals and their crystalline approximants, and for a AlPdMn single grain quasicrystal. Furthermore, {sup 27}Al NQR spectra at 4.2 K have been observed in the AlCuFe and AlCuRu samples. From the quadrupole perturbed NMR spectra at different magnetic fields, and from the zero field NQR spectra, a wide distribution of local electric field gradient (EFG) tensor components and principal axis system orientations was found at the Al site. A model EFG calculation based on a 1/1 AlCuFe approximant was successful in explaining the observed NQR spectra. It is concluded that the average local gradient is largely determined by the p-electron wave function at the Al site, while the width of the distribution is due to the lattice contribution to the EFG. Comparison of {sup 63}Cu NMR with {sup 27}Al NMR shows that the EFG distribution at the two sites is similar, but that the electronic contribution to the EFG is considerably smaller at the Cu site, in agreement with a more s-type wave function of the conduction electrons.

  15. Polymorphism and disorder in natural active ingredients. Low and high-temperature phases of anhydrous caffeine: Spectroscopic ((1)H-(14)N NMR-NQR/(14)N NQR) and solid-state computational modelling (DFT/QTAIM/RDS) study.

    PubMed

    Seliger, Janez; Žagar, Veselko; Apih, Tomaž; Gregorovič, Alan; Latosińska, Magdalena; Olejniczak, Grzegorz Andrzej; Latosińska, Jolanta Natalia

    2016-03-31

    The polymorphism of anhydrous caffeine (1,3,7-trimethylxanthine; 1,3,7-trimethyl-1H-purine-2,6-(3H,7H)-dione) has been studied by (1)H-(14)N NMR-NQR (Nuclear Magnetic Resonance-Nuclear Quadrupole Resonance) double resonance and pure (14)N NQR (Nuclear Quadrupole Resonance) followed by computational modelling (Density Functional Theory, supplemented Quantum Theory of Atoms in Molecules with Reduced Density Gradient) in solid state. For two stable (phase II, form β) and metastable (phase I, form α) polymorphs the complete NQR spectra consisting of 12 lines were recorded. The assignment of signals detected in experiment to particular nitrogen sites was verified with the help of DFT. The shifts of the NQR frequencies, quadrupole coupling constants and asymmetry parameters at each nitrogen site due to polymorphic transition were evaluated. The strongest shifts were observed at N(3) site, while the smallest at N(9) site. The commercial pharmaceutical sample was found to contain approximately 20-25% of phase I and 75-80% of phase II. The orientational disorder in phase II with a local molecular arrangement mimics that in phase I. Substantial differences in the intermolecular interaction phases I and II of caffeine were analysed using computational (DFT/QTAIM/RDS) approach. The analysis of local environment of each nitrogen nucleus permitted drawing some conclusions on the topology of interactions in both polymorphs. For the most stable orientations in phase I and phase II the maps of the principal component qz of EFG tensor and its asymmetry parameter at each point of the molecular system were calculated and visualized. The relevant maps calculated for both phases I and II indicates small variation in electrostatic potential upon phase change. Small differences between packings in phases slightly disturb the neighbourhood of the N(1) and N(7) nitrogens, thus are meaningless from the biological point of view. The composition of two phases in pharmaceutical material

  16. 2H nuclear magnetic resonance order parameter profiles suggest a change of molecular shape for phosphatidylcholines containing a polyunsaturated acyl chain.

    PubMed Central

    Holte, L. L.; Peter, S. A.; Sinnwell, T. M.; Gawrisch, K.

    1995-01-01

    Solid-state 2H nuclear magnetic resonance spectroscopy was used to determine the orientational order parameter profiles for a series of phosphatidylcholines with perdeuterated stearic acid, 18:0d35, in position sn-1 and 18:1 omega 9, 18:2 omega 6, 18:3 omega 3, 20:4 omega 6, 20:5 omega 3, or 22:6 omega 3 in position sn-2. The main phase transition temperatures were derived from a first moment analysis, and order parameter profiles of sn-1 chains were calculated from dePaked nuclear magnetic resonance powder patterns. Comparison of the profiles at 37 degrees C showed that unsaturation causes an inhomogenous disordering along the sn-1 chain. Increasing sn-2 chain unsaturation from one to six double bonds resulted in a 1.6-kHz decrease in quadrupolar splittings of the sn-1 chain in the upper half of the chain (or plateau region) and maximum splitting difference of 4.4 kHz at methylene carbon 14. The change in chain order corresponds to a decrease in the 18:0 chain length of 0.4 +/- 0.2 A with 18:2 omega 6 versus 18:1 omega 9 in position sn-2. Fatty acids containing three or more double bonds in sn-2 showed a decrease in sn-1 chain length of 0.7 +/- 0.2 A compared with 18:1 omega 9. The chain length of all lipids decreased with increasing temperature. Highly unsaturated phosphatidylcholines (three or more double bonds in sn-2) had shorter sn-1 chains, but the chain length was somewhat less sensitive to temperature. The profiles reveal that the sn-1 chain exhibits a selective increase in motional freedom in a region located toward the bottom half of the chain as sn-2 unsaturation is increased. This corresponds to an area increase around carbon atom number 14 that is three to four times greater than the increase for the top part of the chain. A similar asymmetric decrease in order, largest toward the methyl end of the chain, was observed when 1 -palmitoyl-2-oleoylphosphatidylethanolamine goes from a lamellar to an inverse hexagonal (H,,) phase. This is consistent with a

  17. Studies of the electronic structure and biological activity of chosen 1,4-benzodiazepines by 35Cl NQR spectroscopy and DFT calculations

    NASA Astrophysics Data System (ADS)

    Bronisz, K.; Ostafin, M.; Poleshchuk, O. Kh.; Mielcarek, J.; Nogaj, B.

    2006-11-01

    Selected derivatives of 1,4-benzodiazepine: lorazepam, lormetazepam, oxazepam and temazepam, used as active substances in anxiolytic drugs, have been studied by 35Cl NQR method in order to find the correlation between electronic structure and biological activity. The 35Cl NQR resonance frequencies ( νQ) measured at 77 K have been correlated with the following parameters characterising their biological activity: biological half-life period ( t0.5), affinity to benzodiazepine receptor (IC 50) and mean dose equivalent. The results of experimental study of some benzodiazepine derivatives by nuclear quadrupole resonance of 35Cl nuclei are compared with theoretical results based on DFT calculations which were carried out by means of Gaussian'98 W software.

  18. 35Cl NQR study of lattice dynamic and magnetic property of a crystalline coordination polymer {CuCA(phz)(H 2O) 2} n

    NASA Astrophysics Data System (ADS)

    Gotoh, Kazuma; Terao, Takeshi; Asaji, Tetsuo

    2007-01-01

    Copper(II) compounds {CuCA(phz)(H 2O) 2} n (H 2CA = chloranilic acid, phz = phenazine) having a layer structure of -CuCA(H 2O) 2- polymer chains and phenazine were studied by 35Cl nuclear quadrupole resonance (NQR). The single NQR line observed at 35.635 MHz at 261.5 K increased to 35.918 MHz at 4.2 K. The degree of reduction of electric field gradient due to lattice vibrations was similar to that of chloranilic acid crystal. Temperature dependence of spin-lattice relaxation time, T1, of the 35Cl NQR signal below 20 K, between 20 and 210 K, and above 210 K, was explained by (1) a decrease of effective electron-spin density caused by antiferromagnetic interaction, (2) a magnetic interaction between Cl nuclear-spin and electron-spins on paramagnetic Cu(II) ions, and (3) an increasing contribution from reorientation of ligand molecules, respectively. The electron spin-exchange parameter ∣ J∣ between the neighboring Cu(II) electrons was estimated to be 0.33 cm -1 from the T1 value of the range 20-210 K. Comparing this value with that of J = -1.84 cm -1 estimated from the magnetic susceptibility, it is suggested that the magnetic dipolar coupling with the electron spins on Cu(II) ions must be the principal mechanism for the 35Cl NQR spin-lattice relaxation of {CuCA(phz)(H 2O) 2} n but a delocalization of electron spin over the chloranilate ligand has to be taken into account.

  19. Enhancing nuclear quadrupole resonance (NQR) signature detection leveraging interference suppression algorithms

    NASA Astrophysics Data System (ADS)

    DeBardelaben, James A.; Miller, Jeremy K.; Myrick, Wilbur L.; Miller, Joel B.; Gilbreath, G. Charmaine; Bajramaj, Blerta

    2012-06-01

    Nuclear quadrupole resonance (NQR) is a radio frequency (RF) magnetic spectroscopic technique that has been shown to detect and identify a wide range of explosive materials containing quadrupolar nuclei. The NQR response signal provides a unique signature of the material of interest. The signal is, however, very weak and can be masked by non-stationary RF interference (RFI) and thermal noise, limiting detection distance. In this paper, we investigate the bounds on the NQR detection range for ammonium nitrate. We leverage a low-cost RFI data acquisition system composed of inexpensive B-field sensing and commercial-off-the-shelf (COTS) software-defined radios (SDR). Using collected data as RFI reference signals, we apply adaptive filtering algorithms to mitigate RFI and enable NQR detection techniques to approach theoretical range bounds in tactical environments.

  20. N.Q.R measurements of low energy Chiral structures in powdered glassy As2Se3

    NASA Astrophysics Data System (ADS)

    Nelson, Chris

    2012-02-01

    Experimental and theoretical work on the As-chalcogen glasses have shown that in the glassy state the local cylindrical symmetry associated with the elemental pyramidal unit is preserved. Here we introduce a local paracrystalline model of glassy As2Se3. This model is based on a tight binding calculation of the electric field gradient (EFG) at the core of an As atom located at the apex of the pyramidal structure. This EFG is shown to be hyper sensitive to the bond angles and bond lengths the As atom forms with the chalcogen nearest neighbors, as well as the hybrid angle formed with second neighbor As atoms. A continuous variation of the bonding parameters produces a unique set of these pyramidal units which are shown to fit the NQR data for powdered glassy samples. The best fit to the NQR data indicates that the pyramidal units organize themselves into Chiral structures in the glass. A plot of the electronic energy per molecular site shows that the chiral structures have on average a lower electronic energy than a random configuration.

  1. Theoretical studies of the local structures and electron paramagnetic resonance parameters for Cu2+ center in Zn(C3H3O4)2(H2O)2 single crystal

    NASA Astrophysics Data System (ADS)

    Zhang, Hua-Ming; Xiao, Wen-Bo; Wan, Xiong

    2014-07-01

    The electron paramagnetic resonance (EPR) parameters (g factors gxx, gyy, gzz and hyperfine structure constants Axx, Ayy, Azz) are interpreted by taking account of the admixture of d-orbitals in the ground state wave function of the Cu2+ ion in a Zn(C3H3O4)2(H2O)2 (DABMZ) single crystal. Based on the calculation, local structural parameters of the impurity Cu2+ center were obtained (i.e. Ra≈1.92 Å, Rb≈1.96 Å, Rc≈1.99 Å). The theoretical EPR parameters based on the above Cu2+-O2- bond lengths in the DABMZ crystal show good agreement with the observed values and some improvements have been made as compared with those in the previous studies.

  2. NMR and NQR study of Si-doped (6,0) zigzag single-walled aluminum nitride nanotube as n or P-semiconductors.

    PubMed

    Baei, Mohammad T; Peyghan, Ali Ahmadi; Tavakoli, Khadijeh; Babaheydari, Ali Kazemi; Moghimi, Masoumeh

    2012-09-01

    Density functional theory (DFT) calculations were performed to investigate the electronic structure properties of pristine and Si-doped aluminum nitride nanotubes as n or P-semiconductors at the B3LYP/6-31G* level of theory in order to evaluate the influence of Si-doped in the (6,0) zigzag AlNNTs. We extended the DFT calculation to predict the electronic structure properties of Si-doped aluminum nitride nanotubes, which are very important for production of solid-state devices and other applications. To this aim, pristine and Si-doped AlNNT structures in two models (Si(N) and Si(Al)) were optimized, and then the electronic properties, the isotropic (CS(I)) and anisotropic (CS(A)) chemical shielding parameters for the sites of various (27)Al and (14)N atoms, NQR parameters for the sites of various of (27)Al and (14)N atoms, and quantum molecular descriptors were calculated in the optimized structures. The optimized structures, the electronic properties, NMR and NQR parameters, and quantum molecular descriptors for the Si(N) and Si(Al) models show that the Si(N) model is a more reactive material than the pristine or Si(Al) model.

  3. Influence of different organic fertilizers on quality parameters and the delta(15)N, delta(13)C, delta(2)H, delta(34)S, and delta(18)O values of orange fruit (Citrus sinensis L. Osbeck).

    PubMed

    Rapisarda, Paolo; Camin, Federica; Fabroni, Simona; Perini, Matteo; Torrisi, Biagio; Intrigliolo, Francesco

    2010-03-24

    To investigate the influence of different types of fertilizers on quality parameters, N-containing compounds, and the delta(15)N, delta(13)C, delta(2)H, delta (34)S, and delta(18)O values of citrus fruit, a study was performed on the orange fruit cv. 'Valencia late' (Citrus sinensis L. Osbeck), which was harvested in four plots (three organic and one conventional) located on the same farm. The results demonstrated that different types of organic fertilizers containing the same amount of nitrogen did not effect important changes in orange fruit quality parameters. The levels of total N and N-containing compounds such as synephrine in fruit juice were not statistically different among the different treatments. The delta(15)N values of orange fruit grown under fertilizer derived from animal origin as well as from vegetable compost were statistically higher than those grown with mineral fertilizer. Therefore, delta(15)N values can be used as an indicator of citrus fertilization management (organic or conventional), because even when applied organic fertilizers are of different origins, the natural abundance of (15)N in organic citrus fruit remains higher than in conventional ones. These treatments also did not effect differences in the delta(13)C, delta(2)H, delta(34)S, and delta(18)O values of fruit.

  4. Experimental investigation of the EPR parameters and molecular orbital bonding coefficients for VO2+ ion in NaH2PO4·2H2O single crystals

    NASA Astrophysics Data System (ADS)

    Kalfaoğlu, Emel; Karabulut, Bünyamin

    2016-09-01

    Electron paramagnetic resonance (EPR) spectra of VO2+ ions in NaH2PO4·2H2O single crystal have been studied. The spin-Hamiltonian parameters and molecular orbital bonding coefficients were calculated. The angular variation of the EPR spectra shows two different VO2+ complexes. These are located in different chemical environment and each environment contains four magnetically inequivalent VO2+ sites. The crystal field around VO2+ ion is approximately axially symmetric since a strong V=O bond distorts the crystal lattice. Spin Hamiltonian parameters and molecular orbital bonding coefficients were calculated from the EPR data and the nature of bonding in the complex was discussed together.

  5. An analytical method for estimating the {sup 14}N nuclear quadrupole resonance parameters of organic compounds with complex free induction decays for radiation effects studies

    SciTech Connect

    Iselin, L.H.

    1992-12-31

    The use of {sup 14}N nuclear quadrupole resonance (NQR) as a radiation dosimetry tool has only recently been explored. An analytical method for analyzing {sup 14}N NQR complex free induction decays is presented with the background necessary to conduct pulsed NQR experiments. The {sup 14}N NQR energy levels and possible transitions are derived in step-by-step detail. The components of a pulsed NQR spectrometer are discussed along with the experimental techniques for conducting radiation effects experiments using the spectrometer. Three data analysis techniques -- the power spectral density Fourier transform, state space singular value decomposition (HSVD), and nonlinear curve fitting (using the downhill simplex method of global optimization and the Levenberg-Marquart method) -- are explained. These three techniques are integrated into an analytical method which uses these numerical techniques in this order to determine the physical NQR parameters. Sample data sets of urea and guanidine sulfate data are used to demonstrate how these methods can be employed to analyze both simple and complex free induction decays. By determining baseline values for biologically significant organics, radiation effects on the NQR parameters can be studied to provide a link between current radiation dosimetry techniques and the biological effects of radiation.

  6. Methyl quantum tunneling and nitrogen-14 NQR NMR studies using a SQUID magnetic resonance spectrometer

    SciTech Connect

    Black, B.E. |

    1993-07-01

    Nuclear Magnetic Resonance (NMR) and Nuclear Quadrupole Resonance (NQR) techniques have been very successful in obtaining molecular conformation and dynamics information. Unfortunately, standard NMR and NQR spectrometers are unable to adequately detect resonances below a few megahertz due to the frequency dependent sensitivity of their Faraday coil detectors. For this reason a new spectrometer with a dc SQUID (Superconducting Quantum Interference Device) detector, which has no such frequency dependence, has been developed. Previously, this spectrometer was used to observe {sup 11}B and {sup 27}Al NQR resonances. The scope of this study was increased to include {sup 23}Na, {sup 51}V, and {sup 55}Mn NQR transitions. Also, a technique was presented to observe {sup 14}N NQR resonances through cross relaxation of the nitrogen polarization to adjacent proton spins. When the proton Zeeman splitting matches one nitrogen quadrupoler transition the remaining two {sup 14}N transitions can be detected by sweeping a saturating rf field through resonance. Additionally, simultaneous excitation of two nitrogen resonances provides signal enhancement which helps to connect transitions from the same site. In this way, nitrogen-14 resonances were observed in several amino acids and polypeptides. This spectrometer has also been useful in the direct detection of methyl quantum tunneling splittings at 4.2 K. Tunneling, frequencies of a homologous series of carboxylic acids were measured and for solids with equivalent crystal structures, an exponential correlation between the tunneling frequency and the enthalpy of fusion is observed. This correlation provides information about the contribution of intermolecular interactions to the energy barrier for methyl rotation.

  7. The Conformational Changes Induced by Ubiquinone Binding in the Na+-pumping NADH:Ubiquinone Oxidoreductase (Na+-NQR) Are Kinetically Controlled by Conserved Glycines 140 and 141 of the NqrB Subunit*

    PubMed Central

    Strickland, Madeleine; Juárez, Oscar; Neehaul, Yashvin; Cook, Darcie A.; Barquera, Blanca; Hellwig, Petra

    2014-01-01

    Na+-pumping NADH:ubiquinone oxidoreductase (Na+-NQR) is responsible for maintaining a sodium gradient across the inner bacterial membrane. This respiratory enzyme, which couples sodium pumping to the electron transfer between NADH and ubiquinone, is not present in eukaryotes and as such could be a target for antibiotics. In this paper it is shown that the site of ubiquinone reduction is conformationally coupled to the NqrB subunit, which also hosts the final cofactor in the electron transport chain, riboflavin. Previous work showed that mutations in conserved NqrB glycine residues 140 and 141 affect ubiquinone reduction and the proper functioning of the sodium pump. Surprisingly, these mutants did not affect the dissociation constant of ubiquinone or its analog HQNO (2-n-heptyl-4-hydroxyquinoline N-oxide) from Na+-NQR, which indicates that these residues do not participate directly in the ubiquinone binding site but probably control its accessibility. Indeed, redox-induced difference spectroscopy showed that these mutations prevented the conformational change involved in ubiquinone binding but did not modify the signals corresponding to bound ubiquinone. Moreover, data are presented that demonstrate the NqrA subunit is able to bind ubiquinone but with a low non-catalytically relevant affinity. It is also suggested that Na+-NQR contains a single catalytic ubiquinone binding site and a second site that can bind ubiquinone but is not active. PMID:25006248

  8. Dependence of nuclear quadrupole resonance transitions on the electric field gradient asymmetry parameter for nuclides with half-integer spins

    NASA Astrophysics Data System (ADS)

    Cho, Herman

    2016-09-01

    Allowed transition energies and eigenstate expansions have been calculated and tabulated in numerical form as functions of the electric field gradient asymmetry parameter for the zero field Hamiltonian of quadrupolar nuclides with I = 3 / 2 , 5 / 2 , 7 / 2, and 9 / 2. These results are essential to interpret nuclear quadrupole resonance (NQR) spectra and extract accurate values of the electric field gradient tensors. Applications of NQR methods to studies of electronic structure in heavy element systems are proposed.

  9. Dependence of nuclear quadrupole resonance transitions on the electric field gradient asymmetry parameter for nuclides with half-integer spins

    DOE PAGES

    Cho, Herman

    2016-02-28

    Allowed transition energies and eigenstate expansions have been calculated and tabulated in numerical form as functions of the electric field gradient asymmetry parameter for the zero field Hamiltonian of quadrupolar nuclides with I = 3/2,5/2,7/2, and 9/2. These results are essential to interpret nuclear quadrupole resonance (NQR) spectra and extract accurate values of the electric field gradient tensors. Furthermore, applications of NQR methods to studies of electronic structure in heavy element systems are proposed.

  10. NQR application to the study of hydrogen dynamics in hydrogen-bonded molecular dimers

    NASA Astrophysics Data System (ADS)

    Asaji, Tetsuo

    2016-12-01

    The temperature dependences of 1H NMR as well as 35Cl NQR spin-lattice relaxation times T 1 were investigated in order to study the hydrogen transfer dynamics in carboxylic acid dimers in 3,5-dichloro- and 2,6-dichlorobenzoic acids. The asymmetry energy A/ k B and the activation energy V/ k B for the hydrogen transfer were estimated to be 240 K and 900 K, and 840 K and 2500 K, respectively, for these compounds. In spite of a large asymmetric potential the quantum nature of hydrogen transfer is recognized in the slope of the temperature dependence of T 1 on the low-temperature side of the T 1 minimum. The NQR T 1 measurements was revealed to be a good probe for the hydrogen transfer dynamics.

  11. 75As-NQR study of the hybridization gap semiconductor CeOs4As12

    NASA Astrophysics Data System (ADS)

    Yogi, M.; Higa, N.; Niki, H.; Kawata, T.; Sekine, C.

    2016-02-01

    We performed an 75As nuclear quadrupole resonance (NQR) measurement on CeOs4As12. The 75As-NQR spectrum shape demonstrates that the Ce-site filling fraction of our high-pressure synthesized sample is close to unity. A presence of the c — f hybridization gap is confirmed from the temperature dependence of the nuclear spin-lattice relaxation rate 1/T1. An increase of 1/T1 below ∼3 K indicates a development of the spin fluctuations. The 1/T1 for CeOs4As12 shows similar behavior as that for CeOs4Sb12 with different magnitude of the c — f hybridization gap. An absence of phase transition in CeOs4As12 may be caused by the increase of the c — f hybridization, which increases the gap magnitude and reduces the residual density of state inside the gap.

  12. NQR Line Broadening Due to Crystal Lattice Imperfections and Its Relationship to Shock Sensitivity

    NASA Astrophysics Data System (ADS)

    Caulder, S. M.; Buess, M. L.; Garroway, A. N.; Miller, P. J.

    2004-07-01

    The hydrodynamic hot spot model is used to explain the difference between shock sensitive and shock insensitive explosives. Among the major factors that influence the shock sensitivity of energetic compounds are the quality and particle size of the energetic crystals used to formulate the cast plastic bonded explosive. As do all energetic compounds, RDX and HMX exhibit internal crystal defects the magnitude and type of which depend on the manufacturing process used to synthesize and re-crystallize the energetic compound. Nuclear Quadrupole Resonance (NQR) spectroscopy was used to determine the crystal quality of RDX, HMX and CL-20 obtained from various manufacturers. The NQR experimental results are discussed. Cast plastic bonded explosives were made using the RDX and HMX obtained from the various manufacturers and subsequently subjected to the NOL large-scale gap test (LSGT). The results of the LSGT are discussed and correlated with the NQR results. A relationship between the crystal defect density and shock initiation pressure of the plastic bonded explosive is developed and discussed.

  13. Mutual effect of ligands in nitrido and nitroso complexes of osmium and ruthenium from NQR data

    SciTech Connect

    Kravchenko. E.A.; Burtsev, M.Yu.; Sinitsyn, M.N.; Svetlov, A.A.; Kokunov, Ya.V.; Buslaev, A.

    1987-11-01

    The purpose of this investigation was to study by NQR the spectral results of the mutual ligand effect in complex compounds having various types of short bonds. The authors obtained the /sup 35/Cl, /sup 81/Br, and /sup 127/I NQR spectra of a large number of halogen complexes of osmium and ruthenium having short Os=N and M in equilibrium NO bonds of the following types: R(OsNHal/sub 4/) (R = (Ph/sub 4/P)/sup +/, (Bu/sub 4/N)/sup +/; Hal = Cl/sup -/, Br/sup -/, I/sup -/), K/sub 2/(OsNCl/sub 5/), Rb/sub 2/(OsNBr/sub 5/), (NH/sub 4/)/sub 2/(OsNBr/sub 5/), K(OsNHal/sub 4/L) (Hal = Cl/sup -/, Br/sup -/; L = H/sub 2/O, CH/sub 3/CN), K/sub 2/(MNOHal/sub 5/) (M = Os, Ru; Hal = Cl/sup -/, Br/sup -/, I/sup -/). The experimental NQR values measured are connected by the Townes and Dailey theory with the chemical bond characteristics i, sigma, ..pi.., the degree of the ionic, the sigma-covalent, and the ..pi..-covalent natures respectively ( i + sigma + ..pi.. = 1).

  14. 63Cu NQR spectra of dicoordinated Cu(I) cations with imidazole and pyrazole ligands

    NASA Astrophysics Data System (ADS)

    Khajenhouri, Fereidoun; Motallebi, Shahrock; Lucken, Edwin A. C.

    1995-02-01

    The 63Cu NQR spectra of five dicoordinated complex cations of Cu(I) with substituted imidazoles as ligands and six analogous complexes with substituted pyrazoles as ligands are reported. The structures of four of these complexes have been previously determined and the relationship of their 63Cu resonance frequency to the average CuN bond length is compared to that of the analogous lutidine or collidine complexes. It is concluded that there are probably significant differences between the electronic structures of the pyridine complexes and those of the pyrazole or imidazole series.

  15. Roles of the sodium-translocating NADH:quinone oxidoreductase (Na+-NQR) on vibrio cholerae metabolism, motility and osmotic stress resistance.

    PubMed

    Minato, Yusuke; Fassio, Sara R; Kirkwood, Jay S; Halang, Petra; Quinn, Matthew J; Faulkner, Wyatt J; Aagesen, Alisha M; Steuber, Julia; Stevens, Jan F; Häse, Claudia C

    2014-01-01

    The Na+ translocating NADH:quinone oxidoreductase (Na+-NQR) is a unique respiratory enzyme catalyzing the electron transfer from NADH to quinone coupled with the translocation of sodium ions across the membrane. Typically, Vibrio spp., including Vibrio cholerae, have this enzyme but lack the proton-pumping NADH:ubiquinone oxidoreductase (Complex I). Thus, Na+-NQR should significantly contribute to multiple aspects of V. cholerae physiology; however, no detailed characterization of this aspect has been reported so far. In this study, we broadly investigated the effects of loss of Na+-NQR on V. cholerae physiology by using Phenotype Microarray (Biolog), transcriptome and metabolomics analyses. We found that the V. cholerae ΔnqrA-F mutant showed multiple defects in metabolism detected by Phenotype Microarray. Transcriptome analysis revealed that the V. cholerae ΔnqrA-F mutant up-regulates 31 genes and down-regulates 55 genes in both early and mid-growth phases. The most up-regulated genes included the cadA and cadB genes, encoding a lysine decarboxylase and a lysine/cadaverine antiporter, respectively. Increased CadAB activity was further suggested by the metabolomics analysis. The down-regulated genes include sialic acid catabolism genes. Metabolomic analysis also suggested increased reductive pathway of TCA cycle and decreased purine metabolism in the V. cholerae ΔnqrA-F mutant. Lack of Na+-NQR did not affect any of the Na+ pumping-related phenotypes of V. cholerae suggesting that other secondary Na+ pump(s) can compensate for Na+ pumping activity of Na+-NQR. Overall, our study provides important insights into the contribution of Na+-NQR to V. cholerae physiology.

  16. Roles of the Sodium-Translocating NADH:Quinone Oxidoreductase (Na+-NQR) on Vibrio cholerae Metabolism, Motility and Osmotic Stress Resistance

    PubMed Central

    Minato, Yusuke; Halang, Petra; Quinn, Matthew J.; Faulkner, Wyatt J.; Aagesen, Alisha M.; Steuber, Julia; Stevens, Jan F.; Häse, Claudia C.

    2014-01-01

    The Na+ translocating NADH:quinone oxidoreductase (Na+-NQR) is a unique respiratory enzyme catalyzing the electron transfer from NADH to quinone coupled with the translocation of sodium ions across the membrane. Typically, Vibrio spp., including Vibrio cholerae, have this enzyme but lack the proton-pumping NADH:ubiquinone oxidoreductase (Complex I). Thus, Na+-NQR should significantly contribute to multiple aspects of V. cholerae physiology; however, no detailed characterization of this aspect has been reported so far. In this study, we broadly investigated the effects of loss of Na+-NQR on V. cholerae physiology by using Phenotype Microarray (Biolog), transcriptome and metabolomics analyses. We found that the V. cholerae ΔnqrA-F mutant showed multiple defects in metabolism detected by Phenotype Microarray. Transcriptome analysis revealed that the V. cholerae ΔnqrA-F mutant up-regulates 31 genes and down-regulates 55 genes in both early and mid-growth phases. The most up-regulated genes included the cadA and cadB genes, encoding a lysine decarboxylase and a lysine/cadaverine antiporter, respectively. Increased CadAB activity was further suggested by the metabolomics analysis. The down-regulated genes include sialic acid catabolism genes. Metabolomic analysis also suggested increased reductive pathway of TCA cycle and decreased purine metabolism in the V. cholerae ΔnqrA-F mutant. Lack of Na+-NQR did not affect any of the Na+ pumping-related phenotypes of V. cholerae suggesting that other secondary Na+ pump(s) can compensate for Na+ pumping activity of Na+-NQR. Overall, our study provides important insights into the contribution of Na+-NQR to V. cholerae physiology. PMID:24811312

  17. Measurement of in-situ stress in salt and rock using NQR techniques

    SciTech Connect

    Schempp, E.; Hirschfeld, T.; Klainer, S.

    1980-12-01

    A discussion of how stress and strain affect the quantities which can be measured in an NQR experiment shows that, for stresses of the magnitude to be expected at depths up to about 10,000 feet, quadrupole coupling constants will fall in the range of 1 to 10 kHz for both the sodium and chloride ions in NaCl. The most promising system involves pulsed nuclear double resonance detection; and alterative is to observe the quadrupolar splitting of the NMR signal. Choices to be made in the measurement and mapping techniques are discussed. The well-known perturbation of the homogenous stress field in the neighborhood of a borehole is shown to be advantageous from the point of view of obtaining directional information on the stress. Construction and operation of a borehole stress sensor are considered. The NQR technique seems feasible for measuring the magnitude and direction of underground stress with a resolution of about 25 psi, or 2.5% at 1000 psi. Downhole instrumentation suitable for in-situ determinations of stress appears within the state of the art. Additional tasks required on the project are identified.

  18. An electronically tuned wideband probehead for NQR spectroscopy in the VHF range.

    PubMed

    Scharfetter, Hermann

    2016-10-01

    Nuclear quadrupole resonance spectroscopy is an analytical method which allows to characterize materials which contain quadrupolar nuclei, i.e. nuclei with spin ⩾1. The measurement technology is similar to that of NMR except that no static magnetic field is necessary. In contrast to NMR, however, it is frequently necessary to scan spectra with a very large bandwidth with a span of several tens of % of the central frequency so as to localize unknown peaks. Standard NMR probeheads which are typically constructed as resonators must be tuned and matched to comparatively narrow bands and must thus be re-tuned and re-matched very frequently when scanning over a whole NQR spectrum. At low frequencies up to few MHz dedicated circuits without the need for tuning and matching have been developed, but many quadrupole nuclei have transitions in the VHF range between several tens of MHz up to several hundreds of MHz. Currently available commercial NQR probeheads employ stepper motors for setting mechanically tuneable capacitors in standard NMR resonators. These yield high quality factors (Q) and thus high SNR but are relatively large and clumsy and do not allow for fast frequency sweeps. This article presents a new concept for a NQR probehead which combines a previously published no-tune no-match wideband concept for the transmit (TX) pulse with an electronically tuneable receive (RX) part employing varactor diodes. The prototype coil provides a TX frequency range of 57MHz with a center frequency of 97.5MHz with a return loss of ⩽-15dB. During RX the resonator is tuned and matched automatically to the right frequency via control voltages which are read out from a previously generated lookup table, thus providing high SNR. The control voltages which bias the varactors settle very fast and allow for hopping to the next frequency point in the spectrum within less than 100μs. Experiments with a test sample of ZnBr2 proved the feasibility of the method.

  19. An electronically tuned wideband probehead for NQR spectroscopy in the VHF range

    NASA Astrophysics Data System (ADS)

    Scharfetter, Hermann

    2016-10-01

    Nuclear quadrupole resonance spectroscopy is an analytical method which allows to characterize materials which contain quadrupolar nuclei, i.e. nuclei with spin ⩾1. The measurement technology is similar to that of NMR except that no static magnetic field is necessary. In contrast to NMR, however, it is frequently necessary to scan spectra with a very large bandwidth with a span of several tens of % of the central frequency so as to localize unknown peaks. Standard NMR probeheads which are typically constructed as resonators must be tuned and matched to comparatively narrow bands and must thus be re-tuned and re-matched very frequently when scanning over a whole NQR spectrum. At low frequencies up to few MHz dedicated circuits without the need for tuning and matching have been developed, but many quadrupole nuclei have transitions in the VHF range between several tens of MHz up to several hundreds of MHz. Currently available commercial NQR probeheads employ stepper motors for setting mechanically tuneable capacitors in standard NMR resonators. These yield high quality factors (Q) and thus high SNR but are relatively large and clumsy and do not allow for fast frequency sweeps. This article presents a new concept for a NQR probehead which combines a previously published no-tune no-match wideband concept for the transmit (TX) pulse with an electronically tuneable receive (RX) part employing varactor diodes. The prototype coil provides a TX frequency range of 57 MHz with a center frequency of 97.5 MHz with a return loss of ⩽-15 dB. During RX the resonator is tuned and matched automatically to the right frequency via control voltages which are read out from a previously generated lookup table, thus providing high SNR. The control voltages which bias the varactors settle very fast and allow for hopping to the next frequency point in the spectrum within less than 100 μs. Experiments with a test sample of ZnBr2 proved the feasibility of the method.

  20. An electronically tuned wideband probehead for NQR spectroscopy in the VHF range.

    PubMed

    Scharfetter, Hermann

    2016-10-01

    Nuclear quadrupole resonance spectroscopy is an analytical method which allows to characterize materials which contain quadrupolar nuclei, i.e. nuclei with spin ⩾1. The measurement technology is similar to that of NMR except that no static magnetic field is necessary. In contrast to NMR, however, it is frequently necessary to scan spectra with a very large bandwidth with a span of several tens of % of the central frequency so as to localize unknown peaks. Standard NMR probeheads which are typically constructed as resonators must be tuned and matched to comparatively narrow bands and must thus be re-tuned and re-matched very frequently when scanning over a whole NQR spectrum. At low frequencies up to few MHz dedicated circuits without the need for tuning and matching have been developed, but many quadrupole nuclei have transitions in the VHF range between several tens of MHz up to several hundreds of MHz. Currently available commercial NQR probeheads employ stepper motors for setting mechanically tuneable capacitors in standard NMR resonators. These yield high quality factors (Q) and thus high SNR but are relatively large and clumsy and do not allow for fast frequency sweeps. This article presents a new concept for a NQR probehead which combines a previously published no-tune no-match wideband concept for the transmit (TX) pulse with an electronically tuneable receive (RX) part employing varactor diodes. The prototype coil provides a TX frequency range of 57MHz with a center frequency of 97.5MHz with a return loss of ⩽-15dB. During RX the resonator is tuned and matched automatically to the right frequency via control voltages which are read out from a previously generated lookup table, thus providing high SNR. The control voltages which bias the varactors settle very fast and allow for hopping to the next frequency point in the spectrum within less than 100μs. Experiments with a test sample of ZnBr2 proved the feasibility of the method. PMID:27591955

  1. Three-dimensional high-inductance birdcage coil for NQR applications.

    PubMed

    Peshkovsky, A S; Cerioni, L; Osan, T M; Avdievich, N I; Pusiol, D J

    2006-09-01

    A birdcage coil capable of operating simultaneously and independently in three orthogonal dimensions has been developed. A co-rotational end-ring mode producing an RF field in the longitudinal direction was utilized in addition to the two common transverse orthogonal modes. Two conductor turns were used for each of the coil's windows, increasing its inductance by a factor of four, thereby, making the coil suitable for low-frequency applications. Two or three-frequency detection can be easily carried out with this device. Orthogonality of the coil's channels allows arbitrarily close frequency positioning of each resonant mode, potentially useful in wide-line NQR studies, in which simultaneous excitation/detection of signals from three adjacent regions of a single wide line can be performed. The coil's performance was evaluated using a three-dimensional scheme, in which a circularly polarized experiment was combined with a linearly polarized measurement at another frequency, resulting in SNR improvement by 55%.

  2. Structural and Functional Investigation of Flavin Binding Center of the NqrC Subunit of Sodium-Translocating NADH:Quinone Oxidoreductase from Vibrio harveyi

    PubMed Central

    Bertsova, Yulia; Polovinkin, Vitaly; Gushchin, Ivan; Ishchenko, Andrii; Kovalev, Kirill; Mishin, Alexey; Kachalova, Galina; Popov, Alexander; Bogachev, Alexander; Gordeliy, Valentin

    2015-01-01

    Na+-translocating NADH:quinone oxidoreductase (NQR) is a redox-driven sodium pump operating in the respiratory chain of various bacteria, including pathogenic species. The enzyme has a unique set of redox active prosthetic groups, which includes two covalently bound flavin mononucleotide (FMN) residues attached to threonine residues in subunits NqrB and NqrC. The reason of FMN covalent bonding in the subunits has not been established yet. In the current work, binding of free FMN to the apo-form of NqrC from Vibrio harveyi was studied showing very low affinity of NqrC to FMN in the absence of its covalent bonding. To study structural aspects of flavin binding in NqrC, its holo-form was crystallized and its 3D structure was solved at 1.56 Å resolution. It was found that the isoalloxazine moiety of the FMN residue is buried in a hydrophobic cavity and that its pyrimidine ring is squeezed between hydrophobic amino acid residues while its benzene ring is extended from the protein surroundings. This structure of the flavin-binding pocket appears to provide flexibility of the benzene ring, which can help the FMN residue to take the bended conformation and thus to stabilize the one-electron reduced form of the prosthetic group. These properties may also lead to relatively weak noncovalent binding of the flavin. This fact along with periplasmic location of the FMN-binding domains in the vast majority of NqrC-like proteins may explain the necessity of the covalent bonding of this prosthetic group to prevent its loss to the external medium. PMID:25734798

  3. A Cu NQR study in a d-electron heavy-fermion system, CaCu3Ru4O12

    NASA Astrophysics Data System (ADS)

    Kato, Harukazu; Tsuruta, Takuya; Nishioka, Takashi; Matsumura, Masahiro; Sakai, Hironori; Kambe, Shinsaku

    2007-11-01

    Cu nuclear quadrupole resonance (NQR) studies have been carried out for CaCu3Ru4O12, which has been suggested to show a heavy-fermion-like behavior although it possess no f electron. A Lorentzian shape of the Cu NQR line with a narrow width implies that no magnetic ordering appears, at least, down to 5 K. The spin lattice relaxation rate of the Cu nuclei probes a change of the Cu 3d electron nature, resulting in the Fermi liquid state at a low temperature. These facts strongly support that the heavy fermion picture is available in the concerned compound.

  4. C2H observations toward the Orion Bar

    NASA Astrophysics Data System (ADS)

    Nagy, Z.; Ossenkopf, V.; Van der Tak, F. F. S.; Faure, A.; Makai, Z.; Bergin, E. A.

    2015-06-01

    Context. The ethynyl radical (C2H) is one of the first radicals to be detected in the interstellar medium. Its higher rotational transitions have recently become available with the Herschel Space Observatory. Aims: We aim to constrain the physical parameters of the C2H emitting gas toward the Orion Bar. Methods: We analyze the C2H line intensities measured toward the Orion Bar CO+ Peak and Herschel/HIFI maps of C2H, CH, and HCO+ and a NANTEN map of [Ci]. We interpret the observed C2H emission using the combination of Herschel/HIFI and NANTEN data with radiative transfer and PDR models. Results: Five rotational transitions of C2H (from N = 6-5 up to N = 10-9) have been detected in the HIFI frequency range toward the CO+ peak of the Orion Bar. Based on the five detected C2H transitions, a single component rotational diagram analysis gives a rotation temperature of ~64 K and a beam-averaged C2H column density of 4 × 1013 cm-2. The rotational diagram is also consistent with a two-component fit, resulting in rotation temperatures of 43 ± 0.2 K and 123 ± 21 K and in beam-averaged column densities of ~8.3 × 1013 cm-2 and ~2.3 × 1013 cm-2 for the three lower-N and for the three higher-N transitions, respectively. The measured five rotational transitions cannot be explained by any single parameter model. According to a non-LTE model, most of the C2H column density produces the lower-N C2H transitions and traces a warm (Tkin ~ 100-150 K) and dense (n(H2) ~ 105-106 cm-3) gas. A small fraction of the C2H column density is required to reproduce the intensity of the highest-N transitions (N = 9-8 and N = 10-9) originating in a high-density (n(H2) ~5 × 106 cm-3) hot (Tkin ~ 400 K) gas. The total beam-averaged C2H column density in the model is 1014 cm-2. A comparison of the spatial distribution of C2H to those of CH, HCO+, and [Ci] shows the best correlation with CH. Conclusions: Both the non-LTE radiative transfer model and a simple PDR model representing the Orion Bar

  5. Chemical structure and intra-molecular effects on NMR-NQR tensors of harmine and harmaline alkaloids

    NASA Astrophysics Data System (ADS)

    Ahmadinejad, Neda; Tahan, Arezoo; Talebi Tari, Mostafa

    2016-02-01

    Density functional theory (DFT) methods were used to analyze the effects of molecular structure and ring currents on the NMR chemical shielding tensors and NQR frequencies of harmine and harmaline alkaloids in the gas phase. The results demonstrated that NMR tensors and NQR frequencies of 15N nuclei in these compounds depend on chemical environment and resonance interactions. Hence, their values are obviously different in the mentioned structures. The interpretation of natural bond orbital (NBO) data suggests that in harmine structure, the lone pair participation of N9 in π-system electron clouds causes to development of aromaticity nature in pyrrole ring. However, the chemical shielding around N9 atom in harmine structure is higher than in harmaline, while in harmaline structure, lone pair participation of N2 in π-system electron clouds causes to development of aromaticity nature in pyridine ring. Hence, chemical shielding around N2 atom in harmaline structure is higher than in harmine. It can be deduced that by increasing lone pair electrons contribution of nitrogen atoms in ring resonance interactions and aromaticity development, the values of NMR chemical shielding around them increase, while χ and q zz values of these nuclei decrease.

  6. Central role of the Na(+)-translocating NADH:quinone oxidoreductase (Na(+)-NQR) in sodium bioenergetics of Vibrio cholerae.

    PubMed

    Steuber, Julia; Halang, Petra; Vorburger, Thomas; Steffen, Wojtek; Vohl, Georg; Fritz, Günter

    2014-12-01

    Vibrio cholerae is a Gram-negative bacterium that lives in brackish or sea water environments. Strains of V. cholerae carrying the pathogenicity islands infect the human gut and cause the fatal disease cholera. Vibrio cholerae maintains a Na(+) gradient at its cytoplasmic membrane that drives substrate uptake, motility, and efflux of antibiotics. Here, we summarize the major Na(+)-dependent transport processes and describe the central role of the Na(+)-translocating NADH:quinone oxidoreductase (Na(+)-NQR), a primary Na(+) pump, in maintaining a Na(+)-motive force. The Na(+)-NQR is a membrane protein complex with a mass of about 220 kDa that couples the exergonic oxidation of NADH to the transport of Na(+) across the cytoplasmic membrane. We describe the molecular architecture of this respiratory complex and summarize the findings how electron transport might be coupled to Na(+)-translocation. Moreover, recent advances in the determination of the three-dimensional structure of this complex are reported.

  7. Synthesis of [2H7]indatraline.

    PubMed

    Allmendinger, L; Wanner, K T

    2014-11-01

    Deuterium-labelled indatraline was synthesized in high efficiency employing a Friedel-Crafts alkylation of [(2)H6]benzene with (E)-3-(3,4-dichlorophenyl)acrylic acid as a key step. The desired labelling of the final compound was ascertained in two ways, by incorporation of [(2)H6]benzene in the target molecule and additionally by deuterium transfer to the non-deuterated aryl moiety of the Friedel-Crafts alkylation product from [(2)H6]benzene, the latter thus serving as reagent and solvent. PMID:25382822

  8. Global distributions of C2H6, C2H2, HCN, and PAN retrieved from MIPAS reduced spectral resolution measurements

    NASA Astrophysics Data System (ADS)

    Wiegele, A.; Glatthor, N.; Höpfner, M.; Grabowski, U.; Kellmann, S.; Linden, A.; Stiller, G.; von Clarmann, T.

    2011-08-01

    Vertical profiles of mixing ratios of C2H6, C2H2, HCN, and PAN were retrieved from MIPAS reduced spectral resolution nominal mode limb emission measurements. The retrieval strategy followed that of the analysis of MIPAS high resolution measurements, with occasional adjustments to cope with the reduced spectral resolution under which MIPAS is operated since 2005. Largest mixing ratios are found in the troposphere, and reach 1.2 ppbv for C2H6, 1 ppbv for HCN, 600 pptv for PAN, and 450 pptv for C2H2. The estimated precision in case of significantly enhanced mixing ratios (including measurement noise and propagation of uncertain parameters randomly varying in the time domain) and altitude resolution are typically 10 %, 3-4.5 km for C2H6, 15 %, 4-6 km for HCN, 6 %, 2.5-3.5 km for PAN, and 7 %, 2.5-4 km for C2H2.

  9. Magnetic correlations in La(2-x)Sr(x)CuO4 from NQR relaxation and specific heat

    NASA Technical Reports Server (NTRS)

    Borsa, F.; Rigamonti, A.

    1991-01-01

    La-139 and Cu-63 Nuclear Quadrupole Resonance (NQR) relaxation measurements in La(2-x)Sr(x)CuO4 for x ranging from 0 up to 0.3, with particular emphasis on the effect of doping on the Cu(2+) magnetic correlations and dynamics, are reviewed. In the low doping limit, x less than or equal to 0.05, the results can be interpreted consistently in terms of a simple phenomenological 'two-fluids' model whereby the effect of thermally-activated mobile O(2p) holes is the one of disrupting locally the Cu(2+) spin correlations. For x greater than or equal to 0.1, the results indicate the onset, as T approaches T(sub c)(+), of a strong coupling between Cu(2+) spins and the Fermi liquid of O(2p) holes leading to the apparent disappearance of localized Cu(2+) moment in connection with the opening of a superconducting gap.

  10. Stability and molecular dynamics of chloroxylenol (API of antiseptics and drugs) in solid state studied by 35Cl-NQR spectroscopy and DFT calculations

    NASA Astrophysics Data System (ADS)

    Latosińska, J. N.; Tomczak, M. A.; Kasprzak, J.

    2009-02-01

    Thermal stability of 4-chloro-3,5-dimethyl-phenol (chloroxylenol) in solid state has been studied by 35Cl-NQR spectroscopy. Two NQR resonance lines at the frequencies 34.348 and 34.415 MHz at 77 K have been assigned to chlorine atoms from two crystallographically inequivalent molecules on the basis of the B3LYP/6-311++G∗∗ results. The temperature dependence of the resonance frequency and full width at half maximum suggest the occurrence of small-angle torsional oscillations of the mean activation energy of 3.83 kJ/mol and rotation of both methyl groups around their symmetry axis C3 with the activation energies 12.49 and 11.27 kJ/mol for CH3 in molecule A and B, respectively. B3LYP/6-311++G∗∗ method reproduced very well the activation energies of both motions.

  11. Volovik effect and Fermi-liquid behavior in the s-wave superconductor CaPd2As2: As75 NMR-NQR measurements

    DOE PAGES

    Ding, Q. -P.; Wiecki, P.; Anand, V. K.; Sangeetha, N. S.; Lee, Y.; Johnston, D. C.; Furukawa, Y.

    2016-04-07

    The electronic and magnetic properties of the collapsed-tetragonal CaPd2As2 superconductor (SC) with a transition temperature of 1.27 K have been investigated by 75As nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) measurements. The temperature (T) dependence of the nuclear spin lattice relaxation rates (1/T1) and the Knight shifts indicate the absence of magnetic correlations in the normal state. In the SC state, 1/T1 measured by 75As NQR shows a clear Hebel-Slichter (HS) peak just below Tc and decreases exponentially at lower T, confirming a conventional s-wave SC. Additionally, the Volovik effect, also known as the Doppler shift effect, hasmore » been clearly evidenced by the observation of the suppression of the HS peak with applied magnetic field.« less

  12. 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.

  13. Dissociative recombination of N2H+

    NASA Astrophysics Data System (ADS)

    dos Santos, S. Fonseca; Ngassam, V.; Orel, A. E.; Larson, Å.

    2016-08-01

    The direct and indirect mechanisms of dissociative recombination of N2H+ are theoretically studied. At low energies, the electron capture is found to be driven by recombination into bound Rydberg states, while at collision energies above 0.1 eV, the direct capture and dissociation along electronic resonant states becomes important. Electron-scattering calculations using the complex Kohn variational method are performed to obtain the scattering matrix as well as energy positions and autoionization widths of resonant states. Potential-energy surfaces of electronic bound states of N2H and N2H+ are computed using structure calculations with the multireference configuration interaction method. The cross section for the indirect mechanism is calculated using a vibrational frame transformation of the elements of the scattering matrix at energies just above the ionization threshold. Here vibrational excitations of the ionic core from v =0 to v =1 and v =2 for all three normal modes are considered and autoionization is neglected. The cross section for the direct dissociation along electronic resonant states is computed with wave-packet calculations using the multiconfiguration time-dependent Hartree method, where all three internal degrees of freedom are considered. The calculated cross sections are compared to measurements.

  14. Synthesis Of [2h, 13c] And [2h3, 13c]Methyl Aryl Sulfides

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

    2004-03-30

    The present invention is directed to labeled compounds, [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are each independently, hydrogen, a C.sub.1 -C.sub.4 lower alkyl, a halogen, an amino group from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each a C.sub.1 -C.sub.4 lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2,.sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms. The present invention is also directed to the labeled compounds of [.sup.2 H.sub.1, .sup.13 C]methyl iodide and [.sup.2 H.sub.2, .sup.13 C]methyl iodide.

  15. High-resolution solid-state 2H NMR spectroscopy of polymorphs of glycine.

    PubMed

    Aliev, Abil E; Mann, Sam E; Rahman, Aisha S; McMillan, Paul F; Corà, Furio; Iuga, Dinu; Hughes, Colan E; Harris, Kenneth D M

    2011-11-10

    High-resolution solid-state (2)H MAS NMR studies of the α and γ polymorphs of fully deuterated glycine (glycine-d(5)) are reported. Analysis of spinning sideband patterns is used to determine the (2)H quadrupole interaction parameters, and is shown to yield good agreement with the corresponding parameters determined from single-crystal (2)H NMR measurements (the maximum deviation in quadrupole coupling constants determined from these two approaches is only 1%). From analysis of simulated (2)H MAS NMR sideband patterns as a function of reorientational jump frequency (κ) for the -N(+)D(3) group in glycine-d(5), the experimentally observed differences in the (2)H MAS NMR spectrum for the -N(+)D(3) deutrons in the α and γ polymorphs is attributed to differences in the rate of reorientation of the -N(+)D(3) group. These simulations show severe broadening of the (2)H MAS NMR signal in the intermediate motion regime, suggesting that deuterons undergoing reorientational motions at rates in the range κ ≈ 10(4)-10(6) s(-1) are likely to be undetectable in (2)H MAS NMR measurements for materials with natural isotopic abundances. The (1)H NMR chemical shifts for the α and γ polymorphs of glycine have been determined from the (2)H MAS NMR results, taking into account the known second-order shift. Further quantum mechanical calculations of (2)H quadrupole interaction parameters and (1)H chemical shifts reveal the structural dependence of these parameters in the two polymorphs and suggest that the existence of two short intermolecular C-H···O contacts for one of the H atoms of the >CH(2) group in the α polymorph have a significant influence on the (2)H quadrupole coupling and (1)H chemical shift for this site. PMID:21939265

  16. Thz Spectroscopy of D_2H^+

    NASA Astrophysics Data System (ADS)

    Yu, Shanshan; Pearson, John; Amano, Takayoshi

    2015-06-01

    Pure rotational transitions of D_2H^+ observed by high-resolution spectroscopy have been limited so far to the J = 110-101 transition at 691.7 GHz, J=220-211 at 1.370 THz, and J=111-000 at 1.477 THz. As this ion is a light asymmetric-top molecule, spectroscopic characterization and prediction of other rotational transition frequencies are not straightforward. In this presentation, we extended the measurements up to 2 THz by using the JPL frequency multiplier chains, and observed three new THz lines and re-measured the three known transitions. D_2H^+ was generated in an extended negative glow discharge cell cooled to liquid nitrogen temperature. Six rotational transition frequencies together with the combination differences derived from three fundamental bands were subject to least square analysis to determine the molecular constants. New THz measurements are definitely useful for better characterization of spectroscopic properties. The improved molecular constants provide better predictions of other unobserved rotational transitions. T. Hirao and T. Amano, Ap. J.,597, L85 (2003) K. M. Evenson et al cited by O. L. Polyansky and A. R. W. McKellar, J. Chem. Phys., 92, 4039 (1990) O. Asvany et al, Phys. Rev. Lett., 100, 233004 (2008)

  17. Magnetic correlations in La(2-x)Sr(x)CuO4 from NQR relaxation and specific heat

    NASA Technical Reports Server (NTRS)

    Borsa, F.; Rigamonti, A.

    1990-01-01

    La-139 and Cu-63 Nuclear Quadrupole Resonance (NQR) relaxation measurements in La(2-x)Sr(x)CuO4 for O = to or less than 0.3 and in the temperature range 1.6 + 450 K are analyzed in terms of Cu(++) magnetic correlations and dynamics. It is described how the magnetic correlations that would result from Cu-Cu exchange are reduced by mobile charge defects related to x-doping. A comprehensive picture is given which explains satisfactorily the x and T dependence of the correlation time, of the correlation length and of the Neel temperature T(sub n)(x) as well as being consistent with known electrical resistivity and magnetic susceptibility measurements. It is discussed how, in the superconducting samples, the mobile defects also cause the decrease, for T yields T(sub c)(+) of the hyperfine Cu electron-nucleus effective interaction, leading to the coexistence of quasi-localized, reduced magnetic moments from 3d Cu electrons and mobile oxygen p-hole carriers. The temperature dependence of the effective hyperfine field around the superconducting transition yields an activation energy which could be related to the pairing energy. New specific heat measurements are also presented and discussed in terms of the above picture.

  18. Electronic properties of Y-Ba-Cu-O superconductors as seen by Cu and O NMR/NQR

    NASA Technical Reports Server (NTRS)

    Brinkmann, D.

    1995-01-01

    Nuclear Magnetic Resonance (NMR) and Nuclear Quadrupole Resonance (NQR) allow the investigation of electronic properties at the atomic level. We will report on such studies of typical members of the the Y-Ba-Cu-O family such as YBa2Cu30(6 + x) (1-2-3-(6 + x)), YBa2Cu4O8 (1-2-4) and Y2Ba4Cu7015 (2-4-7) with many examples of recent work performed in our laboratory. In particular, we will deal with Knight shift and relaxation studies of copper and oxygen. We will discuss important issues of current studies such as: (1) Existence of a common electronic spin-susceptibility in the planes (and perhaps in the chains) of 1-2-4; (2) Strong evidence for the existence of a pseudo spin-gap of the antiferromagnetic fluctuations in 1-2-4 and 2-4-7; (3) Evidence for d-wave pairing in 1-2-4; (4) Strong coupling of inequivalent Cu-O planes in 2-4-7 and possible origin for the high Tc value of this compound; and (5) The possibility to describe NMR data in the framework of a charge-excitation picture.

  19. B2H6 PLAD Doped PMOS Device Performance

    SciTech Connect

    Fang, Z.; Miller, T.; Winder, E.; Persing, H.; Arevalo, E.; Gupta, A.; Parrill, T.; Singh, V.; Qin, S.; McTeer, A.

    2006-11-13

    Plasma doping (PLAD) achieves high wafer throughput by directly extracting ions across the plasma sheath. PLAD profiles are typically surface peaked instead of retrograde as obtained from beamline (BL) implant. It may require optimization of PLAD energy and dose in order to match BL doping results. From device optimization point of view, it is necessary to understand the impact of doping parameters to device characteristics. In this paper we present the PMOS device performance with the poly gate and source drain (SD) implants carried out using B2H6 PLAD. The BL control conditions are 2-5 keV 11B+ 4-6x1015 cm-2. Equivalent device performance for p+ poly gate doping is obtained using PLAD with B2H6 / H2. In SD doping using same gas mixture, nearly 50% reduction in SD contact resistance is observed in the PLAD splits. The reduction in SD contact resistance leads to 10-15% increase in device on-current, hence demonstrating the process advantages of using PLAD in addition to having a high wafer throughput.

  20. One dimensional 1H, 2H and 3H

    NASA Astrophysics Data System (ADS)

    Vidal, A. J.; Astrakharchik, G. E.; Vranješ Markić, L.; Boronat, J.

    2016-05-01

    The ground-state properties of one-dimensional electron-spin-polarized hydrogen 1H, deuterium 2H, and tritium 3H are obtained by means of quantum Monte Carlo methods. The equations of state of the three isotopes are calculated for a wide range of linear densities. The pair correlation function and the static structure factor are obtained and interpreted within the framework of the Luttinger liquid theory. We report the density dependence of the Luttinger parameter and use it to identify different physical regimes: Bogoliubov Bose gas, super-Tonks-Girardeau gas, and quasi-crystal regimes for bosons; repulsive, attractive Fermi gas, and quasi-crystal regimes for fermions. We find that the tritium isotope is the one with the richest behavior. Our results show unambiguously the relevant role of the isotope mass in the properties of this quantum system.

  1. Rate Coefficients of C2H with C2H4, C2H6, and H2 from 150 to 359 K

    NASA Technical Reports Server (NTRS)

    Opansky, Brian J.; Leone, Stephen R.

    1996-01-01

    Rate coefficients for the reactions C2H with C2H4, C2H6, and H2 are measured over the temperature range 150-359 K using transient infrared laser absorption spectroscopy. The ethynyl radical is formed by photolysis of C2H2 with a pulsed excimer laser at 193 nm, and its transient absorption is monitored with a color center laser on the Q(sub 11)(9) line of the A(sup 2) Pi-Chi(sup 2) Sigma transition at 3593.68 cm(exp -1). Over the experimental temperature range 150-359 K the rate constants of C2H with C2H4, C2H6, and H2 can be fitted to the Arrhenius expressions k(sub C2H4) = (7.8 +/- 0.6) x 10(exp -11) exp[(134 +/- 44)/T], k(sub C2H6) = (3.5 +/- 0.3) x 10(exp -11) exp[(2.9 +/- 16)/T], and k(sub H2) = (1.2 +/- 0.3) x 10(exp -11) exp[(-998 +/- 57)]/T cm(exp 3) molecule(exp -1) sec(exp -1). The data for C2H with C2H4 and C2H6 indicate a negligible activation energy to product formation shown by the mild negative temperature dependence of both reactions. When the H2 data are plotted together with the most recent high-temperature results from 295 to 854 K, a slight curvature is observed. The H2 data can be fit to the non-Arrhenius form k(sub H2) = 9.2 x 10(exp -18) T(sup 2.17 +/- 0.50) exp[(-478 +/- 165)/T] cm(exp 3) molecules(exp -1) sec(exp -1). The curvature in the Arrhenius plot is discussed in terms of both quantum mechanical tunneling of the H atom from H2 to the C2H radical and bending mode contributions to the partition function.

  2. An XPS investigation of the interaction of CH 4, C 2H 2, C 2H 4 and C 2H 6 with a barium surface

    NASA Astrophysics Data System (ADS)

    Verhoeven, J. A. Th.; Van Doveren, H.

    1982-12-01

    The generation and pumping of hydrocarbon gases by a barium getter layer in electronic vacuum devices has been investigated by characterizing a barium film in an ultra high vacuum equipment by means of XPS before, during and after exposures to respectively CH 4, C 2H 2, C 2H 4 and C 2H 6. The reaction conditions (temperatures and pretreatment of the surface, background pressure and exposure doses) closely resemble those in electronic vacuum devices. The probability that a barium layer will react with CH 4 and C 2H 6 was below the detection limit. C 2H 2 and C 2H 4 give rise to the formation of barium carbide compounds and with a high reaction probability. In addition, the interaction with C 2H 2 reveals the formation of carbon-containing surface complexes. Investigations by means of XPS on the C Is spectral features show the presence of at least two groups of carbon-containing surface complexes, which behave differently in response to moderate heating and to an exposure to water vapour. In cases where oxygen is present at the surface, oxygen-containing (hydro) carbon adsorbates are present too. XPS observations of the behaviour of these surface complexes show similarities with reaction steps in the mechanisms proposed for the hydrogenation of CO in the Fischer-Tropsch synthesis of hydrocarbons. Low-pressure hydrogenation of these adsorbates containing hydrocarbons and oxygen can led to the formation of hydrocarbon gases in electronic vacuum devices.

  3. Quantitation of methadone enantiomers in humans using stable isotope-labeled (2H3)-, (2H5)-, and (2H8)Methadone

    SciTech Connect

    Nakamura, K.; Hachey, D.L.; Kreek, M.J.; Irving, C.S.; Klein, P.D.

    1982-01-01

    A new technique for simultaneous stereoselective kinetic studies of methadone enantiomers was developed using three deuterium-labeled forms of methadone and GLC-chemical-ionization mass spectrometry. A racemic mixture (1:1) of (R)-(-)-(2H5)methadone (l-form) and (S)-(R)-(2H3)methadone (d-form) was administered orally in place of a single daily dose of unlabeled (+/-)-(2H0)methadone in long-term maintenance patients. Racemic (+/-)-(2H8)methadone was used as an internal standard for the simultaneous quantitation of (2H0)-, (2H3)-, and (2H5)methadone in plasma and urine. A newly developed extraction procedure, using a short, disposable C18 reversed-phase cartridge and improved chemical-ionization procedures employing ammonia gas, resulted in significant reduction of the background impurities contributing to the ions used for isotopic abundance measurements. These improvements enabled the measurement of labeled plasma methadone levels for 120 hr following a single dose. This methodology was applied to the study of methadone kinetics in two patients; in both patients, the analgesically active l-enantiomer of the drug had a longer plasma elimination half-life and a smaller area under the plasma disappearance curve than did the inactive d-form.

  4. Part I. Analyzing the distribution of gas law questions in chemistry textbooks. Part II. Chlorine-35 NQR spectra of group 1 and silver dichloromethanesulfonates

    NASA Astrophysics Data System (ADS)

    Gillette, Gabriel

    Part I. Two studies involving the gas law questions in eight high school and Advanced Placement/college chemistry textbooks were performed using loglinear analysis to look for associations among six variables. These variables included Bloom's Taxonomy (higher-order, lower-order), Book Type (high school, college), Question Format (multiple-choice, problem, short answer), Question Placement (in-chapter, end-of-chapter, test bank), Representation (macroscopic, microscopic, symbolic), and Arkansas Science Standard (conceptual, mathematical; gas laws, pressure conversion, stoichiometry). The first study, involving the conceptual gas law questions, found the Book Type and Question Placement variables had the biggest impact, each appearing in 5 of the 11 significant associations. The second study, involving the mathematical gas law questions, found the Question Placement had the biggest impact, appearing in 7 of the 11 significant associations, followed by Book Type and the Arkansas Science Standard variables, which appeared in 5 of the 11 significant associations. These studies showed that compared to the high school books, college books have fewer multiple-choice questions (compared to short-answer and problem questions), fewer in-chapter questions (compared to end-of-chapter and test bank questions), fewer questions in the chapters and more questions at the end of the chapters and fewer multiple-choice questions in and at the end of the books and more multiple-choice questions in the test banks. Part II. The dichloromethanesulfonate salts of several +1 charged cations, M+Cl2CHSO3 - (M = Li, Na, K, Rb Ag, Cs Tl) were synthesized and studied by 35Cl nuclear quadrupole resonance (NQR). Dichloromethanesulfonic acid was prepared by the methanolysis of dichloromethanesulfonyl chloride, which was neutralized with the metal carbonates to produce the corresponding metal dichloromethanesulfonate salts. This study completed the NQR investigation of the family of chloroacetates

  5. Synthesis Of [2h, 13c]M [2h2m 13c], And [2h3,, 13c] Methyl Aryl Sulfones And Sulfoxides

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.; Schmidt, Jurgen G.

    2004-07-20

    The present invention is directed to labeled compounds, [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfones and [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfoxides, wherein the .sup.13 C methyl group attached to the sulfur of the sulfone or sulfoxide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently, hydrogen, a C.sub.1 -C.sub.4 lower alkyl, a halogen, an amino group from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each a C.sub.1 -C.sub.4 lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing methyl aryl sulfones and methyl aryl sulfoxides.

  6. Suppression of electron correlations in the collapsed tetragonal phase of CaFe2As2 under ambient pressure demonstrated by As75 NMR/NQR measurements

    NASA Astrophysics Data System (ADS)

    Furukawa, Y.; Roy, B.; Ran, S.; Bud'ko, S. L.; Canfield, P. C.

    2014-03-01

    The static and the dynamic spin correlations in the low-temperature collapsed tetragonal and the high-temperature tetragonal phase in CaFe2As2 have been investigated by As75 nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) measurements. Through the temperature (T) dependence of the nuclear spin lattice relaxation rates (1/T1) and the Knight shifts, although stripe-type antiferromagnetic (AFM) spin correlations are realized in the high-temperature tetragonal phase, no trace of the AFM spin correlations can be found in the nonsuperconducting, low-temperature, collapsed tetragonal (cT) phase. Given that there is no magnetic broadening in As75 NMR spectra, together with the T-independent behavior of magnetic susceptibility χ and the T dependence of 1/T1Tχ, we conclude that Fe spin correlations are completely quenched statically and dynamically in the nonsuperconducting cT phase in CaFe2As2.

  7. Cu NQR Study of Impurity-doped YBa_2(Cu_1-xM_x)_4O8 (M=Ni, Zn)

    NASA Astrophysics Data System (ADS)

    Itoh, Yutaka; Machi, Takato; Watanabe, Nobuaki; Koshizuka, Naoki

    2001-03-01

    We report Cu NQR measurements of ^63Cu(2) nuclear spin-lattice relaxation curves for the impurity-doped powdered YBa_2(Cu_1-xM_x)_4O8 (M=Ni, x=0 ~0.042 M=Zn, x=0 ~0.022) from 4.2 K to 300 K. We estimated the host and the impurity-induced Cu nuclear spin-lattice relaxation times from the nonexponential recovery curves. Near the superconductor-to-semiconductor transition at the critical impurity concentration, we observed that the wipeout effect works at low temperature and that the pseudo spin-gap behavior of the host Cu nuclear spin-lattice relaxation rate (1/T_1T)_HOST is suppressed. We associate these results with the localization effect in conduction. This work was supported by New Energy and Industrial Technology Development Organization (NEDO) as Collaborative Research and Development of Fundamental Technologies for Superconductivity Applications.

  8. TES/Aura L2 Water Vapor (H2O) Limb (TL2H2OL)

    Atmospheric Science Data Center

    2015-02-06

    TES/Aura L2 Water Vapor (H2O) Limb (TL2H2OL) News:  TES News ... Level:  L2 Platform:  TES/Aura L2 Water Vapor Spatial Coverage:  27 x 23 km Limb ... Access: OPeNDAP Parameters:  H2O Water Volume Mixing Radio Precision Vertical Resolution Order ...

  9. Temperature and pressure dependent rate coefficients for the reaction of C2H4 + HO2 on the C2H4O2H potential energy surface.

    PubMed

    Guo, JunJiang; Xu, JiaQi; Li, ZeRong; Tan, NingXin; Li, XiangYuan

    2015-04-01

    The potential energy surface (PES) for reaction C2H4 + HO2 was examined by using the quantum chemical methods. All rates were determined computationally using the CBS-QB3 composite method combined with conventional transition state theory(TST), variational transition-state theory (VTST) and Rice-Ramsberger-Kassel-Marcus/master-equation (RRKM/ME) theory. The geometries optimization and the vibrational frequency analysis of reactants, transition states, and products were performed at the B3LYP/CBSB7 level. The composite CBS-QB3 method was applied for energy calculations. The major product channel of reaction C2H4 + HO2 is the formation C2H4O2H via an OH(···)π complex with 3.7 kcal/mol binding energy which exhibits negative-temperature dependence. We further investigated the reactions related to this complex, which were ignored in previous studies. Thermochemical properties of the species involved in the reactions were determined using the CBS-QB3 method, and enthalpies of formation of species were compared with literature values. The calculated rate constants are in good agreement with those available from literature and given in modified Arrhenius equation form, which are serviceable in combustion modeling of hydrocarbons. Finally, in order to illustrate the effect for low-temperature ignition of our new rate constants, we have implemented them into the existing mechanisms, which can predict ethylene ignition in a shock tube with better performance.

  10. Temperature and pressure dependent rate coefficients for the reaction of C2H4 + HO2 on the C2H4O2H potential energy surface.

    PubMed

    Guo, JunJiang; Xu, JiaQi; Li, ZeRong; Tan, NingXin; Li, XiangYuan

    2015-04-01

    The potential energy surface (PES) for reaction C2H4 + HO2 was examined by using the quantum chemical methods. All rates were determined computationally using the CBS-QB3 composite method combined with conventional transition state theory(TST), variational transition-state theory (VTST) and Rice-Ramsberger-Kassel-Marcus/master-equation (RRKM/ME) theory. The geometries optimization and the vibrational frequency analysis of reactants, transition states, and products were performed at the B3LYP/CBSB7 level. The composite CBS-QB3 method was applied for energy calculations. The major product channel of reaction C2H4 + HO2 is the formation C2H4O2H via an OH(···)π complex with 3.7 kcal/mol binding energy which exhibits negative-temperature dependence. We further investigated the reactions related to this complex, which were ignored in previous studies. Thermochemical properties of the species involved in the reactions were determined using the CBS-QB3 method, and enthalpies of formation of species were compared with literature values. The calculated rate constants are in good agreement with those available from literature and given in modified Arrhenius equation form, which are serviceable in combustion modeling of hydrocarbons. Finally, in order to illustrate the effect for low-temperature ignition of our new rate constants, we have implemented them into the existing mechanisms, which can predict ethylene ignition in a shock tube with better performance. PMID:25774424

  11. Exceptional Point of the Neutral Heavy Higgs System H 2- H 3

    NASA Astrophysics Data System (ADS)

    Félix-Beltrán, O.; Gómez-Bock, M.; Hernández, E.; Mondragón, A.; Mondragón, M.

    2011-07-01

    We study the singularity of the surface that represents the masses of the isolated doublet of heavy, neutral Higgs bosons, H 2- H 3, in a toy model based on the MSSM with CP violation, in parameter space. These two heavy, neutral Higgs bosons are coherent and, for large values of the masses, nearly degenerate. In this scenario, mixing between the mass eigenstates of the H 2- H 3 system could be very large and exact degeneracy is possible. As function of the Lagrangian parameters, the physical mass of the doublet has an algebraic branch point of rank one at the exceptional point where the two masses are equal. The real and imaginary parts of the masses in the doublet have branch cuts that start at the same branch point but extend in opposite directions in parameter space. Associated with this branch point, the propagator of the mixing doublet of neutral heavy Higgs bosons has a double pole in the complex s-plane of the energy squared. We computed the mass surface of the isolated doublet of H 2- H 3 bosons as function of the Lagrangian parameters in the neighbourhood of the exceptional point in a toy model of the system H 2- H 3. We also computed the trajectories of the poles of the transition matrix for values of the Lagrangian parameters close to the exceptional point and explained the characteristic change of identity seen in these trajectories in the s-plane as a manifestation of the topology of the two-sheeted mass surfaces in the space of Lagrangian parameters.

  12. EPR of Cu 2+ and VO 2+ in a cobalt saccharin complex, [Co(sac) 2(H 2O) 4]·2H 2O, single crystals

    NASA Astrophysics Data System (ADS)

    Yerli, Y.; Köksal, F.; Karadag, A.

    2003-09-01

    Cu 2+ and VO 2+ doped single crystals of [Co(sac) 2(H 2O) 4]·2H 2O (Cosacaqua) complex were investigated using EPR technique at ambient temperature. Detailed investigation of the EPR spectra indicated that the Cu 2+ and VO 2+ substitute the Co 2+. Two sites were observed for Cu 2+ and VO 2+. But each site of V 4+ corresponds two different orientations of VO 2+. The principal values of the g and the hyperfine tensors were obtained. The spectra indicate that the ground state for Cu 2+ is mainly 3 dx2- y2. The covalent bonding parameters for Cu 2+ and VO 2+ and Fermi contact terms were obtained.

  13. Heterozygous FA2H mutations in autism spectrum disorders

    PubMed Central

    2013-01-01

    Background Widespread abnormalities in white matter development are frequently reported in cases of autism spectrum disorders (ASD) and could be involved in the disconnectivity suggested in these disorders. Homozygous mutations in the gene coding for fatty-acid 2-hydroxylase (FA2H), an enzyme involved in myelin synthesis, are associated with complex leukodystrophies, but little is known about the functional impact of heterozygous FA2H mutations. We hypothesized that rare deleterious heterozygous mutations of FA2H might constitute risk factors for ASD. Methods We searched deleterious mutations affecting FA2H, by genotyping 1256 independent patients with ASD genotyped using Genome Wide SNP arrays, and also by sequencing in independent set of 186 subjects with ASD and 353 controls. We then explored the impact of the identified mutations by measuring FA2H enzymatic activity and expression, in transfected COS7 cells. Results One heterozygous deletion within 16q22.3-q23.1 including FA2H was observed in two siblings who share symptoms of autism and severe cognitive impairment, axial T2-FLAIR weighted MRI posterior periventricular white matter lesions. Also, two rare non-synonymous mutations (R113W and R113Q) were reported. Although predictive models suggested that R113W should be a deleterious, we did not find that FA2H activity was affected by expression of the R113W mutation in cultured COS cells. Conclusions While our results do not support a major role for FA2H coding variants in ASD, a screening of other genes related to myelin synthesis would allow us to better understand the role of non-neuronal elements in ASD susceptibility. PMID:24299421

  14. I: Low Frequency NMR and NQR Using a dc SQUID. II: Variable-temperature 13C CP/MAS of Organometallics

    SciTech Connect

    Ziegeweid, M.A.

