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Sample records for gas-phase spectroscopic studies

  1. Gas phase spectroscopic study of unstable molecules using FTIR technique

    International Nuclear Information System (INIS)

    Allaf, A.W.; Alibrahim, M.; Kassem, M.

    1998-01-01

    A new route has been developed, leading to the production of phosphorus (III) oxycyanide, OPCN and phosphorus (III) oxycyanate, OPOCN by an on-line process using phosphoryl chloride, POCL 3 as a starting material passed over heated silver at 870 Centigrade and then reacted with AgCN and KOCN heated at 270 Centigrade and 590 Centigrade to produce OPCN and OPOCN respectively. The gas phase fourier transform infrared spectra reported for the first time show the two characterized bonds of OPCN and OPOCN at 2165 cm -1 and 2130 cm -1 , assigned to the C≡N stretching fundamentals of OPCN and OPOCN respectively. (Author)

  2. Spectroscopic studies of molecular iodine emitted into the gas phase by seaweed

    Directory of Open Access Journals (Sweden)

    S. M. Ball

    2010-07-01

    Full Text Available Time profiles of molecular iodine emissions from seven species of seaweed have been measured at high time resolution (7.5 s by direct spectroscopic quantification of the gas phase I2 using broadband cavity enhanced absorption spectroscopy. Substantial differences were found between species, both in the amounts of I2 emitted when the plants were exposed to air and in the shapes of their emission time profiles. Two species of kelp, Laminaria digitata and Laminaria hyperborea, were found to be the most potent emitters, producing an intense burst of I2 when first exposed to air. I2 was also observed from Saccharina latissima and Ascophyllum nodosum but in lower amounts and with broader time profiles. I2 mixing ratios from two Fucus species and Dictyopteris membranacea were at or below the detection limit of the present instrument (25 pptv. A further set of experiments investigated the time dependence of I2 emissions and aerosol particle formation when fragments of L. digitata were exposed to desiccation in air, to ozone and to oligoguluronate stress factors. Particle formation occurred in all L. digitata stress experiments where ozone and light were present, subject to the I2 mixing ratios being above certain threshold amounts. Moreover, the particle number concentrations closely tracked variations in the I2 mixing ratios, confirming the results of previous studies that the condensable particle-forming gases derive from the photochemical oxidation of the plant's I2 emissions. This work also supports the theory that particle nucleation in the coastal atmosphere occurs in "hot-spot" regions of locally elevated concentrations of condensable gases: the greatest atmospheric concentrations of I2 and hence of condensable iodine oxides are likely to be above plants of the most efficiently

  3. Gas-phase spectroscopic studies of heavy elements compounds (group V) using FTIR technique

    International Nuclear Information System (INIS)

    Allaf, A. W.; Ajji, Z.

    1998-12-01

    Antimony oxide trihalide, OSbX3 where X=F, CI and Br, and antimony (III) oxychloride, OSbC1 molecules were produced by an on-line process for the first time using antimony chloride SbC13 passed over heated silver oxide then followed by passing the obtained products over heated NaF and heated KBr for SbOF3 and OSbBr3, respectively. The obtained OSbC13 reacts with heated silver to produce OSbC1. The products have been characterized by the infrared spectra of their vapors. The low resolution gas-phase Fourier transform infrared spectrum, reported for the first time, shows the most characteristic band of OSbX3 at 1272, 1217 and 1200 cm -1 and the bands are assigned to the O=Sb stretching fundamental of OSbX3 were X=F, Cl and Br, respectively. The band at 1200 cm -1 needs more experimental investigation. The band at 924 cm -1 is assigned to the O=Sb stretching fundamental of OSbCl molecule. This result is in consistent with expectation and shifted to lower frequency in comparison with arsenic analogous molecule which is investigated by matrix-isolation technique. The work will be continued in order to cover the bismuth and arsenic compounds of similar structures. (author)

  4. A computational and spectroscopic study of the gas-phase conformers of adrenaline

    Science.gov (United States)

    Çarçabal, P.; Snoek, L. C.; van Mourik, T.

    The conformational landscapes of the neurotransmitter l-adrenaline (l-epinephrine) and its diastereoisomer pseudo-adrenaline, isolated in the gas phase and un-protonated, have been investigated by using a combination of mass-selected ultraviolet and infrared holeburn spectroscopy, following laser desorption of the sample into a pulsed supersonic argon jet, and DFT and ab initio computation (at the B3LYP/6-31+G*, MP2/6-31+G* and MP2/aug-cc-pVDZ levels of theory). Both for adrenaline and its diastereoisomer, pseudo-adrenaline, one dominant molecular conformation, very similar to the one seen in noradrenaline, has been observed. It could be assigned to an extended side-chain structure (AG1a) stabilized by an OH → N intramolecular hydrogen bond. An intramolecular hydrogen bond is also formed between the neighbouring hydroxyl groups on the catechol ring. The presence of further conformers for both diastereoisomers could not be excluded, but overlapping electronic spectra and low ion signals prevented further assignments.

  5. Two dimensional laser induced fluorescence in the gas phase: a spectroscopic tool for studying molecular spectroscopy and dynamics

    Science.gov (United States)

    Gascooke, Jason R.; Lawrance, Warren D.

    2017-11-01

    Two dimensional laser induced fluorescence (2D-LIF) extends the usual laser induced fluorescence technique by adding a second dimension, the wavelength at which excited states emit, thereby significantly enhancing the information that can be extracted. It allows overlapping absorption features, whether they arise from within the same molecule or from different molecules in a mixture, to be associated with their appropriate "parent" state and/or molecule. While the first gas phase version of the technique was published a decade ago, the technique is in its infancy, having been exploited by only a few groups to date. However, its potential in gas phase spectroscopy and dynamics is significant. In this article we provide an overview of the technique and illustrate its potential with examples, with a focus on those utilising high resolution in the dispersed fluorescence dimension.

  6. Study of ions - molecules reactions in the gas phase with collision reaction cell devices: Applications to the direct resolution of spectroscopic interferences in ICP-MS

    International Nuclear Information System (INIS)

    Favre, G.

    2008-12-01

    Inductively Coupled Plasma Mass Spectrometry emerged as the most widespread mass spectrometry technique in inorganic analytical chemistry for determining the concentration of a given isotope or an isotope ratio. The problem of spectroscopic interferences, inherent to this technique, finds a solution through the use of reaction cell devices. An in situ interference removal is feasible with the addition of a well selected gas in the cell. The understanding of the chemistry of ions-molecules interactions in the gas phase is however fundamental to optimize the efficiency of such devices. An accurate knowledge of experimental conditions in the reaction zone according to instrumental parameters appears crucial in order to interpret observed reactivities. This preliminary study is then used for the resolution of two nuclear field characteristic interferences. (author)

  7. Ab initio structural and spectroscopic study of HPS{sup x} and HSP{sup x} (x = 0,+1,−1) in the gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Yaghlane, Saida Ben [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications – LSAMA, Université de Tunis, Tunis (Tunisia); Cotton, C. Eric; Francisco, Joseph S., E-mail: francisc@purdue.edu, E-mail: hochlaf@univ-mlv.fr [Department of Chemistry and Department of Earth and Atmospheric Science, Purdue University, West Lafayette, Indiana 49707 (United States); Linguerri, Roberto; Hochlaf, Majdi, E-mail: francisc@purdue.edu, E-mail: hochlaf@univ-mlv.fr [Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, Université Paris-Est, 5 bd Descartes, 77454 Marne-la-Vallée (France)

    2013-11-07

    Accurate ab initio computations of structural and spectroscopic parameters for the HPS/HSP molecules and corresponding cations and anions have been performed. For the electronic structure computations, standard and explicitly correlated coupled cluster techniques in conjunction with large basis sets have been adopted. In particular, we present equilibrium geometries, rotational constants, harmonic vibrational frequencies, adiabatic ionization energies, electron affinities, and, for the neutral species, singlet-triplet relative energies. Besides, the full-dimensional potential energy surfaces (PESs) for HPS{sup x} and HSP{sup x} (x = −1,0,1) systems have been generated at the standard coupled cluster level with a basis set of augmented quintuple-zeta quality. By applying perturbation theory to the calculated PESs, an extended set of spectroscopic constants, including τ, first-order centrifugal distortion and anharmonic vibrational constants has been obtained. In addition, the potentials have been used in a variational approach to deduce the whole pattern of vibrational levels up to 4000 cm{sup −1} above the minima of the corresponding PESs.

  8. Gas phase absorption studies of photoactive yellow protein chromophore derivatives.

    Science.gov (United States)

    Rocha-Rinza, Toms; Christiansen, Ove; Rajput, Jyoti; Gopalan, Aravind; Rahbek, Dennis B; Andersen, Lars H; Bochenkova, Anastasia V; Granovsky, Alexander A; Bravaya, Ksenia B; Nemukhin, Alexander V; Christiansen, Kasper Lincke; Nielsen, Mogens Brøndsted

    2009-08-27

    Photoabsorption spectra of deprotonated trans p-coumaric acid and two of its methyl substituted derivatives have been studied in gas phase both experimentally and theoretically. We have focused on the spectroscopic effect of the location of the two possible deprotonation sites on the trans p-coumaric acid which originate to either a phenoxide or a carboxylate. Surprisingly, the three chromophores were found to have the same absorption maximum at 430 nm, in spite of having different deprotonation positions. However, the absorption of the chromophore in polar solution is substantially different for the distinct deprotonation locations. We also report on the time scales and pathways of relaxation after photoexcitation for the three photoactive yellow protein chromophore derivatives. As a result of these experiments, we could detect the phenoxide isomer within the deprotonated trans p-coumaric acid in gas phase; however, the occurrence of the carboxylate is uncertain. Several computational methods were used simultaneously to provide insights and assistance in the interpretation of our experimental results. The calculated excitation energies S(0)-S(1) are in good agreement with experiment for those systems having a negative charge on a phenoxide moiety. Although our augmented multiconfigurational quasidegenerate perturbation theory calculations agree with experiment in the description of the absorption spectrum of anions with a carboxylate functional group, there are some puzzling disagreements between experiment and some calculational methods in the description of these systems.

  9. Studies of matrix diffusion in gas phase

    International Nuclear Information System (INIS)

    Hartikainen, K.; Timonen, J.; Vaeaetaeinen, K.; Pietarila, H.

    1994-03-01

    The diffusion of solutes from fractures into rock matrix is an important factor in the safety analysis of disposal of radioactive waste. Laboratory measurements are needed to complement field investigations for a reliable determination of the necessary transport parameters. Measurements of diffusion coefficients in tight rock samples are usually time consuming because the diffusion processes are slow. On the other hand it is well known that diffusion coefficients in the gas phase are roughly four orders of magnitude larger than those in the liquid phase. Therefore, for samples whose structures do not change much upon drying, it is possible to estimate the diffusion properties of the liquid phase when the properties of the gas phase are known. Advantages of the gas method are quick and easy measurements. In the measurements nitrogen was used as the carrier gas and helium as the tracer gas, and standard techniques have been used for helium detection. Techniques have been developed for both channel flow and through-diffusion measurements. The breakthrough curves have been measured in every experiment and all measurements have been modelled by using appropriate analytical models. As a result matrix porosities and effective diffusion coefficients in the gas phase have been determined. (12 refs., 21 figs., 6 tabs.)

  10. Intrinsic folding of small peptide chains: spectroscopic evidence for the formation of beta-turns in the gas phase.

    Science.gov (United States)

    Chin, Wutharath; Dognon, Jean-Pierre; Piuzzi, François; Tardivel, Benjamin; Dimicoli, Iliana; Mons, Michel

    2005-01-19

    Laser desorption of model peptides coupled to laser spectroscopic techniques enables the gas-phase observation of genuine secondary structures of biology. Spectroscopic evidence for the formation of beta-turns in gas-phase peptide chains containing glycine and phenylalanine residues establishes the intrinsic stability of these forms and their ability to compete with other stable structures. The precise characterization of local minima on the potential energy surface from IR spectroscopy constitutes an acute assessment for the state-of-the-art quantum mechanical calculations also presented. The observation of different types of beta-turns depending upon the residue order within the sequence is found to be consistent with the residue propensities in beta-turns of proteins, which suggests that the prevalence of glycine in type II and II' turns stems essentially from an energetic origin, already at play under isolated conditions.

  11. Spectroscopic evidence for gas-phase formation of successive beta-turns in a three-residue peptide chain.

    Science.gov (United States)

    Chin, Wutharath; Compagnon, Isabelle; Dognon, Jean-Pierre; Canuel, Clélia; Piuzzi, François; Dimicoli, Iliana; von Helden, Gert; Meijer, Gerard; Mons, Michel

    2005-02-09

    We report the first gas-phase spectroscopic study of a three-residue model of a peptide chain, Ac-Phe-Gly-Gly-NH2 (Ac = acetyl), using the IR/UV double resonance technique. The existence of at least five different conformers under supersonic expansion conditions is established, most of them exhibiting rather strong intramolecular H-bonds. One of the most populated conformers, however, exhibits a different H-bonding network characterized by two weak H-bonds. Comparison of the amide A and I/II experimental data with density functional theory calculations carried out on a series of selected conformations enables us to assign this conformer to two successive beta-turns along the peptide chain, the two H-bonds being of C10 type, i.e., each of them closing a 10-atom ring in the molecule. The corresponding form is found to be more stable than the 310 helix secondary structure (not observed), presumably because of specific effects due to the glycine residues.

  12. Spectroscopic study

    International Nuclear Information System (INIS)

    Flores, M.; Rodriguez, R.; Arroyo, R.

    1999-01-01

    This work is focused about the spectroscopic properties of a polymer material which consists of Polyacrylic acid (Paa) doped at different concentrations of Europium ions (Eu 3+ ). They show that to stay chemically joined with the polymer by a study of Nuclear Magnetic Resonance (NMR) of 1 H, 13 C and Fourier Transform Infrared Spectroscopy (Ft-IR) they present changes in the intensity of signals, just as too when this material is irradiated at λ = 394 nm. In according with the results obtained experimentally in this type of materials it can say that is possible to unify chemically the polymer with this type of cations, as well as, varying the concentration of them, since that these are distributed homogeneously inside the matrix maintaining its optical properties. These materials can be obtained more quickly and easy in solid or liquid phase and they have the best conditions for to make a quantitative analysis. (Author)

  13. Raman study of vibrational dynamics of aminopropylsilanetriol in gas phase

    Science.gov (United States)

    Volovšek, V.; Dananić, V.; Bistričić, L.; Movre Šapić, I.; Furić, K.

    2014-01-01

    Raman spectrum of aminopropylsilanetriol (APST) in gas phase has been recorded at room temperature in macro chamber utilizing two-mirror technique over the sample tube. Unlike predominantly trans molecular conformation in condensed phase, the spectra of vapor show that the molecules are solely in gauche conformation with intramolecular hydrogen bond N⋯Hsbnd O which reduces the molecular energy in respect to trans conformation by 0.152 eV. The assignment of the molecular spectra based on the DFT calculation is presented. The strong vibrational bands at 354 cm-1, 588 cm-1 and 3022 cm-1 are proposed for verifying the existence of the ring like, hydrogen bonded structure. Special attention was devoted to the high frequency region, where hydrogen bond vibrations are coupled to stretchings of amino and silanol groups.

  14. Conformational Study of Taurine in the Gas Phase

    Science.gov (United States)

    Cortijo, Vanessa; Sanz, M. Eugenia; López, Juan C.; Alonso, José L.

    2009-08-01

    The conformational preferences of the amino sulfonic acid taurine (NH2-CH2-CH2-SO3H) have been investigated in the gas phase by laser ablation molecular beam Fourier transform microwave spectroscopy (LA-MB-FTMW) in the 6-14 GHz frequency range. One conformer has been observed, and its rotational, centrifugal distortion, and hyperfine quadrupole coupling constants have been determined from the analysis of its rotational spectrum. Comparison of the experimental constants with those calculated theoretically identifies the detected conformer unambiguously. The observed conformer of taurine is stabilized by an intramolecular hydrogen bond O-H···N between the hydrogen of the sulfonic acid group and the nitrogen atom of the amino group.

  15. Wigner Distribution Functions as a Tool for Studying Gas Phase Alkali Metal Plus Noble Gas Collisions

    Science.gov (United States)

    2014-03-27

    WIGNER DISTRIBUTION FUNCTIONS AS A TOOL FOR STUDYING GAS PHASE ALKALI METAL PLUS NOBLE GAS COLLISIONS THESIS Keith A. Wyman, Second Lieutenant, USAF...the U.S. Government and is not subject to copyright protection in the United States. AFIT-ENP-14-M-39 WIGNER DISTRIBUTION FUNCTIONS AS A TOOL FOR...APPROVED FOR PUBLIC RELEASE; DISTRIBUTION UNLIMITED AFIT-ENP-14-M-39 WIGNER DISTRIBUTION FUNCTIONS AS A TOOL FOR STUDYING GAS PHASE ALKALI METAL PLUS

  16. Gas phase ion/molecule reactions as studied by Fourier Transform Ion Cyclotron Resonance mass spectrometry

    International Nuclear Information System (INIS)

    Joergensen, S.I.

    1985-01-01

    The subject of this thesis is gas phase ion/molecule reactions as studied by Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometry (chapter 2 contains a short description of this method). Three chapters are mainly concerned with mechanistic aspects of gas phase ion/molecule reactions. An equally important aspect of the thesis is the stability and reactivity of α-thio carbanions, dipole stabilized carbanions and homoenolate anions, dealt with in the other four chapters. (Auth.)

  17. Gas Phase Structure of Amino Acids: La-Mb Studies

    Science.gov (United States)

    Mata, I. Pena S.; Sanz, M. E.; Vaquero, V.; Cabezas, C.; Perez, C.; Blanco, S.; López, J. C.; Alonso, J. L.

    2009-06-01

    Recent improvements in our laser ablation molecular beam Fourier transform microwave (LA-MB-FTMW) spectrometer such as using Laval-type nozzles and picoseconds Nd:YAG lasers (30 to 150 ps) have allowed a major step forward in the capabilities of this experimental technique as demonstrated by the last results in serine cysteine and threonine^a for which seven, six and seven conformers have been respectively identified. Taking advantage of these improvements we have investigated the natural amino acids metionine, aspartic and glutamic acids and the γ-aminobutyric acid (GABA) with the aim of identify and characterize their lower energy conformers. Searches in the rotational spectra have lead to the identification of seven conformers of metionine, six and five of aspartic and glutamic acids, respectively, and seven for the γ-aminobutyric. These conformers have been unambiguously identified by their spectroscopic constants. In particular the ^{14}N nuclear quadrupole coupling constants, that depend heavily on the orientation of the amino group with respect to the principal inertial axes of the molecule, prove to be a unique tool to distinguish unambigously between conformations with similar rotational constants. For the γ-aminobutyric acid two of the seven observed structures are stablized by an intramolecular interaction n-π*. Two new conformers of proline have been identified together with the two previously observed. J. L. Alonso, C. Pérez, M. E. Sanz, J. C. López, S. Blanco, Phys.Chem.Chem.Phys., 2009, 11, 617. D. B. Atkinson, M. A. Smith, Rev. Sci. Instrum. 1995, 66, 4434 S. Blanco, M. E. Sanz, J. C. López, J. L. Alonso, Proc. Natl. Acad. Sci. USA2007, 104, 20183. M. E. Sanz, S. Blanco, J. C. López, J. L. Alonso, Angew. Chem. Int. Ed.,2008, 120, 6312. A. Lesarri, S. Mata, E. J. Cocinero, S. Blanco, J.C. López, J. L. Alonso, Angew. Chem. Int. Ed. , 2002, 41, 4673

  18. Studies of gas phase ion/molecule reactions by Fourier transform ion cyclotron resonance mass spectrometry

    International Nuclear Information System (INIS)

    Kleingeld, J.C.

    1984-01-01

    An important field in which Fourier-transform ion cyclotron resonance has useful applications is that of gas phase ion chemistry, the subject of this thesis. First, the general picture of ion-molecule reactions in the gas phase is discussed. Next, some positive ion-molecule reactions are described, whereas the remaining chapters deal with negative ion-molecule reactions. Most of these studies have been performed using the FT-ICR method. Reactions involving H 3 O - and NH 4 - ions are described whereas the other chapters deal with larger organic complexes. (Auth.)

  19. Study of Iodine Behavior in the Gas Phase during a Severe Accident

    International Nuclear Information System (INIS)

    Kim, Hanchul; Cho, Yeonghun; Ryu, Myunghyun

    2014-01-01

    Among the iodine species, the organic iodides produced from the reaction between iodine and organics such as paint, are not easily trapped by the filters during the containment venting following a severe accident. Korea Institute of Nuclear Safety (KINS) has been studying this issue, joining international research programs such as ISTP-EPICUR, OECDBIP and OECD-STEM. In the course of this study, a simple iodine model, RAIM (Radio-Active Iodine chemistry Model) has been developed (Oh et al., 2011), based on the IMOD methodology, and other previous studies. This paper deals with our recent activities on this study, including the development of the model for the iodine reactions in gas phase. Iodine reactions in gas phase were modeled and added to the RAIM code, taking into account several relevant reactions such as formation of ARP, iodine oxide, and organic iodides in gas phase. RAIM was then applied to analyze the S2-6-5-2 test for which iodine-loaded coupons were tested in gas phase. The analysis results show a reasonable estimation of volatile iodine concentration with the desorption rate constant of about 10 -6 s -1 , while those of the other iodine species overestimated for the whole period of the test. It reveals the need to determine appropriate values for the rate constants for formation of iodine oxides and organic iodides

  20. Assessment of amide I spectroscopic maps for a gas-phase peptide using IR-UV double-resonance spectroscopy and density functional theory calculations

    Energy Technology Data Exchange (ETDEWEB)

    Carr, J. K.; Roy, S.; Skinner, J. L. [Department of Chemistry and Theoretical Chemistry Institute, University of Wisconsin, Madison, Wisconsin 53706 (United States); Zabuga, A. V.; Rizzo, T. R. [Laboratoire de Chimie Physique Moleculaire, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCPM, Station 6, CH-1015 Lausanne (Switzerland)

    2014-06-14

    The spectroscopy of amide I vibrations has become a powerful tool for exploring protein structure and dynamics. To help with spectral interpretation, it is often useful to perform molecular dynamics (MD) simulations. To connect spectroscopic experiments to simulations in an efficient manner, several researchers have proposed “maps,” which relate observables in classical MD simulations to quantum spectroscopic variables. It can be difficult to discern whether errors in the theoretical results (compared to experiment) arise from inaccuracies in the MD trajectories or in the maps themselves. In this work, we evaluate spectroscopic maps independently from MD simulations by comparing experimental and theoretical spectra for a single conformation of the α-helical model peptide Ac-Phe-(Ala){sub 5}-Lys-H{sup +} in the gas phase. Conformation-specific experimental spectra are obtained for the unlabeled peptide and for several singly and doubly {sup 13}C-labeled variants using infrared-ultraviolet double-resonance spectroscopy, and these spectra are found to be well-modeled by density functional theory (DFT) calculations at the B3LYP/6-31G** level. We then compare DFT results for the deuterated and {sup 13}C{sup 18}O-labeled peptide with those from spectroscopic maps developed and used previously by the Skinner group. We find that the maps are typically accurate to within a few cm{sup −1} for both frequencies and couplings, having larger errors only for the frequencies of terminal amides.

  1. Assessment of amide I spectroscopic maps for a gas-phase peptide using IR-UV double-resonance spectroscopy and density functional theory calculations

    International Nuclear Information System (INIS)

    Carr, J. K.; Roy, S.; Skinner, J. L.; Zabuga, A. V.; Rizzo, T. R.

    2014-01-01

    The spectroscopy of amide I vibrations has become a powerful tool for exploring protein structure and dynamics. To help with spectral interpretation, it is often useful to perform molecular dynamics (MD) simulations. To connect spectroscopic experiments to simulations in an efficient manner, several researchers have proposed “maps,” which relate observables in classical MD simulations to quantum spectroscopic variables. It can be difficult to discern whether errors in the theoretical results (compared to experiment) arise from inaccuracies in the MD trajectories or in the maps themselves. In this work, we evaluate spectroscopic maps independently from MD simulations by comparing experimental and theoretical spectra for a single conformation of the α-helical model peptide Ac-Phe-(Ala) 5 -Lys-H + in the gas phase. Conformation-specific experimental spectra are obtained for the unlabeled peptide and for several singly and doubly 13 C-labeled variants using infrared-ultraviolet double-resonance spectroscopy, and these spectra are found to be well-modeled by density functional theory (DFT) calculations at the B3LYP/6-31G** level. We then compare DFT results for the deuterated and 13 C 18 O-labeled peptide with those from spectroscopic maps developed and used previously by the Skinner group. We find that the maps are typically accurate to within a few cm −1 for both frequencies and couplings, having larger errors only for the frequencies of terminal amides

  2. Assessment of amide I spectroscopic maps for a gas-phase peptide using IR-UV double-resonance spectroscopy and density functional theory calculations

    Science.gov (United States)

    Carr, J. K.; Zabuga, A. V.; Roy, S.; Rizzo, T. R.; Skinner, J. L.

    2014-01-01

    The spectroscopy of amide I vibrations has become a powerful tool for exploring protein structure and dynamics. To help with spectral interpretation, it is often useful to perform molecular dynamics (MD) simulations. To connect spectroscopic experiments to simulations in an efficient manner, several researchers have proposed “maps,” which relate observables in classical MD simulations to quantum spectroscopic variables. It can be difficult to discern whether errors in the theoretical results (compared to experiment) arise from inaccuracies in the MD trajectories or in the maps themselves. In this work, we evaluate spectroscopic maps independently from MD simulations by comparing experimental and theoretical spectra for a single conformation of the α-helical model peptide Ac-Phe-(Ala)5-Lys-H+ in the gas phase. Conformation-specific experimental spectra are obtained for the unlabeled peptide and for several singly and doubly 13C-labeled variants using infrared-ultraviolet double-resonance spectroscopy, and these spectra are found to be well-modeled by density functional theory (DFT) calculations at the B3LYP/6-31G** level. We then compare DFT results for the deuterated and 13C18O-labeled peptide with those from spectroscopic maps developed and used previously by the Skinner group. We find that the maps are typically accurate to within a few cm−1 for both frequencies and couplings, having larger errors only for the frequencies of terminal amides. PMID:24929378

  3. LIAD-fs: A novel method for studies of ultrafast processes in gas phase neutral biomolecules

    International Nuclear Information System (INIS)

    Calvert, C R; Kelly, O; Duffy, M J; Belshaw, L; King, R B; Williams, I D; Greenwood, J B

    2012-01-01

    A new experimental technique for femtosecond (fs) pulse studies of gas phase biomolecules is reported. Using Laser-Induced Acoustic Desorption (LIAD) to produce a plume of neutral molecules, a time-delayed fs pulse is employed for ionisation/fragmentation, with subsequent products extracted and mass analysed electrostatically. By varying critical laser pulse parameters, this technique can be used to implement control over molecular fragmentation for a range of small biomolecules, with specific studies of amino acids demonstrated.

  4. ICR studies of some anionic gas phase reactions and FTICR software design

    International Nuclear Information System (INIS)

    Noest, A.J.

    1983-01-01

    This thesis consists of two parts. Part one (Chs. 1-5) reports experimental results from mostly drift-cell ICR studies of negative ion-molecule reactions; part two (Chs. 6-11) concerns the design of software for an FTICR instrument. The author discusses successively: 1. ion cyclotron resonance spectrometry; 2. the gas phase allyl anion; 3. the (M-H) and (M-H2) anions from acetone; 4. negative ion-molecule reactions of aliphatic nitrites studied by cyclotron resonance; 5. homoconjugation versus charge-dipole interaction effects in the stabilization of carbanions in the gas phase; 6. the Fourier Transform ICR method; 7. the FTICR-software; 8. an efficient adaptive matcher filter for fast transient signals; 9. reduction of spectral peak height errors by time-domain weighing; 10. Chirp excitation; 11. Compact data storage. The book concludes with a Dutch and English summary (G.J.P.)

  5. Laser-induced carbon plasma emission spectroscopic measurements on solid targets and in gas-phase optical breakdown

    International Nuclear Information System (INIS)

    Nemes, Laszlo; Keszler, Anna M.; Hornkohl, James O.; Parigger, Christian

    2005-01-01

    We report measurements of time- and spatially averaged spontaneous-emission spectra following laser-induced breakdown on a solid graphite/ambient gas interface and on solid graphite in vacuum, and also emission spectra from gas-phase optical breakdown in allene C3H4 and helium, and in CO2 and helium mixtures. These emission spectra were dominated by CII (singly ionized carbon), CIII (doubly ionized carbon), hydrogen Balmer beta (H b eta), and Swan C2 band features. Using the local thermodynamic equilibrium and thin plasma assumptions, we derived electron number density and electron temperature estimates. The former was in the 1016 cm -3 range, while the latter was found to be near 20000 K. In addition, the vibration-rotation temperature of the Swan bands of the C2 radical was determined to be between 4500 and 7000 K, using an exact theoretical model for simulating diatomic emission spectra. This temperature range is probably caused by the spatial inhomogeneity of the laser-induced plasma plume. Differences are pointed out in the role of ambient CO2 in a solid graphite target and in gas-phase breakdown plasma

  6. Dynamics of gas-phase transient species studied by dissociative photodetachment of molecular anions

    OpenAIRE

    Lu, Zhou

    2007-01-01

    Gas-phase transient species, such as the CH₃CO₂ and HOCO free radicals, play important roles in combustion and environment chemistry. In this thesis work, the dynamics of these two radicals were studied by dissociative photodetachment (DPD) of the negative ions, CH₃CO₂-С and HOCO⁻, respectively. The experiments were carried out with a fast-ion-beam photoelectron-photofragment coincidence (PPC) spectrometer. Mass-selected molecular anions in a fast ion beam were intercepted by a linearly polar...

  7. Conformational Study of DNA Sugars: from the Gas Phase to Solution

    Science.gov (United States)

    Uriarte, Iciar; Vallejo-López, Montserrat; Cocinero, Emilio J.; Corzana, Francisco; Davis, Benjamin G.

    2017-06-01

    Sugars are versatile molecules that play a variety of roles in the organism. For example, they are important in energy storage processes or as structural scaffolds. Here, we focus on the monosaccharide present in DNA by addressing the conformational and puckering properties in the gas phase of α- and β-methyl-2-deoxy-ribofuranoside and α- and β-methyl-2-deoxy-ribopiranoside. Other sugars have been previously studied in the gas phase The work presented here stems from a combination of chemical synthesis, ultrafast vaporization methods, supersonic expansions, microwave spectroscopy (both chirped-pulsed and Balle-Flygare cavity-based spectrometers) and NMR spectroscopy. Previous studies in the gas phase had been performed on 2-deoxyribose, but only piranose forms were detected. However, thanks to the combination of these techniques, we have isolated and characterized for the first time the conformational landscape of the sugar present in DNA in its biologically relevant furanose form. Our gas phase study serves as a probe of the conformational preferences of these biomolecules under isolation conditions. Thanks to the NMR experiments, we can characterize the favored conformations in solution and extract the role of the solvent in the structure and puckering of the monosaccharides. E. J. Cocinero, A. Lesarri, P. Écija, F. J. Basterretxea, J.-U. Grabow, J. A. Fernández, F. Castaño, Angew. Chem. Int. Edit. 2012, 51, 3119. P. Écija, I. Uriarte, L. Spada, B. G. Davis, W. Caminati, F. J. Basterretxea, A. Lesarri, E. J. Cocinero, Chem. Commun. 2016, 52, 6241. I. Peña, E. J. Cocinero, C. Cabezas, A. Lesarri, S. Mata, P. Écija, A. M. Daly, Á. Cimas, C. Bermúdez, F. J. Basterretxea, S. Blanco, J. A. Fernández, J. C. López, F. Castaño, J. L. Alonso, Angew. Chem. Int. Edit. 2013, 52, 11840.

  8. Gas-Phase Molecular Dynamics: Theoretical Studies In Spectroscopy and Chemical Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Yu H. G.; Muckerman, J.T.

    2012-05-29

    The main goal of this program is the development and application of computational methods for studying chemical reaction dynamics and molecular spectroscopy in the gas phase. We are interested in developing rigorous quantum dynamics algorithms for small polyatomic systems and in implementing approximate approaches for complex ones. Particular focus is on the dynamics and kinetics of chemical reactions and on the rovibrational spectra of species involved in combustion processes. This research also explores the potential energy surfaces of these systems of interest using state-of-the-art quantum chemistry methods, and extends them to understand some important properties of materials in condensed phases and interstellar medium as well as in combustion environments.

  9. Gas-Phase Molecular Dynamics: Theoretical Studies in Spectroscopy and Chemical Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Yu, H.G.; Muckerman, J.T.

    2010-06-01

    The goal of this program is the development and application of computational methods for studying chemical reaction dynamics and molecular spectroscopy in the gas phase. We are interested in developing rigorous quantum dynamics algorithms for small polyatomic systems and in implementing approximate approaches for complex ones. Particular focus is on the dynamics and kinetics of chemical reactions and on the rovibrational spectra of species involved in combustion processes. This research also explores the potential energy surfaces of these systems of interest using state-of-the-art quantum chemistry methods.

  10. Headspace analysis gas-phase infrared spectroscopy: a study of xanthate decomposition on mineral surfaces

    Science.gov (United States)

    Vreugdenhil, Andrew J.; Brienne, Stephane H. R.; Markwell, Ross D.; Butler, Ian S.; Finch, James A.