    1995-11-29

    NMR and NQR at low frequencies are difficult prospects due to small nuclear spin polarization. Furthermore, the sensitivity'of the inductive pickup circuitry of standard spectrometers is reduced as the frequency is lowered. I have used a cw-SQUID (Superconducting QUantum Interference Device) spectrometer, which has no such frequency dependence, to study the local atomic environment of {sup 14}N via the quadrupolar interaction. Because {sup 14}N has spin I = 1 and a 0-6 MHz frequency range, it is not possible to obtain well-resolved spectra in high magnetic fields. I have used a technique to observe {sup 14}N NQR resonances via their effect on neighboring protons mediated by the heteronuclear dipolar interaction to study peptides and narcotics. The sensitivity of the SQUID is not enough to measure low-frequency surface (or other low spin density) systems. The application of spin-polarized xenon has been previously used to enhance polarization in conventional NMR experiments. Because xenon only polarizes spins with which it is in contact, it is surface selective. While differences in chemical shifts between surface and bulk spins are not large, it is expected that the differences in quadrupole coupling constant should be very large due to the drastic change of the electric field gradient surrounding spins at the surface. With this in mind, I have taken preliminary steps to measure SQUID detected polarization transfer from Xe to another spin species at 4.2 K and in small magnetic fields (<50 G). In this regime, the spin-lattice relaxation of xenon is dependent on the applied magnetic field. The results of our efforts to characterize the relaxation of xenon are presented. The final section describes the solid-state variable-temperature (VT) one- and two-dimensional {sup 13}C cross polarization (CP)/magic angle spinning (MAS) NMR of Hf({eta}{sup 5}-C{sub 5}H{sub 5}){sub 2}({eta}{sup 1}-C{sub 5}H{sub 5}){sub 2}, Zr({eta}{sup 5}-C{sub 5}H{sub 5}){sub 3}({eta}{sup 1}-C

  15. Meridional Variations of C2H2 and C2H6 in Jupiter's Atmosphere from Cassini CIRS Infrared Spectra

    NASA Technical Reports Server (NTRS)

    Nixon, C. A.; Achterberg, R. K.; Conrath, B. J.; Irwin, P. G. J.; Fouchet, T.; Parrish, P. D.; Romani, P. N.; Abbas, M.; LeClair, A.; Strobel, D.

    2004-01-01

    Hydrocarbons such as acetylene (C2H2) and ethane (C2H6) are important tracers in Jupiter's atmosphere, constraining our models of the chemical and dynamical processes. However, our knowledge of the vertical and meridional variations of their abundances has remained sparse. During the flyby of the Cassini spacecraft in December 2000, the Composite Infrared Spectrometer (CIRS) instrument was used to map the spatial variation of emissions from 10-1400 cm(sup -1) (1000-7 microns). In this paper we analyze a zonally-averaged set of CIRS spectra taken at the highest (0.5 cm(sup -1)) resolution, to infer atmospheric temperatures in the stratosphere at 0.5-20 mbar via the v4 band of CH4, and in the troposphere at 150-400 mbar, via the H2 absorption at 600-800 cm(sup -1). Simultaneously, we retrieve the abundances of C2H2 and C2H6 via the v5 and vg bands respectively. Tropospheric absorption and stratospheric emission are highly anti-correlated at the CIRS resolution, introducing a non-uniqueness into the retrievals, such that vertical gradient and column abundance cannot both be found without additional constraints. Assuming profile gradients from photochemical calculations, we show that the column abundance of C2H2 decreases sharply towards the poles by a factor approximately 4, while C2H6 is unchanged in the north and increasing in the south, by a factor approximately 1.8. An explanation for the meridional trends is proposed in terms of a combination of photochemistry and dynamics. Poleward, the decreasing UV flux is predicted to decrease the abundances of C2H2 and C2H6 by factors 2.7 and 3.5 respectively at a latitude 70 deg. However, the lifetime of C2H6 in the stratosphere (5 x 10(exp 9)) is much longer than the dynamical timescale for meridional motions inferred from SL-9 debris (5 x 10(exp 8 s)), and therefore the constant or rising abundance towards high latitudes likely indicates that meridional mixing dominates over photochemical effects. For C2H2, the opposite

  16. TES/Aura L2 Water Vapor (H2O) Limb (TL2H2OLS)

    Atmospheric Science Data Center

    2015-01-30

    TES/Aura L2 Water Vapor (H2O) Limb (TL2H2OLS) News:  TES News ... Level:  L2 Platform:  TES/Aura L2 Water Vapor Spatial Coverage:  27 x 23 km Limb ... Access:  OPeNDAP Parameters:  H2O Water Volume Mixing Radio Precision Vertical Resolution Order ...

  17. First-principles characterization of potassium intercalation in the hexagonal 2H-MoS2

    SciTech Connect

    Andersen, Amity; Kathmann, Shawn M.; Lilga, Michael A.; Albrecht, Karl O.; Hallen, Richard T.; Mei, Donghai

    2012-01-12

    Periodic density functional theory calculations were performed to study the structural and electronic properties of potassium intercalated into hexagonal MoS{sub 2} (2H-MoS{sub 2}). Metallic potassium (K) atoms are incrementally loaded in the hexagonal sites of the interstitial spaces between MoS2 sheets of the 2H-MoS{sub 2} bulk structure generating 2H-KxMoS2 (0.125 {<=} x {<=} 1.0) structures. To accommodate the potassium atoms, the interstitial spacing c parameter in the 2H-MoS{sub 2} bulk expands from 12.816 {angstrom} in 2H-MoS{sub 2} to 16.086 {angstrom} in 2H-K{sub 0.125}MoS{sub 2}. The second lowest potassium loading concentration (K{sub 0.25}MoS{sub 2}) results in the largest interstitial spacing expansion (to c = 16.726 {angstrom}). Our calculations show that there is a small gradual contraction of the interstitial spacing as the potassium loading increases with c = 14.839 {angstrom} for KMoS{sub 2}. This interstitial contraction is correlated with an in-plane expansion of the MoS{sub 2} sheets, which is in good agreement with experimental X-ray diffraction (XRD) measurements. The electronic analysis shows that potassium readily donates its 4s electron to the conduction band of the 2H-K{sub x}MoS{sub 2}, and is largely ionic in character. As a result of the electron donation, the 2H-K{sub x}MoS{sub 2} system changes from a semiconductor to a more metallic system with increasing potassium intercalation. For loadings 0.25 {<=} x {<=} 0.625, triangular Mo-Mo-Mo moieties are prominent and tend to form rhombitrihexagonal motifs. Intercalation of H{sub 2}O molecules that solvate the K atoms is likely to occur in catalytic conditions. The inclusion of two H{sub 2}O molecules per K atom in the K{sub 0.25}MoS{sub 2} structure shows good agreement with XRD measurements.

  18. Towards ferromagnetic quantum criticality in FeGa3 -xGex :71Ga NQR as a zero-field microscopic probe

    NASA Astrophysics Data System (ADS)

    Majumder, M.; Wagner-Reetz, M.; Cardoso-Gil, R.; Gille, P.; Steglich, F.; Grin, Y.; Baenitz, M.

    2016-02-01

    71Ga NQR, magnetization, and specific-heat measurements have been performed on polycrystalline Ge-doped FeGa3 samples. A crossover from an insulator to a correlated local moment metal in the low-doping regime and the evolution of itinerant ferromagnet upon further doping is found. For the nearly critical concentration at the threshold of ferromagnetic order, xC=0.15, 71(1 /T1T ) exhibits a pronounced T-4 /3 power law over two orders of magnitude in temperature, which indicates three-dimensional quantum critical ferromagnetic fluctuations. Furthermore, for the ordered x =0.2 sample (TC≈6 K), 71(1 /T1T ) could be fitted well in the frame of Moriya's self-consistent renormalization theory for weakly ferromagnetic systems with 1 /T1T ˜χ . In contrast to this, the low-doping regime nicely displays local moment behavior where 1 /T1T ˜χ2 is valid. For T →0 , the Sommerfeld ratio γ =(C /T ) is enhanced (70 mJ /mole K2 for x =0.1 ) , which indicates the formation of heavy 3 d electrons.

  19. Hunting for hydrogen: random structure searching and prediction of NMR parameters of hydrous wadsleyite† †Electronic supplementary information (ESI) available: Further information on the structures generated by AIRSS, alternative structural models, supercell calculations, total enthalpies of all computed structures and further information on 1H/2H NMR parameters. Example input and all raw output files from AIRSS and CASTEP NMR calculations are also included. See DOI: 10.1039/c6cp01529h Click here for additional data file.

    PubMed Central

    Moran, Robert F.; McKay, David; Pickard, Chris J.; Berry, Andrew J.; Griffin, John M.

    2016-01-01

    The structural chemistry of materials containing low levels of nonstoichiometric hydrogen is difficult to determine, and producing structural models is challenging where hydrogen has no fixed crystallographic site. Here we demonstrate a computational approach employing ab initio random structure searching (AIRSS) to generate a series of candidate structures for hydrous wadsleyite (β-Mg2SiO4 with 1.6 wt% H2O), a high-pressure mineral proposed as a repository for water in the Earth's transition zone. Aligning with previous experimental work, we solely consider models with Mg3 (over Mg1, Mg2 or Si) vacancies. We adapt the AIRSS method by starting with anhydrous wadsleyite, removing a single Mg2+ and randomly placing two H+ in a unit cell model, generating 819 candidate structures. 103 geometries were then subjected to more accurate optimisation under periodic DFT. Using this approach, we find the most favourable hydration mechanism involves protonation of two O1 sites around the Mg3 vacancy. The formation of silanol groups on O3 or O4 sites (with loss of stable O1–H hydroxyls) coincides with an increase in total enthalpy. Importantly, the approach we employ allows observables such as NMR parameters to be computed for each structure. We consider hydrous wadsleyite (∼1.6 wt%) to be dominated by protonated O1 sites, with O3/O4–H silanol groups present as defects, a model that maps well onto experimental studies at higher levels of hydration (J. M. Griffin et al., Chem. Sci., 2013, 4, 1523). The AIRSS approach adopted herein provides the crucial link between atomic-scale structure and experimental studies. PMID:27020937

  20. Using Magnetic Coupling to Improve the (1)H/(2)H Double Tuned Circuit.

    PubMed

    Taber, Bob; Zens, Albert

    2015-10-01

    We report in this paper an analysis of double-tuned (1)H/(2)H circuits that are capacitively or inductively matched to 50 Ω ports. In this analysis we use a novel new parameter called the circuit fill factor (CFF). It provides a means of characterizing the performance degradation associated with additional inductors in the circuit in addition to circuit losses. This parameter allows for quick and insightful analysis of multiple tuned circuits for efficiency. It is also shown that magnetically coupled double-tuned circuits are less prone to unwanted spurious resonances due to their general symmetry which eliminates multiple ground paths in the circuit.

  1. Meridional Variations of C2H2 and C2H6 in Jupiter's Atmosphere from Cassini CIRS Infrared Spectra

    NASA Technical Reports Server (NTRS)

    Nixon, C. A.; Achterberg, R. K.; Conrath, B. J.; Irwin, P. G. J.; Fouchet, T.; Parrish, P. D.; Abbas, M.; LeClaire, A.; Romani, P. N.; Simon-Miller, A. A.

    2004-01-01

    The abundances of hydrocarbons such as acetylene (C2H2) and ethane (C2H6) in Jupiter's atmosphere are important physical quantities, constraining our models of the chemical and dynamical processes. However, our knowledge of these quantities and their vertical and latitudinal variations has remained sparse. The flyby of the Cassini spacecraft with Jupiter at the end of 2000 provided an excellent opportunity to observe the infrared spectrum with the Composite Infrared Spectrometer (CIRS) instrument, mapping the spatial variation of emissions from 10-1400 cm-1. CIRS spectra taken at the highest resolution (0.5 cm-1) in early December 2000 have been analysed to infer atmospheric temperatures in the stratosphere at 0.5-20 mbar via the v4 of CH4, and in the troposphere at 100-400 mbar, via the hydrogen collision-induced continuum absorption at 600-800 cm. Simultaneously, we have searched for meridional abundance variations in C2H2 and C2H6 via the v5 and vg bands respectively. Tropospheric absorption and stratospheric emission are highly anti-correlated at the CIM resolution, introducing a non-uniqueness into the retrievals, which means that vertical gradient and column abundance cannot be simultaneously found without additional constraints. If we assume the profile shapes from photochemical model calculations, we show that the column abundance of C2H2 must decrease sharply towards the poles, while C2H6 is constant or slightly increasing. The relevance of these results to current photochemical and dynamical knowledge of Jupiter's atmosphere is discussed.

  2. Evaluation of an electrochemical N2/H2 gas separator

    NASA Technical Reports Server (NTRS)

    Marshall, R. D.; Wynveen, R. A.; Carlson, J. N.

    1973-01-01

    A program was successfully completed to evaluate an electrochemical nitrogen/hydrogen (N2/H2) separator for use in a spacecraft nitrogen (N2) generator. Based on the technical data obtained a N2/H2 separator subsystem consisting of an organic polymer gas permeator first stage and an electrochemical second and third stage was estimated to have the lowest total spared equivalent weight, 257 kg (566 lb), for a 15 lb/day N2 generation rate. A pre-design analysis of the electrochemical N2/H2 separator revealed that its use as a first stage resulted in too high a power requirement to be competitive with the organic polymer membrane and the palladium-silver membrane separation methods. As a result, program emphasis was placed on evaluating the electrochemical. A parametric test program characterized cell performance and established second- and third-stage electrochemical N2/H2 separator operating conditions. A design verification test was completed on the second and third stages. The second stage was then successfully endurance tested for 200 hours.

  3. New Evidences for the observation of the Higgs boson in the Superconductor 2H-NbSe2

    NASA Astrophysics Data System (ADS)

    Measson, Marie-Aude; Clair, Bertrand; Gallais, Yann; Cazayous, Maximilien; Rodière, Pierre; Cario, Laurent; Sacuto, Alain; Squap Team; Systèmes À Fortes Corrélations Électroniques Collaboration; Imn Collaboration

    2013-03-01

    We provide here new evidences for the observation of the amplitude mode of the superconducting order parameter, the so-called Higgs Boson, in 2H-NbSe2. We report quantitatively comparative electronic Raman measurements on the dichalcogenides 2H-NbSe2, whose superconductivity (SC) coexists with a charge density wave order (CDW), and 2H-NbS2, which exhibits only the SC. A SC pair breaking peak develops below Tc in 2H-NbS2 whose intensity is much smaller than the peak associated with the SC in 2H-NbSe2. Thus, the peak observed in 2H-NbSe2 below Tc certainly doesn't get its intensity only from the superconducting condensate. Moreover, we measure precisely a spectral weight transfer from the amplitude mode of the CDW to the SC peak in 2H-NbSe2, versus decreasing temperature. The total spectral weight for both peaks is constant within +/- 3 % . This result is consistent with the theory of the observation of a Higgs mode thanks to its coupling with an amplitudon developed by Littlewood and Varma. This result complements what was firstly observed by Sooryakumar et Klein under magnetic field.

  4. The infrared spectra of C2H4(+) and C2H3 trapped in solid neon.

    PubMed

    Jacox, Marilyn E; Thompson, Warren E

    2011-02-14

    When a mixture of ethylene in a large excess of neon is codeposited at 4.3 K with a beam of neon atoms that have been excited in a microwave discharge, two groups of product absorptions appear in the infrared spectrum of the deposit. Similar studies using C(2)H(4)-1-(13)C and C(2)D(4) aid in product identification. The first group of absorptions arises from a cation product which possesses two identical carbon atoms, giving the first infrared identification of two fundamentals of C(2)H(4)(+) and three of C(2)D(4)(+), as well as a tentative identification of ν(9) of C(2)H(4)(+). The positions of these absorptions are consistent with the results of density functional calculations and of earlier photoelectron studies. All of the members of the second group of product absorptions possess two inequivalent carbon atoms. They are assigned to the vinyl radical, C(2)H(3), and to C(2)D(3), in agreement with other recent infrared assignments for those species.

  5. Observations of CH4, C2H6, and C2H2 in the stratosphere of Jupiter.

    PubMed

    Sada, P V; Bjoraker, G L; Jennings, D E; McCabe, G H; Romani, P N

    1998-12-01

    We have performed high-resolution spectral observations at mid-infrared wavelengths of CH4 (8.14 micrometers), C2H6 (12.16 micrometers), and C2H2 (13.45 micrometers) on Jupiter. These emission features probe the stratosphere of the planet and provide information on the carbon-based photochemical processes taking place in that region of the atmosphere. The observations were performed using our cryogenic echelle spectrometer CELESTE, in conjunction with the McMath-Pierce 1.5-m solar telescope between November 1994 and February 1995. We used the methane observations to derive the temperature profile of the jovian atmosphere in the 1-10 mbar region of the stratosphere. This profile was then used in conjunction with height-dependent mixing ratios of each hydrocarbon to determine global abundances for ethane and acetylene. The resulting mixing ratios are 3.9(+1.9)(-1.3) x 10(-6) for C2H6 (5 mbar pressure level), and 2.3 +/- 0.5 x 10(-8) for C2H2 (8 mbar pressure level), where the quoted uncertainties are derived from model variations in the temperature profile which match the methane observation uncertainties. PMID:11878354

  6. Refractive index and birefringence of 2H silicon carbide

    NASA Technical Reports Server (NTRS)

    Powell, J. A.

    1972-01-01

    The refractive indices of 2H SiC were measured over the wavelength range 435.8 to 650.9 nm by the method of minimum deviation. At the wavelength lambda = 546.1 nm, the ordinary index n sub 0 was 2.6480 and the extraordinary index n sub e was 2.7237. The estimated error (standard deviation) in the measured values is 0.0006 for n sub 0 and 0.0009 for n sub e. The experimental data were curve fitted to the Cauchy equation for the index of refraction as a function of wavelength. The birefringence of 2H SiC was found to vary from 0.0719 at lambda = 650.9 nm to 0.0846 at lambda = 435.8 nm.

  7. Charge transfer in energetic Li^2+ - H collisions

    NASA Astrophysics Data System (ADS)

    Mancev, I.

    2008-07-01

    The total cross sections for charge transfer in Li^2+ - H collisions have been calculated, using the four-body first Born approximation with correct boundary conditions (CB1-4B) and four-body continuum distorted wave method (CDW-4B) in the energy range 10 - 5000 keV/amu. Present results call for additional experimental data at higher impact energies than presently available.

  8. Thermodynamic properties of solid C2H4

    PubMed Central

    Ma, Shao-mu; Eyring, Henry

    1979-01-01

    The significant structures procedure of liquids has been used to calculate the thermodynamic properties of solid C2H4. Two degeneracy terms were used to describe the behavior in the vicinities of the two phase transitions. The calculated entropy and specific heat agree well with experimental results from a few kelvins to the melting point. Less satisfactory agreement is obtained for compressibility and thermal expansion coefficients. This simple model represents surprisingly well the phase transitions in the solid state. PMID:16592659

  9. C(2)H(4) metabolism in morning glory flowers.

    PubMed

    Beyer, E M; Sundin, O

    1978-06-01

    Flowers of Ipomoea tricolor Cav. (cv. Heavenly Blue) were cut at various stages of development and evaluated for their ability to metabolize ethylene. Freshly cut buds or flowers were treated in glass containers for 8 hours with 6 mul/liter of highly purified (14)C(2)H(4). Following removal of dissolved (14)C(2)H(4), radioactivity was determined for the different flower tissues and trappd CO(2). (14)C(2)H(4) oxidation to (14)CO(2) and tissue incorporation occurred at very low to nondetectable levels 2 to 3 days prior to flower opening. About 1 day prior to full bloom, just at the time when mature buds become responsive to ethylene (Kende and Hanson, Plant Physiol 1976, 57: 523-527), there was a dramatic increase in the capacity of the buds to oxidize (14)C(2)H(4) to (14)CO(2). This activity continued to increase until the flower was fully opened reaching a peak activity of 2,500 dpm per three flowers per 8 hours. It then declined as the flower closed and rapidly senesced. A similar but smaller peak occurred in tissue incorporation and it was followed by a second peak during late flower senescence. This first peak in tissue incorporation and the dramatic peak in ethylene oxidation slightly preceded a large peak of natural ethylene production which accompanied flower senescence. The ethylene metabolism observed was clearly dependent on cellular metabolism and did not involve microorganisms since heat killing destroyed this activity and badly contaminated heat-killed flowers were unable to metabolize ethylene.

  10. The distribution of ND2H in LDN 1689N

    NASA Astrophysics Data System (ADS)

    Gerin, M.; Lis, D. C.; Philipp, S.; Güsten, R.; Roueff, E.; Reveret, V.

    2006-08-01

    Aims.Finding tracers of the innermost regions of prestellar cores is important for understanding their chemical and dynamical evolution before the onset of gravitational collapse. While classical molecular tracers, such as CO and CS, have been shown to be strongly depleted in cold, dense gas by condensation on grain mantles, it has been a subject of discussion to what extent nitrogen-bearing species, such as ammonia, are affected by this process. As deuterium fractionation is efficient in cold, dense gas, deuterated species are excellent tracers of prestellar cores. A comparison of the spatial distribution of neutral and ionized deuterated species with the dust continuum emission can thus provide important insights into the physical and chemical structure of such regions. Methods: .We study the spatial distribution of the ground-state 335.5 GHz line of ND2H in LDN 1689N, using APEX, and compare it with the distribution of the DCO+(3-2) line, as well as the 350 μm dust continuum emission observed with the SHARC II bolometer camera at CSO. Results: .While the distribution of the ND2H emission in LDN 1689N is generally similar to that of the 350 μm dust continuum emission, the peak of the ND2H emission is offset by ~10'' to the East from the dust continuum and DCO+ emission peak. ND2H and ND3 share the same spatial distribution. The observed offset between the ND2H and DCO+ emission is consistent with the hypothesis that the deuterium peak in LDN 1689N is an interaction region between the outflow shock from IRAS 16293-2422 and the dense ambient gas. We detect the J = 4 → 3 line of H13CO+ at 346.998 GHz in the image side band serendipitously. This line shows the same spatial distribution as DCO+(3-2), and peaks close to the 350 μm emission maximum which provides further support for the shock interaction scenario.

  11. Measurement of regional cerebral blood flow in cat brain using intracarotid 2H2O and 2H NMR imaging

    SciTech Connect

    Detre, J.A.; Subramanian, V.H.; Mitchell, M.D.; Smith, D.S.; Kobayashi, A.; Zaman, A.; Leigh, J.S. Jr. )

    1990-05-01

    Cerebral blood flow (CBF) was measured in cat brain in vivo at 2.7 T using 2H NMR to monitor the washout of deuterated saline injected into both carotid arteries via the lingual arteries. In anesthetized cats, global CBF varied directly with PaCO{sub 2} over a range of 20-50 mm Hg, and the corresponding global CBF values ranged from 25 to 125 ml.100 g-1.min-1. Regional CBF was measured in a 1-cm axial section of cat brain using intracarotid deuterated saline and gradient-echo 2H NMR imaging. Blood flow images with a maximum pixel resolution of 0.3 x 0.3 x 1.0 cm were generated from the deuterium signal washout at each pixel. Image derived values for CBF agreed well with other determinations, and decreased significantly with hypocapnia.

  12. The rate of the reaction between C2H and C2H2 at interstellar temperatures.

    PubMed

    Herbst, E; Woon, D E

    1997-11-01

    The reaction between the radical C2H and the stable hydrocarbon C2H2 is one of the simplest neutral-neutral hydrocarbon reactions in chemical models of dense interstellar clouds and carbon-rich circumstellar shells. Although known to be rapid at temperatures > or = 300 K, the reaction has yet to be studied at lower temperatures. We present here ab initio calculations of the potential surface for this reaction and dynamical calculations to determine its rate at low temperature. Despite a small potential barrier in the exit channel, the calculated rate is large, showing that this reaction and, most probably, more complex analogs contribute to the formation of complex organic molecules in low-temperature sources.

  13. The rate of the reaction between C2H and C2H2 at interstellar temperatures

    NASA Technical Reports Server (NTRS)

    Herbst, E.; Woon, D. E.

    1997-01-01

    The reaction between the radical C2H and the stable hydrocarbon C2H2 is one of the simplest neutral-neutral hydrocarbon reactions in chemical models of dense interstellar clouds and carbon-rich circumstellar shells. Although known to be rapid at temperatures > or = 300 K, the reaction has yet to be studied at lower temperatures. We present here ab initio calculations of the potential surface for this reaction and dynamical calculations to determine its rate at low temperature. Despite a small potential barrier in the exit channel, the calculated rate is large, showing that this reaction and, most probably, more complex analogs contribute to the formation of complex organic molecules in low-temperature sources.

  14. CO2/H(+) sensing: peripheral and central chemoreception.

    PubMed

    Lahiri, Sukhamay; Forster, Robert E

    2003-10-01

    H(+) is maintained constant in the internal environment at a given body temperature independent of external environment according to Bernard's principle of "milieu interieur". But CO2 relates to ventilation and H(+) to kidney. Hence, the title of the chapter. In order to do this, sensors for H(+) in the internal environment are needed. The sensor-receptor is CO2/H(+) sensing. The sensor-receptor is coupled to integrate and to maintain the body's chemical environment at equilibrium. This chapter dwells on this theme of constancy of H(+) of the blood and of the other internal environments. [H(+)] is regulated jointly by respiratory and renal systems. The respiratory response to [H(+)] originates from the activities of two groups of chemoreceptors in two separate body fluid compartments: (A) carotid and aortic bodies which sense arterial P(O2) and H(+); and (B) the medullary H(+) receptors on the ventrolateral medulla of the central nervous system (CNS). The arterial chemoreceptors function to maintain arterial P(O2) and H(+) constant, and medullary H(+) receptors to maintain H(+) of the brain fluid constant. Any acute change of H(+) in these compartments is taken care of almost instantly by pulmonary ventilation, and slowly by the kidney. This general theme is considered in Section 1. The general principles involving cellular CO2 reactions mediated by carbonic anhydrase (CA), transport of CO2 and H(+) are described in Section 2. Since the rest of the chapter is dependent on these key mechanisms, they are given in detail, including the role of Jacobs-Stewart Cycle and its interaction with carbonic anhydrase. Also, this section deals briefly with the mechanisms of membrane depolarization of the chemoreceptor cells because this is one mechanism on which the responses depend. The metabolic impact of endogenous CO2 appears in the section with a historical twist, in the context of acclimatization to high altitude (Section 3). Because low P(O2) at high altitude stimulates

  15. Theoretical kinetics of O + C2H4

    DOE PAGES

    Li, Xiaohu; Jasper, Ahren W.; Zádor, Judit; Miller, James A.; Klippenstein, Stephen J.

    2016-06-01

    The reaction of atomic oxygen with ethylene is a fundamental oxidation step in combustion and is prototypical of reactions in which oxygen adds to double bonds. For 3O+C2H4 and for this class of reactions generally, decomposition of the initial adduct via spin-allowed reaction channels on the triplet surface competes with intersystem crossing (ISC) and a set of spin-forbidden reaction channels on the ground-state singlet surface. The two surfaces share some bimolecular products but feature different intermediates, pathways, and transition states. In addition, the overall product branching is therefore a sensitive function of the ISC rate. The 3O+C2H4 reaction has beenmore » extensively studied, but previous experimental work has not provided detailed branching information at elevated temperatures, while previous theoretical studies have employed empirical treatments of ISC. Here we predict the kinetics of 3O+C2H4 using an ab initio transition state theory based master equation (AITSTME) approach that includes an a priori description of ISC. Specifically, the ISC rate is calculated using Landau–Zener statistical theory, consideration of the four lowest-energy electronic states, and a direct classical trajectory study of the product branching immediately after ISC. The present theoretical results are largely in good agreement with existing low-temperature experimental kinetics and molecular beam studies. Good agreement is also found with past theoretical work, with the notable exception of the predicted product branching at elevated temperatures. Above ~1000 K, we predict CH2CHO+H and CH2+CH2O as the major products, which differs from the room temperature preference for CH3+HCO (which is assumed to remain at higher temperatures in some models) and from the prediction of a previous detailed master equation study.« less

  16. Near-Infrared Spectroscopy of Ethynyl Radical, C2H

    NASA Astrophysics Data System (ADS)

    Le, Anh T.; Hall, Gregory; Sears, Trevor

    2016-06-01

    The ethynyl radical, C_2H, is a reactive intermediate important in various combustion processes and also widely observed in the interstellar medium. In spite of extensive previous spectroscopic studies, the characterization of the near infrared transitions from the tilde{X}2Σ+ state to the mixed vibrational overtone and tilde{A}2Π states is incomplete. A strong band of C_2H at 7064 cm-1 was first observed in a neon matrix and assigned as the tilde{A}2Π(002)1 - tilde{X}2Σ+ transition by Forney et al. Subsequent theoretical work of Tarroni and Carter attributed the strong absorptions in this region to transitions terminating in two upper states, each a mixture of vibrationally excited tilde{X} states and different zero-order tilde{A}-state bending levels: a 2Σ+ symmetry combination of tilde{X}(0,20,3) and tilde{A}(0,3,0)0κ and a 2Π symmetry combination of tilde{X}(0,31,3) and tilde{A}(0,0,2)1. Transitions to them from the zero point level of the tilde{X} state are calculated to differ in energy by less than 10 cm-1 and to be within a factor of two in intensity. Diode laser transient absorption was used to record Doppler-limited spectra between 7020 and 7130 cm-1, using 193 nm photolysis of CF_3C_2H as a source of C_2H. Two interleaved, rotationally resolved bands were observed, consistent with a 2Σ - 2Σ transition at 7088 cm-1 and a 2Π - 2Σ transition at 7108 cm-1, in good accord with the Tarroni and Carter calculation. Progress on the assignment and fitting of the spectra will be reported. Acknowledgements: Work at Brookhaven National Laboratory was carried out under Contract No. DE-SC0012704 with the U.S. Department of Energy, Office of Science, and supported by its Division of Chemical Sciences, Geosciences, and Biosciences. D. Forney, M.E. Jacox, and W.E. Thompson, J. Mol. Spectrosc. 170, 178 (1995). R. Tarroni and S. Carter, Mol. Phys. 102, 2167 (2004)

  17. Synthesis Of 2h- And 13c-Substituted Dithanes

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

    2004-05-04

    The present invention is directed to labeled compounds, [2-.sup.13 C]dithane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to processes of preparing [2-.sup.13 C]dithane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to labeled compounds, e.g., [.sup.2 H.sub.1-2, .sup.13 C]methanol (arylthio)-, acetates wherein the .sup.13 C atom is directly bonded to exactly one or two deuterium atoms.

  18. Synthesis of 2H- and 13C-substituted dithanes

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

    2003-01-01

    The present invention is directed to labeled compounds, [2-.sup.13 C]dithiane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to processes of preparing [2-.sup.13 C]dithiane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to labeled compounds, e.g., [.sup.2 H.sub.1-2, .sup.13 C]methanol (arylthio)-, acetates wherein the .sup.13 C atom is directly bonded to exactly one or two deuterium atoms.

  19. Analytical Formulae of Molecular Ion Abundances and the N2H+ Ring in Protoplanetary Disks

    NASA Astrophysics Data System (ADS)

    Aikawa, Yuri; Furuya, Kenji; Nomura, Hideko; Qi, Chunhua

    2015-07-01

    We investigate the chemistry of ion molecules in protoplanetary disks, motivated by the detection of the N2H+ ring around TW Hya. While the ring inner radius coincides with the CO snow line, it is not apparent why N2H+ is abundant outside the CO snow line in spite of the similar sublimation temperatures of CO and N2. Using the full gas-grain network model, we reproduced the N2H+ ring in a disk model with millimeter grains. The chemical conversion of CO and N2 to less volatile species (sink effect hereinafter) is found to affect the N2H+ distribution. Since the efficiency of the sink depends on various parameters such as activation barriers of grain-surface reactions, which are not well constrained, we also constructed the no-sink model; the total (gas and ice) CO and N2 abundances are set constant, and their gaseous abundances are given by the balance between adsorption and desorption. Abundances of molecular ions in the no-sink model are calculated by analytical formulae, which are derived by analyzing the full-network model. The N2H+ ring is reproduced by the no-sink model, as well. The 2D (R-Z) distribution of N2H+, however, is different among the full-network model and no-sink model. The column density of N2H+ in the no-sink model depends sensitively on the desorption rate of CO and N2 and the cosmic-ray flux. We also found that N2H+ abundance can peak at the temperature slightly below the CO sublimation, even if the desorption energies of CO and N2 are the same.

  20. NQR investigation of pressure-induced charge transfer in oxygen-deficient YBa{sub 2}Cu{sub 3}O{sub 7-{delta}} ({delta} = 0.38)

    SciTech Connect

    Reyes, A.P.; Ahrens, E.T.; Hammel, P.C.; Heffner, R.H.; Takigawa, M.

    1992-03-01

    Measurements of the pressure dependence of {sup 63}Cu nuclear quadrupole frequency in YBa{sub 2}Cu{sub 3}O{sub 6.62} from ambient pressure up to 1.5 GPa at 4k have been performed. {Tc} was found to increase with pressure: d{Tc}/dp {approximately} 5 K/GPa. All observed NQR lines are linear in pressure: dln{nu}{sub Q}/dp=z. We found positive z for the empty chain sites, consistent with ionic (Cu{sup 1+}) configuration in which the atom simply feels a squeezing lattice. Planar coppers close to the empty chains have positive z, while those that are close to full chains have z {approximately} 0. We present an analysis of the NQR result on the basis of the charge transfer model in which the mobile charges migrate from the chain to the plane sites. We deduced that a transfer of 0.021 holes to the O(2,3) sites would explain the result in YBa{sub 2}Cu{sub 3}O{sub 6.62}, whereas only 0.007 holes transfer in fully oxygenated YBa{sub 2}Cu{sub 3}O{sub 7}.

  1. Electrochemical oxidation of 1H,1H,2H,2H-perfluorooctane sulfonic acid (6:2 FTS) on DSA electrode: operating parameters and mechanism.

    PubMed

    Zhuo, Qiongfang; Li, Xiang; Yan, Feng; Yang, Bo; Deng, Shubo; Huang, Jun; Yu, Gang

    2014-08-01

    The 6:2 FTS was the substitute for perfluorooctane sulfonate (PFOS) in the chrome plating industry in Japan. Electrochemical oxidation of 6:2 FTS was investigated in this study. The degradabilities of PFOS and 6:2 FTS were tested on the Ti/SnO₂-Sb₂O₅-Bi₂O₃ anode. The effects of current density, potential, and supporting electrolyte on the degradation of 6:2 FTS were evaluated. Experimental results showed that 6:2 FTS was more easily degraded than PFOS on the Ti/SnO₂-Sb₂O₅-Bi₂O₃ anode. At a low current density of 1.42 mA/cm², 6:2 FTS was not degraded on Ti/SnO₂-Sb₂O₅-Bi₂O₃, while the degradation ratio increased when the current density ranged from 4.25 to 6.80 mA/cm². The degradation of 6:2 FTS at current density of 6.80 mA/cm² followed pseudo first-order kinetics with the rate constant of 0.074 hr⁻¹. The anodic potential played an important role in the degradation of 6:2 FTS, and the pseudo first-order rate constants increased with the potential. The surface of Ti/SnO₂-Sb₂O₅-Bi₂O₃ was contaminated after electrolysis at constant potential of 3V, while the fouling phenomenon was not observed at 5V. The fouled anode could be regenerated by incinerating at 600°C. The intermediates detected by ultra-performance liquid chromatography coupled with a triple-stage quadrupole mass spectrometer (UPLC-MS/MS) were shorter chain perfluorocarboxylic acids. The 6:2 FTS was first attacked by hydroxyl radical, and then formed perfluorinated carboxylates, which decarboxylated and removed CF2 units to yield shorter-chain perfluorocarboxylic acids.

  2. Investigation of multiaxial molecular dynamics by 2H MAS NMR spectroscopy.

    PubMed

    Kristensen, J H; Hoatson, G L; Vold, R L

    1998-11-01

    The technique of 2H MAS NMR spectroscopy is presented for the investigation of multiaxial molecular dynamics. To evaluate the effects of discrete random reorientation a Lie algebraic formalism based on the stochastic Liouville-von Neumann equation is developed. The solution to the stochastic Liouville-von Neumann equation is obtained both in the presence and absence of rf irradiation. This allows effects of molecular dynamics to be evaluated during rf pulses and extends the applicability of the formalism to arbitrary multiple pulse experiments. Theoretical methods are presented for the description of multiaxial dynamics with particular emphasis on the application of vector parameters to represent molecular rotations. Numerical time and powder integration algorithms are presented that are both efficient and easy to implement computationally. The applicability of 2H MAS NMR spectroscopy for investigating molecular dynamics is evaluated from theoretical spectra. To demonstrate the potential of the technique the dynamics of thiourea-2H4 is investigated experimentally. From a series of variable temperature MAS and quadrupole echo spectra it has been found that the dynamics can be described by composite rotation about the CS and CN bonds. Both experiments are sensitive to the fast CS rotation which is shown to be described by the Arrhenius parameters E(CS) = 46.4 +/- 2.3 kJ mol(-1) and ln(A(CS))= 32.6 +/- 0.9. The MAS experiment represents a significant improvement by simultaneously allowing the dynamics of the slow CN rotation to be fully characterized in terms of E(CN) = 56.3 +/- 3.4 kJ mol(-1) and ln(A(CN)) = 25.3 +/- 1.1. PMID:9875600

  3. The ultraviolet spectrum of Herbig-Haro object 2H

    NASA Technical Reports Server (NTRS)

    Brugel, E. W.; Seab, C. G.; Shull, J. M.

    1982-01-01

    IUE spectra of Herbig-Haro object 2H are presented. The spectra show a strong 'excess' UV continuum and prominent emission lines of C, N, O, Si, Mg, and possibly Al. The continuum, F(lambda), exhibits a turnover shortward of about 1450 A, confirming for the first time the H0 two-photon nature of the emission source. A possible absorption feature near 1680 A, which could result from a new grain or molecular constituent in these protostellar objects is also noted. Recently computed models of steady shocks into partially ionized gas reproduce the two-photon spectral shape, but its observed intensity relative to H-beta and the Balmer continuum is anomalously high. It is suggested that a range of shock velocities, 70-100 km/s, or nonsteady, 'truncated' shocks may be responsible. Future high-sensitivity UV observations of HH objects may be used to probe grain extinction curves in star-forming regions.

  4. Vibrational and Rotational Spectroscopy of CD_2H^+

    NASA Astrophysics Data System (ADS)

    Asvany, Oskar; Jusko, Pavol; Brünken, Sandra; Schlemmer, Stephan

    2016-06-01

    The lowest rotational levels (J=0-5) of the CD_2H^+ ground state have been probed by high-resolution rovibrational and pure rotational spectroscopy in a cryogenic 22-pole ion trap. For this, the ν_1 rovibrational band has been revisited, detecting 107 transitions, among which 35 are new. The use of a frequency comb system allowed to measure the rovibrational transitions with high precision and accuracy, typically better than 1 MHz. The high precision has been confirmed by comparing combination differences in the ground and vibrationally excited state. For the ground state, this allowed for equally precise predictions of pure rotational transitions, 24 of which have been measured directly by a novel IR - mm-wave double resonance method. M.-F. Jagod et al, J. Molec. Spectrosc. 153, 666, 1992 S. Gartner et al, J. Phys. Chem. A 117, 9975, 2013

  5. Detailed Studies of Hydrocarbon Radicals: C2H Dissociation

    SciTech Connect

    Wittig, Curt

    2014-10-06

    A novel experimental technique was examined whose goal was the ejection of radical species into the gas phase from a platform (film) of cold non-reactive material. The underlying principle was one of photo-initiated heat release in a stratum that lies below a layer of CO2 or a layer of amorphous solid water (ASW) and CO2. A molecular precursor to the radical species of interest is deposited near or on the film's surface, where it can be photo-dissociated. It proved unfeasible to avoid the rampant formation of fissures, as opposed to large "flakes." This led to many interesting results, but resulted in our aborting the scheme as a means of launching cold C2H radical into the gas phase. A journal article resulted that is germane to astrophysics but not combustion chemistry.

  6. 2H NMR studies of supercooled and glassy aspirin

    NASA Astrophysics Data System (ADS)

    Nath, R.; Nowaczyk, A.; Geil, B.; Bohmer, R.

    2007-11-01

    Acetyl salicylic acid, deuterated at the methyl group, was investigated using 2H-NMR in its supercooled and glassy states. Just above the glass transition temperature the molecular reorientations were studied using stimulated-echo spectroscopy and demonstrated a large degree of similarity with other glass formers. Deep in the glassy phase the NMR spectra look similar to those reported for the crystal [A. Detken, P. Focke, H. Zimmermann, U. Haeberlen, Z. Olejniczak, Z. T. Lalowicz, Z. Naturforsch. A 50 (1995) 95] and below 20 K they are indicative for rotational tunneling with a relatively large tunneling frequency. Measurements of the spin-lattice relaxation times for temperatures below 150 K reveal a broad distribution of correlation times in the glass. The dominant energy barrier characterizing the slow-down of the methyl group is significantly smaller than the well defined barrier in the crystal.

  7. Doping dependent plasmon dispersion in 2 H -transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Müller, Eric; Büchner, Bernd; Habenicht, Carsten; König, Andreas; Knupfer, Martin; Berger, Helmuth; Huotari, Simo

    2016-07-01

    We report the behavior of the charge carrier plasmon of 2 H -transition metal dichalcogenides (TMDs) as a function of intercalation with alkali metals. Intercalation and concurrent doping of the TMD layers have a substantial impact on plasmon energy and dispersion. While the plasmon energy shifts are related to the intercalation level as expected within a simple homogeneous electron gas picture, the plasmon dispersion changes in a peculiar manner independent of the intercalant and the TMD materials. Starting from a negative dispersion, the slope of the plasmon dispersion changes sign and grows monotonously upon doping. Quantitatively, the increase of this slope depends on the orbital character (4 d or 5 d ) of the conduction bands, which indicates a decisive role of band structure effects on the plasmon behavior.

  8. 2H and 18O Freshwater Isoscapes of Scotland

    NASA Astrophysics Data System (ADS)

    Meier-Augenstein, Wolfram; Hoogewerff, Jurian; Kemp, Helen; Frew, Danny

    2013-04-01

    Scotland's freshwater lochs and reservoirs provide a vital resource for sustaining biodiversity, agriculture, food production as well as for human consumption. Regular monitoring of freshwaters by the Scottish Environment Protection Agency (SEPA) fulfils legislative requirements with regards to water quality but new scientific methods involving stable isotope analysis present an opportunity combining these mandatory monitoring schemes with fundamental research to inform and deliver on current and nascent government policies [1] through gaining a greater understanding of Scottish waters and their importance in the context of climate change, environmental sustainability and food security. For example, 2H and 18O isoscapes of Scottish freshwater could be used to underpin research and its applications in: • Climate change - Using longitudinal changes in the characteristic isotope composition of freshwater lochs and reservoirs as proxy, isoscapes will provide a means to assess if and how changes in temperature and weather patterns might impact on precipitation patterns and amount. • Scottish branding - Location specific stable isotope signatures of Scottish freshwater have the potential to be used as a tool for provenancing and thus protecting premium Scottish produce such as Scottish beef, Scottish soft fruit and Scottish Whisky. During 2011 and 2012, with the support of SEPA more than 110 samples from freshwater lochs and reservoirs were collected from 127 different locations across Scotland including the Highlands and Islands. Here we present the results of this sampling and analysis exercise isotope analyses in form of 2H and 18O isoscapes with an unprecedented grid resolution of 26.5 × 26.5 km (or 16.4 × 16.4 miles). [1] Adaptation Framework - Adapting Our Ways: Managing Scotland's Climate Risk (2009): Scotland's Biodiversity: It's in Your Hands - A strategy for the conservation and enhancement of biodiversity in Scotland (2005); Recipe For Success - Scotland

  9. Probing perturbation of bovine lung surfactant extracts by albumin using DSC and 2H-NMR.

    PubMed

    Nag, Kaushik; Keough, Kevin M W; Morrow, Michael R

    2006-05-15

    Lung surfactant (LS), a lipid-protein mixture, forms films at the lung air-water interface and prevents alveolar collapse at end expiration. In lung disease and injury, the surface activity of LS is inhibited by leakage of serum proteins such as albumin into the alveolar hypophase. Multilamellar vesicular dispersions of a clinically used replacement, bovine lipid extract surfactant (BLES), to which (2% by weight) chain-perdeuterated dipalmitoylphosphatidycholine (DPPG mixtures-d(62)) had been added, were studied using deuterium-NMR spectroscopy ((2)H-NMR) and differential scanning calorimetry (DSC). DSC scans of BLES showed a broad gel to liquid-crystalline phase transition between 10-35 degrees C, with a temperature of maximum heat flow (T(max)) around 27 degrees C. Incorporation of the DPPC-d(62) into BLES-reconstituted vesicles did not alter the T(max) or the transition range as observed by DSC or the hydrocarbon stretching modes of the lipids observed using infrared spectroscopy. Transition enthalpy change and (2)H-NMR order parameter profiles were not significantly altered by addition of calcium and cholesterol to BLES. (2)H-NMR spectra of the DPPC-d(62) probes in these samples were characteristic of a single average lipid environment at all temperatures. This suggested either continuous ordering of the bilayer through the transition during cooling or averaging of the DPPC-d(62) environment by rapid diffusion between small domains on a short timescale relative to that characteristic of the (2)H-NMR experiment. Addition of 10% by weight of soluble bovine serum albumin (1:0.1, BLES/albumin, dry wt/wt) broadened the transition slightly and resulted in the superposition of (2)H-NMR spectral features characteristic of coexisting fluid and ordered phases. This suggests the persistence of phase-separated domains throughout the transition regime (5-35 degrees C) of BLES with albumin. The study suggests albumin can cause segregation of protein bound-lipid domains in

  10. Probing Perturbation of Bovine Lung Surfactant Extracts by Albumin using DSC and 2H-NMR

    PubMed Central

    Nag, Kaushik; Keough, Kevin M. W.; Morrow, Michael R.

    2006-01-01

    Lung surfactant (LS), a lipid-protein mixture, forms films at the lung air-water interface and prevents alveolar collapse at end expiration. In lung disease and injury, the surface activity of LS is inhibited by leakage of serum proteins such as albumin into the alveolar hypophase. Multilamellar vesicular dispersions of a clinically used replacement, bovine lipid extract surfactant (BLES), to which (2% by weight) chain-perdeuterated dipalmitoylphosphatidycholine (DPPG mixtures-d62) had been added, were studied using deuterium-NMR spectroscopy (2H-NMR) and differential scanning calorimetry (DSC). DSC scans of BLES showed a broad gel to liquid-crystalline phase transition between 10–35°C, with a temperature of maximum heat flow (Tmax) around 27°C. Incorporation of the DPPC-d62 into BLES-reconstituted vesicles did not alter the Tmax or the transition range as observed by DSC or the hydrocarbon stretching modes of the lipids observed using infrared spectroscopy. Transition enthalpy change and 2H-NMR order parameter profiles were not significantly altered by addition of calcium and cholesterol to BLES. 2H-NMR spectra of the DPPC-d62 probes in these samples were characteristic of a single average lipid environment at all temperatures. This suggested either continuous ordering of the bilayer through the transition during cooling or averaging of the DPPC-d62 environment by rapid diffusion between small domains on a short timescale relative to that characteristic of the 2H-NMR experiment. Addition of 10% by weight of soluble bovine serum albumin (1:0.1, BLES/albumin, dry wt/wt) broadened the transition slightly and resulted in the superposition of 2H-NMR spectral features characteristic of coexisting fluid and ordered phases. This suggests the persistence of phase-separated domains throughout the transition regime (5–35°C) of BLES with albumin. The study suggests albumin can cause segregation of protein bound-lipid domains in surfactant at NMR timescales (10−5 s

  11. Ab initio study of {sup 2}H(d,{gamma}){sup 4}He, {sup 2}H(d,p){sup 3}H, and {sup 2}H(d,n){sup 4}He reactions and the tensor force

    SciTech Connect

    Arai, K.; Aoyama, S.; Suzuki, Y.; Descouvemont, P.; Baye, D.

    2012-11-12

    The {sup 2}H(d,p){sup 3}H, {sup 2}H(d,n){sup 3}He, and {sup 2}H(d,{gamma}){sup 4}He reactions at low energies are studied with realistic nucleon-nucleon interactions in an ab initio approach. The obtained astrophysical S-factors are all in very good agreement with experiment. The most important channels for both transfer and radiative capture are all found to dominate thanks to the tensor force.

  12. Site-resolved 2H relaxation experiments in solid materials by global line-shape analysis of MAS NMR spectra

    NASA Astrophysics Data System (ADS)

    Lindh, E. L.; Stilbs, P.; Furó, I.

    2016-07-01

    We investigate a way one can achieve good spectral resolution in 2H MAS NMR experiments. The goal is to be able to distinguish between and study sites in various deuterated materials with small chemical shift dispersion. We show that the 2H MAS NMR spectra recorded during a spin-relaxation experiment are amenable to spectral decomposition because of the different evolution of spectral components during the relaxation delay. We verify that the results are robust by global least-square fitting of the spectral series both under the assumption of specific line shapes and without such assumptions (COmponent-REsolved spectroscopy, CORE). In addition, we investigate the reliability of the developed protocol by analyzing spectra simulated with different combinations of spectral parameters. The performance is demonstrated in a model material of deuterated poly(methacrylic acid) that contains two 2H spin populations with similar chemical shifts but different quadrupole splittings. In 2H-exchanged cellulose containing two 2H spin populations with very similar chemical shifts and quadrupole splittings, the method provides new site-selective information about the molecular dynamics.

  13. Model dependence of the {sup 2}H electric dipole moment

    SciTech Connect

    Afnan, I. R.; Gibson, B. F.

    2010-12-15

    Background: Direct measurement of the electric dipole moment (EDM) of the neutron is in the future; measurement of a nuclear EDM may well come first. The deuteron is one nucleus for which exact model calculations are feasible. Purpose: We explore the model dependence of deuteron EDM calculations. Methods: Using a separable potential formulation of the Hamiltonian, we examine the sensitivity of the deuteron EDM to variation in the nucleon-nucleon interaction. We write the EDM as the sum of two terms, the first depending on the target wave function with plane-wave intermediate states, and the second depending on intermediate multiple scattering in the {sup 3}P{sub 1} channel, the latter being sensitive to the off-shell behavior of the {sup 3}P{sub 1} amplitude. Results: We compare the full calculation with the plane-wave approximation result, examine the tensor force contribution to the model results, and explore the effect of short-range repulsion found in realistic, contemporary potential models of the deuteron. Conclusions: Because one-pion exchange dominates the EDM calculation, separable potential model calculations will provide an adequate description of the {sup 2}H EDM until such time as a measurement better than 10% is obtained.

  14. 2F and 2H evaporator loop evaluation closure report

    SciTech Connect

    Bates, W.F.

    1994-01-28

    As a result of the Concentrate Transfer System (CTS) tank ventilation system contamination event, a task team was formed to evaluate instrument loops associated with waste reduction equipment. During the event a conductivity probe designed to provide an alarm and initiate an interlock failed to respond to the presence of liquid. An investigation revealed that the probe had become disconnected from the loop. The daily functional check of the conductivity probe circuit only tested the circuit continuity from the ventilation unit to the control room and did not actually test the probe. To test the continuity, a test switch was used to simulate the conducting probe. Because the functional check did not test each part of the loop, the test could be satisfactorily completed even though the probe itself was inoperable. The function of the task team was to develop a list of loops and interlocks prioritized by importance and likelihood of similar failure. The team evaluated the associated loop calibration and functional test procedures to verify that they are adequate to ensure loop performance on a periodic frequency. This report documents the evaluation findings and associated actions required prior to startup of the 2F and 2H evaporators.

  15. Ca2+/H+ exchange in acidic vacuoles of Trypanosoma brucei.

    PubMed Central

    Vercesi, A E; Moreno, S N; Docampo, R

    1994-01-01

    The use of digitonin to permeabilize the plasma membrane of Trypanosoma brucei procyclic and bloodstream trypomastigotes allowed the identification of a non-mitochondrial nigericin-sensitive Ca2+ compartment. The proton ionophore carbonyl cyanide p-trifluoromethoxyphenylhydrazone (FCCP) was able to cause Ca2+ release from this compartment, which was also sensitive to sodium orthovanadate. Preincubation of the cells with the vacuolar H(+)-ATPase inhibitor bafilomycin A1 greatly reduced the nigericin-sensitive Ca2+ compartment. Bafilomycin A1 inhibited the initial rate of ATP-dependent non-mitochondrial Ca2+ uptake and stimulated the initial rate of nigericin-induced Ca2+ release by permeabilized procyclic trypomastigotes. ATP-dependent and bafilomycin A1- and 7-chloro-4-nitrobenz-2-oxa-1,3-diazole (NBD-Cl)-sensitive Acridine Orange uptake was demonstrated in permeabilized cells. Under these conditions Acridine Orange was concentrated in abundant cytoplasmic round vacuoles by a process inhibited by bafilomycin A1, NBD-Cl, nigericin, and Ca2+. Vanadate or EGTA significantly increased Acridine Orange uptake, while Ca2+ released Acridine Orange from these preparations, thus suggesting that the dye and Ca2+ were being accumulated in the same acidic vacuole. Acridine Orange uptake was reversed by nigericin, bafilomycin A1 and NH4Cl. The results are consistent with the presence of a Ca2+/H(+)-ATPase system pumping Ca2+ into an acidic vacuole, that we tentatively named the acidocalcisome. Images Figure 5 PMID:7998937

  16. 2H NMR studies of glycerol dynamics in protein matrices.

    PubMed

    Herbers, C R; Sauer, D; Vogel, M

    2012-03-28

    We use (2)H NMR spectroscopy to investigate the rotational motion of glycerol molecules in matrices provided by the connective tissue proteins elastin and collagen. Analyzing spin-lattice relaxation, line-shape properties, and stimulated-echo decays, we determine the rates and geometries of the motion as a function of temperature and composition. It is found that embedding glycerol in an elastin matrix leads to a mild slowdown of glycerol reorientation at low temperatures and glycerol concentrations, while the effect vanishes at ambient temperatures or high solvent content. Furthermore, it is observed that the nonexponential character of the rotational correlation functions is much more prominent in the elastin matrix than in the bulk liquid. Results from spin-lattice relaxation and line shape measurements indicate that, in the mixed systems, the strong nonexponentiality is in large part due to the existence of distributions of correlation times, which are broader on the long-time flank and, hence, more symmetric than in the neat system. Stimulated-echo analysis of slow glycerol dynamics reveals that, when elastin is added, the mechanism for the reorientation crosses over from small-angle jump dynamics to large-angle jump dynamics and the geometry of the motion changes from isotropic to anisotropic. The results are discussed against the background of present and previous findings for glycerol and water dynamics in various protein matrices and compared with observations for other dynamically highly asymmetric mixtures so as to ascertain in which way the viscous freezing of a fast component in the matrix of a slow component differs from the glassy slowdown in neat supercooled liquids. PMID:22462878

  17. 2H NMR studies of glycerol dynamics in protein matrices

    NASA Astrophysics Data System (ADS)

    Herbers, C. R.; Sauer, D.; Vogel, M.

    2012-03-01

    We use 2H NMR spectroscopy to investigate the rotational motion of glycerol molecules in matrices provided by the connective tissue proteins elastin and collagen. Analyzing spin-lattice relaxation, line-shape properties, and stimulated-echo decays, we determine the rates and geometries of the motion as a function of temperature and composition. It is found that embedding glycerol in an elastin matrix leads to a mild slowdown of glycerol reorientation at low temperatures and glycerol concentrations, while the effect vanishes at ambient temperatures or high solvent content. Furthermore, it is observed that the nonexponential character of the rotational correlation functions is much more prominent in the elastin matrix than in the bulk liquid. Results from spin-lattice relaxation and line shape measurements indicate that, in the mixed systems, the strong nonexponentiality is in large part due to the existence of distributions of correlation times, which are broader on the long-time flank and, hence, more symmetric than in the neat system. Stimulated-echo analysis of slow glycerol dynamics reveals that, when elastin is added, the mechanism for the reorientation crosses over from small-angle jump dynamics to large-angle jump dynamics and the geometry of the motion changes from isotropic to anisotropic. The results are discussed against the background of present and previous findings for glycerol and water dynamics in various protein matrices and compared with observations for other dynamically highly asymmetric mixtures so as to ascertain in which way the viscous freezing of a fast component in the matrix of a slow component differs from the glassy slowdown in neat supercooled liquids.

  18. Full-dimensional quantum dynamics study of the H2 + C2H → H + C2H2 reaction on an ab initio potential energy surface.

    PubMed

    Chen, Liuyang; Shao, Kejie; Chen, Jun; Yang, Minghui; Zhang, Dong H

    2016-05-21

    This work performs a time-dependent wavepacket study of the H2 + C2H → H + C2H2 reaction on a new ab initio potential energy surface (PES). The PES is constructed using neural network method based on 68 478 geometries with energies calculated at UCCSD(T)-F12a/aug-cc-pVTZ level and covers H2 + C2H↔H + C2H2, H + C2H2 → HCCH2, and HCCH2 radial isomerization reaction regions. The reaction dynamics of H2 + C2H → H + C2H2 are investigated using full-dimensional quantum dynamics method. The initial-state selected reaction probabilities are calculated for reactants in eight vibrational states. The calculated results showed that the H2 vibrational excitation predominantly enhances the reactivity while the excitation of bending mode of C2H slightly inhibits the reaction. The excitations of two stretching modes of C2H molecule have negligible effect on the reactivity. The integral cross section is calculated with J-shift approximation and the mode selectivity in this reaction is discussed. The rate constants over 200-2000 K are calculated and agree well with the experimental measured values.

  19. Ion-neutral reaction of the C2H2N+ cation with C2H2: An experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Fathi, P.; Geppert, W. D.; Kaiser, A.; Ascenzi, D.

    2016-03-01

    The ion-neutral reactions of the C2H2N+ cation with C2H2 have been investigated using a Guided Ion Beam Mass Spectrometer (GIB-MS). The following ionic products were observed: CH3+, C2H2+, C2H3+, HNC+ /HCN+ , HCNH+, C3H+ , C2N+ , C3H3+, HCCN+ and C4H2N+ . Theoretical calculations have been carried out to propose reaction pathways leading to the observed products. These processes are of relevance for the generation of long chain nitrogen-containing species and they may be of interest for the chemistry of Titan's ionosphere or circumstellar envelopes.

  20. Theoretical study of the C-H bond dissociation energies of CH4, C2H2, C2H4, and H2C2O

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

    1991-01-01

    The successive C-H bond dissociation energies of CH4, C2H2, C2H4, and H2C2O (ketene) are determined using large-basis sets and a high level of correlation treatment. For CH4, C2H2, and C2H4 the computed values are in excellent agreement with experiment. Using these results, the values 107.9 + or - 2.0 and 96.7 + or - 2.0 kcal/mol are recommended for the C-H bond dissociation energies of H2C2O and HC2O, respectively.

  1. Herman-Wallis factors in the C2H2nu5 infrared fundamental near 14 microns

    NASA Technical Reports Server (NTRS)

    Maguire, William C.; Hillman, John J.; Weber, Mark; Blass, William E.

    1991-01-01

    The presence of acetylene has been confirmed for some time in the atmospheres of the outer planets Jupiter, Saturn, Neptune, and Saturn's satellite Titan. For these atmospheres, the determination of C2H2 abundances using its strong nu5 fundamental requires laboratory line position and intensity measurements. The 1-m Fourier transform spectrometer at McMath solar telescope of Kitt Peak National Observatory was used to measure C2H2 at an unapodized spectral resolution of 0.0025/cm. Synthetic spectra are generated by convolving a Voigt line shape with an instrument function and varying intensity parameters by means of a nonlinear least squares technique. Intensities of 37 nu5 lines spanning P18 through R20 were measured using 0.123 torr of gas in a 1-cm cell. A Herman-Wallis intensity correction parameter of 1.3(4) x 10 to the -3rd has been derived using a least squares linear fit.

  2. The FORMAMIDE_2-H_2O Complex: Structure and Hydrogen Bond Cooperative Effects

    NASA Astrophysics Data System (ADS)

    Blanco, Susana; Pinacho, Pablo; Lopez, Juan Carlos

    2016-06-01

    The adduct formamide_2-H_20 has been detected in a supersonic expansion and its rotational spectra in the 5-13 GHz frequency region characterized by narrow-band molecular beam Fourier transform microwave spectroscopy (MB-FTMW). The spectrum shows the hyperfine structure due to the presence of two 14N-nuclei. This hyperfine structure has been analyzed and the determined quadrupole coupling constants together with the rotational constants have been a key for the identification of the adduct structure on the light of ab initio computations. The rotational parameters are consistent with the formation of a three body cycle thanks to the double proton acceptor/proton donor character of both formamide and water. The low value of the planar moment of inertia Pcc indicates that the heavy atom skeleton of the cluster is essentially planar. A detailed analysis of the results reveals the subtle effects of hydrogen bond cooperative effects in this system.

  3. Covariance Matrix Adapted Evolution Strategy Based Design of Mixed H2/H ∞ PID Controller

    NASA Astrophysics Data System (ADS)

    Willjuice Iruthayarajan, M.; Baskar, S.

    This paper discusses the application of the covariance matrix adapted evolution strategy (CMAES) technique to the design of the mixed H2/H ∞ PID controller. The optimal robust PID controller is designed by minimizing the weighted sum of integral squared error (ISE) and balanced robust performance criterion involving robust stability and disturbance attenuation performance subjected to robust stability and disturbance attenuation constraints. In CMAES algorithm, these constraints are effectively handled by penalty parameter-less scheme. In order to test the performance of CMAES algorithm, MIMO distillation column model is considered. For the purpose of comparison, reported intelligent genetic algorithm (IGA) method is used. The statistical performances of combined ISE and balanced robust performance criterion in ten independent simulation runs show that a performance of CMAES is better than IGA method. Robustness test conducted on the system also shows that the robust performance of CMAES designed controller is better than IGA based controller under model uncertainty and external disturbances.

  4. An ignored but most favorable channel for NCO+C2H2 reaction.

    PubMed

    Xie, Hong-bin; Wang, Jian; Zhang, Shao-wen; Ding, Yi-hong; Sun, Chia-chung

    2006-09-28

    The NCO+C(2)H(2) reaction has been considered as a prototype for understanding the chemical reactivity of the isocyanate radical towards unsaturated hydrocarbons in fuel-rich combustion. It has also been proposed to provide an effective route for formation of oxazole-containing compounds in organic synthesis, and might have potential applications in interstellar processes. Unfortunately, this reaction has met mechanistic controversy both between experiments and between experiments and theoretical calculations. In this paper, detailed theoretical investigations at the Becke's three parameter Lee-Yang-Parr-B3LYP6-31G(d), B3LYP6-311++G(d,p), quadratic configuration interaction with single and double excitations QCISD6-31G(d), and Gaussian-3 levels are performed for the NCO+C(2)H(2) reaction, covering various entrance, isomerization, and decomposition channels. Also, the highly cost-expensive coupled-cluster theory including single and double excitations and perturbative inclusion of triple excitations CCSD(T)/aug-cc-pVTZ single-point energy calculation is performed for the geometries obtained at the Becke's three parameter Lee-Yang-Parr-B3LYP6-311++G(d,p) level. A previously ignored yet most favorable channel via a four-membered ring intermediate with allyl radical character is found. However, formation of P(3) H+HCCNCO and the five-membered ring channel predicted by previous experimental and theoretical studies is kinetically much less competitive. With the new channel, master equation rate constant calculations over a wide range of temperatures (298-1500 K) and pressures (10-560 Torr) show that the predicted total rate constants exhibit a positive-temperature dependence and no distinct pressure dependence effect. This is in qualitative agreement with available experimental results. Under the experimental conditions, the predicted values are about 50% lower than the latest experimental results. Also, the branching ratio variations of the fragments P(2) HCN+HCCO and P

  5. An ignored but most favorable channel for NCO +C2H2 reaction

    NASA Astrophysics Data System (ADS)

    Xie, Hong-bin; Wang, Jian; Zhang, Shao-wen; Ding, Yi-hong; Sun, Chia-chung

    2006-09-01

    The NCO +C2H2 reaction has been considered as a prototype for understanding the chemical reactivity of the isocyanate radical towards unsaturated hydrocarbons in fuel-rich combustion. It has also been proposed to provide an effective route for formation of oxazole-containing compounds in organic synthesis, and might have potential applications in interstellar processes. Unfortunately, this reaction has met mechanistic controversy both between experiments and between experiments and theoretical calculations. In this paper, detailed theoretical investigations at the Becke's three parameter Lee-Yang-Parr-B3LYP /6-31G(d), B3LYP /6-311++G(d,p), quadratic configuration interaction with single and double excitations QCISD /6-31G(d), and Gaussian-3 levels are performed for the NCO +C2H2 reaction, covering various entrance, isomerization, and decomposition channels. Also, the highly cost-expensive coupled-cluster theory including single and double excitations and perturbative inclusion of triple excitations CCSD(T)/aug-cc-pVTZ single-point energy calculation is performed for the geometries obtained at the Becke's three parameter Lee-Yang-Parr-B3LYP /6-311++G(d,p) level. A previously ignored yet most favorable channel via a four-membered ring intermediate with allyl radical character is found. However, formation of P3 H +HCCNCO and the five-membered ring channel predicted by previous experimental and theoretical studies is kinetically much less competitive. With the new channel, master equation rate constant calculations over a wide range of temperatures (298-1500K) and pressures (10-560Torr) show that the predicted total rate constants exhibit a positive-temperature dependence and no distinct pressure dependence effect. This is in qualitative agreement with available experimental results. Under the experimental conditions, the predicted values are about 50% lower than the latest experimental results. Also, the branching ratio variations of the fragments P2 HCN +HCCO and P5

  6. ANALYTICAL FORMULAE OF MOLECULAR ION ABUNDANCES AND THE N{sub 2}H{sup +} RING IN PROTOPLANETARY DISKS

    SciTech Connect

    Aikawa, Yuri; Furuya, Kenji; Nomura, Hideko; Qi, Chunhua

    2015-07-10

    We investigate the chemistry of ion molecules in protoplanetary disks, motivated by the detection of the N{sub 2}H{sup +} ring around TW Hya. While the ring inner radius coincides with the CO snow line, it is not apparent why N{sub 2}H{sup +} is abundant outside the CO snow line in spite of the similar sublimation temperatures of CO and N{sub 2}. Using the full gas-grain network model, we reproduced the N{sub 2}H{sup +} ring in a disk model with millimeter grains. The chemical conversion of CO and N{sub 2} to less volatile species (sink effect hereinafter) is found to affect the N{sub 2}H{sup +} distribution. Since the efficiency of the sink depends on various parameters such as activation barriers of grain-surface reactions, which are not well constrained, we also constructed the no-sink model; the total (gas and ice) CO and N{sub 2} abundances are set constant, and their gaseous abundances are given by the balance between adsorption and desorption. Abundances of molecular ions in the no-sink model are calculated by analytical formulae, which are derived by analyzing the full-network model. The N{sub 2}H{sup +} ring is reproduced by the no-sink model, as well. The 2D (R-Z) distribution of N{sub 2}H{sup +}, however, is different among the full-network model and no-sink model. The column density of N{sub 2}H{sup +} in the no-sink model depends sensitively on the desorption rate of CO and N{sub 2} and the cosmic-ray flux. We also found that N{sub 2}H{sup +} abundance can peak at the temperature slightly below the CO sublimation, even if the desorption energies of CO and N{sub 2} are the same.

  7. Multi-scale characterization of lyotropic liquid crystals using 2H and diffusion MRI with spatial resolution in three dimensions.

    PubMed

    Bernin, Diana; Koch, Vanessa; Nydén, Magnus; Topgaard, Daniel

    2014-01-01

    The ability of lyotropic liquid crystals to form intricate structures on a range of length scales can be utilized for the synthesis of structurally complex inorganic materials, as well as in devices for controlled drug delivery. Here we employ magnetic resonance imaging (MRI) for non-invasive characterization of nano-, micro-, and millimeter scale structures in liquid crystals. The structure is mirrored in the translational and rotational motion of the water, which we assess by measuring spatially resolved self-diffusion tensors and 2H spectra. Our approach differs from previous works in that the MRI parameters are mapped with spatial resolution in all three dimensions, thus allowing for detailed studies of liquid crystals with complex millimeter-scale morphologies that are stable on the measurement time-scale of 10 hours. The 2H data conveys information on the nanometer-scale structure of the liquid crystalline phase, while the combination of diffusion and 2H data permits an estimate of the orientational distribution of micrometer-scale anisotropic domains. We study lamellar phases consisting of the nonionic surfactant C10E3 in 2H2O, and follow their structural equilibration after a temperature jump and the cessation of shear. Our experimental approach may be useful for detailed characterization of liquid crystalline materials with structures on multiple length scales, as well as for studying the mechanisms of phase transitions.

  8. Isolated versus Condensed Anion Structure II; the Influence of the Cations (1,3-propanediammonium, 1,4-phenylendiammonium, and n-propylammonium) on Structures and Phase Transitions of CdBr2-4Salts A 79,81Br NQR and X-ray Structure Analysis

    NASA Astrophysics Data System (ADS)

    Ishihara, Hideta; Dou, Shi-qi; Horiuchi, Keizo; Krishnan, V. G.; Paulus, Helmut; Fuess, Hartmut; Weiss, Alarich

    1996-12-01

    The influence of the cations on the condensation of anions CdBr42- in salts (A')CdBr4 (II) and (A)2CdBr4 (II) is studied by 79,81Br NQR and X-ray crystal structure determinations. (A')CdBr4 : A' = [H3N(CH2)3NH3]2+ (1) crystallizes with a layer-type anion structure at 298 K and A' = [1,4-(H3N)2C6H4]2+ (2) crystallizes with a chain-type anion structure at 298 K. (A)2 CdBr4 : A = [n-H3C(CH2)2NH3]+ (3) crystallizes with a layer-type anion structure at 293 K. (1) shows successive phase transitions at 328, 363, and 495 K according to the NQR and DSC measurements. Phase IV of (1): at 298 K orthorhombic, Pnma, Z = 4,a = 772.1 (4), b = 1905.4(9), c = 789.8(4) pm. 81Br NQR spectrum showed a doublet at 77 K (phase IV) with ν1= 61.177 and ν2 = 45.934 MHz and also a doublet at 350 K (phase III) with ν1= 57.581 and ν2 = 48.747 MHz. (2): at 295 K orthorhombic, Pnma, Z = 4, a = 802.5(3), b = 1775.1(6), c = 881.9(3) pm; the five-coordinated Cd atom and one-dimensional [CdBr4]2- anion chain structure was observed. This coordination and chain structure are very rare for (A')CdX4 (II) or (A)2CdX4 (II). Two 81Br NQR lines were observed at 77 K: ν1= 70.159 and ν3 = 40.056 MHz. One more line appeared at 85 K: ν2 = 53.622 MHz. A 81Br NQR triplet was observed at 273 K: ν1 = 67.919, ν2 = 56.317, and ν3 = 40.907 MHz. (3) shows successive phase transitions at 121, 135, 165, and 208 K according to the NQR, DSC, and DTA measurements. Phase I of (3): at 293 K orthorhombic, Cmca, Z = 4, a = 783.4(4), b = 2480.2(10), c = 806.5(4) pm. 81Br NQR doublet was observed at 77 K (phase V) and at 300 K (Phase I) with ν1 = 61.060 and ν2 = 54.098 MHz (77 K); v1 = 55.835 and ν2 = 55.964 MHz (373 K). No NQR line could be observed in phases II, III, and IV.

  9. Theoretical study of the radiative capture reactions {sup 2}H(n,{gamma}){sup 3}H and {sup 2}H(p,{gamma}){sup 3}He at low energies

    SciTech Connect

    M. Viviani; R. Schiavilla; A. Kievsky

    1996-02-01

    Correlated Hyperspherical Harmonics wave functions with {Delta}-isobar admixtures obtained from realistic interactions are used to study the thermal neutron radiative capture on deuterium, and the {sup 2}H({rvec p},{gamma}){sup 3}He and p({rvec d},{gamma}){sup 3}He reactions in the center of mass energy range 0-100 keV. The nuclear electromagnetic current includes one and two-body components. Results for the {sup 2}H({rvec d},{gamma}){sup 3}H cross section and photon polarization parameter, as well as for the energy dependence of the astrophysical factor and angular distributions of the differential cross section, vector and tensor analyzing powers, and photon linear polarization coefficient of the {sup 2}H({rvec p},{gamma}){sup 3}He and p({rvec d},{gamma}){sup 3}He reactions are reported. Large effects due to two-body currents, in particular the long-range ones associated with the tensor component of the nucleon-nucleon interaction, are observed in the photon polarization parameter and vector analyzing power. Good, quantitative agreement between theory and experiment is found for all observables, with the exception of the vector analyzing power for which the calculated values underestimate the data by about 30%.

  10. Cell-free conversion of 1 prime -deoxy- sup 2 H-ABA to sup 2 H-ABA in extracts from Cercospora rosicola

    SciTech Connect

    Al-Nimri, L.; Coolbaugh, R.C. )

    1990-05-01

    The characteristics of the enzyme converting 1{prime}-deoxy-ABA into ABA have been studied in the fungus C. rosicola. Enzyme extracts were prepared from cold-pressed mycelia of C. rosicola. The suspension was a high speed supernatant and a microsomal fraction. A cell-free system was developed to convert 1{prime}-deoxy-{sup 2}H-ABA into {sup 2}H-ABA using a reaction mixture containing 300 {mu}l enzyme extract, 10 {mu}m 1{prime}-deoxy-{sup 2}H-ABA. The reaction products were chromatographed by reverse phase HPLC. The presumptive ABA fractions were collected and {sup 2}H-ABA was quantified by GC-MS using a {sup 2}H-(2Z, 4E)-ABA standard curve. 1{prime}-deoxy-{sup 2}H-ABA was converted to an average of 1.47 pmole {sup 2}H-ABA/mg protein per min. Most of the enzymic activity was found in the microsomal fraction. The reaction required NADPH and was enhanced by FAD. The reaction was not inhibited by triarimol.

  11. Comparison of one-particle basis set extrapolation to explicitly correlated methods for the calculation of accurate quartic force fields, vibrational frequencies, and spectroscopic constants: application to H2O, N2H+, NO2+, and C2H2.

    PubMed

    Huang, Xinchuan; Valeev, Edward F; Lee, Timothy J

    2010-12-28

    One-particle basis set extrapolation is compared with one of the new R12 methods for computing highly accurate quartic force fields (QFFs) and spectroscopic data, including molecular structures, rotational constants, and vibrational frequencies for the H(2)O, N(2)H(+), NO(2)(+), and C(2)H(2) molecules. In general, agreement between the spectroscopic data computed from the best R12 and basis set extrapolation methods is very good with the exception of a few parameters for N(2)H(+) where it is concluded that basis set extrapolation is still preferred. The differences for H(2)O and NO(2)(+) are small and it is concluded that the QFFs from both approaches are more or less equivalent in accuracy. For C(2)H(2), however, a known one-particle basis set deficiency for C-C multiple bonds significantly degrades the quality of results obtained from basis set extrapolation and in this case the R12 approach is clearly preferred over one-particle basis set extrapolation. The R12 approach used in the present study was modified in order to obtain high precision electronic energies, which are needed when computing a QFF. We also investigated including core-correlation explicitly in the R12 calculations, but conclude that current approaches are lacking. Hence core-correlation is computed as a correction using conventional methods. Considering the results for all four molecules, it is concluded that R12 methods will soon replace basis set extrapolation approaches for high accuracy electronic structure applications such as computing QFFs and spectroscopic data for comparison to high-resolution laboratory or astronomical observations, provided one uses a robust R12 method as we have done here. The specific R12 method used in the present study, CCSD(T)(R12), incorporated a reformulation of one intermediate matrix in order to attain machine precision in the electronic energies. Final QFFs for N(2)H(+) and NO(2)(+) were computed, including basis set extrapolation, core-correlation, scalar

  12. Environmental, trophic, and ecological factors influencing bone collagen δ2H

    NASA Astrophysics Data System (ADS)

    Topalov, Katarina; Schimmelmann, Arndt; David Polly, P.; Sauer, Peter E.; Lowry, Mark

    2013-06-01

    Organic deuterium/hydrogen stable isotope ratios (i.e., 2H/1H, expressed as δ2H value in ‰) in animal tissues are related to the 2H/1H in diet and ingested water. Bone collagen preserves the biochemical 2H/1H isotopic signal in the δ2H value of collagen's non-exchangeable hydrogen. Therefore, δ2H preserved in bone collagen has the potential to constrain environmental and trophic conditions, which is of interest to researchers studying of both living and fossil vertebrates. Our data examine the relationship of δ2H values of collagen with geographic variation in δ2H of meteoric waters, with local variations in the ecology and trophic level of species, and with the transition from mother's milk to adult diet. Based on 97 individuals from 22 marine and terrestrial vertebrates (predominately mammals), we found the relationships of collagen δ2H to both geographic variation in meteoric water δ2H (R2 = 0.55) and to δ15N in bone collagen (R2 = 0.17) statistically significant but weaker than previously reported. The second strongest control on collagen δ2H in our data is dietary, with nearly 50 percent of the variance in δ2H explained by trophic level (R2 = 0.47). Trophic level effects potentially confound the local meteoric signal if not held constant: herbivores tend to have the lowest δ2H values, omnivores have intermediate ones, and carnivores have the highest values. Body size (most likely related to mass-specific metabolic rates) has a strong influence on collagen δ2H (R2 = 0.30), by causing greater sensitivity in smaller animals to seasonal climate variations and/or high evapotranspiration leading to 2H-enrichment in tissues. In marine mammals weaning produces a dramatic effect on collagen δ2H with adult values being universally higher than pup values (R2 = 0.79). Interestingly, the shift in δ15N at weaning is downward, even though normally hydrogen and nitrogen isotope ratios are positively correlated with one another in respect to trophic level. Our

  13. Estimated critical conditions for UO[sub 2]F[sub 2]--H[sub 2]O systems in fully water-reflected spherical geometry

    SciTech Connect

    Jordan, W.C.; Turner, J.C.

    1992-12-01

    The purpose of this report is to document reference calculations performed using the SCALE-4.0 code system to determine the critical parameters of UO[sub 2]F[sub 2]-H[sub 2]O spheres. The calculations are an extension of those documented in ORNL/CSD/TM-284. Specifically, the data for low-enriched UO[sub 2]F[sub 2]-H[sub 2]O spheres have been extended to highly enriched uranium. These calculations, together with those reported in ORNL/CSD/TM-284, provide a consistent set of critical parameters (k[sub [infinity

  14. Solubilization and Reconstitution of the Mg2+/2H+ Antiporter of the Lutoid Tonoplast from Hevea brasiliensis Latex.

    PubMed Central

    Amalou, Z.; Gibrat, R.; Trouslot, P.; D'Auzac, J.

    1994-01-01

    The Mg2+/2H+ antiporter recently described on lutoid membrane (Z. Amalou, R. Gibrat, C. Brugidou, P. Trouslot, J.d'Auzac [1992] Plant Physiol 100: 255-260) was solubilized by octylglucoside and reconstituted into soybean liposomes using the detergent dilution method. Magnesium efflux or influx experiments were used to generate a H+ influx or efflux, respectively, monitored with the fluorescent probe 9-amino-6-chloro-2-methoxyacridine. Both experiments gave saturable H+ fluxes as a function of internal or external Mg2+ concentrations with similar kinetic parameters Km and Vmax. The Km value for Mg2+ (about 2 mM) was identical to that previously found in lyophilized-resuspended lutoid (reference therein), whereas the Vmax value was 14-fold higher. Since only 10% of the initial proteins were recovered in proteoliposomes, and electrophoretic patterns of the two kinds of vesicles differed significantly, it was inferred that the increase in Vmax was due essentially to an enrichment of the protein antiporter in the reconstituted fraction, owing to a selective effect of octylglucoside at both solubilization and reconstitution steps. None of the various divalent cations used could dissipate the pH gradient of control liposomes of soybean lipids, unless the divalent/H+ exchanger A23187 was added, whereas a rapid dissipation of the pH gradient was observed with reconstituted proteoliposomes from lutoid proteins, with the cation selectivity sequence Zn2+ > Cd2+ > Mg2+ in the millimolar concentration range. The divalent ions Ca2+, Ba2+, and Mn2+ were incapable of generating a H+ efflux in reconstituted proteoliposomes, whereas both Mg2+/H+ and Ca2+/H+ exchanges were observed in lyophilized-resuspended lutoids. Therefore, the lutoid membrane seems to contain separate Mg2+/H+ and Ca2+/H transport systems, the latter being eliminated during the solubilization/reconstitution of lutoid membrane proteins. PMID:12232305

  15. Probing the aromaticity of the [(HtAc)3(μ2-H)6], [(HtTh)3(μ2-H)6],+, and [(HtPa)3(μ2-H)6] clusters

    NASA Astrophysics Data System (ADS)

    Ramírez-Tagle, Rodrigo; Alvarado-Soto, Leonor; Arratia-Perez, Ramiro; Bast, Radovan; Alvarez-Thon, Luis

    2011-09-01

    In this study we report about the aromaticity of the prototypical [(HtAc)3(μ2-H)6], [(HtTh)3(μ2-H)6]+, and [(HtPa)3(μ2-H)6] clusters via two magnetic criteria: nucleus-independent chemical shifts (NICS) and the magnetically induced current density. All-electron density functional theory calculations were carried out using the two-component zeroth-order regular approach and the four-component Dirac-Coulomb Hamiltonian, including scalar and spin-orbit relativistic effects. Four-component current density maps and the integration of induced ring-current susceptibilities clearly show that the clusters [(HtAc)3(μ2-H)6] and [(HtTh)3(μ2-H)6]+ are non-aromatic whereas [(HtPa)3(μ2-H)6] is anti-aromatic. However, for the thorium cluster we find a discrepancy between the current density plots and the classification through the NICS index. Our results also demonstrate the increasing influence of f orbitals, on bonding and magnetic properties, with increasing atomic number in these clusters. We think that the enhanced electron mobility in [(HtPa)3(μ2-H)6] is due the significant 5f character of its valence shell. Also the participation of f orbitals in bonding is the reason why the protactinium cluster has the shortest bond lengths of the three clusters. This study provides another example showing that the magnetically induced current density approach can give more reliable results than the NICS index.

  16. Probing the aromaticity of the [(H(t)Ac)3(μ2-H)6], [(H(t)Th)3(μ2-H)6],(+), and [(H(t)Pa)3(μ2-H)6] clusters.

    PubMed

    Ramírez-Tagle, Rodrigo; Alvarado-Soto, Leonor; Arratia-Perez, Ramiro; Bast, Radovan; Alvarez-Thon, Luis

    2011-09-14

    In this study we report about the aromaticity of the prototypical [(H(t)Ac)(3)(μ(2)-H)(6)], [(H(t)Th)(3)(μ(2)-H)(6)](+), and [(H(t)Pa)(3)(μ(2)-H)(6)] clusters via two magnetic criteria: nucleus-independent chemical shifts (NICS) and the magnetically induced current density. All-electron density functional theory calculations were carried out using the two-component zeroth-order regular approach and the four-component Dirac-Coulomb Hamiltonian, including scalar and spin-orbit relativistic effects. Four-component current density maps and the integration of induced ring-current susceptibilities clearly show that the clusters [(H(t)Ac)(3)(μ(2)-H)(6)] and [(H(t)Th)(3)(μ(2)-H)(6)](+) are non-aromatic whereas [(H(t)Pa)(3)(μ(2)-H)(6)] is anti-aromatic. However, for the thorium cluster we find a discrepancy between the current density plots and the classification through the NICS index. Our results also demonstrate the increasing influence of f orbitals, on bonding and magnetic properties, with increasing atomic number in these clusters. We think that the enhanced electron mobility in [(H(t)Pa)(3)(μ(2)-H)(6)] is due the significant 5f character of its valence shell. Also the participation of f orbitals in bonding is the reason why the protactinium cluster has the shortest bond lengths of the three clusters. This study provides another example showing that the magnetically induced current density approach can give more reliable results than the NICS index.

  17. Probing the aromaticity of the [(H(t)Ac)3(μ2-H)6], [(H(t)Th)3(μ2-H)6],(+), and [(H(t)Pa)3(μ2-H)6] clusters.

    PubMed

    Ramírez-Tagle, Rodrigo; Alvarado-Soto, Leonor; Arratia-Perez, Ramiro; Bast, Radovan; Alvarez-Thon, Luis

    2011-09-14

    In this study we report about the aromaticity of the prototypical [(H(t)Ac)(3)(μ(2)-H)(6)], [(H(t)Th)(3)(μ(2)-H)(6)](+), and [(H(t)Pa)(3)(μ(2)-H)(6)] clusters via two magnetic criteria: nucleus-independent chemical shifts (NICS) and the magnetically induced current density. All-electron density functional theory calculations were carried out using the two-component zeroth-order regular approach and the four-component Dirac-Coulomb Hamiltonian, including scalar and spin-orbit relativistic effects. Four-component current density maps and the integration of induced ring-current susceptibilities clearly show that the clusters [(H(t)Ac)(3)(μ(2)-H)(6)] and [(H(t)Th)(3)(μ(2)-H)(6)](+) are non-aromatic whereas [(H(t)Pa)(3)(μ(2)-H)(6)] is anti-aromatic. However, for the thorium cluster we find a discrepancy between the current density plots and the classification through the NICS index. Our results also demonstrate the increasing influence of f orbitals, on bonding and magnetic properties, with increasing atomic number in these clusters. We think that the enhanced electron mobility in [(H(t)Pa)(3)(μ(2)-H)(6)] is due the significant 5f character of its valence shell. Also the participation of f orbitals in bonding is the reason why the protactinium cluster has the shortest bond lengths of the three clusters. This study provides another example showing that the magnetically induced current density approach can give more reliable results than the NICS index. PMID:21932909

  18. The Microwave Spectrum of the HCOOCD_2H Species of Methyl Formate

    NASA Astrophysics Data System (ADS)

    Coudert, L. H.; Huet, T. R.; Margulès, L.; Motiyenko, R.; Mollendal, H.

    2010-06-01

    Methyl formate is a non-rigid molecule displaying internal rotation of its methyl group. The microwave spectra of its normal and mono deuterated HCOOCH_2D species have already been studied and values for the tunneling splitting due to the internal rotation were determined. The normal species displays a 405 MHz A/E splitting, the mono deuterated one, a smaller 84.76 MHz A'/A'' splitting. For the bideuterated species HCOOCD_2H, the value of this splitting is not known as its microwave spectrum has not been studied yet. In this paper experimental and theoretical investigations of the microwave spectrum of HCOOCD_2H are presented. More than 9000 transitions were measured with a submillimeter wave spectrometer. About 20 lines were recorded with a molecular beam spectrometer. Like for the mono deuterated species,^c depending on the location of the only hydrogen atom of the methyl group, two configurations arise. The C_s-symmetry H-in plane configuration displays a rigid rotator spectrum and its data was analyzed using a Watson-type Hamiltonian. The C_1-symmetry H-out of plane configuration undergoes the large amplitude internal rotation. Its data was analyzed using the so called water dimer formalism which allowed us to accurately reproduce the observed frequencies and to obtain the value of the tunneling splitting as well as the parameters involved in its rotational dependence. The hyperfine structure due to quadrupole coupling at the two deuterium atoms was also analyzed. Unexpectedly, for the H-out of plane configuration, the observed hyperfine patterns are neither those expected for two equivalent deuterium atoms nor those of a rigid molecule. Ilyushin, Kryvda, and Alekseev, J. Mol. Spec. 255 (2009) 32. Margulès, Coudert, Mollendal, Guillemin, Huet, and Janeckovà, J. Mol. Spec. 254 (2009) 55. Hougen, J. Mol. Spec. 114 (1985) 395; and Coudert and Hougen, J. Mol. Spec. 130 (1988) 86.

  19. Hydrogen-deuterium exchange of diborane in superacid solution through diboranonium (B sub 2 H sub 7 sup + ) and diboranium (B sub 2 H sub 5 sup + ) ions

    SciTech Connect

    Olah, G.A.; Aniszfeld, R.; Surya Prakash, G.K.; Williams, R.E.; Lammertsma, K.; Guener, O.F.

    1988-11-09

    The slow proton/deuterium exchange of B{sub 2}H{sub 6} in the superacidic FSO{sub 3}D SbF{sub 5}/SO{sub 2}ClF medium at low temperature involving the corresponding isotopomeric diboranonium ions B{sub 2}H{sub 7}{sup +} is reported here. The structure of the B{sub 2}H{sub 7}{sup +} ion has also been probed by ab inito theoretical calculations. The H/D exchange is rationalized by the pathway that deuteriation occurs exclusively on an unbridged (terminal B-H) bond resulting in a B{sub 2}H{sub 6}D{sup +} ion which is expected to undergo polytopol (bond-to-bond) rearrangement scrambling all hydrogens and deuteriums followed by proton loss leading to the exchanged product. 18 references.

  20. The role of isovalency in the reactions of the cyano (CN), boron monoxide (BO), silicon nitride (SiN), and ethynyl (C2H) radicals with unsaturated hydrocarbons acetylene (C2H2) and ethylene (C2H4).

    PubMed

    Parker, D S N; Mebel, A M; Kaiser, R I

    2014-04-21

    The classification of chemical reactions based on shared characteristics is at the heart of the chemical sciences, and is well exemplified by Langmuir's concept of isovalency, in which 'two molecular entities with the same number of valence electrons have similar chemistries'. Within this account we further investigate the ramifications of the isovalency of four radicals with the same X(2)Σ(+) electronic structure - cyano (CN), boron monoxide (BO), silicon nitride (SiN), and ethynyl (C2H), and their reactions with simple prototype hydrocarbons acetylene (C2H2) and ethylene (C2H4). The fact that these four reactants own the same X(2)Σ(+) electronic ground state should dictate the outcome of their reactions with prototypical hydrocarbons holding a carbon-carbon triple and double bond. However, we find that other factors come into play, namely, atomic radii, bonding orbital overlaps, and preferential location of the radical site. These doublet radical reactions with simple hydrocarbons play significant roles in extreme environments such as the interstellar medium and planetary atmospheres (CN, SiN and C2H), and combustion flames (C2H, BO). PMID:24418936

  1. Primary branching ratios for the low-temperature reaction of state-prepared N2+ with CH4, C2H2, and C2H4.

    PubMed

    Gichuhi, Wilson K; Suits, Arthur G

    2011-06-30

    Product branching ratios (BRs) are reported for ion-molecule reactions of state-prepared nitrogen cation (N(2)(+)) with methane (CH(4)), acetylene (C(2)H(2)). and ethylene (C(2)H(4)) at low temperature using a modified ion imaging apparatus. These reactions are performed in a supersonic nozzle expansion characterized by a rotational temperature of 40 ± 5K. For the N(2)(+) + CH(4) reaction, a BR of 0.83:0.17 is obtained for the dissociative charge-transfer (CT) reaction that gives rise to the formation of CH(3)(+) and CH(2)(+) product ions, respectively. The N(2)(+) + C(2)H(2) ion-molecule reaction proceeds through a nondissociative CT process that results in the sole formation of C(2)H(2)(+) product ions. The reaction of N(2)(+) with C(2)H(4) leads to the formation of C(2)H(3)(+) and C(2)H(2)(+) product ions with a BR of 0.74:0.26, respectively. The reported BR for the N(2)(+) + C(2)H(4) reaction is supportive of a nonresonant dissociative CT mechanism similar to the one that accompanies the N(2)(+) + CH(4) reaction. No dependence of the branching ratios on N(2)(+) rotational level was observed. In addition to providing direct insight into the dynamics of the state-prepared N(2)(+) ion-molecule reactions with the target neutral hydrocarbon molecules, the reported low-temperature BRs are also important for accurate modeling of the nitrogen-dominated upper atmosphere of Saturn's moon, Titan.

  2. Nickel Catalysis Enables Oxidative C(sp(2) )-H/C(sp(2) )-H Cross-Coupling Reactions between Two Heteroarenes.

    PubMed

    Cheng, Yangyang; Wu, Yimin; Tan, Guangyin; You, Jingsong

    2016-09-26

    Nickel can be used to promote oxidative C(sp(2) )-H/C(sp(2) )-H cross-coupling between two heteroarenes. The reaction scope can be extended to aromatic carboxamides as the coupling partner. The reaction exhibits high functional-group compatibility and broad substrate scope. The silver oxidant can be recycled to reduce costs and waste, which is very useful for practical applications. PMID:27596265

  3. Microwave Spectra and Geometries of C2H2\\cdots AuI and C2H4\\cdots AuI

    NASA Astrophysics Data System (ADS)

    Stephens, Susanna Louise; Mullaney, John Connor; Sprawling, Matt John; Tew, David Peter; Walker, Nick; Legon, Anthony

    2014-06-01

    A chirped-pulse Fourier transform microwave spectrometer has been used to measure the microwave spectra of both C2H2\\cdots AuI and C2H4\\cdots AuI. These complexes are generated via laser ablation at 532 nm of a gold surface in the presence of CF3I and either C2H2 or C2H4 and argon and are stabilized by a supersonic expansion. Rotational (A0, B0, C0) and centrifugal distortion constants (ΔJ, ΔJK and δJ) of each molecule have been determined as well the nuclear electric quadrupole coupling constants of gold and iodine atoms (χaa(Au}, χbb-χcc(Au), χaa(I) and χbb-χcc(I)). The spectrum of each molecule is consistent with a C2v structure in which the metal atom interacts with the π-orbital of the ethene or ethyne molecule. Isotopic substitutions of atoms within the C2H2 or C2H4 subunits are in progress and in conjunction with high level ab initio calculations will allow for accurate determination of the geometry of each molecule.

  4. Elucidating proline dynamics in spider dragline silk fibre using 2H-13C HETCOR MAS NMR.

    PubMed

    Shi, Xiangyan; Yarger, Jeffery L; Holland, Gregory P

    2014-05-14

    (2)H-(13)C HETCOR MAS NMR is performed on (2)H/(13)C/(15)N-Pro enriched A. aurantia dragline silk. Proline dynamics are extracted from (2)H NMR line shapes and T1 in a site-specific manner to elucidate the backbone and side chain molecular dynamics for the MaSp2 GPGXX β-turn regions for spider dragline silk in the dry and wet, supercontracted states.

  5. Five years of CO, HCN, C2H6, C2H2, CH3OH, HCOOH, and H2CO total columns measured in the Canadian High Arctic

    NASA Astrophysics Data System (ADS)

    Viatte, C.; Strong, K.; Walker, K. A.; Drummond, J. R.

    2013-12-01

    the Northern Hemisphere, attributed to fossil fuel emission decrease. The importance of poleward transport on the atmospheric budgets of HCN and C2H2 is highlighted. Columns and variabilities of CH3OH, and HCOOH at PEARL are comparable to previous measurements performed at other remote sites. However, the small columns of H2CO in early May might reflect its large atmospheric variability, and/or the effect of the updated spectroscopic parameters used in our retrievals. Overall, emissions from biomass burning contribute to the day-to-day variabilities of the seven tropospheric species observed at Eureka.

  6. Five years of CO, HCN, C2H6, C2H2, CH3OH, HCOOH and H2CO total columns measured in the Canadian high Arctic

    NASA Astrophysics Data System (ADS)

    Viatte, C.; Strong, K.; Walker, K. A.; Drummond, J. R.

    2014-06-01

    Northern Hemisphere, attributed to fossil fuel emission decrease. The importance of poleward transport for the atmospheric budgets of HCN and C2H2 is highlighted. Columns and variabilities of CH3OH and HCOOH at PEARL are comparable to previous measurements performed at other remote sites. However, the small columns of H2CO in early May might reflect its large atmospheric variability and/or the effect of the updated spectroscopic parameters used in our retrievals. Overall, emissions from biomass burning contribute to the day-to-day variabilities of the seven tropospheric species observed at Eureka.

  7. The SNF2H chromatin remodeling enzyme has opposing effects on cytokine gene expression.

    PubMed

    Precht, Patricia; Wurster, Andrea L; Pazin, Michael J

    2010-07-01

    Cytokine gene expression is a key control point in the function of the immune system. Cytokine gene regulation is linked to changes in chromatin structure; however, little is known about the remodeling enzymes mediating these changes. Here we investigated the role of the ATP-dependent chromatin remodeling enzyme SNF2H in mouse T cells; to date, SNF2H has not been investigated in T cells. We found that SNF2H repressed expression of IL-2 and other cytokines in activated cells. By contrast, SNF2H activated expression of IL-3. The ISWI components SNF2H and ACF1 bound to the tested loci, suggesting the regulation was direct. SNF2H decreased accessibility at some binding sites within the IL2 locus, and increased accessibility within some IL3 binding sites. The changes in gene expression positively correlated with accessibility changes, suggesting a simple model that accessibility enables transcription. We also found that loss of the ISWI ATPase SNF2H reduced binding to target genes and protein expression of ACF1, a binding partner for SNF2H, suggesting complex formation stabilized ACF1. Together, these findings reveal a direct role for SNF2H in both repression and activation of cytokine genes.

  8. The SNF2H Chromatin Remodeling Enzyme Has Opposing Effects on Cytokine Gene Expression

    PubMed Central

    Precht, Patricia; Wurster, Andrea L.; Pazin, Michael J.

    2010-01-01

    Cytokine gene expression is a key control point in the function of the immune system. Cytokine gene regulation is linked to changes in chromatin structure; however, little is known about the remodeling enzymes mediating these changes. Here we investigated the role of the ATP-dependent chromatin remodeling enzyme SNF2H in mouse T cells; to date, SNF2H has not been investigated in T cells. We found that SNF2H repressed expression of IL-2 and other cytokines in activated cells. By contrast, SNF2H activated expression of IL-3. The ISWI components SNF2H and ACF1 bound to the tested loci, suggesting the regulation was direct. SNF2H decreased accessibility at some binding sites within the IL2 locus, and increased accessibility within some IL3 binding sites. The changes in gene expression positively correlated with accessibility changes, suggesting a simple model that accessibility enables transcription. We also found that loss of the ISWI ATPase SNF2H reduced binding to target genes and protein expression of ACF1, a binding partner for SNF2H, suggesting complex formation stabilized ACF1. Together, these findings reveal a direct role for SNF2H in both repression and activation of cytokine genes. PMID:20471682

  9. Predicting leaf wax n-alkane 2H/1H ratios: controlled water source and humidity experiments with hydroponically grown trees confirm predictions of Craig-Gordon model.

    PubMed

    Tipple, Brett J; Berke, Melissa A; Hambach, Bastian; Roden, John S; Ehleringer, James R

    2015-06-01

    The extent to which both water source and atmospheric humidity affect δ(2)H values of terrestrial plant leaf waxes will affect the interpretations of δ(2)H variation of leaf waxes as a proxy for hydrological conditions. To elucidate the effects of these parameters, we conducted a long-term experiment in which we grew two tree species, Populus fremontii and Betula occidentalis, hydroponically under combinations of six isotopically distinct waters and two different atmospheric humidities. We observed that leaf n-alkane δ(2)H values of both species were linearly related to source water δ(2)H values, but with slope differences associated with differing humidities. When a modified version of the Craig-Gordon model incorporating plant factors was used to predict the δ(2)H values of leaf water, all modelled leaf water values fit the same linear relationship with n-alkane δ(2)H values. These observations suggested a relatively constant biosynthetic fractionation factor between leaf water and n-alkanes. However, our calculations indicated a small difference in the biosynthetic fractionation factor between the two species, consistent with small differences calculated for species in other studies. At present, it remains unclear if these apparent interspecies differences in biosynthetic fractionation reflect species-specific biochemistry or a common biosynthetic fractionation factor with insufficient model parameterization.

  10. Calculational and Experimental Investigations of the Pressure Effects on Radical - Radical Cross Combinations Reactions: C2H5 + C2H3

    NASA Technical Reports Server (NTRS)

    Fahr, Askar; Halpern, Joshua B.; Tardy, Dwight C.

    2007-01-01

    Pressure-dependent product yields have been experimentally determined for the cross-radical reaction C2H5 + C2H3. These results have been extended by calculations. It is shown that the chemically activated combination adduct, 1-C4H8*, is either stabilized by bimolecular collisions or subject to a variety of unimolecular reactions including cyclizations and decompositions. Therefore the "apparent" combination/disproportionation ratio exhibits a complex pressure dependence. The experimental studies were performed at 298 K and at selected pressures between about 4 Torr (0.5 kPa) and 760 Torr (101 kPa). Ethyl and vinyl radicals were simultaneously produced by 193 nm excimer laser photolysis of C2H5COC2H3 or photolysis of C2H3Br and C2H5COC2H5. Gas chromatograph/mass spectrometry/flame ionization detection (GC/MS/FID) were used to identify and quantify the final reaction products. The major combination reactions at pressures between 500 (66.5 kPa) and 760 Torr are (1c) C2H5 + C2H3 yields 1-butene, (2c) C2H5 + C2H5 yields n-butane, and (3c) C2H3 + C2H3 yields 1,3-butadiene. The major products of the disproportionation reactions are ethane, ethylene, and acetylene. At moderate and lower pressures, secondary products, including propene, propane, isobutene, 2-butene (cis and trans), 1-pentene, 1,4-pentadiene, and 1,5-hexadiene are also observed. Two isomers of C4H6, cyclobutene and/or 1,2-butadiene, were also among the likely products. The pressure-dependent yield of the cross-combination product, 1-butene, was compared to the yield of n-butane, the combination product of reaction (2c), which was found to be independent of pressure over the range of this study. The [ 1-C4H8]/[C4H10] ratio was reduced from approx.1.2 at 760 Torr (101 kPa) to approx.0.5 at 100 Torr (13.3 kPa) and approx.0.1 at pressures lower than about 5 Torr (approx.0.7 kPa). Electronic structure and RRKM calculations were used to simulate both unimolecular and bimolecular processes. The relative importance

  11. Hyperfine excitation of N2H+ by H2: towards a revision of N2H+ abundance in cold molecular clouds

    NASA Astrophysics Data System (ADS)

    Lique, François; Daniel, Fabien; Pagani, Laurent; Feautrier, Nicole

    2015-01-01

    The modelling of emission spectra of molecules seen in interstellar clouds requires the knowledge of collisional rate coefficients. Among the commonly observed species, N2H+ is of particular interest since it was shown to be a good probe of the physical conditions of cold molecular clouds. Thus, we have calculated hyperfine-structure-resolved excitation rate coefficients of N2H+(X1Σ+) by H2(j = 0), the most abundant collisional partner in the cold interstellar medium. The calculations are based on a new potential energy surface, obtained from highly correlated ab initio calculations. State-to-state rate coefficients between the first hyperfine levels were calculated, for temperatures ranging from 5 to 70 K. By comparison with previously published N2H+-He rate coefficients, we found significant differences which cannot be reproduced by a simple scaling relationship. As a first application, we also performed radiative transfer calculations, for physical conditions typical of cold molecular clouds. We found that the simulated line intensities significantly increase when using the new H2 rate coefficients, by comparison with the predictions based on the He rate coefficients. In particular, we revisited the modelling of the N2H+ emission in the LDN 183 core, using the new collisional data, and found that all three of the density, gas kinetic temperature and N2H+ abundance had to be revised.

  12. Exceptional point and degeneracy of the neutral heavy Higgs boson system H{sub 2}-H{sub 3}

    SciTech Connect

    Felix-Beltran, O.; Gomez-Bock, M.; Hernandez, E.; Mondragon, A.; Mondragon, M.

    2010-02-10

    We analyze the masses and mixings of the isolated doublet of neutral, heavy Higgs bosons, H{sub 2} and H{sub 3} of two Higgs doublet models with CP-violation. There is a set of Lagrangian parameter values for which the isolated doublet of mass eigenstates is degenerate. Associated with this singularity, the propagator of the mixing H{sub 2}-H{sub 3} neutral Higgs system has one double pole in the complex energy squared s-plane. This analysis suggests that a detailed study of the lineshape of this Higgs system may provide valuable information on the CP nature of the underlying theory.

  13. Photoabsorption and photoionization cross sections of NH3, PH3, H2S, C2H2, and C2H4 in the VUV region

    NASA Technical Reports Server (NTRS)

    Xia, T. J.; Chien, T. S.; Wu, C. Y. Robert; Judge, D. L.

    1991-01-01

    Using synchrotron radiation as a continuum light source, the photoabsorption and photoionization cross sections of NH3, PH3, H2S, C2H2, and C2H4 have been measured from their respective ionization thresholds to 1060 A. The vibrational constants associated with the nu(2) totally symmetric, out-of-plane bending vibration of the ground electronic state of PH3(+) have been obtained. The cross sections and quantum yields for producing neutral products through photoexcitation of these molecules in the given spectral regions have also been determined. In the present work, autoionization processes were found to be less important than dissociation and predissociation processes in NH3, PH3, and C2H4. Several experimental techniques have been employed in order to examine the various possible systematic errors critically.

  14. 77 FR 74283 - Clearing Requirement Determination Under Section 2(h) of the CEA

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-12-13

    ...\\ Clearing Requirement Determination Under Section 2(h) of the CEA; Proposed Rule, 77 FR 47170 (Aug. 7, 2012... result of these failures, unprecedented governmental intervention was required to ensure the stability of... to Trade Under Section 2(h)(8) of the Commodity Exchange Act, 76 FR 77728 (Dec. 14, 2011)....

  15. SysZNF: the C2H2 zinc finger gene database.

    PubMed

    Ding, Guohui; Lorenz, Peter; Kreutzer, Michael; Li, Yixue; Thiesen, Hans-Juergen

    2009-01-01

    C2H2 zinc finger (C2H2-ZNF) genes are one of the largest and most complex gene super-families in metazoan genomes, with hundreds of members in the human and mouse genome. The ongoing investigation of this huge gene family requires computational support to catalog genotype phenotype comparisons of C2H2-ZNF genes between related species and finally to extend the worldwide knowledge on the evolution of C2H2-ZNF genes in general. Here, we systematically collected all the C2H2-ZNF genes in the human and mouse genome and constructed a database named SysZNF to deposit available datasets related to these genes. In the database, each C2H2-ZNF gene entry consists of physical location, gene model (including different transcript forms), Affymetrix gene expression probes, protein domain structures, homologs (and synteny between human and mouse), PubMed references as well as links to relevant public databases. The clustered organization of the C2H2-ZNF genes is highlighted. The database can be searched using text strings or sequence information. The data are also available for batch download from the web site. Moreover, the graphical gene model/protein view system, sequence retrieval system and some other tools embedded in SysZNF facilitate the research on the C2H2 type ZNF genes under an integrative view. The database can be accessed from the URL http://epgd.biosino.org/SysZNF.

  16. MICROWAVE SPECTRA AND GEOMETRIES OF C2H_{2\\cdots AgI} and C2H_{4\\cdots AgI}

    NASA Astrophysics Data System (ADS)

    Stephens, Susanna L.; Tew, David Peter; Walker, Nick; Legon, Anthony

    2015-06-01

    A chirped-pulse Fourier transform microwave spectrometer has been used to measure the microwave spectra of both C2H_{2\\cdots AgI} and C2H_{4\\cdots AgI}. These complexes are generated via laser ablation at 532 nm of a silver surface in the presence of CF3I and either C2H_{2} or C2H_{4} and argon and are stabilized by a supersonic expansion. Rotational (A0, B0, C0) and centrifugal distortion constants (ΔJ and ΔJK) of each molecule have been determined as well the nuclear electric quadrupole coupling constants the iodine atom (χaa(I) and χbb-χcc(I)). The spectrum of each molecule is consistent with a C2v structure in which the metal atom interacts with the π-orbital of the ethene or ethyne molecule. Isotopic substitutions of atoms within the C2H_{2} or C2H_{4} subunits are in progress and in conjunction with high level ab initio calculations will allow for accurate determination of the geometry of each molecule. These to complexes are put in the context of the recently studied H2S\\cdots AgI, OC\\cdotsAgI, H3N\\cdots AgI and (CH3)_{3N\\cdots AgI}. S.Z. Riaz, S.L. Stephens, W. Mizukami, D.P. Tew, N.R. Walker, A.C. Legon, Chem. Phys. Let., 531, 1-12 (2012) S.L. Stephens, W. Mizukami, D.P. Tew, N.R. Walker, A.C. Legon, J. Chem. Phys., 136(6), 064306 (2012) D.M. Bittner, D.P. Zaleski, S.L. Stephens, N.R. Walker, A.C. Legon, Study in progress.

  17. Bi(OTf)3-catalyzed addition of isocyanides to 2H-chromene acetals: an efficient pathway for accessing 2-carboxamide-2H-chromenes.

    PubMed

    Lyu, Longyun; Jin, Ming Yu; He, Qijie; Xie, Han; Bian, Zhaoxiang; Wang, Jun

    2016-09-14

    Bismuth triflate (Bi(OTf)3) is identified as an efficient catalyst for the direct addition of isocyanides to 2H-chromene acetals. The large scope of isocyanides and chromene acetals makes them suitable substrates in this catalytic system. By this synthetic strategy, a polyfunctional molecular scaffold, 2-carboxamide-2H-chromenes could be prepared efficiently in one step up to 95% yield. In addition, this efficient and practical protocol proceeded smoothly in the gram scale even when the catalytic loading was reduced to 2 mol%. PMID:27503764

  18. The transcriptional regulator c2h2 accelerates mushroom formation in Agaricus bisporus.

    PubMed

    Pelkmans, Jordi F; Vos, Aurin M; Scholtmeijer, Karin; Hendrix, Ed; Baars, Johan J P; Gehrmann, Thies; Reinders, Marcel J T; Lugones, Luis G; Wösten, Han A B

    2016-08-01

    The Cys2His2 zinc finger protein gene c2h2 of Schizophyllum commune is involved in mushroom formation. Its inactivation results in a strain that is arrested at the stage of aggregate formation. In this study, the c2h2 orthologue of Agaricus bisporus was over-expressed in this white button mushroom forming basidiomycete using Agrobacterium-mediated transformation. Morphology, cap expansion rate, and total number and biomass of mushrooms were not affected by over-expression of c2h2. However, yield per day of the c2h2 over-expression strains peaked 1 day earlier. These data and expression analysis indicate that C2H2 impacts timing of mushroom formation at an early stage of development, making its encoding gene a target for breeding of commercial mushroom strains. PMID:27207144

  19. Amplitude Higgs mode in the 2H-NbSe2 superconductor

    NASA Astrophysics Data System (ADS)

    Méasson, M.-A.; Gallais, Y.; Cazayous, M.; Clair, B.; Rodière, P.; Cario, L.; Sacuto, A.

    2014-02-01

    We report experimental evidence for the observation of the superconducting amplitude mode, the so-called ``Higgs" mode, in the charge density wave superconductor 2H-NbSe2 using Raman scattering. By comparing 2H-NbSe2 and its isostructural partner 2H-NbS2 which shows superconductivity but lacks the charge density wave order, we demonstrate that the superconducting mode in 2H-NbSe2 owes its spectral weight to the presence of the coexisting charge density wave order. In addition, temperature dependent measurements in 2H-NbSe2 show a full spectral weight transfer from the charge density wave mode to the superconducting mode upon entering the superconducting phase. Both observations are fully consistent with a superconducting amplitude mode or Higgs mode.

  20. An innovative method for the non-destructive identification of photodegradation products in solid state: 1H-14N NMR-NQR and DFT/QTAIM study of photodegradation of nifedipine (anti-hypertensive) to nitrosonifedipine (potential anti-oxidative).

    PubMed

    Latosińska, J N; Latosińska, M; Seliger, J; Zagar, V

    2012-08-30

    Stability of the antihypertensive drug nifedipine (NIF) has been studied experimentally in solid state by (1)H-(14)N NMR-NQR double resonance (NQDR) and theoretically by the Density Functional Theory (DFT). Photodegradation of NIF to its metabolite in vivo nitrosonifedipine, NO-NIF (antioxidative agent) upon long term daylight exposure was detected and the changes in the molecular structure of NIF were analysed. The photoconversion of NIF to NO-NIF in solid was found to be accompanied with the electron density redistribution at nitrogen sites (NH to N and NO(2) to NO) and proved to be successfully detected with identification of photoproducts by (1)H-(14)N NQDR and DFT methods. The increase in the e(2)qQ/h and η describing EFG tendency towards non-spherical symmetry was significantly greater upon the reduction of NO(2) site than upon hydrogen abstraction from NH site. The level of sensitivity of detection of the photodegradation product was about 1% of the original sample. The Quantum Theory of Atoms in Molecules (QTAIM) analysis has been found useful in predicting photoreactive sites in the molecules and finding the explanation of differences in reactivity between parent NIF and its photoproduct NO-NIF. Using NIF as a model, this study demonstrates the suitability of NQDR supported by DFT for non-destructive determination of the photodegradation products in solid state.

  1. Modeling of collision-induced infrared absorption spectra of H2-H2 pairs in the fundamental band at temperatures from 20 to 300 K. [Planetary atmospheres

    SciTech Connect

    Borysow, A. )

    1991-08-01

    The 20-300 K free-free rotovibrational collision-induced absorption (RV CIA) spectra of H2-H2 pairs are presently obtained by a numerical method which, in addition to closely matching known CIA spectra of H2-H2, can reproduce the results of the quantum-mechanical computations to within a few percent. Since the spectral lineshape parameters are derivable by these means from the lowest three quantum-mechanical spectral moments, these outer-planet atmosphere-pertinent model spectra may be computed on even small computers. 35 refs.

  2. Predicting Phase Diagram of the CaCl2-H2O Binary System from the BET Adsorption Isotherm

    SciTech Connect

    Ally, Moonis Raza

    2008-01-01

    A recent publication in Fluid Phase Equilibria by Zeng (Zeng, Zhou et al. 2007) claimed remarkable accuracy in predicting the solubility of CaCl2-H2O solutions with the Brunaruer-Emett-Teller (BET) model parameters. Their approach necessarily requires prior knowledge of equilibrium water vapor pressures above saturated solutions as a function of temperature for the hydrates of CaCl2 that exist under those conditions. However, the intrinsic BET model does not require prior knowledge of such solubility data that the approach of (Zeng, Zhou et al. 2007) is dependent upon. This paper highlights the differences between the two approaches and covers a much wider range of compositions and temperatures than is done by (Zeng, Zhou et al. 2007). The statistical mechanical description of multilayer adsorption culminating in the BET adsorption isotherm for aqueous electrolytes as developed by Ally and Braunstein (Ally and Braunstein 1993) is used to predict the liquidus behavior of CaCl2-H2O across the entire composition range (from the melting point of pure water to the melting point of anhydrous calcium chloride), including possible metastable crystalline phases. The method requires as input the two BET parameters r, the statistically averaged number of adsorption sites and ε, the energy of adsorption of water in excess of the energy of condensation of pure water. Usually it suffices to keep r and ε constant, typically evaluated at 298.15 K, but in the case of CaCl2-H2O, it is found that both r and ε must be considered temperature dependent in order to predict the liquidus curve, eutectic and peritectic points with reasonable accuracy over the large temperature and compositional range for this binary system.

  3. Synthesis of [.sup.13C] and [.sup.2H] substituted methacrylic acid, [.sup.13C] and [.sup.2H] substituted methyl methacrylate and/or related compounds

    DOEpatents

    Alvarez, Marc A.; Martinez, Rodolfo A.; Unkefer, Clifford J.

    2008-01-22

    The present invention is directed to labeled compounds of the formulae ##STR00001## wherein Q is selected from the group consisting of --S--, --S(.dbd.O)--, and --S(.dbd.O).sub.2--, Z is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl, a halogen, and an amino group selected from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each independently selected from the group consisting of a C.sub.1-C.sub.4 lower alkyl, an aryl, and an alkoxy group, and X is selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl group, and a fully-deuterated C.sub.1-C.sub.4 lower alkyl group. The present invention is also directed to a process of preparing labeled compounds, e.g., process of preparing [.sup.13C]methacrylic acid by reacting a (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13CH.sub.2)-- aryl sulfone precursor with .sup.13CHI to form a (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13C(.sup.13CH.sub.3).sub.2)-- aryl sulfone intermediate, and, reacting the (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13C(.sup.13CH.sub.3).sub.2)-- aryl sulfone intermediate with sodium hydroxide, followed by acid to form [.sup.13C]methacrylic acid. The present invention is further directed to a process of preparing [.sup.2H.sub.8]methyl methacrylate by reacting a (HOOC--C(C.sup.2H.sub.3).sub.2-- aryl sulfinyl intermediate with CD.sub.3I to form a (.sup.2H.sub.3COOC--C(C.sup.2H.sub.3).sub.2)-- aryl sulfinyl intermediate, and heating the(.sup.2H.sub.3COOC--C(C.sup.2H.sub.3).sub.2)-- aryl sulfinyl intermediate at temperatures and for time sufficient to form [.sup.2H.sub.8]methyl methacrylate.

  4. Saturn's latitudinal C 2H 2 and C 2H 6 abundance profiles from Cassini/CIRS and ground-based observations

    NASA Astrophysics Data System (ADS)

    Hesman, Brigette E.; Jennings, Donald E.; Sada, Pedro V.; Bjoraker, Gordon L.; Achterberg, Richard K.; Simon-Miller, Amy A.; Anderson, Carrie M.; Boyle, Robert J.; Nixon, Conor A.; Fletcher, Leigh N.; McCabe, George H.

    2009-07-01

    Hydrocarbons in the upper atmosphere of Saturn are known, from Voyager, ground-based, and early Cassini results, to vary in emission intensity with latitude. Of particular interest is the marked increase in hydrocarbon line intensity near the south pole during southern summer, as the increased line intensity cannot be simply explained by the increased temperatures observed in that region since the variations between C2H2 and C2H6 emission in the south pole region are different. In order to measure the latitudinal variations of hydrocarbons in Saturn's southern hemisphere we have used 3 cm-1 resolution Cassini CIRS data from 2006 and combined this with measurements from the ground in October 2006 at NASA's IRTF using Celeste, an infrared high-resolution cryogenic grating spectrometer. These two data sets have been used to infer the molecular abundances of C2H2 and C2H6 across the southern hemisphere in the 1-10 mbar altitude region. We find that the latitudinal acetylene profile follows the yearly average mean daily insolation except at the southern pole where it peaks in abundance. Near the equator (5° S) the C2H2 abundance at the 1.2 mbar level is (1.6 ± 0.19) ×10-7 and it decreases by a factor of 2.7 from the equator toward the pole. However, at the pole (∼87° S) the C2H2 abundance jumps to (1.8 ± 0.3) ×10-7, approximately the equatorial value. The C2H6 abundance near the equator at the 2 mbar level is (0.7 ± 0.1) ×10-5 and stays approximately constant until mid-latitudes where it increases gradually toward the pole, attaining a value of (1.4 ± 0.4) ×10-5 there. The increase in ethane toward the pole with the corresponding decrease in acetylene is consistent with southern hemisphere meridional winds [Greathouse, T.K., Lacy, J.H., Bézard, B., Moses, J.I., Griffith, C.A., Richter, M.J., 2005. Icarus 177, 18-31]. The localized increase in acetylene at the pole provides evidence that there is dynamical transport of hydrocarbons from the equator to the

  5. Chromatin remodeling enzyme Snf2h regulates embryonic lens differentiation and denucleation.

    PubMed

    He, Shuying; Limi, Saima; McGreal, Rebecca S; Xie, Qing; Brennan, Lisa A; Kantorow, Wanda Lee; Kokavec, Juraj; Majumdar, Romit; Hou, Harry; Edelmann, Winfried; Liu, Wei; Ashery-Padan, Ruth; Zavadil, Jiri; Kantorow, Marc; Skoultchi, Arthur I; Stopka, Tomas; Cvekl, Ales

    2016-06-01

    Ocular lens morphogenesis is a model for investigating mechanisms of cellular differentiation, spatial and temporal gene expression control, and chromatin regulation. Brg1 (Smarca4) and Snf2h (Smarca5) are catalytic subunits of distinct ATP-dependent chromatin remodeling complexes implicated in transcriptional regulation. Previous studies have shown that Brg1 regulates both lens fiber cell differentiation and organized degradation of their nuclei (denucleation). Here, we employed a conditional Snf2h(flox) mouse model to probe the cellular and molecular mechanisms of lens formation. Depletion of Snf2h induces premature and expanded differentiation of lens precursor cells forming the lens vesicle, implicating Snf2h as a key regulator of lens vesicle polarity through spatial control of Prox1, Jag1, p27(Kip1) (Cdkn1b) and p57(Kip2) (Cdkn1c) gene expression. The abnormal Snf2h(-/-) fiber cells also retain their nuclei. RNA profiling of Snf2h(-/) (-) and Brg1(-/-) eyes revealed differences in multiple transcripts, including prominent downregulation of those encoding Hsf4 and DNase IIβ, which are implicated in the denucleation process. In summary, our data suggest that Snf2h is essential for the establishment of lens vesicle polarity, partitioning of prospective lens epithelial and fiber cell compartments, lens fiber cell differentiation, and lens fiber cell nuclear degradation. PMID:27246713

  6. New determination of the {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He reaction rates at astrophysical energies

    SciTech Connect

    Tumino, A.; Spartà, R.; Spitaleri, C.; Pizzone, R. G.; La Cognata, M.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.; Mukhamedzhanov, A. M.; Typel, S.; Tognelli, E.; Degl'Innocenti, S.; Prada Moroni, P. G.; Burjan, V.; Kroha, V.; Hons, Z.; Mrazek, J.; Piskor, S.; Lamia, L.

    2014-04-20

    The cross sections of the {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He reactions have been measured via the Trojan Horse method applied to the quasi-free {sup 2}H({sup 3}He,p {sup 3}H){sup 1}H and {sup 2}H({sup 3}He,n {sup 3}He){sup 1}H processes at 18 MeV off the proton in {sup 3}He. For the first time, the bare nucleus S(E) factors have been determined from 1.5 MeV, across the relevant region for standard Big Bang nucleosynthesis, down to the thermal energies of deuterium burning in the pre-main-sequence (PMS) phase of stellar evolution, as well as of future fusion reactors. Both the energy dependence and the absolute value of the S(E) factors deviate by more than 15% from the available direct data and existing fitting curves, with substantial variations in the electron screening by more than 50%. As a consequence, the reaction rates for astrophysics experience relevant changes, with a maximum increase of up to 20% at the temperatures of the PMS phase. From a recent primordial abundance sensitivity study, it turns out that the {sup 2}H(d,n){sup 3}He reaction is quite influential on {sup 7}Li, and the present change in the reaction rate leads to a decrease in its abundance by up to 10%. The present reaction rates have also been included in an updated version of the FRANEC evolutionary code to analyze their influence on the central deuterium abundance in PMS stars with different masses. The largest variation of about 10%-15% pertains to young stars (≤1 Myr) with masses ≥1 M {sub ☉}.

  7. 14C2H4: Its Incorporation and Metabolism by Pea Seedlings under Aseptic Conditions 1

    PubMed Central

    Beyer, Elmo M.

    1975-01-01

    The effects of various treatments on the recently reported system in pea (Pisum sativum cv. Alaska), which results in (a) the incorporation of 14C2H4 into the tissue and (b) the conversion of 14C2H4 to 14CO2, was investigated using 2-day-old etiolated seedlings which exhibit a maximum response. Heat treatment (80 C, 1 min) completely inhibited both a and b, whereas homogenization completely inhibited b but only partially inhibited a. Detaching the cotyledons from the root-shoot axis immediately before exposing the detached cotyledons together with the root-shoot axis to 14C2H4 markedly reduced both a and b. Increasing the 14C2H4 concentration from 0.14 to over 100 μl/l progressively increased the rate of a and b with tissue incorporation being greater than 14C2H4 to 14CO2 conversion only below 0.3 μl/l 14C2H4. Reduction of the O2 concentration reduced both a and b, with over 99% inhibition occurring under anaerobic conditions. The addition of CO2 (5%) severely inhibited 14C2H4 to 14CO2 conversion without significantly affecting tissue incorporation. Exposure of etiolated seedlings to fluorescent light during 14C2H4 treatment was without effect. Similarly, indoleacetic acid, gibberellic acid, benzyladenine, abscisic acid, and dibutyryl cyclic adenosine monophosphate had no significant effect on either a or b. The possibilities that the incorporation of 14C2H4 into pea tissues and its conversion to 14CO2 is linked to ethylene action, or that it represents a means of reducing the endogenous ethylene level, are discussed. Several problems encountered with the use of polyethylene vials, rubber serum stoppers, Clorox, and microbial contamination are also described. Images PMID:16659286

  8. C(2)H(4): Its Incorporation and Metabolism by Pea Seedlings under Aseptic Conditions.

    PubMed

    Beyer, E M

    1975-08-01

    The effects of various treatments on the recently reported system in pea (Pisum sativum cv. Alaska), which results in (a) the incorporation of (14)C(2)H(4) into the tissue and (b) the conversion of (14)C(2)H(4) to (14)CO(2), was investigated using 2-day-old etiolated seedlings which exhibit a maximum response. Heat treatment (80 C, 1 min) completely inhibited both a and b, whereas homogenization completely inhibited b but only partially inhibited a. Detaching the cotyledons from the root-shoot axis immediately before exposing the detached cotyledons together with the root-shoot axis to (14)C(2)H(4) markedly reduced both a and b. Increasing the (14)C(2)H(4) concentration from 0.14 to over 100 mul/l progressively increased the rate of a and b with tissue incorporation being greater than (14)C(2)H(4) to (14)CO(2) conversion only below 0.3 mul/l (14)C(2)H(4). Reduction of the O(2) concentration reduced both a and b, with over 99% inhibition occurring under anaerobic conditions. The addition of CO(2) (5%) severely inhibited (14)C(2)H(4) to (14)CO(2) conversion without significantly affecting tissue incorporation. Exposure of etiolated seedlings to fluorescent light during (14)C(2)H(4) treatment was without effect. Similarly, indoleacetic acid, gibberellic acid, benzyladenine, abscisic acid, and dibutyryl cyclic adenosine monophosphate had no significant effect on either a or b.The possibilities that the incorporation of (14)C(2)H(4) into pea tissues and its conversion to (14)CO(2) is linked to ethylene action, or that it represents a means of reducing the endogenous ethylene level, are discussed.Several problems encountered with the use of polyethylene vials, rubber serum stoppers, Clorox, and microbial contamination are also described. PMID:16659286

  9. Electron paramagnetic resonance spectral study of [Mn(acs)2(2-pic)2(H2O)2] single crystals

    NASA Astrophysics Data System (ADS)

    Kocakoç, Mehpeyker; Tapramaz, Recep

    2016-03-01

    Acesulfame potassium salt is a synthetic and non-caloric sweetener. It is also important chemically for its capability of being ligand in coordination compounds, because it can bind over Nitrogen and Oxygen atoms of carbonyl and sulfonyl groups and ring oxygen. Some acesulfame containing transition metal ion complexes with mixed ligands exhibit solvato and thermo chromic properties and these properties make them physically important. In this work single crystals of Mn+2 ion complex with mixed ligand, [Mn(acs)2(2-pic)2(H2O)2], was studied with electron paramagnetic resonance (EPR) spectroscopy. EPR parameters were determined. Zero field splitting parameters indicated that the complex was highly symmetric. Variable temperature studies showed no detectable chance in spectra.

  10. Kinetic Resolution of 2H-Azirines by Asymmetric Imine Amidation.

    PubMed

    Hu, Haipeng; Liu, Yangbin; Lin, Lili; Zhang, Yuheng; Liu, Xiaohua; Feng, Xiaoming

    2016-08-16

    Highly efficient kinetic resolution of 2H-azirines by an asymmetric imine amidation was achieved in the presence of a chiral N,N'-dioxide/Sc(III) complex, thus providing a promising method to obtain the enantioenriched 2H-azirine derivatives and protecting-group free aziridines at the same time. It is rare to find an example of N1 of an oxindole participating in a reaction over C3. Moreover, chiral 2H-azirines were stereospecifically transformed into an unprotected aziridine and α-amino ketone. PMID:27384910

  11. Relative high-resolution absorption cross sections of C2H6 at low temperatures

    NASA Astrophysics Data System (ADS)

    Hargreaves, R. J.; Bernath, P. F.; Appadoo, D. R. T.

    2015-09-01

    Synchrotron radiation has been used to record absorption cross sections of ethane, C2H6, in the far-infrared with very high spectral resolution (up to 0.00096 cm-1). C2H6 is present in the atmospheres of the Gas Giant planets and Titan but the vapor pressure at relevant atmospheric temperatures (i.e., between 70 and 200 K) is low. This makes laboratory measurements difficult. We demonstrate the effectiveness of a unique "enclosive flow" cold cell, located at the Australian Synchrotron, that enables high-resolution absorption cross sections of gaseous C2H6 to be recorded at 90 K.

  12. Homotopy Algorithm for Fixed Order Mixed H2/H(infinity) Design

    NASA Technical Reports Server (NTRS)

    Whorton, Mark; Buschek, Harald; Calise, Anthony J.

    1996-01-01

    Recent developments in the field of robust multivariable control have merged the theories of H-infinity and H-2 control. This mixed H-2/H-infinity compensator formulation allows design for nominal performance by H-2 norm minimization while guaranteeing robust stability to unstructured uncertainties by constraining the H-infinity norm. A key difficulty associated with mixed H-2/H-infinity compensation is compensator synthesis. A homotopy algorithm is presented for synthesis of fixed order mixed H-2/H-infinity compensators. Numerical results are presented for a four disk flexible structure to evaluate the efficiency of the algorithm.

  13. A practical way to synthesize chiral fluoro-containing polyhydro-2H-chromenes from monoterpenoids

    PubMed Central

    Mikhalchenko, Oksana S; Korchagina, Dina V; Salakhutdinov, Nariman F

    2016-01-01

    Summary Conditions enabling the single-step preparative synthesis of chiral 4-fluoropolyhydro-2H-chromenes in good yields through a reaction between monoterpenoid alcohols with para-menthane skeleton and aldehydes were developed for the first time. The BF3·Et2O/H2O system is used both as a catalyst and as a fluorine source. The reaction can involve aliphatic aldehydes as well as aromatic aldehydes containing various acceptor and donor substituents. 4-Hydroxyhexahydro-2H-chromenes were demonstrated to be capable of converting to 4-fluorohexahydro-2H-chromenes under the developed conditions, the reaction occurs with inversion of configuration. PMID:27340456

  14. Determination of the delta(2H/1H)of Water: RSIL Lab Code 1574

    USGS Publications Warehouse

    Revesz, Kinga; Coplen, Tyler B.

    2008-01-01

    Reston Stable Isotope Laboratory (RSIL) lab code 1574 describes a method used to determine the relative hydrogen isotope-ratio delta(2H,1H), abbreviated hereafter as d2H of water. The d2H measurement of water also is a component of the National Water Quality Laboratory (NWQL) schedules 1142 and 1172. The water is collected unfiltered in a 60-mL glass bottle and capped with a Polyseal cap. In the laboratory, the water sample is equilibrated with gaseous hydrogen using a platinum catalyst (Horita, 1988; Horita and others, 1989; Coplen and others, 1991). The reaction for the exchange of one hydrogen atom is shown in equation 1.

  15. A practical way to synthesize chiral fluoro-containing polyhydro-2H-chromenes from monoterpenoids.

    PubMed

    Mikhalchenko, Oksana S; Korchagina, Dina V; Volcho, Konstantin P; Salakhutdinov, Nariman F

    2016-01-01

    Conditions enabling the single-step preparative synthesis of chiral 4-fluoropolyhydro-2H-chromenes in good yields through a reaction between monoterpenoid alcohols with para-menthane skeleton and aldehydes were developed for the first time. The BF3·Et2O/H2O system is used both as a catalyst and as a fluorine source. The reaction can involve aliphatic aldehydes as well as aromatic aldehydes containing various acceptor and donor substituents. 4-Hydroxyhexahydro-2H-chromenes were demonstrated to be capable of converting to 4-fluorohexahydro-2H-chromenes under the developed conditions, the reaction occurs with inversion of configuration. PMID:27340456

  16. The Effect of N2 Photoabsorption Cross Section Resolution on C2H6 Production in Titan’s Ionosphere

    NASA Astrophysics Data System (ADS)

    Luspay-Kuti, Adrienn; Mandt, Kathleen E.; Plessis, Sylvain; Greathouse, Thomas K.

    2014-11-01

    Titan’s rich organic chemistry begins with the photochemistry of only two molecules: N2 and CH4. The details on how higher-order hydrocarbons and nitriles are formed from these molecules have key implications for both the structure and evolution of Titan’s atmosphere, and for its surface-atmosphere interactions. Of high importance is the production of C2H6, which is a sink for CH4, and a main component in the polar lakes. Results of photochemical models, though, may be sensitive to the choice of input parameters, such as the N2 photoabsorption cross section resolution, as previously shown for nitrogen (Liang et al. (2007) ApJL 664, 115-118), and CH4 (Lavvas et al. (2011) Icarus 213, 233-251). Here we investigate the possibility of the same effect on the production rates of C2H6. We modeled production and loss rates, as well as mixing ratio and density profiles between an altitude of 600 and 1600 km for low and high resolution N2 cross sections via a coupled ion-neutral-thermal model (De La Haye et al. (2008) Icarus 197, 110-136; Mandt et al. (2012) JGR 117, E10006). Our results show a clear impact of photoabsorption cross section resolution used on all neutral and ion species contributing to C2H6 production. The magnitude of the influence varies amongst species. Ethane production profiles exhibit a significant increase with better resolution; a factor of 1.2 between 750 and 950 km, and a factor of 1.1 in the total column-integrated production rate. These values are lower limits, as additional reactions involving C2H5 not included in the model may also contribute to the production rates. The clear effect on C2H6 (which is not a parent molecule, nor does it bear nitrogen) may have important implications for other molecules in Titan’s atmosphere as well. The possible non-negligible impact of an isotope of nitrogen may argue for the inclusion of isotopes in photochemical models. For future analysis, development of a more efficient and streamlined model called

  17. Alcohol Chemistry: Tentative Detections of Two New Interstellar Big Molecules CH_3OC_2H_5 and (C_2H_5)_2O

    NASA Astrophysics Data System (ADS)

    Kuan, Y.-J.; Charnley, S. B.; Wilson, T. L.; Ohishi, M.; Huang, H.-C.; Snyder, L. E.

    1999-05-01

    Recent modeling of gas-grain chemistry demonstrated that many of the organic species are not the products of grain-surface reactions but are in fact synthesized in the warm gas from simpler species produced on grains. To test gas-grain chemistry, in particular alcohol chemistry, we have thus searched for (C_2H_5)_2O (diethyl ether) and CH_3OC_2H_5 (methyl ethyl ether), using the NRAO 12-m, in the giant molecular cloud cores Sgr B2(N), W51 e1/e2 and Orion-KL, where alcohols have been evaporated from ice mantles. In addition, we have also used the BIMA array to observe the 3-mm transitions of the two molecules toward Sgr B2. The preliminary 12-m results indicate clean detections of various line transitions of the two molecular species in the 1-mm, 2-mm and 3-mm regimes in all 3 molecular cloud cores. Furthermore our BIMA maps show a clear concentration of CH_3OH toward Sgr B2(N), the Large Molecule Heimat; sole detections of CH_3OC_2H_5 and (C_2H_5)_2O toward Sgr B2(N), instead of the more evolved Sgr B2(M), are also observed unambiguously as predicted by alcohol chemistry. Our detections of the two complex molecules not only further confirm the gas-grain chemistry but also require specifically that methanol (CH_3OH) and ethanol (C_2H_5OH) to be formed in grain mantles. In addition, the detections of diethyl ether and methyl ethyl ether lead to the discovery of two new molecules, including the largest ever, (C_2H_5)_2O. This work was partially supported by: NSC grants 87-2112-M-003-007 and 88-2112-M-003-013 of Taiwan, National Taiwan Normal University, Academia Sinica Institute of Astronomy and Astrophysics, NSF AST 96-13999, the University of Illinois, and NASA's Exobiology Program.

  18. Water interactions with varying molecular states of bovine casein: 2H NMR relaxation studies

    SciTech Connect

    Kumosinski, T.F.; Pessen, H.; Prestrelski, S.J.; Farrell, H.M. Jr.

    1987-09-01

    The caseins occur in milk as spherical colloidal complexes of protein and salts with an average diameter of 1200 A, the casein micelles. Removal of Ca2+ is thought to result in their dissociation into smaller protein complexes stabilized by hydrophobic interactions and called submicelles. Whether these submicelles actually occur within the micelles as discrete particles interconnected by calcium phosphate salt bridges has been the subject of much controversy. A variety of physical measurements have shown that casein micelles contain an inordinately high amount of trapped water (2 to 7 g H/sub 2/O/g protein). With this in mind it was of interest to determine if NMR relaxation measurements could detect the presence of this trapped water within the micelles, and to evaluate whether it is a continuum with picosecond correlation times or is associated in part with discrete submicellar structures with nanosecond motions. For this purpose the variations in /sup 2/H NMR longitudinal and transverse relaxation rates of water with protein concentration were determined for bovine casein at various temperatures, under both submicellar and micellar conditions. D/sub 2/O was used instead of H/sub 2/O to eliminate cross-relaxation effects. From the protein concentration dependence of the relaxation rates, the second virial coefficient of the protein was obtained by nonlinear regression analysis. Using either an isotropic tumbling or an intermediate asymmetry model, degrees of hydration, v, and correlation times, tau c, were calculated for the caseins; from the latter parameter the Stokes radius, r, was obtained. Next, estimates of molecular weights were obtained from r and the partial specific volume. Values were in the range of those published from other methodologies for the submicelles.

  19. Monte Carlo simulations of high-pressure phase equilibria of CO2-H2O mixtures.

    PubMed

    Liu, Yang; Panagiotopoulos, Athanassios Z; Debenedetti, Pablo G

    2011-05-26

    Histogram-reweighting grand canonical Monte Carlo simulations were used to obtain the phase behavior of CO(2)-H(2)O mixtures over a broad temperature and pressure range (50 °C ≤ T ≤ 350 °C, 0 ≤ P ≤ 1000 bar). We performed a comprehensive test of several existing water (SPC, TIP4P, TIP4P2005, and exponential-6) and carbon dioxide (EPM2, TraPPE, and exponential-6) models using conventional Lorentz-Berthelot combining rules for the unlike-pair parameters. None of the models we studied reproduce adequately experimental data over the entire temperature and pressure range, but critical assessments were made on the range of T and P where particular model pairs perform better. Away from the critical region (T ≤ 250 °C), the exponential-6 model combination yields the best predictions for the CO(2)-rich phase, whereas the TraPPE/TIP4P2005 model combination provides the most accurate coexistence composition and pressure for the H(2)O-rich phase. Near the critical region (250 °C < T ≤ 350 °C), the critical points are not accurately estimated by any of the models studied, but the exponential-6 models are able to qualitatively capture the critical loci and the shape of the phase envelopes. Local improvements can be achieved at specific temperatures by introducing modification factors to the Lorentz-Berthelot combining rules, but the modified combining rule is still not able to achieve global improvements over the entire temperature and pressure range. Our work points to the challenge and importance of improving current atomistic models so as to accurately predict the phase behavior of this important binary mixture.

  20. (2) H and (139) La NMR Spectroscopy in Aqueous Solutions at Geochemical Pressures.

    PubMed

    Ochoa, Gerardo; Pilgrim, Corey D; Martin, Michele N; Colla, Christopher A; Klavins, Peter; Augustine, Matthew P; Casey, William H

    2015-12-14

    Nuclear spin relaxation rates of (2) H and (139) La in LaCl3 +(2) H2 O and La(ClO4 )3 +(2) H2 O solutions were determined as a function of pressure in order to demonstrate a new NMR probe designed for solution spectroscopy at geochemical pressures. The (2) H longitudinal relaxation rates (T1 ) vary linearly to 1.6 GPa, consistent with previous work at lower pressures. The (139) La T1 values vary both with solution chemistry and pressure, but converge with pressure, suggesting that the combined effects of increased viscosity and enhanced rates of ligand exchange control relaxation. This simple NMR probe design allows experiments on aqueous solutions to pressures corresponding roughly to those at the base of the Earth's continental crust. PMID:26404025

  1. Epitaxial growth and electronic structure of oxyhydride SrVO2H thin films

    NASA Astrophysics Data System (ADS)

    Katayama, Tsukasa; Chikamatsu, Akira; Yamada, Keisuke; Shigematsu, Kei; Onozuka, Tomoya; Minohara, Makoto; Kumigashira, Hiroshi; Ikenaga, Eiji; Hasegawa, Tetsuya

    2016-08-01

    Oxyhydride SrVO2H epitaxial thin films were fabricated on SrTiO3 substrates via topotactic hydridation of oxide SrVO3 films using CaH2. Structural and composition analyses suggested that the SrVO2H film possessed one-dimensionally ordered V-H--V bonds along the out-of-plane direction. The synthesis temperature could be lowered by reducing the film thickness, and the SrVO2H film was reversible to SrVO3 by oxidation through annealing in air. Photoemission and X-ray absorption spectroscopy measurements revealed the V3+ valence state in the SrVO2H film, indicating that the hydrogen existed as hydride. Furthermore, the electronic density of states was highly suppressed at the Fermi energy, consistent with the prediction that tetragonal distortion induces metal to insulation transition.

  2. Infrared and Ultraviolet Spectra of Diborane(6): B2H6 and B2D6.

    PubMed

    Peng, Yu-Chain; Chou, Sheng-Lung; Lo, Jen-Iu; Lin, Meng-Yeh; Lu, Hsiao-Chi; Cheng, Bing-Ming; Ogilvie, J F

    2016-07-21

    We recorded absorption spectra of diborane(6), B2H6 and B2D6, dispersed in solid neon near 4 K in both mid-infrared and ultraviolet regions. For gaseous B2H6 from 105 to 300 nm, we report quantitative absolute cross sections; for solid B2H6 and for B2H6 dispersed in solid neon, we measured ultraviolet absorbance with relative intensities over a wide range. To assign the mid-infrared spectra to specific isotopic variants, we applied the abundance of (11)B and (10)B in natural proportions; we undertook quantum-chemical calculations of wavenumbers associated with anharmonic vibrational modes and the intensities of the harmonic vibrational modes. To aid an interpretation of the ultraviolet spectra, we calculated the energies of electronically excited singlet and triplet states and oscillator strengths for electronic transitions from the electronic ground state. PMID:27351464

  3. A Ring of C2H in the Molecular Disk Orbiting TW Hya

    NASA Astrophysics Data System (ADS)

    Kastner, Joel H.; Qi, Chunhua; Gorti, Uma; Hily-Blant, Pierre; Oberg, Karin; Forveille, Thierry; Andrews, Sean; Wilner, David

    2015-06-01

    We have used the Submillimeter Array to image, at ˜1.″5 resolution, C2H N=3\\to 2 emission from the circumstellar disk orbiting the nearby (D = 54 pc), ˜8 Myr-old, ˜0.8 {{M}⊙ } classical T Tauri star TW Hya. The SMA imaging reveals that the C2H emission exhibits a ring-like morphology. Based on a model in which the C2H column density follows a truncated radial power-law distribution, we find that the inner edge of the ring lies at ˜45 AU, and that the ring extends to at least ˜120 AU. Comparison with previous (single-dish) observations of C2H N=4\\to 3 emission indicates that the C2H molecules are subthermally excited and, hence, that the emission arises from the relatively warm (T≳ 40 K), tenuous (n\\ll {{10}7} cm-3) upper atmosphere of the disk. Based on these results and comparisons of the SMA C2H map with previous submillimeter and scattered-light imaging, we propose that the C2H emission most likely traces particularly efficient photo-destruction of small grains and/or photodesorption and photodissociation of hydrocarbons derived from grain ice mantles in the surface layers of the outer disk. The presence of a C2H ring in the TW Hya disk hence likely serves as a marker of dust grain processing and radial and vertical grain size segregation within the disk.

  4. Recent advances in the chemistry of SmI(2)-H(2)O.

    PubMed

    Sautier, Brice; Procter, David J

    2012-01-01

    Recent work from our laboratories has shown SmI(2)-H(2)O to be a versatile, readily-accessible and non-toxic reductant that is more powerful than SmI(2). This review describes the reduction of functional groups that were previously thought to lie beyond the reach of SmI(2) and complexity-generating cyclisations and cyclisation cascades triggered by the reduction of the ester carbonyl group with SmI(2)-H(2)O.

  5. Synthesis of 2H-Indazoles by the [3 + 2] Dipolar Cycloaddition of Sydnones with Arynes

    PubMed Central

    Fang, Yuesi; Wu, Chunrui; Larock, Richard C.; Shi, Feng

    2011-01-01

    A rapid and efficient synthesis of 2H-indazoles has been developed using a [3 + 2] dipolar cycloaddition of sydnones and arynes. A series of 2H-indazoles have been prepared in good to excellent yields using this protocol, and subsequent Pd-catalyzed coupling reactions can be applied to the halogenated products to generate a structurally diverse library of indazoles. PMID:21970468

  6. Natural-abundance solid-state 2H NMR spectroscopy at high magnetic field.

    PubMed

    Aliev, Abil E; Mann, Sam E; Iuga, Dinu; Hughes, Colan E; Harris, Kenneth D M

    2011-06-01

    High-resolution solid-state (2)H NMR spectroscopy provides a method for measuring (1)H NMR chemical shifts in solids and is advantageous over the direct measurement of high-resolution solid-state (1)H NMR spectra, as it requires only the application of routine magic angle sample spinning (MAS) and routine (1)H decoupling methods, in contrast to the requirement for complex pulse sequences for homonuclear (1)H decoupling and ultrafast MAS in the case of high-resolution solid-state (1)H NMR. However, a significant obstacle to the routine application of high-resolution solid-state (2)H NMR is the very low natural abundance of (2)H, with the consequent problem of inherently low sensitivity. Here, we explore the feasibility of measuring (2)H MAS NMR spectra of various solids with natural isotopic abundances at high magnetic field (850 MHz), focusing on samples of amino acids, peptides, collagen, and various organic solids. The results show that high-resolution solid-state (2)H NMR can be used successfully to measure isotropic (1)H chemical shifts in favorable cases, particularly for mobile functional groups, such as methyl and -N(+)H(3) groups, and in some cases phenyl groups. Furthermore, we demonstrate that routine (2)H MAS NMR measurements can be exploited for assessing the relative dynamics of different functional groups in a molecule and for assessing whole-molecule motions in the solid state. The magnitude and field-dependence of second-order shifts due to the (2)H quadrupole interaction are also investigated, on the basis of analysis of simulated and experimental (1)H and (2)H MAS NMR spectra of fully deuterated and selectively deuterated samples of the α polymorph of glycine at two different magnetic field strengths.

  7. Direct ab initio study of the C6H6 + CH3/C2H5 = C6H5 + CH4/C2H6 reactions

    NASA Astrophysics Data System (ADS)

    Mai, Tam V.-T.; Ratkiewicz, Artur; Duong, Minh v.; Huynh, Lam K.

    2016-02-01

    A kinetic study of the reactions C6H6 + CH3/C2H5 = C6H5 + CH4/C2H6 was carried out in the temperature range of 300-2500 K using high levels of electronic structure theory, namely, CCSD(T)/CBS//BH&HLYP/cc-pVDZ, and canonical variational transition state theory (CVT) with corrections for small curvature tunneling (SCT) and hindered internal rotation (HIR) treatments. It is found that variational effect is not important and both SCT and HIR corrections noticeably affect the rate constants. Being in good agreement with literature data, the calculated results provide solid basis information for the investigation of the polyaromatic hydrocarbon (PAH) + alkyl radical reaction, an important class in combustion and soot formation.

  8. REASSESSMENT OF THE DISSOCIATIVE RECOMBINATION OF N{sub 2}H{sup +} AT CRYRING

    SciTech Connect

    Vigren, E.; Zhaunerchyk, V.; Hamberg, M.; Af Ugglas, M.; Larsson, M.; Thomas, R. D.; Geppert, W. D.; Kaminska, M.; Semaniak, J.

    2012-09-20

    The dissociative recombination (DR) of N{sub 2}H{sup +} has been reinvestigated at the heavy ion storage ring CRYRING at the Manne Siegbahn Laboratory in Stockholm, Sweden. Thermal rate coefficients for electron temperatures between 10 and 1000 K have been deduced. We show that electron recombination is expected to play an approximately equally important role as CO in the removal of N{sub 2}H{sup +} in dark interstellar clouds. We note that a deeper knowledge on the influence of the ions' rotational temperature in the DR of N{sub 2}H{sup +} would be helpful to set further constraints on the relative importance of the different destruction mechanisms for N{sub 2}H{sup +} in these environments. The branching fractions in the DR of N{sub 2}H{sup +} have been reinvestigated at {approx}0 eV relative kinetic energy, showing a strong dominance of the N{sub 2} + H production channel (93{sup +4}{sub -2}%) with the rest leading to NH + N. These results are in good agreement with flowing afterglow experiments and in disagreement with an earlier measurement at CRYRING.

  9. Low-temperature rate coefficients for the reaction of ethynyl radical (C2H) with benzene.

    PubMed

    Goulay, Fabien; Leone, Stephen R

    2006-02-01

    The reaction of the C2H radical with benzene is studied at low temperature using a pulsed Laval nozzle apparatus. The C2H radical is prepared by 193-nm photolysis of acetylene, and the C2H concentration is monitored using CH(A2Delta) chemiluminescence from the C2H + O2 reaction. Measurements at very low photolysis energy are performed using CF3C2H as the C2H precursor to study the influence of benzene photodissociation on the rate coefficient. Rate coefficients are obtained over a temperature range between 105 and 298 K. The average rate coefficient is found to be five times greater than the estimated value presently used in the photochemical modeling of Titan's atmosphere. The reaction exhibits a slight negative temperature dependence which can be fitted to the expression k(cm3 molecule(-1) s(-1)) = 3.28(+/-1.0) x 10(-10) (T/298)(-0.18(+/-0.18)). The results show that this reaction has no barrier and may play an important role in the formation of large molecules and aerosols at low temperature. Our results are consistent with the formation of a short lifetime intermediate that decomposes to give the final products.