    1997-03-01

    The O-ethyldithiocarbonate (ethyl xanthate, CH 3CH 2OCS -2) anion is a widely used reagent in mineral processing for the separation of sulphide minerals by froth flotation. Ethyl xanthate interacts with mineral powders to produce a hydrophobic layer on the mineral surface. A novel infrared technique, headspace analysis gas-phase infrared spectroscopy (HAGIS) has been used to study the in situ thermal decomposition products of ethyl xanthate on mineral surfaces. These products include CS 2, COS, CO 2, CH 4, SO 2, and higher molecular weight alkyl-containing species. Decomposition pathways have been proposed with some information determined from 2H- and 13C-isotope labelling experiments.

  11. Femtosecond time-resolved studies of coherent vibrational Raman scattering in large gas-phase molecules

    International Nuclear Information System (INIS)

    Hayden, C.C.; Chandler, D.W.

    1995-01-01

    Results are presented from femtosecond time-resolved coherent Raman experiments in which we excite and monitor vibrational coherence in gas-phase samples of benzene and 1,3,5-hexatriene. Different physical mechanisms for coherence decay are seen in these two molecules. In benzene, where the Raman polarizability is largely isotropic, the Q branch of the vibrational Raman spectrum is the primary feature excited. Molecules in different rotational states have different Q-branch transition frequencies due to vibration--rotation interaction. Thus, the macroscopic polarization that is observed in these experiments decays because it has many frequency components from molecules in different rotational states, and these frequency components go out of phase with each other. In 1,3,5-hexatriene, the Raman excitation produces molecules in a coherent superposition of rotational states, through (O, P, R, and S branch) transitions that are strong due to the large anisotropy of the Raman polarizability. The coherent superposition of rotational states corresponds to initially spatially oriented, vibrationally excited, molecules that are freely rotating. The rotation of molecules away from the initial orientation is primarily responsible for the coherence decay in this case. These experiments produce large (∼10% efficiency) Raman shifted signals with modest excitation pulse energies (10 μJ) demonstrating the feasibility of this approach for a variety of gas phase studies. copyright 1995 American Institute of Physics

  12. Conformational reduction of DOPA in the gas phase studied by laser desorption supersonic jet laser spectroscopy.

    Science.gov (United States)

    Ishiuchi, Shun-ichi; Mitsuda, Haruhiko; Asakawa, Toshiro; Miyazaki, Mitsuhiko; Fujii, Masaaki

    2011-05-07

    The conformational reduction in catecholamine neurotransmitters was studied by resonance enhanced multi photon ionization (REMPI), ultraviolet-ultraviolet (UV-UV) hole burning and infrared (IR) dip spectroscopy with applying a laser desorption supersonic jet technique to DOPA, which is one of the catecholamine neurotransmitters and has one more phenolic OH group than tyrosine. It is concluded that DOPA has a single observable conformer in the gas phase at low temperature. Quantum chemical calculations at several levels with or without the dispersion correction were also carried out to study stable conformations. From the comparison between the computational IR spectra and the experimental ones, the most stable structure was determined. It is strongly suggested that the conformational reduction is caused by electrostatic interactions, such as a dipole-dipole interaction, between the chain and OH groups. This journal is © the Owner Societies 2011

  13. Gas-Phase Reactions of Dimethyl Disulfide with Aliphatic Carbanions - A Mass Spectrometry and Computational Study

    Science.gov (United States)

    Franczuk, Barbara; Danikiewicz, Witold

    2018-03-01

    Ion-molecule reactions of Me2S2 with a wide range of aliphatic carbanions differing by structure and proton affinity values have been studied in the gas phase using mass spectrometry techniques and DFT calculations. The analysis of the spectra shows a variety of product ions formed via different reaction mechanisms, depending on the structure and proton affinity of the carbanion. Product ions of thiophilic reaction ( m/z 47), SN2 ( m/z 79), and E2 elimination - addition sequence of reactions ( m/z 93) can be observed. Primary products of thiophilic reaction can undergo subsequent SN2 and proton transfer reactions. Gibbs free energy profiles calculated for experimentally observed reactions using PBE0/6-311+G(2d,p) method show good agreement with experimental results. [Figure not available: see fulltext.

  14. Importance of the gas phase role to the prediction of energetic material behavior: An experimental study

    International Nuclear Information System (INIS)

    Ali, A.N.; Son, S.F.; Asay, B.W.; Sander, R.K.

    2005-01-01

    Various thermal (radiative, conductive, and convective) initiation experiments are performed to demonstrate the importance of the gas phase role in combustion modeling of energetic materials (EM). A previously published condensed phase model that includes a predicted critical irradiance above which ignition is not possible is compared to experimental laser ignition results for octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and 2,4,6-trinitrotoluene (TNT). Experimental results conflict with the predicted critical irradiance concept. The failure of the model is believed to result from a misconception about the role of the gas phase in the ignition process of energetic materials. The model assumes that ignition occurs at the surface and that evolution of gases inhibits ignition. High speed video of laser ignition, oven cook-off and hot wire ignition experiments captures the ignition of HMX and TNT in the gas phase. A laser ignition gap test is performed to further evaluate the effect of gas phase laser absorption and gas phase disruption on the ignition process. Results indicate that gas phase absorption of the laser energy is probably not the primary factor governing the gas phase ignition observations. It is discovered that a critical gap between an HMX pellet and a salt window of 6 mm±0.4 mm exists below which ignition by CO 2 laser is not possible at the tested irradiances of 29 W/cm 2 and 38 W/cm 2 for HMX ignition. These observations demonstrate that a significant disruption of the gas phase, in certain scenarios, will inhibit ignition, independent of any condensed phase processes. These results underscore the importance of gas phase processes and illustrate that conditions can exist where simple condensed phase models are inadequate to accurately predict the behavior of energetic materials

  15. Importance of the gas phase role to the prediction of energetic material behavior: An experimental study

    Science.gov (United States)

    Ali, A. N.; Son, S. F.; Asay, B. W.; Sander, R. K.

    2005-03-01

    Various thermal (radiative, conductive, and convective) initiation experiments are performed to demonstrate the importance of the gas phase role in combustion modeling of energetic materials (EM). A previously published condensed phase model that includes a predicted critical irradiance above which ignition is not possible is compared to experimental laser ignition results for octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and 2,4,6-trinitrotoluene (TNT). Experimental results conflict with the predicted critical irradiance concept. The failure of the model is believed to result from a misconception about the role of the gas phase in the ignition process of energetic materials. The model assumes that ignition occurs at the surface and that evolution of gases inhibits ignition. High speed video of laser ignition, oven cook-off and hot wire ignition experiments captures the ignition of HMX and TNT in the gas phase. A laser ignition gap test is performed to further evaluate the effect of gas phase laser absorption and gas phase disruption on the ignition process. Results indicate that gas phase absorption of the laser energy is probably not the primary factor governing the gas phase ignition observations. It is discovered that a critical gap between an HMX pellet and a salt window of 6mm±0.4mm exists below which ignition by CO2 laser is not possible at the tested irradiances of 29W /cm2 and 38W/cm2 for HMX ignition. These observations demonstrate that a significant disruption of the gas phase, in certain scenarios, will inhibit ignition, independent of any condensed phase processes. These results underscore the importance of gas phase processes and illustrate that conditions can exist where simple condensed phase models are inadequate to accurately predict the behavior of energetic materials.

  16. Gas phase pulse radiolysis

    International Nuclear Information System (INIS)

    Jonah, C.D.; Andong Liu; Mulac, W.A.

    1987-01-01

    Gas phase pulse radiolysis, a technique which can be used to study many different phenomena in chemistry and physics, is discussed. As a source of small radicals, pulse radiolysis is important to the field of chemistry, particularly to combustion and atmospheric kinetics. The reactions of 1,3-butadiene, allene, ethylene and acetylene with OH are presented. 52 refs., 1 fig., 1 tab

  17. Gas-Phase Thermolyses

    DEFF Research Database (Denmark)

    Carlsen, Lars; Egsgaard, Helge

    1982-01-01

    The unimolecular gas-phase thermolyses of 1,2,3-oxadithiolan 2-oxide and thiiran 1-oxide have been studied by the flash vacuum thermolysis–field ionization mass spectrometry (f.v.t.–f.i.m.s.) technique in the temperature range from 1 043 to 1 404 K. The reactions are rationalized in terms of sulp...

  18. Gas-Phase Thermolyses

    DEFF Research Database (Denmark)

    Carlsen, Lars; Egsgaard, Helge

    1982-01-01

    The unimolecular gas-phase thermolyses of the four methyl and ethyl monothioacetates (5)–(8) have been studied by the flash vacuum thermolysis–field ionization mass spectrometry technique in the temperature range 883–1 404 K. The types of reactions verified were keten formation, thiono–thiolo rea...

  19. Time-resolved EPR study of singlet oxygen in the gas phase.

    Science.gov (United States)

    Ruzzi, Marco; Sartori, Elena; Moscatelli, Alberto; Khudyakov, Igor V; Turro, Nicholas J

    2013-06-27

    X-band EPR spectra of singlet O2((1)Δg) and triplet O2((3)Σg(-)) were observed in the gas phase under low molecular-oxygen pressures PO2 = 0.175-0.625 Torr, T = 293-323 K. O2((1)Δg) was produced by quenching of photogenerated triplet sensitizers naphthalene C8H10, perdeuterated naphthalene, and perfluoronaphthalene in the gas phase. The EPR spectrum of O2((1)Δg) was also observed under microwave discharge. Integrated intensities and line widths of individual components of the EPR spectrum of O2((3)Σg(-)) were used as internal standards for estimating the concentration of O2 species and PO2 in the EPR cavity. Time-resolved (TR) EPR experiments of C8H10 were the main focus of this Article. Pulsed irradiation of C8H10 in the presence of O2((3)Σg(-)) allowed us to determine the kinetics of formation and decay for each of the four components of the O2((1)Δg) EPR signal, which lasted for only a few seconds. We found that the kinetics of EPR-component decay fit nicely to a biexponential kinetics law. The TR EPR 2D spectrum of the third component of the O2((1)Δg) EPR spectrum was examined in experiments using C8H10. This spectrum vividly presents the time evolution of an EPR component. The largest EPR signal and the longest lifetime of O2((1)Δg), τ = 0.4 s, were observed at medium pressure PO2 = 0.4 Torr, T = 293 K. The mechanism of O2((1)Δg) decay in the presence of photosensitizers is discussed. EPR spectra of O2((1)Δg) evidence that the spin-rotational states of O2((1)Δg) are populated according to Boltzmann distribution in the studied time range of 10-100 ms. We believe that this is the first report dealing with the dependence of O2((1)Δg) EPR line width on PO2 and T.

  20. Direct gas-phase epoxidation of propylene to propylene oxide through radical reactions: A theoretical study

    Science.gov (United States)

    Kizilkaya, Ali Can; Fellah, Mehmet Ferdi; Onal, Isik

    2010-03-01

    The gas-phase radical chain reactions which utilize O 2 as the oxidant to produce propylene oxide (PO) are investigated through theoretical calculations. The transition states and energy profiles were obtained for each path. The rate constants were also calculated. The energetics for the competing pathways indicate that PO can be formed selectively due to its relatively low activation barrier (9.3 kcal/mol) which is in a good agreement with the experimental value (11 kcal/mol) of gas-phase propylene epoxidation. The formation of the acrolein and combustion products have relatively high activation barriers and are not favored. These results also support the recent experimental findings.

  1. A Kinetic Study of the Gas-Phase Reaction of OH with Br2

    Science.gov (United States)

    Bryukov, Mikhail G.; Dellinger, Barry; Knyazev, Vadim D.

    2011-01-01

    An experimental, temperature-dependent kinetic study of the gas-phase reaction of the hydroxyl radical with molecular bromine (reaction 1) has been performed using a pulsed laser photolysis/pulsed-laser-induced fluorescence technique over a wide temperature range of 297 – 766 K, and at pressures between 6.68 and 40.29 kPa of helium. The experimental rate coefficients for reaction 1 demonstrate no correlation with pressure and exhibit a negative temperature dependence with a slight negative curvature in the Arrhenius plot. A non-linear least-squares fit with two floating parameters of the temperature dependent k1(T) data set using an equation of the form k1(T) = ATn yields the recommended expression k1(T) = 1.85×10−9T − 0.66 cm3 molecule−1 s−1 for the temperature dependence of the reaction 1 rate coefficient. The potential energy surface (PES) of reaction 1 was investigated using quantum chemistry methods. The reaction proceeds through formation of a weakly bound OH···Br2 complex and a PES saddle point with an energy below that of the reactants. Temperature dependence of the reaction rate coefficient was modeled using the RRKM method on the basis of the calculated PES. PMID:16854030

  2. Gas-Phase Thermolysis

    DEFF Research Database (Denmark)

    Carlsen, Lars; Egsgaard, Helge; Schaumann, Ernst

    1980-01-01

    The unimolecular gas-phase thermolytic decomposition of three silylated thionocarboxylic acid derivatives (2b), (3), and (8) have been studied by the flash vacuum thermolysis–field ionization mass spectrometry technique in the temperature range from 783 to 1 404 K in order to elucidate its possible...... applicability as a route to thioketens. Only very minor amounts of the expected thioketens were found, whereas the corresponding ketens were obtained as the major products. A possible mechanism for keten formation is discussed....

  3. Ab initio study of gas phase and water-assisted tautomerization of ...

    Indian Academy of Sciences (India)

    WINTEC

    Water-assisted tautomerization in maleimide and formamide showed that difference in energy barrier reduces to 2⋅83 kcal/mol from 10⋅41 kcal/mol (in gas phase) at B3LYP level, which resulted that maleimide readily undergoes tautomerization in water molecule. Keywords. Ab Initio calculations; maleimide; formamide; ...

  4. Gas-phase synthesis of magnesium nanoparticles : A high-resolution transmission electron microscopy study

    NARCIS (Netherlands)

    Kooi, B.J.; Palasantzas, G.; de Hosson, J.T.M.

    2006-01-01

    Magnesium nanoparticles with size above 10 nm, prepared by gas-phase syntheses, were investigated by high-resolution transmission electron microscopy. The dominant particle shape is a hexagonal prism terminated by Mg(0002) and Mg{1010} facets. Oxidation of Mg yields a MgO shell (similar to 3 nm

  5. Evidence for α-helices in the gas phase: a case study using Melittin from honey bee venom.

    Science.gov (United States)

    Florance, Hannah V; Stopford, Andrew P; Kalapothakis, Jason M; McCullough, Bryan J; Bretherick, Andrew; Barran, Perdita E

    2011-09-07

    Gas phase methodologies are increasingly used to study the structure of proteins and peptides. A challenge to the mass spectrometrist is to preserve the structure of the system of interest intact and unaltered from solution into the gas phase. Small peptides are very flexible and can present a number of conformations in solution. In this work we examine Melittin a 26 amino acid peptide that forms the active component of honey bee venom. Melittin is haemolytic and has been shown to form an α-helical tetrameric structure by X-ray crystallography [M. Gribskov et al., The RCSB Protein Data Bank, 1990] and to be helical in high concentrations of methanol. Here we use ion mobility mass spectrometry, molecular dynamics and gas-phase HDX to probe its structure in the gas phase and specifically interrogate whether the helical form can be preserved. All low energy calculated structures possess some helicity. In our experiments we examine the peptide following nano-ESI from solutions with varying methanol content. Ion mobility gives collision cross sections (CCS) that compare well with values found from molecular modelling and from other reported structures, but with inconclusive results regarding the effect of solvent. There is only a slight increase in CCS with charge, showing minimal coloumbically driven unfolding. HDX supports preservation of some helical content into the gas phase and again shows little difference in the exchange rates of species sprayed from different solvents. The [M + 3H](3+) species has two exchanging populations both of which exhibit faster exchange rates than observed for the [M + 2H](2+) species. One interpretation for these results is that the time spent being analysed is sufficient for this peptide to form a helix in the 'ultimate' hydrophobic environment of a vacuum.

  6. Electron Scattering Studies of Gas Phase Molecular Structure at High Temperature

    Science.gov (United States)

    Mawhorter, Richard J., Jr.

    A high precision counting electron diffraction study of the structure of gaseous sulfur dioxide as a function of temperature from 300(DEGREES) to 1000(DEGREES)K is presented. The results agree well with current theory, and yield insight into the effects of anharmonicity on molecular structure. Another aspect of molecular structure is the molecular charge density distribution. The difference (DELTA)(sigma) is between the electron scattering cross sections for the actual molecule and independent atom model (IAM) are a sensitive measure of the change in this distribution due to bond formation. These difference cross sections have been calculated using ab initio methods, and the results for a wide range of simple polyatomic molecules are presented. Such calculations are routinely done for a single, fixed molecular geometry, an approach which neglects the effects of the vibrational motion of real molecules. The effect of vibrational averaging is studied in detail for the three normal vibrational modes of H(,2)O in the ground state. The effects are small, lending credence to the practice of comparing cross sections calculated at a fixed geometry with inherently averaged experimental data. The efficacy of the standard formula used to account for vibrational averaging in the IAM is also examined. Finally, the nature of the ionic bond is probed with an experimental study of the structure of alkali chlorides, NaCl, KCl, RbCl, and CsCl, in the gas phase. Temperatures from 840-960(DEGREES)K were required to achieve the necessary vapor pressures of approximately 0.01 torr. A planar rhombic structure for the dimer molecule is confirmed, with a fairly uniform decrease of the chlorine-alkali-chlorine angle as the alkalis increase in size. The experiment also yields information on the amount of dimer present in the vapor, and these results are compared with thermodynamic values.

  7. Gas phase ion chemistry

    CERN Document Server

    Bowers, Michael T

    1979-01-01

    Gas Phase Ion Chemistry, Volume 2 covers the advances in gas phase ion chemistry. The book discusses the stabilities of positive ions from equilibrium gas-phase basicity measurements; the experimental methods used to determine molecular electron affinities, specifically photoelectron spectroscopy, photodetachment spectroscopy, charge transfer, and collisional ionization; and the gas-phase acidity scale. The text also describes the basis of the technique of chemical ionization mass spectrometry; the energetics and mechanisms of unimolecular reactions of positive ions; and the photodissociation

  8. Intermolecular interactions of trifluorohalomethanes with Lewis bases in the gas phase: an ab initio study.

    Science.gov (United States)

    Wang, Yi-Siang; Yin, Chih-Chien; Chao, Sheng D

    2014-10-07

    We perform an ab initio computational study of molecular complexes with the general formula CF3X-B that involve one trifluorohalomethane CF3X (X = Cl or Br) and one of a series of Lewis bases B in the gas phase. The Lewis bases are so chosen that they provide a range of electron-donating abilities for comparison. Based on the characteristics of their electron pairs, we consider the Lewis bases with a single n-pair (NH3 and PH3), two n-pairs (H2O and H2S), two n-pairs with an unsaturated bond (H2CO and H2CS), and a single π-pair (C2H4) and two π-pairs (C2H2). The aim is to systematically investigate the influence of the electron pair characteristics and the central atom substitution effects on the geometries and energetics of the formed complexes. The counterpoise-corrected supermolecule MP2 and coupled-cluster single double with perturbative triple [CCSD(T)] levels of theory have been employed, together with a series of basis sets up to aug-cc-pVTZ. The angular and radial configurations, the binding energies, and the electrostatic potentials of the stable complexes have been compared and discussed as the Lewis base varies. For those complexes where halogen bonding plays a significant role, the calculated geometries and energetics are consistent with the σ-hole model. Upon formation of stable complexes, the C-X bond lengths shorten, while the C-X vibrational frequencies increase, thus rendering blueshifting halogen bonds. The central atom substitution usually enlarges the intermolecular bond distances while it reduces the net charge transfers, thus weakening the bond strengths. The analysis based on the σ-hole model is grossly reliable but requires suitable modifications incorporating the central atom substitution effects, in particular, when interaction components other than electrostatic contributions are involved.

  9. Sensitivity study of experimental measures for the nuclear liquid-gas phase transition in the statistical multifragmentation model

    Science.gov (United States)

    Lin, W.; Ren, P.; Zheng, H.; Liu, X.; Huang, M.; Wada, R.; Qu, G.

    2018-05-01

    The experimental measures of the multiplicity derivatives—the moment parameters, the bimodal parameter, the fluctuation of maximum fragment charge number (normalized variance of Zmax, or NVZ), the Fisher exponent (τ ), and the Zipf law parameter (ξ )—are examined to search for the liquid-gas phase transition in nuclear multifragmention processes within the framework of the statistical multifragmentation model (SMM). The sensitivities of these measures are studied. All these measures predict a critical signature at or near to the critical point both for the primary and secondary fragments. Among these measures, the total multiplicity derivative and the NVZ provide accurate measures for the critical point from the final cold fragments as well as the primary fragments. The present study will provide a guide for future experiments and analyses in the study of the nuclear liquid-gas phase transition.

  10. Gas-phase synthesis of magnesium nanoparticles: A high-resolution transmission electron microscopy study

    International Nuclear Information System (INIS)

    Kooi, B. J.; Palasantzas, G.; De Hosson, J. Th. M.

    2006-01-01

    Magnesium nanoparticles with size above 10 nm, prepared by gas-phase syntheses, were investigated by high-resolution transmission electron microscopy. The dominant particle shape is a hexagonal prism terminated by Mg(0002) and Mg(1010) facets. Oxidation of Mg yields a MgO shell (∼3 nm thick), which has an orientation relation with the Mg. Inhomogeneous facet oxidation influences their growth kinetics resulting in a relatively broad size and shape distribution. Faceted voids between Mg and MgO shells indicate a fast outward diffusion of Mg and vacancy rearrangement into voids. The faceting of polar (220) planes is assisted by electron irradiation

  11. Theoretical Study On The Interaction Between Xenon And Positive Silver Clusters In Gas Phase And On The (001) Chabazite Surface

    International Nuclear Information System (INIS)

    Hunter, D.

    2009-01-01

    A systematic study on the adsorption of xenon on silver clusters in the gas phase and on the (001) surface of silver-exchanged chabazite is reported. Density functional theory at the B3LYP level with the cluster model was employed. The results indicate that the dominant part of the binding is the σ donation, which is the charge transfer from the 5p orbital of Xe to the 5s orbital of Ag and is not the previously suggested d π -d π back-donation. A correlation between the binding energy and the degree of σ donation is found. Xenon was found to bind strongly to silver cluster cations and not to neutral ones. The binding strength decreases as the cluster size increases for both cases, clusters in the gas-phase and on the chabazite surface. The Ag + cation is the strongest binding site for xenon both in gas phase and on the chabazite surface with the binding energies of 73.9 and 14.5 kJ/mol, respectively. The results also suggest that the smaller silver clusters contribute to the negative chemical shifts observed in the 129 Xe NMR spectra in experiments.

  12. Probing Vitamine C, Aspirin and Paracetamol in the Gas Phase: High Resolution Rotational Studies

    Science.gov (United States)

    Mata, S.; Cabezas, C.; Varela, M.; Pena, I.; Nino, A.; López, J. C.; Alonso, J. L.; Grabow, J.-U.

    2011-06-01

    A solid sample of Vitamin C (m.p. 190°C) vaporized by laser ablation has been investigated in gas phase and characterized through their rotational spectra. Two spectroscopy techniques has been used to obtain the spectra: a new design of broadband chirped pulse Fourier transform microwave spectroscopy with in-phase/quadrature-phase-modulation passage-acquired-coherence technique (IMPACT) and conventional laser ablation molecular beam Fourier transform microwave spectroscopy (LA-MB-FTMW). Up to now, two low-energy conformer have been observed and their rotational constants determined. Ab initio calculations at the MP2/6-311++G (d,p) level of theory predicted rotational constants which helped us to identify these conformers unequivocally. Among the molecules to benefit from the LA-MB-FTMW technique there are common important drugs never observed in the gas phase through rotational spectroscopy. We present here the results on acetyl salicylic acid and acetaminophen (m.p. 136°C), commonly known as aspirin and paracetamol respectively. We have observed two stable conformers of aspirin and two for paracetamol. The internal rotation barrier of the methyl group in aspirin has been determined for both conformers from the analysis of the A-E splittings due to the coupling of internal and overall rotation. J. L. Alonso, C. Pérez, M. E. Sanz, J. C. López, S. Blanco, Phys. Chem. Chem. Phys. 11,617-627 (2009)and references therein

  13. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Jorge, Nelly Lidia [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain); Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Romero, Jorge Marcelo [Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Grand, Andre [INAC, SCIB, Laboratoire ' Lesions des Acides Nucleiques' , UMR CEA-UJF E3, CEA-Grenoble, 17 Rue des Martyrs, 38054 Grenoble cedex 9 (France); Hernandez-Laguna, Alfonso, E-mail: ahlaguna@ugr.es [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain)

    2012-01-17

    Highlights: Black-Right-Pointing-Pointer Kinetic and mechanism of the gas-phase thermolysis of tetroxane were determined. Black-Right-Pointing-Pointer Gas chromatography and computational potential energy surfaces were performed. Black-Right-Pointing-Pointer A mechanism in steps looked like the most probable mechanism. Black-Right-Pointing-Pointer A spin-orbit coupling appeared at the singlet and triple diradical open structures. Black-Right-Pointing-Pointer A non-adiabatic crossing from the singlet to the triplet state occurred. - Abstract: Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463-503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 {+-} 0.8 kcal/mol and 5.2 Multiplication-Sign 10{sup 13} s{sup -1}, respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G{sup Asterisk-Operator Asterisk-Operator} level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin-orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.

  14. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    International Nuclear Information System (INIS)

    Jorge, Nelly Lidia; Romero, Jorge Marcelo; Grand, André; Hernández-Laguna, Alfonso

    2012-01-01

    Highlights: ► Kinetic and mechanism of the gas-phase thermolysis of tetroxane were determined. ► Gas chromatography and computational potential energy surfaces were performed. ► A mechanism in steps looked like the most probable mechanism. ► A spin–orbit coupling appeared at the singlet and triple diradical open structures. ► A non-adiabatic crossing from the singlet to the triplet state occurred. - Abstract: Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463–503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 ± 0.8 kcal/mol and 5.2 × 10 13 s −1 , respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G ∗∗ level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin–orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.

  15. Gas phase 1H NMR studies and kinetic modeling of dihydrogen isotope equilibration catalyzed by Ru-nanoparticles under normal conditions: dissociative vs. associative exchange.

    Science.gov (United States)

    Limbach, Hans-Heinrich; Pery, Tal; Rothermel, Niels; Chaudret, Bruno; Gutmann, Torsten; Buntkowsky, Gerd

    2018-04-25

    The equilibration of H2, HD and D2 between the gas phase and surface hydrides of solid organic-ligand-stabilized Ru metal nanoparticles has been studied by gas phase 1H NMR spectroscopy using closed NMR tubes as batch reactors at room temperature and 800 mbar. When two different nanoparticle systems, Ru/PVP (PVP ≡ polyvinylpyrrolidone) and Ru/HDA (HDA ≡ hexadecylamine) were exposed to D2 gas, only the release of HD from the hydride containing surface could be detected in the initial stages of the reaction, but no H2. In the case of Ru/HDA also the reverse experiment was performed where surface deuterated nanoparticles were exposed to H2. In that case, the conversion of H2 into gaseous HD was detected. In order to analyze the experimental kinetic and spectroscopic data, we explored two different mechanisms taking into account potential kinetic and equilibrium H/D isotope effects. Firstly, we explored the dissociative exchange mechanism consisting of dissociative adsorption of dihydrogen, fast hydride surface diffusion and associative desorption of dihydrogen. It is shown that if D2 is the reaction partner, only H2 will be released in the beginning of the reaction, and HD only in later reaction stages. The second mechanism, dubbed here associative exchange consists of the binding of dihydrogen to Ru surface atoms, followed by a H-transfer to or by H-exchange with an adjacent hydride site, and finally of the associative desorption of dihydrogen. In that case, in the exchange with D2, only HD will be released in the beginning of the reaction. Our experimental results are not compatible with the dissociative exchange but can be explained in terms of the associative exchange. Whereas the former will dominate at low temperatures and pressures, the latter will prevail around room temperature and normal pressures where transition metal nanoparticles are generally used as reaction catalysts.

  16. Studies of cluster-assembled materials: From gas phase to condensed phase

    Science.gov (United States)

    Gao, Lin

    . After being mass gated in a reflectron equipped time-of-flight mass spectrometer (TOF-MS) and deposited onto TEM grids, the resultant specimens can be loaded onto high-resolution TEM investigation via electron diffraction. In conclusion, soft-landing of mass selected clusters has been shown to be a successful approach to obtain structural information on Zr-Met-Car cluster-assembled materials collected from the gas phase. TEM images indicate the richness of the morphologies associated with these cluster crystals. However, passivation methods are expected to be examined further to overcome the limited stabilities of these novel clusters. From this initial study, it's shown the promising opportunity to study other Met-Cars species and more cluster-based materials. Experimental results of reactions run with a solvothermal synthesis method obtained while searching for new Zr-C cluster assembled materials, are reported. One unexpected product in single crystal form was isolated and tentatively identified by X-ray diffraction to be [Zr6i O(OH)O12·2(Bu)4], with space group P2 1/n and lattice parameters of a = 12.44 A, b = 22.06 A, c = 18.40 A, alpha = 90°, beta = 105°, gamma = 90°, V = 4875 A3 and R 1 = 3.15% for the total observed data (I ≥ 2 sigma I) and oR2 = 2.82%. This novel hexanuclear Zr(IV)-oxo-hydroxide cluster anion may be the first member in polyoxometalates class with metal atoms from the IVB group and having Oh symmetry. Alternatively, it may be the first member in {[(Zr6Z)X 12]X6}m- class with halides replaced by oxo- and hydroxyl groups and with an increased oxidation state of Zr. It is predicted to bear application potentials directed by both families. This work could suggest a direction in which the preparation of Zr-C cluster-assembled materials in a liquid environment may be eventually fulfilled. 1,3-Bis(diethylphosphino)propane (depp) protected small gold clusters are studied via multiple techniques, including Electrospray Ionization Mass Spectrometry

  17. Configuration of a pulse radiolysis system for the study of gas-phase reactions and kinetic investigations of the reactions of hydroxyl radicals with methyl and ethyl radicals

    International Nuclear Information System (INIS)

    Fagerstroem, K.

    1993-01-01

    The work that is presented in this thesis deals with the assembling and testing of a pulse radiolysis system for kinetic studies of gas-phase reactions as well as with the kinetics of the gas-phase reactions of hydroxyl radicals with methyl and ethyl radicals. These radicals are very important as these are formed at an early stage in hydrocarbon combustion processes. The two studied reactions are key reactions in those processes. (6 refs., 4 figs., 2 tabs.)

  18. Gas Phase Nanoparticle Synthesis

    Science.gov (United States)

    Granqvist, Claes; Kish, Laszlo; Marlow, William

    This book deals with gas-phase nanoparticle synthesis and is intended for researchers and research students in nanomaterials science and engineering, condensed matter physics and chemistry, and aerosol science. Gas-phase nanoparticle synthesis is instrumental to nanotechnology - a field in current focus that raises hopes for environmentally benign, resource-lean manufacturing. Nanoparticles can be produced by many physical, chemical, and even biological routes. Gas-phase synthesis is particularly interesting since one can achieve accurate manufacturing control and hence industrial viability.

  19. Comprehensive Peptide Ion Structure Studies Using Ion Mobility Techniques: Part 3. Relating Solution-Phase to Gas-Phase Structures.

    Science.gov (United States)

    Kondalaji, Samaneh Ghassabi; Khakinejad, Mahdiar; Valentine, Stephen J

    2018-06-01

    Molecular dynamics (MD) simulations have been utilized to study peptide ion conformer establishment during the electrospray process. An explicit water model is used for nanodroplets containing a model peptide and hydronium ions. Simulations are conducted at 300 K for two different peptide ion charge configurations and for droplets containing varying numbers of hydronium ions. For all conditions, modeling has been performed until production of the gas-phase ions and the resultant conformers have been compared to proposed gas-phase structures. The latter species were obtained from previous studies in which in silico candidate structures were filtered according to ion mobility and hydrogen-deuterium exchange (HDX) reactivity matches. Results from the present study present three key findings namely (1) the evidence from ion production modeling supports previous structure refinement studies based on mobility and HDX reactivity matching, (2) the modeling of the electrospray process is significantly improved by utilizing initial droplets existing below but close to the calculated Rayleigh limit, and (3) peptide ions in the nanodroplets sample significantly different conformers than those in the bulk solution due to altered physicochemical properties of the solvent. Graphical Abstract ᅟ.

  20. Experimental and theoretical studies on gas-phase reactions of NO3 radicals with three methoxyphenols: Guaiacol, creosol, and syringol

    Science.gov (United States)

    Yang, Bo; Zhang, Haixu; Wang, Youfeng; Zhang, Peng; Shu, Jinian; Sun, Wanqi; Ma, Pengkun

    2016-01-01

    Methoxyphenols, lignin pyrolysis products, are major biomass combustion components and are considered potential tracers for wood smoke emissions. Their atmospheric reactivity, however, has not been well characterized. Guaiacol, creosol, and syringol are three typical methoxyphenols generated in relatively high concentrations in fresh wood smoke. In this study, the gas-phase reactions of NO3 radicals with these methoxyphenols were investigated using a laboratory-built vacuum ultraviolet photoionization gas time-of-flight mass spectrometer (VUV-GTOFMS) and off-line GC-MS. By combining experimental and theoretical methods, 4-nitroguaiacol, 6-nitroguaiacol, and 4,6-dinitroguaiacol were determined as the primary degradation products for guaiacol; similarly, 6-nitrocreosol and 3-nitrosyringol were identified for creosol and syringol, respectively. Using the relative rate method, rate constants at 298 K and 1 atm for the gas-phase reactions of guaiacol, creosol, and syringol with NO3 radicals were measured to be 3.2 × 10-12, 2.4 × 10-13, and 4.0 × 10-13 cm3 molecule-1 s-1, respectively. At a typical tropospheric concentration of NO3 radicals (5 × 108 molecule cm-3), atmospheric lifetimes for guaiacol, creosol, and syringol toward NO3 radicals were 0.2, 2.3, and 1.4 h, respectively. These results indicate that the reaction with NO3 radicals can be a major sink for methoxyphenols at night.