  10. Vibrationally resolved photoelectron imaging of Cu2H- and AgCuH- and theoretical calculations.

    PubMed

    Xie, Hua; Li, Xiaoyi; Zhao, Lijuan; Liu, Zhiling; Qin, Zhengbo; Wu, Xia; Tang, Zichao; Xing, Xiaopeng

    2013-02-28

    Vibrationally resolved photoelectron spectra have been obtained for Cu(2)H(-) and AgCuH(-) using photoelectron imaging at 355 nm. Two transition bands X and A are observed for each spectrum. The X bands in both spectra show the vibration progressions of the Cu-H stretching mode and the broad peaks of these progressions indicate significant structural changes from Cu(2)H(-) and AgCuH(-) to their neutral ground states. The A bands in the spectra of Cu(2)H(-) and CuAgH(-) show stretching progressions of Cu-Cu and Ag-Cu, respectively. The contours of these two progressions are pretty narrow, indicating relatively small structural changes from Cu(2)H(-) and AgCuH(-) to their neutral excited states. Calculations based on density functional theory indicate that the ground states of Cu(2)H(-) and AgCuH(-) and the first excited states of their neutrals are linear, whereas their neutral ground states are bent. The photoelectron detachment energies and vibrational frequencies from these calculations are in good agreement with the experimental observations. Especially, the theoretical predication of linear structures for the anions and the neutral excited states are supported by the spectral features of A bands, in which the bending modes are inactive. Comparisons among the vertical detachment energies of Cu(2)H(-), AgCuH(-), and their analogs help to elucidate electronic characteristics of coinage metal elements and hydrogen in small clusters.

  11. C2H4 adsorption on Cu(210), revisited: bonding nature and coverage effects.

    PubMed

    Amino, Shuichi; Arguelles, Elvis; Agerico Diño, Wilson; Okada, Michio; Kasai, Hideaki

    2016-08-24

    With the aid of density functional theory (DFT)-based calculations, we investigate the adsorption of C2H4 on Cu(210). We found two C2H4 adsorption sites, viz., the top of the step-edge atom (S) and the long bridge between two step-edge atoms (SS) of Cu(210). The step-edge atoms on Cu(210) block the otherwise active terrace sites found on copper surfaces with longer step sizes. This results in the preference for π-bonded over di-σ-bonded C2H4. We also found two stable C2H4 adsorption orientations on the S- and SS-sites, viz., with the C2H4 C[double bond, length as m-dash]C bond parallel (fit) and perpendicular (cross) to [001]. Furthermore, we found that the three peaks observed in previous temperature programmed desorption (TPD) experiment [Surf. Sci., 2011, 605, 934-940] could be attributed to C2H4 in the S-fit or S-cross, S-fit and S-cross-fit (S-cross and S-fit configurations that both exist in the same unit cell) configurations on Cu(210). PMID:27506302

  12. Involvement of plant C(2)H(2)-type zinc finger transcription factors in stress responses.

    PubMed

    Kiełbowicz-Matuk, Agnieszka

    2012-04-01

    Abiotic and biotic stresses frequently impose constraints on plant distribution and affect agricultural productivity. Various aspects of the multiplicity and the complexity of stress responsive gene networks have been previously studied. Many of individual transcription factors in plants and their family classes that regulate the expression of several genes in responses to environmental stresses have been identified. One such class of transcription regulators is the C(2)H(2) class of zinc finger proteins. Numerous members of the C(2)H(2)-type zinc finger family have been shown to play diverse roles in the plant stress response and the hormone signal transduction. Transcription profiling analyses have demonstrated that the transcript level of many C(2)H(2)-type zinc finger proteins is elevated under different abiotic stress conditions such as low temperature, salt, drought, osmotic stress and oxidative stress. Some C(2)H(2)-type proteins are additionally involved in the biotic stress signaling pathway. Moreover, it has been reported that overexpression of some C(2)H(2)-type zinc finger protein genes resulted in both the activation of some stress-related genes and enhanced tolerance to various stresses. Current genetic studies have focused on possible interactions between different zinc finger transcription factors during stresses to regulate transcription. This review highlights the role of the C(2)H(2) class of the zinc finger proteins in regulating abiotic and biotic stress tolerance in the plants.

  13. delta(13)C and delta(2)H isotope ratios in amphetamine synthesized from benzaldehyde and nitroethane.

    PubMed

    Collins, Michael; Salouros, Helen; Cawley, Adam T; Robertson, James; Heagney, Aaron C; Arenas-Queralt, Andrea

    2010-06-15

    Previous work in these laboratories and by Butzenlechner et al. and Culp et al. has demonstrated that the delta(2)H isotope value of industrial benzaldehyde produced by the catalytic oxidation of toluene is profoundly positive, usually in the range +300 per thousand to +500 per thousand. Synthetic routes leading to amphetamine, methylamphetamine or their precursors and commencing with such benzaldehyde may be expected to exhibit unusually positive delta(2)H values. Results are presented for delta(13)C and delta(2)H isotope values of 1-phenyl-2-nitropropene synthesized from an industrial source of benzaldehyde, having a positive delta(2)H isotope value, by a Knoevenagel condensation with nitroethane. Results are also presented for delta(13)C and delta(2)H isotope values for amphetamine prepared from the resulting 1-phenyl-2-nitropropene. The values obtained were compared with delta(13)C and delta(2)H isotope values obtained for an amphetamine sample prepared using a synthetic route that did not involve benzaldehyde. Finally, results are presented for samples of benzaldehyde, 1-phenyl-2-nitropropene and amphetamine that had been seized at a clandestine amphetamine laboratory.

  14. Broad N2H+ Emission toward the Protostellar Shock L1157-B1

    NASA Astrophysics Data System (ADS)

    Codella, C.; Viti, S.; Ceccarelli, C.; Lefloch, B.; Benedettini, M.; Busquet, G.; Caselli, P.; Fontani, F.; Gómez-Ruiz, A.; Podio, L.; Vasta, M.

    2013-10-01

    We present the first detection of N2H+ toward a low-mass protostellar outflow, namely, the L1157-B1 shock, at ~0.1 pc from the protostellar cocoon. The detection was obtained with the IRAM 30 m antenna. We observed emission at 93 GHz due to the J = 1-0 hyperfine lines. Analysis of this emission coupled with HIFI CHESS multiline CO observations leads to the conclusion that the observed N2H+(1-0) line originated from the dense (>=105 cm-3) gas associated with the large (20''-25'') cavities opened by the protostellar wind. We find an N2H+ column density of a few 1012 cm-2 corresponding to an abundance of (2-8) × 10-9. The N2H+ abundance can be matched by a model of quiescent gas evolved for more than 104 yr, i.e., for more than the shock kinematical age (sime2000 yr). Modeling of C-shocks confirms that the abundance of N2H+ is not increased by the passage of the shock. In summary, N2H+ is a fossil record of the pre-shock gas, formed when the density of the gas was around 104 cm-3, and then further compressed and accelerated by the shock.

  15. {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He reactions at sub-coulomb energies

    SciTech Connect

    Tumino, A.; Spitaleri, C.; Mukhamedzhanov, A. M.; Typel, S.; Sparta, R.; Aliotta, M.; Kroha, V.; Hons, Z.; La Cognata, M.; Lamia, L.; Pizzone, R. G.; Mrazek, J.; Pizzone, R. G.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.

    2012-11-20

    The {sup 2}H({sup 3}He,p{sup 3}H){sup 1}H and {sup 2}H({sup 3}He,n{sup 3}He){sup 1}H processes have been measured in quasi free kinematics to investigate for the first time the {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He reactions by means of the Trojan Horse Method. The {sup 3}He+d experiment was performed at 18 MeV, corresponding the a d-d energy range from 1.5 MeV down to 2 keV. This range overlaps with the relevant region for Standard Big Bang Nucleosynthesis as well as with the thermal energies of future fusion reactors and deuterium burning in the Pre Main Sequence phase of stellar evolution. This is the first pioneering experiment in quasi free regime where the charged spectator is detected. Both the energy dependence and the absolute value of the bare nucleus S(E) factors have been extracted for the first time. They deviate by more than 15% from available direct data with new S(0) values of 57.4{+-}1.8 MeVb for {sup 3}H+p and 60.1{+-}1.9 MeVb for {sup 3}He+n. None of the existing fitting curves is able to provide the correct slope of the new data in the full range, thus calling for a revision of the theoretical description. This has consequences in the calculation of the reaction rates with more than a 25% increase at the temperatures of future fusion reactors.

  16. DISSOCIATION OF B2H6 AND ADSORPTION OF THE FRAGMENTS OF B2H6 ON THE STEPPED Ge(100) SURFACE

    NASA Astrophysics Data System (ADS)

    Türkmenoğlu, Mustafa; Katircioğlu, Şenay

    2012-06-01

    In this work, the p-type doping of the SA type stepped Ge(100) surface by a diborane (B2H6) gas flow has been simulated by the possible dissociation and adsorption models. The most probable dissociation model of B2H6 and adsorption models of the fragments of B2H6 on the stepped Ge(100) surface have been determined by the local minimum total energy and/or binding energy calculations based on the Density functional (B3LYP/6-3g) and Hartree-Fock (HF/STO-3g) theories, respectively. The present calculations have shown that, the step region (for both up and down terraces) of the stepped Ge(100) surface has the most attractive sites for BH3 molecules determined to be the first dissociation fragments of B2H6 by an external energy of 1.3 eV. It has been found that, at the first step of the adsorption, BH3 can dissociate to BH2 and BH fragments on the stepped Ge(100) surface. While BH3 and BH2 products prefer to be attached to a single surface Ge atom, BH is bridged between two adjacent surface Ge atoms. According to the present optimization calculations, the p-type doping process of the stepped Ge(100) surface has started with the adsorption of BH3 on the electron deficient site (buckled down) of the Ge dimer bond close to the step edge and ended with the substitutional occupation of the Ge site in the layers of the surface by B atom. The beginning of the p-type doping of the stepped Ge(100) surface has been illustrated by the electronic states of B appeared in the optical energy gap of Ge very close to the edge of the HOMO.

  17. Laboratory studies of 2H evaporator scale dissolution in dilute nitric acid

    SciTech Connect

    Oji, L.

    2014-09-23

    The rate of 2H evaporator scale solids dissolution in dilute nitric acid has been experimentally evaluated under laboratory conditions in the SRNL shielded cells. The 2H scale sample used for the dissolution study came from the bottom of the evaporator cone section and the wall section of the evaporator cone. The accumulation rate of aluminum and silicon, assumed to be the two principal elemental constituents of the 2H evaporator scale aluminosilicate mineral, were monitored in solution. Aluminum and silicon concentration changes, with heating time at a constant oven temperature of 90 deg C, were used to ascertain the extent of dissolution of the 2H evaporator scale mineral. The 2H evaporator scale solids, assumed to be composed of mostly aluminosilicate mineral, readily dissolves in 1.5 and 1.25 M dilute nitric acid solutions yielding principal elemental components of aluminum and silicon in solution. The 2H scale dissolution rate constant, based on aluminum accumulation in 1.5 and 1.25 M dilute nitric acid solution are, respectively, 9.21E-04 ± 6.39E-04 min{sup -1} and 1.07E-03 ± 7.51E-05 min{sup -1}. Silicon accumulation rate in solution does track the aluminum accumulation profile during the first few minutes of scale dissolution. It however diverges towards the end of the scale dissolution. This divergence therefore means the aluminum-to-silicon ratio in the first phase of the scale dissolution (non-steady state conditions) is different from the ratio towards the end of the scale dissolution. Possible causes of this change in silicon accumulation in solution as the scale dissolution progresses may include silicon precipitation from solution or the 2H evaporator scale is a heterogeneous mixture of aluminosilicate minerals with several impurities. The average half-life for the decomposition of the 2H evaporator scale mineral in 1.5 M nitric acid is 12.5 hours, while the half-life for the decomposition of the 2H evaporator scale in 1.25 M nitric acid is 10

  18. Global frequency and intensity analysis of the ν10/ν7/ν4/ν12 band system of 12C2H4 at 10 μm using the D2h Top Data System

    NASA Astrophysics Data System (ADS)

    Alkadrou, A.; Bourgeois, M.-T.; Rotger, M.; Boudon, V.; Vander Auwera, J.

    2016-10-01

    A global frequency and intensity analysis of the infrared tetrad of 12C2H4 located in the 600 - 1500cm-1 region was carried out using the tensorial formalism developed in Dijon for X2Y4 asymmetric-top molecules. It relied on spectroscopic information available in the literature and retrieved from high-resolution Fourier transform infrared spectra recorded in Brussels in the frame of either the present or previous work. In particular, 645 and 131 line intensities have been respectively measured for the weak ν10 and ν4 bands. Including the Coriolis interactions affecting the upper vibrational levels 101, 71, 41 and 121, a total of 10 757 line positions and 1645 line intensities have been assigned and fitted with global root mean square deviations of 2.6 ×10-4cm-1 and 2.5%, respectively. Relying on the results of the present work and available in the literature, a list of parameters for 65 776 lines in the ν10, ν7, ν4 and ν12 bands of 12C2H4 was generated. To the best of our knowledge, this is the first time that a global intensity analysis is carried out in this range of the ethylene spectrum.

  19. Poster 1: Global frequency and intensity analysis of the ν10/ν7/ν4/ν12 band system of 12C2H4 at 10 µm using the D2h Top Data System

    NASA Astrophysics Data System (ADS)

    Alkadrou, Abdulsamee; Bourgeois, Marie-Therese; Rotger, Maud; Boudon, Vincent; Vander Auwera, Jean

    2016-06-01

    A global frequency and intensity analysis of the infrared tetrad of 12C2H4 located in the 600-1500 cm-1 region was carried out using the tensorial formalism developed in Dijon for X2Y4 asymmetric-top molecules. It relies on spectroscopic information available in the literature and retrieved from high-resolution Fourier transform infrared spectra recorded in Brussels in the frame of either the present or previous work. In particular, 645 and 131 lines intensities have been respectively measured for the weak ν10 and ν4 bands. Including the Coriolis interactions affecting the upper vibrational levels 101, 71, 41 and 121 , a total of 10,737 line positions and 1,867 line intensities have been assigned and fitted with global root mean square deviations of 2.6 10-4 cm-1 and 2.4 %, respectively. Relying on the results of the present work and available in the literature, a list of parameters for 65,420 lines in the ν10, ν7, ν4 and ν12 bands of 12C2H4 was generated. To the best of our knowledge, this is the first time that a global intensity analysis is carried out in this range of the ethylene spectrum.

  20. Precision measurements of {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He total cross sections at Big Bang nucleosynthesis energies

    SciTech Connect

    Leonard, D.S.; Karwowski, H.J.; Brune, C.R.; Fisher, B.M.; Ludwig, E.J.

    2006-04-15

    Recent Wilkinson Microwave Anisotropy Probe (WMAP) measurements have determined the baryon density of the Universe {omega}{sub b} with a precision of about 4%. With {omega}{sub b} tightly constrained, comparisons of Big Bang nucleosynthesis (BBN) abundance predictions to primordial abundance observations can be made and used to test BBN models and/or to further constrain abundances of isotopes with weak observational limits. To push the limits and improve constraints on BBN models, uncertainties in key nuclear reaction rates must be minimized. To this end, we made new precise measurements of the {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He total cross sections at lab energies from 110 to 650 keV. A complete fit was performed in energy and angle to both angular distribution and normalization data for both reactions simultaneously. By including parameters for experimental variables in the fit, error correlations between detectors, reactions, and reaction energies were accurately tabulated by computational methods. With uncertainties around 2%{+-}1% scale error, these new measurements significantly improve on the existing data set. At relevant temperatures, by using the data of the present work, both reaction rates are found to be about 7% higher than those in the widely used NACRE (nuclear astrophysics compilation of reaction rates) database. These data will thus lead not only to reduced uncertainties, but also to modifications in the BBN abundance predictions.

  1. The condensation and vaporization behavior of ices containing SO2, H2S, and CO2: Implications for Io

    NASA Technical Reports Server (NTRS)

    Sandford, Scott A.; Allamandola, Louis J.

    1993-01-01

    In an extension of previously reported work on ices containing CO, CO2, H2O, CH3OH, NH3, and H2, measurements of the physical and infrared spectral properties of ices containing molecules relevant to Jupiter's moon Io are presented. These include studies on ice systems containing SO2, H2S, and CO2. The condensation and sublimation behaviors of each ice system and surface binding energies of their components are discussed. The surface binding energies can be used to calculate the residence times of the molecules on a surface as a function of temperature and thus represent important parameters for any calculation that attempts to model the transport of these molecules on Io's surface. The derived values indicate that SO2 frosts on Io are likely to anneal rapidly, resulting in less fluffy, 'glassy' ices and that H2S can be trapped in the SO2 ices of Io during night-time hours provided that SO2 deposition rates are on the order of 5 micrometers/hr or larger.

  2. Rototranslational collision-induced absorption by H2-H2 pairs at temperatures from 600 to 7000 K

    NASA Technical Reports Server (NTRS)

    Zheng, Chunguang; Borysow, Aleksandra

    1995-01-01

    The computation of the far-infrared, rototranslational (RT) collision-induced absorption (CIA) spectra of H2-H2 pairs is presented at temperatures from 600 to 7000 K for the first time. Theoretical results are based on the quantum mechanical and semiclassical, three lowest translational spectral moments obtained for H2 pairs. The effective, isotropic H2-H2 interaction potential, suitable for the high-temperature computations, and the ab initio induced dipoles, have been used as input. Special effort has been made to account for the rotational and vibrational states dependence of the dipoles, since it was found to be relevant at the high temperatures employed. The computations of the entire RT band account for all populated vibrational states of hydrogen molecule and include vibrational transitions v tends towards v-prime = v, with v = 0, 1, 2 and 3. The described method makes use of the adequately selected model line shapes with the temperature-dependent parameters. The presented model is useful for the 'model atmospheres' of zero- and low-metallicity, cool and dense stellar atmospheres, where CIA is known to be imporatnt.

  3. The phase diagrams and Pitzer model representations for the system KCl + MgCl2 + H2O at 50 and 75°C

    NASA Astrophysics Data System (ADS)

    Yang, Ji-min; Peng, Jing; Duan, Yu-xia; Tian, Chong; Ping, Mei

    2012-12-01

    The solubilities in the KCl-MgCl2-H2O system were determined at 50 and 75°C and the phase diagrams and the diagram of refractive index vs composition were plotted. Two invariant point, three univariant curves, and three crystallization zones, corresponding to potassium chloride, hexahydrate (MgCl2 · 6H2O) and double salt (KCl · MgCl2 · 6H2O) showed up in the phase diagrams of the ternary system, The mixing parameters θK, Ca and ΨK, Ca, Cl and equilibrium constant K sp were evaluated in KCl-MgCl2-H2O system by least-squares optimization procedure, in which the single-salt Pitzer parameters of KCl and MgCl2 β(0), β(1), β(2), and C ϕ were directly calculated from the literature. The results obtained were in good agreement with the experimental data.

  4. Estimated Critical Conditions for UO(Sub 2)F(Sub 2)-H(Sub 2)O Systems in Fully Water-Reflected Spherical Geometry

    SciTech Connect

    Jordan, W.C.

    1992-01-01

    The purpose of this report is to document reference calculations performed using the SCALE-4.0 code system to determine the critical parameters of UO{sub 2}F{sub 2}-H{sub 2}O spheres. The calculations are an extension of those documented in ORNL/CSD/TM-284. Specifically, the data for low-enriched UO{sub 2}F{sub 2}-H{sub 2}O spheres have been extended to highly enriched uranium. These calculations, together with those reported in ORNL/CSD/TM-284, provide a consistent set of critical parameters (k{sub {infinity}}, volume, mass, mass of water) for UO{sub 2}F{sub 2} and water over the full range of enrichment and moderation ratio.

  5. Estimated critical conditions for UO{sub 2}F{sub 2}--H{sub 2}O systems in fully water-reflected spherical geometry

    SciTech Connect

    Jordan, W.C.; Turner, J.C.

    1992-12-01

    The purpose of this report is to document reference calculations performed using the SCALE-4.0 code system to determine the critical parameters of UO{sub 2}F{sub 2}-H{sub 2}O spheres. The calculations are an extension of those documented in ORNL/CSD/TM-284. Specifically, the data for low-enriched UO{sub 2}F{sub 2}-H{sub 2}O spheres have been extended to highly enriched uranium. These calculations, together with those reported in ORNL/CSD/TM-284, provide a consistent set of critical parameters (k{sub {infinity}}, volume, mass, mass of water) for UO{sub 2}F{sub 2} and water over the full range of enrichment and moderation ratio.

  6. Multi-isotope labelling (13C, 18O, 2H) for studying organic matter cycling within plant-soil systems

    NASA Astrophysics Data System (ADS)

    Studer, M. S.; Abiven, S.; Schmidt, M. W. I.; Siegwolf, R. T. W.

    2012-04-01

    Carbon cycling has become of major interest for the understanding and mitigation of global climatic change. Terrestrial ecosystems have a large carbon sequestration potential, but many processes and fluxes of organic matter (OM) cycling within the plant-soil system are not yet well understood [1]. The dynamics of OM cycling within the plant soil-system are determined by environmental parameters, as well as chemical quality of OM input. A well-known technique to study OM dynamics is to label OM inputs with stable isotopes (e.g 13C). Changes in OM quality in the plant and in the soil can be assessed by compound specific isotopic analysis [2]. These techniques give a precise insight of the OM composition, but are laborious and expensive. Here we suggest a new multi-isotope labelling technique using stable 13C in combination with stable 18O and 2H isotopes, which provides information on OM quality by simple bulk material analysis. The method is based on the creation of an isotopic van Krevelen diagram, which is used to describe different compound groups by plotting the atomic ratios of O/C vs. H/C [3]. We could show that new assimilates can be labelled with 13C, 18O and 2H by adding the stable isotopes (continuously) in the gaseous phase (CO2 and water vapour) to the plants atmosphere. The label has been traced within the bulk material of different compartments of the plant-soil system (e.g. leaves, stems, roots, bulk soil). Our first results showed that after 2, 8 and 14 days of labelling the 18O/13C(new) ratio was notably different in leaf, stem and root tissue (0.0024, 0.0011 and 0.0007, respectively), suggesting a change in OM quality towards more C-rich compounds. d2H analysis will follow and an isotopic van Krevelen diagram will be produced (18O/13C(new) vs. 2H/13C(new)) to describe the changes in OM quality. The new multi-isotope labelling approach represent a powerful tool to address open questions in plant and soil research such as the allocation of organic

  7. Drivers of δ2H variations in an idealized extratropical cyclone

    NASA Astrophysics Data System (ADS)

    Dütsch, Marina; Pfahl, Stephan; Wernli, Heini

    2016-05-01

    Numerical model simulations of stable water isotopes help to improve our understanding of the complex processes driving isotopic variability in atmospheric moisture. We use the isotope-enabled Consortium for Small-Scale Modelling (COSMO) model to study the governing mechanisms of δ2H variations in an idealized extratropical cyclone. A set of experiments with differing initial conditions of δ2H in vapor and partly deactivated isotopic fractionation allows us to quantify the relative roles of cloud fractionation and vertical and horizontal advection for the simulated δ2H signals associated with the cyclone and fronts. Horizontal transport determines the large-scale pattern of δ2H in both vapor and precipitation, while fractionation and vertical transport are more important on a smaller scale, near the fronts. During the passage of the cold front fractionation leads to a V-shaped trend of δ2H in precipitation and vapor, which is, for vapor, superimposed on a gradual decrease caused by the arrival of colder air masses.

  8. Blood brain barrier breakdown was found in non-infarcted area after 2-h MCAO.

    PubMed

    Wang, Xiaona; Liu, Yushan; Sun, Yanyun; Liu, Wenlan; Jin, Xinchun

    2016-04-15

    The blood brain barrier (BBB) could be damaged within the thrombolytic time window and is considered to be a precursor to hemorrhagic transformation during reperfusion. Although we have recently reported the association between BBB damage and tissue injury within the thrombolytic time window, our knowledge about this early BBB damage is limited. In this study, rats were subjected to 2-h middle cerebral artery occlusion (MCAO) followed by 10 min reperfusion with Evan's blue as a tracer to detect BBB damage. Rat brain was sliced into 10 consecutive sections and with TTC staining, a macro and full view of the spatial distribution of BBB damage and tissue injury could be clearly seen in the same group of animals. After 2-h MCAO, tissue injury started from 2nd slice and the BBB leakage started from the 5th slice, of note, there is no colocalization between BBB damage and tissue injury. Fluoro Jade B was employed to explore the localization of neuronal degeneration, and our results showed that 2-h MCAO produced greater number of positive cells in ischemic cortex and dorsal striatum than other areas. More important, 2-h MCAO induced occludin but not claudin-5 degradation in the ischemic hemisphere and pretreatment with MMP inhibitor GM6001 significantly reduced occludin degradation as well as BBB damage detected by IgG leakage. Taken together, our findings demonstrated a "mismatch" between ischemic tissue injury and BBB leakage and a differential degradation of occludin and claudin-5 by MMP-2 after 2-h MCAO. PMID:27000223

  9. Prediction of the existence of the N2H- molecular anion

    NASA Astrophysics Data System (ADS)

    Lique, François; Halvick, Philippe; Stoecklin, Thierry; Hochlaf, Majdi

    2012-06-01

    We predict the existence of the N2H- anion from first principle calculations. We present the three-dimensional potential energy surface and the bound states of the N2H-/D- van der Waals anion. The electronic calculations were performed using state-of-the-art ab initio methods and the nuclear motions were solved using a quantum close-coupling scattering theory. A T-shaped equilibrium structure was found, with a well depth of 349.1 cm-1, where 18 bound states have been located for N2H- and 25 for N2D- for total angular momentum J = 0. We also present the absorption spectra of the N2H- complex. This anion could be formed after low energy collisions between N2 and H- through radiative association. The importance of this prediction in astrophysics and the possible use of N2H- as a tracer of N2 and H- in the interstellar medium is discussed.

  10. Imidacloprid inhibits IgE-mediated RBL-2H3 cell degranulation and passive cutaneous anaphylaxis

    PubMed Central

    Shi, Linbo; Zou, Li; Gao, Jinyan; Xu, Huaing; Shi, Xiaoyun

    2016-01-01

    Background Imidacloprid has been commonly used as a pesticide for crop protection and acts as nicotinic acetylcholine receptor agonists. Little information about the relationship between imidacloprid and allergy is available. Objective This study aims to examine the effects of imidacoprid on IgE-mediated mast cell activation. Methods The rat basophilic leukemia cell line RBL-2H3 (RBL-2H3 cells) were treated with 10-3 – 10-12 mol/L imidacloprid, followed by measuring the mediator production, influx of Ca2+ in IgE-activated RBL-2H3 cells, and the possible effects of imidacoprid on anti-dinitrophenyl IgE-induced passive cutaneous anaphylaxis (PCA). Results It was shown that imidacoprid suppressed the production of histamine, β-hexosaminidase, leukotriene C4, interleukin-6, tumor necrosis factor-α, and Ca2+ mobilization in IgE-activated RBL-2H3 cells and decreased vascular extravasation in IgE-induced PCA. Conclusion It is the first time to show that imidacloprid suppressed the activation of RBL-2H3 cells. PMID:27803884

  11. Synthesis, spectral characterization and larvicidal activity of acridin-1(2H)-one analogues

    NASA Astrophysics Data System (ADS)

    Subashini, R.; Bharathi, A.; Roopan, Selvaraj Mohana; Rajakumar, G.; Abdul Rahuman, A.; Gullanki, Pavan Kumar

    Acridin-1(2H)-one analogue of 7-chloro-3,4-dihydro-9-phenyl-2-[(pyridine-2yl) methylene] acridin-1(2H)-one, 5 was prepared by using 7-chloro-3,4-dihydro-9-phenylacridin-1(2H)-one, 3 and picolinaldehyde, 4 in the presence of KOH at room temperature. These compounds were characterized by analytical and spectral analyses. The purpose of the present study was to assess the efficacy of larvicidal and repellent activity of synthesized 7-chloro-3,4-dihydro-9-phenyl-acridin-1(2H)-one analogues such as compounds 3 and 5 against the early fourth instar larvae of filariasis vector, Culex quinquefasciatus and Japanese encephalitis vector, Culex gelidus (Diptera: Culicidae). The compound exhibited high larvicidal effects at 50 mg/L against both the mosquitoes with LC50 values of 25.02 mg/L (r2 = 0.998) and 26.40 mg/L (r2 = 0.988) against C. quinquefasciatus and C. gelidus, respectively. The 7-chloro-3,4-dihydro-9-phenyl-acridin-1(2H)-one analogues that are reported for the first time to our best of knowledge can be better explored for the control of mosquito population. This is an ideal ecofriendly approach for the control of Japanese encephalitis vectors, C. quinquefasciatus and C. gelidus.

  12. (15)N- and (2)H proteomic stable isotope probing links nitrogen flow to archaeal heterotrophic activity.

    PubMed

    Justice, Nicholas B; Li, Zhou; Wang, Yingfeng; Spaudling, Susan E; Mosier, Annika C; Hettich, Robert L; Pan, Chongle; Banfield, Jillian F

    2014-10-01

    Understanding how individual species contribute to nutrient transformations in a microbial community is critical to prediction of overall ecosystem function. We conducted microcosm experiments in which floating acid mine drainage (AMD) microbial biofilms were submerged - recapitulating the final stage in a natural biofilm life cycle. Biofilms were amended with either (15)NH4(+) or deuterium oxide ((2)H2O) and proteomic stable isotope probing (SIP) was used to track the extent to which different members of the community used these molecules in protein synthesis across anaerobic iron-reducing, aerobic iron-reducing and aerobic iron-oxidizing environments. Sulfobacillus spp. synthesized (15)N-enriched protein almost exclusively under iron-reducing conditions whereas the Leptospirillum spp. synthesized (15)N-enriched protein in all conditions. There were relatively few (15)N-enriched archaeal proteins, and all showed low atom% enrichment, consistent with Archaea synthesizing protein using the predominantly (14)N biomass derived from recycled biomolecules. In parallel experiments using (2)H2O, extensive archaeal protein synthesis was detected in all conditions. In contrast, the bacterial species showed little protein synthesis using (2)H2O. The nearly exclusive ability of Archaea to synthesize proteins using (2)H2O may be due to archaeal heterotrophy, whereby Archaea offset deleterious effects of (2)H by accessing (1)H generated by respiration of organic compounds.

  13. Modeling the rovibrationally excited C2H4OH radicals from the photodissociation of 2-bromoethanol at 193 nm.

    PubMed

    Ratliff, B J; Womack, C C; Tang, X N; Landau, W M; Butler, L J; Szpunar, D E

    2010-04-15

    This study photolytically generates, from 2-bromoethanol photodissociation, the 2-hydroxyethyl radical intermediate of the OH + ethene reaction and measures the velocity distribution of the stable radicals. We introduce an impulsive model to characterize the partitioning of internal energy in the C(2)H(4)OH fragment. It accounts for zero-point and thermal vibrational motion to determine the vibrational energy distribution of the nascent C(2)H(4)OH radicals and the distribution of total angular momentum, J, as a function of the total recoil kinetic energy imparted in the photodissociation. We render this system useful for the study of the subsequent dissociation of the 2-hydroxyethyl radical to the possible asymptotic channels of the OH + ethene reaction. The competition between these channels depends on the internal energy and the J distribution of the radicals. First, we use velocity map imaging to separately resolve the C(2)H(4)OH + Br((2)P(3/2)) and C(2)H(4)OH + Br((2)P(1/2)) photodissociation channels, allowing us to account for the 10.54 kcal/mol partitioned to the Br((2)P(1/2)) cofragment. We determine an improved resonance enhanced multiphoton ionization (REMPI) line strength for the Br transitions at 233.681 nm (5p (4)P(1/2) <-- 4p (2)P(3/2)) and 234.021 nm (5p (2)S(1/2) <-- 4p (2)P(1/2)) and obtain a spin-orbit branching ratio for Br((2)P(1/2)):Br((2)P(3/2)) of 0.26 +/- 0.03:1. Energy and momentum conservation give the distribution of total internal energy, rotational and vibrational, in the C(2)H(4)OH radicals. Then, using 10.5 eV photoionization, we measure the velocity distribution of the radicals that are stable to subsequent dissociation. The onset of dissociation occurs at internal energies much higher than those predicted by theoretical methods and reflects the significant amount of rotational energy imparted to the C(2)H(4)OH photofragment. Instead of estimating the mean rotational energy with an impulsive model from the equilibrium geometry of 2

  14. Elastic positron scattering by C{sub 2}H{sub 2}: Differential cross sections and virtual state formation

    SciTech Connect

    Carvalho, Claudia R.C. de; Varella, Marcio T. do N; Lima, Marco A.P.; Silva, Euclimar P. da

    2003-12-01

    We present calculated elastic differential cross sections for positron-acetylene scattering, obtained by using the Schwinger multichannel method. Our results are in very good agreement with quasielastic experimental data of Kauppila et al. [Nucl. Instrum. Meth. Phys. Res. B 192, 162 (2002)]. We also discuss the existence of a virtual state (zero-energy resonance) in e{sup +}-C{sub 2}H{sub 2} collisions, based on the behavior of the integral cross section and of the s-wave phase shift. As expected the fixed-nuclei cross section and annihilation parameter (Z{sub eff}) present the same energy dependence at very low impact energies. As the virtual state energy approaches zero, the magnitude of both cross section and Z{sub eff} are extremely enhanced (at zero impact energy). The possibility of shifting from a low-lying virtual state to a shallow bound state is not expected to significantly affect room-temperature annihilation rates.

  15. DFT 2H quadrupolar coupling constants of ruthenium complexes: a good probe of the coordination of hydrides in conjuction with experiments.

    PubMed

    del Rosal, Iker; Gutmann, Torsten; Maron, Laurent; Jolibois, Franck; Chaudret, Bruno; Walaszek, Bernadeta; Limbach, Hans-Heinrich; Poteau, Romuald; Buntkowsky, Gerd

    2009-07-21

    Transition metal (TM) hydrides are of great interest in chemistry because of their reactivity and their potential as catalysts for hydrogenation reactions. 2H solid-state NMR can be used in order to get information about the local environment of hydrogen atoms, and more particularly the coordination mode of hydrides in such complexes. In this work we will show that it is possible to establish at the level of density functional theory (DFT) a viable methodological strategy that allows the determination of 2H NMR parameters, namely the quadrupolar coupling constant (C(Q)) respectively the quadrupolar splitting (deltanuQ) and the asymmetry parameter (etaQ). The reliability of the method (B3PW91-DFT) and basis set effects have been first evaluated for simple organic compounds (benzene and fluorene). A good correlation between experimental and theoretical values is systematically obtained if the large basis set cc-pVTZ is used for the computations. 2H NMR properties of five mononuclear ruthenium complexes (namely Cp*RuD3(PPh3), Tp*RuD(THT)2, Tp*RuD(D2)(THT) and Tp*RuD(D2)2 and RuD2(D2)2(PCy3)2) which exhibit different ligands and hydrides involved in different coordination modes (terminal-H or eta2-H2), have been calculated and compared to previous experimental data. The results obtained are in excellent agreement with experiments. Although 2H NMR spectra are not always easy to analyze, assistance by quantum chemistry calculations allows unambiguous assignment of the signals of such spectra. As far as experiments can be achieved at very low temperatures in order to avoid dynamic effects, this hybrid theoretical/experimental tool may give useful insights in the context of the characterization of ruthenium surfaces or nanoparticles with solid-state NMR. PMID:19842483

  16. Photodetectors and birefringence in ZnP2-С2h5 crystals

    NASA Astrophysics Data System (ADS)

    Stamov, I. G.; Syrbu, N. N.; Dorogan, A. V.

    2013-03-01

    The spectral dependences of refractive indexes no(n⊥), ne(n||) and Δn=no(n⊥)-ne(n||) were studied in ZnP2-C2h5 crystals. The intersection of no(n⊥) and ne(n||) was found for λ0=0.906 μm. The crystal possesses positive dispersion Δn=no(n⊥)-ne(n||) in the region where λ>λ0, and a negative dispersion is observed in the region where λ<λ0. The electrical, spectral and azimuth characteristics of monolith n-р- and Ме-n-р-ZnP2C2h5 and discrete ZnP2-C2h5-ZnP2-D48 structures were studied, and a prognosis was made on the usage perspective of these devices.

  17. Analysis Of 2H-Evaporator Scale Pot Bottom Sample [HTF-13-11-28H

    SciTech Connect

    Oji, L. N.

    2013-07-15

    Savannah River Remediation (SRR) is planning to remove a buildup of sodium aluminosilicate scale from the 2H-evaporator pot by loading and soaking the pot with heated 1.5 M nitric acid solution. Sampling and analysis of the scale material from the 2H evaporator has been performed so that the evaporator can be chemically cleaned beginning July of 2013. Historically, since the operation of the Defense Waste Processing Facility (DWPF), silicon in the DWPF recycle stream combines with aluminum in the typical tank farm supernate to form sodium aluminosilicate scale mineral deposits in the 2H-evaporator pot and gravity drain line. The 2H-evaporator scale samples analyzed by Savannah River National Laboratory (SRNL) came from the bottom cone sections of the 2H-evaporator pot. The sample holder from the 2H-evaporator wall was virtually empty and was not included in the analysis. It is worth noting that after the delivery of these 2H-evaporator scale samples to SRNL for the analyses, the plant customer determined that the 2H evaporator could be operated for additional period prior to requiring cleaning. Therefore, there was no need for expedited sample analysis as was presented in the Technical Task Request. However, a second set of 2H evaporator scale samples were expected in May of 2013, which would need expedited sample analysis. X-ray diffraction analysis (XRD) confirmed the bottom cone section sample from the 2H-evaporator pot consisted of nitrated cancrinite, (a crystalline sodium aluminosilicate solid), clarkeite and uranium oxide. There were also mercury compound XRD peaks which could not be matched and further X-ray fluorescence (XRF) analysis of the sample confirmed the existence of elemental mercury or mercuric oxide. On ''as received'' basis, the scale contained an average of 7.09E+00 wt % total uranium (n = 3; st.dev. = 8.31E-01 wt %) with a U-235 enrichment of 5.80E-01 % (n = 3; st.dev. = 3.96E-02 %). The measured U-238 concentration was 7.05E+00 wt % (n=3, st

  18. Detection of C2H4 Neptune from ISO/PHT-S Observations

    NASA Technical Reports Server (NTRS)

    Schulz, B.; Encrenaz, Th.; Bezard, B.; Romani, P. N.; Lellouch, E.; Atreya, S. K.

    1999-01-01

    The 6-12 micrometer spectrum of Neptune has been recorded with the PHT-S instrument of the Infrared Space Observatory (ISO) at a resolution of 0.095 micrometer. In addition to the emissions of CH4, CH3D and C2H6 previously identified, the spectrum shows the first firm identification of ethylene C2H4. The inferred column density above the 0.2-mbar level is in the range (1.1 - 3) x 10(exp 14) molecules/cm. To produce this low amount, previous photochemical models invoked rapid mixing between the source and sink regions of C2H4. We show that this requirement can be relaxed if recent laboratory measurements of CH4 photolysis branching ratios at Lyman alpha are used.

  19. Theoretical study of the C-H bond dissociation energy of C2H

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

    1990-01-01

    A theoretical study of the convergence of the C-H bond dissociation energy D(0) in C2H with respect to both the one- and n-particle spaces is presented. The calculated C-H bond energies of C2H2 and C2H4, which are in excellent agreement with experiment, are used for calibration. The best estimate for D(0) of 112.4 + or - 2.0 kcal/mol is slightly below the recent experimental value of 116.3 + or - 2.6 kcal/mol, but substantially above a previous theoretical estimate of 102 kcal/mol. The remaining discrepancy with experiment may reflect primarily the uncertainty in the experimental D(0) value of C2 required in the analysis.

  20. N2H(+) in the Orion ambient ridge - Cloud clumping versus rotation

    NASA Technical Reports Server (NTRS)

    Womack, Maria; Ziurys, L. M.; Sage, L. J.

    1993-01-01

    The IRAM 30-m telescope is used to obtain spectra of the J = 1 yields 0 transition of N2H(+) over a 2 x 2 arcsec area toward the Orion-KL/IRc2 star-forming region with 26-arcsec angular resolution. The N2H(+) emission, which exclusively traces the ridge gas, exhibits multiple radial velocities which appear to arise from the presence of at least four clouds of quiescent material. It is argued that the velocity structure of N2H(+) does not uniformly change across OMC-1 and, consequently, is inconsistent with the presence of large-scale differential rotation of the extended ridge along the SW-NE axis about IRc2. The coincidence of the two larger clouds with star-forming activity in Orion-KL suggests that either the quiescent gas is being pushed apart or that the star formation may have been triggered by a cloud-cloud interaction.

  1. Short pulse formation in a TEA CO{sub 2} laser using a CO{sub 2} - N{sub 2} - H{sub 2} gas mixture

    SciTech Connect

    Ivashchenko, M V; Karapuzikov, A I; Sherstov, I V

    2001-11-30

    The use of an optimal CO{sub 2} - N{sub 2} - H{sub 2} gas mixture with a high concentration of hydrogen (30% - 40%) was shown to allow the formation of high-power TEA CO{sub 2}-laser pulses with a base duration of {approx} 200 ns whose energy and peak power significantly exceed the parameters of pulses obtained in binary CO{sub 2} - H{sub 2} mixtures. Considering all the parameters, the helium-free 56% CO{sub 2} - 14% N{sub 2} - 30% H{sub 2} gas mixture at a pressure of 0.7 atm is optimal for the generation of short high-power pulses in the TEA CO{sub 2} laser. A small addition of nitrogen ([CO{sub 2}]/[N{sub 2}] {approx} 10 - 12) to the binary CO{sub 2} - H{sub 2} mixture not only substantially increases the pulse energy and peak power (by a factor of 3 - 3.5) but also shortens their duration at half-maximum with retention of the total (base) duration. (control of laser radiation parameters)

  2. Modeling of the nanoparticle coagulation in pulsed radio-frequency capacitively coupled C2H2 discharges

    NASA Astrophysics Data System (ADS)

    Liu, Xiang-Mei; Li, Qi-Nan; Li, Rui

    2015-07-01

    The role of pulse parameters on nanoparticle property is investigated self-consistently based on a couple of fluid model and aerosol dynamics model in a capacitively coupled parallel-plate acetylene (C2H2) discharge. In this model, the mass continuity equation, momentum balance equation, and energy balance equation for neutral gas are taken into account. Thus, the thermophoretic force arises when a gas temperature gradient exists. The typical results of this model are positive and negative ion densities, electron impact collisions rates, nanoparticle density, and charge distributions. The simulation is performed for duty ratio 0.4/0.7/1.0, as well as pulse modulation frequency from 40 kHz to 2.7 MHz for pure C2H2 discharges at a pressure of 500 mTorr. We find that the pulse parameters, especially the duty ratio, have a great affect on the dissociative attachment coefficient and the negative density. More importantly, by decreasing the duty ratio, nanoparticles start to diffuse to the wall. Under the action of gas flow, nanoparticle density peak is created in front of the pulse electrode, where the gas temperature is smaller. Project supported by the Natural Science Foundation of Heilongjiang Province, China (Grant Nos. A2015011 and A2015010), the Postdoctoral Scientific Research Developmental Fund of Heilongjiang Province, China (Grant No. LBH-Q14159), the National Natural Science Foundation of China (Grant No. 11404180), and the Program for Young Teachers Scientific Research in Qiqihar University, China (Grant No. 2014k-Z11).

  3. Terahertz Spectroscopy of the Bending Vibrations of Acetylene 12C2H2

    NASA Astrophysics Data System (ADS)

    Yu, Shanshan; Drouin, Brian J.; Pearson, John C.

    2009-11-01

    Twenty P-branch transitions of 12C2H2 have been measured in the 0.8-1.6 THz region of its bending vibrational difference band. The accuracy of these measurements is estimated to be 100 kHz. The 12C2H2 molecules were generated under room temperature by passing 150 mTorr H2O vapor through calcium carbide (CaC2) powder. The observed transitions were modeled together with prior far-infrared data involving the bending levels with ∑\

  4. Low-temperature solid-state phase transformations in 2H silicon carbide

    NASA Technical Reports Server (NTRS)

    Will, H. A.; Powell, J. A.

    1972-01-01

    Single crystals of 2H SiC were observed to undergo phase transformations at temperatures as low as 400 C. Some 2H crystals transformed to a structure with one-dimensional disorder along the crystal c axis. Others transformed to a faulted cubic/6H structure. The transformation is time and temperature dependent and is greatly enhanced by dislocations. Observations indicate that the transformation takes place by means of a slip process perpendicular to the c axis. Cubic SiC crystals were observed to undergo a solid state transformation above 1400 C.

  5. Implications of C2H photochemistry on the modeling of C2 distributions in comets

    NASA Technical Reports Server (NTRS)

    Jackson, William M.; Bao, Yihan; Urdahl, Randall S.

    1991-01-01

    Laboratory studies of the secondary photolysis of the C2H radical are summarized and used to explain some discrepancies between models of C2 emission in comets. These studies show that several states of the C2 radicals produced in the photolysis of C2H2 at 193 nm have bimodal rotational distributions when plotted as a Boltzmann diagram. They also establish that the C2 radicals are formed with varying degrees of vibrational excitation, so that if they are formed in a similar manner in comets, the C2 radicals must start out with this initial vibrational excitation.

  6. Calculation of the Aluminosilicate Half-Life Formation Time in the 2H Evaporator

    SciTech Connect

    Fondeur, F.F.

    2000-09-21

    The 2H Evaporator contains large quantities of aluminosilicate solids deposited on internal fixtures. The proposed cleaning operations will dissolve the solids in nitric acid. Operations will then neutralize the waste prior to transfer to a waste tank. Combining recent calculations of heat transfer for the 2H Evaporator cleaning operations and laboratory experiments for dissolution of solid samples from the pot, the authors estimated the re-formation rate for aluminosilicates during cooling. The results indicate a half-life formation of 17 hours when evaporator solution cools from 60 degrees C and 9 hours when cooled from 90 degrees C.

  7. Davis–Beirut Reaction: Route to Thiazolo-, Thiazino-, and Thiazepino-2H-indazoles

    PubMed Central

    2015-01-01

    Methods for the construction of thiazolo-, thiazino-, and thiazepino-2H-indazoles from o-nitrobenzaldehydes or o-nitrobenzyl bromides and S-trityl-protected 1°-aminothioalkanes are reported. The process consists of formation of the requisite N-(2-nitrobenzyl)(tritylthio)alkylamine, subsequent deprotection of the trityl moiety with TFA, and immediate treatment with aq. KOH in methanol under Davis–Beirut reaction conditions to deliver the target thiazolo-, thiazino-, or thiazepino-2H-indazole in good overall yield. Subsequent S-oxidation gives the corresponding sulfone. PMID:25019525

  8. High-resolution absorption cross sections of C2H6 at elevated temperatures

    NASA Astrophysics Data System (ADS)

    Hargreaves, Robert J.; Buzan, Eric; Dulick, Michael; Bernath, Peter F.

    2015-11-01

    Infrared absorption cross sections near 3.3 μm have been obtained for ethane, C2H6. These were acquired at elevated temperatures (up to 773 K) using a Fourier transform infrared spectrometer and tube furnace with a resolution of 0.005 cm-1. The integrated absorption was calibrated using composite infrared spectra taken from the Pacific Northwest National Laboratory (PNNL). These new measurements are the first high-resolution infrared C2H6 cross sections at elevated temperatures.

  9. Effect of salinity on 2H/1H fractionation in lipids from continuous cultures of the coccolithophorid Emiliania huxleyi

    NASA Astrophysics Data System (ADS)

    Sachs, Julian P.; Maloney, Ashley E.; Gregersen, Josh; Paschall, Christopher

    2016-09-01

    Salinity and temperature dictate the buoyancy of seawater, and by extension, ocean circulation and heat transport. Yet there remain few widely applicable proxies for salinity with the precision necessary to infer all but the largest hydrographic variations in the past. In the last decade the hydrogen isotope composition (2H/1H or δ2H) of microalgal lipids has been shown to increase systematically with salinity, providing a foundation for its use as a paleosalinity proxy. Culture and field studies have indicated a wide range of sensitivities for this response, ranging from about 0.6-3.3‰ ppt-1 depending on the lipid, location and/or culturing conditions. Lacking in these studies has been the controlled conditions necessary to isolate the response to salinity while keeping all other growth parameters constant. Here we show that the hydrogen isotope composition of lipids in the marine coccolithophorid Emiliania huxleyi grown in chemostats increased by 1.6 ± 0.3‰ ppt-1 (p < 0.05) in eight individual alkenones and by 2.0 ± 0.1‰ ppt-1 (p < 0.05) in three individual fatty acids over the salinity range 20-42 ppt. Hydrogen isotope ratios of phytol and the sterol 24-methyl-cholest-5,22-dien-3β-ol (brassicasterol) also increased with salinity but correlations were weaker than for the acetogenic lipids. For eight individual alkenones, linear regression analyses of the fractionation factors on salinity yielded slopes of 1.2-2.2‰ ppt-1. This sensitivity of δ2Halkenone to salinity is 45-71% of that previously reported for E. huxleyi, which can be attributed to the fact that previous experiments were performed with batch cultures in which growth rates and other parameters differed between salinity treatments. The underlying cause of this response to salinity remains unknown, but may result from changes in (1) the proportion of lipid hydrogen derived from NADPH versus water, (2) the proportion of lipid hydrogen derived from NADPH from Photosystem I versus the oxidative

  10. Unfolding the Quantum Nature of Proton Bound Symmetric Dimers of (MeOH)2H+ and (Me2O)2H+: a Theoretical Study

    NASA Astrophysics Data System (ADS)

    Tan, Jake Acedera; Kuo, Jer-Lai

    2014-06-01

    A proton under a tug of war between two competing Lewis bases is a common motif in biological systems and proton transfer processes. Over the past decades, model compounds for such motifs can be prepared by delicate stoichiometric control of salt solutions. Unfortunately, condensed phase studies, which aims to identify the key vibrational signatures are complicated to analyze. As a result, gas-phase studies do provide promising insights on the behavior of the shared proton. This study attempts to understand the quantum nature of the shared proton under theoretical paradigms. Proton bound symmetric dimers of (MeOH)2H+ and (Me2O)2H+ are chosen as the model compounds. The simulation is performed using Density Functional Theory (DFT) at the B3LYP level with 6-311+G(d,p) as the basis set. It was found out that stretching mode of shared proton couples with several other normal modes and its corresponding oscillator strength do distribute to other normal modes. J.R. Roscioli, L.R. McCunn and M.A. Johnson. Science 2007, 316, 249 T.E. DeCoursey. Physiol. Rev., 2003, 83, 475 E.S. Stoyanov. Psys. Chem. Phys., 2000,2,1137

  11. The conformational dynamics of H2-H3n and S2-H6 in gating ligand entry into the buried binding cavity of vitamin D receptor

    PubMed Central

    Tee, Wei-Ven; Ripen, Adiratna Mat; Mohamad, Saharuddin Bin

    2016-01-01

    Crystal structures of holo vitamin D receptor (VDR) revealed a canonical conformation in which the ligand is entrapped in a hydrophobic cavity buried in the ligand-binding domain (LBD). The mousetrap model postulates that helix 12 is positioned away from the domain to expose the interior cavity. However, the extended form of helix 12 is likely due to artifacts during crystallization. In this study, we set out to investigate conformational dynamics of apo VDR using molecular dynamics simulation on microsecond timescale. Here we show the neighboring backbones of helix 2-helix 3n and beta strand 2-helix 6 of LBD, instead of the helix 12, undergo large-scale motion, possibly gating the entrance of ligand to the ligand binding domain. Docking analysis to the simulated open structure of VDR with the estimated free energy of −37.0 kJ/mol, would emphasise the role of H2-H3n and S2-H6 in facilitating the entrance of calcitriol to the LBD of VDR. PMID:27786277

  12. Distortion of ethyne on coordination to silver acetylide, C2H2ṡṡṡAgCCH, characterised by broadband rotational spectroscopy and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Stephens, Susanna L.; Zaleski, Daniel P.; Mizukami, Wataru; Tew, David P.; Walker, Nicholas R.; Legon, Anthony C.

    2014-03-01

    The rotational spectra of six isotopologues of a complex of ethyne and silver acetylide, C2H2ṡṡṡAgCCH, are measured by both chirped-pulse and Fabry-Perot cavity versions of Fourier-transform microwave spectroscopy. The complex is generated through laser ablation of a silver target in the presence of a gas sample containing 1% C2H2, 1% SF6, and 98% Ar undergoing supersonic expansion. Rotational, A0, B0, C0, and centrifugal distortion ΔJ and ΔJK constants are determined for all isotopologues of C2H2ṡṡṡAgCCH studied. The geometry is planar, C2v and T-shaped in which the C2H2 sub-unit comprises the bar of the "T" and binds to the metal atom through its π electrons. In the r0 geometry, the distance of the Ag atom from the centre of the triple bond in C2H2 is 2.2104(10) Å. The r(HC≡CH) parameter representing the bond distance separating the two carbon atoms and the angle, ∠(CCH), each defined within the C2H2 sub-unit, are determined to be 1.2200(24) Å and 186.0(5)°, respectively. This distortion of the linear geometry of C2H2 involves the hydrogen atoms moving away from the silver atom within the complex. The results thus reveal that the geometry of C2H2 changes measurably on coordination to AgCCH. A value of 59(4) N m-1 is determined for the intermolecular force constant, kσ, confirming that the complex is significantly more strongly bound than hydrogen and halogen-bonded analogues. Ab initio calculations of the re geometry at the CCSD(T)(F12*)/ACVTZ level of theory are consistent with the experimental results. The spectra of the 107Ag13C13CH and 109Ag13C13CH isotopologues of free silver acetylide are also measured for the first time allowing the geometry of the AgCCH monomer to be examined in greater detail than previously.

  13. Pulsed supersonic molecular-beam coherent anti-Stokes Raman spectroscopy of C2H2

    NASA Technical Reports Server (NTRS)

    Duncan, M. D.; Byer, R. L.; Osterlin, P.

    1981-01-01

    A high-resolution coherent anti-Stokes Raman spectrum of C2H2 in a pulsed molecular beam was obtained and the resolved Q-branch spectrum was used to study the properties of the expansion. Cluster formation limited the minimum observed rotational temperature in the pure-acetylene expansion to 30 K.

  14. Preliminary investigations on the synthesis and antitumor activity of 3(2H)-furanones.

    PubMed

    Rappai, J P; Raman, V; Unnikrishnan, P A; Prathapan, S; Thomas, S K; Paulose, C S

    2009-02-01

    Two triaryl-3(2H)-furanones were synthesized and their antitumor activity was evaluated. These compounds inhibited the proliferation of DLA cell line in vitro. In vivo studies also showed that these compounds were active against tumor cell proliferation. PMID:19121938

  15. An improved technique for the 2H/1H analysis of urines from diabetic volunteers

    USGS Publications Warehouse

    Coplen, T.B.; Harper, I.T.

    1994-01-01

    The H2-H2O ambient-temperature equilibration technique for the determination of 2H/1H ratios in urinary waters from diabetic subjects provides improved accuracy over the conventional Zn reduction technique. The standard deviation, ~ 1-2???, is at least a factor of three better than that of the Zn reduction technique on urinary waters from diabetic volunteers. Experiments with pure water and solutions containing glucose, urea and albumen indicate that there is no measurable bias in the hydrogen equilibration technique.The H2-H2O ambient-temperature equilibration technique for the determination of 2H/1H ratios in urinary waters from diabetic subjects provides improved accuracy over the conventional Zn reduction technique. The standard deviation, approximately 1-2%, is at least a factor of three better than that of the Zn reduction technique on urinary waters from diabetic volunteers. Experiments with pure water and solutions containing glucose, urea and albumen indicate that there is no measurable bias in the hydrogen equilibration technique.

  16. Identification of microdomains involved in association of "Arabidopsis" Ca(2+)/H(+) exchangers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In planta, high capacity tonoplast Ca2+/H+ antiport is mediated in part by a family of CAtion Exchangers (CAX). Each CAX can be divided into two weakly homologous halves (N- and C-) at the negatively charged loop between transmembrane (TM) 6 and TM7. Some CAX halves (N+C) co-expressed in yeast cells...

  17. Slow recrystallization of tripalmitoylglycerol from MCT oil observed by 2H NMR.

    PubMed

    Smith, Kevin W; Smith, Paul R; Furó, István; Pettersson, Erik Thyboll; Cain, Fred W; Favre, Loek; Talbot, Geoff

    2007-10-17

    The crystallization and recrystallization of fats have a significant impact on the properties and quality of many food products. While crystallization has been the subject of a number of studies using pure triacylglycerols (TAG), recrystallization in similarly pure systems is rarely studied. In this work, perdeuterated tripalmitoylglycerol ( (2)H-PPP) was dissolved in medium chain triacylglycerol oil (MCT) to yield a saturated solution. The solution was heated to cause partial melting of the solid and dissolution of the molten fraction of (2)H-PPP in MCT and was then cooled to the original temperature to induce recrystallization from the supersaturated solution. (2)H NMR was used to monitor the disappearance of (2)H-PPP from the solution and showed that recrystallization occurred in two steps. The first step was rapid, taking place over a few minutes, and accounted for more than two-thirds of the total recrystallization. The second step was much slower, taking place over a remarkably long timescale of hours to days. It is proposed that dissolution occurs from all parts of the crystals, leaving an etched and pitted surface. The first step of crystallization is the infilling of these pits, while the second step is the continued growth on the smoothed crystal faces.

  18. Photo-induced reactions in the ion-molecule complex Mg+-OCNC2H5

    NASA Astrophysics Data System (ADS)

    Sun, Ju-Long; Liu, Haichuan; Han, Ke-Li; Yang, Shihe

    2003-06-01

    Ion-molecule complexes of magnesium cation with ethyl isocyanate were produced in a laser-ablation supersonic expansion nozzle source. Photo-induced reactions in the 1:1 complexes have been studied in the spectral range of 230-410 nm. Photodissociation mass spectrometry revealed the persistent product Mg+ from nonreactive quenching throughout the entire wavelength range. As for the reactive channels, the photoproducts, Mg+OCN and C2H5+, were produced only in the blue absorption band of the complex with low yields. The action spectrum of Mg+(OCNC2H5) consists of two pronounced peaks on the red and blue sides of the Mg+ 32P←32S atomic transition. The ground state geometry of Mg+-OCNC2H5 was fully optimized at B3LYP/6-31+G** level by using GAUSSIAN 98 package. The calculated absorption spectrum of the complex using the optimized structure of its ground state agrees well with the observed action spectrum. Photofragment branching fractions of the products are almost independent of the photolysis photon energy for the 3Px,y,z excitations. The very low branching ratio of reactive products to nonreactive fragment suggests that evaporation is the main relaxation pathway in the photo-induced reactions of Mg+(OCNC2H5).

  19. Improved watermelon quality using bottle gourd rootstock expressing a Ca(2+)/H(+) antiporter

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Bottle gourd ("Lagenaria siceraria" Standl.) has been commonly used as a source of rootstock for watermelon. To improve its performance as a rootstock without adverse effects on the scion, the bottle gourd was genetically engineered using a modified "Arabidopsis" Ca(2+)/H(+) exchanger sCAX2B. This t...

  20. Fluorescence from photoexcitation of C2H5OH by vacuum ultraviolet radiation

    NASA Technical Reports Server (NTRS)

    Han, J. C.; Suto, Masako; Lee, L. C.

    1989-01-01

    The photoabsorption and fluorescence cross sections of C2H5OH have been measured in the 46-200 nm region. Fluorescence is dispersed to identify the emission systems, which are mainly OH(A-X), CH(A,B-X), and the H Balmer series. The photodissociation processes that produce the observed emissions are discussed.

  1. The Rate Constant for the Reaction H + C2H5 at T = 295 - 150K

    NASA Technical Reports Server (NTRS)

    Pimentel, Andre S.; Payne, Walter A.; Nesbitt, Fred L.; Cody, Regina J.; Stief, Louis J.

    2004-01-01

    The reaction between the hydrogen atom and the ethyl (C2H3) radical is predicted by photochemical modeling to be the most important loss process for C2H5 radicals in the atmospheres of Jupiter and Saturn. This reaction is also one of the major sources for the methyl radicals in these atmospheres. These two simplest hydrocarbon radicals are the initial species for the synthesis of larger hydrocarbons. Previous measurements of the rate constant for the H + C2H5 reaction varied by a factor of five at room temperature, and some studies showed a dependence upon temperature while others showed no such dependence. In addition, the previous studies were at higher temperatures and generally higher pressures than that needed for use in planetary atmospheric models. The rate constant for the reaction H + C2H5 has been measured directly at T = 150, 202 and 295 K and at P = 1.0 Torr He for all temperatures and additionally at P = 0.5 and 2.0 Torr He at T = 202 K. The measurements were performed in a discharge - fast flow system. The decay of the C2H5 radical in the presence of excess hydrogen was monitored by low-energy electron impact mass spectrometry under pseudo-first order conditions. H atoms and C2H5 radicals were generated rapidly and simultaneously by the reaction of fluorine atoms with H2 and C2H6, respectively. The total rate constant was found to be temperature and pressure independent. The measured total rate constant at each temperature are: k(sub 1)(295K) = (1.02+/-0.24)x10(exp -10), k(sub 1)(202K) = (1.02+/-0.22)x10(exp -10) and k(sub 1)(150K) = (0.93+/-0.21)x10(exp -10), all in units of cu cm/molecule/s. The total rate constant derived from all the combined measurements is k(sub 1) = (l.03+/-0.17)x10(exp -10) cu cm/molecule/s. At room temperature our results are about a factor of two higher than the recommended rate constant and a factor of three lower than the most recently published study.

  2. LITERATURE REVIEW ON IMPACT OF GLYCOLATE ON THE 2H EVAPORATOR AND THE EFFLUENT TREATMENT FACILITY

    SciTech Connect

    Adu-Wusu, K.

    2012-05-10

    Glycolic acid (GA) is being studied as an alternate reductant in the Defense Waste Processing Facility (DWPF) feed preparation process. It will either be a total or partial replacement for the formic acid that is currently used. A literature review has been conducted on the impact of glycolate on two post-DWPF downstream systems - the 2H Evaporator system and the Effluent Treatment Facility (ETF). The DWPF recycle stream serves as a portion of the feed to the 2H Evaporator. Glycolate enters the evaporator system from the glycolate in the recycle stream. The overhead (i.e., condensed phase) from the 2H Evaporator serves as a portion of the feed to the ETF. The literature search revealed that virtually no impact is anticipated for the 2H Evaporator. Glycolate may help reduce scale formation in the evaporator due to its high complexing ability. The drawback of the solubilizing ability is the potential impact on the criticality analysis of the 2H Evaporator system. It is recommended that at least a theoretical evaluation to confirm the finding that no self-propagating violent reactions with nitrate/nitrites will occur should be performed. Similarly, identification of sources of ignition relevant to glycolate and/or update of the composite flammability analysis to reflect the effects from the glycolate additions for the 2H Evaporator system are in order. An evaluation of the 2H Evaporator criticality analysis is also needed. A determination of the amount or fraction of the glycolate in the evaporator overhead is critical to more accurately assess its impact on the ETF. Hence, use of predictive models like OLI Environmental Simulation Package Software (OLI/ESP) and/or testing are recommended for the determination of the glycolate concentration in the overhead. The impact on the ETF depends on the concentration of glycolate in the ETF feed. The impact is classified as minor for feed glycolate concentrations {le} 33 mg/L or 0.44 mM. The ETF unit operations that will have

  3. Equations of state for H2, H2O, and H2-H2O fluid mixtures at temperatures above 0.01° C and at high pressures

    NASA Astrophysics Data System (ADS)

    Rimbach, Helmut; Chatterjee, Niranjan D.

    1987-11-01

    Modified Redlich-Kwong (MRK) equations of state have been derived for the pure fluid species H2 and H2O by expressing the parameter a as a function of T and P, and b as as a function of P only. These equations are valid above 0° and 0.01° C, respectively. For H2O, the prediction of volumes is successful not only in the supercritical, but also in the subcritical range. As a result of this, the saturation curve of H2O can be calculated with a maximum deviation of ±1.4 bar in the range 100 350° C. Between 350° C and the critical point (374.15° C), the uncertainty increases somewhat; this is due to a fundamental inadequacy of the Redlich-Kwong equation itself. These equations of state permit extrapolations to pressures of 100 kbar for H2 and at least 200 kbar for H2O and are, therefore, eminently suited for geochemical applications. Formulation of the MRK of the binary H2-H2O mixtures was achieved by assuming the quadratic mixing rule for the parameters a mix and b+mix. To derive the cross coefficients, aH2-H2Oand b H 2-H 2O, adjustable corrective factors ɛ and τ had to be introduced. The T- and P-dependences of ɛ and τ are based on P-V-T-X H 2 data (Seward and Franck 1981) to 440° C and 2500 bar. The resulting equation of state very satisfactorily reproduces the volumes observed experimentally at various sets of T, P, and X H 2. At a total pressure of 2 kbar, positive deviation from ideal mixing behaviour is still perceptible at as high a temperature as 1000° C. At some temperature around 380° C, phase separation sets in, an aqueous solution with dissolved H2 coexisting in equilibrium with an H2-rich fluid with dissolved H2O. The computed P-T-X H 2 surface of this two-phase region agrees well with that observed in Seward and Franck's (1981) experiments. An independent proof of the validity of this equation of state is the accuracy with which H {m/ex}can be predicted. Calorimetric measurements of H {m/ex}(Smith et al. 1983, Wormald and Colling 1985

  4. Dynamics of adipose tissue development by 2H2O labeling.

    PubMed

    Pouteau, Etienne; Beysen, Carine; Saad, Nabil; Turner, Scott

    2009-01-01

    Adipose tissue development undergoes remodeling in terms of newly synthesized cells (hyperplasia) and newly synthesized lipids that accumulate in adipocytes (hypertrophy). Synthesis and/or breakdown rates of adipose cells and lipids follow a continuous and dynamic pattern, e.g., during obesity development. This chapter describes a unique in vivo method to measure the dynamics of adipose tissue growth using 2H2O labeling and mass spectrometry analyses. The approach uses 2H2O as a metabolic tracer to label the adipose tissue components such as the triglycerides (TG), the fatty acids, and the genomic DNA. Deuterium from 2H2O incorporates in the C-H bonds of glycerol moiety of TG through glyceroneogenesis as well as in palmitate moiety through de novo lipogenesis (DNL). Deuterium also incorporates into DNA through the de novo nucleoside synthesis pathway. The labeled water, 2H2O, is administrated intraperitoneally and/or orally in rodents or in humans for a defined duration and biopsies are collected at the end of the labeling period. We describe the procedure to extract, isolate, and purify the adipose components (TG-glycerol, TG-palmitate, and genomic DNA) and the derivation procedure to analyze the isotopic 2H-enrichment of these components by gas chromatography/mass spectrometry. The calculation principles are described to obtain the fractional and absolute synthesis rates of TG, of DNL, and of DNA measured in the adipose tissues. The method is nonradioactive, nonhazardous, accurate, reproducible, and very sensitive. We present recent in vivo data on the ontogeny of adipose tissue growth dynamics in young and adult obese Zucker rats compared with lean Zucker rats. PMID:19763484

  5. Microbial H2 cycling does not affect δ2H values of ground water

    USGS Publications Warehouse

    Landmeyer, J.E.; Chapelle, F.H.; Bradley, P.M.

    2000-01-01

    Stable hydrogen-isotope values of ground water (δ2H) and dissolved hydrogen concentrations (H(2(aq)) were quantified in a petroleum-hydrocarbon contaminated aquifer to determine whether the production/consumption of H2 by subsurface microorganisms affects ground water &delta2H values. The range of &delta2H observed in monitoring wells sampled (-27.8 ‰c to -15.5 ‰c) was best explained, however, by seasonal differences in recharge temperature as indicated using ground water δ18O values, rather than isotopic exchange reactions involving the microbial cycling of H2 during anaerobic petroleum-hydrocarbon biodegradation. The absence of a measurable hydrogen-isotope exchange between microbially cycled H2 and ground water reflects the fact that the amount of H2 available from the anaerobic decomposition of petroleum hydrocarbons is small relative to the amount of hydrogen present in water, even though milligram per liter concentrations of readily biodegradable contaminants are present at the study site. Additionally, isotopic fractionation calculations indicate that in order for H2 cycling processes to affect δ2H values of ground water, relatively high concentrations of H2 (>0.080 M) would have to be maintained, considerably higher than the 0.2 to 26 nM present at this site and characteristic of anaerobic conditions in general. These observations suggest that the conventional approach of using δ2H and δ18O values to determine recharge history is appropriate even for those ground water systems characterized by anaerobic conditions and extensive microbial H2 cycling.

  6. The 13C/2H-glucose test for determination of small intestinal lactase activity.

    PubMed

    Vonk, R J; Stellaard, F; Priebe, M G; Koetse, H A; Hagedoorn, R E; De Bruijn, S; Elzinga, H; Lenoir-Wijnkoop, I; Antoine, J M

    2001-03-01

    To diagnose hypolactasia, determination of lactase enzyme activity in small intestinal biopsy material is considered to be the golden standard. Because of its strongly invasive character and the sampling problems, alternative methods have been looked for. We analysed the 13C-glucose response in serum after consumption of 25 g of naturally enriched 13C-lactose. As an internal standard, 0.5 g of 2H-glucose was added and the 2H-glucose response in serum was measured simultaneously. The studies were performed in healthy volunteers with a background of genetically determined lactase nonpersistence (n = 12; low lactase activity) and lactase persistence (n = 27; high lactase activity). The results were compared with those of the lactose hydrogen breath test, the lactose 13CO2 breath test and the previously described 13C-lactose digestion test. After consumption of 13C-lactose and 2H-glucose, the mean ratio 13C-glucose/2H-glucose concentration in serum at 45-75 min was 0.26 +/- 0.09 in the low lactase activity group and 0.93 +/- 0.17 in the high lactase activity group (P < 0.01). Threshold of the ratio between digesters and maldigesters was calculated as 0.46. Accuracy of the new test was superior to all other tests. We conclude that the 13C/2H-glucose test has the potential of determining the small intestinal lactase activity in vivo and of estimating the amount of lactose which is digested in the small intestine. PMID:11264650

  7. The 13C/2H-glucose test for determination of small intestinal lactase activity.

    PubMed

    Vonk, R J; Stellaard, F; Priebe, M G; Koetse, H A; Hagedoorn, R E; De Bruijn, S; Elzinga, H; Lenoir-Wijnkoop, I; Antoine, J M

    2001-03-01

    To diagnose hypolactasia, determination of lactase enzyme activity in small intestinal biopsy material is considered to be the golden standard. Because of its strongly invasive character and the sampling problems, alternative methods have been looked for. We analysed the 13C-glucose response in serum after consumption of 25 g of naturally enriched 13C-lactose. As an internal standard, 0.5 g of 2H-glucose was added and the 2H-glucose response in serum was measured simultaneously. The studies were performed in healthy volunteers with a background of genetically determined lactase nonpersistence (n = 12; low lactase activity) and lactase persistence (n = 27; high lactase activity). The results were compared with those of the lactose hydrogen breath test, the lactose 13CO2 breath test and the previously described 13C-lactose digestion test. After consumption of 13C-lactose and 2H-glucose, the mean ratio 13C-glucose/2H-glucose concentration in serum at 45-75 min was 0.26 +/- 0.09 in the low lactase activity group and 0.93 +/- 0.17 in the high lactase activity group (P < 0.01). Threshold of the ratio between digesters and maldigesters was calculated as 0.46. Accuracy of the new test was superior to all other tests. We conclude that the 13C/2H-glucose test has the potential of determining the small intestinal lactase activity in vivo and of estimating the amount of lactose which is digested in the small intestine.

  8. Accurate experimental determination of the isotope effects on the triple point temperature of water. I. Dependence on the 2H abundance

    NASA Astrophysics Data System (ADS)

    Faghihi, V.; Peruzzi, A.; Aerts-Bijma, A. T.; Jansen, H. G.; Spriensma, J. J.; van Geel, J.; Meijer, H. A. J.

    2015-12-01

    Variation in the isotopic composition of water is one of the major contributors to uncertainty in the realization of the triple point of water (TPW). Although the dependence of the TPW on the isotopic composition of the water has been known for years, there is still a lack of a detailed and accurate experimental determination of the values for the correction constants. This paper is the first of two articles (Part I and Part II) that address quantification of isotope abundance effects on the triple point temperature of water. In this paper, we describe our experimental assessment of the 2H isotope effect. We manufactured five triple point cells with prepared water mixtures with a range of 2H isotopic abundances encompassing widely the natural abundance range, while the 18O and 17O isotopic abundance were kept approximately constant and the 18O  -  17O ratio was close to the Meijer-Li relationship for natural waters. The selected range of 2H isotopic abundances led to cells that realised TPW temperatures between approximately  -140 μK to  +2500 μK with respect to the TPW temperature as realized by VSMOW (Vienna Standard Mean Ocean Water). Our experiment led to determination of the value for the δ2H correction parameter of A2H  =  673 μK / (‰ deviation of δ2H from VSMOW) with a combined uncertainty of 4 μK (k  =  1, or 1σ).

  9. Helix-Capping Histidines: Diversity of N-H···N Hydrogen Bond Strength Revealed by (2h)JNN Scalar Couplings.

    PubMed

    Preimesberger, Matthew R; Majumdar, Ananya; Rice, Selena L; Que, Lauren; Lecomte, Juliette T J

    2015-11-24

    In addition to its well-known roles as an electrophile and general acid, the side chain of histidine often serves as a hydrogen bond (H-bond) acceptor. These H-bonds provide a convenient pH-dependent switch for local structure and functional motifs. In hundreds of instances, a histidine caps the N-terminus of α- and 310-helices by forming a backbone NH···Nδ1 H-bond. To characterize the resilience and dynamics of the histidine cap, we measured the trans H-bond scalar coupling constant, (2h)JNN, in several forms of Group 1 truncated hemoglobins and cytochrome b5. The set of 19 measured (2h)JNN values were between 4.0 and 5.4 Hz, generally smaller than in nucleic acids (~6-10 Hz) and indicative of longer, weaker bonds in the studied proteins. A positive linear correlation between (2h)JNN and the difference in imidazole ring (15)N chemical shift (Δ(15)N = |δ(15)Nδ1 - δ(15)Nε2|) was found to be consistent with variable H-bond length and variable cap population related to the ionization of histidine in the capping and noncapping states. The relative ease of (2h)JNN detection suggests that this parameter can become part of the standard arsenal for describing histidines in helix caps and other key structural and catalytic elements involving NH···N H-bonds. The combined nucleic acid and protein data extend the utility of (2h)JNN as a sensitive marker of local structural, dynamic, and thermodynamic properties in biomolecules. PMID:26523621

  10. Backbone motions in a crystalline protein from field-dependent 2H-NMR relaxation and line-shape analysis.

    PubMed

    Mack, J W; Usha, M G; Long, J; Griffin, R G; Wittebort, R J

    2000-01-01

    We have used 2H-nmr to study backbone dynamics of the 2H-labeled, slowly exchanging amide sites of fully hydrated, crystalline hen egg white lysozyme. Order parameters are determined from the residual quadrupole coupling and values increase from S2 = 0.85 at 290 K to S2 = 0.94 at 200 K. Dynamical rates are determined from spin-lattice relaxation at three nmr frequencies (38.8, 61.5, and 76.7 MHz). The approach used here is thus distinct from solution nmr studies where dynamical amplitudes and rates are both determined from relaxation measurements. At temperatures below 250 K, relaxation is independent of the nmr frequency indicating that backbone motions are fast compared to the nmr frequencies. However, as the temperature is increased above 250 K, relaxation is significantly more efficient at the lowest frequency, which shows, in addition, the presence of motions that are slow compared to the nmr frequencies. Using the values of S2 determined from the residual quadrupole coupling and a model-free relaxation formalism that allows for fast and slow internal motions, we conclude that these slow motions have correlation times in the range of 0.1 to 1.0 microsecond and are effectively frozen out at 250 K where fast motions of the amide planes with approximately 15 ps effective correlation times and 9 degrees rms amplitudes dominate relaxation. The fast internal motions increase slightly in amplitude as the temperature rises toward 290 K, but the correlation time, as is also observed in solution nmr studies of RNase H, is approximately constant. These findings are consistent with hypotheses of dynamic glass transitions in hydrated proteins arising from temperature-dependent damping of harmonic modes of motion above the transition point.

  11. Effect of divalent cations on the structure of dipalmitoylphosphatidylcholine and phosphatidylcholine/phosphatidylglycerol bilayers: An 2H-NMR study

    SciTech Connect

    Zidovetzki, R.; Atiya, A.W.; De Boeck, H. )

    1989-01-01

    The interactions of CaCl2 or MgCl2 with multilamellar phospholipid bilayers were studied by 2H-NMR. Two model membrane systems were used: (1) dipalmitoylphosphatidylcholine (DPPC) bilayers and (2) bilayers composed of a mixture of phosphatidylcholine and phosphatidylglycerol at a molar ratio of 5:1. Addition of 0.25 M CaCl2 to DPPC bilayers resulted in significant uniform increase of the order parameters of the lipid side chains; the effect of 0.25 M MgCl2 was insignificant. Both phosphatidylcholine and phosphatidylglycerol components of the mixed bilayers were affected by the presence of 0.25 M CaCl2 and, to a much smaller degree, by MgCl2. The addition of Ca2+ induced significantly larger increase of the order parameters of the phosphatidylcholine component. The results are consistent with the long-range effects of Ca2+ binding on the packing of the lipid membranes.

  12. Optically pumped CHClF2 and C2H5I submillimeter wave lasers

    NASA Astrophysics Data System (ADS)

    Tobin, M. S.; Daley, T. W.

    1980-06-01

    Submillimeter wave laser action is reported for optically pumped chlorodifluoromethane gas and ethyl iodide vapor. The compounds were pumped by an electrically chopped CO2 laser at 10 Hz coupled to a metallic waveguide unoptimized 3.5 mm output-hole-coupled resonator with plunger mirrors. Coincidences between CO2 pump lines and molecular absorption lines were detected at three lines in the 9-micron R region in CHClF2 and two lines in the 10-micron R and P regions in C2H5I for chopped and not CW laser regimes. Comparison of the molecular structures of the two species with the CW FIR laser material selection criteria of Danielewicz and Weiss (1978) reveals that CHClF2 satisfies these criteria (although CHClF2 absorption does not overlap with many CO2 pump lines), while C2H5I does not, in agreement with experimental results.

  13. Synthesis and Stereochemical Assignment of Crypto-Optically Active (2) H6 -Neopentane.

    PubMed

    Masarwa, Ahmad; Gerbig, Dennis; Oskar, Liron; Loewenstein, Aharon; Reisenauer, Hans Peter; Lesot, Philippe; Schreiner, Peter R; Marek, Ilan

    2015-10-26

    The determination of the absolute configuration of chiral molecules is at the heart of asymmetric synthesis. Here we probe the spectroscopic limits for chiral discrimination with NMR spectroscopy in chiral aligned media and with vibrational circular dichroism spectroscopy of the sixfold-deuterated chiral neopentane. The study of this compound presents formidable challenges since its stereogenicity is only due to small mass differences. For this purpose, we selectively prepared both enantiomers of (2) H6 -1 through a concise synthesis utilizing multifunctional intermediates. While NMR spectroscopy in chiral aligned media could be used to characterize the precursors to (2) H6 -1, the final assignment could only be accomplished with VCD spectroscopy, despite the fleetingly small dichroic properties of 1. Both enantiomers were assigned by matching the VCD spectra with those computed with density functional theory. PMID:26480341

  14. Synthesis and Stereochemical Assignment of Crypto-Optically Active (2) H6 -Neopentane.

    PubMed

    Masarwa, Ahmad; Gerbig, Dennis; Oskar, Liron; Loewenstein, Aharon; Reisenauer, Hans Peter; Lesot, Philippe; Schreiner, Peter R; Marek, Ilan

    2015-10-26

    The determination of the absolute configuration of chiral molecules is at the heart of asymmetric synthesis. Here we probe the spectroscopic limits for chiral discrimination with NMR spectroscopy in chiral aligned media and with vibrational circular dichroism spectroscopy of the sixfold-deuterated chiral neopentane. The study of this compound presents formidable challenges since its stereogenicity is only due to small mass differences. For this purpose, we selectively prepared both enantiomers of (2) H6 -1 through a concise synthesis utilizing multifunctional intermediates. While NMR spectroscopy in chiral aligned media could be used to characterize the precursors to (2) H6 -1, the final assignment could only be accomplished with VCD spectroscopy, despite the fleetingly small dichroic properties of 1. Both enantiomers were assigned by matching the VCD spectra with those computed with density functional theory.

  15. ALMA observations of Titan : Vertical and spatial distribution of HNC and C2H5CN

    NASA Astrophysics Data System (ADS)

    Moreno, Raphael; Lellouch, Emmanuel; Vinatier, Sandrine; Gurwell, Mark A.; Moullet, Arielle; Hidayat, Taufiq

    2016-10-01

    We report submm observations of Titan performed with the ALMA interferometer centered at the rotational frequencies of HCN(4-3) and HNC(4-3), i.e. 354 and 362 GHz. These measurements yielded disk-resolved emission spectra of Titan with an angular resolution of ~0.47''. Titan's angular surface diameter was 0.77''. Data were acquired in summer 2012 near the greatest eastern and western elongations of Titan at a spectral resolution of 122 kHz (λ/d λ = 3106).We have obtained maps of several nitriles present in Titan' stratosphere: HCN, HC3N, CH3CN, HNC, C2H5CN and other weak lines (isotopes, vibrationnally excited lines).We will present radiative transfer analysis of the spectra acquired focused on HNC and C2H5CN. With the combination of all these detected rotational lines, we will constrain the spatial and vertical distribution of these species.

  16. The interaction of cannabinoid receptor agonists, CP55940 and WIN55212-2 with membranes using solid state 2H NMR

    PubMed Central

    Tian, Xiaoyu; Pavlopoulos, Spiro; Yang, De-Ping; Makriyannis, Alexandros

    2013-01-01

    Two key commonly used cannabinergic agonists, CP55940 and WIN55212-2, are investigated for their effects on the lipid membrane bilayer using 2H solid state NMR, and the results are compared with our earlier work with delta-9-tetrahydrocannabinol (Δ9-THC). To study the effects of these ligands we used hydrated bilayers of dipalmitoylphosphatidylcholine (DPPC) deuterated at the 2′ and 16′ positions of both acyl chains with deuterium atoms serving as probes for the dynamic and phase changes at the membrane interface and at the bilayer center respectively. All three cannabinergic ligands lower the phospholipid membrane phase transition temperature, increase the lipid sn-2 chain order parameter at the membrane interface and decrease the order at the center of the bilayer. Our studies show that the cannabinoid ligands induce lateral phase separation in the lipid membrane at physiological temperatures. During the lipid membrane phase transition, the cooperative dynamic process whereby the C-2H segments at the interface and center of the bilayer spontaneously reach the fast exchange regime (2H NMR timescale) is distinctively modulated by the two cannabinoids. Specifically, CP55940 is slightly more efficient at inducing liquid crystalline-type 2H NMR spectral features at the membrane interface compared to WIN55212-2. In contrast, WIN55212-2 has a far superior ability to induce liquid crystalline-type spectral features at the center of the bilayer, and it increases the order parameter of the sn-1 chain in addition to the sn-2 chain of the lipids. These observations suggest the cannabinoid ligands may influence lipid membrane domain formations and there may be contributions to their cannabinergic activities through lipid membrane microdomain related mechanisms. Our work demonstrates that experimental design strategies utilizing specifically deuterium labeled lipids yield more detailed insights concerning the properties of lipid bilayers. PMID:21129361

  17. Palladium-catalyzed cross-dehydrogenative functionalization of C(sp(2))-H Bonds.

    PubMed

    Wu, Yinuo; Wang, Jun; Mao, Fei; Kwong, Fuk Yee

    2014-01-01

    The catalytic cross-dehydrogenative coupling (CDC) reaction has received intense attention in recent years. The attractive feature of this coupling process is the formation of a C-C bond from two C-H moieties under oxidative conditions. In this Focus Review, recent advances in the palladium-catalyzed CDC reactions of C(sp(2) )-H bond are summarized, with a focus on the period from 2011 to early 2013. PMID:24123795

  18. Temporal and spatial distributions of δ18O and δ2H in precipitation in Romania

    NASA Astrophysics Data System (ADS)

    Nagavciuc, Viorica; Bădăluță, Carmen-Andreea; Perșoiu, Aurel

    2015-04-01

    Stable isotope ratios of meteoric water have an important role in climatic, paleoclimatic, hydrological and meteorological studies. While such data are available from most of Europe, so far, in Romania (East Central Europe), no systematic study of the stable isotopic composition of precipitation exists. In this context, the aim of this study is to analyze the isotopic composition of rainwater, its temporal and spatial distribution, the identification of the main factors influencing these variations and the creation of the first map of spatial distribution of stable isotopes in precipitation in Romania. Between March 2012 and March 2014 we have collected monthly samples from 22 stations in Romania, which were subsequently analyzed for their δ18O and δ2H at the Stable Isotopes Laboratory, Stefan cel Mare University, Suceava, Romania. Precipitation in W and NW Romania plot along the GMWL, while those in the East are slightly below it, on an evaporative trend. The LMWL for Romania is defined as δ2H=7,27*δ18O + 6,92. The W-E gradient in the distribution of δ18O and δ2H are less marked than the N-S ones, with local influences dominating in areas of strong evaporation (intramountain basins, rain-shadow areas etc). In SW, and especially in autumn and winter, Meditteranean cyclones carry moisture from the Eastern Mediterranean, the δ18O and δ2H values in precipitation in the area plotting between the GMWL and the Eastern Mediterranean Meteoric Water Line. The isotopic composition of rainwater in Romania correlates well with air temperature, and is influenced to a lesser extent by other factors such as the amount of precipitation, topography configuration, the effect of continentalism and season of the year.

  19. OVRO N2H+ Observations of Class 0 Protostars: Constraints on the Formation of Binary Stars

    NASA Astrophysics Data System (ADS)

    Chen, Xuepeng; Launhardt, Ralf; Henning, Thomas

    2007-11-01

    We present the results of an interferometric study of the N2H+ (1-0) emission from nine nearby, isolated, low-mass protostellar cores, using the Owens Valley Radio Observatory (OVRO) millimeter array. The main goal of this study is the kinematic characterization of the cores in terms of rotation, turbulence, and fragmentation. Eight of the nine objects have compact N2H+ cores with FWHM radii of 1200-3500 AU, spatially coinciding with the thermal dust continuum emission. The one more evolved (Class I) object in the sample (CB 188) shows only faint and extended N2H+ emission. The mean N2H+ line width was found to be 0.37 km s-1. Estimated virial masses range from 0.3 to 1.2 Msolar. We find that thermal and turbulent energy support are about equally important in these cores, while rotational support is negligible. The measured velocity gradients across the cores range from 6 to 24 km s-1 pc-1. Assuming these gradients are produced by bulk rotation, we find that the specific angular momenta of the observed Class 0 protostellar cores are intermediate between those of dense (prestellar) molecular cloud cores and the orbital angular momenta of wide pre-main-sequence (PMS) binary systems. There appears to be no evolution (decrease) of angular momentum from the smallest prestellar cores via protostellar cores to wide PMS binary systems. In the context that most protostellar cores are assumed to fragment and form binary stars, this means that most of the angular momentum contained in the collapse region is transformed into orbital angular momentum of the resulting stellar binary systems.

  20. Electron Impact Ionization and Dissociative Ionization of C2H2

    NASA Technical Reports Server (NTRS)

    Srivastava, S. K.

    1995-01-01

    By utilizing a crossed electron beam collision geometry, a combination of time-of-flight (TOF) and quadrupole mass spectrometers, and the relative flow technique1 normalized values of cross sections and appearance energies (AP) were obtained for the formation of singly and multiply ionized species resulting from the ionization and dissociation of C2H2. Details ont he apparatus and technique have been published previously.2,3.

  1. SIRT6 recruits SNF2H to DNA break sites, preventing genomic instability through chromatin remodeling.

    PubMed

    Toiber, Debra; Erdel, Fabian; Bouazoune, Karim; Silberman, Dafne M; Zhong, Lei; Mulligan, Peter; Sebastian, Carlos; Cosentino, Claudia; Martinez-Pastor, Barbara; Giacosa, Sofia; D'Urso, Agustina; Näär, Anders M; Kingston, Robert; Rippe, Karsten; Mostoslavsky, Raul

    2013-08-22

    DNA damage is linked to multiple human diseases, such as cancer, neurodegeneration, and aging. Little is known about the role of chromatin accessibility in DNA repair. Here, we find that the deacetylase sirtuin 6 (SIRT6) is one of the earliest factors recruited to double-strand breaks (DSBs). SIRT6 recruits the chromatin remodeler SNF2H to DSBs and focally deacetylates histone H3K56. Lack of SIRT6 and SNF2H impairs chromatin remodeling, increasing sensitivity to genotoxic damage and recruitment of downstream factors such as 53BP1 and breast cancer 1 (BRCA1). Remarkably, SIRT6-deficient mice exhibit lower levels of chromatin-associated SNF2H in specific tissues, a phenotype accompanied by DNA damage. We demonstrate that SIRT6 is critical for recruitment of a chromatin remodeler as an early step in the DNA damage response, indicating that proper unfolding of chromatin plays a rate-limiting role. We present a unique crosstalk between a histone modifier and a chromatin remodeler, regulating a coordinated response to prevent DNA damage.

  2. A structural approach reveals how neighbouring C2H2 zinc fingers influence DNA binding specificity.

    PubMed

    Garton, Michael; Najafabadi, Hamed S; Schmitges, Frank W; Radovani, Ernest; Hughes, Timothy R; Kim, Philip M

    2015-10-30

    Development of an accurate protein-DNA recognition code that can predict DNA specificity from protein sequence is a central problem in biology. C2H2 zinc fingers constitute by far the largest family of DNA binding domains and their binding specificity has been studied intensively. However, despite decades of research, accurate prediction of DNA specificity remains elusive. A major obstacle is thought to be the inability of current methods to account for the influence of neighbouring domains. Here we show that this problem can be addressed using a structural approach: we build structural models for all C2H2-ZF-DNA complexes with known binding motifs and find six distinct binding modes. Each mode changes the orientation of specificity residues with respect to the DNA, thereby modulating base preference. Most importantly, the structural analysis shows that residues at the domain interface strongly and predictably influence the binding mode, and hence specificity. Accounting for predicted binding mode significantly improves prediction accuracy of predicted motifs. This new insight into the fundamental behaviour of C2H2-ZFs has implications for both improving the prediction of natural zinc finger-binding sites, and for prioritizing further experiments to complete the code. It also provides a new design feature for zinc finger engineering. PMID:26384429

  3. Electronics and atomic scale properties of defects and dopants in 2H-MoTe2

    NASA Astrophysics Data System (ADS)

    Longobardi, Maria; Ubaldini, Alberto; Giannini, Enrico; Bowler, David R.; Renner, Christoph

    2015-03-01

    We present a detailed STM/STS investigation and corresponding DFT modeling of native dopants and atomic scale defects and their influence on the local electron density of states of 2H-MoTe2. Semiconducting transition metal dichalcogenides (TMDs) are attracting increasing interest in the field of electronics and optoelectronics owing to their layered structure and the indirect-to-direct band gap transition when approaching the single-layer limit. 2H-MoTe2 is a semiconducting TMD with a bulk band gap of around 1.0 eV. This compound shows very high mobility at room temperature and strong absorption throughout the solar spectrum. Previous studies demonstrated the possibility to achieve gate-induced ambipolar transport at the surface. 2H-MoTe2 is thus an attractive candidate for novel optoelectronic devices such as light-emitting diodes, photo detectors and solar cell technology. Controlling the atomic nature and density of defects and dopants is crucial for the development of the aforementioned applications and devices.

  4. CO2/H2 separation using a highly permeable polyurethane membrane: Molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Azizi, Morteza; Mousavi, Seyyed Abbas

    2015-11-01

    In this study, Molecular Dynamics (MD) and Grand Canonical Monte Carlo (GCMC) simulations were conducted to investigate the diffusivity, solubility, and permeability of CO2, CO, H2, and H2O in a polyurethane membrane at three different temperatures. The characterization of the simulated structures was carried out using XRD, FFV, Tg and density calculation, and cavity size distribution. The obtained results were within the expectations reported data in the literature based on the experimental approach, indicating the authenticity of approached in this work. The results showed that the highest diffusivity and permeability coefficients were observed for H2; while the highest values of solubility coefficient were found for H2O and CO2 gases. The increase of operating temperature from 298 K to 318 K has a positive effect on the permeation of all gases and a corresponding negative effect on the selectivity of the gas pair CO2/H2. Also, the results vividly showed that CO2 and H2O gases have a profound affinity with hard phase of polyurethane, while H2 and CO were conversely adsorbed by soft one. Moreover, the enhancement of permeability and permselectivity of CO2/H2 pair confirmed using Robeson Upper-Bond graph showed its good capacity for CO2/H2 separation application.

  5. NMR resonance splitting of urea in stretched hydrogels: proton exchange and (1)H/(2)H isotopologues.

    PubMed

    Kuchel, Philip W; Naumann, Christoph; Chapman, Bogdan E; Shishmarev, Dmitry; Håkansson, Pär; Bacskay, George; Hush, Noel S

    2014-10-01

    Urea at ∼12 M in concentrated gelatin gel, that was stretched, gave (1)H and (2)H NMR spectral splitting patterns that varied in a predictable way with changes in the relative proportions of (1)H2O and (2)H2O in the medium. This required consideration of the combinatorics of the two amide groups in urea that have a total of four protonation/deuteration sites giving rise to 16 different isotopologues, if all the atoms were separately identifiable. The rate constant that characterized the exchange of the protons with water was estimated by back-transformation analysis of 2D-EXSY spectra. There was no (1)H NMR spectral evidence that the chiral gelatin medium had caused in-equivalence in the protons bonded to each amide nitrogen atom. The spectral splitting patterns in (1)H and (2)H NMR spectra were accounted for by intra-molecular scalar and dipolar interactions, and quadrupolar interactions with the electric field gradients of the gelatin matrix, respectively.

  6. Angular momentum of the N2H+ cores in the Orion A cloud

    NASA Astrophysics Data System (ADS)

    Tatematsu, Ken'ichi; Ohashi, Satoshi; Sanhueza, Patricio; Nguyen Luong, Quang; Umemoto, Tomofumi; Mizuno, Norikazu

    2016-04-01

    We have analyzed the angular momentum of the molecular cloud cores in the Orion A giant molecular cloud observed in the N2H+ J = 1-0 line with the Nobeyama 45 m radio telescope. We have measured the velocity gradient using position-velocity diagrams passing through core centers, and made sinusoidal fits against the position angle. Twenty-seven out of 34 N2H+ cores allowed us to measure the velocity gradient without serious confusion. The derived velocity gradient ranges from 0.5 to 7.8 km s-1 pc-1. We marginally found that the specific angular momentum J/M (against the core radius R) of the Orion N2H+ cores tends to be systematically larger than that of molecular cloud cores in cold dark clouds obtained by Goodman et al., in the J/M-R relation. The ratio β of rotational to gravitational energy is derived to be β = 10-2.3±0.7, and is similar to that obtained for cold dark cloud cores in a consistent definition. The large-scale rotation of the ∫-shaped filament of the Orion A giant molecular cloud does not likely govern the core rotation at smaller scales.

  7. Frequency Comb Assisted IR Measurements of H_3^+, H_2D^+ and D_2H^+ Transitions

    NASA Astrophysics Data System (ADS)

    Jusko, Pavol; Asvany, Oskar; Schlemmer, Stephan

    2016-06-01

    We present recent measurements of the fundamental transitions of H_3^+, H_2D^+ and D_2H^+ in a 4 K 22-pole trap by action spectroscopic techniques. Either Laser Induced Inhibition of Cluster Growth (He attachment at T≈4 K), endothermic reaction of H_3^+ with O_2, or deuterium exchange has been used as measurement scheme. We used a 3 μm optical parametric oscillator coupled to a frequency comb in order to achieve accuracy generally below 1 MHz. Five transitions of H_3^+, eleven of H_2D^+ and ten of D_2H^+ were recorder in our spectral range. We compare our H_3^+ results with two previous frequency comb assisted works. Moreover, accurate determination of the frequency allows us to predict pure rotational transitions for H_2D^+ and D_2H^+ in the THz range. P. Jusko, C. Konietzko, S. Schlemmer, O. Asvany, J. Mol. Spec. 319 (2016) 55 O. Asvany, S. Brünken, L. Kluge, S. Schlemmer, Appl. Phys. B 114 (2014) 203 O. Asvany, J. Krieg, S. Schlemmer, Rev. Sci. Instr. 83 (2012) 093110 J.N. Hodges, A.J. Perry, P.A. Jenkins, B.M. Siller, B.J. McCall, J. Chem. Phys. 139 (2013) 164201 H.-C. Chen, C.-Y. Hsiao, J.-L. Peng, T. Amano, J.-T. Shy, Phys. Rev. Lett. 109 (2012) 263002

  8. NMR resonance splitting of urea in stretched hydrogels: proton exchange and (1)H/(2)H isotopologues.

    PubMed

    Kuchel, Philip W; Naumann, Christoph; Chapman, Bogdan E; Shishmarev, Dmitry; Håkansson, Pär; Bacskay, George; Hush, Noel S

    2014-10-01

    Urea at ∼12 M in concentrated gelatin gel, that was stretched, gave (1)H and (2)H NMR spectral splitting patterns that varied in a predictable way with changes in the relative proportions of (1)H2O and (2)H2O in the medium. This required consideration of the combinatorics of the two amide groups in urea that have a total of four protonation/deuteration sites giving rise to 16 different isotopologues, if all the atoms were separately identifiable. The rate constant that characterized the exchange of the protons with water was estimated by back-transformation analysis of 2D-EXSY spectra. There was no (1)H NMR spectral evidence that the chiral gelatin medium had caused in-equivalence in the protons bonded to each amide nitrogen atom. The spectral splitting patterns in (1)H and (2)H NMR spectra were accounted for by intra-molecular scalar and dipolar interactions, and quadrupolar interactions with the electric field gradients of the gelatin matrix, respectively. PMID:25241007

  9. Exotic SiO2H2 Isomers: Theory and Experiment Working in Harmony.

    PubMed

    McCarthy, Michael C; Gauss, Jürgen

    2016-05-19

    Replacing carbon with silicon can result in dramatic and unanticipated changes in isomeric stability, as the well-studied CO2H2 and the essentially unknown SiO2H2 systems illustrate. Guided by coupled-cluster calculations, three SiO2H2 isomers have been detected and spectroscopically characterized in a molecular beam discharge source using rotational spectroscopy. The cis,trans conformer of dihydroxysilylene HOSiOH, the ground-state isomer, and the high-energy, metastable dioxasilirane c-H2SiO2 are abundantly produced in a dilute SiH4/O2 electrical discharge, enabling precise structural determinations of both by a combination of isotopic measurements and calculated vibrational corrections. The isotopic studies also provide insight into their formation route, suggesting that c-H2SiO2 is formed promptly in the expansion but that cis,trans-HOSiOH is likely formed by secondary reactions following formation of the most stable dissociation pair, SiO + H2O. Although less abundant, the rotational spectrum of trans-silanoic acid, the silicon analogue of formic acid, HSi(O)OH, has also been observed. PMID:27139016

  10. Regulated release of Ca2+ from respiring mitochondria by Ca2+/2H+ antiport.

    PubMed

    Fiskum, G; Lehninger, A L

    1979-07-25

    Simultaneous measurements of oxygen consumption and transmembrane transport of Ca2+, H+, and phosphate show that the efflux of Ca2+ from respiring tightly coupled rat liver mitochondria takes place by an electroneutral Ca2+/2H+ antiport process that is ruthenium red-insensitive and that is regulated by the oxidation-reduction state of the mitochondrial pyridine nucleotides. When mitochondrial pyridine nucleotides are kept in a reduced steady state, the efflux of Ca2+ is inhibited; when they are in an oxidized state, Ca2+ efflux is activated. These processes were demonstrated by allowing phosphate-depleted mitochondria respiring on succinate in the presence of rotenone to take up Ca2+ from the medium. Upon subsequent addition of ruthenium red to block Ca2+ transport via the electrophoretic influx pathway, and acetoacetate, to bring mitochondrial pyridine nucleotides into the oxidized state, Ca2+ efflux and H+ influx ensued. The observed H+ influx/Ca2+ efflux ratio was close to the value 2.0 predicted for the operation of an electrically neutral Ca2+/2H+ antiport process.

  11. Liquid water on Mars - An energy balance climate model for CO2/H2O atmospheres

    NASA Technical Reports Server (NTRS)

    Hoffert, M. I.; Callegari, A. J.; Hsieh, C. T.; Ziegler, W.

    1981-01-01

    A simple climatic model is developed for a Mars atmosphere containing CO2 and sufficient liquid water to account for the observed hydrologic surface features by the existence of a CO2/H2O greenhouse effect. A latitude-resolved climate model originally devised for terrestrial climate studies is applied to Martian conditions, with the difference between absorbed solar flux and emitted long-wave flux to space per unit area attributed to the divergence of the meridional heat flux and the poleward heat flux assumed to equal the atmospheric eddy heat flux. The global mean energy balance is calculated as a function of atmospheric pressure to assess the CO2/H2O greenhouse liquid water hypothesis, and some latitude-resolved cases are examined in detail in order to clarify the role of atmospheric transport and temperature-albedo feedback. It is shown that the combined CO2/H2O greenhouse at plausible early surface pressures may account for climates hot enough to support a hydrological cycle and running water at present-day insolation and visible albedo levels.

  12. Detection of interstellar ethylene oxide (c-C2H4O).

    PubMed

    Dickens, J E; Irvine, W M; Ohishi, M; Ikeda, M; Ishikawa, S; Nummelin, A; Hjalmarson, A

    1997-11-10

    We report the identification of 10 transitions that support the detection of the small cyclic molecule ethylene oxide (c-C2H4O) in Sgr B2N. Although one of these transitions is severely blended, so that an accurate intensity and line width could not be determined, and two other lines are only marginally detected, we have done Gaussian fits to the remaining seven lines and have performed a rotation diagram analysis. Our results indicate a rotation temperature T(rot) = 18 K and a molecular column density N(c-C2H4O) = 3.3 x 10(14) cm-2, corresponding to a fractional abundance relative to molecular hydrogen of order 6 x 10(-11). This is a factor of more than 200 higher than the abundance for this molecule suggested by the "new standard" chemistry model of Lee, Bettens, & Herbst. This result suggests that grain chemistry might play an effective role in the production of c-C2H4O. No transitions of this molecule were detected in either Sgr B2M or Sgr B2NW.

  13. Preparation of bis-(1(2)H-tetrazol-5-yl)-amine monohydrate

    DOEpatents

    Naud, Darren L.; Hiskey, Michael A.

    2003-05-27

    A process of preparing bis-(1(2)H-tetrazol-5-yl)-amine monohydrate is provided including combining a dicyanamide salt, an azide salt and water to form a first reaction mixture, adding a solution of a first strong acid characterized as having a pKa of less than about 1 to said first reaction mixture over a period of time characterized as providing a controlled reaction rate so as to gradually form hydrazoic acid without loss of significant quantities of hydrazoic acid from the solution while heating the first reaction mixture at temperatures greater than about 65.degree. C., heating the resultant reaction mixture at temperatures greater than about 65.degree. C. for a period of time sufficient to substantially completely form a reaction product, treating the reaction product with a solution of a second strong acid to form a product of bis-(1(2)H-tetrazol-5-yl)-amine monohydrate, and, recovering the bis-(1(2)H-tetrazol-5-yl)-amine monohydrate product.

  14. 2Q NMR of 2H2O ordering at solid interfaces

    NASA Astrophysics Data System (ADS)

    Krivokhizhina, Tatiana V.; Wittebort, R. J.

    2014-06-01

    Solvent ordering at an interface can be studied by multiple-quantum NMR. Quantitative studies of 2H2O ordering require clean double-quantum (2Q) filtration and an analysis of 2Q buildup curves that accounts for relaxation and, if randomly oriented samples are used, the distribution of residual couplings. A pulse sequence with absorption mode detection is extended for separating coherences by order and measuring relaxation times such as the 2Q filtered T2. Coherence separation is used to verify 2Q filtration and the 2Q filtered T2 is required to extract the coupling from the 2Q buildup curve when it is unresolved. With our analysis, the coupling extracted from the buildup curve in 2H2O hydrated collagen was equivalent to the resolved coupling measured in the usual 1D experiment and the 2Q to 1Q signal ratio was in accord with theory. Application to buildup curves from 2H2O hydrated elastin, which has an unresolved coupling, revealed a large increase in the 2Q signal upon mechanical stretch that is due to an increase in the ordered water fraction while changes in the residual coupling and T2 are small.

  15. Application of a quantum cascade laser for time-resolved, in situ probing of CH4/H2 and C2H2/H2 gas mixtures during microwave plasma enhanced chemical vapor deposition of diamond.

    PubMed

    Cheesman, A; Smith, J A; Ashfold, M N R; Langford, N; Wright, S; Duxbury, G

    2006-03-01

    First illustrations of the utility of pulsed quantum cascade lasers for in situ probing of the chemistry prevailing in microwave plasma activated hydrocarbon/Ar/H2 gas mixtures used for diamond thin film growth are reported. CH4 and C2H2 molecules, and their interconversion, have been monitored by line-of-sight single pass absorption methods, as a function of process conditions (e.g., choice of input hydrocarbon (CH4 or C2H2), hydrocarbon mole fraction, total gas pressure, and applied microwave power). The observed trends can be rationalized, qualitatively, within the framework of the previously reported modeling of the gas-phase chemistry prevailing in hot filament activated hydrocarbon/H2 gas mixtures (Ashfold et al. Phys. Chem. Chem. Phys. 2001, 3, 3471). Column densities of vibrationally excited C2H2(v5=1) molecules at low input carbon fractions are shown to be far higher than expected on the basis of local thermodynamic equilibrium. The presence of vibrationally excited C2H2 molecules (C2H2(double dagger)) can be attributed to the exothermicity of the C2H3 + H <==> C2H2 + H2 elementary reaction within the overall multistep CH4 --> C2H2 conversion. Diagnostic methods that sample just C2H2(v=0) molecules thus run the risk of underestimating total C2H2 column densities in hydrocarbon/H2 mixtures operated under conditions where the production rate of C2H2(double dagger) molecules exceeds their vibrational relaxation (and thermal equilibration) rates.

  16. High-frequency observations of δ2H and δ18O in storm rainfall

    NASA Astrophysics Data System (ADS)

    Stoecker, F.; Klaus, J.; Pangle, L. A.; Garland, C.; McDonnell, J. J.

    2012-12-01

    Stable isotopes ratios of hydrogen (2H/1H) and oxygen (18O/16O) are indispensable tools for investigation of the hydrologic cycle. Recent technological advances with laser spectroscopy now enable high-frequency measurement of key water cycle components. While the controls on rainfall isotope composition have been known generally for some time, our understanding of the effect of inter- and intra-storm processes on fine scale rainfall isotope composition is poorly understood. Here we present a new approach to observe inter- and intra-storm isotope variability in precipitation in high-frequency. We investigate the temporal development of δ2H and δ18O within and between discrete rainstorm. δ2H and δ18O in precipitation was measured from November 2011 to February 2012 in Corvallis, OR using a flow-cell combined with a Liquid Water Isotope Analyzer (LWIA-24d, Los Gatos Research, Inc.). The average sample frequency was 15 samples per hour, resulting in more than 3100 samples during the observation period. 27 separate rainstorms were identified in the dataset based on minimum inter-event time, minimum precipitation depth, and minimum number of isotope measurements. Event meteoric water lines were developed for each event. We observed short-term isotopic patterns (e.g., V-shaped trends), high-rate changes (5.3‰/h) and large absolute changes in isotopic composition (20‰) on intra-event scale. V-shaped trends appeared to be related to individual storm fronts detected by air temperature, cloud heights (NEXRAD radar echo tops) and cloud trajectories (Hybrid Single Particle Lagrangian Integrated Trajectory Model (HYSPLIT)). Despite this, we could detect no linear correlation between event-based isotopic variables (slope, δ2H-intercept, δ2H, δ18O) and the event meteoric water line. Furthermore, the composite event meteoric water line (i.e. the local meteoric water line) showed a wider spread for heavy isotopes than for light isotopes, caused presumably by different

  17. Gas-phase CO2, C2H2, and HCN toward Orion-KL

    NASA Astrophysics Data System (ADS)

    Boonman, A. M. S.; van Dishoeck, E. F.; Lahuis, F.; Doty, S. D.; Wright, C. M.; Rosenthal, D.

    2003-03-01

    The infrared spectra toward Orion-IRc2, Peak 1 and Peak 2 in the 13.5-15.5 mu m wavelength range are presented, obtained with the Short Wavelength Spectrometer on board the Infrared Space Observatory. The spectra show absorption and emission features of the vibration-rotation bands of gas-phase CO2, HCN, and C2H2, respectively. Toward the deeply embedded massive young stellar object IRc2 all three bands appear in absorption, while toward the shocked region Peak 2 CO2, HCN, and C2H2 are seen in emission. Toward Peak 1 only CO2 has been detected in emission. Analysis of these bands shows that the absorption features toward IRc2 are characterized by excitation temperatures of ~ 175-275 K, which can be explained by an origin in the shocked plateau gas. HCN and C2H2 are only seen in absorption in the direction of IRc2, whereas the CO2 absorption is probably more widespread. The CO2 emission toward Peak 1 and 2 is best explained with excitation by infrared radiation from dust mixed with the gas in the warm component of the shock. The similarity of the CO2 emission and absorption line shapes toward IRc2, Peak 1 and Peak 2 suggests that the CO2 is located in the warm component of the shock (T ~ 200 K) toward all three positions. The CO2 abundances of ~ 10-8 for Peak 1 and 2, and of a few times 10-7 toward IRc2 can be explained by grain mantle evaporation and/or reformation in the gas-phase after destruction by the shock. The HCN and C2H2 emission detected toward Peak 2 is narrower (T ~ 50-150 K) and originates either in the warm component of the shock or in the extended ridge. In the case of an origin in the warm component of the shock, the low HCN and C2H2 abundances of ~ 10-9 suggest that they are destroyed by the shock or have only been in the warm gas for a short time (t <~ 104 yr). In the case of an origin in the extended ridge, the inferred abundances are much higher and do not agree with predictions from current chemical models at low temperatures. Based on

  18. 2H Stable Isotope Analysis of Tooth Enamel: A Pilot Study

    NASA Astrophysics Data System (ADS)

    Holobinko, Anastasia; Kemp, Helen; Meier-Augenstein, Wolfram; Prowse, Tracy; Ford, Susan

    2010-05-01

    Stable isotope analysis of biogenic tissues such as tooth enamel and bone mineral has become a well recognized and increasingly important method for determining provenance of human remains, and has been used successfully in bioarchaeological studies as well as forensic investigations (Lee-Thorp, 2008; Meier-Augenstein and Fraser, 2008). Particularly, 18O and 2H stable isotopes are well established proxies as environmental indicators of climate (temperature) and source water and are therefore considered as indicators of geographic life trajectories of animals and humans (Hobson et al., 2004; Schwarcz and Walker, 2006). While methodology for 2H analysis of human hair, fingernails, and bone collagen is currently used to determine geographic origin and identify possible migration patterns, studies involving the analysis of 2H in tooth enamel appear to be nonexistent in the scientific literature. The apparent lack of research in this area is believed to have two main reasons. (1) Compared to the mineral calcium hydroxylapatite Ca10(PO4)6(OH)2, in tooth enamel forming bio-apatite carbonate ions replace some of the hydroxyl ions at a rate of one CO32 replacing two OH, yet published figures for the degree of substitution vary (Wopenka and Pasteris, 2005). (2) Most probably due to the aforementioned no published protocols exist for sample preparation and analytical method to obtain δ2H-values from the hydroxyl fraction of tooth enamel. This dilemma has been addressed through a pilot study to establish feasibility of 2H stable isotope analysis of ground tooth enamel by continuous-flow isotope ratio mass spectrometry (IRMS) coupled on-line to a high-temperature conversion elemental analyzer (TC/EA). An array of archaeological and modern teeth has been analyzed under different experimental conditions, and results from this pilot study are being presented. References: Lee-Thorp, J.A. (2008) Archaeometry, 50, 925-950 Meier-Augenstein, W. and Fraser, I. (2008) Science & Justice

  19. Planar B3S2H3(-) and B3S2H3 clusters with a five-membered B3S2 ring: boron-sulfur hydride analogues of cyclopentadiene.

    PubMed

    Li, Da-Zhi; Li, Rui; Zhang, Li-Juan; Ou, Ting; Zhai, Hua-Jin

    2016-08-21

    Boron clusters can serve as inorganic analogues of hydrocarbons or polycyclic aromatic hydrocarbons (PAHs). We present herein, based upon global searches and electronic structural calculations at the B3LYP and CCSD(T) levels, the global-minimum structures of two boron-sulfur hydride clusters: C2v B3S2H3(-) (1, (2)B1) and C2v B3S2H3 (2, (1)A1). Both species are perfectly planar and feature a five-membered B3S2 ring as the structural core, with three H atoms attached terminally to the B sites. Chemical bonding analysis shows that C2v B3S2H3(-) (1) has a delocalized 5π system within a heteroatomic B3S2 ring, analogous to the π bonding in cyclopentadiene, D5h C5H5. The corresponding closed-shell C2v B3S2H3(2-) (3, (1)A1) dianion is only a local minimum. At the single-point CCSD(T) level, it is 5.7 kcal mol(-1) above the chain-like C1 ((1)A) open structure. This situation is in contrast to the cyclopentadienyl anion, C5H5(-), a prototypical aromatic hydrocarbon with a π sextet. The C2v B3S2H3 (2) neutral cluster is readily obtained upon removal of one π electron from C2v B3S2H3(-) (1). The anion photoelectron spectrum of C2v B3S2H3(-) (1) and the infrared absorption spectrum of C2v B3S2H3 (2) are predicted. The C2v B3S2H3(-) (1) species can be stabilized in sandwich-type C2h [(B3S2H3)2Fe](2-) and salt C2h [(B3S2H3)2Fe]Li2 complexes. An intriguing difference is observed between the pattern of π sextet in C2v B3S2H3(2-) (3) dianion and that in cyclopentadienyl anion. The present work also sheds light on the mechanism of structural evolution in the B3S2H3(0/-/2-) series with charge states. PMID:27424889

  20. Planar B3S2H3(-) and B3S2H3 clusters with a five-membered B3S2 ring: boron-sulfur hydride analogues of cyclopentadiene.

    PubMed

    Li, Da-Zhi; Li, Rui; Zhang, Li-Juan; Ou, Ting; Zhai, Hua-Jin

    2016-08-21

    Boron clusters can serve as inorganic analogues of hydrocarbons or polycyclic aromatic hydrocarbons (PAHs). We present herein, based upon global searches and electronic structural calculations at the B3LYP and CCSD(T) levels, the global-minimum structures of two boron-sulfur hydride clusters: C2v B3S2H3(-) (1, (2)B1) and C2v B3S2H3 (2, (1)A1). Both species are perfectly planar and feature a five-membered B3S2 ring as the structural core, with three H atoms attached terminally to the B sites. Chemical bonding analysis shows that C2v B3S2H3(-) (1) has a delocalized 5π system within a heteroatomic B3S2 ring, analogous to the π bonding in cyclopentadiene, D5h C5H5. The corresponding closed-shell C2v B3S2H3(2-) (3, (1)A1) dianion is only a local minimum. At the single-point CCSD(T) level, it is 5.7 kcal mol(-1) above the chain-like C1 ((1)A) open structure. This situation is in contrast to the cyclopentadienyl anion, C5H5(-), a prototypical aromatic hydrocarbon with a π sextet. The C2v B3S2H3 (2) neutral cluster is readily obtained upon removal of one π electron from C2v B3S2H3(-) (1). The anion photoelectron spectrum of C2v B3S2H3(-) (1) and the infrared absorption spectrum of C2v B3S2H3 (2) are predicted. The C2v B3S2H3(-) (1) species can be stabilized in sandwich-type C2h [(B3S2H3)2Fe](2-) and salt C2h [(B3S2H3)2Fe]Li2 complexes. An intriguing difference is observed between the pattern of π sextet in C2v B3S2H3(2-) (3) dianion and that in cyclopentadienyl anion. The present work also sheds light on the mechanism of structural evolution in the B3S2H3(0/-/2-) series with charge states.

  1. First-Principles Electronic Structure Calculations of N2H4 Adsorbed on Single-Wall Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Yu, M.; Tian, W. Q.; Jayanthi, C. S.; Wu, S. Y.

    2008-03-01

    Recent experiments conducted by Desai et al. [1] reveal that single-wall carbon nanotube (SWCNT) networks exposed to N2H4 vapor at various pressures exhibit considerable drop in resistance with respect to the pristine sample. Experimental findings reveal: (i) n-type behavior for the adsorption of N2H4/SWCNT, and (ii) the binding of N2H4 on SWCNT as chemisorption. In the present work, we have performed first-principles electronic structure calculations [2] for the N2H4 adsorbed on the (14, 0) SWCNT, where several orientations for the N2H4 molecule were considered. Calculations for the combined system were performed using 3 unit cells with the DFT/GGA and ultra soft pseudo-potentials. Our calculations reveal: (i) the binding of N2H4 on SWCNT as physisorption, and (ii) the electronic structure of SWCNT to be practically unaltered by the adsorption of N2H4, suggesting that there will not be a dramatic drop in resistance for N2H4/SWCNT. This is in disagreement with the experimental findings. To further understand the experimental observations, we will discuss mechanisms that may alter the binding nature of N2H4 on SWCNT. [1] S. Desai, G. Sumanasekera, et al. (APS, March 2008). [2] G. Kresse and J. Furthmuller, Phys. Rev. B 54, 11169 (1996).

  2. Reactions of ethynyl radicals - Rate constants with CH4, C2H6, and C2D6

    NASA Technical Reports Server (NTRS)

    Laufer, A. H.

    1981-01-01

    An experiment to measure ethynyl radical reactivity with other simple molecules is described. Flash photolysis of CF3C2H, a C2H precursor, was kinetically and spectroscopically analyzed for C2H reactions with CH4, C2H6, and C2D6 and rate constants for the abstraction reaction at room temperature were determined. The experimental apparatus is described, and the acetylene feedstock purification procedures are outlined. Rate constants are provided, and additional examination of the effects of added helium showed no alterations over the pressure range 20-700 torr.

  3. Cometary implications of recent laboratory experiments on the photochemistry of the C2H and C3H2 radicals

    NASA Technical Reports Server (NTRS)

    Jackson, William M.; Bao, Yihan; Urdahl, Randall S.; Song, Xueyu; Gosine, Jai; Lu, Chi

    1992-01-01

    Recent laboratory results on the photodissociation of the C2H and C3H2 radicals are described. These studies show that the C2 and C3 radicals are produced by the 193 nm photolysis of the C2H and C3H2 radicals, respectively. The quantum state distributions that were determined for the C2 radicals put certain constraints on the initial conditions for any models of the observed C2 cometary spectra. Experimental observations of C2 formed by the 212.8 nm photolysis of C2H are used to calculate a range of photochemical lifetimes for the C2H radical.

  4. GTE_TRACEP_DC8 Parameters 4

    Atmospheric Science Data Center

    2013-02-18

    ... (-90, 90)(-180,180) Parameters:  Methyl nitrate (CH3ONO2) Ethyl nitrate (C2H5ONO2) Isopropyl nitrate ... Halon-1301 (CBrF3) Halon-1202 (CBr2F2) Methyl bromide (CH3Br) Bromopropane (C3H7Br) Methyl Chloride(CH3Cl) Ethyl ...

  5. GTE_TRACEP_DC8 Parameters 16

    Atmospheric Science Data Center

    2013-02-18

    ... (-90, 90)(-180,180) Parameters:  Chloride (Cl-) Nitrate (NO3-) Sulfate (SO4-) Oxalate (C2H2O4) ... Ammonium (NH4-) Potassium (K-) Magnesium (Mg2) Calcium (Ca2-) Beryllium 7 (7Be) Nitric Acid (HNO3) Sulfur dioxide ...

  6. Obstruction of dengue virus maturation by Fab fragments of the 2H2 antibody.

    PubMed

    Wang, Zhiqing; Li, Long; Pennington, Janice G; Sheng, Ju; Yap, Moh Lan; Plevka, Pavel; Meng, Geng; Sun, Lei; Jiang, Wen; Rossmann, Michael G

    2013-08-01

    The 2H2 monoclonal antibody recognizes the precursor peptide on immature dengue virus and might therefore be a useful tool for investigating the conformational change that occurs when the immature virus enters an acidic environment. During dengue virus maturation, spiky, immature, noninfectious virions change their structure to form smooth-surfaced particles in the slightly acidic environment of the trans-Golgi network, thereby allowing cellular furin to cleave the precursor-membrane proteins. The dengue virions become fully infectious when they release the cleaved precursor peptide upon reaching the neutral-pH environment of the extracellular space. Here we report on the cryo-electron microscopy structures of the immature virus complexed with the 2H2 antigen binding fragments (Fab) at different concentrations and under various pH conditions. At neutral pH and a high concentration of Fab molecules, three Fab molecules bind to three precursor-membrane proteins on each spike of the immature virus. However, at a low concentration of Fab molecules and pH 7.0, only two Fab molecules bind to each spike. Changing to a slightly acidic pH caused no detectable change of structure for the sample with a high Fab concentration but caused severe structural damage to the low-concentration sample. Therefore, the 2H2 Fab inhibits the maturation process of immature dengue virus when Fab molecules are present at a high concentration, because the three Fab molecules on each spike hold the precursor-membrane molecules together, thereby inhibiting the normal conformational change that occurs during maturation.

  7. Volume-discharge formed in SF6 and C2H6 mixtures without preionization

    NASA Astrophysics Data System (ADS)

    Zhang, Ge; Ke, Changjun; Zhang, Shujuan

    2014-11-01

    A new approach to obtain glow discharge in working mixtures of non-chain HF laser has been brought forward. The most advantage of the approach is without pre-ionization, so the contamination of pre-ionization will not happen and the laser equipment is compact and simple. It is found, if the cathode surface is equally rough, we can obtain uniform volume-discharge in SF6 mixtures without any pre-ionization, and dispense with uniform electric field electrode profile. The form of Self-Sustained Volume Discharge (SSVD) is a Self-Initiated Volume Discharge (SIVD). We show here the possibility of obtaining SIVD with a uniform energy deposition in a system of electrodes with non-uniform electric field. Experiments show that, with rough cathode and even anode, a volume discharge is forming in non-uniform electric-field without pre-ionization in SF6 and C2H6 mixtures. At the beginning of the discharge, many diffuse channels attached to bright circular cathode spots, then, diverge towards the anode, with the channels overlapping, form a spatially uniform glow discharge. SIVD has been performed at a total mixture pressure up to 8kPa and energy deposition up to 200J/l. We also report measurements of the V-I characteristics of SIVD with SF6 and C2H6 mixtures at pressure up to about 8kPa. The experimental results indicate that SSVD in SF6 and C2H6 mixtures develops in the form of SIVD is promising for creation of high energy and pulse-periodic HF laser.

  8. Sources of ground water salinity on islands using 18O, 2H, and 34S.

    PubMed

    Allen, D M

    2004-01-01

    Stable isotopes of 18O and 2H in water, and 34S and 18O in dissolved SO4, are used to verify the interpretation of the chemical evolution and proposed sources of salinity for two islands that have undergone postglacial rebound. Results for delta18O and delta34S in dissolved SO4 on the Gulf Islands, southwest British Columbia, Canada, suggest a three-component mixing between (1) atmospheric SO4 derived largely from recharge of meteoric origin, (2) modern marine SO4 associated with either modern-day salt water intrusion or Pleistocene age sea water, and (3) terrestrial SO4. The age of the marine SO4 is uncertain based on the geochemistry and SO4 isotopes alone. Two options for mixing of saline ground waters are proposed--either between current-day marine SO4 and atmospheric SO4, or between older (Pleistocene age) marine SO4 and atmospheric SO4, delta18O and delta2H compositions are relatively consistent between both islands, with a few samples showing evidence of mixing with water that is a hybrid mixture of Fraser River water and ocean water. The isotopic composition of this hybrid water is approximately delta18O = 10 per thousand. delta18O and delta2H values for many saline ground waters plot close to the global meteoric water line, which is distinctly different from the local meteoric water line. This suggests a meteoric origin for ground waters that is different from the current isotopic composition of meteoric waters. It is proposed these waters may be late Pleistocene in age and were recharged when the island was submerged below sea level and prior to rebound at the end of the last glaciation. PMID:14763614

  9. Quinolone-1-(2H)-ones as hedgehog signalling pathway inhibitors.

    PubMed

    Trinh, Trieu N; McLaughlin, Eileen A; Abdel-Hamid, Mohammed K; Gordon, Christopher P; Bernstein, Ilana R; Pye, Victoria; Cossar, Peter; Sakoff, Jennette A; McCluskey, Adam

    2016-07-14

    A series of quinolone-2-(1H)-ones derived from the Ugi-Knoevenagel three- and four-component reaction were prepared exhibiting low micromolar cytotoxicity against a panel of eight human cancer cell lines known to possess the Hedgehog Signalling Pathway (HSP) components, as well as the seminoma TCAM-2 cell line. A focused SAR study was conducted and revealed core characteristics of the quinolone-2-(1H)-ones required for cytotoxicity. These requirements included a C3-tethered indole moiety, an indole C5-methyl moiety, an aliphatic tail or an ester, as well as an additional aromatic moiety. Further investigation in the SAG-activated Shh-LIGHT2 cell line with the most active analogues: 2-(3-cyano-2-oxo-4-phenylquinolin-1(2H)-yl)-2-(1-methyl-1H-indol-3-yl)-N-(pentan-2-yl)acetamide (5), 2-(3-cyano-2-oxo-4-phenylquinolin-1(2H)-yl)-2-(5-methyl-1H-indol-3-yl)-N-(pentan-2-yl)acetamide (23) and ethyl (2-(3-cyano-2-oxo-4-phenylquinolin-1(2H)-yl)-2-(5-methyl-1H-indol-3-yl)acetyl)glycinate (24) demonstrated a down regulation of the HSP via a reduction in Gli expression, and in the mRNA levels of Ptch1 and Gli2. Analogues 5, 23 and 24 returned in cell inhibition values of 11.6, 2.9 and 3.1 μM, respectively, making this new HSP-inhibitor pharmacophore amongst the most potent non-Smo targeted inhibitors thus far reported. PMID:27272335

  10. Thermal neutron capture cross sections for 16,171,18O and 2H

    NASA Astrophysics Data System (ADS)

    Firestone, R. B.; Revay, Zs.

    2016-04-01

    Thermal neutron capture γ -ray spectra for 16,17,18O and 2H have been measured with guided cold neutron beams from the Forschungs-Neutronenquelle Heinz Maier-Leibnitz (FRM II) reactor and the Budapest Research Reactor (BRR) on natural and O,1817 enriched D2O targets. Complete neutron capture γ -ray decay schemes for the 16,17,18O(n ,γ ) reactions were measured. Absolute transition probabilities were determined for each reaction by a least-squares fit of the γ -ray intensities to the decay schemes after accounting for the contribution from internal conversion. The transition probability for the 870.76-keV γ ray from 16O(n ,γ ) was measured as Pγ(871 )=96.6 ±0.5 % and the thermal neutron cross section for this γ ray was determined as 0.164 ±0.003 mb by internal standardization with multiple targets containing oxygen and stoichiometric quantities of hydrogen, nitrogen, and carbon whose γ -ray cross sections were previously standardized. The γ -ray cross sections for the O,1817(n ,γ ) and 2H(n ,γ ) reactions were then determined relative to the 870.76-keV γ -ray cross section after accounting for the isotopic abundances in the targets. We determined the following total radiative thermal neutron cross sections for each isotope from the γ -ray cross sections and transition probabilities; σ0(16O )=0.170 ±0.003 mb; σ0(17O )=0.67 ±0.07 mb; σ0(18O )=0.141 ±0.006 mb; and σ0(2H )=0.489 ±0.006 mb.

  11. Terahertz Spectroscopy and Global Analysis of the Bending Vibrations of ^{12}C_2H_2 and ^{12}C_2D_2

    NASA Astrophysics Data System (ADS)

    Yu, Shanshan; Drouin, Brian J.; Pearson, John C.; Pickett, Herbert M.; Lattanzi, Valerio; Walters, Adam

    2009-06-01

    Symmetric molecules have no permanent dipole moment and are undetectable by rotational spectroscopy. Their interstellar observations have previously been limited to mid-infrared vibration-rotation spectroscopy. Although relatively weak, vibrational difference bands provide a means for detection of non polar molecules by terahertz techniques with microwave precision. Herschel, SOFIA, and ALMA have the potential to identify a number of difference bands of light symmetric species, e.g., C_2H_2, CH_4 and C_3. This paper reports the results of the laboratory study on ^{12}C_2H_2 and ^{12}C_2D_2. The symmetric isotopomers of acetylene have two bending modes, the trans bending ν_4 (^1{π}_g), and the cis bending ν_5 (^1{π}_u). For ^{12}C_2H_2, the two bending modes occur at 612 and 729 cm^{-1}, respectively. For ^{12}C_2D_2, the two bending modes occur at 511 and 538 cm^{-1}. The ν_5-ν_4 difference bands are allowed and occur in the microwave, terahertz, and far-infrared wavelengths, with band origins at 117 cm^{-1} (3500 GHz) for ^{12}C_2H_2 and 27 cm^{-1} (900 GHz) for ^{12}C_2D_2. Two hundred and fifty-one ^{12}C_2D_2 transitions, which are from ν_5-ν_4, (ν_5+ν_4)-2ν_4 and 2ν_5-(ν_5+ν_4) bands, have been measured in the 0.2-1.6 THz region, and 202 of them were observed for the first time. The precision of these measurements is estimated to be from 50 kHz to 100 kHz. A multistate analysis was carried out for the bending vibrational modes ν_4 and ν_5 of ^{12}C_2D_2, which includes the lines observed in this work and prior microwave, far-infrared and infrared data on the pure bending levels. Significantly improved molecular parameters were obtained for ^{12}C_2D_2 by adding the new measurements to the old data set which had only 10 lines with microwave measurement precision. The experiments on ^{12}C_2H_2 are in progress and ten P branch lines have been observed. We will present the ^{12}C_2H_2 results to date.

  12. Laboratory Spectra of Mixtures of CH4, C2H6, and CH3OH

    NASA Technical Reports Server (NTRS)

    Mastrapa, Rachel; Berry, Matthew T.; Sandford, Scott

    2011-01-01

    Infrared spectroscopy is commonly used as a tool for identifying the composition of objects in the Solar System and beyond. Using laboratory spectra, optical constants can be calculated and used to create model spectra for comparison to spectra obtained from infrared telescopes. In this study, the optical constants of mixtures of simple organics, including CH4, C2H6, and CH3OH were calculated from 15 to 70 K, in the frequency range of 9000-500 cm(sup -1) (1.1-20 micrometers), at a spectral resolution of 1 cm(sup -1).

  13. Characterization Results for the 2014 HTF 3H & 2H Evaporator Overhead Samples

    SciTech Connect

    Washington, A.

    2015-05-11

    This report tabulates the radiochemical analysis of the 3H and 2H evaporator overhead samples for 137Cs, 90Sr, and 129I to meet the requirements in the Effluent Treatment Project (ETP) Waste Acceptance Criteria (WAC) (rev. 6). This report identifies the sample receipt date, preparation method, and analysis performed in the accumulation of the listed values. All data was found to be within the ETP WAC (rev. 6) specification for the Waste Water Collection Tanks (WWCT).

  14. Gold-Catalyzed Highly Selective Photoredox C(sp(2) )-H Difluoroalkylation and Perfluoroalkylation of Hydrazones.

    PubMed

    Xie, Jin; Zhang, Tuo; Chen, Fei; Mehrkens, Nina; Rominger, Frank; Rudolph, Matthias; Hashmi, A Stephen K

    2016-02-18

    The first gold-catalyzed photoredox C(sp(2) )-H difluoroalkylation and perfluoroalkylation of hydrazones with readily available RF -Br reagents is reported. The resulting gem-difluoromethylated and perfluoroalkylated hydrazones are highly functionalized, versatile molecules. A mild reduction of the coupling products can efficiently produce gem-difluoromethylated β-amino phosphonic acids and β-amino acid derivatives. In mechanistic studies, a difluoroalkyl radical intermediate was detected by an EPR spin-trapping experiment, indicating that a gold-catalyzed radical pathway is operating. PMID:26800002

  15. Early Gravitropic Events in Roots of Arabidopsis: Ca(2+)H(+) Fluxes in the Columella Cells

    NASA Technical Reports Server (NTRS)

    Feldman, Lewis

    2003-01-01

    Despite the wealth of information derived from physiological approaches, molecular mechanisms for sensing and responding to gravity in plants remain largely uncharacterized. Roots of higher plants offer many advantages for studying the sensing and responding phases. In roots, gravisensing occurs in specialized cells, the columella cells in which earlier studies have indicated an involvement of the cytoskeleton, Ca(2+), H(+) and auxin in processing the gravity signal. The overall goal of this project was to characterize gravity-stimulated Ca(2+) and H(+) fluxes in the columella cells of a model plant Arabidopsis thaliana and to define their regulation. For this work we used intact Arabidopsis roots.

  16. Charge transfer in energetic Li2+-H and He+-He+ collisions

    NASA Astrophysics Data System (ADS)

    Mančev, I.

    2009-02-01

    The total cross sections for charge transfer in Li2+-H and He+-He+ collisions have been calculated, using the four body first Born approximation with correct boundary conditions (CB1-4B) and four body continuum distorted wave method (CDW-4B) in the energy range 10-5000 keV/amu. The role of dynamic electron correlations is examined as a function of the impact energy. The present results call for additional experimental data at higher impact energies than presently available.

  17. Low-temperature solid-state phase transformations in 2H silicon carbide.

    NASA Technical Reports Server (NTRS)

    Powell, J. A.; Will, H. A.

    1972-01-01

    Study of the phase transformations taking place in 2H SiC single crystals at temperatures as low as 400 C. Some crystals transformed to a structure with one-dimensional disorder along the crystal c axis. Others transformed to a faulted cubic/6H structure. The transformation is time and temperature dependent, and is greatly enhanced by dislocations. The transformation takes place by means of a slip process perpendicular to the c axis. Cubic SiC crystals were observed to undergo a solid-state transformation above 1400 C.

  18. Ethyl 2-[(2-oxo-2H-chromen-7-yl)­oxy]acetate

    PubMed Central

    Fun, Hoong-Kun; Quah, Ching Kheng; Aich, Krishnendu; Das, Sangita; Goswami, Shyamaprosad

    2013-01-01

    In the title compound, C13H12O5, the mean plane of the 2H-chromene ring system (r.m.s deviation = 0.026 Å) forms a dihedral angle of 81.71 (6)° with the mean plane of ethyl 2-hy­droxy­acetate moiety (r.m.s deviation = 0.034 Å). In the crystal, C—H⋯O hydrogen bonds result in the formation of zigzag layers parallel to the bc plane. PMID:23634050

  19. N-Glucosides as human sodium-dependent glucose cotransporter 2 (hSGLT2) inhibitors.

    PubMed

    Yamamoto, Yasuo; Kawanishi, Eiji; Koga, Yuichi; Sakamaki, Shigeki; Sakamoto, Toshiaki; Ueta, Kiichiro; Matsushita, Yasuaki; Kuriyama, Chiaki; Tsuda-Tsukimoto, Minoru; Nomura, Sumihiro

    2013-10-15

    Inhibition of renal sodium-dependent glucose cotransporter 2 (SGLT2) increases urinary glucose excretion (UGE), and thus reduces blood glucose levels in hyperglycemia. A series of N-glucosides was synthesized for biological evaluation as human SGLT2 (hSGLT2) inhibitors. Among these compounds, N-glucoside 9d possessing an indole core structure showed good in vitro activity (IC50=7.1 nM against hSGLT2). Furthermore, 9d exhibited favorable in vivo potency with regard to UGE in rats based on good pharmacokinetic profiles. PMID:23999047

  20. Electronic effect directed Au(I)-catalyzed cyclic C2-H bond functionalization of 3-allenylindoles.

    PubMed

    Chen, Bo; Fan, Wu; Chai, Guobi; Ma, Shengming

    2012-07-20

    Gold-catalyzed cyclization reactions of indoles with an electron-deficient allene at the 3-position led to formation of dihydrocyclopenta[b]indole derivatives in moderate to excellent yields via C2-H bond functionalization of the indole unit. The presence of the electron-withdrawing alkoxycarbonyl, dialkoxyphosphono, or phenyl is crutial for this transformation. The potential synthetic dihydrocyclopenta[b]indole with the electron-withdrawing group has been demonstrated by applying a [3 + 2] cycloaddition reaction to construct the tretracycloskeleton.

  1. Quantum effects in the scattering of argon from 2H-W(100)

    SciTech Connect

    Schweizer, E. K.; Rettner, C. T.

    1989-06-26

    Diffraction has been observed in the scattering of Ar from a 2H-W(100) surface. Results are found to be consistent with an effective surface corrugation amplitude of about 0.05 A, which is similar to values obtained for He and Ne diffraction from this surface. The temperature dependence yields a surface Debye temperature of /similar to/400 K. We also find that the shape and behavior of surface scattering rainbows observed in this system are best accounted for by a quantum mechanical treatment of the Ar-surface interaction.

  2. The leptonic CP phase from T2(H)K and μ+ decay at rest

    DOE PAGES

    Evslin, Jarah; Ge, Shao-Feng; Hagiwara, Kaoru

    2016-02-22

    Combining v oscillations at T2K or T2HK withmore » $$\\bar{v}$$ oscillations from μ+ decay at rest (DAR) allows a determination of the leptonic CP-violating phase . The degeneracies of this phase with θ13 and θ23 are broken and δ can be reliably distinguished from 180° - δ. In this study, we present the sensitivity to δ of T2(H)K together with a μ+ DAR experiment using Super-K as a near detector and Hyper-K at the Tochibora site as a far detector.« less

  3. Specific heat anomaly in ferroelectric: Bis(imidazolium) pentachloroantimonate(III) (C3 N2 H5)2[SbCl5

    NASA Astrophysics Data System (ADS)

    Przesławski, J.; Piecha-Bisiorek, A.; Jakubas, R.

    2016-04-01

    Single crystals of ferroelectric bis(imidazolium) pentachloroantimonate(III) (C3N2H5)2 [SbCl5 ] have been grown and the heat capacity was measured by the use of AC calorimetric method. The temperature dependence of excess heat capacity and excess entropy in the ferroelectric phase can be described in the frame of the classical Landau-Devonshire theory of phase transitions. The results of experimental studies were analyzed and the α, γ and δ values of the Landau potential coefficients were calculated. The temperature dependence of the order parameter was also evaluated from the heat capacity data.

  4. Probing anisotropic interaction potentials of unsaturated hydrocarbons with He*(2 3S) metastable atom: Attractive-site preference of σ-direction in C2H2 and π-direction in C2H4

    NASA Astrophysics Data System (ADS)

    Horio, Takuya; Hatamoto, Takuro; Maeda, Satoshi; Kishimoto, Naoki; Ohno, Koichi

    2006-03-01

    State-resolved collision energy dependence of Penning ionization cross sections of acetylene (C2H2) and ethylene (C2H4) with He*(2S3) metastable atoms was observed in a wide collision energy range from 20to350meV. A recently developed discharge nozzle source with a liquid N2 circulator was employed for the measurements in the low-energy range from 20to80meV. Based on classical trajectory calculations for the energy dependence of the partial ionization cross sections, anisotropic potential energy surfaces for the present systems were obtained by optimizing ab initio model potentials for the chemically related systems Li +C2H2 and C2H4. In the case of C2H2, the global minimum was found to be located around the H atom along the molecular axis with a well depth of 48meV (ca. 1.1kcal/mol). On the other hand, a dominant attractive well with a depth of 62meV (ca. 1.4kcal/mol) was found in the πCC electron region of C2H4. These findings were discussed in connection with orbital interactions between molecular orbitals of the target molecules and atomic orbitals of the metastable atom. It is concluded that σ-type unoccupied molecular orbitals of C2H2 and a πCC-type highest occupied molecular orbital of C2H4 play a significant role for the attractive-site preference of σ direction in C2H2 and π direction in C2H4, respectively.

  5. Towards the study of 2H(p, γ)3He reaction in the Big Bang Nucleosynthesis energy range in LUNA

    NASA Astrophysics Data System (ADS)

    Kochanek, Izabela

    2016-04-01

    The Big Bang Nucleosynthesis began a few minutes after the Big Bang, when the Universe was sufficiently cold to allow deuterium nuclei to survive photo-disintegration. The total amount of deuterium produced in the Universe during the first minutes depends on the cosmological parameters (like the energy density in baryons, Ω bh 2, and the effective neutrino number, Neff ) and on the nuclear cross sections of the relevant reactions. The main source of uncertainty in the deuterium estimation comes from the 2H(p, γ)3He cross section. Measurements of Cosmic Microwave Background (CMB) anisotropies obtained by the Planck satellite are in very good agreement with the theoretical predictions of the minimal ΛCDM cosmological model, significantly reducing the uncertainty on its parameters. The Planck data allows to indirectly deduce with very high precision the abundances of primodial nuclides, such as the primodial deuterium fraction 2H/H = (2.65 ± 0.07) .10-5 (68% C.L.). The astrophysical observations in damped Lyman-a systems at high redshifts provide a second high accuracy measurement of the primodial abundance of deuterium 2H/H = (2.53 ± 0.04) · 10-5 (68% C.L.). The present experimental status on the astrophysical S-factor of the 2H(p, γ)3He reaction in the BBN energy range, gives a systematic uncertainties of 9%. Also the difference between ab-initio calculations and experimental values of S12 is at the level of 10%. In order to clarify the actual scenario, a measurement of 2H(p, γ)3He cross section with a precision of a few percent in the 70-400 keV energy range is planned at LUNA in 2016. A feasibility test of the measurement has been performed in October 2014, giving the preliminary results on the cross section. The experimental setup for the test and final measurement campaign will be presented.

  6. Emergence of coherence in the charge-density wave state of 2H-NbSe2

    DOE PAGES

    Chatterjee, U.; Zhao, J.; Iavarone, M.; Di Capua, R.; Castellan, J. P.; Karapetrov, G.; Malliakas, C. D.; Kanatzidis, M. G.; Claus, H.; Ruff, J. P. C.; et al

    2015-02-17

    A charge-density wave (CDW) state has a broken symmetry described by a complex order parameter with an amplitude and a phase. The conventional view, based on clean, weak-coupling systems, is that a finite amplitude and long-range phase coherence set in simultaneously at the CDW transition temperature Tcdw. Here we investigate, using photoemission, X-ray scattering and scanning tunnelling microscopy, the canonical CDW compound 2H-NbSe2 intercalated with Mn and Co, and show that the conventional view is untenable. We find that, either at high temperature or at large intercalation, CDW order becomes short-ranged with a well-defined amplitude, which has impacts on themore » electronic dispersion, giving rise to an energy gap. The phase transition at Tcdw marks the onset of long-range order with global phase coherence, leading to sharp electronic excitations. As a result, our observations emphasize the importance of phase fluctuations in strongly coupled CDW systems and provide insights into the significance of phase incoherence in ‘pseudogap’ states.« less

  7. FIRST MEASUREMENTS OF {sup 15}N FRACTIONATION IN N{sub 2}H{sup +} TOWARD HIGH-MASS STAR-FORMING CORES

    SciTech Connect

    Fontani, F.; Caselli, P.; Bizzocchi, L.; Palau, A.; Ceccarelli, C.

    2015-08-01

    We report on the first measurements of the isotopic ratio {sup 14}N/{sup 15}N in N{sub 2}H{sup +} toward a statistically significant sample of high-mass star-forming cores. The sources belong to the three main evolutionary categories of the high-mass star formation process: high-mass starless cores, high-mass protostellar objects, and ultracompact H ii regions. Simultaneous measurements of the {sup 14}N/{sup 15}N ratio in CN have been made. The {sup 14}N/{sup 15}N ratios derived from N{sub 2}H{sup +} show a large spread (from ∼180 up to ∼1300), while those derived from CN are in between the value measured in the terrestrial atmosphere (∼270) and that of the proto-solar nebula (∼440) for the large majority of the sources within the errors. However, this different spread might be due to the fact that the sources detected in the N{sub 2}H{sup +} isotopologues are more than those detected in the CN ones. The {sup 14}N/{sup 15}N ratio does not change significantly with the source evolutionary stage, which indicates that time seems to be irrelevant for the fractionation of nitrogen. We also find a possible anticorrelation between the {sup 14}N/{sup 15}N (as derived from N{sub 2}H{sup +}) and the H/D isotopic ratios. This suggests that {sup 15}N enrichment could not be linked to the parameters that cause D enrichment, in agreement with the prediction by recent chemical models. These models, however, are not able to reproduce the observed large spread in {sup 14}N/{sup 15}N, pointing out that some important routes of nitrogen fractionation could be still missing in the models.

  8. Low-temperature mechanisms for the formation of substituted azanaphthalenes through consecutive CN and C2H additions to styrene and N-methylenebenzenamine: a theoretical study.

    PubMed

    Landera, Alexander; Mebel, Alexander M

    2013-05-15

    Ab initio G3(MP2,CC)/B3LYP/6-311G** calculations of potential energy surfaces (PESs) for the reactions of cyano and ethynyl radicals with styrene and N-methylenebenzenamine have been performed to investigate a possible formation mechanism of the prototype nitrogen-containing polycyclic aromatic compounds: (substituted) 1- and 2-azanaphthalenes. The computed PESs and molecular parameters have been used for RRKM and RRKM-Master Equation calculations of reaction rate constants and product branching ratios under single-collision conditions and at pressures from 3 to 10(-6) mbar and temperatures of 90-200 K relevant to the organic aerosol formation regions in the stratosphere of a Saturn's moon Titan. The results show that ethynyl-substituted 1- and 2-azanaphthalenes can be produced by consecutive CN and C2H additions to styrene or by two C2H additions to N-methylenebenzenamine. All CN and C2H radical addition complexes are formed in the entrance channels without barriers, and the reactions are computed to be exothermic, with all intermediates and transition states along the favorable pathways residing lower in energy than the respective initial reactants. The reactions are completed by dissociation of chemically activated radical intermediates via H losses, so that collisional stabilization of the intermediates is not required to form the final products. These features make the proposed mechanism viable even at very low temperatures and under single-collision conditions and especially significant for astrochemical environments. In Titan's stratosphere, collisional stabilization of the initial CN + styrene reaction adducts may be significant, but substantial amounts of 2-vinylbenzonitrile and 2-ethynyl-N-methylenebenzenamine can still be produced and then react with C2H to form substituted azanaphthalenes.

  9. EVIDENCE OF DIFFERENTIAL PH REGULATION OF THE ARABIDOPSIS VACUOLAR CA2+/H+ ANTIPORTERS CAX1 AND CAX2

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The Arabidopsis Ca(2+)/H(+) antiporters cation exchanger (CAX) 1 and 2 utilise an electrochemical gradient to transport Ca(2+) into the vacuole to help mediate Ca(2+) homeostasis. Previous whole plant studies indicate that activity of Ca(2+)/H(+) antiporters is regulated by pH. However, the pH regul...

  10. Functionalization of liquid-exfoliated two-dimensional 2H-MoS2.

    PubMed

    Backes, Claudia; Berner, Nina C; Chen, Xin; Lafargue, Paul; LaPlace, Pierre; Freeley, Mark; Duesberg, Georg S; Coleman, Jonathan N; McDonald, Aidan R

    2015-02-23

    Layered two-dimensional (2D) inorganic transition-metal dichalchogenides (TMDs) have attracted great interest as a result of their potential application in optoelectronics, catalysis, and medicine. However, methods to functionalize and process such 2D TMDs remain scarce. We have established a facile route towards functionalized layered MoS2 . We found that the reaction of liquid-exfoliated 2D MoS2 , with M(OAc)2 salts (M=Ni, Cu, Zn; OAc=acetate) yielded functionalized MoS2 -M(OAc)2 materials. Importantly, this method furnished the 2H-polytype of MoS2 which is a semiconductor. X-ray photoelectron spectroscopy (XPS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT-IR), and thermogravimetric analysis (TGA) provide strong evidence for the coordination of MoS2 surface sulfur atoms to the M(OAc)2 salt. Interestingly, functionalization of 2H-MoS2 allows for its dispersion/processing in more conventional laboratory solvents.

  11. Volumetric Properties and Fluid Phase Equilibria of CO2 + H2O

    SciTech Connect

    Capobianco, Ryan; Gruszkiewicz, Miroslaw {Mirek} S; Wesolowski, David J; Cole, David R; Bodnar, Robert

    2013-01-01

    The need for accurate modeling of fluid-mineral processes over wide ranges of temperature, pressure and composition highlighted considerable uncertainties of available property data and equations of state, even for the CO2 + H2O binary system. In particular, the solubility, activity, and ionic dissociation equilibrium data for the CO2-rich phase, which are essential for understanding dissolution/precipitation, fluid-matrix reactions, and solute transport, are uncertain or missing. In this paper we report the results of a new experimental study of volumetric and phase equilibrium properties of CO2 + H2O, to be followed by measurements for bulk and confined multicomponent fluid mixtures. Mixture densities were measured by vibrating tube densimetry (VTD) over the entire composition range at T = 200 and 250 C and P = 20, 40, 60, and 80 MPa. Initial analysis of the mutual solubilities, determined from volumetric data, shows good agreement with earlier results for the aqueous phase, but finds that the data of Takenouchi and Kennedy (1964) significantly overestimated the solubility of water in supercritical CO2 (by a factor of more than two at 200 C). Resolving this well-known discrepancy will have a direct impact on the accuracy of predictive modeling of CO2 injection in geothermal reservoirs and geological carbon sequestration through improved equations of state, needed for calibration of predictive molecular-scale models and large-scale reactive transport simulations.

  12. Advanced Low-Cost O2/H2 Engines for the SSTO Application

    NASA Technical Reports Server (NTRS)

    Goracke, B. David; Levack, Daniel J. H.; Nixon, Robert F.

    1994-01-01

    The recent NASA Access to Space study examined future Earth to orbit (ETO) transportation needs and fleets out to 2030. The baseline in the option 3 assessment was a single stage to orbit (SSTO) vehicle. A study was conducted to assess the use of new advanced low cost O2/H2 engines for this SSTO application. The study defined baseline configurations and ground rules and defined six engine cycles to explore engine performance. The cycles included an open cycle, and a series of closed cycles with varying abilities to extract energy from the propellants to power he turbomachinery. The cycles thus varied in the maximum chamber pressure they could reach and in their weights at any given chamber pressure. The weight of each cycle was calculated for two technology levels versus chamber pressure up to the power limit of the cycle. The performance in the SSTO mission was then modeled using the resulting engine weights and specific impulse performance using the Access to Space option 3 vehicle. The results showed that new O2/H2 engines are viable and competitive candidates for the SSTO application using chamber pressures of 4,000 psi.