  1. Gas-phase water-mediated equilibrium between methylglyoxal and its geminal diol

    Science.gov (United States)

    Axson, Jessica L.; Takahashi, Kaito; De Haan, David O.; Vaida, Veronica

    2010-01-01

    In aqueous solution, aldehydes, and to a lesser extent ketones, hydrate to form geminal diols. We investigate the hydration of methylglyoxal (MG) in the gas phase, a process not previously considered to occur in water-restricted environments. In this study, we spectroscopically identified methylglyoxal diol (MGD) and obtained the gas-phase partial pressures of MG and MGD. These results, in conjunction with the relative humidity, were used to obtain the equilibrium constant, KP, for the water-mediated hydration of MG in the gas phase. The Gibbs free energy for this process, ΔG°, obtained as a result, suggests a larger than expected gas-phase diol concentration. This may have significant implications for understanding the role of organics in atmospheric chemistry. PMID:20142510

  2. KINETIC STUDY OF SELECTIVE GAS-PHASE OXIDATION OF ISOPROPANOL TO ACETONE USING MONOCLINIC ZRO2 AS A CATALYST

    Directory of Open Access Journals (Sweden)

    Mohammad Sadiq

    2015-08-01

    Full Text Available Zirconia was prepared by a precipitation method and calcined at 723 K, 1023 K, and 1253 K in order to obtain monoclinic zirconia. The prepared zirconia was characterized by XRD, SEM, EDX, surface area and pore size analyzer, and particle size analyzer. Monoclinic ZrO2 as a catalyst was used for the gas-phase oxidation of isopropanol to acetone in a Pyrex-glass-flow-type reactor with a temperature range of 443 K - 473 K. It was found that monoclinic ZrO2 shows remarkable catalytic activity (68% and selectivity (100% for the oxidation of isopropanol to acetone. This kinetic study reveals that the oxidation of isopropanol to acetone follows the L-H mechanism.

  3. Gas phase ion chemistry

    CERN Document Server

    Bowers, Michael T

    1979-01-01

    Gas Phase Ion Chemistry, Volume 1 covers papers on the advances of gas phase ion chemistry. The book discusses the advances in flow tubes and the measurement of ion-molecule rate coefficients and product distributions; the ion chemistry of the earth's atmosphere; and the classical ion-molecule collision theory. The text also describes statistical methods in reaction dynamics; the state selection by photoion-photoelectron coincidence; and the effects of temperature and pressure in the kinetics of ion-molecule reactions. The energy distribution in the unimolecular decomposition of ions, as well

  4. Theoretical spectroscopic investigations of HNS{sup q} and HSN{sup q} (q = 0, +1, −1) in the gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Ben Yaghlane, S., E-mail: roberto.linguerri@u-pem.fr, E-mail: saidayagh@gmail.com; Jaidane, N.-E. [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications - LSAMA, Université de Tunis El Manar, Tunis (Tunisia); Cotton, C. E.; Francisco, J. S. [Department of Chemistry and Department of Earth and Atmospheric Science, Purdue University, West Lafayette, Indiana 49707 (United States); Al Mogren, M. M. [Chemistry Department, Faculty of Science, King Saud University, PO Box 2455, Riyadh 11451 (Saudi Arabia); Linguerri, R., E-mail: roberto.linguerri@u-pem.fr, E-mail: saidayagh@gmail.com; Hochlaf, M. [Laboratoire Modélisation et Simulation Multi Echelle, Université Paris-Est, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France)

    2014-06-28

    We performed accurate ab initio investigations of the geometric parameters and the vibrational structure of neutral HNS/HSN triatomics and their singly charged anions and cations. We used standard and explicitly correlated coupled cluster approaches in connection with large basis sets. At the highest levels of description, we show that results nicely approach those obtained at the complete basis set limit. Moreover, we generated the three-dimensional potential energy surfaces (3D PESs) for these molecular entities at the coupled cluster level with singles and doubles and a perturbative treatment of triple excitations, along with a basis set of augmented quintuple-zeta quality (aug-cc-pV5Z). A full set of spectroscopic constants are deduced from these potentials by applying perturbation theory. In addition, these 3D PESs are incorporated into variational treatment of the nuclear motions. The pattern of the lowest vibrational levels and corresponding wavefunctions, up to around 4000 cm{sup −1} above the corresponding potential energy minimum, is presented for the first time.

  5. DFT study of the reactions of Mo and Mo with CO2 in gas phase

    Indian Academy of Sciences (India)

    understanding the mechanism of second-row metal reacting with CO2. The minimum energy ... et al.18 performed an IR study on the reaction of laser- ablated Mo atom .... indicate that the weak electrostatic interaction between. Mo. + and CO2 ...

  6. Kinetic study of the reaction of chlorine atoms with hydroxyacetone in gas-phase

    Science.gov (United States)

    Stoeffler, Clara; Joly, Lilian; Durry, Georges; Cousin, Julien; Dumelié, Nicolas; Bruyant, Aurélien; Roth, Estelle; Chakir, Abdelkhaleq

    2013-12-01

    In this letter the kinetics of the reaction of hydroxyacetone CH3C(O)CH2OH with Cl atoms is investigated using the relative rate technique. Experiments are carried out in a 65 L multipass photoreactor in the temperature range of 281-350 K. A mid-infrared spectrometer based on a quantum cascade laser in external cavity emitting at 9.5 μm is used to analyze the reactants. The determined rate coefficient for the investigated reaction is (1.7 ± 0.3) × 10-11exp(381.5 ± 57.3/T). The results are presented and discussed in terms of precision and compared with those obtained previously. The impact of Cl atoms on the atmospheric life time of hydroxyacetone is also discussed. Developing analytical techniques to quantify this compound in the atmosphere. Several methods of measurement have been used including the technique of proton transfer mass spectrometry (PTR-MS) [2] and derivatization with a chemical agent such as dinitrophenylhydrazine (DNPH) [3,4] followed by GC/MS or HPLC analyses. The HA amount in the troposphere was found to be in the order of a few hundred parts per trillion by volume [4], Performing laboratory experiments in order to study the HA reactivity with atmospheric oxidants. The first study on the kinetic of the reaction between OH radicals and HA was made by Dagault et al. [5] whose work was performed at room temperature by flash photolysis-resonance fluorescence. The determined rate constant implies a lifetime of a few days for HA relative to oxidation by OH radicals. Orlando et al. performed mechanistic and kinetics studies of the reaction of HA with OH radicals and Cl atoms at room temperature using a relative method [6]. Products detection was performed using FTIR spectroscopy. Moreover, these authors studied the photolysis of HA to determine its quantum yield and UV absorption spectrum. These studies showed that HA is principally removed from the atmosphere by reaction with OH radicals. Kinetic studies of the reaction of OH radicals with HA as a

  7. The reaction of nitromethane with hydrogen and deuterium atoms in the gas phase. A mechanistic study

    DEFF Research Database (Denmark)

    Lund Thomsen, E.; Nielsen, O.J.; Egsgaard, H.

    1993-01-01

    The mechanism of the reaction between H and CH3NO2, has been studied in a discharge flow system using electron paramagnetic resonance and modulated molecular beam mass spectrometry for the detection of reactants and products. Deuterium atoms have, in addition to CD3NO2, been used to support...... the proposed reaction mechanism. The reaction was studied with the atomic reactant in slight excess at 298 K and a total pressure of 2 Torr. Two concurrent reaction channels: (1a) H+CH3NO2-->HONO+.CH3 and (1b) H+CH3NO2-->CH3NO+.OH were observed. The branching ratio, k1a/(k1a+k1b), is 0.7+/-0.2....

  8. Applied quantum chemistry: Spectroscopic detection and characterization of the F2BS and Cl2BS free radicals in the gas phase

    International Nuclear Information System (INIS)

    Jin, Bing; Clouthier, Dennis J.; Sheridan, Phillip M.

    2015-01-01

    In this and previous work [D. J. Clouthier, J. Chem. Phys. 141, 244309 (2014)], the spectroscopic signatures of the X 2 BY (X = H, halogen, Y = O, S) free radicals have been predicted using high level ab initio theory. The theoretical results have been used to calculate the electronic absorption and single vibronic level (SVL) emission spectra of the radicals under typical jet-cooled conditions. Using these diagnostic predictions, the previously unknown F 2 BS and Cl 2 BS free radicals have been identified and characterized. The radicals were prepared in a free jet expansion by subjecting precursor mixtures of BF 3 or BCl 3 and CS 2 vapor to an electric discharge at the exit of a pulsed molecular beam valve. The B ~2 A 1 –X ~ 2 B 2 laser-induced fluorescence spectra were found within 150 cm −1 of their theoretically predicted positions with vibronic structure consistent with our Franck-Condon simulations. The B ~2 A 1 state emits down to the ground state and to the low-lying A ~2 B 1 excited state and the correspondence between the observed and theoretically derived SVL emission Franck-Condon profiles was used to positively identify the radicals and make assignments. Excited state Coriolis coupling effects complicate the emission spectra of both radicals. In addition, a forbidden component of the electronically allowed B ~ –X ~ band system of Cl 2 BS is evident, as signaled by the activity in the b 2 modes in the spectrum. Symmetry arguments indicate that this component gains intensity due to a vibronic interaction of the B ~2 A 1 state with a nearby electronic state of 2 B 2 symmetry

  9. Gas-phase studies of copper catalyzed aerobic cross coupling of thiol esters and arylboronic acids

    Czech Academy of Sciences Publication Activity Database

    Tsybizová, A.; Schröder, Detlef; Roithová, J.; Henke, A.; Šrogl, Jiří

    2014-01-01

    Roč. 27, č. 3 (2014), s. 198-203 ISSN 0894-3230 R&D Projects: GA ČR GAP207/12/0846 Grant - others:GA ČR(CZ) GAP207/11/0338 Institutional support: RVO:61388963 Keywords : boronic acids * catalysis * copper * cross coupling * electrospray ionization * mass spectrometry * kinetic studies Subject RIV: CC - Organic Chemistry Impact factor: 1.380, year: 2014

  10. Gas-phase studies of AunOm+ interacting with carbon monoxide

    Science.gov (United States)

    Kimble, M. L.; Castleman, A. W.

    2004-04-01

    The results of reactions between preformed cationic gold oxide clusters and carbon monoxide have been investigated utilizing a fast-flow reactor mass spectrometer. From these studies, it was found that all AunOm+ produced in the cluster source disappeared with CO addition at the reactant gas inlet. Furthermore, with CO addition, intermediate peaks of the form AunOm(CO)x+ (n=1-2, m=0-3, x=0-2) were produced, with some of the species continuing to react at higher CO flows.

  11. Quantum chemical study on gas phase pyrolysis of p-isopropenylphenol.

    Science.gov (United States)

    Mohan Verma, Anand; Kawale, Harshal D; Agrawal, Kushagra; Kishore, Nanda

    2018-05-01

    In the pyrolysis of Sphagnum moss species, p-isopropenylphenol (p-IPP) is a major product which has been considered in this density functional theory based computational study for its conversion to various products such as benzene, phenol, 4-propenylphenol, indan-5-ol, 4-propylcyclohexanone, 4-cyclopropylphenol, etc. In order to achieve these products, eight different reaction schemes are performed using B3LYP/6-311 + g (d,p) level of theory. Further, thermodynamic properties such as reaction free energies and reaction enthalpies associated with these eight reaction schemes are developed in the temperature range of 298-898 K. The reaction schemes that include partial hydrogenation of the aromatic carbon followed by elimination of functional groups are found to demand low activation energy. The production of benzene from p-IPP with isopropenylbenzene as an intermediate product requiring only 19.83 kcal/mol of activation energy is the rate limiting reaction step. Indan-5-ol produced from p-IPP is validated with the literature results and found excellent agreement between two results. Furthermore, the temperature is found to have phenomenal effect in each reaction scheme. Copyright © 2018 Elsevier Inc. All rights reserved.

  12. Gas-phase formaldehyde adsorption isotherm studies on activated carbon: correlations of adsorption capacity to surface functional group density.

    Science.gov (United States)

    Carter, Ellison M; Katz, Lynn E; Speitel, Gerald E; Ramirez, David

    2011-08-01

    Formaldehyde (HCHO) adsorption isotherms were developed for the first time on three activated carbons representing one activated carbon fiber (ACF) cloth, one all-purpose granular activated carbon (GAC), and one GAC commercially promoted for gas-phase HCHO removal. The three activated carbons were evaluated for HCHO removal in the low-ppm(v) range and for water vapor adsorption from relative pressures of 0.1-0.9 at 26 °C where, according to the IUPAC isotherm classification system, the adsorption isotherms observed exhibited Type V behavior. A Type V adsorption isotherm model recently proposed by Qi and LeVan (Q-L) was selected to model the observed adsorption behavior because it reduces to a finite, nonzero limit at low partial pressures and it describes the entire range of adsorption considered in this study. The Q-L model was applied to a polar organic adsorbate to fit HCHO adsorption isotherms for the three activated carbons. The physical and chemical characteristics of the activated carbon surfaces were characterized using nitrogen adsorption isotherms, X-ray photoelectron spectroscopy (XPS), and Boehm titrations. At low concentrations, HCHO adsorption capacity was most strongly related to the density of basic surface functional groups (SFGs), while water vapor adsorption was most strongly influenced by the density of acidic SFGs.

  13. Gas phase chemical studies of superheavy elements using the Dubna gas-filled recoil separator - Stopping range determination

    International Nuclear Information System (INIS)

    Wittwer, D.; Abdullin, F.Sh.; Aksenov, N.V.; Albin, Yu.V.; Bozhikov, G.A.; Dmitriev, S.N.; Dressler, R.; Eichler, R.; Gaeggeler, H.W.; Henderson, R.A.; Huebener, S.; Kenneally, J.M.; Lebedev, V.Ya.; Lobanov, Yu.V.; Moody, K.J.; Oganessian, Yu.Ts.; Petrushkin, O.V.; Polyakov, A.N.; Piguet, D.; Rasmussen, P.

    2010-01-01

    Currently, gas phase chemistry experiments with heaviest elements are usually performed with the gas-jet technique with the disadvantage that all reaction products are collected in a gas-filled thermalisation chamber adjacent to the target. The incorporation of a physical preseparation device between target and collection chamber opens up the perspective to perform new chemical studies. But this approach requires detailed knowledge of the stopping force (STF) of the heaviest elements in various materials. Measurements of the energy loss of mercury (Hg), radon (Rn), and nobelium (No) in Mylar and argon (Ar) were performed at low kinetic energies of around (40-270) keV per nucleon. The experimentally obtained values were compared with STF calculations of the commonly used program for calculating stopping and ranges of ions in matter (SRIM). Using the obtained data points an extrapolation of the STF up to element 114, eka-lead, in the same stopping media was carried out. These estimations were applied to design and to perform a first chemical experiment with a superheavy element behind a physical preseparator using the nuclear fusion reaction 244 Pu( 48 Ca; 3n) 289 114. One decay chain assigned to an atom of 285 112, the α-decay product of 289 114, was observed.

  14. Nuclear spectroscopic studies

    International Nuclear Information System (INIS)

    Bingham, C.R.; Guidry, M.W.; Riedinger, L.L.; Sorensen, S.P.

    1994-01-01

    The Nuclear Physics group at UTK is involved in heavy-ion physics including both nuclear structure and reaction mechanisms. During the last year experimental work has been in 3 broad areas: structure of nuclei at high angular momentum, structure of nuclei far from stability, and ultra-relativistic heavy-ion physics. Results in these areas are described in this document under: properties of high-spin states, study of low-energy levels of nuclei far from stability, and high-energy heavy-ion physics (PHENIX, etc.). Another important component of the work is theoretical interpretation of experimental results (Joint Institute for Heavy Ion Research)

  15. Nuclear spectroscopic studies

    Energy Technology Data Exchange (ETDEWEB)

    Bingham, C.R.; Guidry, M.W.; Riedinger, L.L.; Sorensen, S.P.

    1993-02-08

    The Nuclear Physics group at the University of Tennessee, Knoxville is involved in several aspects of heavy-ion physics including both nuclear structure and reaction mechanisms. While our main emphasis is on experimental problems involving heavy-ion accelerators, we have maintained a strong collaboration with several theorists in order to best pursue the physics of our measurements. During the last year we have led several experiments at the Holifield Heavy Ion Research Facility and participated in others at Argonne National Laboratory. Also, we continue to be very active in the collaboration to study ultra-relativistic heavy ion physics utilizing the SPS accelerator at CERN in Geneva, Switzerland and in a RHIC detector R D project. Our experimental work is in four broad areas: (1) the structure of nuclei at high angular momentum, (2) heavy-ion induced transfer reactions, (3) the structure of nuclei far from stability, and (4) ultra-relativistic heavy-ion physics. The results of studies in these particular areas will be described in this document in sections IIA, IIB, IIC, and IID, respectively. Areas (1), (3), and (4) concentrate on the structure of nuclear matter in extreme conditions of rotational motion, imbalance of neutrons and protons, or very high temperature and density. Area (2) pursues the transfer of nucleons to states with high angular momentum, both to learn about their structure and to understand the transfer of particles, energy, and angular momentum in collisions between heavy ions. An important component of our program is the strong emphasis on the theoretical aspects of nuclear structure and reactions.

  16. Nuclear spectroscopic studies

    International Nuclear Information System (INIS)

    Bingham, C.R.; Guidry, M.W.; Riedinger, L.L.; Sorensen, S.P.

    1993-01-01

    The Nuclear Physics group at the University of Tennessee, Knoxville is involved in several aspects of heavy-ion physics including both nuclear structure and reaction mechanisms. While our main emphasis is on experimental problems involving heavy-ion accelerators, we have maintained a strong collaboration with several theorists in order to best pursue the physics of our measurements. During the last year we have led several experiments at the Holifield Heavy Ion Research Facility and participated in others at Argonne National Laboratory. Also, we continue to be very active in the collaboration to study ultra-relativistic heavy ion physics utilizing the SPS accelerator at CERN in Geneva, Switzerland and in a RHIC detector R ampersand D project. Our experimental work is in four broad areas: (1) the structure of nuclei at high angular momentum, (2) heavy-ion induced transfer reactions, (3) the structure of nuclei far from stability, and (4) ultra-relativistic heavy-ion physics. The results of studies in these particular areas will be described in this document in sections IIA, IIB, IIC, and IID, respectively. Areas (1), (3), and (4) concentrate on the structure of nuclear matter in extreme conditions of rotational motion, imbalance of neutrons and protons, or very high temperature and density. Area (2) pursues the transfer of nucleons to states with high angular momentum, both to learn about their structure and to understand the transfer of particles, energy, and angular momentum in collisions between heavy ions. An important component of our program is the strong emphasis on the theoretical aspects of nuclear structure and reactions

  17. Nuclear spectroscopic studies

    International Nuclear Information System (INIS)

    Bingham, C.R.; Guidry, M.W.; Riedinger, L.L.; Sorensen, S.P.

    1988-01-01

    The Nuclear Physics group at the University of Tennessee, Knoxville is involved in several aspects of heavy-ion physics including both nuclear structure and reaction mechanisms. While our main emphasis is on experimental problems involving heavy-ion accelerators, we have maintained a strong collaboration with several theorists in order to best pursue the physics of our measurements. During the last year we have led experiments at the Holifield Heavy Ion Research Facility, the SuperHILAC at Berkeley, and Chalk River Tandem Accelerator. Also, we have joined a collaboration to study ultra-relativistic heavy ion physics and one of our group has spent all of 1987 at CERN to work on the WA80 experiment. Our experimental work is in four broad areas: (1) the structure of nuclei at high angular momentum, (2) heavy-ion induced transfer reactions, (3) the structure of nuclei far from stability, and (4) ultra-relativistic heavy-ion physics. These results will be described in this document in sections 2A, 2B, 2C, and 2D, respectively. Areas (1), (3), and (4) concentrate on the structure of nuclear matter in extreme conditions of rotational motion, imbalance of neutrons and protons or very high temperature and density. Area (2) pursues the transfer of nucleons to states with high angular momentum, both to learn about their structure and to understand the transfer of particles, energy and angular momentum in collisions between heavy ions. An important component of our program is the strong emphasis on the theoretical aspects of nuclear structure and reactions

  18. Nuclear spectroscopic studies

    International Nuclear Information System (INIS)

    Bingham, C.R.; Guidry, M.W.; Riedinger, L.L.; Sorensen, S.P.

    1991-01-01

    The Nuclear Physics group at the University of Tennessee, Knoxville is involved in several aspects of heavy-ion physics including both nuclear structure and reaction mechanisms. While our main emphasis is on experimental problems involving heavy-ion accelerators, we have maintained a strong collaboration with several theorists in order to best pursue the physics of our measurements. During the last year we have led experiments at the Holifield Heavy Ion Research Facility, the SuperHILAC at Berkeley, and Chalk River Tandem Accelerator. Also, we have joined a collaboration to study ultra-relativistic heavy ion physics and one of our group has spent all of 1987 at CERN to work on the WA80 experiment. Our experimental work is in four broad areas: (1) the structure of nuclei at high angular momentum, (2) heavy-ion induced transfer reactions, (3) the structure of nuclei far from stability, and (4) ultra-relativistic heavy-ion physics. These results will be described in this document in sections IIA, IIB, and IID, respectively. Areas (1), (3), and (4) concentrate on the structure of nuclear matter in extreme conditions of rotational motion, imbalance of neutrons and protons, or very high temperature and density. Area (2) pursues the transfer of nucleons to states with high angular momentum, both to learn about their structure and to understand the transfer of particles, energy and angular momentum in collisions between heavy ions. An important component of our program is the strong emphasis on the theoretical aspects of nuclear structure and reactions

  19. Studies of some elementary processes involving electrons in the gas phase by pulse-radiolysis microwave-cavity technique

    International Nuclear Information System (INIS)

    Sunagawa, Takeyoshi; Makita, Takeshi; Musasa, Hirofumi; Tatsumi, Yoshitsugu; Shimamori, Hiroshi

    1995-01-01

    The pulse radiolysis-microwave cavity technique has been employed for detection of free electrons in the gas phase. Presented are results of the observation of electron disappearance by attachment to molecules, the electron thermalization (energy loss) processes in the presence of an electron-attaching compound, and the formation of electrons by Penning ionization. (author)

  20. Mossbauer spectroscopic studies in ferroboron

    Science.gov (United States)

    Yadav, Ravi Kumar; Govindaraj, R.; Amarendra, G.

    2017-05-01

    Mossbauer spectroscopic studies have been carried out in a detailed manner on ferroboron in order to understand the local structure and magnetic properties of the system. Evolution of the local structure and magnetic properties of the amorphous and crystalline phases and their thermal stability have been addressed in a detailed manner in this study. Role of bonding between Fe 4s and/or 4p electrons with valence electrons of boron (2s,2p) in influencing the stability and magnetic properties of Fe-B system is elucidated.

  1. Laser spectroscopy and gas-phase chemistry in CVD

    International Nuclear Information System (INIS)

    Ho, P.; Breiland, W.G.; Coltrin, M.E.

    1986-01-01

    The experimental work involves the use of laser spectroscopic techniques for in situ measurements on the gas phase in a chemical vapor deposition reactor. The theoretical part of the program consists of a computer model of the coupled fluid mechanics and gas-phase chemical kinetics of silane decomposition and subsequent reactions of intermediate species. The laser measurements provide extensive data for thoroughly testing the predictive capabilities of the model

  2. A long-term study of new particle formation in a coastal environment: meteorology, gas phase and solar radiation implications.

    Science.gov (United States)

    Sorribas, M; Adame, J A; Olmo, F J; Vilaplana, J M; Gil-Ojeda, M; Alados-Arboledas, L

    2015-04-01

    New particle formation (NPF) was investigated at a coastal background site in Southwest Spain over a four-year period using a Scanning Particle Mobility Sizer (SMPS). The goals of the study were to characterise the NPF and to investigate their relationship to meteorology, gas phase (O3, SO2, CO and NO2) and solar radiation (UVA, UVB and global). A methodology for identifying and classifying the NPF was implemented using the wind direction and modal concentrations as inputs. NPF events showed a frequency of 24% of the total days analysed. The mean duration was 9.2±4.2 h. Contrary to previous studies conducted in other locations, the NPF frequency reached its maximum during cold seasons for approximately 30% of the days. The lowest frequency took place in July with 10%, and the seasonal wind pattern was found to be the most important parameter influencing the NPF frequency. The mean formation rate was 2.2±1.7 cm(-3) s(-1), with a maximum in the spring and early autumn and a minimum during the summer and winter. The mean growth rate was 3.8±2.4 nm h(-1) with higher values occurring from spring to autumn. The mean and seasonal formation and growth rates are in agreement with previous observations from continental sites in the Northern Hemisphere. NPF classification of different classes was conducted to explore the effect of synoptic and regional-scale patterns on NPF and growth. The results show that under a breeze regime, the temperature indirectly affects NPF events. Higher temperatures increase the strength of the breeze recirculation, favouring gas accumulation and subsequent NPF appearance. Additionally, the role of high relative humidity in inhibiting the NPF was evinced during synoptic scenarios. The remaining meteorological variables (RH), trace gases (CO and NO), solar radiation, PM10 and condensation sink, showed a moderate or high connection with both formation and growth rates. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. A long-term study of new particle formation in a coastal environment: Meteorology, gas phase and solar radiation implications

    Energy Technology Data Exchange (ETDEWEB)

    Sorribas, M., E-mail: sorribas@ugr.es [Department of Applied Physics, University of Granada, Granada, 18071 (Spain); Andalusian Institute for Earth System Research (IISTA), University of Granada, 18006 (Spain); Adame, J.A. [‘El Arenosillo’ — Atmospheric Sounding Station, Atmospheric Research and Instrumentation Branch, National Institute for Aerospace Technology (INTA), Mazagón, Huelva, 21130 (Spain); Olmo, F.J. [Department of Applied Physics, University of Granada, Granada, 18071 (Spain); Andalusian Institute for Earth System Research (IISTA), University of Granada, 18006 (Spain); Vilaplana, J.M.; Gil-Ojeda, M. [‘El Arenosillo’ — Atmospheric Sounding Station, Atmospheric Research and Instrumentation Branch, National Institute for Aerospace Technology (INTA), Mazagón, Huelva, 21130 (Spain); Alados-Arboledas, L. [Department of Applied Physics, University of Granada, Granada, 18071 (Spain); Andalusian Institute for Earth System Research (IISTA), University of Granada, 18006 (Spain)

    2015-04-01

    New particle formation (NPF) was investigated at a coastal background site in Southwest Spain over a four-year period using a Scanning Particle Mobility Sizer (SMPS). The goals of the study were to characterise the NPF and to investigate their relationship to meteorology, gas phase (O{sub 3}, SO{sub 2}, CO and NO{sub 2}) and solar radiation (UVA, UVB and global). A methodology for identifying and classifying the NPF was implemented using the wind direction and modal concentrations as inputs. NPF events showed a frequency of 24% of the total days analysed. The mean duration was 9.2 ± 4.2 h. Contrary to previous studies conducted in other locations, the NPF frequency reached its maximum during cold seasons for approximately 30% of the days. The lowest frequency took place in July with 10%, and the seasonal wind pattern was found to be the most important parameter influencing the NPF frequency. The mean formation rate was 2.2 ± 1.7 cm{sup −3} s{sup −1}, with a maximum in the spring and early autumn and a minimum during the summer and winter. The mean growth rate was 3.8 ± 2.4 nm h{sup −1} with higher values occurring from spring to autumn. The mean and seasonal formation and growth rates are in agreement with previous observations from continental sites in the Northern Hemisphere. NPF classification of different classes was conducted to explore the effect of synoptic and regional-scale patterns on NPF and growth. The results show that under a breeze regime, the temperature indirectly affects NPF events. Higher temperatures increase the strength of the breeze recirculation, favouring gas accumulation and subsequent NPF appearance. Additionally, the role of high relative humidity in inhibiting the NPF was evinced during synoptic scenarios. The remaining meteorological variables (RH), trace gases (CO and NO), solar radiation, PM{sub 10} and condensation sink, showed a moderate or high connection with both formation and growth rates. - Highlights: • New

  4. Discriminating Properties of Alkali Metal Ions Towards the Constituents of Proteins and Nucleic Acids. Conclusions from Gas-Phase and Theoretical Studies.

    Science.gov (United States)

    Rodgers, Mary T; Armentrout, Peter B

    2016-01-01

    Quantitative insight into the structures and thermodynamics of alkali metal cations interacting with biological molecules can be obtained from studies in the gas phase combined with theoretical work. In this chapter, the fundamentals of the experimental and theoretical techniques are first summarized and results for such work on complexes of alkali metal cations with amino acids, small peptides, and nucleobases are reviewed. Periodic trends in how these interactions vary as the alkali metal cations get heavier are highlighted.

  5. Distribution of Gas Phase Polycyclic Aromatic Hydrocarbons (PAHs in Selected Indoor and Outdoor Air Samples of Malaysia: a Case Study in Serdang, Selangor and Bachang, Malacca

    Directory of Open Access Journals (Sweden)

    Haris Hafizal Abd Hamid

    2017-07-01

    Full Text Available Distribution of 10 polycyclic aromatic hydrocarbons (PAHs in the gas phase of air from selected indoor and outdoor areas of Selangor and Malacca, Malaysia has been investigated. A locally designed Semi Permeable Membrane Device (SPMD was applied for passive air sampling for 37 days at selected locations. Cleanup was carried out with Gas Purge - Micro Syringe Extraction (GP-MSE and the final analysis was using Gas Chromatography-Mass Spectrometry (GC-MS. In this study, 6 indoor and 12 outdoor locations were selected for air sampling. A total of 10 compounds of PAHs (Ʃ10PAHs were determined in the range of 0.218 ng/m3 - 1.692 ng/m3 and 0.378 ng/m3 - 1.492 ng/m3 in outdoor and indoor samples respectively. In the outdoor samples, locations such as near a petrol station and heavy traffic showed the maximum levels of Ʃ10PAHs, while rooftop samples showed the lowest Ʃ10PAHs. The distribution of gas phase Ʃ10PAHs was influenced by vehicular emission. Low molecular weight (LMW compounds (2-3 rings were dominant in all samples (>70% indicating that SPMD has successfully sampled the gas phase of the air.

  6. Raman Spectroscopic Studies of Methane Gas Hydrates

    DEFF Research Database (Denmark)

    Hansen, Susanne Brunsgaard; Berg, Rolf W.

    2009-01-01

    A brief review of the Raman spectroscopic studies of methane gas hydrates is given, supported by some new measurements done in our laboratory.......A brief review of the Raman spectroscopic studies of methane gas hydrates is given, supported by some new measurements done in our laboratory....

  7. A Numerical Study on Effect of Gas-Phase Radiative Heat Loss on Extinction of Hydrogen Diffusion Flames

    International Nuclear Information System (INIS)

    Sohn, Chae Hoon

    2007-01-01

    Extinction characteristics of hydrogen-air diffusion flames are investigated numerically by adopting counterflow flame configuration. At various pressures, effect of radiative heat loss on flame extinction is examined. Only gas-phase radiation is considered here. Radiative heat loss depends on flame thickness, temperature, H 2 O concentration, and pressure. From flame structures at various pressures, flame thickness decreases with pressure, but its gradient decreases at high pressure. Flame temperature and mole fraction of H 2 O increase slightly with pressure. Accordingly, as pressure increases, radiative heat loss becomes dominant. When radiative heat loss is considered, radiation-induced extinction is observed at low strain rate in addition to transport-induced extinction. As pressure increases, flammable region shifts to the high-temperature region and then, shrunk to the point on the coordinate plane of flame temperature and strain rate

  8. Density Functional Theory Study of Competitive Reaction Pathways of Ti+ with Fluorinated Acetone in the Gas Phase

    International Nuclear Information System (INIS)

    Hong, Kiryong; Kim, Tae Kyu

    2012-01-01

    We investigate the doublet and quartet potential energy surfaces associated with the gas-phase reaction between Ti + and CF 3 COCH 3 for two plausible reaction pathways, TiF 2 + and TiO + formation pathways by using the density functional theory (DFT) method. The molecular structures of intermediates and transition states involved in these reaction pathways are optimized at the DFT level by using the PBE0 functional. All transition states are identified by using the intrinsic reaction coordinate (IRC) method, and the resulting reaction coordinates describe how Ti + activates CF 3 COCH 3 and produces TiF 2 + and TiO + as products. On the basis of presented results, we propose the most favorable reaction pathway in the reaction between Ti + and CF 3 COCH 3

  9. Application of structured illumination to gas phase thermometry using thermographic phosphor particles: a study for averaged imaging

    Science.gov (United States)

    Zentgraf, Florian; Stephan, Michael; Berrocal, Edouard; Albert, Barbara; Böhm, Benjamin; Dreizler, Andreas

    2017-07-01

    Structured laser illumination planar imaging (SLIPI) is combined with gas phase thermometry measurements using thermographic phosphor (TGP) particles. The technique is applied to a heated jet surrounded by a coflow which is operated at ambient temperature. The respective air flows are seeded with a powder of BaMgAl10O17:Eu2+ (BAM) which is used as temperature-sensitive gas phase tracer. Upon pulsed excitation in the ultraviolet spectral range, the temperature is extracted based on the two-color ratio method combined with SLIPI. The main advantage of applying the SLIPI approach to phosphor thermometry is the reduction of particle-to-particle multiple light scattering and diffuse wall reflections, yielding a more robust calibration procedure as well as improving the measurement accuracy, precision, and sensitivity. For demonstration, this paper focuses on sample-averaged measurements of temperature fields in a jet-in-coflow configuration. Using the conventional approach, which in contrast to SLIPI is based on imaging with an unmodulated laser light sheet, we show that for the present setup typically 40% of the recorded signal is affected by the contribution of multiply scattered photons. At locations close to walls even up to 75% of the apparent signal is due to diffuse reflection and wall luminescence of BAM sticking at the surface. Those contributions lead to erroneous temperature fields. Using SLIPI, an unbiased two-color ratio field is recovered allowing for two-dimensional mean temperature reconstructions which exhibit a more realistic physical behavior. This is in contrast to results deduced by the conventional approach. Furthermore, using the SLIPI approach it is shown that the temperature sensitivity is enhanced by a factor of up to 2 at 270 °C. Finally, an outlook towards instantaneous SLIPI phosphorescence thermometry is provided.

  10. Excited-state dynamics of a ruthenium(II) catalyst studied by transient photofragmentation in gas phase and transient absorption in solution

    Energy Technology Data Exchange (ETDEWEB)

    Imanbaew, D.; Nosenko, Y. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Kerner, C. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Chevalier, K.; Rupp, F. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Riehn, C., E-mail: riehn@chemie.uni-kl.de [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Forschungszentrum OPTIMAS, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany); Thiel, W.R. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 52–54, 67663 Kaiserslautern (Germany); Diller, R. [Fachbereich Physik, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663 Kaiserslautern (Germany)

    2014-10-17

    Graphical abstract: - Highlights: • Ultrafast dynamics of new Ru(II) catalysts investigated in gas phase and solution. • Catalyst activation (HCl loss) achieved in ion trap by UV photoexcitation. • Electronic relaxation proceeds by IVR and IC followed by ground state dissociation. • No triplet formation in contrast to other Ru-polypyridine complexes. • Solvent prohibits catalyst activation in solution by fast vibrational cooling. - Abstract: We report studies on the excited state dynamics of new ruthenium(II) complexes [(η{sup 6}-cymene)RuCl(apypm)]PF{sub 6} (apypm=2-NR{sub 2}-4-(pyridine-2-yl)-pyrimidine, R=CH{sub 3} (1)/H (2)) which, in their active form [1{sup +}-HCl] and [2{sup +}-HCl], catalyze the transfer hydrogenation of arylalkyl ketones in the absence of a base. The investigations encompass femtosecond pump–probe transient mass spectrometry under isolated conditions and transient absorption spectroscopy in acetonitrile solution, both on the cations [(η{sup 6}-cymene)RuCl(apypm)]{sup +} (1{sup +}, 2{sup +}). Gas phase studies on mass selected ions were performed in an ESI ion trap mass spectrometer by transient photofragmentation, unambiguously proving the formation of the activated catalyst species [1{sup +}-HCl] or [2{sup +}-HCl] after photoexcitation being the only fragmentation channel. The primary excited state dynamics in the gas phase could be fitted to a biexponential decay, yielding time constants of <100 fs and 1–3 ps. Transient absorption spectroscopy performed in acetonitrile solution using femtosecond UV/Vis and IR probe laser pulses revealed additional deactivation processes on longer time scales (∼7–12 ps). However, the formation of the active catalyst species after photoexcitation could not be observed in solution. The results from both studies are compared to former CID investigations and DFT calculations concerning the activation mechanism.

  11. Gas-phase optical fiber photocatalytic reactors for indoor air application: a preliminary study on performance indicators

    Science.gov (United States)

    Palmiste, Ü.; Voll, H.

    2017-10-01

    The development of advanced air cleaning technologies aims to reduce building energy consumption by reduction of outdoor air flow rates while keeping the indoor air quality at an acceptable level by air cleaning. Photocatalytic oxidation is an emerging technology for gas-phase air cleaning that can be applied in a standalone unit or a subsystem of a building mechanical ventilation system. Quantitative information on photocatalytic reactor performance is required to evaluate the technical and economic viability of the advanced air cleaning by PCO technology as an energy conservation measure in a building air conditioning system. Photocatalytic reactors applying optical fibers as light guide or photocatalyst coating support have been reported as an approach to address the current light utilization problems and thus, improve the overall efficiency. The aim of the paper is to present a preliminary evaluation on continuous flow optical fiber photocatalytic reactors based on performance indicators commonly applied for air cleaners. Based on experimental data, monolith-type optical fiber reactor performance surpasses annular-type optical fiber reactors in single-pass removal efficiency, clean air delivery rate and operating cost efficiency.

  12. Silanization of silica and glass slides for DNA microarrays by impregnation and gas phase protocols: A comparative study

    International Nuclear Information System (INIS)

    Phaner-Goutorbe, Magali; Dugas, Vincent; Chevolot, Yann; Souteyrand, Eliane

    2011-01-01

    Surface immobilization of oligonucleotide probes (oligoprobes) is a key issue in the development of DNA-chips. The immobilization protocol should guarantee good availability of the probes, low non-specific adsorption and reproducibility. We have previously reported a silanization protocol with tert-butyl-11-(dimethylamino)silylundecanoate performed by impregnation (Impregnation Protocol, IP) of silica substrates from dilute silane solutions, leading to surfaces bearing carboxylic groups. In this paper, the Impregnation protocol is compared with a Gas phase Protocol (GP) which is more suited to industrial requirements such as reliable and robust processing, cost efficiency, etc.... The morphology of the oligoprobe films at the nanoscale (characterized by Atomic Force Microscopy) and the reproducibility of subsequent oligoprobes immobilization steps have been investigated for the two protocols on thermal silica (Si/SiO 2 ) and glass slide substrates. IP leads to smooth surfaces whereas GP induces the formation of islands features suggesting a non-continuous silane layer. The reproducibility of the overall surface layer (18.75 mm 2 ) has been evaluated through the covalent immobilization of a fluorescent oligoprobes. Average fluorescent signals of 6 (a.u.) and 4 (a.u.) were observed for IP and GP, respectively, with a standard deviation of 1 for both protocols. Thus, despite a morphological difference of the silane layer at the nanometer scale, the density of the immobilized probes remained similar.

  13. An Experimental and Computational Study of the Gas-Phase Acidities of the Common Amino Acid Amides.

    Science.gov (United States)

    Plummer, Chelsea E; Stover, Michele L; Bokatzian, Samantha S; Davis, John T M; Dixon, David A; Cassady, Carolyn J

    2015-07-30

    Using proton-transfer reactions in a Fourier transform ion cyclotron resonance mass spectrometer and correlated molecular orbital theory at the G3(MP2) level, gas-phase acidities (GAs) and the associated structures for amides corresponding to the common amino acids have been determined for the first time. These values are important because amino acid amides are models for residues in peptides and proteins. For compounds whose most acidic site is the C-terminal amide nitrogen, two ions populations were observed experimentally with GAs that differ by 4-7 kcal/mol. The lower energy, more acidic structure accounts for the majority of the ions formed by electrospray ionization. G3(MP2) calculations predict that the lowest energy anionic conformer has a cis-like orientation of the [-C(═O)NH](-) group whereas the higher energy, less acidic conformer has a trans-like orientation of this group. These two distinct conformers were predicted for compounds with aliphatic, amide, basic, hydroxyl, and thioether side chains. For the most acidic amino acid amides (tyrosine, cysteine, tryptophan, histidine, aspartic acid, and glutamic acid amides) only one conformer was observed experimentally, and its experimental GA correlates with the theoretical GA related to side chain deprotonation.

  14. Raman spectroscopic studies of hydrogen clathrate hydrates.

    Science.gov (United States)

    Strobel, Timothy A; Sloan, E Dendy; Koh, Carolyn A

    2009-01-07

    Raman spectroscopic measurements of simple hydrogen and tetrahydrofuran+hydrogen sII clathrate hydrates have been performed. Both the roton and vibron bands illuminate interesting quantum dynamics of enclathrated H(2) molecules. The complex vibron region of the Raman spectrum has been interpreted by observing the change in population of these bands with temperature, measuring the absolute H(2) content as a function of pressure, and with D(2) isotopic substitution. Quadruple occupancy of the large sII clathrate cavity shows the highest H(2) vibrational frequency, followed by triple and double occupancies. Singly occupied small cavities display the lowest vibrational frequency. The vibrational frequencies of H(2) within all cavity environments are redshifted from the free gas phase value. At 76 K, the progression from ortho- to para-H(2) occurs over a relatively slow time period (days). The rotational degeneracy of H(2) molecules within the clathrate cavities is lifted, observed directly in splitting of the para-H(2) roton band. Raman spectra from H(2) and D(2) hydrates suggest that the occupancy patterns between the two hydrates are analogous, increasing confidence that D(2) is a suitable substitute for H(2). The measurements suggest that Raman is an effective and convenient method to determine the relative occupancy of hydrogen molecules in different clathrate cavities.

  15. Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces.

    Science.gov (United States)

    Spezia, Riccardo; Martínez-Nuñez, Emilio; Vazquez, Saulo; Hase, William L

    2017-04-28

    In this Introduction, we show the basic problems of non-statistical and non-equilibrium phenomena related to the papers collected in this themed issue. Over the past few years, significant advances in both computing power and development of theories have allowed the study of larger systems, increasing the time length of simulations and improving the quality of potential energy surfaces. In particular, the possibility of using quantum chemistry to calculate energies and forces 'on the fly' has paved the way to directly study chemical reactions. This has provided a valuable tool to explore molecular mechanisms at given temperatures and energies and to see whether these reactive trajectories follow statistical laws and/or minimum energy pathways. This themed issue collects different aspects of the problem and gives an overview of recent works and developments in different contexts, from the gas phase to the condensed phase to excited states.This article is part of the themed issue 'Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces'. © 2017 The Author(s).

  16. Resolving Gas-Phase Metallicity In Galaxies

    Science.gov (United States)

    Carton, David

    2017-06-01

    Chapter 2: As part of the Bluedisk survey we analyse the radial gas-phase metallicity profiles of 50 late-type galaxies. We compare the metallicity profiles of a sample of HI-rich galaxies against a control sample of HI-'normal' galaxies. We find the metallicity gradient of a galaxy to be strongly correlated with its HI mass fraction {M}{HI}) / {M}_{\\ast}). We note that some galaxies exhibit a steeper metallicity profile in the outer disc than in the inner disc. These galaxies are found in both the HI-rich and control samples. This contradicts a previous indication that these outer drops are exclusive to HI-rich galaxies. These effects are not driven by bars, although we do find some indication that barred galaxies have flatter metallicity profiles. By applying a simple analytical model we are able to account for the variety of metallicity profiles that the two samples present. The success of this model implies that the metallicity in these isolated galaxies may be in a local equilibrium, regulated by star formation. This insight could provide an explanation of the observed local mass-metallicity relation. Chapter 3 We present a method to recover the gas-phase metallicity gradients from integral field spectroscopic (IFS) observations of barely resolved galaxies. We take a forward modelling approach and compare our models to the observed spatial distribution of emission line fluxes, accounting for the degrading effects of seeing and spatial binning. The method is flexible and is not limited to particular emission lines or instruments. We test the model through comparison to synthetic observations and use downgraded observations of nearby galaxies to validate this work. As a proof of concept we also apply the model to real IFS observations of high-redshift galaxies. From our testing we show that the inferred metallicity gradients and central metallicities are fairly insensitive to the assumptions made in the model and that they are reliably recovered for galaxies

  17. Gas Phase Molecular Dynamics

    International Nuclear Information System (INIS)

    Hall, G.E.; Prrese, J.M.; Sears, T.J.; Weston, R.E.

    1999-01-01

    The goal of this research is the understanding of elementary chemical and physical processes important in the combustion of fossil fuels. Interest centers on reactions involving short-lived chemical intermediates and their properties. High-resolution high-sensitivity laser absorption methods are augmented by high temperature flow-tube reaction kinetics studies with mass spectrometric sampling. These experiments provide information on the energy levels, structures and reactivity of molecular flee radical species and, in turn, provide new tools for the study of energy flow and chemical bond cleavage in the radicals in chemical systems. The experimental work is supported by theoretical and computational work using time-dependent quantum wave packet calculations that provide insights into energy flow between the vibrational modes of the molecule

  18. Spectroscopic studies of copper enzymes

    International Nuclear Information System (INIS)

    Dooley, D.M.; Moog, R.; Zumft, W.; Koenig, S.H.; Scott, R.A.; Cote, C.E.; McGuirl, M.

    1986-01-01

    Several spectroscopic methods, including absorption, circular dichroism (CD), magnetic CD (MCD), X-ray absorption, resonance Raman, EPR, NMR, and quasi-elastic light-scattering spectroscopy, have been used to probe the structures of copper-containing amine oxidases, nitrite reductase, and nitrous oxide reductase. The basic goals are to determine the copper site structure, electronic properties, and to generate structure-reactivity correlations. Collectively, the results on the amine oxidases permit a detailed model for the Cu(II) sites in these enzymes to be constructed that, in turn, rationalizes the ligand-binding chemistry. Resonance Raman spectra of the phenylhydrazine and 2,4-dinitrophenyl-hydrazine derivatives of bovine plasma amine oxidase and models for its organic cofactor, e.g. pyridoxal, methoxatin, are most consistent with methoxatin being the intrinsic cofactor. The structure of the Cu(I) forms of the amine oxidases have been investigated by X-ray absorption spectroscopy (XAS); the copper coordination geometry is significantly different in the oxidized and reduced forms. Some anomalous properties of the amine oxidases in solution are explicable in terms of their reversible aggregation, which the authors have characterized via light scattering. Nitrite and nitrous oxide reductases display several novel spectral properties. The data suggest that new types of copper sites are present

  19. Gas-Phase Reactivity of Microsolvated Anions

    DEFF Research Database (Denmark)

    Thomsen, Ditte Linde

    the gas-phase α-effect. The experimental studies are performed by means of the flowing after glow selected ion flow tube technique, and these are supplemented by electronic structure calculations. The α-nucleophile employed is the microsolvated hydrogen peroxide anion whose reactivity is compared......Gas-phase studies of ion-molecule reactions shed light on the intrinsic factors that govern reactivity; and even solvent effects can be examined in the gasphase environment by employing microsolvated ions. An area that has received considerable attention with regard to the interplay between...... to that of a series of microsolvated oxygen centered anions. The association of the nucleophiles with a single water or methanol molecule allows the α-effect to be observed in the SN2 reaction with methyl chloride; this effect was not apparent in the reactions of the unsolvated anions. The results suggest...

  20. Spectroscopic, thermal and biological studies of coordination

    Indian Academy of Sciences (India)

    Spectroscopic, thermal and biological studies of coordination compounds of sulfasalazine drug: Mn(II), Hg(II), Cr(III), ZrO(II), VO(II) and Y(III) transition metal ... The thermal decomposition of the complexes as well as thermodynamic parameters ( *}, *, * and *) were estimated using Coats–Redfern and ...

  1. GAS PHASE SELECTIVE PHOTOXIDATION OF ALCOHOLS USING LIGHT-ACTIVATED TITANIUM DIOXIDE AND MOLECULAR OXYGEN

    Science.gov (United States)

    Gas Phase Selective Oxidation of Alcohols Using Light-Activated Titanium Dioxide and Molecular Oxygen Gas phase selective oxidations of various primary and secondary alcohols are studied in an indigenously built stainless steel up-flow photochemical reactor using ultravi...

  2. Rate constants of hydroxyl radical oxidation of polychlorinated biphenyls in the gas phase: A single−descriptor based QSAR and DFT study

    International Nuclear Information System (INIS)

    Yang, Zhihui; Luo, Shuang; Wei, Zongsu; Ye, Tiantian; Spinney, Richard; Chen, Dong; Xiao, Ruiyang

    2016-01-01

    The second‒order rate constants (k) of hydroxyl radical (·OH) with polychlorinated biphenyls (PCBs) in the gas phase are of scientific and regulatory importance for assessing their global distribution and fate in the atmosphere. Due to the limited number of measured k values, there is a need to model the k values for unknown PCBs congeners. In the present study, we developed a quantitative structure–activity relationship (QSAR) model with quantum chemical descriptors using a sequential approach, including correlation analysis, principal component analysis, multi−linear regression, validation, and estimation of applicability domain. The result indicates that the single descriptor, polarizability (α), plays an important role in determining the reactivity with a global standardized function of lnk = −0.054 × α ‒ 19.49 at 298 K. In order to validate the QSAR predicted k values and expand the current k value database for PCBs congeners, an independent method, density functional theory (DFT), was employed to calculate the kinetics and thermodynamics of the gas‒phase ·OH oxidation of 2,4′,5-trichlorobiphenyl (PCB31), 2,2′,4,4′-tetrachlorobiphenyl (PCB47), 2,3,4,5,6-pentachlorobiphenyl (PCB116), 3,3′,4,4′,5,5′-hexachlorobiphenyl (PCB169), and 2,3,3′,4,5,5′,6-heptachlorobiphenyl (PCB192) at 298 K at B3LYP/6–311++G**//B3LYP/6–31 + G** level of theory. The QSAR predicted and DFT calculated k values for ·OH oxidation of these PCB congeners exhibit excellent agreement with the experimental k values, indicating the robustness and predictive power of the single–descriptor based QSAR model we developed. - Highlights: • We developed a single−descriptor based QSAR model for ·OH oxidation of PCBs. • We independently validated the QSAR predicted k values of five PCB congeners with the DFT method. • The QSAR predicted and DFT calculated k for the five PCB congeners exhibit excellent agreement. - We developed a single

  3. Nanostructured diamine-fullerene derivatives: computational density functional theory study and experimental evidence for their formation via gas-phase functionalization.

    Science.gov (United States)

    Contreras-Torres, Flavio F; Basiuk, Elena V; Basiuk, Vladimir A; Meza-Laguna, Víctor; Gromovoy, Taras Yu

    2012-02-16

    Nanostructure derivatives of fullerene C(60) are used in emerging applications of composite matrices, including protective and decorative coating, superadsorbent material, thin films, and lightweight high-strength fiber-reinforced materials, etc. In this study, quantum chemical calculations and experimental studies were performed to analyze the derivatives of diamine-fullerene prepared by the gas-phase solvent-free functionalization technique. In particular, the aliphatic 1,8-diamino-octane and the aromatic 1,5-diaminonaphthalene, which are diamines volatile in vacuum, were studied. We addressed two alternative mechanisms of the amination reaction via polyaddition and cross-linking of C(60) with diamines, using the pure GGA BLYP, PW91, and PBE functionals; further validation calculations were performed using the semiempirical dispersion GGA B97-D functional which contains parameters that have been specially adjusted by a more realistic view on dispersion contributions. In addition, we looked for experimental evidence for the covalent functionalization by using laser desorption/ionization time-of-flight mass spectrometry, thermogravimetric analysis, and atomic force microscopy.

  4. Infrared gas phase study on plasma-polymer interactions in high-current diffuse dielectric barrier discharge

    NARCIS (Netherlands)

    Liu, Y.; Welzel, S.; Starostin, S. A.; van de Sanden, M. C. M.; Engeln, R.; de Vries, H. W.

    2017-01-01

    A roll-to-roll high-current diffuse dielectric barrier discharge at atmospheric pressure was operated in air and Ar/N2/O2 gas mixtures. The exhaust gas from the discharge was studied using a high-resolution Fourier-transform infrared spectrometer in the range from 3000 to 750?cm-1 to unravel the

  5. DEMONSTRATION OF FUEL CELLS TO RECOVER ENERGY FROM ANAEROBIC DIGESTER GAS - PHASE I. CONCEPTUAL DESIGN, PRELIMINARY COST, AND EVALUATION STUDY

    Science.gov (United States)

    The report discusses Phase I (a conceptual design, preliminary cost, and evaluation study) of a program to demonstrate the recovery of energy from waste methane produced by anaerobic digestion of waste water treatment sludge. The fuel cell is being used for this application becau...

  6. GAS PHASE ION CHEMISTRY OF COUMARINS: AB INITIO ...

    African Journals Online (AJOL)

    B. S. Chandravanshi

    The gas phase ion chemistry of coumarins using electron ionization (EI), positive chemical ionization (PCI) and ... Figure 1. Generic chemical structures of the coumarins in this study. ..... Part of this work was conducted using the resources of ...

  7. Study of the composition and gas-phase release characteristics of salt material extracted from MSW ash particles using STA

    DEFF Research Database (Denmark)

    Arvelakis, Stelios; Frandsen, Flemming; Koukios, E.G.

    2007-01-01

    material extracted from MSW ash particles using a six-stage leaching process is studied using simultaneous thermal analysis (STA). The produced results provide useful information regarding the composition of the salt material and its melting behavior that is considered to play an important role...... to deposition and corrosion problems at MSW incinerators. The results may be used to model the deposition process and to the better understanding of the corrosion process during MSW incineration....

  8. Impact of the spectral and spatial properties of natural light on indoor gas-phase chemistry: Experimental and modeling study.

    Science.gov (United States)

    Blocquet, M; Guo, F; Mendez, M; Ward, M; Coudert, S; Batut, S; Hecquet, C; Blond, N; Fittschen, C; Schoemaecker, C

    2018-05-01

    The characteristics of indoor light (intensity, spectral, spatial distribution) originating from outdoors have been studied using experimental and modeling tools. They are influenced by many parameters such as building location, meteorological conditions, and the type of window. They have a direct impact on indoor air quality through a change in chemical processes by varying the photolysis rates of indoor pollutants. Transmittances of different windows have been measured and exhibit different wavelength cutoffs, thus influencing the potential of different species to be photolysed. The spectral distribution of light entering indoors through the windows was measured under different conditions and was found to be weakly dependent on the time of day for indirect cloudy, direct sunshine, partly cloudy conditions contrary to the light intensity, in agreement with calculations of the transmittance as a function of the zenithal angle and the calculated outdoor spectral distribution. The same conclusion can be drawn concerning the position within the room. The impact of these light characteristics on the indoor chemistry has been studied using the INCA-Indoor model by considering the variation in the photolysis rates of key indoor species. Depending on the conditions, photolysis processes can lead to a significant production of radicals and secondary species. © 2018 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  9. Fundamental study of hydrogen-attachment-induced peptide fragmentation occurring in the gas phase and during the matrix-assisted laser desorption/ionization process.

    Science.gov (United States)

    Asakawa, Daiki; Takahashi, Hidenori; Iwamoto, Shinichi; Tanaka, Koichi

    2018-05-09

    Mass spectrometry with hydrogen-radical-mediated fragmentation techniques has been used for the sequencing of proteins/peptides. The two methods, matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) and hydrogen attachment/abstraction dissociation (HAD) are known as hydrogen-radical-mediated fragmentation techniques. MALDI-ISD occurs during laser induced desorption processes, whereas HAD utilizes the association of hydrogen with peptide ions in the gas phase. In this study, the general mechanisms of MALDI-ISD and HAD of peptides were investigated. We demonstrated the fragmentation of four model peptides and investigated the fragment formation pathways using density functional theory (DFT) calculations. The current experimental and computational joint study indicated that MALDI-ISD and HAD produce aminoketyl radical intermediates, which immediately undergo radical-induced cleavage at the N-Cα bond located on the C-terminal side of the radical site, leading to the c'/z˙ fragment pair. In the case of MALDI-ISD, the z˙ fragments undergo a subsequent reaction with the matrix to give z' and matrix adducts of the z fragments. In contrast, the c' and z˙ fragments react with hydrogen atoms during the HAD processes, and various fragment species, such as c˙, c', z˙ and z', were observed in the HAD-MS/MS mass spectra.

  10. Experimental Study of Heating of a Liquid Cathode and Transfer of Its Components into the Gas Phase under the Action of a DC Discharge

    Science.gov (United States)

    Sirotkin, N. A.; Titov, V. A.

    2018-04-01

    An atmospheric-pressure dc discharge in air ( i = 10-50 mA) with metal and liquid electrolyte electrodes was studied experimentally. An aqueous solution of sodium chloride (0.5 mol/L) was used as the cathode or anode. The electric field strength in the plasma and the cathode (anode) voltage drops were obtained from the measured dependences of the discharge voltage on the electrode gap length. The gas temperature was deduced from the spectral distribution of nitrogen emission in the band N2( C 3Π u → B 3Π g , 0-2). The time dependences of the temperatures of the liquid electrolyte electrodes during the discharge and in its afterglow, as well as the evaporation rate of the solution, were determined experimentally. The contributions of ion bombardment and heat flux from the plasma to the heating of the liquid electrode and transfer of solvent (water) into the gas phase are discussed using the experimental data obtained.

  11. A low temperature investigation of the gas-phase N(2D) + NO reaction. Towards a viable source of N(2D) atoms for kinetic studies in astrochemistry.

    Science.gov (United States)

    Nuñez-Reyes, Dianailys; Hickson, Kevin M

    2018-06-18

    The gas-phase reaction of metastable atomic nitrogen N(2D) with nitric oxide has been investigated over the 296-50 K temperature range using a supersonic flow reactor. As N(2D) could not be produced photolytically in the present work, these excited state atoms were generated instead through the C(3P) + NO → N(2D) + CO reaction while C(3P) atoms were created in situ by the 266 nm pulsed laser photolysis of CBr4 precursor molecules. The kinetics of N(2D) atoms were followed on-resonance by vacuum ultraviolet laser induced fluorescence at 116.7 nm. The measured rate constants for the N(2D) + NO reaction are in excellent agreement with most of the earlier work at room temperature and represent the only available kinetic data for this process below 296 K. The rate constants are seen to increase slightly as the temperature falls to 100 K with a more substantial increase at even lower temperature; a finding which is not reproduced by theoretical work. The prospects for using this chemical source of N(2D) atoms in future studies of a wide range of N(2D) atom reactions are discussed.

  12. Spectroscopic studies of the transplutonium elements

    International Nuclear Information System (INIS)

    Carnall, W.T.; Conway, J.G.

    1983-01-01

    The challenging opportunity to develop insights into both atomic structure and the effects of bonding in compounds makes the study of actinide spectroscopy a particularly fruitful and exciting area of scientific endeavor. It is also the interpretation of f-element spectra that has stimulated the development of the most sophisticated theoretical modeling attempted for any elements in the periodic table. The unique nature of the spectra and the wealth of fine detail revealed make possible sensitive tests of both physical models and the results of Hartree-Fock type ab initio calculations. This paper focuses on the unique character of heavy actinide spectroscopy. It discusses how it differs from that of the lighter member of the series and what are the special properties that are manifested. Following the introduction, the paper covers the following: (1) the role of systematic studies and the relationships of heavy-actinide spectroscopy to ongoing spectroscopic investigations of the lighter members of the series; (2) atomic (free-ion) spectra which covers the present status of spectroscopic studies with transplutonium elements, and future needs and directions in atomic spectroscopy; (3) the spectra of actinide compounds which covers the present status and future directions of spectroscopic studies with compounds of the transplutonium elements; and other spectroscopies. 1 figure, 2 tables

  13. Spectroscopic studies of hydrogen collisions

    International Nuclear Information System (INIS)

    Kielkopf, J.

    1991-01-01

    Low energy collisions involving neutral excited states of hydrogen are being studied with vacuum ultraviolet spectroscopy. Atomic hydrogen is generated by focusing an energetic pulse of ArF, KrF, or YAG laser light into a cell of molecular hydrogen, where a plasma is created near the focal point. The H 2 molecules in and near this region are dissociated, and the cooling atomic hydrogen gas is examined with laser and dispersive optical spectroscopy. In related experiments, we are also investigating neutral H + O and H + metal - atom collisions in these laser-generated plasmas

  14. Nuclear spectroscopic studies. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    Bingham, C.R.; Guidry, M.W.; Riedinger, L.L.; Sorensen, S.P.

    1993-02-08

    The Nuclear Physics group at the University of Tennessee, Knoxville is involved in several aspects of heavy-ion physics including both nuclear structure and reaction mechanisms. While our main emphasis is on experimental problems involving heavy-ion accelerators, we have maintained a strong collaboration with several theorists in order to best pursue the physics of our measurements. During the last year we have led several experiments at the Holifield Heavy Ion Research Facility and participated in others at Argonne National Laboratory. Also, we continue to be very active in the collaboration to study ultra-relativistic heavy ion physics utilizing the SPS accelerator at CERN in Geneva, Switzerland and in a RHIC detector R&D project. Our experimental work is in four broad areas: (1) the structure of nuclei at high angular momentum, (2) heavy-ion induced transfer reactions, (3) the structure of nuclei far from stability, and (4) ultra-relativistic heavy-ion physics. The results of studies in these particular areas will be described in this document in sections IIA, IIB, IIC, and IID, respectively. Areas (1), (3), and (4) concentrate on the structure of nuclear matter in extreme conditions of rotational motion, imbalance of neutrons and protons, or very high temperature and density. Area (2) pursues the transfer of nucleons to states with high angular momentum, both to learn about their structure and to understand the transfer of particles, energy, and angular momentum in collisions between heavy ions. An important component of our program is the strong emphasis on the theoretical aspects of nuclear structure and reactions.

  15. Spectroscopic Signatures and Structural Motifs of Dopamine: a Computational Study

    Science.gov (United States)

    Srivastava, Santosh Kumar; Singh, Vipin Bahadur

    2016-06-01

    Dopamine (DA) is an essential neurotransmitter in the central nervous system and it plays integral role in numerous brain functions including behaviour, cognition, emotion, working memory and associated learning. In the present work the conformational landscapes of neutral and protonated dopamine have been investigated in the gas phase and in aqueous solution by MP2 and DFT (M06-2X, ωB97X-D, B3LYP and B3LYP-D3) methods. Twenty lowest energy structures of neutral DA were subjected to geometry optimization and the gauche conformer, GIa, was found to be the lowest gas phase structure at the each level of theory in agreement with the experimental rotational spectroscopy. All folded gauche conformers (GI) where lone electron pair of the NH2 group is directed towards the π system of the aromatic ring ( 'non up' ) are found more stable in the gas phase. While in aqueous solution, all those gauche conformers (GII) where lone electron pair of the NH2 group is directed opposite from the π system of the aromatic ring ('up' structures) are stabilized significantly.Nine lowest energy structures, protonated at the amino group, are optimized at the same MP2/aug-cc-pVDZ level of theory. In the most stable gauche structures, g-1 and g+1, mainly electrostatic cation - π interaction is further stabilized by significant dispersion forces as predicted by the substantial differences between the DFT and dispersion corrected DFT-D3 calculations. In aqueous environment the intra-molecular cation- π distance in g-1 and g+1 isomers, slightly increases compared to the gas phase and the magnitude of the cation- π interaction is reduced relative to the gas phase, because solvation of the cation decreases its interaction energy with the π face of aromatic system. The IR intensity of the bound N-H+ stretching mode provides characteristic 'IR spectroscopic signatures' which can reflect the strength of cation- π interaction energy. The CC2 lowest lying S1 ( 1ππ* ) excited state of neutral

  16. Nuclear spectroscopic studies: Progress report

    International Nuclear Information System (INIS)

    Bingham, C.R.; Guidry, M.W.; Riedinger, L.L.; Sorensen, S.P.

    1989-01-01

    The Nuclear Physics Group at the University of Tennessee, Knoxville (UTK) is involved in several aspects of heavy-ion physics including both nuclear structure and reaction mechanisms. While our main emphasis is on experimental problems involving heavy-ion accelerators, we have maintained a strong collaboration with several theorists in order to best pursue the physics of our measurements. During the last year we have led experiments at the Holifield Heavy Ion Research Facility (HHIRF) and the Niels Bohr Institute Tandem Accelerator. Also, we are active in a collaboration (WA80) to study ultra-relativistic heavy ion physics utilizing the SPS accelerator at CERN in Geneva, Switzerland. Our experimental work is four broad areas: (1) the structure of nuclei at high angular momentum, (2) heavy-ion induced transfer reactions, (3) the structure of nuclei far from stability, and (4) ultra-relativistic heavy-ion physics. These results will be described in this document. Areas (1), (3), and (4) concentrate on the structure of nuclear matter in extreme conditions of rotational motion, imbalance of neutrons and protons, or very high temperature and density. Area (2) pursues the transfer of nucleons to states with high angular momentum, both to learn about their structure and to understand the transfer of particles, energy, and angular momentum in collisions between heavy ions. An important component of our program is the strong emphasis on the theoretical aspects of nuclear structure and reactions

  17. Gas phase reactive collisions, experimental approach

    Directory of Open Access Journals (Sweden)

    Canosa A.

    2012-01-01

    Full Text Available Since 1937 when the first molecule in space has been identified, more than 150 molecules have been detected. Understanding the fate of these molecules requires having a perfect view of their photochemistry and reactivity with other partners. It is then crucial to identify the main processes that will produce and destroy them. In this chapter, a general view of experimental techniques able to deliver gas phase chemical kinetics data at low and very low temperatures will be presented. These techniques apply to the study of reactions between neutral reactants on the one hand and reactions involving charge species on the other hand.

  18. Spectroscopic and theoretical study of the o-vanillin hydrazone of the mycobactericidal drug isoniazid

    Science.gov (United States)

    González-Baró, Ana C.; Pis-Diez, Reinaldo; Parajón-Costa, Beatriz S.; Rey, Nicolás A.