  13. VUV photoionization cross sections of HO2, H2O2, and H2CO.

    PubMed

    Dodson, Leah G; Shen, Linhan; Savee, John D; Eddingsaas, Nathan C; Welz, Oliver; Taatjes, Craig A; Osborn, David L; Sander, Stanley P; Okumura, Mitchio

    2015-02-26

    The absolute vacuum ultraviolet (VUV) photoionization spectra of the hydroperoxyl radical (HO2), hydrogen peroxide (H2O2), and formaldehyde (H2CO) have been measured from their first ionization thresholds to 12.008 eV. HO2, H2O2, and H2CO were generated from the oxidation of methanol initiated by pulsed-laser-photolysis of Cl2 in a low-pressure slow flow reactor. Reactants, intermediates, and products were detected by time-resolved multiplexed synchrotron photoionization mass spectrometry. Absolute concentrations were obtained from the time-dependent photoion signals by modeling the kinetics of the methanol oxidation chemistry. Photoionization cross sections were determined at several photon energies relative to the cross section of methanol, which was in turn determined relative to that of propene. These measurements were used to place relative photoionization spectra of HO2, H2O2, and H2CO on an absolute scale, resulting in absolute photoionization spectra. PMID:25621533

  14. Heteropathogenic virulence and phylogeny reveal phased pathogenic metamorphosis in Escherichia coli O2:H6

    PubMed Central

    Bielaszewska, Martina; Schiller, Roswitha; Lammers, Lydia; Bauwens, Andreas; Fruth, Angelika; Middendorf, Barbara; Schmidt, M Alexander; Tarr, Phillip I; Dobrindt, Ulrich; Karch, Helge; Mellmann, Alexander

    2014-01-01

    Extraintestinal pathogenic and intestinal pathogenic (diarrheagenic) Escherichia coli differ phylogenetically and by virulence profiles. Classic theory teaches simple linear descent in this species, where non-pathogens acquire virulence traits and emerge as pathogens. However, diarrheagenic Shiga toxin-producing E. coli (STEC) O2:H6 not only possess and express virulence factors associated with diarrheagenic and uropathogenic E. coli but also cause diarrhea and urinary tract infections. These organisms are phylogenetically positioned between members of an intestinal pathogenic group (STEC) and extraintestinal pathogenic E. coli. STEC O2:H6 is, therefore, a ‘heteropathogen,’ and the first such hybrid virulent E. coli identified. The phylogeny of these E. coli and the repertoire of virulence traits they possess compel consideration of an alternate view of pathogen emergence, whereby one pathogroup of E. coli undergoes phased metamorphosis into another. By understanding the evolutionary mechanisms of bacterial pathogens, rational strategies for counteracting their detrimental effects on humans can be developed. Subject Categories Microbiology, Virology & Host Pathogen Interaction PMID:24413188

  15. Identification of a Ca2+/H+ antiport in the plant chloroplast thylakoid membrane

    PubMed

    Ettinger; Clear; Fanning; Peck

    1999-04-01

    To assess the availability of Ca2+ in the lumen of the thylakoid membrane that is required to support the assembly of the oxygen-evolving complex of photosystem II, we have investigated the mechanism of 45Ca2+ transport into the lumen of pea (Pisum sativum) thylakoid membranes using silicone-oil centrifugation. Trans-thylakoid Ca2+ transport is dependent on light or, in the dark, on exogenously added ATP. Both light and ATP hydrolysis are coupled to Ca2+ transport through the formation of a transthylakoid pH gradient. The H+-transporting ionophores nigericin/K+ and carbonyl cyanide 3-chlorophenylhydrazone inhibit the transport of Ca2+. Thylakoid membranes are capable of accumulating up to 30 nmol Ca2+ mg-1 chlorophyll from external concentrations of 15 μM over the course of a 15-min reaction. These results are consistent with the presence of an active Ca2+/H+ antiport in the thylakoid membrane. Ca2+ transport across the thylakoid membrane has significant implications for chloroplast and plant Ca2+ homeostasis. We propose a model of chloroplast Ca2+ regulation whereby the activity of the Ca2+/H+ antiporter facilitates the light-dependent uptake of Ca2+ by chloroplasts and reduces stromal Ca2+ levels.

  16. Overtone spectroscopy of H2D+ and D2H+ using laser induced reactions

    NASA Astrophysics Data System (ADS)

    Asvany, Oskar; Hugo, Edouard; Müller, Frank; Kühnemann, Frank; Schiller, Stephan; Tennyson, Jonathan; Schlemmer, Stephan

    2007-10-01

    The method of laser induced reaction is used to obtain high-resolution IR spectra of H2D+ and D2H+ in collision with n-H2 at a nominal temperature of 17K. For this purpose three cw-laser systems have been coupled to a 22-pole ion trap apparatus, two commercial diode laser systems in the ranges of 6100-6600cm-1 and 6760-7300cm-1, respectively, and a high-power optical parametric oscillator tunable in the range of 2600-3200cm-1. In total, 27 new overtone and combination transitions have been detected for H2D + and D2H+, as well as a weak line in the ν1 vibrational band of H2D+ (220←101) at 3164.118cm-1. The line positions are compared to high accuracy ab initio calculations, showing small but mode-dependent differences, being largest for three vibrational quanta in the ν2 symmetric bending of H2D+. Within the experimental accuracy, the relative values of the ab initio predicted Einstein B coefficients are confirmed.

  17. Refinements in an Mg/MgH2/H2O-Based Hydrogen Generator

    NASA Technical Reports Server (NTRS)

    Kindler, Andrew; Huang, Yuhong

    2010-01-01

    Some refinements have been conceived for a proposed apparatus that would generate hydrogen (for use in a fuel cell) by means of chemical reactions among magnesium, magnesium hydride, and steam. The refinements lie in tailoring spatial and temporal distributions of steam and liquid water so as to obtain greater overall energy-storage or energy-generation efficiency than would otherwise be possible. A description of the prior art is prerequisite to a meaningful description of the present refinements. The hydrogen-generating apparatus in question is one of two versions of what was called the "advanced hydrogen generator" in "Fuel-Cell Power Systems Incorporating Mg-Based H2 Generators" (NPO-43554), NASA Tech Briefs, Vol. 33, No. 1 (January 2009), page 52. To recapitulate: The apparatus would include a reactor vessel that would be initially charged with magnesium hydride. The apparatus would exploit two reactions: The endothermic decomposition reaction MgH2-->Mg + H2, which occurs at a temperature greater than or equal to 300 C, and The exothermic oxidation reaction MgH2 + H2O MgO + 2H2, which occurs at a temperature greater than or equal to 330 C.

  18. CCQE, 2p2h excitations and ν—energy reconstruction

    SciTech Connect

    Nieves, J.; Simo, I. Ruiz; Sánchez, F.; Vacas, M. J. Vicente

    2015-05-15

    We analyze the MiniBooNE muon neutrino CCQE-like dσ/dT{sub μ} d cos θ{sub μ} data using a theoretical model that, among other nuclear effects, includes RPA correlations and 2p2h (multinucleon) mechanisms. These corrections turn out to be essential for the description of the data. We find that MiniBooNE CCQE-like data are fully compatible with former determinations of the nucleon axial mass M{sub A} ∼ 1.05 GeV. This is in sharp contrast with several previous analysis where anomalously large values of M{sub A} ∼ 1.4 GeV have been suggested. We also show that because of the the multinucleon mechanism effects, the algorithm used to reconstruct the neutrino energy is not adequate when dealing with quasielastic-like events. Finally, we analyze the MiniBooNE unfolded cross section, and show that it exhibits an excess (deficit) of low (high) energy neutrinos, which is an artifact of the unfolding process that ignores 2p2h mechanisms.

  19. sup 2 H Nuclear magnetic resonance of the gramicidin A backbone in a phospholipid bilayer

    SciTech Connect

    Prosser, R.S.; Davis, J.H. ); Dahlquist, F.W.; Lindorfer, M.A. )

    1991-05-14

    Solid-state {sup 2}H NMR spectroscopy has been employed to study the channel conformation of gramicidin A (GA) in unoriented 1,2-dimyristoyl-sn-glycerol-3-phosphocholine (DMPC) multilayers. Quadrupolar echo spectra were obtained at 44{degree}C and 53{degree}C, from gramicidin A labels in which the proton attached to the {alpha} carbon of residue 3,4,5,10,12, or 14 was replaced with deuterium. Because of the nearly axially symmetric electric field gradient tensor, the quadrupolar splittings obtained from an unoriented multilamellar dispersion of DMPC and singly labeled GA directly yield unambiguous orientational constraints on the C-{sup 2}H bonds. The authors conclude that the helix sense of the channel conformation of GA is right-handed. Assuming that the dominant motions are fast axial diffusion of the gramicidin molecule and reorientation of the diffusion axis with respect to the local bilayer normal, then the theoretical splittings may all be scaled down by a constant motional narrowing factor.

  20. Affordable uniform isotope labeling with (2)H, (13)C and (15)N in insect cells.

    PubMed

    Sitarska, Agnieszka; Skora, Lukasz; Klopp, Julia; Roest, Susan; Fernández, César; Shrestha, Binesh; Gossert, Alvar D

    2015-06-01

    For a wide range of proteins of high interest, the major obstacle for NMR studies is the lack of an affordable eukaryotic expression system for isotope labeling. Here, a simple and affordable protocol is presented to produce uniform labeled proteins in the most prevalent eukaryotic expression system for structural biology, namely Spodoptera frugiperda insect cells. Incorporation levels of 80% can be achieved for (15)N and (13)C with yields comparable to expression in full media. For (2)H,(15)N and (2)H,(13)C,(15)N labeling, incorporation is only slightly lower with 75 and 73%, respectively, and yields are typically twofold reduced. The media were optimized for isotope incorporation, reproducibility, simplicity and cost. High isotope incorporation levels for all labeling patterns are achieved by using labeled algal amino acid extracts and exploiting well-known biochemical pathways. The final formulation consists of just five commercially available components, at costs 12-fold lower than labeling media from vendors. The approach was applied to several cytosolic and secreted target proteins. PMID:25929326

  1. Density functional theory study of 3R- and 2H-CuAlO2 under pressure

    NASA Astrophysics Data System (ADS)

    Liu, Qi-Jun; Liu, Zheng-Tang; Feng, Li-Ping; Tian, Hao; Liu, Wen-Ting; Yan, Feng

    2010-10-01

    We present a first-principles density-functional theory based study of the impact of pressure on the structural and elastic properties of bulk 3R- and 2H-CuAlO2. The ground state properties of 3R- and 2H-CuAlO2 are obtained, which are in good agreement with previous experimental and theoretical data. The analysis of enthalpy variation with pressure indicates the phase transition pressure between 3R and 2H is 15.4 GPa. The independent elastic constants of 3R- and 2H-CuAlO2 are calculated. As the applied pressure increases, the calculations show the presences of mechanical instability at 26.2 and 27.8 GPa for 3R- and 2H-CuAlO2, which are possibly related with the phase transitions.

  2. Petrological mapping of a Low Velocity Zone (LVZ) induced by CO2-H2O-bearing incipient melts

    NASA Astrophysics Data System (ADS)

    Massuyeau, M.; Gardés, E.; Morizet, Y.; Le Trong, E.; Gaillard, F.

    2014-12-01

    The link between volatiles and mantle melting has so far been illuminated by experiments, revealing that ppm concentration levels of carbon and other volatiles in the Earth's mantle induce partial melting. Pressure-temperature conditions of incipient melting for CO2-H2O-peridotite [1] match fairly well with the upper part of the LVZ, as the redox melting [2] with the lower part. Recent experimental studies about the Earth mantle conductivity have shown the importance of small amounts of hydrated CO2-rich melts in the geophysical signature of the LVZ [3]. Although such melts are stable under the P-T-fO2 conditions of the LVZ [1-2, 4-6], the variability of these parameters complicates the definition of their chemical composition. Using Margules' formalisms, we established a multi-component model describing the Gibbs free energy of melt produced by mantle melting in presence of CO2-H2O, that are carbonatite-carbonated melt-nephilinite-basanite and basalt with increasing degree of partial melting. This parameterization is calibrated on crystal-liquid, redox, fluid-liquid and liquid-liquid equilibria obtained by experimental studies in the P-T range 1-10 GPa and 900-1800°C. We propose a calculation of the composition of melts produced in the oceanic LVZ as a function of ages (temperature) and chemical heterogeneities (water, alkalis). At about 80 km depth, we show that the composition of the melts is > 30 wt% SiO2 for ages < 30 Ma, and comes closer to the carbonatitic terms for older lithosphere. Besides lateral chemical variations, our model calculates the melt composition along an oceanic ridge adiabat, predicting an abrupt compositional transition between a H2O-rich carbonatitic melt and a carbonated silicate melt, between 130 km and 100 km. We propose a chemical mapping of the melt composition (and of the degree of partial melting) as a function of the distance to the ridge and of the depth. Our model represents an innovating attempt to connect the chemical

  3. Low-Temperature Rate Coefficients of C2H with CH4 and CD4 from 154 to 359 K

    NASA Technical Reports Server (NTRS)

    Opansky, Brian J.; Leone, Stephen R.

    1996-01-01

    Rate coefficients for the reaction C2H + CH4 yields C2H2 + CH3 and C2H + CD4 yields C2HD + CD3 are measured over the temperature range 154-359 K using transient infrared laser absorption spectroscopy. Ethynyl radicals are produced by pulsed laser photolysis of C2H2 in a variable temperature flow cell, and a tunable color center laser probes the transient removal of C2H (Chi(exp 2) Sigma(+) (0,0,0)) in absorption. The rate coefficients for the reactions of C2H with CH4 and CD4 both show a positive temperature dependence over the range 154-359 K, which can be expressed as k(sub CH4) = (1.2 +/- 0.1) x 10(exp -11) exp((-491 +/- 12)/T) and k(sub CD4) = (8.7 +/- 1.8) x 10(exp -12) exp((-650 +/- 61)/T) cm(exp 3) molecule(exp -1) s(exp -1), respectively. The reaction of C2H + CH4 exhibits a significant kinetic isotope effect at 300 K of k(sub CH4)/k(sub CD4) = 2.5 +/- 0.2. Temperature dependent rate constants for C2H + C2H2 were also remeasured over an increased temperature range from 143 to 359 K and found to show a slight negative temperature dependence, which can be expressed as k(sub C2H2) = 8.6 x 10(exp -16) T(exp 1.8) exp((474 +/- 90)/T) cm(exp 3) molecule(exp -1) s(exp -1).

  4. Interconversion of FeC{sub 2}H{sub 3}{sup +} and HFeC{sub 2}H{sub 2}{sup +}: An FTICR and density functional study

    SciTech Connect

    Chen, H.; Jacobson, D.B.; Freiser, B.S.

    1999-12-20

    The geometries and energetics of four FeC{sub 2}H{sub 3}{sup +} isomers have been studied by a hybrid of density functional theory (DFT) and the Hartree-Fock approach (BECKE3LYP). The bond dissociation energy D{degree}(FeH{sup +}-C{sub 2}H{sub 2}) for the quintet ground state is predicted to be 32.9 kcal/mol, which compares well with the experimentally measured D{degree}(Fe{sup +}-C{sub 2}H{sub 2}) value of 32 kcal/mol. The [Fe, C{sub 2}, H{sub 3}]{sup +} system is also studied experimentally by using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). In situ synthesis of FeC{sub 2}H{sub 3}{sup +} is achieved by a complex, multistep procedure involving ion/molecule reactions in conjunction with CID and SORI-CID techniques. Kinetics for H/D exchange reactions between FeH{sup +}/FeD{sup +} and C{sub 2}D{sub 4}/C{sub 2}H{sub 4} are also measured and provide complementary information to Schwarz's studies of the [Fe, C{sub 2}, H{sub 5}]{sup +} system.

  5. 2H 2O quadrupolar splitting used to measure water exchange in erythrocytes

    NASA Astrophysics Data System (ADS)

    Kuchel, Philip W.; Naumann, Christoph

    2008-05-01

    The 2H NMR resonance from HDO (D = 2H) in human red blood cells (RBCs) suspended in gelatin that was held stretched in a special apparatus was distinct from the two signals that were symmetrically arranged on either side of it, which were assigned to extracellular HDO. The large extracellular splitting is due to the interaction of the electric quadrupole moment of the 2H nuclei with the electric field gradient tensor of the stretched, partially aligned gelatin. Lack of resolved splitting of the intracellular resonance indicated greatly diminished or absent ordering of the HDO inside RBCs. The separate resonances enabled the application of a saturation transfer method to estimate the rate constants of transmembrane exchange of water in RBCs. However both the theory and the practical applications needed modifications because even in the absence of RBCs the HDO resonances were maximally suppressed when the saturating radio-frequency radiation was applied exactly at the central frequency between the two resonances of the quadrupolar HDO doublet. More statistically robust estimates of the exchange rate constants were obtained by applying two-dimensional exchange spectroscopy (2D EXSY), with back-transformation analysis. A monotonic dependence of the estimates of the efflux rate constants on the mixing time, tmix, used in the 2D EXSY experiment were seen. Extrapolation to tmix = 0, gave an estimate of the efflux rate constant at 15 °C of 31.5 ± 2.2 s -1 while at 25 °C it was ˜50 s -1. These values are close to, but less than, those estimated by an NMR relaxation-enhancement method that uses Mn 2+ doping of the extracellular medium. The basis for this difference is thought to include the high viscosity of the extracellular gel. At the abstract level of quantum mechanics we have used the quadrupolar Hamiltonian to provide chemical shift separation between signals from spin populations across cell membranes; this is the first time, to our knowledge, that this has been

  6. 242-16H 2H EVAPORATOR POT SAMPLING FINAL REPORT

    SciTech Connect

    Krementz, D; William Cheng, W

    2008-06-11

    Due to the materials that are processed through 2H Evaporator, scale is constantly being deposited on the surfaces of the evaporator pot. In order to meet the requirements of the Nuclear Criticality Safety Analysis/Evaluation (NCSA/NCSE) for 2H Evaporator, inspections of the pot are performed to determine the extent of scaling. Once the volume of scale reaches a certain threshold, the pot must be chemically cleaned to remove the scale. Prior to cleaning the pot, samples of the scale are obtained to determine the concentration of uranium and plutonium and also to provide information to assist with pot cleaning. Savannah River National Laboratory (SRNL) was requested by Liquid Waste Organization (LWO) Engineering to obtain these samples from two locations within the evaporator. Past experience has proven the difficulty of successfully obtaining solids samples from the 2H Evaporator pot. To mitigate this risk, a total of four samplers were designed and fabricated to ensure that two samples could be obtained. Samples had previously been obtained from the cone surface directly below the vertical access riser using a custom scraping tool. This tool was fabricated and deployed successfully. A second scraper was designed to obtain sample from the nearby vertical thermowell and a third scraper was designed to obtain sample from the vertical pot wall. The newly developed scrapers both employed a pneumatically actuated elbow. The scrapers were designed to be easily attached/removed from the elbow assembly. These tools were fabricated and deployed successfully. A fourth tool was designed to obtain sample from the opposite side of the pot under the tube bundle. This tool was fabricated and tested, but the additional modifications required to make the tool field-ready could not be complete in time to meet the aggressive deployment schedule. Two samples were obtained near the pot entry location, one from the pot wall and the other from the evaporator feed pipe. Since a third

  7. Modeling Ice Giant Interiors Using Constraints on the H2-H2O Critical Curve

    NASA Astrophysics Data System (ADS)

    Bailey, E.; Stevenson, D. J.

    2015-12-01

    We present a range of models of Uranus and Neptune, taking into account recent experimental data (Bali, 2013) implying the location of the critical curve of the H2-H2O system at pressures up to 2.6 GPa. The models presented satisfy the observed total mass of each planet and the radius at the observed 1-bar pressure level. We assume the existence of three regions at different depths: an outer adiabatic envelope composed predominately of H2 and He, with a helium mass fraction 0.26, a water-rich layer including varied amounts of rock and hydrogen, and a chemically homogeneous rock core. Using measured rotation rates of Uranus and Neptune, and a density profile obtained for each model using constituent equations of state and the assumption of hydrostatic equilibrium, we calculate the gravitational harmonics J2 and J4 for comparison with observed values as an additional constraint. The H2-H2O critical curve provides information about the nature of the boundary between the outer, hydrogen-rich envelope and underlying water-rich layer. The extrapolated critical curve for hydrogen-water mixtures crosses the adiabat of the outer atmospheric shell in these models at two depths, implying a shallow outer region of limited miscibility, an intermediate region between ~90 and 98 percent of the total planet radius within which hydrogen and water can mix in all proportions, and another, deeper region of limited miscibility at less than ~90 percent of the total planet radius. The pressure and temperature of the gaseous adiabatic shell at the depth of the shallowest extent of the water-rich layer determines whether a gradual compositional transition or an ocean surface boundary may exist at depth in these planets. To satisfy the observed J2, the outer extent of the water-rich layer in these models must be located between approximately 80 and 85 percent of the total planet radius, within the deep region of limited H2-H2O miscibility, implying an ocean surface is possible within the

  8. Core-mass nonadiabatic corrections to molecules: H2, H2+, and isotopologues.

    PubMed

    Diniz, Leonardo G; Alijah, Alexander; Mohallem, José Rachid

    2012-10-28

    For high-precision calculations of rovibrational states of light molecules, it is essential to include non-adiabatic corrections. In the absence of crossings of potential energy surfaces, they can be incorporated in a single surface picture through coordinate-dependent vibrational and rotational reduced masses. We present a compact method for their evaluation and relate in particular the vibrational mass to a well defined nuclear core mass derived from a Mulliken analysis of the electronic density. For the rotational mass we propose a simple, but very effective parametrization. The use of these masses in the nuclear Schrödinger equation yields numerical data for the corrections of a much higher quality than can be obtained with optimized constant masses, typically better than 0.1 cm(-1). We demonstrate the method for H(2), H(2)(+), and singly deuterated isotopologues. Isotopic asymmetry does not present any particular difficulty. Generalization to polyatomic molecules is straightforward. PMID:23126719

  9. Natural abundance 2H-ERETIC-NMR authentication of the origin of methyl salicylate.

    PubMed

    Le Grand, Flore; George, Gerard; Akoka, Serge

    2005-06-29

    Methyl salicylate is a compound currently used in the creation of many flavors. It can be obtained by synthesis or from two natural sources: essential oil of wintergreen and essential oil of sweet birch bark. Deuterium site-specific natural isotope abundance (A(i)) determination by NMR spectroscopy with the method of reference ERETIC ((2)H-ERETIC-NMR) has been applied to this compound. A(i) measurements have been performed on 19 samples of methyl salicylate from different origins, natural/synthetic and commercial/extracted. This study demonstrates that appropriate treatment performed on the data allows discrimination between synthetic and natural samples. Moreover, the representation of intramolecular ratios R(6/5) as a function of R(3/2) distinguishes between synthetics, wintergreen oils, and sweet birch bark oils.

  10. RNF20-SNF2H Pathway of Chromatin Relaxation in DNA Double-Strand Break Repair

    PubMed Central

    Kato, Akihiro; Komatsu, Kenshi

    2015-01-01

    Rapid progress in the study on the association of histone modifications with chromatin remodeling factors has broadened our understanding of chromatin dynamics in DNA transactions. In DNA double-strand break (DSB) repair, the well-known mark of histones is the phosphorylation of the H2A variant, H2AX, which has been used as a surrogate marker of DSBs. The ubiquitylation of histone H2B by RNF20 E3 ligase was recently found to be a DNA damage-induced histone modification. This modification is required for DSB repair and regulated by a distinctive pathway from that of histone H2AX phosphorylation. Moreover, the connection between H2B ubiquitylation and the chromatin remodeling activity of SNF2H has been elucidated. In this review, we summarize the current knowledge of RNF20-mediated processes and the molecular link to H2AX-mediated processes during DSB repair. PMID:26184323

  11. Clonal diversity of Shiga toxin-producing Escherichia coli O103:H2/H(-) in Germany.

    PubMed

    Prager, Rita; Liesegang, Almut; Voigt, W; Rabsch, W; Fruth, Angelika; Tschäpe, H

    2002-07-01

    Shiga toxin producing Escherichia coli O103:H2/H(-) belong to the third most frequently isolated EHEC serotypes in Germany following isolates of O157:H7/H(-) and O26:H11/H(-). A total of 145 respective E. coli 103 isolates from single cases of diarrhoea and haemolytic uremic syndrome (HUS) in 1997-2000 were characterised by a range of molecular subtyping methods (PFGE, P-gene profiling, ribotyping, electrotyping) and phage typing in order to analyse their genetic relatedness and the practicability for new epidemiological tracing back. All isolates cluster into a distinct EHEC subgroup and reveal a high clonal diversity together with a considerable stability. Since strains of this serotype rank up to the third most frequently isolated EHEC in Germany a large population of this serotype, and therefore, a great supply of such strains may exist in this country. PMID:12798005

  12. 2H nuclear magnetic resonance study of deuterated water dynamics in perfluorosulfonic acid ionomer Nafion

    NASA Astrophysics Data System (ADS)

    Han, Jun Hee; Lee, Kyu Won; Lee, Cheol Eui

    2016-11-01

    We have employed deuteron nuclear magnetic resonance (NMR) spectroscopy in order to study the dynamics of the deuterated water (D2O) molecules introduced into a perfluorosulfonic acid ionomer Nafion (NR-211) film. According to the 2H NMR spectral analysis, the deuterated water molecules at low temperatures occupied either relatively rigid or mobile sites up to the temperature TM=240 K where all the deuterated water molecules became mobile. The temperature-dependent NMR linewidths sensitively reflected the motional narrowing of the rigid and mobile sites, and the NMR chemical shift reflected significant changes in the hydrogen bonds of the deuterated water. While a slow- to fast-limit motional transition was manifested at TM in the laboratory-frame NMR spin-lattice relaxation, the rotating-frame spin-lattice relaxation indicated no bulk liquid water state down to 200 K.

  13. Ca2+/H+ exchange by acidic organelles regulates cell migration in vivo

    PubMed Central

    Melchionda, Manuela; Pittman, Jon K.

    2016-01-01

    Increasing evidence implicates Ca2+ in the control of cell migration. However, the underlying mechanisms are incompletely understood. Acidic Ca2+ stores are fast emerging as signaling centers. But how Ca2+ is taken up by these organelles in metazoans and the physiological relevance for migration is unclear. Here, we identify a vertebrate Ca2+/H+ exchanger (CAX) as part of a widespread family of homologues in animals. CAX is expressed in neural crest cells and required for their migration in vivo. It localizes to acidic organelles, tempers evoked Ca2+ signals, and regulates cell-matrix adhesion during migration. Our data provide new molecular insight into how Ca2+ is handled by acidic organelles and link this to migration, thereby underscoring the role of noncanonical Ca2+ stores in the control of Ca2+-dependent function. PMID:27002171

  14. Spectrum sensing of trace C(2)H(2) detection in differential optical absorption spectroscopy technique.

    PubMed

    Chen, Xi; Dong, Xiaopeng

    2014-09-10

    An improved algorithm for trace C(2)H(2) detection is presented in this paper. The trace concentration is accurately calculated by focusing on the absorption spectrum from the frequency domain perspective. The advantage of the absorption spectroscopy frequency domain algorithm is its anti-interference capability. First, the influence of the background noise on the minimum detectable concentration is greatly reduced. Second, the time-consuming preprocess of spectra calibration in the differential optical absorption spectroscopy technique is skipped. Experimental results showed the detection limit of 50 ppm is achieved at a lightpath length of 0.2 m. This algorithm can be used in real-time spectrum analysis with high accuracy.

  15. Competition between charge exchange and chemical reaction - The D2/+/ + H system

    NASA Technical Reports Server (NTRS)

    Preston, R. K.; Cross, R. J., Jr.

    1973-01-01

    Study of the special features of molecular charge exchange and its competition with chemical reaction in the case of the D2(+) + H system. The trajectory surface hopping (TSH) model proposed by Tully and Preston (1971) is used to study this competition for a number of reactions involving the above system. The diatomics-in-molecules zero-overlap approximation is used to calculate the three adiabatic surfaces - one triplet and two singlet - which are needed to describe this system. One of the significant results of this study is that the chemical reaction and charge exchange are strongly coupled. It is also found that the number of trajectories passing into the chemical regions of the three surfaces depends very strongly on the surface crossings.-

  16. The rate of the reaction between CN and C2H2 at interstellar temperatures

    NASA Technical Reports Server (NTRS)

    Woon, D. E.; Herbst, E.

    1997-01-01

    The rate coefficient for the important interstellar reaction between CN and C2H2 has been calculated as a function of temperature between 10 and 300 K. The potential surface for this reaction has been determined through ab initio quantum chemical techniques; the potential exhibits no barrier in the entrance channel but does show a small exit channel barrier, which lies below the energy of reactants. Phase-space calculations for the reaction dynamics, which take the exit channel barrier into account, show the same unusual temperature dependence as determined by experiment, in which the rate coefficient at first increases as the temperature is reduced below room temperature and then starts to decrease as the temperature drops below 50-100 K. The agreement between theory and experiment provides strong confirmation that the reaction occurs appreciably at cool interstellar temperatures.

  17. Laser-modified charge-transfer processes in He2++H collisions

    NASA Astrophysics Data System (ADS)

    Liu, C. L.; He, B.; Zou, S. Y.; Wang, J. G.

    2016-10-01

    Laser-modified electron capture processes are studied for the He2++H collision system in the low projectile energy region by solving the time-dependent Schrödinger equation. An obvious enhancement of the total and dominant state-selective charge-transfer cross sections are observed with respect to laser-free and weaker laser cases for low projectile energy. The influence of the laser pulse phase upon the cross sections is also studied and the reduction of the cross section is observed at some pulse phases with the increasing of the projectile energy. The time evolution for the dynamics of the collision system is analyzed in order to explore the dependence of the cross sections upon the pulse phase.

  18. Core-mass nonadiabatic corrections to molecules: H2, H2+, and isotopologues

    NASA Astrophysics Data System (ADS)

    Diniz, Leonardo G.; Alijah, Alexander; Mohallem, José Rachid

    2012-10-01

    For high-precision calculations of rovibrational states of light molecules, it is essential to include non-adiabatic corrections. In the absence of crossings of potential energy surfaces, they can be incorporated in a single surface picture through coordinate-dependent vibrational and rotational reduced masses. We present a compact method for their evaluation and relate in particular the vibrational mass to a well defined nuclear core mass derived from a Mulliken analysis of the electronic density. For the rotational mass we propose a simple, but very effective parametrization. The use of these masses in the nuclear Schrödinger equation yields numerical data for the corrections of a much higher quality than can be obtained with optimized constant masses, typically better than 0.1 cm^{-1}. We demonstrate the method for H_2, H_2^+, and singly deuterated isotopologues. Isotopic asymmetry does not present any particular difficulty. Generalization to polyatomic molecules is straightforward.

  19. Ca2+/H+ exchange by acidic organelles regulates cell migration in vivo.

    PubMed

    Melchionda, Manuela; Pittman, Jon K; Mayor, Roberto; Patel, Sandip

    2016-03-28

    Increasing evidence implicates Ca(2+) in the control of cell migration. However, the underlying mechanisms are incompletely understood. Acidic Ca(2+) stores are fast emerging as signaling centers. But how Ca(2+) is taken up by these organelles in metazoans and the physiological relevance for migration is unclear. Here, we identify a vertebrate Ca(2+)/H(+)exchanger (CAX) as part of a widespread family of homologues in animals. CAX is expressed in neural crest cells and required for their migration in vivo. It localizes to acidic organelles, tempers evoked Ca(2+) signals, and regulates cell-matrix adhesion during migration. Our data provide new molecular insight into how Ca(2+) is handled by acidic organelles and link this to migration, thereby underscoring the role of noncanonical Ca(2+) stores in the control of Ca(2+)-dependent function. PMID:27002171

  20. Equilibrium concentrations of N2H4 and its decomposition products at elevated temperatures and pressures

    NASA Technical Reports Server (NTRS)

    Smetana, F. O.; Fairchild, H. N., III; Martin, G. L.

    1973-01-01

    Liquid hydrazine is considered as a convenient source of hydrogen rather than just as a rocket fuel. For such purposes, the hydrogen is usually obtained by passing the hydrazine through a heated catalytic bed. One convenient measure of the effectiveness of a catalytic decomposition device as a whole is to compare the quantity of hydrogen produced with the equilibrium concentration of the gaseous species N2H4, NH3, N3, and H2 which would exist at the temperature and pressure found in various parts of the device. Calculations of the concentrations were carried out and are reported here. Following presentation of the results in both tabular and graphical forms is a comparison between the computed equilibrium concentrations and available experimental data.

  1. Elusive 2H-1,2-oxasiletes through reactions of an isolable dialkylsilylene with diazocarbonyl compounds.

    PubMed

    Dong, Zhaowen; Xiao, Xu-Qiong; Li, Zhifang; Lu, Qiong; Lai, Guoqiao; Kira, Mitsuo

    2015-09-28

    The reactions of isolable dialkysilylene 1 with 2-diazo-1,2-diphenylethanone and ethyl 2-diazo-2-phenylacetate gave elusive silacycles, 2H-1,2-oxasiletes 2 and 3, respectively, in high yields. Because these reactions occur at low temperatures of ca.-30 °C, initial complexation of the silylene to the carbonyl oxygen of the diazocarbonyl compounds is suggested to trigger dinitrogen elimination followed by cyclization. In contrast, a six-membered cyclic diazo compound 8 and 1-sila-2,3-diazabicyclo[3.3.0]oct-3-ene 10 were obtained in good yields by the reaction of 1 with less reactive ethyl 2-diazo-3-oxo-3-phenylpropanoate 7 and trimethylsilyldiazomethane 9. Molecular structures of 2, 3, 8 and 10 were determined by X-ray crystallography.

  2. Effect of (2)H and (18)O water isotopes in kinesin-1 gliding assay.

    PubMed

    Maloney, Andy; Herskowitz, Lawrence J; Koch, Steven J

    2014-01-01

    We show for the first time the effects of heavy-hydrogen water ((2)H2O) and heavy-oxygen water (H2 (18)O) on the gliding speed of microtubules on kinesin-1 coated surfaces. Increased fractions of isotopic waters used in the motility solution decreased the gliding speed of microtubules by a maximum of 21% for heavy-hydrogen and 5% for heavy-oxygen water. We also show that gliding microtubule speed returns to its original speed after being treated with heavy-hydrogen water. We discuss possible interpretations of these results and the importance for future studies of water effects on kinesin and microtubules. We also discuss the implication for using heavy waters in biomolecular devices incorporating molecular motors. PMID:24711961

  3. Effect of 2H and 18O water isotopes in kinesin-1 gliding assay

    PubMed Central

    Herskowitz, Lawrence J.; Koch, Steven J.

    2014-01-01

    We show for the first time the effects of heavy-hydrogen water (2H2O) and heavy-oxygen water (H218O) on the gliding speed of microtubules on kinesin-1 coated surfaces. Increased fractions of isotopic waters used in the motility solution decreased the gliding speed of microtubules by a maximum of 21% for heavy-hydrogen and 5% for heavy-oxygen water. We also show that gliding microtubule speed returns to its original speed after being treated with heavy-hydrogen water. We discuss possible interpretations of these results and the importance for future studies of water effects on kinesin and microtubules. We also discuss the implication for using heavy waters in biomolecular devices incorporating molecular motors. PMID:24711961

  4. Dimensionality of collective pinning in 2H-NbSe{sub 2} single crystals

    SciTech Connect

    Angurel, L.A.; Amin, F.; Polichetti, M.; Aarts, J.; Kes, P.H.

    1997-08-01

    ac susceptibility measurements have been used to determine the dimensionality of the collective pinning in 2H-NbSe{sub 2} crystals. We have analyzed the thickness dependence of the critical current versus field [J{sub c}(H)] curves for thicknesses between 6 and 166 {mu}m. Down to 15 {mu}m J{sub c}(H) is independent of the thickness showing that the pinning is three dimensional. This is in agreement with estimates from collective pinning theory. Deviations occur for the 6 {mu}m thick sample near the peak-effect regime, possibly indicating a crossover to two-dimensional behavior. In the thicker samples the peak effect clearly cannot be assigned to a dimensional crossover. The frequency dependence reflects a crossover from a Campbell regime to a nonlinear regime related to small flux creep effects. {copyright} {ital 1997} {ital The American Physical Society}

  5. Direct N2H4/H2O2 Fuel Cells Powered by Nanoporous Gold Leaves

    PubMed Central

    Yan, Xiuling; Meng, Fanhui; Xie, Yun; Liu, Jianguo; Ding, Yi

    2012-01-01

    Dealloyed nanoporous gold leaves (NPGLs) are found to exhibit high electrocatalytic properties toward both hydrazine (N2H4) oxidation and hydrogen peroxide (H2O2) reduction. This observation allows the implementation of a direct hydrazine-hydrogen peroxide fuel cell (DHHPFC) based on these novel porous membrane catalysts. The effects of fuel and oxidizer flow rate, concentration and cell temperature on the performance of DHHPFC are systematically investigated. With a loading of ~0.1 mg cm−2 Au on each side, an open circuit voltage (OCV) of 1.2 V is obtained at 80°C with a maximum power density 195 mW cm−2, which is 22 times higher than that of commercial Pt/C electrocatalyst at the same noble metal loading. NPGLs thus hold great potential as effective and stable electrocatalysts for DHHPFCs. PMID:23230507

  6. Modelling of c-C2H4O Formation on Grain-Surfaces

    NASA Astrophysics Data System (ADS)

    Occhiogrosso, Angela; Viti, S.; Ward, M. D.; Price, S. D.

    2013-01-01

    Ethylene oxide (c-C2H4O) is a ring-shaped organic compound that may lead to the synthesis of amino acids and the early metabolic pathways in the interstellar medium (ISM) (Cleaves 2003; Miller & Schlesinger 1993). This molecule has been detected towards several high-mass star forming regions (Ikeda et al. 2001) but to date, its observational abundances cannot be reproduced by chemical models. We include new experimental results in the UCL_CHEM chemical model with the aim of reproducing the abundances of ethylene oxide across high-mass sources. In particular, we focused on the solid state reaction investigated by Ward & Price (2011). By comparing our theoretical column densities with those from the observations we found that the reaction between atomic oxygen and ethylene on grains is a viable route of formation for ethylene oxide (Occhiogrosso et al., accepted by MNRAS).

  7. Phase-Engineered Synthesis of Centimeter-Scale 1T'- and 2H-Molybdenum Ditelluride Thin Films.

    PubMed

    Park, Jin Cheol; Yun, Seok Joon; Kim, Hyun; Park, Ji-Hoon; Chae, Sang Hoon; An, Sung-Jin; Kim, Jeong-Gyun; Kim, Soo Min; Kim, Ki Kang; Lee, Young Hee

    2015-06-23

    We report the synthesis of centimeter-scale, uniform 1T'- and 2H-MoTe2 thin films via the tellurization of Mo thin films. 1T'-MoTe2 was initially grown and converted gradually to 2H-MoTe2 over a prolonged growth time under a Te atmosphere. Maintaining excessive Te was essential for obtaining the stable stoichiometric 2H-MoTe2 phase. Further annealing under a lower partial pressure of Te at the same temperature, followed by a rapid quenching, led to the reverse phase transition from 2H-MoTe2 to 1T'-MoTe2. The orientation of the 2H-MoTe2 film was determined by the tellurization rate. Slow tellurization was the key for obtaining a highly oriented 2H-MoTe2 film over the entire area, while fast tellurization led to a 2H-MoTe2 film with a randomly oriented c-axis. PMID:26042796

  8. Satellite observations of ethylene (C2H4) from the Aura Tropospheric Emission Spectrometer: A scoping study

    NASA Astrophysics Data System (ADS)

    Dolan, Wayana; Payne, Vivienne H.; Kualwik, Susan S.; Bowman, Kevin W.

    2016-09-01

    We present a study focusing on detection and initial quantitative estimates of ethylene (C2H4) in observations from the Tropospheric Emission Spectrometer (TES), a Fourier transform spectrometer aboard the Aura satellite that measures thermal infrared radiances with high spectral resolution (0.1 cm-1). We analyze observations taken in support of the 2008 Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission and demonstrate the feasibility of future development of C2H4 into a TES standard product. In the Northern Hemisphere, C2H4 is commonly associated with boreal fire plumes, motor vehicle exhaust and petrochemical emissions. It has a short lifetime (∼14-32 h) in the troposphere due to its reaction with OH and O3. Chemical destruction of C2H4 in the atmosphere leads to the production of ozone and other species such as carbon monoxide (CO) and formaldehyde. Results indicate a correlation between C2H4 and CO in boreal fire plumes. Quantitative C2H4 estimates are sensitive to assumptions about the plume height and width. We find that C2H4 greater than 2-3 ppbv can be detected in a single TES observation (for a fire plume at 3 km altitude and 1.5 km width). Spatial averaging will be needed for surface-peaking profiles where TES sensitivity is lower.

  9. Mutation screening and association study of the UBE2H gene on chromosome 7q32 in autistic disorder.

    PubMed

    Vourc'h, Patrick; Martin, Isabelle; Bonnet-Brilhault, Frédérique; Marouillat, Sylviane; Barthélémy, Catherine; Pierre Müh, Jean; Andres, Christian

    2003-12-01

    Autistic disorder is a severe neurodevelopmental disorder most probably caused by a complex interaction of genetic factors. Several genomewide scans identified multipoint LOD score peaks in region 7q32. In this region, UBE2H encodes an E2 enzyme of the ubiquitin-dependent proteolytic system. Mutations in another member of this system, the UBE3A gene, cause Angelman syndrome. The participation of E2 (ubiquitin-conjugating enzymes) or E3 (ubiquitin ligases) enzymes in neural development recently emerged. Given its physical location and function, we examined UBE2H as a candidate for involvement in autistic disorder. We confirmed by reverse transcription-polymerase chain reaction that the UBE2H gene was expressed in the rat and the human central nervous system. The rat UBE2H and human UBE2H deduced amino acid sequences are identical. We screened the seven exons of the UBE2H gene in autistic patients using single-strand conformation analysis. We observed a silent A-->G transition at position 336. A case-control association study was performed using this A/G polymorphism. A significant association was found between the G allele and a subgroup of autistic patients with developmental quotient higher than 30 (P=0.004). Although further studies are required, these results suggest that the UBE2H gene could be one of the 7q-susceptibility loci for autistic disorder.

  10. Stable isotope (2H, 17O, 18O) and hydro chemical patterns of precipitation collected in weekly resolution at Hannover, Germany

    NASA Astrophysics Data System (ADS)

    Koeniger, Paul; Himmelsbach, Thomas

    2016-04-01

    Long-term observations of stable isotopes (δ18O and δ2H) in precipitation were initiated in May 2008 at the Federal Institute of Geosciences and Natural Resources (BGR) in Hannover, Germany. In 2014 all precipitation samples were re-analyzed because a purchase of a new laser spectrometer (Picarro L2140-i) now allowed measurements of δ17O and a calculation of the 17O-excess parameter. Starting in October 2015 a routine analysis of hydro chemical parameters was added whenever enough sample aliquot was available (major ions, trace elements). A discussion of the stable isotope data of the seven year series of weekly precipitation samples (n = 370) will be presented. Beneath general patterns (seasonality and trends) we also focus on importance of amount weighing procedures, corrections for minor rain amounts, aspects of sample storage and re-analyzes, as well as impacts through changes in analytical equipment (IRMS, CRD spectroscopy) which is visible from the data. For stable isotopes a Thermo Fisher delta plus IRMS (Gasbench and H-Device) was used until 2011 and from 2012 on a Picarro L2120-i water vapor analyzer with long-term accuracies for quality check samples better than 0.2‰ and 0.8‰ for δ18O and δ2H, respectively.

  11. The thermal decomposition of C{sub 2}H{sub 5}I

    SciTech Connect

    Kumaran, S.S.; Su, M.C.; Lim, K.P.; Michael, J.V.

    1996-06-01

    The high temperature thermal dissociation of C{sub 2}H{sub 5}I has been characterized in this study. Kinetics and overall yield experiments were performed over the temperature range, 946--2,046 K, using the atomic resonance absorption spectrometric technique (ARAS) for the temporal detection of both product H- and I-atoms behind reflected shock waves. The C{sub 2}H{sub 5}I decomposition proceeds by both C-I fission and HI elimination. Rate constants for the C-I fission process, measured over the temperature and density ranges, 946--1,303 K and 0.82--4.4 {times} 10{sup 18} cm{sup {minus}3}, respectively, can be well represented to within {+-}37% by the first-order expression: k = 6.34 {times} 10{sup 9} exp({minus}15,894 K/T) s{sup {minus}1}. Overall yield data for atomic product gave a branching ratio for C-I fission of (0.87 {+-} 0.11) suggesting that 13% of the reaction proceeds through molecular HI elimination. This conclusion is consistent with earlier studies that showed C-I fission to be the dominant dissociation channel. The temperature and pressure dependences of the dissociation rate constants and the yield data have been theoretically described using three formulations of unimolecular rate theory. The best description was obtained with a full Master`s equation analysis. However, all three calculations confirm that the HI elimination pathway is lower lying than the C-I fission process by {approximately} 3 kcal/mole.

  12. Equilibrium 2H/ 1H fractionations in organic molecules: I. Experimental calibration of ab initio calculations

    NASA Astrophysics Data System (ADS)

    Wang, Ying; Sessions, Alex L.; Nielsen, Robert J.; Goddard, William A., III

    2009-12-01

    Carbon-bound hydrogen in sedimentary organic matter can undergo exchange over geologic timescales, altering its isotopic composition. Studies investigating the natural abundance distribution of 1H and 2H in such molecules must account for this exchange, which in turn requires quantitative knowledge regarding the endpoint of exchange, i.e., the equilibrium isotopic fractionation factor ( α eq). To date, relevant data have been lacking for molecules larger than methane. Here we describe an experimental method to measure α eq for C-bound H positions adjacent to carbonyl group (H α) in ketones. H at these positions equilibrates on a timescale of days as a result of keto-enol tautomerism, allowing equilibrium 2H/ 1H distributions to be indirectly measured. Molecular vibrations for the same ketone molecules are then computed using Density Functional Theory at the B3LYP/6-311G∗∗ level and used to calculate α eq values for H α. Comparison of experimental and computational results for six different straight and branched ketones yields a temperature-dependent linear calibration curve with slope = 1.081-0.00376 T and intercept = 8.404-0.387 T, where T is temperature in degrees Celsius. Since the dominant systematic error in the calculation (omission of anharmonicity) is of the same size for ketones and C-bound H in most other linear compounds, we propose that this calibration can be applied to analogous calculations for a wide variety of organic molecules with linear carbon skeletons for temperatures below 100 °C. In a companion paper ( Wang et al., 2009) we use this new calibration dataset to calculate the temperature-dependent equilibrium isotopic fractionation factors for a range of linear hydrocarbons, alcohols, ethers, ketones, esters and acids.

  13. Direct Detection of C_2H_2 in Air and Human Breath by Cw-Crds

    NASA Astrophysics Data System (ADS)

    Schmidt, Florian M.; Vaittinen, Olavi; Metsälä, Markus; Halonen, Lauri

    2010-06-01

    Continuous wave cavity ring-down spectroscopy (cw-CRDS) is an established cavity-enhanced absorption technique that can provide the necessary sensitivity, selectivity and fast acquisition time for many applications involving the detection of trace species. We present a simple but highly sensitive cw-CRDS spectrometer based on an external cavity diode laser operating in the near-infrared region. This instrument allows us to directly detect acetylene (C_2H_2) mixing ratios in air with a detection limit of 120 parts per trillion by volume (pptv) measuring on a C_2H_2 absorption line at 6565.620 cm-1. Acetylene is a combustion product that is routinely used in environmental monitoring as a marker for anthropogenic emissions. In a recent work, the spectrometer was employed to measure the level of acetylene in indoor and outdoor air in Helsinki. Continuous flow measurements with high time resolution (one minute) revealed strong fluctuations in the acetylene mixing ratio in outdoor air during daytime. Due to its non-invasive nature and fast response time, the analysis of exhaled breath for medical diagnostics is an excellent and straightforward alternative to methods using urine or blood samples. In an ongoing study, the cw-CRDS instrument is used to establish the baseline level of acetylene in the breath of the healthy population. An elevated amount of acetylene in breath could indicate exposure to combustion exhausts or other volatile organic compound (VOC) rich sources. The latest results of this investigation will be presented. F. M. Schmidt, O. Vaittinen, M. Metsälä, P. Kraus and L. Halonen, submitted for publication in Appl. Phys. B.

  14. Interplay of charge density wave and multiband superconductivity in 2H-PdxTaSe2.

    PubMed

    Bhoi, D; Khim, S; Nam, W; Lee, B S; Kim, Chanhee; Jeon, B-G; Min, B H; Park, S; Kim, Kee Hoon

    2016-04-05

    2H-TaSe2 has been one of unique transition metal dichalcogenides exhibiting several phase transitions due to a delicate balance among competing electronic ground states. An unusual metallic state at high-T is sequentially followed by an incommensurate charge density wave (ICDW) state at ≈122 K and a commensurate charge density wave (CCDW) state at ≈90 K, and superconductivity at TC ~ 0.14 K. Upon systematic intercalation of Pd ions into TaSe2, we find that CCDW order is destabilized more rapidly than ICDW to indicate a hidden quantum phase transition point at x ~ 0.09-0.10. Moreover, TC shows a dramatic enhancement up to 3.3 K at x = 0.08, ~24 times of TC in 2H-TaSe2, in proportional to the density of states N(EF). Investigations of upper critical fields Hc2 in single crystals reveal evidences of multiband superconductivity as temperature-dependent anisotropy factor γH = , quasi-linear increase of , and an upward, positive-curvature in near TC. Furthermore, analysis of temperature-dependent electronic specific heat corroborates the presence of multiple superconducting gaps. Based on above findings and electronic phase diagram vs x, we propose that the increase of N(EF) and effective electron-phonon coupling in the vicinity of CDW quantum phase transition should be a key to the large enhancement of TC in PdxTaSe2.

  15. The First Detailed 2H and 18O Isoscapes of Freshwater in Scotland

    NASA Astrophysics Data System (ADS)

    Meier-Augenstein, W.; Hoogewerff, J.; Kemp, H. F.; Frew, D.

    2012-04-01

    Scotland's freshwater lochs and reservoirs provide a vital resource for sustaining biodiversity, agriculture, food production as well as for human consumption. Regular monitoring of freshwater quality by the Scottish Environmental Protection Agency (SEPA) fulfils the legislative requirements but new scientific methods involving stable isotope analysis present an opportunity for delivering on current and nascent government policies [1] and gaining a greater understanding of Scottish waters and their importance in the context of climate change, environmental sustainability and the aforementioned functions. In brief, 2H and 18O isoscapes of Scottish freshwater could be used to support fundamental and applied research in: • Climate change - These first ever isoscapes will provide a baseline against which future environmental impact can be assessed due to changes in the characteristic isotope composition of freshwater lochs and reservoirs. • Scottish branding - Location specific stable isotope signatures of Scottish freshwater have the potential to be used as a tool for provenancing and thus protecting premium Scottish produce such as Scottish beef, Scottish berries and Scottish Whisky. During 2011, freshwater samples were collected with the support of SEPA from more than 80 freshwater lochs and reservoirs across Scotland. Here we present the result of the 2H and 18O stable isotope analyses of these water samples together with the first isoscapes generated based on these data. [1] Adaptation Framework - Adapting Our Ways: Managing Scotland's Climate Risk (2009): Scotland's Biodiversity: It's in Your Hands - A strategy for the conservation and enhancement of biodiversity in Scotland (2005); Recipe For Success - Scotland's National Food and Drink Policy (2009); Scottish Planning Policy Environmental Report (2009); Scottish Planning Policy (SPP) 15 Planning for Rural Development (2005); National Planning Policy Guideline (NPPG) 14: Natural Heritage (1999).

  16. Interplay of charge density wave and multiband superconductivity in 2H-PdxTaSe2

    PubMed Central

    Bhoi, D.; Khim, S.; Nam, W.; Lee, B. S.; Kim, Chanhee; Jeon, B.-G.; Min, B. H.; Park, S.; Kim, Kee Hoon

    2016-01-01

    2H-TaSe2 has been one of unique transition metal dichalcogenides exhibiting several phase transitions due to a delicate balance among competing electronic ground states. An unusual metallic state at high-T is sequentially followed by an incommensurate charge density wave (ICDW) state at ≈122 K and a commensurate charge density wave (CCDW) state at ≈90 K, and superconductivity at TC ~ 0.14 K. Upon systematic intercalation of Pd ions into TaSe2, we find that CCDW order is destabilized more rapidly than ICDW to indicate a hidden quantum phase transition point at x ~ 0.09–0.10. Moreover, TC shows a dramatic enhancement up to 3.3 K at x = 0.08, ~24 times of TC in 2H-TaSe2, in proportional to the density of states N(EF). Investigations of upper critical fields Hc2 in single crystals reveal evidences of multiband superconductivity as temperature-dependent anisotropy factor γH = , quasi-linear increase of , and an upward, positive-curvature in near TC. Furthermore, analysis of temperature-dependent electronic specific heat corroborates the presence of multiple superconducting gaps. Based on above findings and electronic phase diagram vs x, we propose that the increase of N(EF) and effective electron-phonon coupling in the vicinity of CDW quantum phase transition should be a key to the large enhancement of TC in PdxTaSe2. PMID:27045426

  17. The effects of maternal anxiety during pregnancy on IGF2/H19 methylation in cord blood.

    PubMed

    Mansell, T; Novakovic, B; Meyer, B; Rzehak, P; Vuillermin, P; Ponsonby, A-L; Collier, F; Burgner, D; Saffery, R; Ryan, J

    2016-01-01

    Compelling evidence suggests that maternal mental health in pregnancy can influence fetal development. The imprinted genes, insulin-like growth factor 2 (IGF2) and H19, are involved in fetal growth and each is regulated by DNA methylation. This study aimed to determine the association between maternal mental well-being during pregnancy and differentially methylated regions (DMRs) of IGF2 (DMR0) and the IGF2/H19 imprinting control region (ICR) in newborn offspring. Maternal depression, anxiety and perceived stress were assessed at 28 weeks of pregnancy in the Barwon Infant Study (n=576). DNA methylation was measured in purified cord blood mononuclear cells using the Sequenom MassArray Platform. Maternal anxiety was associated with a decrease in average ICR methylation (Δ=-2.23%; 95% CI=-3.68 to -0.77%), and across all six of the individual CpG units in anxious compared with non-anxious groups. Birth weight and sex modified the association between prenatal anxiety and infant methylation. When stratified into lower (⩽3530 g) and higher (>3530 g) birth weight groups using the median birth weight, there was a stronger association between anxiety and ICR methylation in the lower birth weight group (Δ=-3.89%; 95% CI=-6.06 to -1.72%), with no association in the higher birth weight group. When stratified by infant sex, there was a stronger association in female infants (Δ=-3.70%; 95% CI=-5.90 to -1.51%) and no association in males. All the linear regression models were adjusted for maternal age, smoking and folate intake. These findings show that maternal anxiety in pregnancy is associated with decreased IGF2/H19 ICR DNA methylation in progeny at birth, particularly in female, low birth weight neonates. ICR methylation may help link poor maternal mental health and adverse birth outcomes, but further investigation is needed. PMID:27023171

  18. HCO+ and N2H+ Spectroscopy of Sources in the Bolocam Galactic Plane Survey

    NASA Astrophysics Data System (ADS)

    Schlingman, Wayne M.; Shirley, Y. L.; Bally, J.; Battersby, C.; Bolin, D. E.; Dunham, M. K.; Ellsworth-Bowers, T.; Evans, N. J., II; Ginsburg, A.; Rosolowsky, E.; Stringfellow, G. S.

    2011-01-01

    We present the results of observations of 1882 sources in the Bolocam Galactic Plane Survey (BGPS) at 1.1mm with the 10m Heinrich Hertz Telescope simultaneously in HCO+ J = 3 - 2 and N2H+ J = 3 - 2. We detect 77% of these sources in HCO+ and 51% in N2H+. We find a strong correlation between both dense gas tracers and the 1.1 mm dust emission of BGPS sources. We determine kinematic distances and break the distance ambiguity for 435 sources for which we derive the size, mass, and average density. The median size of BGPS clumps is 0.86 pc with a median mass of 330 Msun. The median HCO+ linewidth is 3.1 km/s indicating that BGPS clumps are dominated by supersonic turbulence or unresolved kinematic motions. We find no evidence for a size-linewidth relationship for BGPS clumps. We analyze the effects of the assumed dust temperature on the derived clump properties with a Monte Carlo simulation. The observed differential mass histogram has a power-law slope that is intermediate between that observed for diffuse CO clouds and the stellar IMF. BGPS clumps represent a wide range of objects (from dense cores to more diffuse clumps) and are typically characterized by larger sizes and lower densities than previous published surveys of high-mass star forming regions. This collection of objects is a less-biased sample of star forming regions in the Milky Way that likely span a wide range of evolutionary states.

  19. Exploring water binding motifs to an excess electron via X2(-)(H2O) [X = O, F].

    PubMed

    Chiou, Mong-Feng; Sheu, Wen-Shyan

    2012-07-26

    X(2)(-)(H(2)O) [X = O, F] is utilized to explore water binding motifs to an excess electron via ab initio calculations at the MP4(SDQ)/aug-cc-pVDZ + diffs(2s2p,2s2p) level of theory. X(2)(-)(H(2)O) can be regarded as a water molecule that binds to an excess electron, the distribution of which is gauged by X(2). By varying the interatomic distance of X(2), r(X1-X2), the distribution of the excess electron is altered, and the water binding motifs to the excess electron is then examined. Depending on r(X1-X2), both binding motifs of C(s) and C(2v) forms are found with a critical distance of ∼1.37 Å and ∼1.71 Å for O(2)(-)(H(2)O) and F(2)(-)(H(2)O), respectively. The energetic and geometrical features of O(2)(-)(H(2)O) and F(2)(-)(H(2)O) are compared. In addition, various electronic properties of X(2)(-)(H(2)O) are examined. For both O(2)(-)(H(2)O) and F(2)(-)(H(2)O), the C(s) binding motif appears to prevail at a compact distribution of the excess electron. However, when the electron is diffuse, characterized by the radius of gyration in the direction of the X(2) bond axis with a threshold of ∼0.84 Å, the C(2v) binding motif is formed.

  20. Theoretical study of the bonding of Sc, Y, and La singly charged and dipositive ions to C2H2, C2H4, and C3H6

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

    1991-01-01

    The interaction of the Sc and Y singly-charged and dipositive ions with C2H2, C2H4, and C3H6 is studied using electronic structure calculations that include high levels of electron correlation. These results are compared with comparable calculations performed previously for La(+) and La(2+). For C2H2 and C2H4, all three metal ions insert into the C-C pi bond, making a three-membered ring. The optimal structures for the MC3H6(+) ions all involve rearrangement to make a four-membered ring. The strength of the metal-ligand bond for the singly charged ions follows the order La greater than Sc equal to about Y. In contrast, the bonds involving the dipositive ions are electrostatic, so that the binding energy increases as the size of the ion decreases, leading to the trend Sc greater than Y greater than La.

  1. Microwave-assisted 1T to 2H phase reversion of MoS2 in solution: a fast route to processable dispersions of 2H-MoS2 nanosheets and nanocomposites

    NASA Astrophysics Data System (ADS)

    Xu, Danyun; Zhu, Yuanzhi; Liu, Jiapeng; Li, Yang; Peng, Wenchao; Zhang, Guoliang; Zhang, Fengbao; Fan, Xiaobin

    2016-09-01

    Exfoliated molybdenum disulfide (MoS2) has unique 2H phase and semiconductor properties and potential applications across a wide range of fields. However, the chemically exfoliated MoS2 nanosheets from Li x MoS2 have a 1T phase, and searching for a fast route to get processable 2H-MoS2 nanosheets and its nanocomposites is still an urgent task. This study reports on a simple, fast and efficient microwave strategy to achieve the 1T to 2H phase conversion of MoS2 and the successful preparation of processable 2H-MoS2 nanosheets and their nanocomposites. The method here may be easily changed to achieve the phase change of other exfoliated TMDs.

  2. Microwave-assisted 1T to 2H phase reversion of MoS2 in solution: a fast route to processable dispersions of 2H-MoS2 nanosheets and nanocomposites.

    PubMed

    Xu, Danyun; Zhu, Yuanzhi; Liu, Jiapeng; Li, Yang; Peng, Wenchao; Zhang, Guoliang; Zhang, Fengbao; Fan, Xiaobin

    2016-09-23

    Exfoliated molybdenum disulfide (MoS2) has unique 2H phase and semiconductor properties and potential applications across a wide range of fields. However, the chemically exfoliated MoS2 nanosheets from Li x MoS2 have a 1T phase, and searching for a fast route to get processable 2H-MoS2 nanosheets and its nanocomposites is still an urgent task. This study reports on a simple, fast and efficient microwave strategy to achieve the 1T to 2H phase conversion of MoS2 and the successful preparation of processable 2H-MoS2 nanosheets and their nanocomposites. The method here may be easily changed to achieve the phase change of other exfoliated TMDs. PMID:27528593

  3. Microwave-assisted 1T to 2H phase reversion of MoS2 in solution: a fast route to processable dispersions of 2H-MoS2 nanosheets and nanocomposites.

    PubMed

    Xu, Danyun; Zhu, Yuanzhi; Liu, Jiapeng; Li, Yang; Peng, Wenchao; Zhang, Guoliang; Zhang, Fengbao; Fan, Xiaobin

    2016-09-23

    Exfoliated molybdenum disulfide (MoS2) has unique 2H phase and semiconductor properties and potential applications across a wide range of fields. However, the chemically exfoliated MoS2 nanosheets from Li x MoS2 have a 1T phase, and searching for a fast route to get processable 2H-MoS2 nanosheets and its nanocomposites is still an urgent task. This study reports on a simple, fast and efficient microwave strategy to achieve the 1T to 2H phase conversion of MoS2 and the successful preparation of processable 2H-MoS2 nanosheets and their nanocomposites. The method here may be easily changed to achieve the phase change of other exfoliated TMDs.

  4. Rhodium-catalyzed cascade oxidative annulation leading to substituted naphtho[1,8-bc]pyrans by sequential cleavage of C(sp2)-H/C(sp3)-H and C(sp2)-H/O-H bonds.

    PubMed

    Tan, Xing; Liu, Bingxian; Li, Xiangyu; Li, Bin; Xu, Shansheng; Song, Haibin; Wang, Baiquan

    2012-10-01

    The cascade oxidative annulation reactions of benzoylacetonitrile with internal alkynes proceed efficiently in the presence of a rhodium catalyst and a copper oxidant to give substituted naphtho[1,8-bc]pyrans by sequential cleavage of C(sp(2))-H/C(sp(3))-H and C(sp(2))-H/O-H bonds. These cascade reactions are highly regioselective with unsymmetrical alkynes. Experiments reveal that the first-step reaction proceeds by sequential cleavage of C(sp(2))-H/C(sp(3))-H bonds and annulation with alkynes, leading to 1-naphthols as the intermediate products. Subsequently, 1-naphthols react with alkynes by cleavage of C(sp(2))-H/O-H bonds, affording the 1:2 coupling products. Moreover, some of the naphtho[1,8-bc]pyran products exhibit intense fluorescence in the solid state. PMID:22989331

  5. Stability evaluation of a rocket engine for gaseous oxygen difluoride (OF2) and gaseous diborane (B2H6) propellants

    NASA Technical Reports Server (NTRS)

    Clayton, R. M.

    1972-01-01

    Results of an experimental evaluation of the dynamic stability of a candidate combustor for the space storable propellants gaseous OF2/B2H6 show that the combustor is unstable without supplementary damping. A computer analysis indicated that the uninhibited engine could be unstable. The experiments, conducted with O2/C2H4 substitute propellants and with 70-30 FLOX/B2H6 (OF2 simulated with FLOX), show that the uninhibited combustor has a low stability margin to starting transient perturbations, but that is relatively insensitive to bomb disturbances. Damping cavities are shown to provide stability.

  6. Brønsted Acid/Lewis Acid Cooperatively Catalyzed Addition of Diazoester to 2H-chromene Acetals

    PubMed Central

    Luan, Yi; Qi, Yue; Gao, Hongyi; Ma, Qianqian; Schaus, Scott E.

    2014-01-01

    A novel Brønsted acid/Lewis acid dual catalyst system has been developed to promote an efficient C–C bond formation between a range of oxocarbenium precursors derived from chromene acetals and ethyl diazoacetate. The reaction proceeds under mild conditions and is tolerant of common functionalized 2H-chromene and isochromene acetals. In addition, an asymmetric variant of diazoacetate addition towards 2H-chromene acetal is described. Continued investigations include the further optimization of asymmetric induction towards the formation of diazo ester substituted 2H-chromene. PMID:25411552

  7. Copper-catalysed asymmetric allylic alkylation of alkylzirconocenes to racemic 3,6-dihydro-2H-pyrans

    PubMed Central

    Rideau, Emeline

    2015-01-01

    Summary Asymmetric allylic alkylation is a powerful reaction that allows the enantioselective formation of C–C bonds. Here we describe the asymmetric alkylation of alkylzirconium species to racemic 3,6-dihydro-2H-pyrans. Two systems were examined: 3-chloro-3,6-dihydro-2H-pyran using linear optimization (45–93% ee, up to 33% yield, 5 examples) and 3,6-dihydro-2H-pyran-3-yl diethyl phosphate with the assistance of a design of experiments statistical approach (83% ee, 12% yield). 1H NMR spectroscopy was used to gain insight into the reaction mechanisms. PMID:26734091

  8. Full-dimensional, high-level ab initio potential energy surfaces for H2(H2O) and H2(H2O)2 with application to hydrogen clathrate hydrates.

    PubMed

    Homayoon, Zahra; Conte, Riccardo; Qu, Chen; Bowman, Joel M

    2015-08-28

    New, full-dimensional potential energy surfaces (PESs), obtained using precise least-squares fitting of high-level electronic energy databases, are reported for intrinsic H2(H2O) two-body and H2(H2O)2 three-body potentials. The database for H2(H2O) consists of approximately 44 000 energies at the coupled cluster singles and doubles plus perturbative triples (CCSD(T))-F12a/haQZ (aug-cc-pVQZ for O and cc-pVQZ for H) level of theory, while the database for the three-body interaction consists of more than 36 000 energies at the CCSD(T)-F12a/haTZ (aug-cc-pVTZ for O, cc-pVTZ for H) level of theory. Two precise potentials are based on the invariant-polynomial technique and are compared to computationally faster ones obtained via "purified" symmetrization. All fits use reduced permutational symmetry appropriate for these non-covalent interactions. These intrinsic potentials are employed together with existing ones for H2, H2O, and (H2O)2, to obtain full PESs for H2(H2O) and H2(H2O)2. Properties of these full PESs are presented, including a diffusion Monte Carlo calculation of the zero-point energy and wavefunction, and dissociation energy of the H2(H2O) dimer. These PESs together with an existing one for water clusters are used in a many-body representation of the PES of hydrogen clathrate hydrates, illustrated for H2@(H2O)20. An analysis of this hydrate is presented, including the electronic dissociation energy to remove H2 from the calculated equilibrium structure.

  9. Supergranular Parameters

    NASA Astrophysics Data System (ADS)

    Udayashankar, Paniveni

    2016-07-01

    I study the complexity of supergranular cells using intensity patterns from Kodaikanal solar observatory. The chaotic and turbulent aspect of the solar supergranulation can be studied by examining the interrelationships amongst the parameters characterizing supergranular cells namely size, horizontal flow field, lifetime and physical dimensions of the cells and the fractal dimension deduced from the size data. The findings are supportive of Kolmogorov's theory of turbulence. The Data consists of visually identified supergranular cells, from which a fractal dimension 'D' for supergranulation is obtained according to the relation P α AD/2 where 'A' is the area and 'P' is the perimeter of the supergranular cells. I find a fractal dimension close to about 1.3 which is consistent with that for isobars and suggests a possible turbulent origin. The cell circularity shows a dependence on the perimeter with a peak around (1.1-1.2) x 105 m. The findings are supportive of Kolmogorov's theory of turbulence.

  10. The Chromatin Remodelling Enzymes SNF2H and SNF2L Position Nucleosomes adjacent to CTCF and Other Transcription Factors

    PubMed Central

    Wiechens, Nicola; Gkikopoulos, Triantaffyllos; Schofield, Pieta; Rocha, Sonia; Owen-Hughes, Tom

    2016-01-01

    Within the genomes of metazoans, nucleosomes are highly organised adjacent to the binding sites for a subset of transcription factors. Here we have sought to investigate which chromatin remodelling enzymes are responsible for this. We find that the ATP-dependent chromatin remodelling enzyme SNF2H plays a major role organising arrays of nucleosomes adjacent to the binding sites for the architectural transcription factor CTCF sites and acts to promote CTCF binding. At many other factor binding sites SNF2H and the related enzyme SNF2L contribute to nucleosome organisation. The action of SNF2H at CTCF sites is functionally important as depletion of CTCF or SNF2H affects transcription of a common group of genes. This suggests that chromatin remodelling ATPase’s most closely related to the Drosophila ISWI protein contribute to the function of many human gene regulatory elements. PMID:27019336

  11. Thermal Dehydrogenation of Base-Stabilized B2H5(+) Complexes and Its Role in C-H Borylation.

    PubMed

    Prokofjevs, Aleksandrs

    2015-11-01

    Thermally induced dehydrogenation of the H-bridged cation L2B2H5(+) (L=Lewis base) is proposed to be the key step in the intramolecular C-H borylation of tertiary amine boranes activated with catalytic amounts of strong "hydridophiles". Loss of H2 from L2B2H5(+) generates the highly reactive cation L2B2H3(+), which in its sp(2)-sp(3) diborane(4) form then undergoes either an intramolecular C-H insertion with B-B bond cleavage, or captures BH3 to produce L2B3H6(+). The effect of the counterion stability on the outcome of the reaction is illustrated by formation of LBH2C6F5 complexes through disproportionation of L2B2H5(+) HB(C6F5)3(-) . PMID:26377358

  12. The Chromatin Remodelling Enzymes SNF2H and SNF2L Position Nucleosomes adjacent to CTCF and Other Transcription Factors.

    PubMed

    Wiechens, Nicola; Singh, Vijender; Gkikopoulos, Triantaffyllos; Schofield, Pieta; Rocha, Sonia; Owen-Hughes, Tom

    2016-03-01

    Within the genomes of metazoans, nucleosomes are highly organised adjacent to the binding sites for a subset of transcription factors. Here we have sought to investigate which chromatin remodelling enzymes are responsible for this. We find that the ATP-dependent chromatin remodelling enzyme SNF2H plays a major role organising arrays of nucleosomes adjacent to the binding sites for the architectural transcription factor CTCF sites and acts to promote CTCF binding. At many other factor binding sites SNF2H and the related enzyme SNF2L contribute to nucleosome organisation. The action of SNF2H at CTCF sites is functionally important as depletion of CTCF or SNF2H affects transcription of a common group of genes. This suggests that chromatin remodelling ATPase's most closely related to the Drosophila ISWI protein contribute to the function of many human gene regulatory elements.

  13. The effects of maternal anxiety during pregnancy on IGF2/H19 methylation in cord blood

    PubMed Central

    Mansell, T; Novakovic, B; Meyer, B; Rzehak, P; Vuillermin, P; Ponsonby, A-L; Collier, F; Burgner, D; Saffery, R; Ryan, J; Vuillermin, Peter; Ponsonby, Anne-Louise; Carlin, John B; Allen, Katie J; Tang, Mimi L; Saffery, Richard; Ranganathan, Sarath; Burgner, David; Dwyer, Terry; Jachno, Kim; Sly, Peter

    2016-01-01

    Compelling evidence suggests that maternal mental health in pregnancy can influence fetal development. The imprinted genes, insulin-like growth factor 2 (IGF2) and H19, are involved in fetal growth and each is regulated by DNA methylation. This study aimed to determine the association between maternal mental well-being during pregnancy and differentially methylated regions (DMRs) of IGF2 (DMR0) and the IGF2/H19 imprinting control region (ICR) in newborn offspring. Maternal depression, anxiety and perceived stress were assessed at 28 weeks of pregnancy in the Barwon Infant Study (n=576). DNA methylation was measured in purified cord blood mononuclear cells using the Sequenom MassArray Platform. Maternal anxiety was associated with a decrease in average ICR methylation (Δ=−2.23% 95% CI=−3.68 to −0.77%), and across all six of the individual CpG units in anxious compared with non-anxious groups. Birth weight and sex modified the association between prenatal anxiety and infant methylation. When stratified into lower (⩽3530 g) and higher (>3530 g) birth weight groups using the median birth weight, there was a stronger association between anxiety and ICR methylation in the lower birth weight group (Δ=−3.89% 95% CI=−6.06 to −1.72%), with no association in the higher birth weight group. When stratified by infant sex, there was a stronger association in female infants (Δ=−3.70% 95% CI=−5.90 to −1.51%) and no association in males. All the linear regression models were adjusted for maternal age, smoking and folate intake. These findings show that maternal anxiety in pregnancy is associated with decreased IGF2/H19 ICR DNA methylation in progeny at birth, particularly in female, low birth weight neonates. ICR methylation may help link poor maternal mental health and adverse birth outcomes, but further investigation is needed. PMID:27023171

  14. Hydrochemistry and 18O/16O and 2H/1H Ratios of Ugandan Waters

    NASA Astrophysics Data System (ADS)

    Gebremichael, M. G.; Jasechko, S.

    2013-12-01

    Today, 70% of the 35 million people living in Uganda have access to an improved water source, ranking Uganda 148 out of 179 nations reporting in 2010 (Millennium Development Goals Indicators). 80% of Ugandans rely on groundwater as their primary drinking water source, collecting at springs or from shallow wells. Similarly, 80% of Ugandans rely upon agriculture - usually rain fed - as their primary income source. Despite lack of access to protected water sources faced by 10 million Ugandans, and the importance of the blue economy to Uganda's continued development, a country-wide investigation of the chemistry and the stable oxygen and hydrogen isotope compositions of waters has yet to be completed. Here we present 250 analyses of 18O/16O, 2H/1H and dissolved ion concentrations of Ugandan lakes, rivers, groundwaters and springs collected during July, 2013. We use the new data to characterize regional scale groundwater recharge sources, advection pathways and interactions with surface waters. Large lakes - Albert, Edward and Victoria - show increases in 18O/16O and 2H/1H ratios consistent with open water evaporation, and are shown to be distinct from nearby groundwaters, suggesting minimal recharge from large lakes to the subsurface. Salinities of eastern Ugandan groundwaters are elevated relative to samples collected from the central and western regions, suggesting that longer groundwater residence times and enhanced water-rock interactions characterize these waters. Springs from western Uganda show a shift in 18O/16O to higher values as a result of hydrothermal water-rock exchanges. Dissolved ion and noble gas concentrations show potential for use in assessing geothermal energy resources, perhaps aiding the Ugandan Ministry for Energy, Minerals and Development to meet their goal of increasing renewable energy from 4% (current) to 61% of total use by 2017 (Nyakabwa-Atwoki, 2013). Millennium Development Goals Indicators. mdgs.un.org/unsd/mdg/data.aspx Nyakabwa

  15. Equilibrium 2H/1H fractionation in organic molecules: III. Cyclic ketones and hydrocarbons

    NASA Astrophysics Data System (ADS)

    Wang, Ying; Sessions, Alex L.; Nielsen, Robert J.; Goddard, William A.