    2012-01-01

    A complete and detailed study of the hydrazone obtained from condensation of antituberculous isoniazid (hydrazide of the isonicotinic acid, INH) and o-vanillin (2-hydroxy-3-methoxybenzaldehyde, o-HVa) is performed. It includes structural and spectroscopic analyses, comparing experimental and theoretical results. The compound was obtained as a chloride of the pyridinic salt (INHOVA +Cl -) but it will be referred as INHOVA for the sake of simplicity. The conformational space was searched and optimized geometries were determined both in gas phase and including solvent effects. Vibrational (IR and Raman), electronic and NMR spectra were registered and assigned with the help of computational methods based on the Density Functional Theory. Isoniazid hydrazones are good candidates for therapeutic agents against tuberculosis with conserved efficiency and lower toxicity and resistance than parent INH.

  19. Spectroscopic study of jet-cooled indole-3-carbinol by thermal evaporation

    International Nuclear Information System (INIS)

    Moon, Cheol Joo; Kim, Eun Bin; Min, Ahreum; Ahn, Ahreum; Seong, Yeon Guk; Choi, Myong Yong

    2016-01-01

    Cruciferous vegetables such as cabbage, kale, broccoli, and cauliflower have relatively high levels of indole-3-carbinol (I3C), which can be used as a possible cancer preventative agent particularly for breast, cervical, colorectal, and other hormone-related cancers. Thus, this naturally occurring substance, I3C, is now being used in dietary supplements. In conclusion, we have succeeded in obtaining the R2PI spectrum of a thermally unstable sample, I3C, by using a thermal buffer (herein, uracil) for the first time. Use of thermal evaporation method for thermally unstable biomolecules using thermal buffers will allow us to explore more gas phase spectroscopic studies for their intrinsic physiological properties in the near future

  20. Spectroscopic study of jet-cooled indole-3-carbinol by thermal evaporation

    Energy Technology Data Exchange (ETDEWEB)

    Moon, Cheol Joo; Kim, Eun Bin; Min, Ahreum; Ahn, Ahreum; Seong, Yeon Guk; Choi, Myong Yong [Gyeongsang National University, Jinju (Korea, Republic of)

    2016-10-15

    Cruciferous vegetables such as cabbage, kale, broccoli, and cauliflower have relatively high levels of indole-3-carbinol (I3C), which can be used as a possible cancer preventative agent particularly for breast, cervical, colorectal, and other hormone-related cancers. Thus, this naturally occurring substance, I3C, is now being used in dietary supplements. In conclusion, we have succeeded in obtaining the R2PI spectrum of a thermally unstable sample, I3C, by using a thermal buffer (herein, uracil) for the first time. Use of thermal evaporation method for thermally unstable biomolecules using thermal buffers will allow us to explore more gas phase spectroscopic studies for their intrinsic physiological properties in the near future.

  1. Vibrational spectroscopic study of fluticasone propionate

    Science.gov (United States)

    Ali, H. R. H.; Edwards, H. G. M.; Kendrick, J.; Scowen, I. J.

    2009-03-01

    Fluticasone propionate is a synthetic glucocorticoid with potent anti-inflammatory activity that has been used effectively in the treatment of chronic asthma. The present work reports a vibrational spectroscopic study of fluticasone propionate and gives proposed molecular assignments on the basis of ab initio calculations using BLYP density functional theory with a 6-31G* basis set and vibrational frequencies predicted within the quasi-harmonic approximation. Several spectral features and band intensities are explained. This study generated a library of information that can be employed to aid the process monitoring of fluticasone propionate.

  2. Synchrotron and small bio-molecules in gas phase and liquid environment: new opportunities in Brazil

    Energy Technology Data Exchange (ETDEWEB)

    Naves de Brito, A. [State University of Campinas (UNICAMP), SP (Brazil). Dept. of Applied Physics

    2011-07-01

    Full text: Two techniques are critically related to the photoelectric law, namely: photoelectron spectroscopy and photoelectron-photoion coincidence spectroscopy. Both are strongly used now a day within synchrotron laboratories. Our group is employing both to investigate fragmentation of bio-molecules in gas phase such as amino acids and DNA basis using V UV and soft x-ray photons. In the near future lager scale instruments developed in Brazil will allow unique opportunities to apply these two spectroscopic methods to molecules immersed in liquids such as water. We will present details from this advanced x-ray source and experimental stations with capabilities not present in other places in the world. Experiments connected to the molecular origin of live will be shown. Among them an experiment where we mimic the atmosphere at Titan moon producing bio- molecules will discussed. Another experiment will be presented where we test the Panspermia viability using special bacteria. We will also present experiments where frozen simple molecules connected to pre-biotic mate- rial are bombardment by UV photons and energetic particles showing interesting trends. Spectroscopic studies of gas phase photo-fragmentation of bio-molecules may be critical to understand in the future these molecules immersed in liquids. We plan to spend some time showing our recent results in this area. (author)

  3. Iodine removal from a gas phase

    International Nuclear Information System (INIS)

    Vikis, A. Ch.

    1982-01-01

    Iodine, e.g. radioactive iodine, present as one or more organic iodides, optionally with elemental iodine, in a gas phase (e.g. air) are removed by photochemically decomposing the organic iodides to elemental iodine, reacting the iodine produced, and any initially present with excess ozone, preferably photochemically produced in situ in the gas phase to produce solid iodine oxides, and removing the solid oxides from the gas phase. (author)

  4. Iodine removal from a gas phase

    International Nuclear Information System (INIS)

    Vikis, A.C.

    1984-01-01

    Iodine, e.g. radioactive iodine, present as one or more organic iodides, optionally with elemental iodine, in a gas phase (e.g. air) are removed by photochemically decomposing the organic iodides to elemental iodine, reacting the iodine produced, and any initially present with excess ozone, preferably photochemically produced in situ in the gas phase to produce solid iodine oxides, and removing the solid oxides from the gas phase

  5. MOLECULAR SPECTROSCPY AND REACTIONS OF ACTINIDES IN THE GAS PHASE AND CRYOGENIC MATRICES

    Energy Technology Data Exchange (ETDEWEB)

    Heaven, Michael C.; Gibson, John K.; Marcalo, Joaquim

    2009-02-01

    In this chapter we review the spectroscopic data for actinide molecules and the reaction dynamics for atomic and molecular actinides that have been examined in the gas phase or in inert cryogenic matrices. The motivation for this type of investigation is that physical properties and reactions can be studied in the absence of external perturbations (gas phase) or under minimally perturbing conditions (cryogenic matrices). This information can be compared directly with the results from high-level theoretical models. The interplay between experiment and theory is critically important for advancing our understanding of actinide chemistry. For example, elucidation of the role of the 5f electrons in bonding and reactivity can only be achieved through the application of experimentally verified theoretical models. Theoretical calculations for the actinides are challenging due the large numbers of electrons that must be treated explicitly and the presence of strong relativistic effects. This topic has been reviewed in depth in Chapter 17 of this series. One of the goals of the experimental work described in this chapter has been to provide benchmark data that can be used to evaluate both empirical and ab initio theoretical models. While gas-phase data are the most suitable for comparison with theoretical calculations, there are technical difficulties entailed in generating workable densities of gas-phase actinide molecules that have limited the range of species that have been characterized. Many of the compounds of interest are refractory, and problems associated with the use of high temperature vapors have complicated measurements of spectra, ionization energies, and reactions. One approach that has proved to be especially valuable in overcoming this difficulty has been the use of pulsed laser ablation to generate plumes of vapor from refractory actinide-containing materials. The vapor is entrained in an inert gas, which can be used to cool the actinide species to room

  6. Spectroscopic studies of pulsed-power plasmas

    International Nuclear Information System (INIS)

    Maron, Y.; Arad, R.; Dadusc, G.; Davara, G.; Duvall, R.E.; Fisher, V.; Foord, M.E.; Fruchtman, A.; Gregorian, L.; Krasik, Ya.

    1993-01-01

    Recently developed spectroscopic diagnostic techniques are used to investigate the plasma behavior in a Magnetically Insulated Ion Diode, a Plasma Opening Switch, and a gas-puffed Z-pinch. Measurements with relatively high spectral, temporal, and spatial resolutions are performed. The particle velocity and density distributions within a few tens of microns from the dielectric-anode surface are observed using laser spectroscopy. Collective fluctuating electric fields in the plasma are inferred from anisotropic Stark broadening. For the Plasma Opening Switch experiment, a novel gaseous plasma source was developed which is mounted inside the high-voltage inner conductor. The properties of this source, together with spectroscopic observations of the electron density and particle velocities of the injected plasma, are described. Emission line intensities and spectral profiles give the electron kinetic energies during the switch operation and the ion velocity distributions. Secondary plasma ejection from the electrodes is also studied. In the Z-pinch experiment, spectral emission-line profiles are studied during the implosion phase. Doppler line shifts and widths yield the radial velocity distributions for various charge states in various regions of the plasma. Effects of plasma ejection from the cathode are also studied

  7. Raman Spectroscopic Study of the Vapour Phase of 1-Methylimidazolium Ethanoate, a Protic Ionic Liquid

    DEFF Research Database (Denmark)

    Berg, Rolf W.; Canongia Lopes, Jose N.; Ferreira, Rui

    2010-01-01

    The gas phase over the ionic liquid 1-methylimidazolium ethanoate, [Hmim][O2CCH3], was studied by means of Raman spectroscopy. Raman spectra are presented, the species in the gas phase are identified, and their bands are assigned. The results are interpreted using ab initio quantum mechanical...

  8. Full-dimensional analytical potential energy surface describing the gas-phase Cl + C2H6 reaction and kinetics study of rate constants and kinetic isotope effects.

    Science.gov (United States)

    Rangel, Cipriano; Espinosa-Garcia, Joaquin

    2018-02-07

    Within the Born-Oppenheimer approximation a full-dimensional analytical potential energy surface, PES-2017, was developed for the gas-phase hydrogen abstraction reaction between the chlorine atom and ethane, which is a nine body system. This surface presents a valence-bond/molecular mechanics functional form dependent on 60 parameters and is fitted to high-level ab initio calculations. This reaction presents little exothermicity, -2.30 kcal mol -1 , with a low height barrier, 2.44 kcal mol -1 , and intermediate complexes in the entrance and exit channels. We found that the energetic description was strongly dependent on the ab initio level used and it presented a very flat topology in the entrance channel, which represents a theoretical challenge in the fitting process. In general, PES-2017 reproduces the ab initio information used as input, which is merely a test of self-consistency. As a first test of the quality of the PES-2017, a theoretical kinetics study was performed in the temperature range 200-1400 K using two approaches, i.e. the variational transition-state theory and quasi-classical trajectory calculations, with spin-orbit effects. The rate constants show reasonable agreement with experiments in the whole temperature range, with the largest differences at the lowest temperatures, and this behaviour agrees with previous theoretical studies, thus indicating the inherent difficulties in the theoretical simulation of the kinetics of the title reaction. Different sources of error were analysed, such as the limitations of the PES and theoretical methods, recrossing effects, and the tunnelling effect, which is negligible in this reaction, and the manner in which the spin-orbit effects were included in this non-relativistic study. We found that the variation of spin-orbit coupling along the reaction path, and the influence of the reactivity of the excited Cl( 2 P 1/2 ) state, have relative importance, but do not explain the whole discrepancy. Finally, the

  9. SVOC partitioning between the gas phase and settled dust indoors

    Science.gov (United States)

    Weschler, Charles J.; Nazaroff, William W.

    2010-09-01

    Semivolatile organic compounds (SVOCs) are a major class of indoor pollutants. Understanding SVOC partitioning between the gas phase and settled dust is important for characterizing the fate of these species indoors and the pathways by which humans are exposed to them. Such knowledge also helps in crafting measurement programs for epidemiological studies designed to probe potential associations between exposure to these compounds and adverse health effects. In this paper, we analyze published data from nineteen studies that cumulatively report measurements of dustborne and airborne SVOCs in more than a thousand buildings, mostly residences, in seven countries. In aggregate, measured median data are reported in these studies for 66 different SVOCs whose octanol-air partition coefficients ( Koa) span more than five orders of magnitude. We use these data to test a simple equilibrium model for estimating the partitioning of an SVOC between the gas phase and settled dust indoors. The results demonstrate, in central tendency, that a compound's octanol-air partition coefficient is a strong predictor of its abundance in settled dust relative to its gas phase concentration. Using median measured results for each SVOC in each study, dustborne mass fractions predicted using Koa and gas-phase concentrations correlate reasonably well with measured dustborne mass fractions ( R2 = 0.76). Combined with theoretical understanding of SVOC partitioning kinetics, the empirical evidence also suggests that for SVOCs with high Koa values, the mass fraction in settled dust may not have sufficient time to equilibrate with the gas phase concentration.

  10. Formation of CuInSe{sub 2} films from metal sulfide and selenide precursor nanocrystals by gas-phase selenization, an in-situ XRD study

    Energy Technology Data Exchange (ETDEWEB)

    Capon, B., E-mail: boris.capon@ugent.be [Department of Solid State Sciences, Ghent University, Krijgslaan 281-S1, B-9000 Ghent (Belgium); Dierick, R. [Physics and Chemistry of Nanostructures, Ghent University, Krijgslaan 281-S3, B-9000 Ghent (Belgium); Hens, Z. [Physics and Chemistry of Nanostructures, Ghent University, Krijgslaan 281-S3, B-9000 Ghent (Belgium); Center for Nano and Biophotonics, Ghent University, Ghent (Belgium); Detavernier, C. [Department of Solid State Sciences, Ghent University, Krijgslaan 281-S1, B-9000 Ghent (Belgium)

    2016-08-01

    In this work phase pure CuInSe{sub 2} thin flms were obtained by selenization of ternary CuInSe{sub 2} and CuInS{sub 2} nanocrystals and mixtures of binary nanocrystals such as CuS, In{sub 2}S{sub 3}, Cu{sub 2}Se and In{sub 2}Se{sub 3}. The temperature of the selenium source was kept at 400 °C during selenization. Monitoring the process using in-situ x-ray diffraction, the effect of selenization on the phase formation and grain growth in the precursor film was investigated. Whereas CuInSe{sub 2} and CuInS{sub 2} nanocrystals exhibit little grain growth, we found that mixtures of binary nanocrystals can show significant sintering depending on the reaction conditions. For the mixture of CuS and In{sub 2}S{sub 3} nanocrystals, the crystallinity and the morphology of the obtained fims strongly depends on the Cu/In ratio, with a Cu excess strongly promoting grain growth. With mixtures of Cu{sub 2}Se and In{sub 2}Se{sub 3} nanocrystals the selenium partial pressure plays a crucial role. Selenium evaporation from the mixed compounds results in CuInSe{sub 2} films composed of relatively small crystallites. Higher selenium partial pressures however resulted in improved sintering. Incomplete propagation of the selenization reaction through the layer was observed though, only leading to a well sintered CuInSe{sub 2} top layer above a fine grained bottom layer. - Highlights: • Different types of colloidal nanocrystals were used as precursors to obtain CuInSe{sub 2} films by gas-phase selenization. • In-situ XRD was used to study the effect of selenization on the phase formation and grain growth in the precursor films. • For a mixture of binary metal sulfides the crystallinity and the morphology strongly depend on the Cu/In ratio. • Higher selenium partial pressures result in improved sintering for a mixture of binary metal selenides.

  11. Laboratory Studies on the Formation of Carbon-Bearing Molecules in Extraterrestrial Environments: From the Gas Phase to the Solid State

    Science.gov (United States)

    Jamieson, C. S.; Guo, Y.; Gu, X.; Zhang, F.; Bennett, C. J.; Kaiser, R. I.

    2006-01-01

    A detailed knowledge of the formation of carbon-bearing molecules in interstellar ices and in the gas phase of the interstellar medium is of paramount interest to understand the astrochemical evolution of extraterrestrial environments (1). This research also holds strong implications to comprehend the chemical processing of Solar System environments such as icy planets and their moons together with the atmospheres of planets and their satellites (2). Since the present composition of each interstellar and Solar System environment reflects the matter from which it was formed and the processes which have changed the chemical nature since the origin (solar wind, planetary magnetospheres, cosmic ray exposure, photolysis, chemical reactions), a detailed investigation of the physicochemical mechanisms altering the pristine environment is of paramount importance to grasp the contemporary composition. Once these underlying processes have been unraveled, we can identify those molecules, which belonged to the nascent setting, distinguish molecular species synthesized in a later stage, and predict the imminent chemical evolution of, for instance, molecular clouds. Laboratory experiments under controlled physicochemical conditions (temperature, pressure, chemical composition, high energy components) present ideal tools for simulating the chemical evolution of interstellar and Solar System environments. Here, laboratory experiments can predict where and how (reaction mechanisms; chemicals necessary) in extraterrestrial environments and in the interstellar medium complex, carbon bearing molecules can be formed on interstellar grains and in the gas phase. This paper overviews the experimental setups utilized in our laboratory to mimic the chemical processing of gas phase and solid state (ices) environments. These are a crossed molecular beams machine (3) and a surface scattering setup (4). We also present typical results of each setup (formation of amino acids, aldehydes, epoxides

  12. A NEW NETWORK FOR HIGHER-TEMPERATURE GAS-PHASE CHEMISTRY. I. A PRELIMINARY STUDY OF ACCRETION DISKS IN ACTIVE GALACTIC NUCLEI

    International Nuclear Information System (INIS)

    Harada, Nanase; Herbst, Eric; Wakelam, Valentine

    2010-01-01

    We present a new interstellar chemical gas-phase reaction network for time-dependent kinetics that can be used for modeling high-temperature sources up to ∼800 K. This network contains an extended set of reactions based on the Ohio State University (OSU) gas-phase chemical network. The additional reactions include processes with significant activation energies, reverse reactions, proton exchange reactions, charge exchange reactions, and collisional dissociation. Rate coefficients already in the OSU network are modified for H 2 formation on grains, ion-neutral dipole reactions, and some radiative association reactions. The abundance of H 2 O is enhanced at high temperature by hydrogenation of atomic O. Much of the elemental oxygen is in the form of water at T ≥ 300 K, leading to effective carbon-rich conditions, which can efficiently produce carbon-chain species such as C 2 H 2 . At higher temperatures, HCN and NH 3 are also produced much more efficiently. We have applied the extended network to a simplified model of the accretion disk of an active galactic nucleus.

  13. Laser spectroscopic and theoretical studies of the structures and encapsulation motifs of functional molecules

    Energy Technology Data Exchange (ETDEWEB)

    Ebata, Takayuki; Kusaka, Ryoji [Department of Chemistry, Graduate School of Science, Hiroshima University, Kagamiyama 1-3-1, Higashi-Hiroshima, 739-8526 (Japan); Xantheas, Sotiris S. [Chemical and Materials Sciences Division, Pacific Northwest National Laboratory, 902 Battelle Boulevard, P.O. Box 999, MS K1-83, Richland, WA 99352 (United States)

    2015-01-22

    Extensive laser spectroscopic and theoretical studies have been recently carried out with the aim to reveal the structure and dynamics of encapsulation complexes in the gas phase. The characteristics of the encapsulation complexes are governed by the fact that (i) most of the host molecules are flexible and (ii) the complexes form high dimensional structures by using weak non-covalent interactions. These characteristics result in the possibility of the coexistence of many conformers in close energetic proximity. The combination of supersonic jet/laser spectroscopy and high level quantum chemical calculations is essential in tackling these challenging problems. In this report we describe our recent studies on the structures and dynamics of the encapsulation complexes formed by calix[4]arene (C4A), dibenzo-18-crown-6-ether (DB18C6), and benzo-18-crown-6-ether (B18C6) 'hosts' interacting with N{sub 2}, acetylene, water, and ammonia 'guest' molecules. The gaseous host-guest complexes are generated under jet-cooled conditions. We apply various laser spectroscopic methods to obtain the conformer- and isomer-specified electronic and IR spectra. The experimental results are complemented with quantum chemical calculations ranging from density functional theory to high level first principles calculations at the MP2 and CCSD(T) levels of theory. We discuss the possible conformations of the bare host molecules, the structural changes they undergo upon complexation, and the key interactions that are responsible in stabilizing the specific complexes.

  14. An Introduction to the Gas Phase

    Science.gov (United States)

    Vallance, Claire

    2017-11-01

    'An Introduction to the Gas Phase' is adapted from a set of lecture notes for a core first year lecture course in physical chemistry taught at the University of Oxford. The book is intended to give a relatively concise introduction to the gas phase at a level suitable for any undergraduate scientist. After defining the gas phase, properties of gases such as temperature, pressure, and volume are discussed. The relationships between these properties are explained at a molecular level, and simple models are introduced that allow the various gas laws to be derived from first principles. Finally, the collisional behaviour of gases is used to explain a number of gas-phase phenomena, such as effusion, diffusion, and thermal conductivity.

  15. Fundamental spectroscopic studies of carbenes and hydrocarbon radicals

    Energy Technology Data Exchange (ETDEWEB)

    Gottlieb, C.A.; Thaddeus, P. [Harvard Univ., Cambridge, MA (United States)

    1993-12-01

    Highly reactive carbenes and carbon-chain radicals are studied at millimeter wavelengths by observing their rotational spectra. The purpose is to provide definitive spectroscopic identification, accurate spectroscopic constants in the lowest vibrational states, and reliable structures of the key intermediates in reactions leading to aromatic hydrocarbons and soot particles in combustion.

  16. Spectroscopic study of ohmically heated Tokamak discharges

    International Nuclear Information System (INIS)

    Breton, C.; Michelis, C. de; Mattioli, M.

    1980-07-01

    Tokamak discharges interact strongly with the wall and/or the current aperture limiter producing recycling particles, which penetrate into the discharge and which can be studied spectroscopically. Working gas (hydrogen or deuterium) is usually studied observing visible Balmer lines at several toroidal locations. Absolute measurements allow to obtain both the recycling flux and the global particle confinement time. With sufficiently high resolution the isotopic plasma composition can be obtained. The impurity elements can be divided into desorbed elements (mainly oxygen) and eroded elements (metals from both walls and limiter) according to the plasma-wall interaction processes originating them. Space-and time-resolved emission in the VUV region down to about 20 A will be reviewed for ohmically-heated discharges. The time evolution can be divided into four phases, not always clearly separated in a particular discharge: a) the initial phase, lasting less than 10 ms (the so-called burn-out phase), b) the period of increasing plasma current and electron temperature, lasting typically 10 - 100 ms, c) an eventual steady state (plateau of the plasma current with almost constant density and temperature), d) the increase of the electron density up to or just below the maximum value attainable in a given device. For all these phases the results reported from different devices will be described and compared

  17. Photoacoustic spectroscopic studies of polycyclic aromatic hydrocarbons

    Science.gov (United States)

    Zaidi, Zahid H.; Kumar, Pardeep; Garg, R. K.

    1999-02-01

    Because of their involvement in environmental pollutants, in carcinogenic activity, plastics, pharmaceuticals, synthesis of some laser dyes and presence in interstellar space etc., Polycyclic aromatic hydrocarbons (PAHs) are important. As their structure and properties can be varied systematically, they form a beautiful class of molecules for experimental and quantum chemical investigations. These molecules are being studied for last several years by using conventional spectroscopy. In recent years, Photoacoustic (PA) spectroscopy has emerged as a new non-destructive technique with unique capability and sensitivity. The PA effect is the process of generation of acoustic waves in a sample resulting from the absorption of photons. This technique not only reveals non- radiative transitions but also provides information about forbidden singlet-triplet transitions which are not observed normally by the conventional spectroscopy. The present paper deals with the spectroscopic studies of some PAH molecules by PA spectroscopy in the region 250 - 400 nm. The CNDO/S-CI method is used to calculate the electronic transitions with the optimized geometries. A good agreement is found between the experimental and calculated results.

  18. Continuous-wave terahertz by photomixing: applications to gas phase pollutant detection and quantification

    Science.gov (United States)

    Hindle, Francis; Cuisset, Arnaud; Bocquet, Robin; Mouret, Gaël

    2008-03-01

    Recent advances in the development of monochromatic continuous-wave terahertz sources suitable for high resolution gas phase spectroscopy and pollution monitoring are reviewed. Details of a source using an ultra fast opto-electronic photomixing element are presented. The construction of a terahertz spectrometer using this source has allowed spectroscopic characterisation and application studies to be completed. Analysis of H 2S and OCS under laboratory conditions are used to demonstrate the spectrometer performance, and the determination of the transition line strengths and pressure self broadening coefficients for pure rotational transitions of OCS. The spectral purity 5 MHz, tunability 0.3 to 3 THz, and long wavelength ≈200 μm of this source have been exploited to identify and quantify numerous chemical species in cigarette smoke. The key advantages of this frequency domain are its high species selectivity and the possibility to make reliable measurements of gas phase samples heavily contaminated by aerosols and particles. To cite this article: F. Hindle et al., C. R. Physique 9 (2008).

  19. Submillimeter Spectroscopic Study of Semiconductor Processing Plasmas

    Science.gov (United States)

    Helal, Yaser H.

    Plasmas used for manufacturing processes of semiconductor devices are complex and challenging to characterize. The development and improvement of plasma processes and models rely on feedback from experimental measurements. Current diagnostic methods are not capable of measuring absolute densities of plasma species with high resolution without altering the plasma, or without input from other measurements. At pressures below 100 mTorr, spectroscopic measurements of rotational transitions in the submillimeter/terahertz (SMM) spectral region are narrow enough in relation to the sparsity of spectral lines that absolute specificity of measurement is possible. The frequency resolution of SMM sources is such that spectral absorption features can be fully resolved. Processing plasmas are a similar pressure and temperature to the environment used to study astrophysical species in the SMM spectral region. Many of the molecular neutrals, radicals, and ions present in processing plasmas have been studied in the laboratory and their absorption spectra have been cataloged or are in the literature for the purpose of astrophysical study. Recent developments in SMM devices have made its technology commercially available for applications outside of specialized laboratories. The methods developed over several decades in the SMM spectral region for these laboratory studies are directly applicable for diagnostic measurements in the semiconductor manufacturing industry. In this work, a continuous wave, intensity calibrated SMM absorption spectrometer was developed as a remote sensor of gas and plasma species. A major advantage of intensity calibrated rotational absorption spectroscopy is its ability to determine absolute concentrations and temperatures of plasma species from first principles without altering the plasma environment. An important part of this work was the design of the optical components which couple 500 - 750 GHz radiation through a commercial inductively coupled plasma

  20. Nuclear spectroscopic studies in 162Yb

    International Nuclear Information System (INIS)

    Behrens, H.

    1980-01-01

    The decay of the highly excited 162 Yb nuclei formed in the reaction 150 Sm( 16 O,4n) 162 Yb to the ground state was studied using different gamma detectors and an electron spectrometer, a so called mini-orange. The isotope 162 Yb was moreover produced and spectroscoped by the beta-decay of 162 Lu. For the identification of decay cascades, which were passed after the fusion, and for the determination of the multipolarity of the contributing energy transitions a series of experiments took place: The excitation functions and the angular distributions of the emitted gamma radiation was measured, the conversion coefficients of important transitions were determined, and coincidence events between two detectors occasionally were registrated and analyzed. In the beta decay measurement an assignment of gamma transitions to 162 Yb followed due to the lifetime, under which they occured. The found states of 162 Yb upto spins of 22 h/2π and excitation energies above 5 MeV belong to five rotational bands. The yrast band shows a weak backbending. Corresponding to their spins and parities the bands can be reduced to intrinsic excitation of two quasineutrons. The analysis of the beta-decay of 162 Lu, which takes place from three states in 162 Lu, leads to the lowest levels of the gamma-vibrational band and the band head of the beta band. The microscopic interpretation of the rotational bands and the description of the backbending behaviour are as the interpretation of the states involved at the beta decay in agreement with experimental and theoretical results for neighbouring ytterbium isotopes. (orig.) [de

  1. Theoretical investigation of the long-lived metastable AlO{sup 2+} dication in gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Sghaier, Onsi [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France); Abdallah, Hassan H. [Computational Nanotechnology Research Lab. CNRL, Salahaddin University, 44001 Erbil (Iraq); Department of Chemistry, College of Education, Salahaddin University, 44001 Erbil (Iraq); Abdullah, Hewa Y. [Computational Nanotechnology Research Lab. CNRL, Salahaddin University, 44001 Erbil (Iraq); Department of Physics, College of Education, Salahaddin University, 44001 Erbil (Iraq); Jaidane, Nejm Eddine [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications – LSAMA, Université de Tunis, Tunis (Tunisia); Al Mogren, Muneerah Mogren [Chemistry Department, Faculty of Science, King Saud University, PO Box 2455, Riyadh 11451 (Saudi Arabia); Hochlaf, Majdi, E-mail: hochlaf@univ-mlv.fr [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France)

    2016-09-30

    Highlights: • Theoretical investigation of gas-phase molecular species AlO{sup 2+}. • Spectroscopic parameters of this dication in its electronic ground and exited states. • Theoretical double ionization spectrum of AlO. - Abstract: We report the results of a detailed theoretical study of the electronic ground and excited states of the gas-phase doubly charged ion AlO{sup 2+} using high-level ab initio computer calculations. Both standard and explicitly correlated methods were used to calculate their potential energy curves and spectroscopic parameters. These computations show that the ground state of AlO{sup 2+} is X{sup 2}Π. The internuclear equilibrium distance of AlO{sup 2+}(X{sup 2}Π) is computed 1.725 Å. We also deduced the adiabatic double ionization and charge stripping energies of AlO to be about 27.45 eV and 17.80 eV, respectively.

  2. Determination of molecular structure of succinic acid in a very complex conformational landscape: Gas-phase electron diffraction (GED) and ab initio studies

    Science.gov (United States)

    Vogt, Natalja; Abaev, Maxim A.; Rykov, Anatolii N.; Shishkov, Igor F.

    2011-06-01

    The molecular structure of succinic acid has been investigated by the gas-phase electron diffraction (GED) method for the first time. According to predictions of MP2/cc-pVTZ calculations, the molecule has 18 stable conformers with the C sbnd C sbnd C sbnd C chain in the gauche ( G) or anti ( A) configuration, and four of them, I ( G), II ( A), III ( G) and IV ( A) belonging to the C 2, C 2h, C 1 and C 1 point groups, respectively, with relative energies ΔE ZPE within 2.2 kcal/mol can be present at the experimental temperature of 445 K in noticeable amounts. The ratio of the conformers I:II:III:IV = 45(15):20(15):10(assumed):25(15) (in %) has been determined in the GED analysis guided by theoretical predictions. To take into account vibrational effects, the corrections Δ( r e - r a) to the experimental r a bond lengths were calculated from the MP2/cc-pVTZ quadratic and cubic force constants. The obtained equilibrium structural parameters of the dominant conformer I are the following (bond lengths in Å, angles in degrees): r e(C sp3sbnd C sp3) = 1.508(3), r e(C sp3sbnd C sp2) = 1.499(2), r e(C sbnd O) = 1.343(2), r e(C dbnd O) = 1.202(1), e(C sbnd C sbnd C) = 111.8(4), e(C sbnd C sbnd O) = 112.0(4), e(O sbnd C dbnd O) = 123.0(1), τ(C sbnd C sbnd C sbnd C) = 69.9(11). Yielding the best agreement with the GED structure, the MP2/cc-pVQZ approximation overestimates the C sbnd O and C dbnd O bond lengths by ca. 0.005(2) Å.

  3. Charge Mediated Compaction and Rearrangement of Gas-Phase Proteins: A Case Study Considering Two Proteins at Opposing Ends of the Structure-Disorder Continuum

    Science.gov (United States)

    Jhingree, Jacquelyn R.; Bellina, Bruno; Pacholarz, Kamila J.; Barran, Perdita E.

    2017-07-01

    Charge reduction in the gas phase provides a direct means of manipulating protein charge state, and when coupled to ion mobility mass spectrometry (IM-MS), it is possible to monitor the effect of charge on protein conformation in the absence of solution. Use of the electron transfer reagent 1,3-dicyanobenzene, coupled with IM-MS, allows us to monitor the effect of charge reduction on the conformation of two proteins deliberately chosen from opposite sides of the order to disorder continuum: bovine pancreatic trypsin inhibitor (BPTI) and beta casein. The ordered BPTI presents compact conformers for each of three charge states accompanied by narrow collision cross-section distributions (TWCCSDN2→He). Upon reduction of BPTI, irrespective of precursor charge state, the TWCCSN2→He decreases to a similar distribution as found for the nESI generated ion of identical charge. The behavior of beta casein upon charge reduction is more complex. It presents over a wide charge state range (9-28), and intermediate charge states (13-18) have broad TWCCSDN2→He with multiple conformations, where both compaction and rearrangement are seen. Further, we see that the TWCCSDN2→He of the latter charge states are even affected by the presence of radical anions. Overall, we conclude that the flexible nature of some proteins result in broad conformational distributions comprised of many families, even for single charge states, and the barrier between different states can be easily overcome by an alteration of the net charge.

  4. Spectroscopic studies on colloid-borne uranium

    International Nuclear Information System (INIS)

    Ulrich, K.U.; Weiss, S.; Foerstendorf, H.; Brendler, V.; Zaenker, H.; Rossberg, A.; Scheinost, A.C.

    2005-01-01

    Full text of publication follows: Information on molecular speciation provides a basis for the reliable assessment of actinide migration in the environment. We use several methods for the separation of colloids from liquids (e.g. ultracentrifugation, ultrafiltration) in combination with spectroscopic techniques (EXAFS, ATR-FTIR, Moessbauer) and modeling of surface complexation reactions. This enables us to investigate the speciation of colloid-borne uranium in waters occurring in or escaping from abandoned uranium mines during the remediation process. Mine flooding was simulated on a 100 L scale by mixing acid mine water of elevated U concentration with oxic, near-neutral groundwater until pH ∼ 5.5 was reached. The freshly formed colloids adsorbed 95% of the total uranium and consisted mainly of 2-line ferri-hydrite (Fh) besides traces of aluminum, sulfur, silica, and carbon compounds. EXAFS analysis at the U-LIII absorption edge suggested a bidentate surface complex of UO 2 2+ on FeO 6 octahedra, but two minor backscattering contributions in close vicinity to the absorber remained unexplained. Since only Al could be excluded as backscattering atom, we studied U sorption on Fh at pH 5.5 in presence and in absence of sulfate, silicate, and atmospheric CO 2 to clarify the bond structure. EXAFS showed the unknown backscattering contributions in all the sorption samples regardless of the presence or absence of the tested components. Contrary to structural models proposed in the literature, bi-dentately complexed carbonate ligands do not explain our experimental EXAFS data. But ATR-IR spectra showed that U-carbonato complexes must be involved in the sorption of uranyl on Fh. These results are not contradictory if the carbonate ligands were bound mono-dentately. Nevertheless, carbon cannot act as backscattering atom in carbonate-free samples prepared in N 2 atmosphere. We propose a new structural model including exclusively Fe, H, and O atoms in which the bi

  5. Nuclear resonance vibrational spectroscopic studies of iron-containing biomolecules

    International Nuclear Information System (INIS)

    Ohta, Takehiro; Seto, Makoto

    2014-01-01

    In this review, we report recent nuclear resonance vibrational spectroscopic (NRVS) studies of iron-containing biomolecules and their model complexes. The NRVS is synchrotron-based element-specific vibrational spectroscopic methods. Unlike Raman and infrared spectroscopy, the NRVS can investigate all iron motions without selection rules, which provide atomic level insights into the structure/reactivity correlation of biologically relevant iron complexes. (author)

  6. Fuel cells: spectroscopic studies in the electrocatalysis of alcohol oxidation

    OpenAIRE

    Iwasita Teresa

    2002-01-01

    Modern spectroscopic methods are useful for elucidating complex electrochemical mechanisms as those occurring during the oxidation of small organic molecules (CH3OH, HCOH, HCOOH). In the present paper it is shown the use of spectroscopic methods to study the oxidation of alcohols on platinum or Pt-based binary electrodes. These reactions are of importance in conexion with the development of anode systems for use in fuel cells. Mass spectrometry and FT infrared spectroscopy allow to establishi...

  7. SILP catalysis in gas-phase hydroformylation and carbonylation

    Energy Technology Data Exchange (ETDEWEB)

    Riisager, A.; Fehrmann, R. [Technical Univ. of Denmark, Lyngby (Denmark). Dept. of Chemistry; Haumann, M.; Wasserscheid, P. [Univ. Erlangen-Nuernberg (Germany). Lehrstuhl fuer Chemische Reaktionstechnik

    2006-07-01

    Supported ionic liquid phase (SILP) catalysts are new materials consisting of an ionic liquid-metal catalyst solution highly dispersed on a porous support. The use of a non-volatile, ionic liquid catalyst phase in SILP catalysts results in a stable heterogeneous-type material with selectivity and efficiency like homogeneous catalysts. The silica-supported SILP Rh-bisphosphine hydroformylation catalyst exhibited good activities and excellent selectivities in gas phase hydroformylation with stability exceeding 700 hours time-on-stream. Spectroscopic and kinetic data confirmed the homogeneous nature of the catalyst. In the Rh- SILP catalysed carbonylation of methanol the formation of undesired by-products could be suppressed by variation of residence time and gas pressure. (orig.)

  8. Techniques in Gas Phase Thermolyses

    DEFF Research Database (Denmark)

    Egsgaard, Helge; Larsen, Elfinn; Carlsen, Lars

    1982-01-01

    Basic principles, capabilities and limitations of collision activation mass spectrometry are reported, with special reference to real-time analysis of flash vacuum thermolytically generated products. The analytical utility is demonstrated in terms of structure elucidation and isomerization studies...

  9. Un-catalyzed peptide bond formation between two monomers of glycine, alanine, serine, threonine, and aspartic acid in gas phase: a density functional theory study

    Science.gov (United States)

    Bhunia, Snehasis; Singh, Ajeet; Ojha, Animesh K.

    2016-05-01

    In the present report, un-catalyzed peptide bond formation between two monomers of glycine (Gly), alanine (Ala), serine (Ser), threonine (Thr), and aspartic acid (Asp) has been investigated in gas phase via two steps reaction mechanism and concerted mechanism at B3LYP/6-31G(d,p) and M062X/6-31G(d,p) level of theories. The peptide bond is formed through a nucleophilic reaction via transition states, TS1 and TS2 in stepwise mechanism. The TS1 reveals formation of a new C-N bond while TS2 illustrate the formation of C=O bond. In case of concerted mechanism, C-N bond is formed by a single four-centre transition state (TS3). The energy barrier is used to explain the involvement of energy at each step of the reaction. The energy barrier (20-48 kcal/mol) is required for the transformation of reactant state R1 to TS1 state and intermediate state I1 to TS2 state. The large value of energy barrier is explained in terms of distortion and interaction energies for stepwise mechanism. The energy barrier of TS3 in concerted mechanism is very close to the energy barrier of the first transition state (TS1) of the stepwise mechanism for the formation of Gly-Gly and Ala-Ala di- peptide. However, in case of Ser-Ser, Thr-Thr and Asp-Asp di-peptide, the energy barrier of TS3 is relatively high than that of the energy barrier of TS1 calculated at B3LYP/6-31G(d,p) and M062X/6-31G(d,p) level of theories. In both the mechanisms, the value of energy barrier calculated at B3LYP/6-31G(d,p) level of theory is greater than that of the value calculated at M062X/6-31G(d,p) level of theory.

  10. Long-lived gas-phase radicals from combustion

    Energy Technology Data Exchange (ETDEWEB)

    Kaneko, Takashi; Furusawa, Koji; Amano, Toshiji; Okubo, Yoichi; Tsuchiya, Jun' ichi; Yoshizawa, Fujiroku; Akutsu, Yoshiaki; Tamura, Masamitsu; Yoshida, Tadao (Univ. of Tokyo (Japan))

    1989-04-20

    On indoor air pollution or fire, it is feared that the gas-phase radicals from the combustion of inflammables or fuel seriously exert an influence on the organisms as harmful matter. The gas-phase radicals were studied using the electron spin resonance (ESR) spin-trapping technique. For the spin trap solution, 0.1 mol solution of {alpha}-phenyl-N-t-butylnitron in benzene was used. As a result, apparently long-lived and highly reactive oxygen-centered radicals were detected in the smoke from polyethylene, polypropylene, polystyrene, polymethylmethacrylate, cellulose, kerosene, benzene, acetone, methanol and butylalcohol. It is suggested that the production mechanism for the radicals should be different from olefin-NOx-air system reaction, which is considered for the radicals from cigarette smoke. 11 refs., 6 figs., 2 tabs.

  11. Ab initio treatment of gas phase GeO{sup 2+} doubly charged ion

    Energy Technology Data Exchange (ETDEWEB)

    Mogren Al Mogren, M. [Chemistry Department, Faculty of Science, King Saud University, PO Box 2455, Riyadh 11451 (Saudi Arabia); Ben Abdallah, D. [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications – LSAMA, Université de Tunis, Tunis (Tunisia); Department of General Studies, Riyadh Corporation of Technology, Technical and Vocational Training Corporation, PO Box 42826, Riyadh 11551 (Saudi Arabia); Hochlaf, M., E-mail: hochlaf@univ-mlv.fr [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France)

    2015-01-13

    Highlights: • Theoretical investigation of the novel gas-phase molecular species GeO{sup 2+}. • Spectroscopic parameters of this dication in its electronic ground and exited states. • Theoretical double ionization spectrum of GeO. - Abstract: Using multi reference configuration interaction methodology in connection with a large basis set, we show that GeO{sup 2+} is a metastable species either in the ground or in the electronically excited states. This confirms the observation of this dication in gas phase by mass spectrometry. In addition, we derived a set of accurate spectroscopic terms for GeO{sup 2+} bound states. At the MRCI/aug-cc-pV5Z level of theory, the adiabatic double ionization energy of GeO is computed to be ∼28.93 eV.

  12. Nonlinear spectroscopic studies of chiral media

    International Nuclear Information System (INIS)

    Belkin, Mikhail Alexandrovich

    2004-01-01

    Molecular chirality plays an important role in chemistry, biology, and medicine. Traditional optical techniques for probing chirality, such as circular dichroism and Raman optical activity rely on electric-dipole forbidden transitions. As a result, their intrinsic low sensitivity limits their use to probe bulk chirality rather than chiral surfaces, monolayers or thin films often important for chemical or biological systems. Contrary to the traditional chirality probes, chiral signal in sum-frequency generation (SFG) is electric-dipole allowed both on chiral surface and in chiral bulk making it a much more promising tool for probing molecular chirality. SFG from a chiral medium was first proposed in 1965, but had never been experimentally confirmed until this thesis work was performed. This thesis describes a set of experiments successfully demonstrating that chiral SFG responses from chiral monolayers and liquids are observable. It shows that, with tunable inputs, SFG can be used as a sensitive spectroscopic tool to probe chirality in both electronic and vibrational resonances of chiral molecules. The monolayer sensitivity is feasible in both cases. It also discusses the relevant theoretical models explaining the origin and the strength of the chiral signal in vibrational and electronic SFG spectroscopies

  13. Laser diagnostics of a diamond depositing chemical vapour deposition gas-phase environment

    Energy Technology Data Exchange (ETDEWEB)

    Smith, James Anthony

    2002-07-01

    Studies have been carried out to understand the gas-phase chemistry underpinning diamond deposition in hot filament and DC-arcjet chemical vapour deposition (CVD) systems. Resonance enhanced Multiphoton lonisation (REMPI) techniques were used to measure the relative H atom and CH{sub 3} radical number densities and local gas temperatures prevalent in a hot filament reactor, operating on Ch{sub 4}/H{sub 2} and C{sub 2}H{sub 2}/H{sub 2} gas mixtures. These results were compared to a 3D-computer simulation, and hence provided an insight into the nature of the gas-phase chemistry with particular reference to C{sub 2}{yields}C{sub 1} species conversion. Similar experimental and theoretical studies were also carried out to explain the chemistry involved in NH{sub 3}/CH{sub 4}/H{sub 2} and N{sub 2}/CH{sub 4}/H{sub 2} gas mixtures. It was demonstrated that the reactive nature of the filament surface was dependent on the addition of NH{sub 3}, influencing atomic hydrogen production, and thus the H/C/N gas-phase chemistry. Studies of the DC-arcjet diamond CVD reactor consisted of optical emission spectroscopic studies of the plume during deposition from an Ar/H{sub 2}/CH{sub 4}/N{sub 2} gas mixture. Spatially resolved species emission intensity maps were obtained for C{sub 2}(d{yields}a), CN(B{yields}X) and H{sub {beta}} from Abel-inverted datasets. The C{sub 2}(d{yields}a) and CN(B{yields}X) emission intensity maps both show local maxima near the substrate surface. SEM and Laser Raman analyses indicate that N{sub 2} additions lead to a reduction in film quality and growth rate. Photoluminescence and SIMS analyses of the grown films provide conclusive evidence of nitrogen incorporation (as chemically bonded CN). Absolute column densities of C{sub 2}(a) in a DC-arcjet reactor operating on an Ar/H{sub 2}/CH{sub 4} gas mixture, were measured using Cavity ring down spectroscopy. Simulations of the measured C{sub 2}(v=0) transition revealed a rotational temperature of {approx

  14. Laser diagnostics of a diamond depositing chemical vapour deposition gas-phase environment

    International Nuclear Information System (INIS)

    Smith, James Anthony

    2002-01-01

    Studies have been carried out to understand the gas-phase chemistry underpinning diamond deposition in hot filament and DC-arcjet chemical vapour deposition (CVD) systems. Resonance enhanced Multiphoton lonisation (REMPI) techniques were used to measure the relative H atom and CH 3 radical number densities and local gas temperatures prevalent in a hot filament reactor, operating on Ch 4 /H 2 and C 2 H 2 /H 2 gas mixtures. These results were compared to a 3D-computer simulation, and hence provided an insight into the nature of the gas-phase chemistry with particular reference to C 2 →C 1 species conversion. Similar experimental and theoretical studies were also carried out to explain the chemistry involved in NH 3 /CH 4 /H 2 and N 2 /CH 4 /H 2 gas mixtures. It was demonstrated that the reactive nature of the filament surface was dependent on the addition of NH 3 , influencing atomic hydrogen production, and thus the H/C/N gas-phase chemistry. Studies of the DC-arcjet diamond CVD reactor consisted of optical emission spectroscopic studies of the plume during deposition from an Ar/H 2 /CH 4 /N 2 gas mixture. Spatially resolved species emission intensity maps were obtained for C 2 (d→a), CN(B→X) and H β from Abel-inverted datasets. The C 2 (d→a) and CN(B→X) emission intensity maps both show local maxima near the substrate surface. SEM and Laser Raman analyses indicate that N 2 additions lead to a reduction in film quality and growth rate. Photoluminescence and SIMS analyses of the grown films provide conclusive evidence of nitrogen incorporation (as chemically bonded CN). Absolute column densities of C 2 (a) in a DC-arcjet reactor operating on an Ar/H 2 /CH 4 gas mixture, were measured using Cavity ring down spectroscopy. Simulations of the measured C 2 (v=0) transition revealed a rotational temperature of ∼3300 K. This gas temperature is similar to that deduced from optical emission spectroscopy studies of the C 2 (d→a) transition. (author)

  15. Liquid and Gas Phase Chemistry of Hypergolic Reactions between MMH and NTO or RFNA

    Science.gov (United States)

    Black, Ariel

    -step liquid phase chemical reaction model. These defining constants have never before been experimentally determined for MMH-NTO and can be employed to improve the accuracy of CFD combustion simulations. Induction delay times for MMH-RFNA ranged from 30 to 100 microseconds, agreeing with previously reported data, while MMH-NTO delays varied from 10 to 100 microseconds. Advanced ultraviolet and visible (UV-Vis) spectroscopic techniques were applied to conventional drop test analysis in order to study the emitting species in MMH-NTO and MMH-RFNA combustion reactions. A streak camera coupled with a spectrometer provided temporally resolved spectra for species emitting wavelengths from 250 to 950 nm within a one millimeter diameter point of interest above the reaction. The spectra were compared to known MMH-RFNA gas-phase reaction mechanisms and spectroscopic data reported in literature in an attempt to partially validate the proposed full and reduced MMH-RFNA reaction mechanisms and derive a connection to elementary reactions of MMH-NTO. MMH-NTO consistently produced brighter flames than MMH-RFNA and as such generally generated higher intensity signals for a given spectrometer setting. Both propellant combinations revealed conclusive evidence of OH and NH radicals and probable evidence of CN and/or CH radicals. In most tests OH* yielded the highest intensity signals with both RFNA and NTO. MMH-NTO revealed greater NH* intensity than MMH-RFNA. Additionally, species appeared later but peaked sooner relative to ignition for MMH-RFNA than for MMH-NTO. Efforts to draw correlations between these experimental results and existing reaction mechanisms proved to be challenging and are ongoing. A dominant, high intensity signal characteristic of sodium was an unexpected, but apparently not uncommon, observation, with varying opinions as to its origin.

  16. Spectroscopic and antimicrobial studies of polystyrene films under ...

    Indian Academy of Sciences (India)

    Spectroscopic and antimicrobial studies of polystyrene films under air plasma and He-Ne laser treatment ... The parameters such as (1) surface area by contact angle measurements, (2) quality of material before and after treatment by SEM and FTIR spectra and (3) material characterization by UV-vis spectra were studied.

  17. Spectroscopic study of low-lying 16N levels

    International Nuclear Information System (INIS)

    Bardayan, Daniel W.; O'Malley, Patrick; Blackmon, Jeff C.; Chae, K.Y.; Chipps, K.; Cizewski, J.A.; Hatarik, Robert; Jones, K.L.; Kozub, R. L.; Matei, Catalin; Moazen, Brian; Nesaraja, Caroline D.; Pain, Steven D.; Paulauskas, Stanley; Peters, W.A.; Pittman, S.T.; Schmitt, Kyle; Shriner, J.F. Jr.; Smith, Michael Scott

    2008-01-01

    The magnitude of the 15N(n,gamma)16N reaction rate in asymptotic giant branch stars depends directly on the neutron spectroscopic factors of low-lying 16N levels. A new study of the 15N(d,p)16N reaction is reported populating the ground and first three excited states in 16N. The measured spectroscopic factors are near unity as expected from shell model calculations, resolving a long-standing discrepancy with earlier measurements that had never been confirmed or understood. Updated 15N(n,gamma)16N reaction rates are presented

  18. Fundamental thermochemical properties of amino acids: gas-phase and aqueous acidities and gas-phase heats of formation.

    Science.gov (United States)

    Stover, Michele L; Jackson, Virgil E; Matus, Myrna H; Adams, Margaret A; Cassady, Carolyn J; Dixon, David A

    2012-03-08

    The gas-phase acidities of the 20 L-amino acids have been predicted at the composite G3(MP2) level. A broad range of structures of the neutral and anion were studied to determine the lowest energy conformer. Excellent agreement is found with the available experimental gas-phase deprotonation enthalpies, and the calculated values are within experimental error. We predict that tyrosine is deprotonated at the CO(2)H site. Cysteine is predicted to be deprotonated at the SH but the proton on the CO(2)H is shared with the S(-) site. Self-consistent reaction field (SCRF) calculations with the COSMO parametrization were used to predict the pK(a)'s of the non-zwitterion form in aqueous solution. The differences in the non-zwitterion pK(a) values were used to estimate the free energy difference between the zwitterion and nonzwitterion forms in solution. The heats of formation of the neutral compounds were calculated from atomization energies and isodesmic reactions to provide the first reliable set of these values in the gas phase. Further calculations were performed on five rare amino acids to predict their heats of formation, acidities, and pK(a) values.

  19. Experimental station for gas phase fluorescence spectroscopy

    International Nuclear Information System (INIS)

    Stankiewicz, M.; Garcia, E. Melero; Ruiz, J. Alvarez; Erman, P.; Hatherly, P.A.; Kivimaeki, A.; Rachlew, E.; Rius i Riu, J.

    2004-01-01

    The details of an experimental setup for gas phase atomic and molecular fluorescence measurements using synchrotron radiation are described in this article. The most significant part of the apparatus is an optical arrangement, which allows for simultaneous measurements of dispersed as well as total fluorescence intensity using an effusive gas jet and an inbuilt gas cell assembled in a convenient plug and measure configuration. The first measurements concerning fluorescence of the N 2 molecule around the N 1s edge obtained with this setup are presented

  20. Activation of methane by zinc: gas-phase synthesis, structure, and bonding of HZnCH3.

    Science.gov (United States)

    Flory, Michael A; Apponi, Aldo J; Zack, Lindsay N; Ziurys, Lucy M

    2010-12-08

    The methylzinc hydride molecule, HZnCH3, has been observed in the gas phase for the first time in the monomeric form using high-resolution spectroscopic techniques. The molecule was synthesized by two methods: the reaction of dimethylzinc with hydrogen gas and methane in an AC discharge and the reaction of zinc vapor produced in a Broida-type oven with methane in a DC discharge. HZnCH3 was identified on the basis of its pure rotational spectrum, which was recorded using millimeter/submillimeter direct-absorption and Fourier transform microwave techniques over the frequency ranges 332-516 GHz and 18-41 GHz, respectively. Multiple rotational transitions were measured for this molecule in seven isotopic variants. K-ladder structure was clearly present in all of the spectra, indicating a molecule with C3v symmetry and a (1)A1 ground electronic state. Extensive quadrupole hyperfine structure arising from the (67)Zn nucleus was observed for the H(67)ZnCH3 species, suggesting covalent bonding to the zinc atom. From the multiple isotopic substitutions, a precise structure for HZnCH3 has been determined. The influence of the axial hydrogen atom slightly distorts the methyl group but stabilizes the Zn-C bond. This study suggests that HZnCH3 can be formed through the oxidative addition of zinc to methane in the gas phase under certain conditions. HZnCH3 is the first metal-methane insertion complex to be structurally characterized.

  1. An atmospheric pressure flow reactor: Gas phase kinetics and mechanism in tropospheric conditions without wall effects

    Science.gov (United States)

    Koontz, Steven L.; Davis, Dennis D.; Hansen, Merrill

    1988-01-01

    A new type of gas phase flow reactor, designed to permit the study of gas phase reactions near 1 atm of pressure, is described. A general solution to the flow/diffusion/reaction equations describing reactor performance under pseudo-first-order kinetic conditions is presented along with a discussion of critical reactor parameters and reactor limitations. The results of numerical simulations of the reactions of ozone with monomethylhydrazine and hydrazine are discussed, and performance data from a prototype flow reactor are presented.

  2. Molecular structure determination of cyclootane by ab initio and electron diffraction methods in the gas phase

    OpenAIRE

    De Almeida, Wagner B.

    2000-01-01

    The determination of the molecular structure of molecules is of fundamental importance in chemistry. X-rays and electron diffraction methods constitute in important tools for the elucidation of the molecular structure of systems in the solid state and gas phase, respectively. The use of quantum mechanical molecular orbital ab initio methods offer an alternative for conformational analysis studies. Comparison between theoretical results and those obtained experimentally in the gas phase can ma...

  3. Kinetics and thermochemistry of the reversible gas phase reaction HONO+NH3->3N-HONO studied by infrared diode laser spectroscopy

    DEFF Research Database (Denmark)

    Pagsberg, P.; Ratajczak, E.; Sillesen, A.

    1994-01-01

    The kinetics of the reversible reaction HONO+NH3 reversible H3N-HONO (1) was studied by monitoring trans-HONO relaxation kinetics. The rate of approach towards equilibrium was studied as a function of the ammonia concentration to obtain values of the rate constants for the forward and reverse rea...

  4. An absolute- and relative-rate study of the gas-phase reaction of OH radicals and Cl atoms with n-alkyl nitrates

    DEFF Research Database (Denmark)

    Nielsen, O.J.; Sidebottom, H.W.; Donlon, M.

    1991-01-01

    combined with kinetic spectroscopy and a conventional photolytic relative-rate method. The Cl rate constants were measured using only the relative-rate method. Evidence is presented from the kinetic studies that reaction of OH radicals with alkyl nitrates may involve both addition and abstraction pathways...

  5. Atomic and molecular gas phase spectrometry

    Science.gov (United States)

    Winefordner, J. D.

    1985-10-01

    The major goals of this research have been to develop diagnostical spectroscopic methods for measuring spatial/temporal temperatures and species of combustion flames and plasmas and to develop sensitive, selective, precise, reliable, rapid spectrometric methods of trace analysis of elements present in jet engine lubricating oils, metallurgical samples, and engine exhausts. The diagnostical approaches have been based upon the measurement of metal probes introduced into the flame or plasmas and the measurement of OH in flames. The measurement approaches have involved the use of laser-excited fluorescence, saturated absorption, polarization, and linear absorption. The spatial resolution in most studies is less than 1 cu mm and the temporal resolution is less than 10 ns with the use of pulsed lasers. Single pulse temperature and species measurements have also been carried out. Other diagnostical studies have involved the measurement of collisional redistribution of radiatively excited levels of Na and Tl in acetylene/02/Ar flames and the measurement of lifetimes and quantum efficiencies of atoms and ions in the inductively coupled plasmas, ICP. The latter studies indicate that the high electron number densities in ICPs are not efficient quenchers of excited atoms/ions. Temperatures of microwave atmospheric plasmas produced capacitatively and cool metastable N2 discharge produced by a dielectric discharge have also been measured.

  6. Pulse radiolysis study of reactions of alkyl and alkylperoxy radicals originating from methyl tert-butyl ether in the gas phase

    DEFF Research Database (Denmark)

    Langer, S.; Ljungström, E.; Ellermann, T.

    1995-01-01

    UV spectra and kinetics for the reactions of alkyl and alkylperoxy radicals from methyl tert-butyl ether (MTBE) were studied in 1 atm of SF6 by the pulse radiolysis-UV absorption technique. UV spectra for the radical mixtures were quantified from 215 to 340 nm. At 240 nm, sigma(R) = (2.6 +/- 0.4) X...... and the alkylperoxy radicals with NO and NO2 are (9.1 +/- 1.5) X 10(-13), (4.3 +/- 1.6) X 10(-12) and (1.2 +/- 0.3) X 10(-11) cm(3) molecule(-1) s(-1), respectively. The rate constants given above refer to reaction at the tert-butyl side of the molecule....

  7. Aqueous solvation of Mg(ii) and Ca(ii): A Born-Oppenheimer molecular dynamics study of microhydrated gas phase clusters

    Science.gov (United States)

    León-Pimentel, C. I.; Amaro-Estrada, J. I.; Hernández-Cobos, J.; Saint-Martin, H.; Ramírez-Solís, A.

    2018-04-01

    The hydration features of [Mg(H2O)n ] 2 + and [Ca(H2O)n ] 2 + clusters with n = 3-6, 8, 18, and 27 were studied by means of Born-Oppenheimer molecular dynamics simulations at the B3LYP/6-31+G** level of theory. For both ions, it is energetically more favorable to have all water molecules in the first hydration shell when n ≤ 6, but stable lower coordination average structures with one water molecule not directly interacting with the ion were found for Mg2+ at room temperature, showing signatures of proton transfer events for the smaller cation but not for the larger one. A more rigid octahedral-type structure for Mg2+ than for Ca2+ was observed in all simulations, with no exchange of water molecules to the second hydration shell. Significant thermal effects on the average structure of clusters were found: while static optimizations lead to compact, spherically symmetric hydration geometries, the effects introduced by finite-temperature dynamics yield more prolate configurations. The calculated vibrational spectra are in agreement with infrared spectroscopy results. Previous studies proposed an increase in the coordination number (CN) from six to eight water molecules for [Ca(H2O)n ] 2 + clusters when n ≥ 12; however, in agreement with recent measurements of binding energies, no transition to a larger CN was found when n > 8. Moreover, the excellent agreement found between the calculated extended X-ray absorption fine structure spectroscopy spectra for the larger cluster and the experimental data of the aqueous solution supports a CN of six for Ca2+.

  8. Kinetic and Mechanistic Studies for the Gas-phase Reaction of Ozone with 2, 3-Dimethyl-2-Butene and 1, 3-Butadiene

    Directory of Open Access Journals (Sweden)

    Ismael Abdulsatar AL Mulla

    2017-09-01

    Full Text Available The reactions of ozone with 2,3-Dimethyl-2-Butene (CH32C=C(CH32 and 1,3-Butadiene CH2=CHCH=CH2 have been investigated under atmospheric conditions at 298±3K in air using both relative and absolute rate techniques, and the measured rate coefficients are found to be in good agreement in both techniques used. The obtained results show the addition of ozone to the double bond in these compounds and how it acts as function of the methyl group substituent situated on the double bond. The yields of all the main products have been determined using FTIR and GC-FID and the product studies of these reactions establish a very good idea for the decomposition pathways for the primary formed compounds (ozonides and give a good information for the effect of the methyl group on the degradation pathways. The results have been discussed from the view point of their importance in the atmospheric oxidation of these pollutants.

  9. GAS-PHASE SYNTHESIS OF PRECURSORS OF INTERSTELLAR GLYCINE: A COMPUTATIONAL STUDY OF THE REACTIONS OF ACETIC ACID WITH HYDROXYLAMINE AND ITS IONIZED AND PROTONATED DERIVATIVES

    Energy Technology Data Exchange (ETDEWEB)

    Barrientos, Carmen; Redondo, Pilar; Largo, Laura; Rayon, Victor M.; Largo, Antonio, E-mail: alargo@qf.uva.es [Departamento de Quimica Fisica y Quimica Inorganica, Facultad de Ciencias, Universidad de Valladolid, 47005 Valladolid (Spain)

    2012-04-01

    A computational study of the reactions of hydroxylamine and its ionized and protonated derivatives with acetic acid is provided. The reaction of neutral hydroxylamine with acetic acid, despite being clearly exothermic, involves a very large energy barrier. The reaction of ionized hydroxylamine with acetic acid is also clearly exothermic, but again a significant energy barrier is found (around 24 kcal mol{sup -1} at the CCSD(T) level). The reaction of the most stable protonated isomer of hydroxylamine, NH{sub 3}OH{sup +}, with acetic acid also involves a high barrier (more than 27 kcal mol{sup -1} at the CCSD(T) level). Only the higher energy isomer, NH{sub 2}OH{sup +}{sub 2}, leads to a sensibly lower energy barrier (about 2.3 kcal mol{sup -1} at the CCSD(T) level). Nevertheless, an estimate of the reaction coefficient at low temperatures such as those reigning in the interstellar medium gives very low values. Therefore, it seems that precursors of interstellar glycine could not be efficiently produced from the reactions of hydroxylamine-derived ions with acetic acid.

  10. GAS-PHASE SYNTHESIS OF PRECURSORS OF INTERSTELLAR GLYCINE: A COMPUTATIONAL STUDY OF THE REACTIONS OF ACETIC ACID WITH HYDROXYLAMINE AND ITS IONIZED AND PROTONATED DERIVATIVES

    International Nuclear Information System (INIS)

    Barrientos, Carmen; Redondo, Pilar; Largo, Laura; Rayón, Víctor M.; Largo, Antonio

    2012-01-01

    A computational study of the reactions of hydroxylamine and its ionized and protonated derivatives with acetic acid is provided. The reaction of neutral hydroxylamine with acetic acid, despite being clearly exothermic, involves a very large energy barrier. The reaction of ionized hydroxylamine with acetic acid is also clearly exothermic, but again a significant energy barrier is found (around 24 kcal mol –1 at the CCSD(T) level). The reaction of the most stable protonated isomer of hydroxylamine, NH 3 OH + , with acetic acid also involves a high barrier (more than 27 kcal mol –1 at the CCSD(T) level). Only the higher energy isomer, NH 2 OH + 2 , leads to a sensibly lower energy barrier (about 2.3 kcal mol –1 at the CCSD(T) level). Nevertheless, an estimate of the reaction coefficient at low temperatures such as those reigning in the interstellar medium gives very low values. Therefore, it seems that precursors of interstellar glycine could not be efficiently produced from the reactions of hydroxylamine-derived ions with acetic acid.

  11. Unravelling Mechanistic Aspects of the Gas-Phase Ethanol Conversion: An Experimental and Computational Study on the Thermal Reactions of MO2 (+) (M=Mo, W) with Ethanol.

    Science.gov (United States)

    González-Navarrete, Patricio; Schlangen, Maria; Wu, Xiao-Nan; Schwarz, Helmut

    2016-02-24

    The ion/molecule reactions of molybdenum and tungsten dioxide cations with ethanol have been studied by Fourier transform ion-cyclotron resonance mass spectrometry (FT-ICR MS) and density functional theory (DFT) calculations. Dehydration of ethanol has been found as the dominant reaction channel, while generation of the ethyl cation corresponds to a minor product. Cleary, the reactions are mainly governed by the Lewis acidity of the metal center. Computational results, together with isotopic labeling experiments, show that the dehydration of ethanol can proceed either through a conventional concerted [1,2]-elimination mechanism or a step-wise process; the latter occurs via a hydroxyethoxy intermediate. Formation of C2 H5 (+) takes place by transfer of OH(-) from ethanol to the metal center of MO2 (+) . The molybdenum and tungsten dioxide cations exhibit comparable reactivities toward ethanol, and this is reflected in similar reaction rate constants and branching ratios. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Inhibition of urinary calculi -- a spectroscopic study

    Science.gov (United States)

    Manciu, Felicia; Govani, Jayesh; Durrer, William; Reza, Layra; Pinales, Luis

    2008-10-01

    Although a considerable number of investigations have already been undertaken and many causes such as life habits, metabolic disorders, and genetic factors have been noted as sources that accelerate calculi depositions and aggregations, there are still plenty of unanswered questions regarding efficient inhibition and treatment mechanisms. Thus, in an attempt to acquire more insights, we propose here a detailed scientific study of kidney stone formation and growth inhibition based on a traditional medicine approach with Rotula Aquatica Lour (RAL) herbal extracts. A simplified single diffusion gel growth technique was used for synthesizing the samples for the present study. The unexpected Zn presence in the sample with RAL inhibitor, as revealed by XPS measurements, explains the inhibition process and the dramatic reflectance of the incident light observed in the infrared transmission studies. Raman data demonstrate potential binding of the inhibitor with the oxygen of the kidney stone. Photoluminescence results corroborate to provide additional evidence of Zn-related inhibition.

  13. Frequency metrology of a photomixing source for gas phase spectroscopy

    Science.gov (United States)

    Hindle, Francis; Mouret, Gael; Yang, Chun; Cuisset, Arnaud; Bocquet, Robin; Lours, Michel; Rovera, Daniele

    2010-08-01

    The availability of frequency combs has opened new possibilities for the measurement of optical frequencies. Photomixing is an attractive solution for high resolution THz spectroscopy of gases due to the narrow spectral resolution and ability to access the 100 GHz to 3.5 THz range. One limitation of present photomixing spectrometers is the accuracy with which the THz frequency is established. Measurement of the centre frequency gas phase molecular transitions requires an accuracy better than 100 kHz in order to allow spectroscopic constants to be determined. Standard optical techniques like those employed in wavelength meters can only provide accuracies in the order of 50 MHz. We have used a turnkey fibre based frequency comb and a standard photomixing configuration to realize a THz synthesizer with an accuracy of around 50kHz. Two ECDLs used to pump the photomixer are phase locked onto the frequency comb and provide a tuning range of 10 MHz. In order to extend the tuning range an additional phase locked ECLD has been added to obtain a range in excess of 100 MHz. The absorption profiles of many Doppler limited transitions of carbonyl sulphide and formaldehyde have been measured to validate this instrument.