    2013-04-01

    Quantitative interpretation of stable hydrogen isotope ratios (2H/1H) in organic compounds is greatly aided by knowledge of the relevant equilibrium fractionation factors (ɛeq). Previous efforts have combined experimental measurements and hybrid Density Functional Theory (DFT) calculations to accurately predict equilibrium fractionations in linear (acyclic) organic molecules (Wang et al., 2009a,b), but the calibration produced by that study is not applicable to cyclic compounds. Here we report experimental measurements of equilibrium 2H/1H fractionation in six cyclic ketones, and use those data to evaluate DFT calculations of fractionation in diverse monocyclic and polycyclic compounds commonly found in sedimentary organic matter and petroleum. At 25, 50, and 75 °C, the experimentally measured ɛeq values for secondary and tertiary Hα in isotopic equilibrium with water are in the ranges of -130‰ to -150‰ and +10‰ to -40‰ respectively. Measured data are similar to DFT calculations of ɛeq for axial Hα but not equatorial Hα. In tertiary Cα positions with methyl substituents, this can be understood as a result of the methyl group forcing Hα atoms into a dominantly axial position. For secondary Cα positions containing both axial and equatorial Hα atoms, we propose that axial Hα exchanges with water significantly faster than the equatorial Hα does, due to the hyperconjugation-stabilized transition state. Interconversion of axial and equatorial positions via ring flipping is much faster than isotopic exchange at either position, and as a result the steady-state isotopic composition of both H's is strongly weighted toward that of axial Hα. Based on comparison with measured ɛeq values, a total uncertainty of 10-30‰ remains for theoretical ɛeq values. Using DFT, we systematically estimated the ɛeq values for individual H positions in various cyclic structures. By summing over all individual H positions, the molecular equilibrium fractionation was

  16. Reactivity of organic complexes at mineral-CO2-H2O interfaces

    NASA Astrophysics Data System (ADS)

    Miller, Q. R.; Schaef, T.; Kaszuba, J. P.; Qiu, L.; Bowden, M. E.; McGrail, B. P.

    2015-12-01

    Understanding the interactions between minerals and organics in H2O-CO2 fluids is important, as they are the two most abundant volatiles in the crust. CO2-rich fluids in natural and anthropogenic environments, such as metamorphic aureoles and carbon storage reservoirs, respectively, produce a complex geochemical setting in which CO2-rich fluids containing dissolved water and organic compounds interact with rocks and minerals. We have undertaken experimental and theoretical studies to evaluate how organics impact carbonate mineralization and to determine the partitioning behavior of organic complexes between CO2, H2O, and mineral interfaces. The first groups of experiments have clarified how the type and concentration of simple organic ligands impact the degree and type of carbonation in interfacial water films. In these experiments, salts of simple organic ligands were equilibrated with wet supercritical CO2, which was reacted with the model mineral forsterite (Mg2SiO4). The forsterite dissolution and coupled carbonate precipitation reactions were followed with time-resolved pressurized X-ray diffraction (XRD) at 50 °C and 90 bar. The extent of carbonation and the relative abundance of anhydrous magnesite (MgCO3) precipitated relative to hydrated nesquehonite (MgCO3·3H2O) was impacted by the type of organic ligand. Magnesite enhancement was observed with the trend of citrate>oxalate≈malonate>acetate>organic-free control. This indicates that the organic ligands complexed Mg2+ in the interfacial water film environment and helped alleviate kinetic barriers to magnesite formation. Additional XRD experiments with varying concentrations of citrate verified the dependence of magnesite enhancement and the degree of overall carbonation on the amount of organic present in the water film. Lastly, our ongoing work concerning the partitioning of organic and metal-organic complexes between CO2, H2O, and interfacial water films will be presented. This experimental work, which

  17. Pressure dependence of the absolute rate constant for the reaction Cl + C2H2 from 210-361 K

    NASA Technical Reports Server (NTRS)

    Brunning, J.; Stief, L. J.

    1985-01-01

    In recent years, considerable attention has been given to the role of chlorine compounds in the catalytic destruction of stratospheric ozone. However, while some reactions have been studied extensively, the kinetic data for the reaction of Cl with C2H2 is sparse with only three known determinations of the rate constant k3. The reactions involved are Cl + C2H2 yields reversibly ClC2H2(asterisk) (3a) and ClC2H2(asterisk) + M yields ClC2H2 + M (3b). In the present study, flash photolysis coupled with chlorine atomic resonance fluorescence have been employed to determine the pressure and temperature dependence of k3 with the third body M = Ar. Room temperature values are also reported for M = N2. The pressure dependence observed in the experiments confirms the expectation that the reaction involves addition of Cl to the unsaturated C2H2 molecule followed by collisional stabilization of the resulting adduct radical.

  18. Ligand-induced substrate steering and reshaping of [Ag2(H)](+) scaffold for selective CO2 extrusion from formic acid.

    PubMed

    Zavras, Athanasios; Khairallah, George N; Krstić, Marjan; Girod, Marion; Daly, Steven; Antoine, Rodolphe; Maitre, Philippe; Mulder, Roger J; Alexander, Stefanie-Ann; Bonačić-Koutecký, Vlasta; Dugourd, Philippe; O'Hair, Richard A J

    2016-01-01

    Metalloenzymes preorganize the reaction environment to steer substrate(s) along the required reaction coordinate. Here, we show that phosphine ligands selectively facilitate protonation of binuclear silver hydride cations, [LAg2(H)](+) by optimizing the geometry of the active site. This is a key step in the selective, catalysed extrusion of carbon dioxide from formic acid, HO2CH, with important applications (for example, hydrogen storage). Gas-phase ion-molecule reactions, collision-induced dissociation (CID), infrared and ultraviolet action spectroscopy and computational chemistry link structure to reactivity and mechanism. [Ag2(H)](+) and [Ph3PAg2(H)](+) react with formic acid yielding Lewis adducts, while [(Ph3P)2Ag2(H)](+) is unreactive. Using bis(diphenylphosphino)methane (dppm) reshapes the geometry of the binuclear Ag2(H)(+) scaffold, triggering reactivity towards formic acid, to produce [dppmAg2(O2CH)](+) and H2. Decarboxylation of [dppmAg2(O2CH)](+) via CID regenerates [dppmAg2(H)](+). These gas-phase insights inspired variable temperature NMR studies that show CO2 and H2 production at 70 °C from solutions containing dppm, AgBF4, NaO2CH and HO2CH. PMID:27265868

  19. Calculation of anharmonic effects in the unimolecular dissociation of M2+(H2O)2 (M = Be, Mg, and Ca)

    NASA Astrophysics Data System (ADS)

    Li, Qian; Yao, Li; Xia, Wenwen; Lin, S. H.

    2015-11-01

    The anharmonic and harmonic rate constants of the unimolecular dissociation of M2+(H2O)2 (M = Be, Mg, and Ca) were calculated using the Rice-Ramsperger-Kassel-Marcus theory. The anharmonic effects of the reactions were investigated. The results show that the energy barrier of the dissociation of Be2+(H2O)2 is 68.47 kcal/mol, and the anharmonic (T4000K = 4.28×108 s-1) and harmonic (T4000K = 4.22×108 s-1) rate constants were close in value in both the canonical and microcanonical systems. The energy barriers of the two steps for the dissociation, Mg2+(H2O)2 → MgOH++H3O+, were 37.41 and 11.39 kcal/mol, and those for the dissociation, Ca2+(H2O)2 → CaOH++H3O+, were 21.15 and 26.42 kcal/mol. The anharmonic effect of the two reactions is significant and cannot be neglected in both the canonical and microcanonical systems. The comparison also shows that the rate constants of the dissociation of Ca2+(H2O)2 have the maximum values, while those of Be2+(H2O)2 have the minimum values in the three reactions; however, the anharmonic effect also shows the similar trend in the comparison.

  20. Linking Hydrogen (δ2H) Isotopes in Feathers and Precipitation: Sources of Variance and Consequences for Assignment to Isoscapes

    PubMed Central

    Hobson, Keith A.; Van Wilgenburg, Steven L.; Wassenaar, Leonard I.; Larson, Keith

    2012-01-01

    Background Tracking small migrant organisms worldwide has been hampered by technological and recovery limitations and sampling bias inherent in exogenous markers. Naturally occurring stable isotopes of H (δ2H) in feathers provide an alternative intrinsic marker of animal origin due to the predictable spatial linkage to underlying hydrologically driven flow of H isotopes into foodwebs. This approach can assess the likelihood that a migrant animal originated from a given location(s) within a continent but requires a robust algorithm linking H isotopes in tissues of interest to an appropriate hydrological isotopic spatio-temporal pattern, such as weighted-annual rainfall. However, a number of factors contribute to or alter expected isotopic patterns in animals. We present results of an extensive investigation into taxonomic and environmental factors influencing feather δ2H patterns across North America. Principal Findings Stable isotope data were measured from 544 feathers from 40 species and 140 known locations. For δ2H, the most parsimonious model explaining 83% of the isotopic variance was found with amount-weighted growing-season precipitation δ2H, foraging substrate and migratory strategy. Conclusions/Significance This extensive H isotopic analysis of known-origin feathers of songbirds in North America and elsewhere reconfirmed the strong coupling between tissue δ2H and global hydrologic δ2H patterns, and accounting for variance associated with foraging substrate and migratory strategy, can be used in conservation and research for the purpose of assigning birds and other species to their approximate origin. PMID:22509393

  1. Ligand-induced substrate steering and reshaping of [Ag2(H)]+ scaffold for selective CO2 extrusion from formic acid

    PubMed Central

    Zavras, Athanasios; Khairallah, George N.; Krstić, Marjan; Girod, Marion; Daly, Steven; Antoine, Rodolphe; Maitre, Philippe; Mulder, Roger J.; Alexander, Stefanie-Ann; Bonačić-Koutecký, Vlasta; Dugourd, Philippe; O'Hair, Richard A. J.

    2016-01-01

    Metalloenzymes preorganize the reaction environment to steer substrate(s) along the required reaction coordinate. Here, we show that phosphine ligands selectively facilitate protonation of binuclear silver hydride cations, [LAg2(H)]+ by optimizing the geometry of the active site. This is a key step in the selective, catalysed extrusion of carbon dioxide from formic acid, HO2CH, with important applications (for example, hydrogen storage). Gas-phase ion-molecule reactions, collision-induced dissociation (CID), infrared and ultraviolet action spectroscopy and computational chemistry link structure to reactivity and mechanism. [Ag2(H)]+ and [Ph3PAg2(H)]+ react with formic acid yielding Lewis adducts, while [(Ph3P)2Ag2(H)]+ is unreactive. Using bis(diphenylphosphino)methane (dppm) reshapes the geometry of the binuclear Ag2(H)+ scaffold, triggering reactivity towards formic acid, to produce [dppmAg2(O2CH)]+ and H2. Decarboxylation of [dppmAg2(O2CH)]+ via CID regenerates [dppmAg2(H)]+. These gas-phase insights inspired variable temperature NMR studies that show CO2 and H2 production at 70 °C from solutions containing dppm, AgBF4, NaO2CH and HO2CH. PMID:27265868

  2. Preparation of hydrogenated diamond-like carbon films using high-density pulsed plasmas of Ar/C2H2 and Ne/C2H2 mixture

    NASA Astrophysics Data System (ADS)

    Kimura, Takashi; Kamata, Hikaru

    2016-07-01

    Hydrogenated diamond-like carbon films are prepared using reactive high-density pulsed plasmas of Ar/C2H2 and Ne/C2H2 mixture in the total pressure range from 0.5 to 2 Pa. The plasmas are produced using a reactive high-power impulse magnetron sputtering (HiPIMS) system. A negative pulse voltage of -500 V is applied to the substrate for a period of 15 µs in the afterglow mode. The growth rate does not strongly depend on the type of ambient gas but it markedly increases to about 2.7 µm/h at a C2H2 fraction of 10% and a total pressure of 2 Pa with increasing C2H2 fraction. The marked increase in the growth rate means that the HiPIMS system can be regarded as a plasma source for the chemical vapor deposition process. The hardness of the films prepared by Ne/C2H2 plasmas is somewhat higher than that of the films prepared by Ar/C2H2 plasmas under the same operating conditions, and the difference becomes larger as the pressure increases. The hardness of the films prepared by Ne/C2H2 plasmas ranges between 11 and 18 GPa. In the Raman spectra, two very broad overlapping bands are assigned as the G (graphite) and D (disorder) bands. The peak position of the G band is roughly independent of the total pressure, whereas the FWHM of the G peak decreases with increasing total pressure as a whole.

  3. Preparation of hydrogenated diamond-like carbon films using high-density pulsed plasmas of Ar/C2H2 and Ne/C2H2 mixture

    NASA Astrophysics Data System (ADS)

    Kimura, Takashi; Kamata, Hikaru

    2016-07-01

    Hydrogenated diamond-like carbon films are prepared using reactive high-density pulsed plasmas of Ar/C2H2 and Ne/C2H2 mixture in the total pressure range from 0.5 to 2 Pa. The plasmas are produced using a reactive high-power impulse magnetron sputtering (HiPIMS) system. A negative pulse voltage of ‑500 V is applied to the substrate for a period of 15 µs in the afterglow mode. The growth rate does not strongly depend on the type of ambient gas but it markedly increases to about 2.7 µm/h at a C2H2 fraction of 10% and a total pressure of 2 Pa with increasing C2H2 fraction. The marked increase in the growth rate means that the HiPIMS system can be regarded as a plasma source for the chemical vapor deposition process. The hardness of the films prepared by Ne/C2H2 plasmas is somewhat higher than that of the films prepared by Ar/C2H2 plasmas under the same operating conditions, and the difference becomes larger as the pressure increases. The hardness of the films prepared by Ne/C2H2 plasmas ranges between 11 and 18 GPa. In the Raman spectra, two very broad overlapping bands are assigned as the G (graphite) and D (disorder) bands. The peak position of the G band is roughly independent of the total pressure, whereas the FWHM of the G peak decreases with increasing total pressure as a whole.

  4. The H2O2-H2O Hypothesis: Extremophiles Adapted to Conditions on Mars?

    NASA Astrophysics Data System (ADS)

    Houtkooper, Joop M.; Schulze-Makuch, Dirk

    2007-08-01

    The discovery of extremophiles on Earth is a sequence of discoveries of life in environments where it had been deemed impossible a few decades ago. The next frontier may be the Martian surface environment: could life have adapted to this harsh environment? What we learned from terrestrial extremophiles is that life adapts to every available niche where energy, liquid water and organic materials are available so that in principle metabolism and propagation are possible. A feasible adaptation mechanism to the Martian surface environment would be the incorporation of a high concentration of hydrogen peroxide in the intracellular fluid of organisms. The H2O2-H2O hypothesis suggests the existence of Martian organisms that have a mixture of H2O2 and H2O instead of salty water as their intracellular liquid (Houtkooper and Schulze-Makuch, 2007). The advantages are that the freezing point is low (the eutectic freezes at 56.5°C) and that the mixture is hygroscopic. This would enable the organisms to scavenge water from the atmosphere or from the adsorbed layers of water molecules on mineral grains, with H2O2 being also a source of oxygen. Moreover, below its freezing point the H2O2-H2O mixture has the tendency to supercool. Hydrogen peroxide is not unknown to biochemistry on Earth. There are organisms for which H2O2 plays a significant role: the bombardier beetle, Brachinus crepitans, produces a 25% H2O2 solution and, when attacked by a predator, mixes it with a fluid containing hydroquinone and a catalyst, which produces an audible steam explosion and noxious fumes. Another example is Acetobacter peroxidans, which uses H2O2 in its metabolism. H2O2 plays various other roles, such as the mediation of physiological responses such as cell proliferation, differentiation, and migration. Moreover, most eukaryotic cells contain an organelle, the peroxisome, which mediates the reactions involving H2O2. Therefore it is feasible that in the course of evolution, water-based organisms

  5. Phthalocyanines of a novel structure: Dinaphthotetraazaporphyrins with D[sub 2h] symmetry

    SciTech Connect

    Kobayashi, Nagao; Ashida, Tohru; Osa, Tetsuo Tohoku Univ., Kathahira, Sendai ); Konami, Hideo

    1994-04-27

    Phthalocyanines (Pcs) are compounds in which a benzene ring is fused to each of the four pyrrole rings of tetraazaporphyrins (TAPs). In addition to traditional uses as dyes and in xerography, they are now rapidly increasing in importance in many fields such as batteries, photodynamic cancer therapy, chemical sensors, molecular metals, and liquid crystals. Two naphthalene molecule-fused tetraazaporphyrins (TAPs) with D[sub 2h] symmetry have been synthesized, and some of their spectroscopic and electrochemical properties are reported. These compounds are structural isomers of phthalocyanines (Pcs) in the sense that four benzene units are fused to the TAP skeleton. In contrast to MPcs (M = metal) with D[sub 4h] symmetry, both the Q[sub o-o] and Soret bands split into two as a result of the lowering of the molecular symmetry. Magnetic circular dichroism (MCD) shows Faraday B terms corresponding to the peaks and shoulders of the electronic absorption spectra, indicating that no degenerate state is included. The fluorescence quantum yield of the zinc complex is much smaller than in ZnPc with D[sub 4h] symmetry. The electronic absorption and electrochemical redox data of these complexes are reproduced by molecular orbital (MO) calculations within the framework of the Pariser-Parr-Pople (PPP) approximation. The results are compared with those of Pcs and mononaphtho-TAPs.

  6. Hexagonal 2H-MoSe2 broad spectrum active photocatalyst for Cr(VI) reduction

    NASA Astrophysics Data System (ADS)

    Chu, Haipeng; Liu, Xinjuan; Liu, Baibai; Zhu, Guang; Lei, Wenyan; Du, Huigang; Liu, Junying; Li, Jianwei; Li, Can; Sun, Changqing

    2016-10-01

    To make full use of the solar energy, exploring broad spectrum active photocatalysts has become one of the core issues for photocatalysis. Here we report a novel hexagonal 2H-MoSe2 photocatalyst with ultraviolet (UV)-visible-near infrared (NIR) light response for the first time. The results indicate that the MoSe2 displays excellent photo-absorption and photocatalytic activity in the reduction of Cr(VI) under UV and visible even NIR light irradiation. MoSe2 synthesized at pH value of 2 achieves the highest Cr(VI) reduction rates of 99%, 91% and 100% under UV, visible and NIR light irradiation, respectively, which should be attributed to its comparatively higher light absorption, efficient charge separation and transfer as well as relatively large number of surface active sites. The excellent broad spectrum active photocatalytic activity makes the MoSe2 to be a promising photocatalyst for the effective utilization of solar energy.

  7. Surfactant effect on persistence of oxadiazolyl 3(2H)-pyridazinones against Pseudaletia separata walker.

    PubMed

    Huang, Qingchun; Wu, Jihua; Kong, Yuping; Liu, Manhui; Cao, Song

    2007-01-01

    The photodynamic decomposition of two new insect-growth inhibitors (IGRs), 2-tert-butyl-5-[5'-aryl-2'-(1',3',4'-oxadiazolyl)methoxy]-3(2H)-pyridazinones (OPB) and its 4-chloro substituted derivative (OPC), and effect of surfactants on persistence of their bioactivity were taken into investigation. Both chemicals were significantly induced to photolysis by ultraviolet light at 365 nm wavelength and their inhibitory activities against Pseudaletia separata larvae decreased with the increasing irradiation time. However, irradiation at 254 nm wavelength didn't cause their photodegradation. Triton X-100 and Succinic-sulfonie acidic sodium but not Tween 60 possessed strong capability to slow down the decomposition and obviously prolonged the half life of OPC in laboratory and field whilst effects of the three surfactants almost did not preserve the inhibitory activity of OPB. Data suggested that electron-withdrawing halogen (-Cl) on the pi electron system in planar benzene-oxadialyl structures might reduce the efficiency of OPC on ultraviolet (UV) photoabsorption, and its hydrophobic interaction with the surfactants might be beneficial for forming stable micellar solubilization, thus sustaining the chemical's bioactivity.

  8. Experimental ion mobility measurements in Ar-C2H6 mixtures

    NASA Astrophysics Data System (ADS)

    Cortez, A. F. V.; Garcia, A. N. C.; Neves, P. N. B.; Santos, F. P.; Borges, F. I. G. M.; Barata, J. A. S.; Conde, C. A. N.

    2013-12-01

    In this paper we present the experimental results for the mobility of ions in argon-ethane gaseous mixtures (Ar-C2H6) for pressures ranging from 6 to 10 Torr and for reduced electric fields in the 10 Td to 25 Td range, at room temperature. For Ar concentrations below 80% two peaks were observed in the time of arrival spectra which were attributed to ion species with 3-carbons (C3H7+, C3H8+ and C3H9+) and with 4-carbons (which includes C4H7+, C4H9+, C4H10+ and C4H12+ ions). For Ar concentrations above 80% a third peak appears, which may belong to C5H11+. The time of arrival spectra for Ar concentrations of 80%, 85%, 90% and 95% are displayed in the present paper as well as the reduced mobilities determined from the peaks observed for a typical reduced electric field used in gaseous detectors (E/N = 15 Td).

  9. Infrared fingerprints and periodic formation of nanoparticles in Ar/C2H2 plasmas

    NASA Astrophysics Data System (ADS)

    Kovačević, Eva; Stefanović, Ilija; Berndt, Johannes; Winter, Jörg

    2003-03-01

    The formation of dust particles in argon diluted C2H2 plasmas was studied by means of Fourier transform infrared absorption spectroscopy and mass spectroscopy. The detection limit for infrared absorption was significantly improved by the use of a multipass technique. Measuring the intensity of the Rayleigh/Mie scattering of the infrared signal we found a periodicity of dust formation/vanishing (period of about 35 min in our experimental conditions). The fast disappearance of the dust from the plasma region at the end of every period is the evidence of a narrow particle size distribution, as confirmed by secondary electron micrographs of the collected powder. Characteristic infrared absorption features have their origin in absorption within the dust particles. Besides the strong presence of aliphatic hydrocarbons characteristic for amorphous hydrocarbon films, a significant amount of aromatic structures was detected. Heavy positive ions measured by ion-mass spectroscopy originate from polyacetilenic (C2nH2) and aromatic compounds. Time resolved mass spectra gave insight into the plasma response to the dust formation.

  10. Spectroscopic measurement of HO2, H2O2, and OH in the stratosphere

    NASA Technical Reports Server (NTRS)

    Park, J. H.; Carli, B.

    1991-01-01

    Stratospheric concentrations of HO2, H2O2, and OH have been retrieved simultaneously from the far-infrared emission spectra obtained with a balloon-borne Fourier transform spectrometer in June 1983 at 32 deg N latitude. Retrieved concentrations of HO2 and H2O2 are reported, along with vertical distributions of OH which were reported in an earlier paper for the afternoon, sunset, and nighttime periods for altitudes from 26 to 38 km. HO2 distributions are obtained with uncertainties that are about the same as OH for the same vertical range and for the afternoon and sunset periods. H2O2 concentration is obtained at an altitude of 30 km for the period that covers afternoon and sunset hours. The retrieved concentrations of these HO(x) species agree well with other individually measured results and the steady state photochemical predictions. The ratio HO2/OH at around 32 km seems to increase from the afternoon period to the sunset period.

  11. Optimization of electrode characteristics for the Br-2/H-2 redox flow cell

    SciTech Connect

    Tucker, MC; Cho, KT; Weber, AZ; Lin, GY; Nguyen, TV

    2014-10-17

    The Br-2/H-2 redox flow cell shows promise as a high-power, low-cost energy storage device. The effect of various aspects of material selection, processing, and assembly of electrodes on the operation, performance, and efficiency of the system is determined. In particular, (+) electrode thickness, cell compression, hydrogen pressure, and (-) electrode architecture are investigated. Increasing hydrogen pressure and depositing the (-) catalyst layer on the membrane instead of on the carbon paper backing layers have a large positive impact on performance, enabling a limiting current density above 2 A cm(-2) and a peak power density of 1.4 W cm(-2). Maximum energy efficiency of 79 % is achieved. In addition, the root cause of limiting-current behavior in this system is elucidated, where it is found that Br- reversibly adsorbs at the Pt (-) electrode for potentials exceeding a critical value, and the extent of Br- coverage is potential-dependent. This phenomenon limits maximum cell current density and must be addressed in system modeling and design. These findings are expected to lower system cost and enable higher efficiency.

  12. Synthesis and characterization of visible-active molybdenum disulfide (2H-MoS2) nanospheres

    NASA Astrophysics Data System (ADS)

    Cheah, A. J.; Chiu, W. S.; Khiew, P. S.; Radiman, S.; Hamid, M. A. A.

    2015-07-01

    In current study, a novel 2H-MoS2 nanospheres were successfully synthesized and underwent structural- as well as optical-property characterizations. The MoS2 were prepared by one pot hydrothermal approach through adopting L-cysteine as environmentally-benignchalcogenide precursor. TEM image shows that the as-synthesized MoS2 appear to be spherical in shape with size distribution in the range of 120 nm - 180 nm. HRTEM lattice-fringes imaging further elucidate that the interlayer spacing at the edges is equal to be 0.62 nm that correspond to (002) plane stacking. Also, the HRTEM image clearly-illustrate that the internal microstructure of MoS2 composed of randomly-arrayed alternating layers, which render the postulation that the formation of nanosphere is driven by self-assembly of individual layers into globular morphology. XRD diffractogram that appear to be broad and unresolved reveal the partially crystalline nature of the sample. Optical-absorption spectra depicts the sample is visible active with featureless absorption, which can attribute to indirect transition of the excitions generated. By using Tauc plot, the bandgap energy is determined to be 1.75 eV, which reflect the nanospheres are indeed visible-active nanostructures.

  13. Isomerization, Perturbations, Calculations and the S_{1} State of C_{2}H_{2}

    NASA Astrophysics Data System (ADS)

    Baraban, J. H.; Changala, P. B.; Berk, J. R. P.; Field, R. W.; Stanton, J. F.; Merer, A. J.

    2013-06-01

    Preliminary analysis of the energy region of the cis-trans isomerization transition state on the S_{1} surface of C_{2}H_{2} has revealed novel patterns and surprising perturbations, including unusually large (and high-order) anharmonicities, as well as K-staggerings of several vibrational levels. These effects complicate the analysis considerably, and require new models and calculations to account for and predict features of the observed spectra. The ˜{A}-˜{X} spectrum of acetylene has been studied both experimentally and theoretically for almost a century, and this cycle of unexpected phenomena eliciting innovative responses is found throughout its history. Especially in the last ten years, progress in understanding the S_{1} state rovibrational level structure and cis-trans isomerization has been accelerated by combining the information available from both ab initio computation and spectroscopic observations. The resulting dialogue has then frequently suggested fruitful avenues for further experiments and calculations. Current challenges and recent results in understanding the cis-trans isomerization transition state region will be discussed in this context.

  14. Particle-in-Cell Simulations of Atmospheric Pressure He/2%H2O Discharges

    NASA Astrophysics Data System (ADS)

    Kawamura, E.; Lieberman, M. A.; Lichtenberg, A. J.; Graves, D. B.; Gopalakrishnan, R.

    2015-09-01

    Atmospheric pressure micro-discharges in contact with liquid surfaces are of increasing interest, especially in the bio-medical field. We conduct 1D3v particle-in-cell (PIC) simulations of a voltage-driven 1 mm width atmospheric pressure He/2% H2O plasma discharge in series with an 0.5 mm width liquid H2O layer and a 1mm width quartz dielectric layer. A previously developed two-temperature hybrid global model of atmospheric pressure He/H2O discharges was used to determine the most important species and collisional reactions to use in the PIC simulations. We found that H13O6+, H5O3-, and electrons were the most prominent charged species, while most of the metastable helium He* was quenched via Penning ionization. The ion-induced secondary emission coefficient γi was assumed to be 0.15 at all surfaces. A series of simulations were conducted at 27.12 MHz with Jrf ~ 800-2200 A/m2. The H2O rotational and vibrational excitation losses were so high that electrons reached the walls at thermal temperatures. We also simulated a much lower frequency case of 50 kHz with Vrf = 10 kV. In this case, the discharge ran in a pure time-varying γ-mode. This work was supported by the Department of Energy Office of Fusion Energy Science Contract DE-SC0001939.

  15. Supramolecular order and structural dynamics: A STM study of 2H-tetraphenylporphycene on Cu(111)

    SciTech Connect

    Stark, Michael; Träg, Johannes; Ditze, Stefanie; Steinrück, Hans-Peter; Marbach, Hubertus; Brenner, Wolfgang; Jux, Norbert

    2015-03-14

    The adsorption of 2H-tetraphenylporphycene (2HTPPc) on Cu(111) was investigated by scanning tunneling microscopy (STM). At medium coverages, supramolecular ordered islands are observed. The individual 2HTPPc molecules appear as two pairs of intense protrusions which are separated by an elongated depression. In the islands, the molecules are organized in rows oriented along one of the close packed Cu(111) substrate rows; the structure is stabilized by T-type interactions of the phenyl substituents of neighboring molecules. Two types of rows are observed, namely, highly ordered rows in which all molecules exhibit the same orientation, and less ordered rows in which the molecules exhibit two perpendicular orientations. Altogether, three different azimuthal orientations of 2HTPPc are observed within one domain, all of them rotated by 15° ± 1° relative to one closed packed Cu direction. The highly ordered rows are always separated by either one or two less ordered rows, with the latter structure being the thermodynamically more stable one. The situation in the islands is highly dynamic, such that molecules in the less ordered rows occasionally change orientation, also complete highly ordered rows can move. The supramolecular order and structural dynamics are discussed on the basis of the specific molecule-substrate and molecule-molecule interactions.

  16. High pressure-temperature Raman spectroscopy of H2-H2O clathrate.

    NASA Astrophysics Data System (ADS)

    Somayazulu, Maddury; Levedahl, Alexander; Goncharov, Alexander; Mao, Ho-Kwang; Hemley, Russell

    2007-03-01

    The melting curve of the C2 clathrate H2-H2O has been determined by in-situ Raman spectroscopy measurements in an externally heated diamond anvil cell. We have determined the melting curve to a maximum pressure of 27 GPa. These are the first measurements on the melting line in this clathrate. Depending on the stoichiometry of the starting mixture of H2 and H2O, we are able to study either a mixture of C2 and H2O or C2 and H2. In either case, we were able to pinpoint the melting of the clathrate from the measurements of the molecular stretching mode (vibron) in the clathrate. In the case of C2 + Ice VII, we observe the vibron in the clathrate at a frequency higher than in pure H2 at the same pressure. We have cross-calibrated the melting temperatures using the Stokes-anti Stokes ratio of the diamond first order and Raman active TO phonon of cubic Boron Nitride. We find that the clathrate melts well above the H2 melting at all pressures studied indicating that the stabilization of this clathrate at high pressures is indeed due to interactions between the host and guest molecules.

  17. Cold denaturation and sup 2 H sub 2 O stabilization of a staphylococcal nuclease mutant

    SciTech Connect

    Antonino, L.C.; Nakano, Takayuki; Fink, A.L. ); Kautz, R.A.; Fox, R.O. )

    1991-09-01

    Cold denaturation is now recognized as a general property of proteins but has been observed only under destabilizing conditions, such as moderate denaturant concentration of low pH. By destabilizing the protein using site-directed mutagenesis, the authors have observed cold denaturation at pH 7.0 in the absence of denaturants in a mutant of staphylococcal nuclease, which the authors call NCA S28G for a hybrid protein between staphylococcal nuclease and concanavalin A in which there is the point mutation Ser-28{yields}Gly. The temperature of maximum stability (t{sub max}) as determined by circular dichroism (CD) was 18.1C, and the midpoints of the thermal unfolding transitions (t{sub m}) were 0.6C and 30.0C. These values may be compared with the t{sub m} of 52.5C for wild-type staphylococcal nuclease, for which no cold denaturation was observed under these conditions. When the stability of the mutant was examined in {sup 2}H{sub 2}O by NMR, CD, or fluorescence, a substantial increase in the amount of folded protein at the t{sub max} was noted as well as a decrease in t{sub max}, reflecting increased stability.

  18. Hexagonal 2H-MoSe2 broad spectrum active photocatalyst for Cr(VI) reduction

    PubMed Central

    Chu, Haipeng; Liu, Xinjuan; Liu, Baibai; Zhu, Guang; Lei, Wenyan; Du, Huigang; Liu, Junying; Li, Jianwei; Li, Can; Sun, Changqing

    2016-01-01

    To make full use of the solar energy, exploring broad spectrum active photocatalysts has become one of the core issues for photocatalysis. Here we report a novel hexagonal 2H-MoSe2 photocatalyst with ultraviolet (UV)-visible-near infrared (NIR) light response for the first time. The results indicate that the MoSe2 displays excellent photo-absorption and photocatalytic activity in the reduction of Cr(VI) under UV and visible even NIR light irradiation. MoSe2 synthesized at pH value of 2 achieves the highest Cr(VI) reduction rates of 99%, 91% and 100% under UV, visible and NIR light irradiation, respectively, which should be attributed to its comparatively higher light absorption, efficient charge separation and transfer as well as relatively large number of surface active sites. The excellent broad spectrum active photocatalytic activity makes the MoSe2 to be a promising photocatalyst for the effective utilization of solar energy. PMID:27734974

  19. Synthesis, structure and NMR characterization of a new monomeric aluminophosphate [ dl-Co(en) 3] 2[Al(HPO 4) 2(H 1.5PO 4) 2(H 2PO 4) 2](H 3PO 4) 4 containing four different types of monophosphates

    NASA Astrophysics Data System (ADS)

    Chen, Peng; Li, Jiyang; Xu, Jun; Duan, Fangzheng; Deng, Feng; Xu, Ruren

    2009-03-01

    A new zero-dimensional (0D) aluminophosphate monomer [ dl-Co(en) 3] 2[Al(HPO 4) 2(H 1.5PO 4) 2(H 2PO 4) 2](H 3PO 4) 4 (designated AlPO-CJ38) with Al/P ratio of 1/6 has been solvothermally prepared by using racemic cobalt complex dl-Co(en) 3Cl 3 as the template. The Al atom is octahedrally linked to six P atoms via bridging oxygen atoms, forming a unique [Al(HPO 4) 2(H 1.5PO 4) 2(H 2PO 4) 2] 6- monomer. Notably, there exists intramolecular symmetrical O⋯H⋯O bonds, which results in pseudo-4-rings stabilized by the strong H-bonding interactions. The structure is also featured by the existence of four different types of monophosphates that have been confirmed by 31P NMR and 1H NMR spectra. The crystal data are as follows: AlPO-CJ38, [ dl-Co(en) 3] 2[Al(HPO 4) 2(H 1.5PO 4) 2(H 2PO 4) 2](H 3PO 4) 4, M = 1476.33, monoclinic, C2/ c (No. 15), a = 36.028(7) Å, b = 8.9877(18) Å, c = 16.006(3) Å, β = 100.68(3)°, U = 5093.2(18) Å 3,Z = 4, R1 = 0.0509 ( I > 2 σ( I)) and wR2 = 0.1074 (all data). CCDC number 689491.

  20. Preparation of hydrogen from water by reduction with lithium aluminium hydride for the analysis of delta(2)H by isotope ratio mass spectrometry.

    PubMed

    Ward, S; Scantlebury, M; Król, E; Thomson, P J; Sparling, C; Speakman, J R

    2000-01-01

    An off-line technique is described for the preparation of H(2) from water prior to analysis of delta(2)H by dual-inlet isotope ratio mass spectrometry. H(2) is produced from sample water by reaction with LiAlH(4). This provides a rapid and inexpensive method for the analysis of delta(2)H in small (10 microL) samples of water. Precision was +/- 4.2 to 8.0 (1sigma(n), n = 8) delta(2)H(VSMOW) for samples between 428 and 1500 delta(2)H(VSMOW), +/- 14.5 delta(2)H(VSMOW) for water enriched to 3750 delta(2)H(VSMOW) and +/- 26.0 delta(2)H(VSMOW) for water enriched to 6100 delta(2)H(VSMOW). Accuracy was +/- 1.1 to 4.2 delta(2)H(VSMOW) for water standards from natural abundance to 1000 delta(2)H(VSMOW) (the highest enrichment at which water of accepted delta(2)H is currently available). This method for delta(2)H determination is most appropriate for use with small (<50 microL) samples of high delta(2)H enrichment such as those produced from doubly labelled water studies of small animals. The levels of measurement precision of delta(2)H would contribute 2.6-3.8% to the precision error in estimates of small animal energy expenditure made using the doubly labelled water technique when duplicate analyses are performed. PMID:10717654

  1. 2H2O incorporation into hepatic acetyl-CoA and de novo lipogenesis as measured by Krebs cycle-mediated 2H-enrichment of glutamate and glutamine.

    PubMed

    Silva, Ana Maria; Martins, Fatima; Jones, John G; Carvalho, Rui

    2011-12-01

    Deuterated water is widely used for measuring de novo lipogenesis on the basis of quantifying lipid (2)H-enrichment relative to that of body water. However, incorporation of (2)H-enrichment from body water into newly synthesized lipid molecules is incomplete therefore the true lipid precursor enrichment differs from that of body water. We describe a novel measurement of de novo lipogenesis that is based on a true precursor-product analysis of hepatic acetyl-CoA and triglyceride methyl enrichments from deuterated water. After deuterated water administration to seven in situ and seven perfused livers, acetyl-CoA methyl enrichment was inferred from (2)H nuclear magnetic resonance analysis of hepatic glutamate/glutamine (Glx) enrichment and triglyceride methyl enrichment was directly determined by (2)H nuclear magnetic resonance of triglycerides. Acetyl-CoA (2) H-enrichment was 71% ± 1% that of body water for in situ livers and 53% ± 2% of perfusate water for perfused livers. From the ratio of triglyceride-methyl/acetyl-CoA enrichments, fractional de novo lipogenesis rates of 0.97% ± 0.09%/2 hr and 7.92% ± 1.47%/48 hr were obtained for perfused and in situ liver triglycerides, respectively. Our method reveals that acetyl-CoA enrichment is significantly less than body water both for in situ and perfused livers. Furthermore, the difference between acetyl-CoA and body water enrichments is sensitive to the experimental setting.

  2. The composition of Saturn's atmosphere at northern temperate latitudes from Voyager IRIS spectra - NH3, PH3, C2H2, C2H6, CH3D, CH4, and the Saturnian D/H isotopic ratio

    NASA Technical Reports Server (NTRS)

    Courtin, R.; Gautier, D.; Marten, A.; Bezard, B.; Hanel, R.

    1984-01-01

    The vertical distributions and mixing ratios of minor constituents in the northern hemisphere of Saturn are investigated. Results are obtained for NH3, PH3, C2H2, C2H6, CH3D, and CH4; the D/H ratio is obtained from the CH4 and CH3D abundances. The NH3 mixing ratio in the upper atmosphere is found to be compatible with the saturated partial pressure. The inferred PH3/H2 ratio of 1.4 + or - 0.8 x 10 to the -6th is higher than the value derived from the solar P/H ratio. The stratospheric C2H2/H2 and C2H6/H2 ratios are, respectively, 2.1 + or - 1.4 x 10 to the -7th and 3.0 + or - 1.1 x 10 to the -6th; the latter decreases sharply below the 20-50 mbar level. The results for CH3D/H2 and CH4/H2 imply an enrichment of Saturn's upper atmosphere in carbon by a factor of at least three over the solar abundance. The interpretation of two NH3 lines in the five-micron window suggests a NH3/H2 ratio at the two bar level below the solar value.

  3. Photoion-pair formation and photoelectron-induced dissociative attachment in C2H2: D0(HCC-H)

    NASA Astrophysics Data System (ADS)

    Ruscic, B.; Berkowitz, J.

    1990-10-01

    The formation of C2H- is observed in two broad resonance bands when C2H2 is irradiated with vuv light. The higher-energy band has partially resolved structure, approximately linear pressure dependence, and a threshold at 16.335±0.021 eV. It is attributed to photoion-pair formation (C2H-+H+) consequent upon predissociation of one or more Rydberg states. This threshold, together with IP(H) and EA(C2H), gives D0(HCC-H)≤5.706±0.022 eV≡131.6±0.5 kcal/mol, or ΔH0f0 (C2H)≤134.5±0.5 kcal/mol. The lower-energy band has an approximately quadratic pressure dependence and curved step-like structure. It is attributed to photoelectron-induced dissociative attachment mediated by a πg shape resonance. The threshold, at 878.5±2.0 Å, corresponds to a photoelectron energy of 2.715±0.032 eV. This threshold combined with EA(C2H)=2.969±0.010 eV, yields D0(HCC-H)≤5.684±0.033 eV≡131.1±0.7 kcal/mol, or ΔH0f0 (C2H)=134.0±0.7 kcal/mol.

  4. The generation of HCl in the system CaCl2-H2O: Vapor-liquid relations from 380-500°C

    USGS Publications Warehouse

    Bischoff, James L.; Rosenbauer, Robert J.; Fournier, Robert O.

    1996-01-01

    We determined vapor-liquid relations (P-T-x) and derived critical parameters for the system CaCl2-H2O from 380-500??C. Results show that the two-phase region of this system is extremely large and occupies a significant portion of the P-T space to which circulation of fluids in the Earth's crust is constrained. Results also show the system generates significant amounts of HCl (as much as 0.1 mol/kg) in the vapor phase buffered by the liquid at surprisingly high pressures (???230 bars at 380??C, <580 bars at 500??C), presumably by hydrolysis of CaCl2: CaCl2 + 2H2O = Ca(OH)2 + 2HCl. We interpret the abundance of HCl in the vapor as due to its preference for the vapor phase, and by the preference of Ca(OH)2 for either the liquid phase or solid. The recent recognition of the abundance of CaCl2 in deep brines of the Earth's crust and their hydrothermal mobilization makes the hydrolysis of CaCl2 geologically important. The boiling of Ca-rich brines produces abundant HCl buffered by the presence of the liquid at moderate pressures. The resultant Ca(OH)2 generated by this process reacts with silicates to form a variety of alteration products, such as epidote, whereas the vapor produces acid-alteration of rocks through which it ascends.

  5. PRECISE THz MEASUREMENTS OF HCO{sup +}, N{sub 2}H{sup +}, AND CF{sup +} FOR ASTROPHYSICAL OBSERVATIONS

    SciTech Connect

    Cazzoli, Gabriele; Cludi, Lino; Puzzarini, Cristina; Buffa, Giovanni

    2012-11-15

    Ground-state rotational spectra of HCO{sup +}, N{sub 2}H{sup +}, and CF{sup +} (both {sup 12}C- and {sup 13}C-containing isotopologues) have been recorded in the 1.0-1.6 THz frequency range. Present measurements allowed us to improve the spectroscopic parameters, which in turn enabled the prediction of rotational transitions up to 2.0-2.5 THz with good accuracy. We therefore consider the present results to be of great value in view of the extended spectral coverage made available by the Herschel Space Observatory, Stratospheric Observatory for Infrared Astronomy, and the Atacama Large Millimeter Array. Furthermore, we re-investigated the ground-state rotational spectrum of N{sub 2}H{sup +} in the 93-750 GHz frequency range, thus addressing the open issue of the frequency of the J = 1 <- 0 transition as well as resolving the hyperfine structure of the J + 1 <- J transitions with J = 1, 2, and 3 for the first time.

  6. Effects of pH and cholesterol on DMPA membranes: a solid state 2H- and 31P-NMR study.

    PubMed Central

    Pott, T; Maillet, J C; Dufourc, E J

    1995-01-01

    The effect of pH and cholesterol on the dimyristoylphosphatidic acid (DMPA) model membrane system has been investigated by solid state 2H- and 31P-NMR. It has been shown that each of the three protonation states of the DMPA molecule corresponds to a 31P-NMR powder pattern with characteristic delta sigma values; this implies additionally that the proton exchange on the membrane surface is slow on the NMR time scale (millisecond range). Under these conditions, the 2H-labeled lipid chains sense only one magnetic environment, indicating that the three spectra detected by 31P-NMR are related to charge-dependent local dynamics or orientations of the phosphate headgroup or both. Chain ordering in the fluid phase is also found to depend weakly on the charge at the interface. In addition, it has also been found that the first pK of the DMPA membrane is modified by changes in the lipid lateral packing (gel or fluid phases or in the presence of cholesterol) in contrast to the second pK. The incorporation of 30 mol% cholesterol affects the phosphatidic acid bilayer in a way similar to what has been reported for phosphatidylcholine/cholesterol membranes, but to an extent comparable to 10-20 mol % sterol in phosphatidylcholines. However, the orientation and molecular order parameter of cholesterol in DMPA are similar to those found in dimyristoylphosphatidylcholine. PMID:8580333

  7. Fast Response, vertically oriented graphene nanosheet electric double layer capacitors synthesized from C(2)H(2).

    PubMed

    Cai, Minzhen; Outlaw, Ronald A; Quinlan, Ronald A; Premathilake, Dilshan; Butler, Sue M; Miller, John R

    2014-06-24

    The growth and electrical characteristics of vertically oriented graphene nanosheets grown by radio frequency plasma-enhanced chemical vapor deposition from C2H2 feedstock on nickel substrates and used as electrodes in symmetric electric double layer capacitors (EDLC) are presented. The nanosheets exhibited 2.7 times faster growth rate and much greater specific capacitance for a given growth time than CH4 synthesized films. Raman spectra showed that the intensity ratio of the D band to G band versus temperature initially decreased to a minimum value of 0.45 at a growth temperature of 750 °C, but increased rapidly with further temperature increase (1.15 at 850 °C). The AC specific capacitance at 120 Hz of these EDLC devices increased in a linear fashion with growth temperature, up to 265 μF/cm(2) (2 μm high film, 850 °C with 10 min growth). These devices exhibited ultrafast frequency response: the frequency response at -45° phase angle reached over 20 kHz. Consistent with the increase in D band to G band ratio, the morphology of the films became less vertical, less crystalline, and disordered at substrate temperatures of 800 °C and above. This deterioration in morphology resulted in an increase in graphene surface area and defect density, which, in turn, contributed to the increased capacitance, as well as a slight decrease in frequency response. The low equivalent series resistance varied from 0.07 to 0.08 Ω and was attributed to the significant carbon incorporation into the Ni substrate. PMID:24797018

  8. Full Dimensional Rovibrational Variational Calculations of the S_1 State of C_2H_2

    NASA Astrophysics Data System (ADS)

    Changala, Bryan; Baraban, Joshua H.; Stanton, John F.

    2015-06-01

    Rovibrational variational calculations on global potential energy surfaces are often essential for investigating large amplitude vibrational motion and isomerization between multiple stable conformers, as well as for understanding the spectroscopic signatures of such dynamics. The efficient and accurate representation of high dimensional potential energy surfaces and the diagonalization of large rovibrational Hamiltonians make these calculations a technically non-trivial task. The first excited singlet electronic state of acetylene (C_2H_2) is an ideal model isomerizing system. The S_1 state supports both a trans conformer and a higher energy cis conformer (Tecis-Tetrans ≈ 2700 wn), separated by a planar near-half-linear transition state (TeTS-Tetrans ≈ 5000 wn). The low-energy structure of the trans well is complicated by strong Coriolis and Darling-Dennison interactions between the near-resonant torsion and asymmetric bending modes. The resulting polyad patterns are eventually broken as the internal vibrational energy approaches that of the barrier to isomerization. In this region, qualitatively new spectroscopic patterns emerge, such as rotational K-staggering and vibrational effective frequency dips. We examine these effects with an efficient ab initio variational treatment. Our global potential energy surface is constructed as a hybrid of a high-level reduced dimension surface, which excludes the two rCH bond lengths, and a lower-level full dimensional surface incorporating the effects of rtext{CH} displacement. Diagonalization of the large, sparse Hamiltonian, which contains an exact internal coordinate rovibrational kinetic energy operator, is achieved with an efficient restarted Lanczos algorithm that generates variational energies and wavefunctions. We discuss how our results elucidate the S_1 state's rich variety of spectroscopic features and the insights they provide into the isomerization process.

  9. The 2H(e, e' p)n reaction at large energy transfers

    NASA Astrophysics Data System (ADS)

    Willering, Hendrik Willem

    2003-04-01

    At the ELSA accelerator facillity in Bonn, Germany, we have measured the deutron breakup reaction 2H(e, e' p)n at four-momentum transfers around Q2 = -0 .20(GeV/c)2 with an electron beam energy of E0 = 1.6 GeV. The cross section has been determined for energy transfers extending from the quasielastic region to just below the Delta(1232)-resonance, and for proton polar angles up to Thetanp = 145 o in the center-of-momentum system. This angular range represents missing momenta up to pm = 1000 MeV/c. By detecting the scattered protons in two segmented 3 3 m2 scintillator time-of-flight detectors, we have covered a considerable part of the out-of-plane region. The clearly visible variation of the cross section with the proton azimuthal angle fnp has enabled us to extract values for the longitudinal-transverse interference form factor fLT and for a combination of the non-interference form factors fL and fT for proton angles up to Thetanp = 40o in the center-of-momentum system. The experimental results have been compared to the full model calculations by Arenhövel et al. For the major part of our kinematical range the shape of the cross section and of the form factors is reproduced by the model, but some differences remain in the normalization, especially at higher energy transfers. Our results corroborate the conclusions from other recent experiments concerning the importance of subnuclear degrees-of-freedom beyond the quasielastic region, but the discrepancy indicates that the model can still be improved

  10. Dilution space ratio of 2H and 18O of doubly labeled water method in humans.

    PubMed

    Sagayama, Hiroyuki; Yamada, Yosuke; Racine, Natalie M; Shriver, Timothy C; Schoeller, Dale A

    2016-06-01

    Variation of the dilution space ratio (Nd/No) between deuterium ((2)H) and oxygen-18 ((18)O) impacts the calculation of total energy expenditure (TEE) by doubly labeled water (DLW). Our aim was to examine the physiological and methodological sources of variation of Nd/No in humans. We analyzed data from 2,297 humans (0.25-89 yr old). This included the variables Nd/No, total body water, TEE, body mass index (BMI), and percent body fat (%fat). To differentiate between physiologic and methodologic sources of variation, the urine samples from 54 subjects were divided and blinded and analyzed separately, and repeated DLW dosing was performed in an additional 55 participants after 6 mo. Sex, BMI, and %fat did not significantly affect Nd/No, for which the interindividual SD was 0.017. The measurement error from the duplicate urine sample sets was 0.010, and intraindividual SD of Nd/No in repeats experiments was 0.013. An additional SD of 0.008 was contributed by calibration of the DLW dose water. The variation of measured Nd/No in humans was distributed within a small range and measurement error accounted for 68% of this variation. There was no evidence that Nd/No differed with respect to sex, BMI, and age between 1 and 80 yr, and thus use of a constant value is suggested to minimize the effect of stable isotope analysis error on calculation of TEE in the DLW studies in humans. Based on a review of 103 publications, the average dilution space ratio is 1.036 for individuals between 1 and 80 yr of age. PMID:26989221

  11. Fast Response, vertically oriented graphene nanosheet electric double layer capacitors synthesized from C(2)H(2).

    PubMed

    Cai, Minzhen; Outlaw, Ronald A; Quinlan, Ronald A; Premathilake, Dilshan; Butler, Sue M; Miller, John R

    2014-06-24

    The growth and electrical characteristics of vertically oriented graphene nanosheets grown by radio frequency plasma-enhanced chemical vapor deposition from C2H2 feedstock on nickel substrates and used as electrodes in symmetric electric double layer capacitors (EDLC) are presented. The nanosheets exhibited 2.7 times faster growth rate and much greater specific capacitance for a given growth time than CH4 synthesized films. Raman spectra showed that the intensity ratio of the D band to G band versus temperature initially decreased to a minimum value of 0.45 at a growth temperature of 750 °C, but increased rapidly with further temperature increase (1.15 at 850 °C). The AC specific capacitance at 120 Hz of these EDLC devices increased in a linear fashion with growth temperature, up to 265 μF/cm(2) (2 μm high film, 850 °C with 10 min growth). These devices exhibited ultrafast frequency response: the frequency response at -45° phase angle reached over 20 kHz. Consistent with the increase in D band to G band ratio, the morphology of the films became less vertical, less crystalline, and disordered at substrate temperatures of 800 °C and above. This deterioration in morphology resulted in an increase in graphene surface area and defect density, which, in turn, contributed to the increased capacitance, as well as a slight decrease in frequency response. The low equivalent series resistance varied from 0.07 to 0.08 Ω and was attributed to the significant carbon incorporation into the Ni substrate.

  12. Meridional Mapping of Ethane (C2H6) Infrared Emission from Saturn's Southern (Summer) Stratosphere

    NASA Astrophysics Data System (ADS)

    Livengood, T. A.; Kostiuk, T.; Sonnabend, G.; Romani, P. N.; Fast, K. E.; Hewagama, T.; Annen, J. N.; Buhl, D.

    2004-11-01

    Thermally-excited infrared emission from ethane (C2H6), formed in Saturn's southern (summer) stratosphere, was observed in February 2004 using line-resolved spectroscopy. Measured spectra were acquired at 15o intervals along Saturn's East limb, from 15o - 90o south at longitude offset from the central meridian selected to obtain a uniform viewing angle of 64o. Additional spectra were acquired on Saturn's southern auroral zone near the limb and at the central meridian, at ≈ 78oS latitude, testing for the presence at millibar pressures of zonal wind driven by ionospheric currents, as recently reported by Stallard et al. (Icarus 167, 204--211, 2004) for the nanobar-to-microbar pressure regime. The observations were conducted using the Goddard Space Flight Center Heterodyne Instrument for Planetary Wind And Composition (HIPWAC) at the NASA Infrared Telescope Facility on Mauna Kea, Hawaii. The spectrum obtained from the HIPWAC optical front-end was measured and recorded independently using an RF filter-bank system to obtain resolving power λ /Δ λ = 1-5 × 106 and by an acousto-optic spectrometer (AOS) system to obtain resolving power λ /Δ λ = 25 × 106, at 11.744 μm and at 11.816 μm wavelength. The detailed lineshape and the ratio of strong and weak line features separately constrain the temperature and ethane mole fraction within the region of line formation. These measurements complement the Cassini CIRS observation program for Saturn, which will have much higher spatial resolution and spectral bandwidth but much lower spectral resolving power than the present observations. These observations are part of an on-going program observing seasonal change in Saturn's stratosphere since 1989. This work was supported by the NASA Planetary Astronomy Program.

  13. Structures of the Phosphorylated and VO3-bound 2H-Phosphatase Domain of Sts-2

    SciTech Connect

    Chen, Y.; Jakoncic, J.; Parker, K.A.; Carpino, N; Nassar, N.

    2009-09-23

    The C-terminal domain of the suppressor of T cell receptor (TCR) signaling 1 and 2 (Sts-1 and -2) proteins has homology to the 2H-phosphatase family of enzymes. The phosphatase activity of the correspondent Sts-1 domain, Sts-1{sub PGM}, is key for its ability to negatively regulate the signaling of membrane-bound receptors including TCR and the epidermal growth factor receptor (EGFR). A nucleophilic histidine, which is transiently phosphorylated during the phosphatase reaction, is essential for the activity. Here, we present the crystal structure of Sts-2{sub PGM} in the phosphorylated active form and bound to VO{sub 3}, which represent structures of an intermediate and of a transition state analogue along the path of the dephosphorylation reaction. In the former structure, the proposed nucleophilic His366 is the only phoshorylated residue and is stabilized by several interactions with conserved basic residues within the active site. In the latter structure, the vanadium atom sits in the middle of a trigonal bipyramid formed by the three oxygen atoms of the VO{sub 3} molecule, atom NE2 of His366, and an apical water molecule Wa. The V-NE2 bond length (2.25 {angstrom}) suggests that VO{sub 3} is not covalently attached to His366 and that the reaction mechanism is partially associative. The two structures also suggest a role for Glu476 in activating a uniquely positioned water molecule. In both structures, the conformation of the active site is remarkably similar to the one seen in apo-Sts-2{sub PGM} suggesting that the spatial arrangement of the catalytic residues does not change during the dephosphorylation reaction.

  14. Long path monitoring of tropospheric O3, NO2, H2CO and SO2

    NASA Technical Reports Server (NTRS)

    Vandaele, A. C.; Carleer, M.; Colin, R.; Simon, P. C.

    1994-01-01

    Concentrations of tropospheric O3, NO2, H2CO, and SO2 have been measured on the Campus of the 'Universite Libre de Bruxelles' on a routine basis since October 1990. The long path system consists of a source lamp, a first 30 cm f/8 Cassegrain type telescope which collimates the light onto a slightly parabolic mirror placed on the roof of a building situated 394 m away from the laboratory. The light is sent back into a second 30 cm Cassegrain telescope. This telescope has been modified so that the output beam is a 5 cm diameter parallel beam. This beam is then focused onto the entrance aperture of the BRUKER IFS120HR fourier transform spectrometer. The two telescopes are mounted on alignment devices and the external mirror is equipped with a driving system operated from the laboratory. The choice of the light source (either a 1000 W high pressure 'ozone free' xenon lamp or a 250 W tungsten filament) and of the detector (either a solar blind UV-diode or a silicon diode) depended on the spectral region studied. These regions lie respectively from 26,000 cm(exp -1) to 30,000 cm(exp -1) (260-380 nm) and from 14,000 cm(exp -1) to 30,000 cm(exp -1) (330-700 nm). The spectra have been recorded at the resolution of 16 cm(exp -1) and with a dispersion of 7.7 cm(exp -1). They have been measured during the forward and the backward movements of the mobile mirror, in double sided mode; each spectrum is an average of 2000 scans. The time required to record a spectrum is about 45 minutes. The shape of the raw spectra in the two investigated regions are represented.

  15. Theoretical study of electronic and tribological properties of h-BNC2/graphene, h-BNC2/h-BN and h-BNC2/h-BNC2 bilayers.

    PubMed

    Ansari, Narjes; Nazari, Fariba; Illas, Francesc

    2015-05-21

    Density functional theory based methods are used to investigate the interlayer sliding energy landscape (ISEL), binding energy and interlayer spacing between h-BNC2/graphene (I), h-BNC2/h-BN (II) and h-BNC2/h-BNC2 (III) bilayer structures for three, six and fourteen different stacking patterns, respectively. Our results show that, in the studied cases, increasing the atomic variety of the ingredient monolayers leads to an ISEL corrugation increase as well. For the studied bilayers the ISEL is obtained by means of the registry index. For sufficiently large flakes of h-BNC2 on graphene sheets with the largest incommensurability and the least monolayer anisotropy, a robust superlubricity occurs regardless of the relative interlayer orientation. On the other hand, for the h-BNC2/h-BNC2 bilayer exhibiting the least incommensurability and the most monolayer anisotropy, the occurrence of robust superlubricity depends on the relative interlayer orientation.

  16. Solid-liquid phase equilibria at 50 and 75°C in the NaCl + MgCl2 + H2O system and the pitzer model representations

    NASA Astrophysics Data System (ADS)

    Yang, Ji-min; Zhang, Rui-zhi; Liu, Hong; Ma, Si-hong

    2013-12-01

    The solubilities in the NaCl-MgCl2-H2O system were determined at 50 and 75°C and the phase diagrams were constructed on the base of experimental data. One invariant point, two univariant curves, and two crystallization zones, corresponding to sodium chloride and dihydrate (MgCl2 · 6H2O) showed up in the phase diagrams of the ternary system, The mixing parameters θNa,Mg and ΨNa,Mg, Cl and equilibrium constant K sp were evaluated in NaCl-MgCl2-H2O system by least-squares optimization procedure, in which the single-salt Pitzer parameters of NaCl and MgCl2β(0), β(1), and C φ were directly calculated from the literature. The results obtained were in good agreement with the experimental data.

  17. Revisiting Mt. Kilimanjaro: Do n-alkane biomarkers in soils reflect the δ2H isotopic composition of precipitation?

    NASA Astrophysics Data System (ADS)

    Zech, M.; Zech, R.; Rozanski, K.; Hemp, A.; Gleixner, G.; Zech, W.

    2014-06-01

    During the last decade compound-specific deuterium (δ2H) analysis of plant leaf wax-derived n-alkanes has become a promising and popular tool in paleoclimate research. This is based on the widely accepted assumption that n-alkanes in soils and sediments generally reflect δ2H of precipitation (δ2Hprec). Recently, several authors suggested that δ2H of n-alkanes (δ2H,sub>n-alkanes) can also be used as proxy in paleoaltimetry studies. Here we present results from a δ2H transect study (~1500 to 4000 m a.s.l.) carried out on precipitation and soil samples taken from the humid southern slopes of Mt. Kilimanjaro. Contrary to earlier suggestions, a distinct altitude effect in δ2Hprec is present above ~2000 m a.s.l., i.e. δ2Hprec values become more negative with increasing altitude. The compound-specific δ2H values of nC27 and nC29 do not confirm this altitudinal trend, but rather become more positive both in the O-layers (organic layers) and the Ah-horizons (mineral topsoils). Although our δ2Hn-alkane results are in agreement with previously published results from the southern slopes of Mt. Kilimanjaro (Peterse et al., 2009, BG, 6, 2799-2807), a major re-interpretation is required given that the δ2Hn-alkane results do not reflect the δ2Hprec results. The theoretical framework for this re-interpretation is based on the evaporative isotopic enrichment of leaf water associated with transpiration process. Modelling results show that relative humidity, decreasing considerably along the southern slopes of Mt. Kilimanjaro (from 78% at ~ 2000 m a.s.l. to 51% at 4000 m a.s.l.), strongly controls δ2Hleaf water. The modelled δ2H leaf water enrichment along the altitudinal transect matches well the measured 2H leaf water enrichment as assessed by using the δ2Hprec and δ2Hn-alkane results and biosynthetic fractionation during n-alkane biosynthesis in leaves. Given that our results clearly demonstrate that n-alkanes in soils do not simply reflect δ2Hprec but rather δ2

  18. Synthesis and antifungal activity of 2H-1,4-benzoxazin-3(4H)-one derivatives.

    PubMed

    Śmist, Małgorzata; Kwiecień, Halina; Krawczyk, Maria

    2016-01-01

    A series of 2-alkyl-2H-1,4-benzoxazin-3(4H)-ones (4a-l) was easily synthesized by two-step process involving O-alkylation of 2-nitrophenols with methyl 2-bromoalkanoates and next "green" catalytic reductive cyclization of the obtained 2-nitro ester intermediates (3a-l). Further, 6,7-dibromo (5a-c) and N-acetyl (6) derivatives were prepared by bromination and acetylation of unsubstituted 2-alkyl-2H-1,4-benzoxazin-3(4H)-ones (4a-c). The novel compounds (3a-l, 4d-l, 5a-c and 6) were fully characterized by spectroscopic methods (MS, (1)H and (13)C NMR). 2-Alkyl-2H-1,4-benzoxazin-3(4H)-ones (4a-l, 5a-c and 6) were screened for antifungal activity. Preliminary assays were performed using two methods: in vitro against seven phytopathogenic fungi-Botrytis cinerea, Phythophtora cactorum, Rhizoctonia solani, Phoma betae, Fusarium culmorum, Fusarium oxysporum and Alternaria alternata-and in vivo against barley powdery mildew Blumeria graminis. The tested compounds displayed moderate to good antifungal activity at high concentration (200 mg L(-1)). The most potent compounds were 2-ethyl-2H-1,4-benzoxazin-3(4H)-one (4a), 2-ethyl-7-fluoro-2H-1,4-benzoxazin-3(4H)-one (4g) and 4-acetyl-2-ethyl-2H-1,4-benzoxazin-3(4H)-one (6), which completely inhibited the mycelial growth of seven agricultural fungi at the concentration of 200 mg L(-1) in the in vitro tests. Moreover, 2-ethyl-2H-1,4-benzoxazin-3(4H)-one (4a) and 4-acetyl-2-ethyl-2H-1,4-benzoxazin-3(4H)-one (6) were also screened for antifungal activity at concentrations of 100 mg L(-1) and 20 mg L(-1). In the concentration of 100 mg L(-1), the N-acetyl derivative (6) completely inhibited the growth of three strains of fungi (F. culmorum, P. cactorum and R. solani), while 2-ethyl-2H-1,4-benzoxazin-3(4H)-one (4a) completely inhibited only R. solani strain. At the concentration of 20 mg L(-1), compound 6 showed good activity only against P. cactorum strain (72%). PMID:26963527

  19. Grasping hydrogen adsorption and dynamics in metal-organic frameworks using (2)H solid-state NMR.

    PubMed

    Lucier, Bryan E G; Zhang, Yue; Lee, Kelly J; Lu, Yuanjun; Huang, Yining

    2016-06-18

    Record greenhouse gas emissions have spurred the search for clean energy sources such as hydrogen (H2) fuel cells. Metal-organic frameworks (MOFs) are promising H2 adsorption and storage media, but knowledge of H2 dynamics and adsorption strengths in these materials is lacking. Variable-temperature (VT) (2)H solid-state NMR (SSNMR) experiments targeting (2)H2 gas (i.e., D2) shed light on D2 adsorption and dynamics within six representative MOFs: UiO-66, M-MOF-74 (M = Zn, Mg, Ni), and α-M3(COOH)6 (M = Mg, Zn). D2 binding is relatively strong in Mg-MOF-74, Ni-MOF-74, α-Mg3(COOH)6, and α-Zn3(COOH)6, giving rise to broad (2)H SSNMR powder patterns. In contrast, D2 adsorption is weaker in UiO-66 and Zn-MOF-74, as evidenced by the narrow (2)H resonances that correspond to rapid reorientation of the D2 molecules. Employing (2)H SSNMR experiments in this fashion holds great promise for the correlation of MOF structural features and functional groups/metal centers to H2 dynamics and host-guest interactions. PMID:27181834

  20. /sup 2/H-NMR studies of hypocotyl cell walls of germinating beams supplied with perdeuterated myo-inositol

    SciTech Connect

    Sasaki, K.; Wallace, J.C.; MacKay, A.L.; Balza, F.; Taylor, I.E.P.

    1987-04-01

    When myo-(2-/sup 3/H) inositol (MI) was supplied to bean seeds by imbibition, only uronic acid, arabinose and xylose residues of cell wall polysaccharides were labeled. To study the structural mobility of the uronic acid- and/or pentose-rich polysaccharides in cell wall using /sup 2/H-NMR, the authors supplied perdeuterated MI with (2-/sup 3/H) MI to germinating bean seeds. Perdeuterated MI was prepared by the /sup 1/H-/sup 2/H exchange reaction of MI in deuterium oxide with Raney nickel. During the exchange reaction, extensive epimerization occurred and at least 6 inositol epimers in addition to MI were identified in the reaction mixture of GC/MS. The perdeuterated MI was completely resolved from other inositol epimers and purified by anion-exchange chromatography using Dowex 1 (borate form) and by crystallization. The /sup 2/H-NMR analysis resolved the /sup 2/H-labeled hypocotyl cell walls into two components (rigid and mobile components). They also report the distribution of /sup 2/H and /sup 3/H from perdeuterated and (2-/sup 3/H) MI in the cell wall sugar residues.

  1. Dynamical structure of paramagnetic [M(H2O)6][SiF6] (M = Fe2+,Ni2+) crystal studied by means of 2H nuclear magnetic resonance

    NASA Astrophysics Data System (ADS)

    Mizuno, M.; Iijima, T.; Suhara, M.

    2000-08-01

    The temperature dependences of the 2H nuclear magnetic resonance (NMR) spectra and the spin-lattice relaxation time T1 were measured for [Ni(H2O)6][SiF6] and [Fe(H2O)6][SiF6]. The motional modes for both compounds were discussed on the basis of the spectral simulation. The temperature variations of the 2H NMR spectra at high temperatures could be explained by three-site jumps of [Ni(H2O)6]2+ about the C3 axis for [Ni(H2O)6][SiF6]. For [Fe(H2O)6][SiF6], however, six-site jumps of [Fe(H2O)6]2+ about the C3 axis were found to be most probable form of motion at high temperatures. At low temperatures, the 2H NMR spectra of both compounds could be explained by 180° flips of the water molecule. The 2H NMR T1 was dominated by the fluctuations of the electric field gradient caused by the molecular motion and of the magnetic interaction between the 2H nucleus and the unpaired electron spin in the metal ion. T1 was analysed in terms of the motional modes predicted from the spectral simulation. The activation energies, the jumping rates at infinite temperature for each form of motion and the quadrupole interaction parameters (e2Qq/h,η) were obtained from the 2H NMR spectra and T1. The conclusions from the spectral simulation are in good agreement with the results for T1. These results suggest that [Fe(H2O)6][SiF6] possesses dynamic disorder structure in the high-temperature phase.

  2. Cascade alkylarylation of substituted N-allylbenzamides for the construction of dihydroisoquinolin-1(2H)-ones and isoquinoline-1,3(2H,4H)-diones

    PubMed Central

    Qian, Ping; Du, Bingnan; Jiao, Wei; Mei, Haibo

    2016-01-01

    Summary An oxidative reaction for the synthesis of 4-alkyl-substituted dihydroisoquinolin-1(2H)-ones with N-allylbenzamide derivatives as starting materials has been developed. The radical alkylarylation reaction proceeds through a sequence of alkylation and intramolecular cyclization. The substituent on the C–C double bond was found to play a key role for the progress of the reaction to give the expected products with good chemical yields. Additionally, N-methacryloylbenzamides were also suitable substrates for the current reaction and provided the alkyl-substituted isoquinoline-1,3(2H,4H)-diones in good yield. PMID:26977189

  3. Full-dimensional, high-level ab initio potential energy surfaces for H{sub 2}(H{sub 2}O) and H{sub 2}(H{sub 2}O){sub 2} with application to hydrogen clathrate hydrates

    SciTech Connect

    Homayoon, Zahra; Conte, Riccardo; Qu, Chen; Bowman, Joel M.

    2015-08-28

    New, full-dimensional potential energy surfaces (PESs), obtained using precise least-squares fitting of high-level electronic energy databases, are reported for intrinsic H{sub 2}(H{sub 2}O) two-body and H{sub 2}(H{sub 2}O){sub 2} three-body potentials. The database for H{sub 2}(H{sub 2}O) consists of approximately 44 000 energies at the coupled cluster singles and doubles plus perturbative triples (CCSD(T))-F12a/haQZ (aug-cc-pVQZ for O and cc-pVQZ for H) level of theory, while the database for the three-body interaction consists of more than 36 000 energies at the CCSD(T)-F12a/haTZ (aug-cc-pVTZ for O, cc-pVTZ for H) level of theory. Two precise potentials are based on the invariant-polynomial technique and are compared to computationally faster ones obtained via “purified” symmetrization. All fits use reduced permutational symmetry appropriate for these non-covalent interactions. These intrinsic potentials are employed together with existing ones for H{sub 2}, H{sub 2}O, and (H{sub 2}O){sub 2}, to obtain full PESs for H{sub 2}(H{sub 2}O) and H{sub 2}(H{sub 2}O){sub 2}. Properties of these full PESs are presented, including a diffusion Monte Carlo calculation of the zero-point energy and wavefunction, and dissociation energy of the H{sub 2}(H{sub 2}O) dimer. These PESs together with an existing one for water clusters are used in a many-body representation of the PES of hydrogen clathrate hydrates, illustrated for H{sub 2}@(H{sub 2}O){sub 20}. An analysis of this hydrate is presented, including the electronic dissociation energy to remove H{sub 2} from the calculated equilibrium structure.

  4. A new diabatic representation of the coupled potential energy surfaces for Na(3p P-2) + H2 yields Na(3s S-2) + H2 or NaH + H

    NASA Technical Reports Server (NTRS)

    Halvick, Philippe; Truhlar, Donald G.

    1992-01-01

    A diabatic representation is presented of the coupled potential-energy surfaces for Na(3p P-2) + H2 yields Na (3s S-2) + H2 or NaH + H. The representation is designed to yield, upon diagonalization, realistic values for the two lowest energy adiabatic states at both asymptotes of the chemical reaction as well as near the conical intersection in the three-body interaction region. It is economical to evaluate and portable. It is suitable for dynamics calculations on both the quenching process and the electronically nonadiabatic chemical reaction.

  5. Auger-electron angular distributions calculated without the two-step approximation: Calculation of angle-resolved resonant Auger spectra of C2 H2

    NASA Astrophysics Data System (ADS)

    Colle, Renato; Embriaco, Davide; Massini, Michol; Simonucci, Stefano; Taioli, Simone

    2004-10-01

    Analytic expressions for the direct, resonant, and interference contributions to the differential cross section of a resonant Auger process, produced by the inner-shell photoionization of a linear molecule either “fixed in space” or belonging to a gas of randomly oriented molecules, have been derived following Dill’s procedures [ Dill , Phys. Rev. Lett. 45, 1393 (1980) ], but going beyond the two-step approximation. Angle-resolved Auger spectra of the C2H2 molecule measured on top of the C1s→π* resonance [ Kivimäki , J. Phys. B 30, 4279 (1997) ] have been calculated together with asymmetry parameters, analyzing also the different contributions to the electron angular distributions.

  6. Microwave-assisted synthesis of novel 2H-chromene derivatives bearing phenylthiazolidinones and their biological activity assessment.

    PubMed

    El Azab, Islam H; Youssef, Mohamed M; Amin, Mahmoud A

    2014-01-01

    6-Hydroxy-2-oxo-2H-chromene-4-carbaldehyde (2), 6-chloro-2-oxo-2H-chromene-4-carbaldehyde (3) and 6-hydrazinyl-4-methyl-2H-chromen-2-one (5) were prepared as single-pharmacophore motif key intermediates. Compounds 2, 3 and 5 were incorporated in a series of multicomponent reactions (MCRs), under microwave assistance as well as conventional chemical synthesis processes, to afford a series of three and/or four-pharmacophoric-motif conjugates 8a,b, 11, 13, 16, 17, 19 and 20 in good yields. The newly synthesized compounds were characterized by IR, NMR, 13C-NMR, MS and elemental analyses. Finally the synthesized compounds have been screened for their biological activity whereupon they exhibited remarkable antimicrobial activity on different classes of bacteria and the fungus. PMID:25432014

  7. Direct measurements of collisional Raman line broadening in the S-branch transitions of acetylene (C2H2)

    NASA Astrophysics Data System (ADS)

    Hsu, Paul S.; Stauffer, Hans U.; Jiang, Naibo; Gord, James R.; Roy, Sukesh

    2013-10-01

    We report direct measurements of the self- and N2-broadened Raman S-branch linewidths of acetylene (C2H2), obtained by employing time-resolved picosecond rotational coherent anti-Stokes Raman scattering spectroscopy. Using broadband 115-ps pump and Stokes pulses (˜135 cm-1 bandwidth) and a spectrally narrowed 90-ps probe pulse (˜0.2 cm-1 bandwidth), Raman-coherence lifetimes are measured at room temperature for the S-branch (ΔJ = +2) transitions associated with rotational quantum number J = 3-25. These directly measured Raman-coherence lifetimes, when converted to collisional linewidth broadening coefficients, differ from the previously reported broadening coefficients extracted from theoretical calculations by 6%-35% for self-broadening for C2H2 and by up to 60% for N2-broadened C2H2.