  14. Mechanistic Study of the Gas-Phase In-Source Hofmann Elimination of Doubly Quaternized Cinchona-Alkaloid Based Phase-Transfer Catalysts by (+)-Electrospray Ionization/Tandem Mass Spectrometry

    Science.gov (United States)

    Yang, Rong-Sheng; Sheng, Huaming; Lexa, Katrina W.; Sherer, Edward C.; Zhang, Li-Kang; Xiang, Bangping; Helmy, Roy; Mao, Bing

    2017-03-01

    An unusual in-source fragmentation pattern observed for 14 doubly quaternized cinchona alkaloid-based phase-transfer catalysts (PTC) was studied using (+)-ESI high resolution mass spectrometry. Loss of the substituted benzyl cation (R1 or R2) was found to be the major product ion [M2+ - R1 + or R2 +]+ in MS spectra of all PTC compounds. A Hofmann elimination product ion [M - H]+ was also observed. Only a small amount of the doubly charged M2+ ions were observed in the MS spectra, likely due to strong Columbic repulsion between the two quaternary ammonium cations in the gas phase. The positive voltage in the MS inlet but not the ESI probe was found to induce this extensive fragmentation for all PTC diboromo-salts. Compound 1 was used as an example to illustrate the proposed in-source fragmentation mechanism. The mechanism of formation of the Hofmann elimination product ion [M - H]+ was further investigated using HRMS/MS, H/D exchange, and DFT calculations. The proposed formation of 2b as the major Hofmann elimination product ion was supported both by HRMS/MS and DFT calculations. Formation of product ion 2b through a concerted unimolecular Ei elimination pathway is proposed rather than a bimolecular E2 elimination pathway for common solution Hofmann eliminations.

  15. Mechanistic Study of the Gas-Phase In-Source Hofmann Elimination of Doubly Quaternized Cinchona-Alkaloid Based Phase-Transfer Catalysts by (+)-Electrospray Ionization/Tandem Mass Spectrometry.

    Science.gov (United States)

    Yang, Rong-Sheng; Sheng, Huaming; Lexa, Katrina W; Sherer, Edward C; Zhang, Li-Kang; Xiang, Bangping; Helmy, Roy; Mao, Bing

    2017-03-01

    An unusual in-source fragmentation pattern observed for 14 doubly quaternized cinchona alkaloid-based phase-transfer catalysts (PTC) was studied using (+)-ESI high resolution mass spectrometry. Loss of the substituted benzyl cation (R1 or R2) was found to be the major product ion [M 2+ - R 1 + or R 2 + ] + in MS spectra of all PTC compounds. A Hofmann elimination product ion [M - H] + was also observed. Only a small amount of the doubly charged M 2+ ions were observed in the MS spectra, likely due to strong Columbic repulsion between the two quaternary ammonium cations in the gas phase. The positive voltage in the MS inlet but not the ESI probe was found to induce this extensive fragmentation for all PTC diboromo-salts. Compound 1 was used as an example to illustrate the proposed in-source fragmentation mechanism. The mechanism of formation of the Hofmann elimination product ion [M - H] + was further investigated using HRMS/MS, H/D exchange, and DFT calculations. The proposed formation of 2b as the major Hofmann elimination product ion was supported both by HRMS/MS and DFT calculations. Formation of product ion 2b through a concerted unimolecular E i elimination pathway is proposed rather than a bimolecular E2 elimination pathway for common solution Hofmann eliminations. Graphical Abstract ᅟ.

  16. INFRARED AND RAMAN SPECTROSCOPIC STUDY OF ION ...

    African Journals Online (AJOL)

    Infrared and Raman spectroscopy techniques have been used to study the ionic interactions of strontium(II) and barium(II) with thiocyanate ion in liquid ammonia. A number of bands were observed in both n (CN) and n (CS) regions of infrared and Raman spectra and these were assigned to 1:1 contact ion pair, ...

  17. PREPARATION, SPECTROSCOPIC STUDIES AND X-RAY ...

    African Journals Online (AJOL)

    Molar conductance measurements in dmf indicate 1:3 electrolytes in all cases. Magnetic moment values are close proximity of the Van Vleck values. IR studies suggest the coordination of the ligand is through the azomethine, the phenolic oxygen atom and the carbonyl oxygen of the hydrazonic moiety. The nitrate ion is also ...

  18. Gas phase structure of transition metal dihydrides

    International Nuclear Information System (INIS)

    Demuynck, J.; Schaefer, H.F. III

    1980-01-01

    ESR and infrared spectroscopic measurements on matrix isolated MnH 2 and CrH 2 have recently suggested that these simple molecules may be bent. This result would be the opposite of that found experimentally for the transition metal dihalides MX 2 , known to be linear. Here the geometrical structure of MnH 2 has been investigated by molecular electronic structure theory. A large contracted Gaussian basis set [Mn(14s11p6p/9s8p3d), H(5s1p/3s1p)] was used in conjunction with self-consistent field and configuration interaction methods. These suggest that the 6 A 1 ground state of MnH 2 is linear. Further studies of the 3 A 1 state (one of several low-lying states) of TiH 2 also favor linearity, although this potential energy surface is extremely flat with respect to bending. Thus it appears probable that most MH 2 molecules, like the related MX 2 family, are linear

  19. Spectroscopic studies of hydrogen atom and molecule collisions: Performance report

    International Nuclear Information System (INIS)

    Kielkopf, J.

    1986-01-01

    This research is concerned with spectroscopic measurements of collisions in atomic and molecular hydrogen in order to clarify the basic physical processes that take place during radiative collisions and to provide experimental values for systems where the theoretical analysis is tractable. To this end, we proposed to measure from the cores to the far wings the profiles of the spectral lines of atomic hydrogen broadened by molecular hydrogen and noble gases, and to study energy transfer in the atom and molecule

  20. Spectroscopic study of gamma irradiated bovine hemoglobin

    International Nuclear Information System (INIS)

    Maghraby, Ahmed Mohamed; Ali, Maha Anwar

    2007-01-01

    In the present study, the effects of ionizing radiation of Cs-137 and Co-60 from 4.95 to 743.14 Gy and from 40 Gy to 300 kGy, respectively, on some bovine hemoglobin characteristics were studied. Such an effect was evaluated using electron paramagnetic resonance (EPR) spectroscopy, and infra-red (IR) spectroscopy. Bovine hemoglobin EPR spectra were recorded and analyzed before and after irradiation and changes were explained in detail. IR spectra of unirradiated and irradiated Bovine hemoglobin were recorded and analyzed also. It was found that ionizing radiation may lead to the increase of free radicals production, the decrease in α-helices contents, which reflects the degradation of hemoglobin molecular structure, or at least its incomplete performance. Results also show that the combined application of EPR and FTIR spectroscopy is a powerful tool for determining structural modification of bovine hemoglobin samples exposed to gamma irradiation

  1. Spectroscopic Study of NGC 281 West

    Science.gov (United States)

    Hasan, Priya

    2018-04-01

    NGC 281 is a complex region of star formation at 2.8 kpc. This complex is situated 300 pc above the Galactic plane, and appears to be part of a 270 pc diameter ring of atomic and molecular clouds expanding at 22 km/s (Megeath et al. 2003). It appears that two modes of triggered star formation are at work here: an initial supernova to trigger the ring complex and the initial O stars and the subsequent triggering of low mass star formation by photoevaporation driven molecular core compression. To get a complete census of the young stellar population, we use observations from Chandra ACIS 100 ksec coupled with data from 2MASS and Spitzer. The Master X-ray catalog has 446 sources detected in different bandpasses. We present the spatial distribution of Class I, II and III sources to study the progress of star formation. We also determine the gas to dust ratio NH/AK to be 1.93 ± 0.47 ×1022 cm‑2 mag‑1 for this region. In this article, we present NGC 281 as a good target to study with the 3.6-m Devasthal Optical Telescope (DOT) in spectroscopy. With these spectra, we look for evidence for the pre-main-sequence (PMS) nature of the objects, study the properties of the detected emission lines as a function of evolutionary class, and obtain spectral types for the observed young stellar objects (YSOs). The temperatures implied by the spectral types can be combined with luminosities determined from the near-infrared (NIR) photometry to construct Hertzsprung–Russell (HR) diagrams for the clusters. By comparing the positions of the YSOs in the HR diagrams with the PMS tracks, we can determine the ages of the embedded sources and study the relative ages of the YSOs with and without optically thick circumstellar disks.

  2. Betulinic acid spectroscopic studies by NMR

    International Nuclear Information System (INIS)

    Junges, Mario Jose; Fernandes, Joao Batista; Rodrigues Filho, Edson; Vieira, Paulo Cezar; Silva, Maria Fatima das G. Fernandes da

    1995-01-01

    HMQC, HMBC, COSY 1 H- 1 H, DEPT, COSYHLR were used to assign the hydrogen and carbon chemical shifts of betulinic acid. On base in this study it is proposed to change the δ of the carbons 6, 11, 18, 19 and 26 and of the methyls hydrogen in the literature for betulinic acid, as well as of the compounds where betulinic acid was used as model. It was verified that H-5, δ 0,82, is in position strongly shielded. (author)

  3. Progress report on nuclear spectroscopic studies

    International Nuclear Information System (INIS)

    Bingham, C.R.; Guidry, M.W.; Riedinger, L.L.; Sorensen, S.P.

    1994-01-01

    The Nuclear Physics group at the University of Tennessee, Knoxville (UTK) is involved in several aspects of heavy-ion physics including both nuclear structure and reaction mechanisms. While the main emphasis is on experimental problems, the authors have maintained a strong collaboration with several theorists in order to best pursue the physics of their measurements. During the last year they have had several experiments at the ATLAS at Argonne National Laboratory, the GAMMASPHERE at the LBL 88 Cyclotron, and with the NORDBALL at the Niels Bohr Institute Tandem. Also, they continue to be very active in the WA93/98 collaboration studying ultra-relativistic heavy ion physics utilizing the SPS accelerator at CERN in Geneva, Switzerland and in the PHENIX Collaboration at the RHIC accelerator under construction at Brookhaven National Laboratory. During the last year their experimental work has been in three broad areas: (1) the structure of nuclei at high angular momentum, (2) the structure of nuclei far from stability, and (3) ultra-relativistic heavy-ion physics. The results of studies in these particular areas are described in this document. These studies concentrate on the structure of nuclear matter in extreme conditions of rotational motion, imbalance of neutrons and protons, or very high temperature and density. Another area of research is heavy-ion-induced transfer reactions, which utilize the transfer of nucleons to states with high angular momentum to learn about their structure and to understand the transfer of particles, energy, and angular momentum in collisions between heavy ions

  4. Spectroscopic analysis of bones for forensic studies

    Energy Technology Data Exchange (ETDEWEB)

    Tofanelli, Mirko [Applied and Laser Spectroscopy Laboratory, Institute of Chemistry of Organometallic Compounds, Research Area of CNR, Via G. Moruzzi, 1, 56124 Pisa (Italy); Pardini, Lorenzo [Institut für Physik und IRIS Adlershof, Humboldt-Universität zu Berlin, Zum Großen Windkanal 6, 12489 Berlin (Germany); Borrini, Matteo [Research Centre in Evolutionary Anthropology and Palaeoecology, School of Natural Sciences and Psychology, Liverpool John Moores University, Byrom Street, Liverpool (United Kingdom); Bartoli, Fulvio; Bacci, Alessandra [Department of Biology, University of Pisa, Via A. Volta, 4, 56126 Pisa (Italy); D’Ulivo, Alessandro; Pitzalis, Emanuela; Mascherpa, Marco Carlo; Legnaioli, Stefano; Lorenzetti, Giulia; Pagnotta, Stefano [Applied and Laser Spectroscopy Laboratory, Institute of Chemistry of Organometallic Compounds, Research Area of CNR, Via G. Moruzzi, 1, 56124 Pisa (Italy); Holanda Cavalcanti, Gildo de [Instituto de Fìsica, Universidade Federal Fluminense, Av. Gal. Milton Tavares de Souza, s/no Campus da Praia Vermelha, CEP 24210-346, Niterói, Rio de Janeiro (Brazil); Lezzerini, Marco [Department of Earth Sciences, University of Pisa, Via Santa Maria, 53, 56126 Pisa (Italy); Palleschi, Vincenzo, E-mail: vincenzo.palleschi@cnr.it [Applied and Laser Spectroscopy Laboratory, Institute of Chemistry of Organometallic Compounds, Research Area of CNR, Via G. Moruzzi, 1, 56124 Pisa (Italy)

    2014-09-01

    The elemental analysis of human bones can give information about the dietary habits of the deceased, especially in the last years of their lives, which can be useful for forensic studies. The most important requirement that must be satisfied for this kind of analysis is that the concentrations of analyzed elements are the same as ante mortem. In this work, a set of bones was analyzed using Laser-Induced Breakdown Spectroscopy (LIBS) and validated using Inductively Coupled Plasma–Optical Emission Spectroscopy (ICP-OES), in order to compare those two techniques and to investigate the effect of possible alterations in the elemental concentrations' proportion resulting from the treatment usually applied for preparing the bones for traditional forensic analysis. The possibility that elemental concentrations' changes would occur after accidental or intentional burning of the bones was also studied. - Highlights: • The LIBS analysis of (animal) bones is presented, to establish its feasibility for forensic studies. • Untreated bones and bones subjected to high temperatures (boiled, burned) were analyzed. • A simple calibration, using a single reference sample, gave reasonable quantitative results. • The comparison of the results demonstrates that LIBS analysis can provide nutritional information. • The nutritional information obtained are the same on untreated, boiled and burned bones.

  5. Spectroscopic analysis of bones for forensic studies

    International Nuclear Information System (INIS)

    Tofanelli, Mirko; Pardini, Lorenzo; Borrini, Matteo; Bartoli, Fulvio; Bacci, Alessandra; D’Ulivo, Alessandro; Pitzalis, Emanuela; Mascherpa, Marco Carlo; Legnaioli, Stefano; Lorenzetti, Giulia; Pagnotta, Stefano; Holanda Cavalcanti, Gildo de; Lezzerini, Marco; Palleschi, Vincenzo

    2014-01-01

    The elemental analysis of human bones can give information about the dietary habits of the deceased, especially in the last years of their lives, which can be useful for forensic studies. The most important requirement that must be satisfied for this kind of analysis is that the concentrations of analyzed elements are the same as ante mortem. In this work, a set of bones was analyzed using Laser-Induced Breakdown Spectroscopy (LIBS) and validated using Inductively Coupled Plasma–Optical Emission Spectroscopy (ICP-OES), in order to compare those two techniques and to investigate the effect of possible alterations in the elemental concentrations' proportion resulting from the treatment usually applied for preparing the bones for traditional forensic analysis. The possibility that elemental concentrations' changes would occur after accidental or intentional burning of the bones was also studied. - Highlights: • The LIBS analysis of (animal) bones is presented, to establish its feasibility for forensic studies. • Untreated bones and bones subjected to high temperatures (boiled, burned) were analyzed. • A simple calibration, using a single reference sample, gave reasonable quantitative results. • The comparison of the results demonstrates that LIBS analysis can provide nutritional information. • The nutritional information obtained are the same on untreated, boiled and burned bones

  6. Infrared spectroscopic study of decomposition of Ti(N(CH3)2)4

    NARCIS (Netherlands)

    Driessen, J.P.A.M.; Schoonman, J.; Jensen, K.F.

    2001-01-01

    The decomposition of Ti(N(CH3)2)4 (TDMAT) has been studied in N2 and H2 environments and surface temperatures between 473 and 623 K by using Fourier transform infrared spectroscopy. The pressure in the system was 5 Torr, with a TDMAT partial pressure of 0.3 Torr. The evolution of gas-phase species

  7. Vibrational spectroscopic study of terbutaline hemisulphate

    Science.gov (United States)

    Ali, H. R. H.; Edwards, H. G. M.; Kendrick, J.; Scowen, I. J.

    2009-05-01

    The Raman spectrum of terbutaline hemisulphate is reported for the first time, and molecular assignments are proposed on the basis of ab initio BLYP DFT calculations with a 6-31G* basis set and vibrational frequencies predicted within the quasi-harmonic approximation; these predictions compare favourably with the observed vibrational spectra. Comparison with previously published infrared data explains several spectral features. The results from this study provide data that can be used for the preparative process monitoring of terbutaline hemisulphate, an important β 2 agonist drug in various dosage forms and its interaction with excipients and other components.

  8. Progress report on nuclear spectroscopic studies

    International Nuclear Information System (INIS)

    Bingham, C.R.; Riedinger, L.L.; Sorensen, S.P.

    1996-01-01

    The experimental program in nuclear physics at the University of Tennessee, Knoxville, is led by Professors Carrol Bingham, Lee Riedinger, and Soren Sorenseni who respectively lead the studies of the exotic decay modes of nuclei far from stability, the program of high-spin research, and our effort in relativistic heavy-ion physics. Over the years, this broad program of research has been successful partially because of the shared University resources applied to this group effort. The proximity of the Oak Ridge National Laboratory has allowed us to build extremely strong programs of joint research, and in addition to play an important leadership role in the Joint Institute for Heavy Ion Research (JIHIR). Our experimental program is also very closely linked with those at other national laboratories: Argonne (collaborations involving the Fragment Mass Analyzer (FMA) and γ-ray arrays), Brookhaven (the RHIC and Phenix projects), and Berkeley (GAMMASPHERE). We have worked closely with a variety of university groups in the last three years, especially those in the UNISOR and now UNIRIB collaborations. And, in all aspects of our program, we have maintained close collaborations with theorists, both to inspire the most exciting experiments to perform and to extract the pertinent physics from the results. The specific areas discussed in this report are: properties of high-spin states; study of low-energy levels of nuclei far from stability; and high energy heavy-ion physics

  9. Nonlinear spectroscopic studies of interfacial molecular ordering

    International Nuclear Information System (INIS)

    Superfine, R.

    1991-07-01

    The second order nonlinear optical processes of second harmonic generation and sum frequency generation are powerful new probes of surfaces. They possess unusual surface sensitivity due to the symmetry properties of the nonlinear susceptibility. In particular, infrared-visible sum frequency generation (SFG) can obtain the vibrational spectrum of sub-monolayer coverages of molecules. In this thesis, we explore the unique information that can be obtained from SFG. We take advantage of the sensitivity of SFG to the conformation of alkane chains to study the interaction between adsorbed liquid crystal molecules and surfactant treated surfaces. The sign of the SFG susceptibility depends on the sign of the molecular polarizability and the orientation, up or down, of the molecule. We experimentally determine the sign of the susceptibility and use it to determine the absolute orientation to obtain the sign of the molecular polarizability and show that this quantity contains important information about the dynamics of molecular charge distributions. Finally, we study the vibrational spectra and the molecular orientation at the pure liquid/vapor interface of methanol and water and present the most detailed evidence yet obtained for the structure of the pure water surface. 32 refs., 4 figs., 2 tabs

  10. Spectroscopic studies of silver boro tellurite glasses

    Science.gov (United States)

    Kumar, E. Ramesh; Kumari, K. Rajani; Rao, B. Appa; Bhikshamaiah, G.

    2014-04-01

    The FTIR absorption and Raman scattering studies were used to obtain the structural information of AgI-Ag2O-[(1-x)B2O3-xTeO2] (x=0 to 1 mol% in steps of 0.2) glasses. The glassy nature of the compounds has been confirmed by X-ray diffraction. FTIR and Raman spectra were recorded for all samples at room temperature. FTIR spectra which provides the information about the change in bond structure of the glasses. Raman spectra provide the effect of TeO2 on SBT glass system is that as increasing the concentration of TeO2 the band intensity at 707 cm-1 increase.

  11. Spectroscopic studies of silver boro tellurite glasses

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, E. Ramesh, E-mail: apparao.bojja@gmail.com; Kumari, K. Rajani, E-mail: apparao.bojja@gmail.com; Rao, B. Appa, E-mail: apparao.bojja@gmail.com; Bhikshamaiah, G., E-mail: apparao.bojja@gmail.com [Department of Physics, Osmania University, Hyderabad-500007 (India)

    2014-04-24

    The FTIR absorption and Raman scattering studies were used to obtain the structural information of AgI−Ag{sub 2}O−[(1−x)B{sub 2}O{sub 3}−xTeO{sub 2}] (x=0 to 1 mol% in steps of 0.2) glasses. The glassy nature of the compounds has been confirmed by X-ray diffraction. FTIR and Raman spectra were recorded for all samples at room temperature. FTIR spectra which provides the information about the change in bond structure of the glasses. Raman spectra provide the effect of TeO{sub 2} on SBT glass system is that as increasing the concentration of TeO{sub 2} the band intensity at 707 cm{sup −1} increase.

  12. Fuel cells: spectroscopic studies in the electrocatalysis of alcohol oxidation

    Directory of Open Access Journals (Sweden)

    Iwasita Teresa

    2002-01-01

    Full Text Available Modern spectroscopic methods are useful for elucidating complex electrochemical mechanisms as those occurring during the oxidation of small organic molecules (CH3OH, HCOH, HCOOH. In the present paper it is shown the use of spectroscopic methods to study the oxidation of alcohols on platinum or Pt-based binary electrodes. These reactions are of importance in conexion with the development of anode systems for use in fuel cells. Mass spectrometry and FT infrared spectroscopy allow to establishing the reaction intermediates and products and the dependence of the amount of species on the applied potential. FTIR and scanning tunneling microscopy contribute to understand the effects of the surface structure on the rate of reaction. Examples are presented for methanol and ethanol oxidation at pure and modified Pt catalysts.

  13. A Photoelectron Spectroscopic Study of Di-t-butylphosphazene

    DEFF Research Database (Denmark)

    Elbel, S.; Ellis, A.; Niecke, E.

    1985-01-01

    Gaseous trans-ButPNBut, generated by mild gas-phase thermolysis of its more stable [2 + 1] cyclodimer, has been characterized by field-ionization mass spectrometry and U.V. photoelectron spectroscopy. The photoelectron spectrum has been assigned based on SCC-Xα model calculations for representat......Gaseous trans-ButPNBut, generated by mild gas-phase thermolysis of its more stable [2 + 1] cyclodimer, has been characterized by field-ionization mass spectrometry and U.V. photoelectron spectroscopy. The photoelectron spectrum has been assigned based on SCC-Xα model calculations...

  14. Electrochemical impedance spectroscopic study of passive zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Ai Jiahe; Chen Yingzi [Center for Electrochemical Science and Technology, Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA 16802 (United States); Urquidi-Macdonald, Mirna [Department of Engineering Science and Mechanics, Pennsylvania State University, University Park, PA 16802 (United States); Macdonald, Digby D. [Center for Electrochemical Science and Technology, Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA 16802 (United States)], E-mail: ddm2@psu.edu

    2008-09-30

    Spent, unreproccessed nuclear fuel is generally contained within the operational fuel sheathing fabricated from a zirconium alloy (Zircaloy 2, Zircaloy 4, or Zirlo) and is then stored in a swimming pool and/or dry storage facilities until permanent disposal in a licensed repository. During this period, which begins with irradiation of the fuel in the reactor during operation, the fuel sheathing is exposed to various, aggressive environments. The objective of the present study was to characterize the nature of the passive film that forms on pure zirconium in contact with an aqueous phase [0.1 M B(OH){sub 3} + 0.001 M LiOH, pH 6.94] at elevated temperatures (in this case, 250 deg. C), prior to storage, using electrochemical impedance spectroscopy (EIS) with the data being interpreted in terms of the point defect model (PDM). The results show that the corrosion resistance of zirconium in high temperature, de-aerated aqueous solutions is dominated by the outer layer. The extracted model parameter values can be used in deterministic models for predicting the accumulation of general corrosion damage to zirconium under a wide range of conditions that might exist in some repositories.

  15. Spectroscopic study of biologically active glasses

    Science.gov (United States)

    Szumera, M.; Wacławska, I.; Mozgawa, W.; Sitarz, M.

    2005-06-01

    It is known that the chemical activity phenomenon is characteristic for some inorganic glasses and they are able to participate in biological processes of living organisms (plants, animals and human bodies). An example here is the selective removal of silicate-phosphate glass components under the influence of biological solutions, which has been applied in designing glasses acting as ecological fertilizers of controlled release rate of the nutrients for plants. The structure of model silicate-phosphate glasses containing the different amounts of the glass network formers, i.e. Ca 2+ and Mg 2+, as a binding components were studied. These elements besides other are indispensable of the normal growth of plants. In order to establish the function and position occupied by the particular components in the glass structure, the glasses were examined by FTIR spectroscopy (with spectra decomposition) and XRD methods. It has been found that the increasing amount of MgO in the structure of silicate-phosphate glasses causes the formation of domains the structure of which changes systematically from a structure of the cristobalite type to a structure corresponding to forsterite type. Whilst the increasing content of CaO in the structure of silicate-phosphate glasses causes the formation of domains the structure of which changes from a structure typical for cristobalite through one similar to the structure of calcium orthophosphate, to a structure corresponding to calcium silicates. The changing character of domains structure is the reason of different chemical activity of glasses.

  16. Spectroscopic Studies of Exotic Nuclei at ISOLDE

    CERN Multimedia

    2002-01-01

    Experiment IS50 is designed to: a) Investigate the full range of the @b strength function of heavy (A~$>$~48)~K nuclei b)~Study the decay of isomeric states in n-deficient bromine nuclei (A~=~72 and 70). The heavy K isotopes appeared to have complex decay schemes, including feeding by the @b-decay of levels having open neutron channels (Beta decay energy Q(@b) exceeds neutron binding energy S^n); in addition, a large fraction of the delayed transitions populate excited levels in the daughter nuclei. The allowed @b-decay selects states in the daughter nucleus with wave functions having a large overlap with the initial state. Hence, the @b strength functions, deduced from these deca reveal simple structures correlated to the particle-hole excitation energies in the Ca nuclei. These results are valuable for the application of the shell-model calculations far from stability. The delayed neutron spectra are measured with a large area curved scintillator in coincidence either with high resolution Ge(Li) detectors, ...

  17. Statistical spectroscopic studies in nuclear structure physics

    International Nuclear Information System (INIS)

    Halemane, T.R.

    1979-01-01

    The spectral distribution theory establishes the centroid and width of the energy spectrum as quantities of fundamental importance and gives credence to a geometry associated with averages of the product of pairs of operators acting within a model space. Utilizing this fact and partitioning the model space according to different group symmetries, simple and physically meaningful expansions are obtained for the model interactions. In the process, a global measure for the goodness of group symmetries is also developed. This procedure could eventually lead to a new way of constructing model interactions for nuclear structure studies. Numerical results for six (ds)-shell interactions and for scalar-isospin, configuration-isospin, space symmetry, supermultiplet and SU(e) x SU(4) group structures are presented. The notion of simultaneous propagation of operator averages in the irreps of two or more groups (not necessarily commuting) is also introduced. The non-energy-weighted sum rule (NEWSR) for electric and magnetic multipole excitations in the (ds)-shell nuclei 20 Ne, 24 Mg, 28 Si, 32 S, and 36 Ar are evaluated. A generally applicable procedure for evaluating the eigenvalue bound to the NEWSR is presented and numerical results obtained for the said excitations and nuclei. Comparisons are made with experimental data and shell-model results. Further, a general theory is given for the linear-energy-weighted sum rule (LEWSR). When the Hamiltonian is one-body, this has a very simple form (expressible in terms of occupancies) and amounts to an extension of the Kurath sum rule to other types of excitations and to arbitrary one-body Hamiltonians. Finally, we develop a statistical approach to perturbation theory and inverse-energy-weighted sum rules, and indicate some applications

  18. Spectroscopic Studies of the Nucleus GOLD-195

    Science.gov (United States)

    Fischer, Susan Marie

    The nucleus ^{195}Au has been studied via in-beam gamma -ray and electron spectroscopy with the reactions ^{196}Pt(p,2n)^ {195}Au at beam energies of 12 and 16 MeV, and the reaction ^{rm nat }Ir(alpha,2n) ^{195}Au at a beam energy of 26 MeV. All experiments were performed at the University of Notre Dame tandem accelerator facility and utilized elements of the University of Pittsburgh multi-detector gamma-array and ICEBall mini-orange electron spectrometer. Fifty-five new transitions and thirty-six new energy levels have been observed. The U(6/4) supersymmetric algebra has been proposed to provide a simultaneous description for the positive parity states of the pair of nuclei ^{194 }Pt and ^{195}Au. The observed energy spectra for these nuclei show satisfactory agreement with the U(6/4) predicted spectra. The collective properties including relative B(E2) values for the Pt and Au nuclei in this mass region are also consistent with theoretical predictions. However, the measured E2/M1 mixing ratios for transitions in ^{195} Au indicate that the single particle description for the odd-A nucleus is incomplete. The new data for ^{195}Au is further combined with the existing data for ^{194} Pt and ^{195}Pt within the context of the larger U_{ nu}(6/12) otimes U_{pi}(6/4) supersymmetry. A consistent fit to the energy eigenvalue equation is obtained and a modified prediction for the negative parity states in the odd-odd nucleus ^{196} Au is made. Thus, the proposal of an underlying supersymmetry for the quartet of nuclei ^ {194}Pt-^{195} Pt-^{195}Au- ^{196}Au also appears valid. New transitions and levels involved in the negative parity h_{11/2} decoupled band in ^{195}Au have also been observed. The band appears to be much more fragmented at high spins than the analogous structures in the lighter odd-A Au nuclei, but it is unclear what the source of this difference is. It is, however, proposed that a consistent description for both the positive and negative parity

  19. Soft X-ray photoemission spectroscopy of selected neurotransmitters in the gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Maris, Assimo; Melandri, Sonia; Evangelisti, Luca; Caminati, Walther [Dipartimento di Chimica ' G. Ciamician' dell' Universita, Via Selmi 2, I-40126 Bologna (Italy); Giuliano, Barbara M. [Departamento de Quimica da Universidade de Coimbra, 3004-535 Coimbra (Portugal); Plekan, Oksana [Sincrotrone Trieste, in Area Science Park, I-34149 Basovizza, Trieste (Italy); Feyer, Vitaliy [Sincrotrone Trieste, in Area Science Park, I-34149 Basovizza, Trieste (Italy); Electronic Properties (PGI-6), Peter Gruenberg Institute, Forschungszentrum Juelich GmbH, Leo-Brandt-Strasse, 52428 Juelich (Germany); Richter, Robert [Sincrotrone Trieste, in Area Science Park, I-34149 Basovizza, Trieste (Italy); Coreno, Marcello [CNR-IMIP, Montelibretti, I-00016 Rome (Italy); Prince, Kevin C., E-mail: kevin.prince@elettra.trieste.it [Sincrotrone Trieste, in Area Science Park, I-34149 Basovizza, Trieste (Italy); CNR-IOM, Laboratorio TASC, I-34149 Basovizza, Trieste (Italy)

    2012-09-15

    Highlights: Black-Right-Pointing-Pointer Neurotransmitter molecules. Black-Right-Pointing-Pointer Photoelectron spectroscopy. Black-Right-Pointing-Pointer Electronic structure. Black-Right-Pointing-Pointer Weak hydrogen bonding. -- Abstract: The valence molecular orbitals and core levels of tyramine, tryptamine and tryptophol in the gas phase have been studied using X-ray photoelectron spectroscopy (XPS) and theoretical methods. The energies of the outer valence region spectrum are found to be in agreement with previously reported He I spectra, while new data on the inner valence molecular orbitals are reported. The structures in the carbon, nitrogen and oxygen core level spectra of these molecules have been identified and assigned. These compounds are characterised by conformers with hydrogen bonding in which the {pi} systems of the phenol and indole groups act as hydrogen acceptors, but a spectroscopic signature of this hydrogen bond was not observed. This is in contrast with our previous spectra of amino acids, where conformers with specific hydrogen bonding showed strong effects in core level spectra. We attribute the difference to the weaker strength of the {pi}-hydrogen bonding.

  20. Closed-cage tungsten oxide clusters in the gas phase.

    Science.gov (United States)

    Singh, D M David Jeba; Pradeep, T; Thirumoorthy, Krishnan; Balasubramanian, Krishnan

    2010-05-06

    During the course of a study on the clustering of W-Se and W-S mixtures in the gas phase using laser desorption ionization (LDI) mass spectrometry, we observed several anionic W-O clusters. Three distinct species, W(6)O(19)(-), W(13)O(29)(-), and W(14)O(32)(-), stand out as intense peaks in the regular mass spectral pattern of tungsten oxide clusters suggesting unusual stabilities for them. Moreover, these clusters do not fragment in the postsource decay analysis. While trying to understand the precursor material, which produced these clusters, we found the presence of nanoscale forms of tungsten oxide. The structure and thermodynamic parameters of tungsten clusters have been explored using relativistic quantum chemical methods. Our computed results of atomization energy are consistent with the observed LDI mass spectra. The computational results suggest that the clusters observed have closed-cage structure. These distinct W(13) and W(14) clusters were observed for the first time in the gas phase.