  8. A compact laser-based spectrometer for detection of C2H2 in exhaled breath and HCN in vitro

    NASA Astrophysics Data System (ADS)

    Marchenko, D.; Neerincx, A. H.; Mandon, J.; Zhang, J.; Boerkamp, M.; Mink, J.; Cristescu, S. M.; Hekkert, S. te Lintel; Harren, F. J. M.

    2015-02-01

    We report on the development of a compact prototype near-infrared DBR laser-based spectrometer employing off-axis integrated cavity output spectroscopy. The spectrometer is capable of simultaneous detection of acetylene (C2H2) and CO2 at 1,529.2 nm as well as hydrogen cyanide (HCN) at 1,533.5 nm. The detection limits of 8 ppbv for C2H2 and 80 ppbv for HCN are achieved for the acquisition time of 1 s. The setup has been tested for online measurements of C2H2 in exhaled breath of a smoking subject and HCN resulting from the metabolism of Pseudomonas aeruginosa bacteria in vitro. Further improvements of the performance of the spectrometer are discussed.

  9. Detection of NO sub x,C2H4 concentrations by using CO and CO2 lasers

    NASA Technical Reports Server (NTRS)

    Gengchen, W.; Qinxin, K.

    1986-01-01

    A laser, especially the infrared line tunable laser, opens up a new way to monitor the atmospheric environment, and already has gotten effective practical application. One of the most serious problems in open path remote measurement at atmospheric pressure is the broadening effect which leads to increased linewidths, spectral interferences, and, as a result, tends to reduce detection sensitivity, so measuring laser wavelengths should be selected carefully, and interaction between the measuring wavelength and gas to be measured must be known very well. Therefore, N2O, No, NO2, CH4, NH3 and C2H4 absorption properties at some lines of CO and CO2 line tunable lasers were studied. The absorption coefficients of NO, NO2, and C2H4; some results on detection of NO sub x, C2H4 concentrations in both laboratory and field; and selection of measuring wavelengths and error analysis are discussed.

  10. Synthesis, Photochemical Properties, and Cytotoxicities of 2H-Naphtho[1,2-b]pyran and Its Photodimers.

    PubMed

    Ota, Motohiro; Sasamori, Takahiro; Tokitoh, Norihiro; Onodera, Takefumi; Mizushina, Yoshiyuki; Kuramochi, Kouji; Tsubaki, Kazunori

    2015-06-01

    A 2H-naphtho[1,2-b]pyran, prepared by dimerization of 2-bromo-3-methyl-1,4-naphthoquinone and O-methylation, readily undergoes solid-state [2 + 2] photodimerization to give a photodimer in excellent yield and with excellent selectivity. Retro [2 + 2] cycloaddition can be achieved by irradiation of a solution of the photodimer in chloroform. Interestingly, the 2H-naphtho[1,2-b]pyran dimerizes with a skeletal rearrangement to afford 2,5-dihydro-1-benzoxepin dimers upon irradiation in methanol or via irradiation with hexamethylditin. Furthermore, treatment of the resulting dimers with triethylamine regenerates the 2H-naphtho[1,2-b]pyran monomer. Significant differences in the color, fluorescence, and cytotoxic properties of the monomer and dimers were observed. PMID:25927340

  11. Osmium(IV) complexes with 1H- and 2H-indazoles: tautomer identity versus spectroscopic properties and antiproliferative activity.

    PubMed

    Büchel, Gabriel E; Stepanenko, Iryna N; Hejl, Michaela; Jakupec, Michael A; Keppler, Bernhard K; Heffeter, Petra; Berger, Walter; Arion, Vladimir B

    2012-08-01

    A one-pot synthesis of osmium(IV) complexes with two different tautomers of indazole, 1H-indazole and 2H-indazole, namely (H(2)ind)[Os(IV)Cl(5)(2H-ind)] (1) and (H(2)ind)[Os(IV)Cl(5)(1H-ind)] (2) is reported. Both compounds have been comprehensively characterized by NMR spectroscopy, ESI (electrospray ionization) mass spectrometry, electronic absorption spectroscopy, IR spectroscopy, cyclic voltammetry and tested for antiproliferative activity in vitro in three human cancer cell lines, CH1 (ovarian carcinoma), A549 (non-small cell lung cancer) and SW480 (colon carcinoma), as well as in vivo in a Hep3B SCID mouse xeno-transplantation model. 2H-Indazole tautomer stabilization in 1 has been confirmed by X-ray diffraction.

  12. Osmium(IV) complexes with 1H- and 2H-indazoles: Tautomer identity versus spectroscopic properties and antiproliferative activity

    PubMed Central

    Büchel, Gabriel E.; Stepanenko, Iryna N.; Hejl, Michaela; Jakupec, Michael A.; Keppler, Bernhard K.; Heffeter, Petra; Berger, Walter; Arion, Vladimir B.

    2012-01-01

    A one-pot synthesis of osmium(IV) complexes with two different tautomers of indazole, 1H-indazole and 2H-indazole, namely (H2ind)[OsIVCl5(2H-ind)] (1) and (H2ind)[OsIVCl5(1H-ind)] (2) is reported. Both compounds have been comprehensively characterized by NMR spectroscopy, ESI (electrospray ionization) mass spectrometry, electronic absorption spectroscopy, IR spectroscopy, cyclic voltammetry and tested for antiproliferative activity in vitro in three human cancer cell lines, CH1 (ovarian carcinoma), A549 (non-small cell lung cancer) and SW480 (colon carcinoma), as well as in vivo in a Hep3B SCID mouse xeno-transplantation model. 2H-Indazole tautomer stabilization in 1 has been confirmed by X-ray diffraction. PMID:22687494

  13. Quasiparticle interference, quasiparticle interactions, and the origin of the charge density wave in 2H-NbSe2.

    PubMed

    Arguello, C J; Rosenthal, E P; Andrade, E F; Jin, W; Yeh, P C; Zaki, N; Jia, S; Cava, R J; Fernandes, R M; Millis, A J; Valla, T; Osgood, R M; Pasupathy, A N

    2015-01-23

    We show that a small number of intentionally introduced defects can be used as a spectroscopic tool to amplify quasiparticle interference in 2H-NbSe2 that we measure by scanning tunneling spectroscopic imaging. We show, from the momentum and energy dependence of the quasiparticle interference, that Fermi surface nesting is inconsequential to charge density wave formation in 2H-NbSe2. We demonstrate that, by combining quasiparticle interference data with additional knowledge of the quasiparticle band structure from angle resolved photoemission measurements, one can extract the wave vector and energy dependence of the important electronic scattering processes thereby obtaining direct information both about the fermiology and the interactions. In 2H-NbSe2, we use this combination to confirm that the important near-Fermi-surface electronic physics is dominated by the coupling of the quasiparticles to soft mode phonons at a wave vector different from the charge density wave ordering wave vector.

  14. Local structure and molecular motions in imidazolium hydrogen malonate crystal as studied by 2H and 13C NMR

    NASA Astrophysics Data System (ADS)

    Mizuno, M.; Chizuwa, M.; Umiyama, T.; Kumagai, Y.; Miyatou, T.; Ohashi, R.; Ida, T.; Tansho, M.; Shimizu, T.

    2015-04-01

    The local structure and molecular motion of the imidazolium hydrogen malonate crystal were investigated using solid-state 2H and 13C NMR. The imidazolium ion undergoes isotropic rotation, which is correlated with a defect in the crystal, as observed by 2H NMR broadline spectra above 263 K. A 180∘ flip of the imidazolium ion in the regular site was observed from 2H NMR quadrupole Carr-Purcell-Meiboom-Gill (QCPMG) spectra. The Grotthuss mechanism was accompanied by a 180∘ flip of the imidazolium ion in regular sites. Moreover, the proton transfer associated with the imidazolium ion of the defective crystal is important for proton conductivity of the imidazolium hydrogen malonate crystal.

  15. Antibacterial agent triclosan suppresses RBL-2H3 mast cell function

    SciTech Connect

    Palmer, Rachel K.; Hutchinson, Lee M.; Burpee, Benjamin T.; Tupper, Emily J.; Pelletier, Jonathan H.; Kormendy, Zsolt; Hopke, Alex R.; Malay, Ethan T.; Evans, Brieana L.; Velez, Alejandro; Gosse, Julie A.

    2012-01-01

    Triclosan is a broad-spectrum antibacterial agent, which has been shown previously to alleviate human allergic skin disease. The purpose of this study was to investigate the hypothesis that the mechanism of this action of triclosan is, in part, due to effects on mast cell function. Mast cells play important roles in allergy, asthma, parasite defense, and carcinogenesis. In response to various stimuli, mast cells degranulate, releasing allergic mediators such as histamine. In order to investigate the potential anti-inflammatory effect of triclosan on mast cells, we monitored the level of degranulation in a mast cell model, rat basophilic leukemia cells, clone 2H3. Having functional homology to human mast cells, as well as a very well defined signaling pathway leading to degranulation, this cell line has been widely used to gain insight into mast-cell driven allergic disorders in humans. Using a fluorescent microplate assay, we determined that triclosan strongly dampened the release of granules from activated rat mast cells starting at 2 μM treatment, with dose-responsive suppression through 30 μM. These concentrations were found to be non-cytotoxic. The inhibition was found to persist when early signaling events (such as IgE receptor aggregation and tyrosine phosphorylation) were bypassed by using calcium ionophore stimulation, indicating that the target for triclosan in this pathway is likely downstream of the calcium signaling event. Triclosan also strongly suppressed F-actin remodeling and cell membrane ruffling, a physiological process that accompanies degranulation. Our finding that triclosan inhibits mast cell function may explain the clinical data mentioned above and supports the use of triclosan or a mechanistically similar compound as a topical treatment for allergic skin disease, such as eczema. -- Highlights: ►The effects of triclosan on mast cell function using a murine mast cell model. ►Triclosan strongly inhibits degranulation of mast cells.

  16. The ν17 band of C2H5D from 770 to 880 cm-1

    NASA Astrophysics Data System (ADS)

    Daly, Adam M.; Drouin, Brian J.; Pearson, John C.; Sung, Keeyoon; Brown, Linda R.; Mantz, Arlan; Smith, Mary Ann H.

    2015-10-01

    Atmospheric investigations rely heavily on the availability of accurate spectral information of hydrocarbons. To extend the ethane database we recorded a 0.0028 cm-1 resolution spectrum of 12C2H5D from 650 to 1500 cm-1 using a Bruker Fourier Transform spectrometer IFS-125HR at the Jet Propulsion Laboratory. The 98% deuterium-enriched sample was contained in a 0.2038 m absorption cell; one spectrum was obtained with the sample cryogenically cooled to 130.5 K and another at room temperature. From the cold data, we retrieved line positions and intensities of 8704 individual absorption features from 770 to 880 cm-1 using a least squares curve fitting algorithm. From this set of measurements, we assigned 5035 transitions to the v17 fundamental at 805.342729(27) cm-1; this band is a c-type vibration, with often-resolved A and E components arising from internal rotation. The positions were modeled to a 22 term torsional Hamiltonian using SPFIT to fit the spectrum to a standard deviation of 7 × 10-4 cm-1 (21 MHz). The prediction of the 5035 line intensities at 130.5 K agreed with observed intensities, but a small centrifugal distortion type correction to the transition dipole was needed to model the intensity of high Ka R and P transitions. The integrated band intensities of 3.6628 × 10-19 cm-1/(molecule cm-2) at 296 K in the 770-880 cm-1 region was obtained. To predict line intensities at different temperatures, the partition function values were determined at nine temperatures between 9.8 and 300 K by summing individual energy levels up to J = 99 and Ka = 99 for the six states up through ν17 at 805 cm-1. We found the energy of A and E are inverted as compared to ground state (with the E state lower than the A state) and the splitting, -241.8(10) MHz, lies between the ground state value of +74.167(18) MHz and the first torsional state (ν18 = 271.1 cm-1) value of -3382.23(34) MHz. The proximity of the energy splitting to the ground state suggests that the ν17 state

  17. New estimates of global CH4 and C2H6 production in the Precambrian crust

    NASA Astrophysics Data System (ADS)

    Sutcliffe, Chelsea N.; Lacrampe-Couloume, Georges; Ballentine, Chris J.; Sherwood Lollar, Barbara

    2015-04-01

    Saline fracture fluids found deep within the Precambrian shield possess isotopic and geochemical signatures consistent with prolonged water rock interaction. Noble gas-derived residence times of these fluids, on the order of millions to billions of years, highlight their significance as an ancient deep hydrosphere (Lippmann-Pipke et al., 2011; Holland et al., 2013). With mM concentrations of dissolved gases such as H2 and hydrocarbons, these fracture fluids are energy rich and capable of sustaining microbial communities of H2-utilizing methanogens and sulphate reducers (Lin et al., 2006). Globally, Precambrian rocks constitute over 70% of the volume of the continental crust (Goodwin, 1996) and represent a substantial under-investigated source of such dissolved gases. Recent calculations of global H2 production from these Precambrian Shield rocks, including both hydration reactions and radiolysis, doubles previous estimates to an increased rate of 0.4-2.3 x 1011 mol/yr (Sherwood Lollar et al., 2014). This has important consequences for hydrocarbon production, reflected in the high abundance of CH4 and C2H6 in dissolved fracture gases, up to 80 and 10 vol %, respectively. Given the long residence times of these fluids, hydrocarbon production could have persisted on geological timescales. To date, production from this source has not been incorporated into models of evolution of the early atmosphere. Additionally, the quantification of abiotic sources of methane and ethane in the analogous terrestrial Precambrian crust could contribute to our understanding of the origin of the episodic traces of methane recently detected on Mars (Webster et al., 2014). Investigating the origin of these gases has important implications for the global carbon cycle, as well as the distribution of life in the terrestrial deep subsurface and on other planets. We examine the isotopic evolution of these fracture fluids in the Canadian Shield and provide the first attempts to estimate methane

  18. Pharmacokinetic equivalence of 5(ethyl(/sup 2/H)5)- and unlabelled phenobarbitone

    SciTech Connect

    Benchekroun, Y.; Ribon, B.; Falconnet, J.B.; Cherrah, Y.; Brazier, J.L.

    1989-02-01

    The present study shows the absence of in vivo pharmacokinetic isotope effect on phenobarbitone (PB) C5-ethyl deuteration (PBd5) following oral administration to man of equimolar PB/PBd5 mixtures (0.40 mmol each). Plasma PB and PBd5 (17 days) and urine PB, PBd5 and parahydroxy-metabolites (PBOH, PBHOd5) levels were determined by GC-MS. Isotope effect research includes comparison of pharmacokinetic parameters, study of time-dependence of isotope ratios (IRs) in plasma and urine (linearity test), comparison of IRs between samples and administered mixtures (Mann Whitney's test) and comparison of PBOH/PBOHd5 ratios before and after urine enzymatic hydrolysis (Student's two tailed t-test). No significant isotope effect was observed on pharmacokinetic parameters, PB hydroxylation or PBOH conjugation (x less than or equal to 5%); which the absence of pentadeuteration-induced alteration in PB's HSA binding parameters (binding mode, Ka, N) corroborates (x less than or equal to 5%). These results establish bioequivalence of PB and PBd5; the latter can be used with benefit in stable-isotope clinical pharmacology (steady state pharmacokinetics, drug interactions...) investigations as well as bioavailability studies of PB preparations.

  19. 2H/1H composition of soil n-alkanes along two altitudinal transects in East Africa

    NASA Astrophysics Data System (ADS)

    Coffinet, Sarah; Huguet, Arnaud; Pedentchouk, Nikolai; Omuombo, Christine; Williamson, David; Bergonzini, Laurent; Wagner, Thomas; Derenne, Sylvie

    2015-04-01

    Long chains n-alkanes are components of terrestrial plant leaf waxes that are ubiquitously found in geological archives. They have been extensively used to track environmental and ecological variations in the past, notably changes in vegetation communities. Recent analytical developments led to the possibility of measuring their deuterium to hydrogen isotopic ratio (δ2Hwax). This parameter is suggested to be linked to hydrogen isotope ratio of precipitations (δ2Hp). In 2008, Jia et al. proposed to use soil derived δ2 Hwax as a paleoelevation proxy since precipitations are known to get more depleted in deuterium with altitude. They found a linear correlation (R2 0.73) between δ2Hwax in surface soils and altitude along Mt. Gongga (China). Since then, the correlation between δ2Hwax and δ2Hp was shown for several other altitudinal transects. Contrary to these previous observations, however, no trend with altitude was observed in East Africa along an altitudinal gradient in Mt. Kilimanjaro (North eastern, Tanzania, Peterse et al., 2009 and Zech et al., 2014). What is the reason for this absence of trend? Is it because of a difference between African and Asian soils? Or is it specific to Mt. Kilimanjaro? To get an insight into this problem, we determined δ2Hwax in 41 surface soils sampled along two altitudinal transects: from 500 to 2800 m in Mt. Rungwe (South-western Tanzania) and from 1897 to 3268 m in Mt. Kenya (Central Kenya). The goal of the study was to further investigate the conditions of applicability of this proxy in East Africa. A correlation between soil derived δ2Hwax and altitude was observed along Mt. Kenya (δ2Hwax=20.2*ALT-88.0, R2=0.51) but not along Mt. Rungwe - similarly to Mt. Kilimanjaro (Peterse et al., 2009; Zech et al., 2014). This contrast between Mt. Kenya on one hand and Mts. Rungwe and Kilimanjaro on the other hand may be explained by differences in topography. These results highlight the complexity of the signal recorded by δ2H, and

  20. Carbohydrate ingestion does not influence the change in energy cost during a 2-h run in well-trained triathletes.

    PubMed

    Brisswalter, J; Hausswirth, C; Vercruyssen, F; Collardeau, M; Vallier, J M; Lepers, R; Goubault, C

    2000-01-01

    The aim of this study was to examine whether the increase in the energy cost of running (C(r)), previously reported to occur at the end of a prolonged run, could be influenced by the ingestion of either an artificially sweetened placebo (Pl) or a 5.5% carbohydrate (CHO) solution. Ten well-trained triathletes completed three testing sessions within a 3-week period. The aim of the first session was to determine maximal oxygen uptake (VO(2)(max)) and the velocity associated with ventilatory threshold (nu(VT)). The second and the third sessions were composed of two submaximal treadmill runs (20 min long, 0% grade, performed at nu(VT)), before and after an 80-min overground run, also conducted at nu(VT). During these submaximal tests, the subjects ingested (in a random order) either a Pl or CHO solution prior to the first submaximal run and every 20 min after that. During the first session, ventilatory threshold (VT) occurred at [mean (SD)] 81.2 (2.5)% VO(2)(max) and 16.5 (0.6) km. h(-1). A significant effect of exercise duration was found on C(r) (DeltaC(r)) at the end of the run, whatever the solution ingested (DeltaC(r) = 5.7% and 7.01% for CHO and Pl, respectively). A reduction in the respiratory exchange ratio (from 0.98 to 0.90) was observed only at the end of the Pl trial. In this study, C(r) seems to be affected only to a minor extent by substrate turnover. Moreover, the increase in the demand for oxygen, estimated from the increase in ventilation, accounted for only a minor proportion of the increase in C(r) (11% and 17% for CHO and Pl, respectively). No correlation was found between the changes in C(r) and the changes in the other physiological parameters recorded. These results suggest, indirectly, that C(r) increases during a 2-h run at 80% VO(2)(max) in well-trained subjects can be explained mainly by alterations in neuromuscular performance, which lead to a decrease in muscle efficiency. PMID:10552274

  1. Controls on compound specific 2H/1H of leaf waxes along a North American monsoonal transect

    NASA Astrophysics Data System (ADS)

    Berke, M. A.; Tipple, B. J.; Hambach, B.; Ehleringer, J. R.

    2013-12-01

    The use of hydrogen isotope ratios of sedimentary n-alkanes from leaf waxes has become an important method for the reconstruction of paleohydrologic conditions. Ideally, the relationship between lipid 2H/1H values and source water is one-to-one. But the extent to which the 2H/1H values are altered between initial source water and lipid 2H/1H values varies by plant type and environment. Additionally, these variables may be confounded by use of varied source waters by plants in the same ecosystem. Here, we use a transect study across the arid southwestern landscape of the United States, which is heavily influenced by the North American Monsoon, to study the variability in 2H/1H values of leaf waxes in co-occurring plants from Tucson, Arizona to Salt Lake City, Utah. Perennials, including rabbit brush (Chrysothamnus nauseosus), sagebrush (Artemisia tridentata), and gambel oak (Quercus gambelii) and an annual plant, sunflower (Helianthus annuus), were chosen for their wide geographic distribution along the entire transect. Our results indicate that n-alkane distribution for each plant was similar and generally showed no relationship to environmental variables (elevation, mean annual precipitation, latitude, and temperature). However, we find evidence of n-alkane 2H/1H value relating to transect latitude, a relationship that is weaker for all samples combined than the strong individual correlation for each plant species. Further, these 2H/1H values suggest that not all plants in the monsoon region utilize monsoon-delivered precipitation. These results imply an adaptation to discontinuous spatial coverage and amount of monsoonal precipitation and suggest care must be taken when assuming consistent source water for different plants, particularly in regions with highly seasonal precipitation delivery.

  2. BROAD N{sub 2}H{sup +} EMISSION TOWARD THE PROTOSTELLAR SHOCK L1157-B1

    SciTech Connect

    Codella, C.; Fontani, F.; Gómez-Ruiz, A.; Vasta, M.; Viti, S.; Ceccarelli, C.; Lefloch, B.; Podio, L.; Caselli, P.

    2013-10-10

    We present the first detection of N{sub 2}H{sup +} toward a low-mass protostellar outflow, namely, the L1157-B1 shock, at ∼0.1 pc from the protostellar cocoon. The detection was obtained with the IRAM 30 m antenna. We observed emission at 93 GHz due to the J = 1-0 hyperfine lines. Analysis of this emission coupled with HIFI CHESS multiline CO observations leads to the conclusion that the observed N{sub 2}H{sup +}(1-0) line originated from the dense (≥10{sup 5} cm{sup –3}) gas associated with the large (20''-25'') cavities opened by the protostellar wind. We find an N{sub 2}H{sup +} column density of a few 10{sup 12} cm{sup –2} corresponding to an abundance of (2-8) × 10{sup –9}. The N{sub 2}H{sup +} abundance can be matched by a model of quiescent gas evolved for more than 10{sup 4} yr, i.e., for more than the shock kinematical age (≅2000 yr). Modeling of C-shocks confirms that the abundance of N{sub 2}H{sup +} is not increased by the passage of the shock. In summary, N{sub 2}H{sup +} is a fossil record of the pre-shock gas, formed when the density of the gas was around 10{sup 4} cm{sup –3}, and then further compressed and accelerated by the shock.

  3. Oxidation of disinfectants with Cl-substituted structure by a Fenton-like system Cu(2+)/H2O2 and analysis on their structure-reactivity relationship.

    PubMed

    Peng, Jianbiao; Li, Jianhua; Shi, Huanhuan; Wang, Zunyao; Gao, Shixiang

    2016-01-01

    As widely used chemicals intended to protect human being from infection of microorganisms, disinfectants are ubiquitous in the environment. Among them chlorine-substituted phenol is a basic structure in many disinfectant molecules. Removal of these pollutants from wastewater is of great concern. The oxidative degradation of antimicrobial agents such as triclosan, chlorofene, and dichlorofene by a Fenton-like system Cu(2+)/H2O2 was examined. Reaction conditions such as temperature, initial concentrations of H2O2 and Cu(2+), and pH were optimized using triclosan as a representative. The degradation kinetics of the above disinfectants followed pseudo-first-order kinetics under the investigated conditions. Fourteen chlorophenols (CPs) with different chlorine substitution were also studied to evaluate the influence of molecular structure on the degradation process in the Cu(2+)/H2O2 system. Fourteen structure-related parameters were calculated using Gaussian 09 program. A quantitative structure-activity relationship (QSAR) model was established using SPSS software with measured rate constant (k) as dependent variable and calculated molecular descriptors as independent variables. A three-parameter model including energy of HOMO (E homo), molar heat capacity at constant volume (Cv(θ)), and the most positive net charge of hydrogen atoms (qH(+)) was selected for k prediction, with correlation coefficient R(2) = 0.878. Analyses of the model demonstrated that the Cv(θ) was the most significant factor affecting the k of chlorophenols. Variance analysis and standard t-value test were used to validate the model.

  4. Oxidation of disinfectants with Cl-substituted structure by a Fenton-like system Cu(2+)/H2O2 and analysis on their structure-reactivity relationship.

    PubMed

    Peng, Jianbiao; Li, Jianhua; Shi, Huanhuan; Wang, Zunyao; Gao, Shixiang

    2016-01-01

    As widely used chemicals intended to protect human being from infection of microorganisms, disinfectants are ubiquitous in the environment. Among them chlorine-substituted phenol is a basic structure in many disinfectant molecules. Removal of these pollutants from wastewater is of great concern. The oxidative degradation of antimicrobial agents such as triclosan, chlorofene, and dichlorofene by a Fenton-like system Cu(2+)/H2O2 was examined. Reaction conditions such as temperature, initial concentrations of H2O2 and Cu(2+), and pH were optimized using triclosan as a representative. The degradation kinetics of the above disinfectants followed pseudo-first-order kinetics under the investigated conditions. Fourteen chlorophenols (CPs) with different chlorine substitution were also studied to evaluate the influence of molecular structure on the degradation process in the Cu(2+)/H2O2 system. Fourteen structure-related parameters were calculated using Gaussian 09 program. A quantitative structure-activity relationship (QSAR) model was established using SPSS software with measured rate constant (k) as dependent variable and calculated molecular descriptors as independent variables. A three-parameter model including energy of HOMO (E homo), molar heat capacity at constant volume (Cv(θ)), and the most positive net charge of hydrogen atoms (qH(+)) was selected for k prediction, with correlation coefficient R(2) = 0.878. Analyses of the model demonstrated that the Cv(θ) was the most significant factor affecting the k of chlorophenols. Variance analysis and standard t-value test were used to validate the model. PMID:26408114

  5. A tandem Mannich addition–palladium catalyzed ring-closing route toward 4-substituted-3(2H)-furanones

    PubMed Central

    John, Jubi; Târcoveanu, Eliza; Jones, Peter G

    2014-01-01

    Summary A facile route towards highly functionalized 3(2H)-furanones via a sequential Mannich addition–palladium catalyzed ring closing has been elaborated. The reaction of 4-chloroacetoacetate esters with imines derived from aliphatic and aromatic aldehydes under palladium catalysis afforded 4-substituted furanones in good to excellent yields. 4-Hydrazino-3(2H)-furanones could also be synthesized from diazo esters in excellent yields by utilising the developed strategy. We could also efficiently transform the substituted furanones to aza-prostaglandin analogues. PMID:24991301

  6. The Organocatalytic Approach to Enantiopure 2H- and 3H-Pyrroles: Inhibitors of the Hedgehog Signaling Pathway.

    PubMed

    Kötzner, Lisa; Leutzsch, Markus; Sievers, Sonja; Patil, Sumersing; Waldmann, Herbert; Zheng, Yiying; Thiel, Walter; List, Benjamin

    2016-06-27

    A divergent approach to enantioenriched 2H- and 3H-pyrroles catalyzed by a spirocyclic phosphoric acid is reported that makes use of a Fischer-type indolization and a [1,5]-alkyl shift. Catalyzed by the chiral phosphoric acid STRIP, good to excellent yields and enantioselectivities could be obtained. Remarkably, biological evaluation reveals one of these novel 2H-pyrroles to be a potent but nontoxic inhibitor of the Hedgehog signaling pathway by binding to the Smoothened protein. PMID:27239757

  7. Charge Dynamics of 2H- TaSe2 along the Less-Conducting c-Axis

    NASA Astrophysics Data System (ADS)

    Ruzicka, B.; Degiorgi, L.; Berger, H.; Gaál, R.; Forró, L.

    2001-04-01

    We present an optical study of 2H-TaSe2 along the less conducting c-axis. This dichalcogenide compound belongs to a large class of conductors called ``bad metals'' (with a mean free path smaller than the lattice constant along the c-axis), which also includes the superconducting cuprates. The optical response shows the progressive development of a pseudogaplike feature with decreasing temperature. The spectral weight lost by the opening of such a pseudogap goes into the narrow Drude component, developing at low frequency and temperature. There is no violation of the sum rule in 2H-TaSe2 contrary to the cuprates.

  8. Azirinium ylides from α-diazoketones and 2H-azirines on the route to 2H-1,4-oxazines: three-membered ring opening vs 1,5-cyclization

    PubMed Central

    Rostovskii, Nikolai V; Khlebnikov, Alexander F; Starova, Galina L; Avdontseva, Margarita S

    2015-01-01

    Summary Strained azirinium ylides derived from 2H-azirines and α-diazoketones under Rh(II)-catalysis can undergo either irreversible ring opening across the N–C2 bond to 2-azabuta-1,3-dienes that further cyclize to 2H-1,4-oxazines or reversibly undergo a 1,5-cyclization to dihydroazireno[2,1-b]oxazoles. Dihydroazireno[2,1-b]oxazoles derived from 3-aryl-2H-azirines and 3-diazoacetylacetone or ethyl diazoacetoacetate are able to cycloadd to acetyl(methyl)ketene generated from 3-diazoacetylacetone under Rh(II) catalysis to give 4,6-dioxa-1-azabicyclo[3.2.1]oct-2-ene and/or 5,7-dioxa-1-azabicyclo[4.3.1]deca-3,8-diene-2-one derivatives. According to DFT calculations (B3LYP/6-31+G(d,p)), the cycloaddition can involve two modes of nucleophilic attack of the dihydroazireno[2,1-b]oxazole intermediate on acetyl(methyl)ketene followed by aziridine ring opening into atropoisomeric oxazolium betaines and cyclization. Azirinium ylides generated from 2,3-di- and 2,2,3-triaryl-substituted azirines give rise to only 2-azabuta-1,3-dienes and/or 2H-1,4-oxazines. PMID:25815084

  9. High-Resolution Stimulated Raman Spectroscopy and Analysis of ν_2 and ν_3 Bands of of 13C_2H_4 Using the D2h Top Data System

    NASA Astrophysics Data System (ADS)

    Alkadrou, Abdulsamee; Rotger, Maud; Bermejo, Dionisio; Domenech, Jose Luis; Boudon, Vincent

    2016-06-01

    High resolution stimulated Raman spectra of 13C_2H_4 in the regions of the ν_2 and ν_3 Raman active modes have been recorded at at two temperatures (145 and 296 K) based on the quasi continuous-wave (cw) stimulated Raman spectrometer at Instituto de Estructura de la Materia (CSIC) in Madrid. A tensorial formalism adapted to X2Y4 planar asymmetric tops with D2h symmetry has been developed in Dijon and a program suite called D2hTDS (now part of the XTDS/SPVIEW spectroscopic software was proposed to calculate their high-resolution spectra. The effective Hamiltonian operator, involving a polyad structure, and transition moment (dipole moment and polarizability) operators can be systematically expanded to carry out global analyses of many rovibrational bands. A total of 103 and 51 lines corresponding to ν_2 and ν_3 Raman active modes have been assigned and fitted in frequency with a global root mean square deviation of 0.54 × 10-3 cm-1 and 0.36 × 10-3 cm-1, respectively. The figures below shows the stimulated Raman spectrum of the ν_2 and ν_3 bands of 13C_2H_4, compared to the simulation at 296 K. Raballand W, Rotger M, Boudon V, Loëte M. J Mol Spectrosc 2003;217:239-48. Wenger Ch, Boudon V, Rotger M, Champion JP, Sanzharov M. J Mol Spectrosc 2008;251:102-13.

  10. Redetermination of ruizite, Ca2Mn3+ 2[Si4O11(OH)2](OH)2·2H2O

    PubMed Central

    Fendrich, Kim V.; Downs, Robert T.; Origlieri, Marcus J.

    2016-01-01

    The crystal structure of ruizite, ideally Ca2Mn3+ 2[Si4O11(OH)2](OH)2·2H2O [dicalcium dimanganese(III) tetra­silicate tetra­hydroxide dihydrate] was first determined in space group A2 with an isotropic displacement parameter model (R = 5.6%) [Hawthorne (1984 ▸). Tschermaks Mineral. Petrogr. Mitt. 33, 135–146]. A subsequent refinement in space group C2/m with anisotropic displacement parameters for non-H atoms converged with R = 8.4% [Moore et al. (1985 ▸). Am. Mineral. 70, 171–181]. The current study reports a redetermination of the ruizite structure by means of single-crystal X-ray diffraction data of a natural sample from the Wessels mine, Kalahari Manganese Field, Northern Cape Province, South Africa. Our data (R 1 = 3.0%) confirm that the space group of ruizite is that of the first study rather than C2/m. This work improves upon the structure reported by Hawthorne (1984 ▸) in that all non-H atoms were refined with anisotropic displacement parameters and all hydrogen atoms were located. The crystal structure consists of [010] chains of edge-sharing MnO6 octa­hedra flanked by finite [Si4O11(OH)2] chains. The Ca2+ cations are situated in the cavities of this arrangement and exhibit a coordination number of seven. PMID:27555940

  11. Precise ro-vibrational analysis of molecular bands forbidden in absorption: The ν8 +ν10 band of 13C2H4

    NASA Astrophysics Data System (ADS)

    Ulenikov, O. N.; Gromova, O. V.; Bekhtereva, E. S.; Kashirina, N. V.; Maul, C.; Bauerecker, S.

    2015-10-01

    The high resolution spectra of the 13C2H4 molecule was recorded with a Bruker IFS 120 Fourier transform spectrometer and theoretically analyzed in the 1650 - 1800cm-1 region of the ν8 +ν10 band which is forbidden in absorption. About 1200 experimental transitions with the maximum values of quantum numbers Jmax. = 34 and Kamax. = 17 were assigned to the ν8 +ν10 band. On that basis the 516 high accuracy ro-vibrational energies of the (v8=v10=1) vibrational state, as well as energy levels with J ≤ 2 of the (v4 =v8 = 1) and (v7 =v8 = 1) vibrational states, were determined which then were used as input data in the weighted fit of spectroscopic parameters of the Hamiltonian (strong local resonance interactions of the ν8 +ν10 band with the bands ν4 +ν8 and ν7 +ν8 have been taken into account). A set of 34 vibrational, rotational, centrifugal distortion, and resonance interaction parameters was obtained from the fit. These parameters reproduce positions of about 1200 experimentally recorded and assigned transitions with the rms error drms = 0.00018cm-1 (blended and very weak transitions are not taken into account in that case).

  12. Distortion of ethyne on coordination to silver acetylide, C{sub 2}H{sub 2}⋅⋅⋅AgCCH, characterised by broadband rotational spectroscopy and ab initio calculations

    SciTech Connect

    Stephens, Susanna L.; Zaleski, Daniel P.; Walker, Nicholas R. E-mail: a.c.legon@bristol.ac.uk; Mizukami, Wataru; Tew, David P.; Legon, Anthony C. E-mail: a.c.legon@bristol.ac.uk

    2014-03-28

    The rotational spectra of six isotopologues of a complex of ethyne and silver acetylide, C{sub 2}H{sub 2}⋅⋅⋅AgCCH, are measured by both chirped-pulse and Fabry-Perot cavity versions of Fourier-transform microwave spectroscopy. The complex is generated through laser ablation of a silver target in the presence of a gas sample containing 1% C{sub 2}H{sub 2}, 1% SF{sub 6}, and 98% Ar undergoing supersonic expansion. Rotational, A{sub 0}, B{sub 0}, C{sub 0}, and centrifugal distortion Δ{sub J} and Δ{sub JK} constants are determined for all isotopologues of C{sub 2}H{sub 2}⋅⋅⋅AgCCH studied. The geometry is planar, C{sub 2v} and T-shaped in which the C{sub 2}H{sub 2} sub-unit comprises the bar of the “T” and binds to the metal atom through its π electrons. In the r{sub 0} geometry, the distance of the Ag atom from the centre of the triple bond in C{sub 2}H{sub 2} is 2.2104(10) Å. The r(HC≡CH) parameter representing the bond distance separating the two carbon atoms and the angle, ∠(CCH), each defined within the C{sub 2}H{sub 2} sub-unit, are determined to be 1.2200(24) Å and 186.0(5)°, respectively. This distortion of the linear geometry of C{sub 2}H{sub 2} involves the hydrogen atoms moving away from the silver atom within the complex. The results thus reveal that the geometry of C{sub 2}H{sub 2} changes measurably on coordination to AgCCH. A value of 59(4) N m{sup −1} is determined for the intermolecular force constant, k{sub σ}, confirming that the complex is significantly more strongly bound than hydrogen and halogen-bonded analogues. Ab initio calculations of the r{sub e} geometry at the CCSD(T)(F12{sup *})/ACVTZ level of theory are consistent with the experimental results. The spectra of the {sup 107}Ag{sup 13}C{sup 13}CH and {sup 109}Ag{sup 13}C{sup 13}CH isotopologues of free silver acetylide are also measured for the first time allowing the geometry of the AgCCH monomer to be examined in greater detail than previously.

  13. The ^2H(e,e'p)n Reaction at High Four-Momentum Transfer

    SciTech Connect

    Hassan Ibrahim

    2006-12-31

    in June 2002 and the high Q^2 kinematics were completed in November 2002. Before the start of the experiment many preparations were made to assure the quality of the collected data. Approximately two Terabytes of data were collected by the end of the experiment. The cross section results in this dissertation show clearly the effect of final state interactions between the two final state nucleons. The cross section ratio to the Laget PWBA+FSI calculation has a wiggle at P_miss ~ 300 MeV. It is yet to be seen whether this is merely due to the lack of MEC and IC in the present theoretical calculation. However, a similar feature was observed in a previous Hall A experiment. Further, discrepancies at very low P_miss cast some doubt on neutron form factor measurements using the deuteron as target. This study will add to the already growing body of systematic data for the ^2H(e,e'p)n reaction to better understand the N N short range and to provide vital input for heavier nuclei.

  14. Highly enantioselective Michael addition reactions of 2-substituted benzofuran-3(2H)-ones to nitroolefins.

    PubMed

    Zhang, Zhi-Pei; Dong, Nan; Li, Xin; Cheng, Jin-Pei

    2015-10-21

    A highly enantioselective Michael addition reaction of 2-substituted benzofuran-3(2H)-ones to nitroolefins was promoted by a bifunctional squaramide catalyst. As a result, a number of chiral 2,2'-substituted benzofuran-3-one derivatives, bearing adjacent quaternary-tertiary stereocenters, were efficiently synthesized with excellent enantioselectivities.

  15. Identification of Unsaturated and 2H Polyfluorocarboxylate Homologous Series and Their Detection in Environmental Samples and as Polymer Degradation Products

    EPA Science Inventory

    A pair of homologous series of polyfluorinated degradation products have been identified, both having structures similar to perfluorocarboxylic acids but (i) having a H substitution for F on the α carbon for 2H polyfluorocarboxylic acids (2HPFCAs) and (ii) bearing a double ...

  16. Atomic structures and electronic properties of 2H-NbSe{sub 2}: The impact of Ti doping

    SciTech Connect

    Li, Hongping E-mail: zcwang@wpi-aimr.tohoku.ac.jp; Chen, Lin; Zhang, Kun; Liang, Jiaqing; Tang, Hua; Li, Changsheng; Liu, Xiaojuan; Meng, Jian; Wang, Zhongchang E-mail: zcwang@wpi-aimr.tohoku.ac.jp

    2014-09-14

    Layered transition metal dichalcogenides have aroused renewed interest as electronic materials, yet their electronic performances could be modified by chemical doping. Here, we perform a systematic first-principles calculation to investigate the effect of Ti doping on atomic structure and electronic properties of the 2H-NbSe{sub 2}. We consider a total of three possible Ti-doping models and find that both the substitution and intercalated models are chemically preferred with the intercalation model being more favorable than the substitution one. Structural analyses reveal a slight lattice distortion triggered by Ti doping, but the original structure of 2H-NbSe{sub 2} is maintained. We also observe an expansion of c axis in the substituted model, which is attributed to the reduced van der Waals interaction arising from the increased Se-Se bond length. Our calculations also predict that the electron transport properties can be enhanced by the Ti doping, especially for the Ti-intercalated 2H-NbSe{sub 2}, which should be beneficial for the realization of superconductivity. Furthermore, the covalence element is found in the Ti-Se bonds, which is ascribed to the hybridization of Ti 3d and Se 4p orbitals. The findings indicate that doping of transition metals can be regarded as a useful way to tailor electronic states so as to improve electron transport properties of 2H-NbSe{sub 2}.

  17. The inhibitory effect of piperine from Fructus piperis extract on the degranulation of RBL-2H3 cells.

    PubMed

    Huang, Jing; Zhang, Tao; Han, Shengli; Cao, Jingjing; Chen, Qinhua; Wang, Sicen

    2014-12-01

    Allergy is an abnormal immune response to an allergen. Type I hypersensitivity is an immunoglobulin (Ig) E-mediated allergic disorder. Fructus piperis is derived from the ripe fruit of the pepper, which is widely used as a spice in human diets and is also administered as a medicine in many countries. Piperine has been shown to have anti-oxidant, anti-depressant, anti-tumor, and anti-inflammatory activities. However, the effect of piperine on IgE-mediated allergic responses has not been reported. Here, the rat basophilic leukemia cells by membrane chromatography (RBL-2H3/CMC) coupled to high performance liquid chromatography/mass spectrometry (HPLC/MS) to discover and identify piperine can bind to RBL-2H3 cell membranes. Piperine inhibited the expression of cytokines, and the release of both β-hexosaminidase and histamine, which could be stimulated by antigen in RBL-2H3 mast cells. We found that the levels of intracellular Ca(2+) also decreased. Furthermore, RT-PCR showed that the mRNA expression levels of IL-4, IL-13, and TNF-α were significantly suppressed by piperine. The inhibitory effect of piperine on IgE-mediated degranulation and cytokine production by RBL-2H3 cells may be caused by the inhibition of IgE-mediated signaling pathways, including the phosphorylation of Lyn, p38, Erk, and Ras. In summary, piperine can inhibit antigen-induced allergic reactions that control degranulation. PMID:25307563

  18. The inhibitory effect of piperine from Fructus piperis extract on the degranulation of RBL-2H3 cells.

    PubMed

    Huang, Jing; Zhang, Tao; Han, Shengli; Cao, Jingjing; Chen, Qinhua; Wang, Sicen

    2014-12-01

    Allergy is an abnormal immune response to an allergen. Type I hypersensitivity is an immunoglobulin (Ig) E-mediated allergic disorder. Fructus piperis is derived from the ripe fruit of the pepper, which is widely used as a spice in human diets and is also administered as a medicine in many countries. Piperine has been shown to have anti-oxidant, anti-depressant, anti-tumor, and anti-inflammatory activities. However, the effect of piperine on IgE-mediated allergic responses has not been reported. Here, the rat basophilic leukemia cells by membrane chromatography (RBL-2H3/CMC) coupled to high performance liquid chromatography/mass spectrometry (HPLC/MS) to discover and identify piperine can bind to RBL-2H3 cell membranes. Piperine inhibited the expression of cytokines, and the release of both β-hexosaminidase and histamine, which could be stimulated by antigen in RBL-2H3 mast cells. We found that the levels of intracellular Ca(2+) also decreased. Furthermore, RT-PCR showed that the mRNA expression levels of IL-4, IL-13, and TNF-α were significantly suppressed by piperine. The inhibitory effect of piperine on IgE-mediated degranulation and cytokine production by RBL-2H3 cells may be caused by the inhibition of IgE-mediated signaling pathways, including the phosphorylation of Lyn, p38, Erk, and Ras. In summary, piperine can inhibit antigen-induced allergic reactions that control degranulation.

  19. TES/Aura L2 Water Vapor (H2O) Lite Nadir (TL2H2OLN)

    Atmospheric Science Data Center

    2015-06-16

    TES/Aura L2 Water Vapor (H2O) Lite Nadir (TL2H2OLN) News:  TES News ... Level:  L2 Instrument:  TES/Aura L2 Water Vapor Spatial Coverage:  5.3 km nadir ... HDFView Read Software Level 2 Google Earth Visualizations Related Data:  Level 2 Lite Survey ...

  20. Laser photoacoustic trace detection of C2H4 revealing adverse environmental effects of atmospheric pollution on plant material

    NASA Astrophysics Data System (ADS)

    Harren, Frans J. M.; Petruzzelli, Luciana

    1993-03-01

    The photoacoustic detection method for trace gases in the atmosphere is well developed towards very low limits of detection, in the last years. Due to the combination of a sensitive photoacoustic cell placed intracavity in an infrared CO2 laser we were able to detect C2H4 at ultralow (< 1:1011) concentrations within 10 seconds, C2H4 in a plant hormone which seems to play an important role throughout all the life stages of a plant, including seed germination. In addition, various types of stress have been reported to promote ethylene production from different plant tissues. As part of our ongoing research on the role of ethylene in seed germination, we have compared our laser photoacoustic set-up to a gaschromatograph for measuring C2H4 produced by germinating Pisum sativum L. seeds within the first days of imbibition. C2H4 evolution by intact seeds shows a maximum at about 25 hours of germination. Thereafter, the rate of ethylene measured by gaschromatograph continues to decrease while that measured by the laser-driven photoacoustic system shows further increases. Most of the ethylene produced by seeds is found in isolated embryonic axes. The fumigation with ozone affects the growth of seedlings and their ethylene evolution.

  1. A [4 + 1] Cyclative Capture Access to Indolizines via Cobalt(III)-Catalyzed Csp(2)-H Bond Functionalization.

    PubMed

    Chen, Xun; Hu, Xinwei; Deng, Yuanfu; Jiang, Huanfeng; Zeng, Wei

    2016-09-16

    A Co(III)-catalyzed [4 + 1] cycloaddition of 2-arylpyridines or 2-alkenylpyridines with aldehydes through Csp(2)-H bond activation has been developed. This protocol provides a facile approach to structurally diverse indolizines including benzoindolizines with a broad range of functional group tolerance. PMID:27584706

  2. Annulation Reactions of Donor-Acceptor Cyclopropanes with (1-Azidovinyl)benzene and 3-Phenyl-2H-azirine.

    PubMed

    Curiel Tejeda, Joanne E; Irwin, Lauren C; Kerr, Michael A

    2016-09-16

    Under the influence of heat and Lewis acid, donor/acceptor cyclopropanes underwent annulation reactions with (1-azidovinyl)benzene and 3-phenyl-2H-azirine to form an unusual azabicyclic scaffold with an imbedded aziridine. The mechanism of reaction is believed to proceed via a vinyl nitrene intermediate. PMID:27598518

  3. N2H+ and N15NH+ toward the prestellar core 16293E in L1689N

    NASA Astrophysics Data System (ADS)

    Daniel, F.; Faure, A.; Pagani, L.; Lique, F.; Gérin, M.; Lis, D.; Hily-Blant, P.; Bacmann, A.; Roueff, E.

    2016-07-01

    Context. Understanding the processes that could lead to an enrichment of molecules in 15N atoms is of particular interest because this may shed light on the relatively strong variations observed in the 14N/15N ratio in various solar system environments. Aims: The sample of molecular clouds where 14N/15N ratios have been measured currently is small and has to be enlarged to allow statistically significant studies. In particular, the N2H+ molecule currently shows the broadest spread of 14N/15N ratios in high-mass star-forming regions. However, the 14N/15N ratio in N2H+ was obtained in only two low-mass star-forming regions (L1544 and B1b). We here extend this sample to a third dark cloud. Methods: We targeted the 16293E prestellar core, where the N15NH+J = 1-0 line was detected. Using a model previously developed for the physical structure of the source, we solved the molecular excitation with a nonlocal radiative transfer code. For this purpose, we computed specific collisional rate coefficients for the N15NH+-H2 collisional system. As a first step of the analysis, the N2H+ abundance profile was constrained by reproducing the N2H+J = 1-0 and 3-2 maps. A scaling factor was then applied to this profile to match the N15NH+J = 1-0 spectrum. Results: We derive a column density ratio N2H+/N15NH. Conclusions: We performed a detailed analysis of the excitation of N2H+ and N15NH+ in the direction of the 16293E core with modern models that solve the radiative transfer and with the most accurate collisional rate coefficients available to date. We obtained the third estimate of the N2H+/N15NH+ column density ratio in the direction of a cold prestellar core. The current estimate ~330 agrees with the typical value of the elemental isotopic ratio in the local interstellar medium. It is lower than in some other cores, however, where values as high as 1300 have been reported.

  4. First-principles analysis of C2H2 molecule diffusion and its dissociation process on the ferromagnetic bcc-Fe(110) surface

    NASA Astrophysics Data System (ADS)

    Ikeda, Minoru; Yamasaki, Takahiro; Kaneta, Chioko

    2010-09-01

    Using the projector-augmented plane wave method, we study diffusion and dissociation processes of C2H2 molecules on the ferromagnetic bcc-Fe(110) surface and investigate the formation process of graphene created by C2H2 molecules. The most stable site for C2H2 on the Fe surface is a hollow site and its adsorption energy is - 3.5 eV. In order to study the diffusion process of the C2H2 molecule, the barrier height energies for the C atom, C2-dimer and CH as well as the C2H2 molecule are estimated using the nudged elastic band method. The barrier height energy for C2H2 is 0.71 eV and this indicates that the C2H2 diffuses easily on this FM bcc-Fe(110) surface. We further investigate the two step dissociation process of C2H2 on Fe. The first step is the dissociation of C2H2 into C2H and H, and the second step is that of C2H into C2 and H. Their dissociation energies are 0.9 and 1.2 eV, respectively. These energies are relatively small compared to the dissociation energy 7.5 eV of C2H2 into C2H and H in the vacuum. Thus, the Fe surface shows catalytic effects. We further investigate the initial formation process of graphene by increasing the coverage of C2H2. The formation process of the benzene molecule on the FM bcc(110) surface is also discussed. We find that there exists a critical coverage of C2H2 which characterizes the beginning of the formation of the graphene.

  5. Analyses of Weapons-Grade MOX VVER-1000 Neutronics Benchmarks: Pin-Cell Calculations with SCALE/SAS2H

    SciTech Connect

    Ellis, R.J.

    2001-01-11

    A series of unit pin-cell benchmark problems have been analyzed related to irradiation of mixed oxide fuel in VVER-1000s (water-water energetic reactors). One-dimensional, discrete-ordinates eigenvalue calculations of these benchmarks were performed at ORNL using the SAS2H control sequence module of the SCALE-4.3 computational code system, as part of the Fissile Materials Disposition Program (FMDP) of the US DOE. Calculations were also performed using the SCALE module CSAS to confirm the results. The 238 neutron energy group SCALE nuclear data library 238GROUPNDF5 (based on ENDF/B-V) was used for all calculations. The VVER-1000 pin-cell benchmark cases modeled with SAS2H included zero-burnup calculations for eight fuel material variants (from LEU UO{sub 2} to weapons-grade MOX) at five different reactor states, and three fuel depletion cases up to high burnup. Results of the SAS2H analyses of the VVER-1000 neutronics benchmarks are presented in this report. Good general agreement was obtained between the SAS2H results, the ORNL results using HELIOS-1.4 with ENDF/B-VI nuclear data, and the results from several Russian benchmark studies using the codes TVS-M, MCU-RFFI/A, and WIMS-ABBN. This SAS2H benchmark study is useful for the verification of HELIOS calculations, the HELIOS code being the principal computational tool at ORNL for physics studies of assembly design for weapons-grade plutonium disposition in Russian reactors.

  6. Acetylene (C2H2) and hydrogen cyanide (HCN) from IASI satellite observations: global distributions, validation, and comparison with model

    NASA Astrophysics Data System (ADS)

    Duflot, V.; Wespes, C.; Clarisse, L.; Hurtmans, D.; Ngadi, Y.; Jones, N.; Paton-Walsh, C.; Hadji-Lazaro, J.; Vigouroux, C.; De Mazière, M.; Metzger, J.-M.; Mahieu, E.; Servais, C.; Hase, F.; Schneider, M.; Clerbaux, C.; Coheur, P.-F.

    2015-09-01

    We present global distributions of C2H2 and hydrogen cyanide (HCN) total columns derived from the Infrared Atmospheric Sounding Interferometer (IASI) for the years 2008-2010. These distributions are obtained with a fast method allowing to retrieve C2H2 abundance globally with a 5 % precision and HCN abundance in the tropical (subtropical) belt with a 10 % (25 %) precision. IASI data are compared for validation purposes with ground-based Fourier transform infrared (FTIR) spectrometer measurements at four selected stations. We show that there is an overall agreement between the ground-based and space measurements with correlation coefficients for daily mean measurements ranging from 0.28 to 0.81, depending on the site. Global C2H2 and subtropical HCN abundances retrieved from IASI spectra show the expected seasonality linked to variations in the anthropogenic emissions and seasonal biomass burning activity, as well as exceptional events, and are in good agreement with previous spaceborne studies. Total columns simulated by the Model for Ozone and Related Chemical Tracers, version 4 (MOZART-4) are compared to the ground-based FTIR measurements at the four selected stations. The model is able to capture the seasonality in the two species in most of the cases, with correlation coefficients for daily mean measurements ranging from 0.50 to 0.86, depending on the site. IASI measurements are also compared to the distributions from MOZART-4. Seasonal cycles observed from satellite data are reasonably well reproduced by the model with correlation coefficients ranging from -0.31 to 0.93 for C2H2 daily means, and from 0.09 to 0.86 for HCN daily means, depending on the considered region. However, the anthropogenic (biomass burning) emissions used in the model seem to be overestimated (underestimated), and a negative global mean bias of 1 % (16 %) of the model relative to the satellite observations was found for C2H2 (HCN).

  7. Isotopic Water Analyzer for Highly Precise Measurements of δ2H, δ18O, and δ17O

    NASA Astrophysics Data System (ADS)

    Berman, E. S.; Fortson, S.; Snaith, S.; Gupta, M.

    2012-12-01

    Measurements of the stable isotope ratios (δ2H, δ18O and δ17O) of both liquid water and water vapor are widely used in hydrology, atmospheric sciences, and biogeochemistry to determine the migration of water through an ecosystem. Previously, discrete samples were collected (or condensed) and transported to an isotope ratio mass spectrometer for characterization. Due to the expense and labor associated with such sampling, isotope studies were generally limited in scope and in temporal resolution. We report on the continued development of a field-portable Isotopic Water Analyzer that exploits cavity-enhanced absorption spectrometry (e.g. Off-Axis ICOS) to accurately and rapidly quantify δ2H, δ18O and δ17O of both liquid water and water vapor. The instrument is thermally-controlled to better than ±8 mK and is capable of measuring over 90 liquid samples/day with δ2H, δ18O and δ17O precisions exceeding ±0.2 ‰, ±0.05 ‰, and ±0.06 ‰ respectively. Subsequent averaging yields δ2H, δ18O and δ17O precisions exceeding ±0.077 ‰, ±0.023 ‰, and ±0.03 ‰ respectively with over 22 samples/day. The accuracy of the liquid analyzer was confirmed over a very wide dynamic range (δ2H = -455 to +671 ‰ with comparable δ18O and δ17O values) by direct comparison to isotope ratio mass spectrometry. Moreover, the ability to directly measure 17O-excess, vapor samples, and unnatural waters (e.g. plant water, soil water, urine, blood, saliva…) will also be presented.

  8. Formation and Fragmentation of Unsaturated Fatty Acid [M - 2H + Na]- Ions: Stabilized Carbanions for Charge-Directed Fragmentation

    NASA Astrophysics Data System (ADS)

    Thomas, Michael C.; Kirk, Benjamin B.; Altvater, Jens; Blanksby, Stephen J.; Nette, Geoffrey W.

    2013-12-01

    Fatty acids are long-chain carboxylic acids that readily produce [M - H]- ions upon negative ion electrospray ionization (ESI) and cationic complexes with alkali, alkaline earth, and transition metals in positive ion ESI. In contrast, only one anionic monomeric fatty acid-metal ion complex has been reported in the literature, namely [M - 2H + FeIICl]-. In this manuscript, we present two methods to form anionic unsaturated fatty acid-sodium ion complexes (i.e., [M - 2H + Na]-). We find that these ions may be generated efficiently by two distinct methods: (1) negative ion ESI of a methanolic solution containing the fatty acid and sodium fluoride forming an [M - H + NaF]- ion. Subsequent collision-induced dissociation (CID) results in the desired [M - 2H + Na]- ion via the neutral loss of HF. (2) Direct formation of the [M - 2H + Na]- ion by negative ion ESI of a methanolic solution containing the fatty acid and sodium hydroxide or bicarbonate. In addition to deprotonation of the carboxylic acid moiety, formation of [M - 2H + Na]- ions requires the removal of a proton from the fatty acid acyl chain. We propose that this deprotonation occurs at the bis-allylic position(s) of polyunsaturated fatty acids resulting in the formation of a resonance-stabilized carbanion. This proposal is supported by ab initio calculations, which reveal that removal of a proton from the bis-allylic position, followed by neutral loss of HX (where X = F- and -OH), is the lowest energy dissociation pathway.

  9. Deuterium NMR of Val1. (2-2H)Ala3. gramicidin A in oriented DMPC bilayers

    SciTech Connect

    Hing, A.W.; Adams, S.P.; Silbert, D.F.; Norberg, R.E. )

    1990-05-01

    Deuterium NMR is used to study the selectively labeled Val1...(2-2H)Ala3...gramicidin A molecule to investigate the structure and dynamics of the C alpha-2H bond in the Ala3 residue of gramicidin. Val1...(2-2H)Ala3...gramicidin A is synthesized, purified, and characterized and then incorporated into oriented bilayers of dimyristoylphosphatidylcholine sandwiched between glass coverslips. Phosphorus NMR line shapes obtained from this sample are consistent with the presence of the bilayer phase and indicate that no nonbilayer phases are present in significant amounts. Deuterium NMR line shapes obtained from this sample indicate that the motional axis of the gramicidin Ala3 residue is parallel to the coverslip normal, that the distribution of motional axis orientations has a width of 2 degrees, and that only one major conformational and dynamical state of the Ala3 C alpha-2H bond is observed on the NMR time scale. Furthermore, the Ala3 C alpha-2H bond angle relative to the motional axis is 19-20 degrees if fast axial rotation is assumed to be the only motion present but is less than or equal to 19-20 degrees in the absence of such an assumption. This result indicates that various double-stranded, helical dimer models are very unlikely to represent the structure of gramicidin in the sample studied but that the single-stranded, beta 6.3 helical dimer models are consistent with the experimental data. However, a definitive distinction between the left-handed, single-stranded, beta 6.3 helical dimer model and the right-handed, single-stranded, beta 6.3 helical dimer model cannot be made on the basis of the experimental data obtained in this study.

  10. FTIR time-series of biomass burning products (HCN, C2H6, C2H2, CH3OH, and HCOOH) at Reunion Island (21° S, 55° E) and comparisons with model data

    NASA Astrophysics Data System (ADS)

    Vigouroux, C.; Stavrakou, T.; Whaley, C.; Dils, B.; Duflot, V.; Hermans, C.; Kumps, N.; Metzger, J.-M.; Scolas, F.; Vanhaelewyn, G.; Müller, J.-F.; Jones, D. B. A.; Li, Q.; De Mazière, M.

    2012-11-01

    Reunion Island (21° S, 55° E), situated in the Indian Ocean at about 800 km east of Madagascar, is appropriately located to monitor the outflow of biomass burning pollution from Southern Africa and Madagascar, in the case of short-lived compounds, and from other Southern Hemispheric landmasses such as South America, in the case of longer-lived species. Ground-based Fourier transform infrared (FTIR) solar absorption observations are sensitive to a large number of biomass burning products. We present in this work the FTIR retrieval strategies, suitable for very humid sites such as Reunion Island, for hydrogen cyanide (HCN), ethane (C2H6), acetylene (C2H2), methanol (CH3OH), and formic acid (HCOOH). We provide their total columns time-series obtained from the measurements during August-October 2004, May-October 2007, and May 2009-December 2010. We show that biomass burning explains a large part of the observed seasonal and interannual variability of the chemical species. The correlations between the daily mean total columns of each of the species and those of CO, also measured with our FTIR spectrometer at Reunion Island, are very good from August to November (R ≥ 0.86). This allows us to derive, for that period, the following enhancement ratios with respect to CO: 0.0047, 0.0078, 0.0020, 0.012, and 0.0046 for HCN, C2H6, C2H2, CH3OH, and HCOOH, respectively. The HCN ground-based data are compared to the chemical transport model GEOS-Chem, while the data for the other species are compared to the IMAGESv2 model. We show that using the HCN/CO ratio derived from our measurements (0.0047) in GEOS-Chem reduces the underestimation of the modeled HCN columns compared with the FTIR measurements. The comparisons between IMAGESv2 and the long-lived species C2H6 and C2H2 indicate that the biomass burning emissions used in the model (from the GFED3 inventory) are probably underestimated in the late September-October period for all years of measurements, and especially in

  11. Molecular hydrogen complexes of the transition metals. 2. Evidence for a new complex, Mo(CO) (dppe)/sub 2/(H/sub 2/), and for solution equilibrium between dihydrogen and dihydride forms, M-eta/sup 2/-H/sub 2/ in equilibrium H-M-H, in W(CO)/sub 3/(PR/sub 3/)/sub 2/(H/sub 2/)

    SciTech Connect

    Kubas, G.J.; Ryan, R.R.; Wrobleski, D.A.

    1986-03-19

    Coordination of molecular hydrogen to transition metals is now firmly established, initially in the stable, structurally characterized complexes M(CO)/sub 3/(PR/sub 3/)/sub 2/(eta/sup 2/-H/sub 2/) (M = Mo, W; R = Cy, i-Pr), then in low-temperature stable Cr(CO)/sub 5/(H/sub 2/), and recently in IrH(H/sub 2/)(PPh/sub 3/)/sub 2/(C/sub 13/H/sub 8/N))SbF/sub 6/, (IrH/sub 2/(H/sub 2/)/sub 2/L/sub 2/)/sup +/, and (FeH(H/sub 2/)(dppe)/sub 2/)BF/sub 4/. In order to better define the steric and electronic requirements for H/sub 2/ to bind in molecular fashion rather than being cleaved to hydride ligands, reported here is new stable H/sub 2/ complex, Mo(CO)(dppe)/sub 2/(H/sub 2/) (dppe = diphenylphosphinoethane). Also, NMR evidence is presented for a dynamic equilibrium between the H/sub 2/ complex W(CO)/sub 3/(P-i-Pr/sub 3/)/sub 2/(eta/sup 2/-H/sub 2/), and an apparent dihydride complex, WH/sub 2/(CO)/sub 3/)P-i-Pr/sub 3/)/sub 2/, derived by oxidative addition of the H/sub 2/ ligand. 16 references, 2 figures.

  12. Large-scale upper tropospheric pollution observed by MIPAS HCN and C2H6 global distributions

    NASA Astrophysics Data System (ADS)

    Glatthor, N.; von Clarmann, T.; Stiller, G. P.; Funke, B.; Koukouli, M. E.; Fischer, H.; Grabowski, U.; Höpfner, M.; Kellmann, S.; Linden, A.

    2009-12-01

    We present global upper tropospheric HCN and C2H6 amounts derived from MIPAS/ENVISAT limb emission spectra. HCN and C2H6 are retrieved in the spectral regions 715.5-782.7 cm-1 and 811.5-835.7 cm-1, respectively. The datasets consist of 54 days between September 2003 and March 2004. This period covers the peak and decline of the southern hemispheric biomass burning period and some months thereafter. HCN is a nearly unambiguous tracer of biomass burning with an assumed tropospheric lifetime of several months. Indeed, the most significant feature in the MIPAS HCN dataset is an upper tropospheric plume of enhanced values caused by southern hemispheric biomass burning, which in September and October 2003 extended from tropical South America over Africa, Australia to the Southern Pacific. The spatial extent of this plume agrees well with the MOPITT CO distribution of September 2003. Further there is good agreement with the shapes and mixing ratios of the southern hemispheric HCN and C2H6 fields measured by the ACE experiment between September and November 2005. The MIPAS HCN plume extended from the lowermost observation height of 8 km up to about 16 km altitude, with maximum values of 500-600 pptv in October 2003. It was still clearly visible in December 2003, but had strongly decreased by March 2004, confirming the assumed tropospheric lifetime. The main sources of C2H6 are production and transmission of fossil fuels, followed by biofuel use and biomass burning. The C2H6 distribution also clearly reflected the southern hemispheric biomass burning plume and its seasonal variation, with maximum amounts of 600-700 pptv. Generally there was good spatial overlap between the southern hemispheric distributions of both pollution tracers, except for the region between Peru and the mid-Pacific. Here C2H6was considerably enhanced, whereas the HCN amounts were low. Backward trajectory calculations suggested that industrial pollution was responsible for the elevated C2H6

  13. On the physical structure of IRC +10216. Ground-based and Herschel observations of CO and C2H

    NASA Astrophysics Data System (ADS)

    De Beck, E.; Lombaert, R.; Agúndez, M.; Daniel, F.; Decin, L.; Cernicharo, J.; Müller, H. S. P.; Min, M.; Royer, P.; Vandenbussche, B.; de Koter, A.; Waters, L. B. F. M.; Groenewegen, M. A. T.; Barlow, M. J.; Guélin, M.; Kahane, C.; Pearson, J. C.; Encrenaz, P.; Szczerba, R.; Schmidt, M. R.

    2012-03-01

    Context. The carbon-rich asymptotic giant branch star IRC +10 216 undergoes strong mass loss, and quasi-periodic enhancements of the density of the circumstellar matter have previously been reported. The star's circumstellar environment is a well-studied and complex astrochemical laboratory, in which many molecular species have been proved to be present. CO is ubiquitous in the circumstellar envelope, while emission from the ethynyl (C2H) radical is detected in a spatially confined shell around IRC +10 216. We recently detected unexpectedly strong emission from the N = 4-3, 6-5, 7-6, 8-7, and 9-8 transitions of C2H with the IRAM 30 m telescope and with Herschel/HIFI, which challenges the available chemical and physical models. Aims: We aim to constrain the physical properties of the circumstellar envelope of IRC +10 216, including the effect of episodic mass loss on the observed emission lines. In particular, we aim to determine the excitation region and conditions of C2H to explain the recent detections and to reconcile them with interferometric maps of the N = 1-0 transition of C2H. Methods: Using radiative-transfer modelling, we provide a physical description of the circumstellar envelope of IRC +10 216, constrained by the spectral-energy distribution and a sample of 20 high-resolution and 29 low-resolution CO lines - to date, the largest modelled range of CO lines towards an evolved star. We furthermore present the most detailed radiative-transfer analysis of C2H that has been done so far. Results: Assuming a distance of 150 pc to IRC +10 216, the spectral-energy distribution was modelled with a stellar luminosity of 11300 L⊙ and a dust-mass-loss rate of 4.0 × 10-8 M⊙ yr-1. Based on the analysis of the 20 high-frequency-resolution CO observations, an average gas-mass-loss rate for the last 1000 years of 1.5 × 10-5 M⊙ yr-1 was derived. This results in a gas-to-dust-mass ratio of 375, typical for this type of star. The kinetic temperature throughout the

  14. Different cation-protonation patterns in mol-ecular salts of unsymmetrical dimethyhydrazine: C2H9N2·Br and C2H9N2·H2PO3.

    PubMed

    Katinaitė, Judita; Harrison, William T A

    2016-08-01

    We describe the syntheses and crystal structures of two mol-ecular salts containing the 1,1-di-methyl-hydrazinium cation, namely 1,1-di-methyl-hydrazin-1-ium bromide, C2H9N2 (+)·Br(-), (I), and 2,2-di-methyl-hydrazin-1-ium di-hydrogen phosphite, C2H9N2 (+)·H2PO3 (-), (II). In (I), the cation is protonated at the methyl-ated N atom and N-H⋯Br hydrogen bonds generate [010] chains in the crystal. In (II), the cation is protonated at the terminal N atom and cation-to-anion N-H⋯O and anion-to-anion O-H⋯O hydrogen bonds generate (001) sheets. PMID:27536415

  15. Different cation-protonation patterns in mol­ecular salts of unsymmetrical dimethyhydrazine: C2H9N2·Br and C2H9N2·H2PO3

    PubMed Central

    Katinaitė, Judita; Harrison, William T. A.

    2016-01-01

    We describe the syntheses and crystal structures of two mol­ecular salts containing the 1,1-di­methyl­hydrazinium cation, namely 1,1-di­methyl­hydrazin-1-ium bromide, C2H9N2 +·Br−, (I), and 2,2-di­methyl­hydrazin-1-ium di­hydrogen phosphite, C2H9N2 +·H2PO3 −, (II). In (I), the cation is protonated at the methyl­ated N atom and N—H⋯Br hydrogen bonds generate [010] chains in the crystal. In (II), the cation is protonated at the terminal N atom and cation-to-anion N—H⋯O and anion-to-anion O—H⋯O hydrogen bonds generate (001) sheets. PMID:27536415

  16. Synthesis and the crystal and molecular structure of the silver(I)-germanium(IV) polymeric complex with citrate anions {[Ag2Ge(H Cit)2(H2O)2] • 2H2O} n

    NASA Astrophysics Data System (ADS)

    Sergienko, V. S.; Martsinko, E. E.; Seifullina, I. I.; Churakov, A. V.; Chebanenko, E. A.

    2016-03-01

    The synthesis and X-ray diffraction study of compound {[Ag2Ge(H Cit)2(H2O)2] • 2H2O} n , where H4 Cit is the citric acid, are performed. In the polymeric structure, the H Cit 3- ligand fulfils the tetradentate chelate-μ4-bridging (3Ag, Ge) function (tridentate with respect to Ge and Ag atoms). The Ge atom is octahedrally coordinated by six O atoms of two H Cit 3-ligands. The coordination polyhedron of the Ag atom is an irregular five-vertex polyhedron [four O atoms of four H Cit 3- ligands and the O(H2O) atom]. An extended system of O-H···O hydrogen bonds connects complex molecules into a supramolecular 3D-framework.

  17. Covariance mapping of two-photon double core hole states in C 2 H 2 and C 2 H 6 produced by an x-ray free electron laser

    DOE PAGES

    Mucke, M; Zhaunerchyk, V; Frasinski, L J; Squibb, R J; Siano, M; Eland, J H D; Linusson, P; Salén, P; Meulen, P v d; Thomas, R D; et al

    2015-07-01

    Few-photon ionization and relaxation processes in acetylene (C2H2) and ethane (C2H6) were investigated at the linac coherent light source x-ray free electron laser (FEL) at SLAC, Stanford using a highly efficient multi-particle correlation spectroscopy technique based on a magnetic bottle. The analysis method of covariance mapping has been applied and enhanced, allowing us to identify electron pairs associated with double core hole (DCH) production and competing multiple ionization processes including Auger decay sequences. The experimental technique and the analysis procedure are discussed in the light of earlier investigations of DCH studies carried out at the same FEL and at thirdmore » generation synchrotron radiation sources. In particular, we demonstrate the capability of the covariance mapping technique to disentangle the formation of molecular DCH states which is barely feasible with conventional electron spectroscopy methods.« less

  18. 2H NMR and 13C-IRMS analyses of acetic acid from vinegar, 18O-IRMS analysis of water in vinegar: international collaborative study report.

    PubMed

    Thomas, Freddy; Jamin, Eric

    2009-09-01

    An international collaborative study of isotopic methods applied to control the authenticity of vinegar was organized in order to support the recognition of these procedures as official methods. The determination of the 2H/1H ratio of the methyl site of acetic acid by SNIF-NMR (site-specific natural isotopic fractionation-nuclear magnetic resonance) and the determination of the 13C/12C ratio, by IRMS (isotope ratio mass spectrometry) provide complementary information to characterize the botanical origin of acetic acid and to detect adulterations of vinegar using synthetic acetic acid. Both methods use the same initial steps to recover pure acetic acid from vinegar. In the case of wine vinegar, the determination of the 18O/16O ratio of water by IRMS allows to differentiate wine vinegar from vinegars made from dried grapes. The same set of vinegar samples was used to validate these three determinations. The precision parameters of the method for measuring delta13C (carbon isotopic deviation) were found to be similar to the values previously obtained for similar methods applied to wine ethanol or sugars extracted from fruit juices: the average repeatability (r) was 0.45 per thousand, and the average reproducibility (R) was 0.91 per thousand. As expected from previous in-house study of the uncertainties, the precision parameters of the method for measuring the 2H/1H ratio of the methyl site were found to be slightly higher than the values previously obtained for similar methods applied to wine ethanol or fermentation ethanol in fruit juices: the average repeatability was 1.34 ppm, and the average reproducibility was 1.62 ppm. This precision is still significantly smaller than the differences between various acetic acid sources (delta13C and delta18O) and allows a satisfactory discrimination of vinegar types. The precision parameters of the method for measuring delta18O were found to be similar to the values previously obtained for other methods applied to wine and

  19. Multipole analysis of {sup 2}H({gamma},p)n in the {Delta} resonance region

    SciTech Connect

    Whisnant, C.S.; Mize, W.K.; Pomarede, D.; Sandorfi, A.M.

    1998-07-01

    An energy-dependent multipole analysis of the photodisintegration of deuterium has been performed for photon energies between 187 and 314 MeV using recent data taken with linearly polarized photons. A good fit is obtained with 11 free parameters determining eight multipoles. A wide variety of multipole solutions has been examined and in all cases the cross section with photon polarization parallel to the reaction plane is dominated by electric transitions, with E2{bold {center_dot}}E1 interference responsible for the observed forward-backward angular asymmetry. The cross sections observed in perpendicular kinematics are dominated by magnetic multipoles. Several recent N{Delta}/NN coupled-channel calculations have predicted a pronounced 90{degree} dip in the cross section that is absent from the data. This dip can be reproduced by changing the M2 strength distribution in our fit. A comparison is made with multipoles calculated by Wilhelm and Arenh{umlt o}vel at 300 MeV. {copyright} {ital 1998} {ital The American Physical Society}

  20. Detection of Anisotropy in Cartilage Using 2H Double-Quantum-Filtered NMR-Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sharf, Y.; Eliav, U.; Shinar, H.; Navon, G.

    Double-quantum-filtered (DQF) NMR spectroscopy of I = 1 spin systems is a diagnostic tool for the detection of anisotropy in macroscopically disordered systems. For deuterium, this method reveals the presence of a residual quadrupolar interaction for D 2O in bovine nasal cartilage. This tissue is not macroscopically ordered and the quadrupolar splitting is not resolved. Fitting the calculated spectral lineshapes to the experimental results was possible only when a distribution of the residual quadrupolar interaction, omega(q), was assumed. The series of DQF lineshapes obtained for different creation times in the DQF experiment could be fitted using a single set of three parameters: the average residual quadrupolar interaction overlineω q/2π = 110 Hz, its standard deviation Δω q/2π = 73 Hz, and the transverse relaxation rate of 63 s -1. Separate deuterium DQF measurements for the constituents of the cartilage, collagen, and chondroitin sulfate indicated that the DQF spectra of cartilage are the result of anisotropic motion of D 2O due to binding to the fibrous collagen in the tissue.