  1. Transferring pharmaceuticals into the gas phase

    Science.gov (United States)

    Christen, Wolfgang; Krause, Tim; Rademann, Klaus

    2008-11-01

    The dissolution of molecules of biological interest in supercritical carbon dioxide is investigated using pulsed molecular beam mass spectrometry. Due to the mild processing temperatures of most supercritical fluids, their adiabatic expansion into vacuum permits to transfer even thermally very sensitive substances into the gas phase, which is particularly attractive for pharmaceutical and biomedical applications. In addition, supercritical CO2constitutes a chemically inert solvent that is compatible with hydrocarbon-free ultrahigh vacuum conditions. Here, we report on the dissolution and pulsed supersonic jet expansion of caffeine (C8H10N4O2), the provitamin menadione (C11H8O2), and the amino acid derivative l-phenylalanine tert-butyl ester hydrochloride (C6H5CH2CH(NH2)COOC(CH3)3[dot operator]HCl), into vacuum. An on-axis residual gas analyzer is used to monitor the relative amounts of solute and solvent in the molecular beam as a function of solvent densityE The excellent selectivity and sensitivity provided by mass spectrometry permits to probe even trace amounts of solutes. The strong density variation of CO2 close to the critical point results in a pronounced pressure dependence of the relative ion currents of solute and solvent molecules, reflecting a substantial change in solubility.

  2. Spectroscopic and dynamical studies of highly energized small polyatomic molecules

    Energy Technology Data Exchange (ETDEWEB)

    Field, R.W.; Silbey, R.J. [Massachusetts Institute of Technology, Cambridge (United States)

    1993-12-01

    The authors have initiated a program to perform spectroscopic and dynamic studies of small molecules. Large amplitude motions in excited acetylene were discussed along with plans to record the dispersed fluorescence (DF) and the stimulated emission pumping (SEP) spectra. SEP spectra were reported for the formyl radical. A Fourier transform spectrometer was discussed with respect to its ability to probe the structure of radicals. This instrument is capable of performing studies using various techniques such as magnetic rotation spectroscopy and sub-Doppler sideband-OODR Zeman (SOODRZ) spectroscopy.

  3. Comparison of catalytic ethylene polymerization in slurry and gas phase

    NARCIS (Netherlands)

    Daftaribesheli, Majid

    2009-01-01

    Polyethylene (PE) with the annual consumption of 70 million tones in 2007 is mostly produced in slurry, gas-phase or combination of both processes. This work focuses on a comparison between the slurry and gas phase processes. Why does PE produced in theses two processes can show extremely different

  4. Spectroscopic studies of carbon impurities in PISCES-A

    International Nuclear Information System (INIS)

    Ra, Y.; Hirooka, Y.; Leung, W.K.; Conn, R.W.; Pospieszczyk, A.

    1989-08-01

    The graphite used for the limiter of the tokamak reactor produces carbon-containing molecular impurities as a result of the interactions with the edge plasma. The behavior of these molecular impurities has been studied using emission spectroscopy. The present study includes: finding molecular bands and atomic lines in the visible spectral range which can be used for the study of the molecular impurities, studying the breakup processes of the molecular impurities on their way from the source into the plasma, developing a spectroscopic diagnostic method for the absolute measurement of the molecular impurity flux resulting from graphite erosion. For these studies, carbon-containing molecules such as CH 4 , C 2 H 2 , C 2 H 4 , and CO 2 were injected into the tokamak-boundary,like plasma generated by PISCES-A. The spectrograms of these gases were taken. Many useful bands and lines were determined from the spectrograms. The breakup processes of these gases were studied by observing the spatial profiles of the emission of the molecules and their radicals for different plasma conditions. For the absolute measurement of the eroded molecular impurity flux, the photon efficiency of the lines and bands were found by measuring the absolute number of the emitted photons and injected gas molecules. The chemical sputtering yield of graphite by hydrogen plasma was spectroscopically measured using the previously obtained photon efficiencies. It showed good agreement with results obtained by weight loss measurements. 16 refs., 7 figs., 1 tab

  5. Mueller matrix spectroscopic ellipsometry study of chiral nanocrystalline cellulose films

    Science.gov (United States)

    Mendoza-Galván, Arturo; Muñoz-Pineda, Eloy; Ribeiro, Sidney J. L.; Santos, Moliria V.; Järrendahl, Kenneth; Arwin, Hans

    2018-02-01

    Chiral nanocrystalline cellulose (NCC) free-standing films were prepared through slow evaporation of aqueous suspensions of cellulose nanocrystals in a nematic chiral liquid crystal phase. Mueller matrix (MM) spectroscopic ellipsometry is used to study the polarization and depolarization properties of the chiral films. In the reflection mode, the MM is similar to the matrices reported for the cuticle of some beetles reflecting near circular left-handed polarized light in the visible range. The polarization properties of light transmitted at normal incidence for different polarization states of incident light are discussed. By using a differential decomposition of the MM, the structural circular birefringence and dichroism of a NCC chiral film are evaluated.

  6. Liquid-gas phase transition and isospin fractionation in intermediate energy heavy ion collisions

    International Nuclear Information System (INIS)

    Xing Yongzhong; Liu Jianye; Guo Wenjun

    2004-01-01

    The liquid-gas phase transition in the heavy ion collisions and nuclear matter has been an important topic and got achievements, such as, based on the studies by H.Q. Song et al the critical temperature of liquid-gas phase transition enhances with increasing the mass of system and reduces as the increase of the neutron proton ratio of system. As authors know that both the liquid-gas phase transition and the isospin fractionation occur in the spinodal instability region at the nuclear density below the normal nuclear density. In particular, these two dynamical processes lead to the separation of nuclear matter into the liquid phase and gas phase. In this case to compare their dynamical behaviors is interested. The authors investigate the dependence of isospin fractionation degree on the mass and neutron proton ratio of system by using the isospin dependent quantum molecular dynamics model. The authors found that the degree of isospin fractionation (N/Z) n /(N/Z) imf decreases with increasing the mass of the system. This is just similar to the enhance of the critical temperature of liquid-gas phase transition T c as the increase of system mass. Because the enhance of T c is not favorable for the liquid-gas transition taking place, which reduces the isospin fractionation process and leads to decrease of (N/Z) n /(N/Z) imf . However the degree of isospin fractionation enhances with increasing the neutron proton ratio of the system. It is just corresponding to the reduce of T c of the liquid-gas phase transition as the increase of the isospin fractionation of the system. Because the reduce of T c enhances the liquid-gas phase transition process and also prompts the isospin fractionation process leading the increase of the isospin fractionation degree. To sum up, there are very similar dynamical behaviors for the degree of isospin fractionation and the critical temperature of the liquid-gas phase transition. So dynamical properties of the liquid-gas phase transition can

  7. Synthesis and Gas Phase Thermochemistry of Germanium-Containing Compounds

    Energy Technology Data Exchange (ETDEWEB)

    Classen, Nathan Robert [Iowa State Univ., Ames, IA (United States)

    2002-01-01

    The driving force behind much of the work in this dissertation was to gain further understanding of the unique olefin to carbene isomerization observed in the thermolysis of 1,1-dimethyl-2-methylenesilacyclobutane by finding new examples of it in other silicon and germanium compounds. This lead to the examination of a novel phenylmethylenesilacyclobut-2-ene, which did not undergo olefin to carbene rearrangement. A synthetic route to methylenegermacyclobutanes was developed, but the methylenegermacyclobutane system exhibited kinetic instability, making the study of the system difficult. In any case the germanium system decomposed through a complex mechanism which may not include olefin to carbene isomerization. However, this work lead to the study of the gas phase thermochemistry of a series of dialkylgermylene precursors in order to better understand the mechanism of the thermal decomposition of dialkylgermylenes. The resulting dialkylgermylenes were found to undergo a reversible intramolecular β C-H insertion mechanism.

  8. Gas phase chromatography of halides of elements 104 and 105

    International Nuclear Information System (INIS)

    Tuerler, A.; Gregorich, K.E.; Czerwinski, K.R.; Hannink, N.J.; Henderson, R.A.; Hoffman, D.C.; Kacher, C.D.; Kadkhodayan, B.; Kreek, S.A.; Lee, D.M.; Leyba, J.D.; Nurmia, M.J.; Gaeggeler, H.W.; Jost, D.T.; Kovacs, J.; Scherer, U.W.; Vermeulen, D.; Weber, A.; Barth, H.; Gober, M.K.; Kratz, J.V.; Bruechle, W.; Schaedel, M.; Schimpf, E.; Gober, M.K.; Kratz, J.V.; Zimmermann, H.P.

    1991-04-01

    On-line isothermal gas phase chromatography was used to study halides of 261 104 (T 1/2 = 65 s) and 262,263 105 (T 1/2 = 34 s and 27 s) produced an atom-at-a time via the reactions 248 Cm( 18 O, 5n) and 249 Bk( 18 O, 5n, 4n), respectively. Using HBr and HCl gas as halogenating agents, we were able to produce volatile bromides and chlorides of the above mentioned elements and study their behavior compared to their lighter homologs in Groups 4 or 5 of the periodic table. Element 104 formed more volatile bromides than its homolog Hf. In contrast, element 105 bromides were found to be less volatile than the bromides of the group 5 elements Nb and Ta. Both 104 and Hf chlorides were observed to be more volatile than their respective bromides. 31 refs., 8 figs

  9. Research in Korea on Gas Phase Synthesis and Control of Nanoparticles

    International Nuclear Information System (INIS)

    Choi, Mansoo

    2001-01-01

    Research activity into the gas phase synthesis of nanoparticles has witnessed rapid growth on a worldwide basis, which is also reflected by Korean research efforts. Nanoparticle research is inherently a multi-disciplinary activity involving both science and engineering. In this paper, the recent studies undertaken in Korea on the gas phase synthesis and control of nanoparticles are reviewed. Studies on the synthesis of various kinds of nanoparticles are first discussed with a focus on the different types of reactors used. Recent experimental and theoretical studies and newly developed methods of measuring and modeling nanoparticle growth are also reviewed

  10. Photoresponse of the protonated Schiff-base retinal chromophore in the gas phase

    DEFF Research Database (Denmark)

    Toker, Jonathan; Rahbek, Dennis Bo; Kiefer, H V

    2013-01-01

    The fragmentation, initiated by photoexcitation as well as collisionally-induced excitation, of several retinal chromophores was studied in the gas phase. The chromophore in the protonated Schiff-base form (RPSB), essential for mammalian vision, shows a remarkably selective photoresponse. The sel......The fragmentation, initiated by photoexcitation as well as collisionally-induced excitation, of several retinal chromophores was studied in the gas phase. The chromophore in the protonated Schiff-base form (RPSB), essential for mammalian vision, shows a remarkably selective photoresponse...... modifications of the chromophore. We propose that isomerizations play an important role in the photoresponse of gas-phase retinal chromophores and guide internal conversion through conical intersections. The role of protein interactions is then to control the specificity of the photoisomerization in the primary...

  11. Charged particle reaction studies on /sup 14/C. [Spectroscopic factors

    Energy Technology Data Exchange (ETDEWEB)

    Cecil, F E; Shepard, J R; Anderson, R E; Peterson, R J; Kaczkowski, P [Colorado Univ., Boulder (USA). Nuclear Physics Lab.

    1975-12-22

    The reactions /sup 14/C(p,d), (d,d') and (d,p) have been measured for E/sub p/ = 27 MeV and E/sub d/ = 17 MeV. The (d,d') and (d,p) reactions were studied between theta/sub lab/ = 15/sup 0/ and 85/sup 0/; the (p,d) reactions, between theta/sub lab/ = 5/sup 0/ and 40/sup 0/. The /sup 14/C deformation parameters were deduced from the deuteron inelastic scattering and found to agree with deformations measured in nearby doubly even nuclei. The spectroscopic factors deduced from the (p,d) reaction allowed a /sup 14/C ground-state wave function to be deduced which compares favorably with a theoretically deduced wave function. The (p,d) and (d,p) spectroscopic factors are consistent. The implications of our /sup 14/C ground-state wave function regarding the problem of the /sup 14/C hindered beta decay are discussed.

  12. Albumin adsorption on oxide thin films studied by spectroscopic ellipsometry

    Energy Technology Data Exchange (ETDEWEB)

    Silva-Bermudez, P., E-mail: suriel21@yahoo.com [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, Circuito Exterior s/n, C.U., 04510, Mexico D.F. (Mexico); Unidad de Posgrado, Facultad de Odontologia, Universidad Nacional Autonoma de Mexico, CU, 04510, Mexico D.F. (Mexico); Rodil, S.E.; Muhl, S. [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, Circuito Exterior s/n, C.U., 04510, Mexico D.F. (Mexico)

    2011-12-15

    Thin films of tantalum, niobium, zirconium and titanium oxides were deposited by reactive magnetron sputtering and their wettability and surface energy, optical properties, roughness, chemical composition and microstructure were characterized using contact angle measurements, spectroscopic ellipsometry, profilometry, X-ray photoelectron spectroscopy and X-ray diffraction, respectively. The purpose of the work was to correlate the surface properties of the films to the Bovine Serum Albumin (BSA) adsorption, as a first step into the development of an initial in vitro test of the films biocompatibility, based on standardized protein adsorption essays. The films were immersed into BSA solutions with different protein concentrations and protein adsorption was monitored in situ by dynamic ellipsometry; the adsorption-rate was dependent on the solution concentration and the immersion time. The overall BSA adsorption was studied in situ using spectroscopic ellipsometry and it was found to be influenced by the wettability of the films; larger BSA adsorption occurred on the more hydrophobic surface, the ZrO{sub 2} film. On the Ta{sub 2}O{sub 5}, Nb{sub 2}O{sub 5} and TiO{sub 2} films, hydrophilic surfaces, the overall BSA adsorption increased with the surface roughness or the polar component of the surface energy.

  13. Zpif's law in the liquid gas phase transition of nuclei

    International Nuclear Information System (INIS)

    Ma, Y.G.

    1999-01-01

    Zpif's law in the field of linguistics is tested in the nuclear disassembly within the framework of isospin dependent lattice gas model. It is found that the average cluster charge (or mass) of rank n in the charge (or mass) list shows exactly inversely to its rank, i.e., there exists Zpif's law, at the phase transition temperature. This novel criterion shall be helpful to search the nuclear liquid gas phase transition experimentally and theoretically. In addition, the finite size scaling of the effective phase transition temperature at which the Zpif's law appears is studied for several systems with different mass and the critical exponents of ν and β are tentatively extracted. (orig.)

  14. Gas-Phase Thermolysis of a Thioketen-S-Oxide

    DEFF Research Database (Denmark)

    Carlsen, Lars; Egsgaard, Helge; Schaumann, Ernst

    1980-01-01

    The unimolecular gas-phase thermolytic decomposition of 1,1,3,3-tetramethyl-2-thiocarbonylcyclohexane S-oxide (3) has been studied as a function of temperature by a flash vacuum thermolysis (f.v.t.) technique. The products detected are the carbenes (4) and (5), the ketone (6), the keten (7......), the thioketone (8), and the thioketen (9). The product ratio is highly dependent on the thermolysis temperature. The thermolysis of (3) is mechanistically rationalized by assuming the existence of only two concurrent primary processes, which are (a) extrusion of atomic oxygen, leading to the thioketen (9...... and CSO leading to the carbenes (5) and (4), respectively, are observed. Owing to an apparently very short half-life of the oxathiiran (10), only the decomposition products of the three-membered ring compound have been detected. These are the thioketone (8), formed by rearrangement of (10) into the α...

  15. Oxidative potential of gas phase combustion emissions - An underestimated and potentially harmful component of air pollution from combustion processes

    Science.gov (United States)

    Stevanovic, S.; Vaughan, A.; Hedayat, F.; Salimi, F.; Rahman, M. M.; Zare, A.; Brown, R. A.; Brown, R. J.; Wang, H.; Zhang, Z.; Wang, X.; Bottle, S. E.; Yang, I. A.; Ristovski, Z. D.

    2017-06-01

    The oxidative potential (OP) of the gas phase is an important and neglected aspect of environmental toxicity. Whilst prolonged exposure to particulate matter (PM) associated reactive oxygen species (ROS) have been shown to lead to negative health effects, the potential for compounds in gas phase to cause similar effects is yet to be understood. In this study we describe: the significance of the gas phase OP generated through vehicle emissions; discuss the origin and evolution of species contributing to measured OP; and report on the impact of gas phase OP on human lung cells. The model aerosol for this study was exhaust emitted from a Euro III Common-rail diesel engine fuelled with different blends of diesel and biodiesel. The gas phase of these emissions was found to be potentially as hazardous as the particle phase. Fuel oxygen content was found to negatively correlate with the gas phase OP, and positively correlate with particle phase OP. This signifies a complex interaction between reactive species present in gas and particle phase. Furthermore, this interaction has an overarching effect on the OP of both particle and gas phase, and therefore the toxicity of combustion emissions.

  16. Acrolein Production by Gas-Phase Glycerol Dehydration Using PO₄/Nb₂O5 Catalysts.

    Science.gov (United States)

    Lee, Kyu Am; Ryoo, HeeKyoung; Ma, Byung Chol; Kim, Youngchul

    2018-02-01

    In this study, modified niobium oxide were prepared to study the addictive effects on the catalytic performance for gas-phase glycerol dehydration. The catalysts were characterized by N2 adsorption/desorption, XRD, NH3-TPD, FT-IR. The amount of phosphoric acid was up to 50 wt% in niobium. As a result, the highest glycerol conversion was achieved over 20 wt% PO4/Nb2O5. It indicates that the optimal amount of phosphoric acid leads the catalyst to have appropriate acidity which is an important factor for gas-phase glycerol dehydration.

  17. Molecular structure and conformational composition of 1,3-dihydroxyacetone studied by combined analysis of gas-phase electron diffraction data, rotational constants, and results of theoretical calculations. Ideal gas thermodynamic properties of 1,3-dihydroxyacetone.

    Science.gov (United States)

    Dorofeeva, Olga V; Vogt, Natalja; Vogt, Jürgen; Popik, Mikhail V; Rykov, Anatolii N; Vilkov, Lev V

    2007-07-19

    The molecular structure of 1,3-dihydroxyacetone (DHA) has been studied by gas-phase electron diffraction (GED), combined analysis of GED and microwave (MW) data, ab initio, and density functional theory calculations. The equilibrium re structure of DHA was determined by a joint analysis of the GED data and rotational constants taken from the literature. The anharmonic vibrational corrections to the internuclear distances (re-ra) and to the rotational constants (B(i)e-B(i)0) needed for the estimation of the re structure were calculated from the B3LYP/cc-pVTZ cubic force field. It was found that the experimental data are well reproduced by assuming that DHA consists of a mixture of three conformers. The most stable conformer of C2v symmetry has two hydrogen bonds, whereas the next two lowest energy conformers (Cs and C1 symmetry) have one hydrogen bond and their abundance is about 30% in total. A combined analysis of GED and MW data led to the following equilibrium structural parameters (re) of the most abundant conformer of DHA (the uncertainties in parentheses are 3 times the standard deviations): r(C=O)=1.215(2) A, r(C-C)=1.516(2) A, r(C-O)=1.393(2) A, r(C-H)=1.096(4) A, r(O-H)=0.967(4) A, angleC-C=O=119.9(2) degrees, angleC-C-O=111.0(2) degrees, angleC-C-H=108.2(7) degrees, angleC-O-H=106.5(7) degrees. These structural parameters reproduce the experimental B(i)0 values within 0.05 MHz. The experimental structural parameters are in good agreement with those obtained from theoretical calculations. Ideal gas thermodynamic functions (S degrees (T), C degrees p(T), and H degrees (T)-H degrees (0)) of DHA were calculated on the basis of experimental and theoretical molecular parameters obtained in this work. The enthalpy of formation of DHA, -523+/-4 kJ/mol, was calculated by the atomization procedure using the G3X method.

  18. Radical Reactions in the Gas Phase: Recent Development and Application in Biomolecules

    Directory of Open Access Journals (Sweden)

    Yang Gao

    2014-01-01

    Full Text Available This review summarizes recent literature describing the use of gas phase radical reactions for structural characterization of complex biomolecules other than peptides. Specifically, chemical derivatization, in-source chemical reaction, and gas phase ion/ion reactions have been demonstrated as effective ways to generate radical precursor ions that yield structural informative fragments complementary to those from conventional collision-induced dissociation (CID. Radical driven dissociation has been applied to a variety of biomolecules including peptides, nucleic acids, carbohydrates, and phospholipids. The majority of the molecules discussed in this review see limited fragmentation from conventional CID, and the gas phase radical reactions open up completely new dissociation channels for these molecules and therefore yield high fidelity confirmation of the structures of the target molecules. Due to the extensively studied peptide fragmentation, this review focuses only on nonpeptide biomolecules such as nucleic acids, carbohydrates, and phospholipids.

  19. Molecular structure determination of cyclooctane by Ab Initio and electron diffraction methods in the gas phase

    International Nuclear Information System (INIS)

    Almeida, Wagner B. de

    2000-01-01

    The determination of the molecular structure of molecules is of fundamental importance in chemistry. X-rays and electron diffraction methods constitute in important tools for the elucidation of the molecular structure of systems in the solid state and gas phase, respectively. The use of quantum mechanical molecular orbital ab initio methods offer an alternative for conformational analysis studies. Comparison between theoretical results and those obtained experimentally in the gas phase can make a significant contribution for an unambiguous determination of the geometrical parameters. In this article the determination for an unambiguous determination of the geometrical parameters. In this article the determination of the molecular structure of the cyclooctane molecule by electron diffraction in the gas phase an initio calculations will be addressed, providing an example of a comparative analysis of theoretical and experimental predictions. (author)

  20. Spectroscopic Studies on Complex Formation of U(VI)-thiosalicylate

    Energy Technology Data Exchange (ETDEWEB)

    Cha, Wan Sik; Cho, Hye Ryun; Park, Kyoung Kyun; Jung, Euo Chang [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2011-05-15

    The dynamic interaction between radionuclides and organic ligands is largely dependent on the composition of functional groups in a ligand chemical structure. Therefore, the structural mimics of natural ligands possessing specific functional groups, such as hydroxy, phenol, carboxyl, thiol and amine groups, have been studied to understand their influence on the migration of radionuclides including actinide species under geological groundwater conditions. In previous studies, we demonstrated that the fraction of hydrolyzed U(VI) species occurring in weak acidic solutions (pH {approx}4.5) is significantly influenced by the presence of salicylate (Sal) ligand due to the simultaneous participation of both phenol and carboxyl groups in the formation of U(VI)-complexes. Thiosalicylic acid (TSalH{sub 2}) is a good model compound for studying the effects of both carboxyl and thiol (-SH) groups. The fraction of di-anionic ligand form (TSal{sup 2-}) is higher at near neutral pH due to the lower pKa ({approx} 8) of the thiol group than the case of salicylic acid (pKa, {approx}13 for salicylic -OH), despite the structural similarity. In addition, the redox capability of the thiol group is expected to influence the reducible radiouclides and the chemical structures of natural ligands by creating cross-linkage (-S-S-) upon oxidation. The goal of the present study is to investigate aqueous U(VI)-TSal complexation equilibrium via laser-based spectroscopic techniques including time resolved laser-induced fluorescence spectroscopy (TRLFS). In this preliminary work, we report the results of spectroscopic studies using conventional UVVis absorbance and fluorescence (FL) measurement methods. The photo-stability of U(VI)-TSal complex or ligand itself upon exposure to a series of laser pulses is estimated by monitoring the change in their absorption bands. Additionally, TSal FL-quenching effect by U(VI) ions is discussed in comparison with that of Sal FL-quenching

  1. Laser spectroscopy of a halocarbocation in the gas phase: CH2I+.

    Science.gov (United States)

    Tao, Chong; Mukarakate, Calvin; Reid, Scott A

    2006-07-26

    We report the first gas-phase observation of the electronic spectrum of a simple halocarbocation, CH2I+. The ion was generated rotationally cold (Trot approximately 20 K) using pulsed discharge methods and was detected via laser spectroscopy. The identity of the spectral carrier was confirmed by modeling the rotational contour observed in the excitation spectra and by comparison of ground state vibrational frequencies determined by single vibronic level emission spectroscopy with Density Functional Theory (DFT) predictions. The transition was assigned as 3A1 gas phase should open new avenues for study of the structure and reactivity of these important ions.

  2. Gas phase THz spectroscopy of toxic agent simulant compounds using the AILES synchrotron beamline

    Science.gov (United States)

    Cuisset, A.; Smirnova, I.; Bocquet, R.; Hindle, F.; Mouret, G.; Yang, C.; Pirali, O.; Roy, P.

    2010-02-01

    A new study is currently underway aiming at recording and assigning the gas phase rovibrational spectra of several organophosphorus and organosulphur compounds in the THz frequency domain. Thanks to the exceptional properties of flux, brilliance and spectral range of the AILES beamline coupled to the FTIR spectrometer, the gas phase vibrational spectra of low volatility organophosphorous compounds have been recorded across the entire THz frequency range. High resolution FTIR spectroscopy was used to record the pure rotational and the low-frequency rovibrational spectrum of DMSO. A comparison between the spectra measured with the AILES beamline and the spectra obtained with optoelectronic THz sources is possible.

  3. Fischer Indole Synthesis in the Gas Phase, the Solution Phase, and at the Electrospray Droplet Interface.

    Science.gov (United States)

    Bain, Ryan M; Ayrton, Stephen T; Cooks, R Graham

    2017-07-01

    Previous reports have shown that reactions occurring in the microdroplets formed during electrospray ionization can, under the right conditions, exhibit significantly greater rates than the corresponding bulk solution-phase reactions. The observed acceleration under electrospray ionization could result from a solution-phase, a gas-phase, or an interfacial reaction. This study shows that a gas-phase ion/molecule (or ion/ion) reaction is not responsible for the observed rate enhancement in the particular case of the Fischer indole synthesis. The results show that the accelerated reaction proceeds in the microdroplets, and evidence is provided that an interfacial process is involved. Graphical Abstract GRAPHICAL ABSTRACT TEXT HERE] -->.

  4. The Ultrafast Wolff Rearrangement in the Gas Phase

    Science.gov (United States)

    Steinbacher, Andreas; Roeding, Sebastian; Brixner, Tobias; Nuernberger, Patrick

    The Wolff rearrangement of gas-phase 5-diazo Meldrum's acid is disclosed with femtosecond ion spectroscopy. Distinct differences are found for 267 nm and 200 nm excitation, the latter leading to even two ultrafast rearrangement reactions.

  5. Reticulated Vitreous Carbon Electrodes for Gas Phase Pulsed Corona Reactors

    National Research Council Canada - National Science Library

    Locke, B

    1998-01-01

    A new design for gas phase pulsed corona reactors incorporating reticulated vitreous carbon electrodes is demonstrated to be effective for the removal of nitrogen oxides from synthetic air mixtures...

  6. Reticulated Vitreous Carbon Electrodes for Gas Phase Pulsed Corona Reactors

    National Research Council Canada - National Science Library

    LOCKE, B

    1999-01-01

    A new design for gas phase pulsed corona reactors incorporating reticulated vitreous carbon electrodes is demonstrated to be effective for the removal of nitrogen oxides from synthetic air mixtures...

  7. Diode Laser Raman Scattering Prototype Gas-Phase Environmental Monitoring

    National Research Council Canada - National Science Library

    Benner, Robert

    1999-01-01

    We proposed developing a diode-laser-based, full spectrum Raman scattering instrument incorporating a multipass, external cavity enhancement cell for full spectrum, gas phase analysis of environmental pollutants...

  8. Spectroscopic study of photo and thermal destruction of riboflavin

    Science.gov (United States)

    Astanov, Salikh; Sharipov, Mirzo Z.; Fayzullaev, Askar R.; Kurtaliev, Eldar N.; Nizomov, Negmat

    2014-08-01

    Influence of temperature and light irradiation on the spectroscopic properties of aqueous solutions of riboflavin was studied using linear dichroism method, absorption and fluorescence spectroscopy. It was established that in a wide temperature range 290-423 K there is a decline of absorbance and fluorescence ability, which is explained by thermodestruction of riboflavin. It is shown that the proportion of molecules, which have undergone degradation, are in the range of 4-28%, and depends on the concentration and quantity of temperature effects. Introduction of hydrochloric and sulfuric acids, as well as different metal ions leads to an increase in the photostability of riboflavin solutions by 2-2.5 times. The observed phenomena are explained by the formation protonation form of riboflavin and a complex between the metal ions and oxygen atoms of the carbonyl group of riboflavin, respectively.

  9. Raman spectroscopic study of "The Malatesta": a Renaissance painting?

    Science.gov (United States)

    Edwards, Howell G M; Vandenabeele, Peter; Benoy, Timothy J

    2015-02-25

    Raman spectroscopic analysis of the pigments on an Italian painting described as a "Full Length Portrait of a Gentleman", known also as the "Malatesta", and attributed to the Renaissance period has established that these are consistent with the historical research provenance undertaken earlier. Evidence is found for the early 19th Century addition of chrome yellow to highlighted yellow ochre areas in comparison with a similar painting executed in 1801 by Sir Thomas Lawrence of John Kemble in the role of Hamlet, Prince of Denmark. The Raman data are novel in that no analytical studies have previously been made on this painting and reinforces the procedure whereby scientific analyses are accompanied by parallel historical research. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. A detailed spectroscopic study of an Italian fresco

    International Nuclear Information System (INIS)

    Barilaro, Donatella; Crupi, Vincenza; Majolino, Domenico; Barone, Germana; Ponterio, Rosina

    2005-01-01

    In the present work we characterized samples of plasters and pictorial layers taken from a fresco in the Acireale Cathedral. The fresco represents the Coronation of Saint Venera, patron saint of this Ionian town. By performing a detailed spectroscopic analysis of the plaster preparation layer by Fourier-transform infrared (FTIR) spectroscopy and x-ray diffraction (XRD), and of the painting layer by FTIR and confocal Raman microspectroscopy, scanning electron microscopy+energy dispersive x-ray spectroscopy, and XRD, we were able to identify the pigments and the binders present. In particular, Raman investigation was crucial to the characterization of the pigments thanks to the high resolution of the confocal apparatus used. It is worth stressing that the simultaneous use of complementary techniques was able to provide more complete information for the conservation of the artifact we studied

  11. Precision electron-gamma spectroscopic studies in 111Cd

    International Nuclear Information System (INIS)

    Sai Vignesh, T.; Chhetri, Premaditya; Vijay Sai, K.; Gowrishankar, R.; Venkataramaniah, K.; Deepa, S.; Rao, Dwarakarani; Kailas, S.

    2011-01-01

    The energy levels of 111 Cd has formerly been considered in terms of the states available to the 63rd neutron which is in the 3s 1/2 sub-shell. Kisslinger and Sorensen have used the pairing plus-quadrupole model to predict the energy levels. In the Coulomb excitation experiment only five levels have been excited. The decay of 111 Ag has been investigated only by few workers, Burmistov and Didorenko, Shevlev et al and Goswamy et al. The previous data on level energies, gamma energies and intensities differ considerably even for intense gamma transitions. There has been no detailed study of the internal conversion spectrum. There have been no multipolarity assignments for some of the transitions. An extensive experimental investigation of the gamma and conversion electron spectra has been undertaken to provide precision spectroscopic information on the low lying levels of 111 Cd from the beta decay of 111 Ag

  12. Molecular spectroscopic study for suggested mechanism of chrome tanned leather

    Science.gov (United States)

    Nashy, Elshahat H. A.; Osman, Osama; Mahmoud, Abdel Aziz; Ibrahim, Medhat

    2012-03-01

    Collagen represents the structural protein of the extracellular matrix, which gives strength of hides and/or skin under tanning process. Chrome tan is the most important tanning agent all over the world. The methods for production of leather evolved over several centuries as art and engineering with little understanding of the underlying science. The present work is devoted to suggest the most probable mechanistic action of chrome tan on hide proteins. First the affect of Cr upon hide protein is indicated by the studied mechanical properties. Then the spectroscopic characterization of the hide protein as well as chrome tanned leather was carried out with Horizontal Attenuated Total Reflection (HATR) FT-IR. The obtained results indicate how the chromium can attached with the active sites of collagen. Molecular modeling confirms that chromium can react with amino as well as carboxylate groups. Four schemes were obtained to describe the possible interactions of chrome tan with hide proteins.

  13. Comparison of catalytic ethylene polymerization in slurry and gas phase

    OpenAIRE

    Daftaribesheli, Majid

    2009-01-01

    Polyethylene (PE) with the annual consumption of 70 million tones in 2007 is mostly produced in slurry, gas-phase or combination of both processes. This work focuses on a comparison between the slurry and gas phase processes. Why does PE produced in theses two processes can show extremely different properties and extremely different reaction behaviour even if the same Ziegler-Natta (ZN) catalyst is used? Generally, it is known that the reason can be found in the differences of local condition...

  14. Heterogeneity-enhanced gas phase formation in shallow aquifers during leakage of CO2-saturated water from geologic sequestration sites

    DEFF Research Database (Denmark)

    Plampin, Michael R.; Lassen, Rune Nørbæk; Sakaki, Toshihiro

    2014-01-01

    sands. Soil moisture sensors were utilized to observe the formation of gas phase near the porous media interfaces. Results indicate that the conditions under which heterogeneity controls gas phase evolution can be successfully predicted through analysis of simple parameters, including the dissolved CO2......, it is important to understand the physical processes that CO2 will undergo as it moves through naturally heterogeneous porous media formations. Previous studies have shown that heterogeneity can enhance the evolution of gas phase CO2 in some cases, but the conditions under which this occurs have not yet been...... quantitatively defined, nor tested through laboratory experiments. This study quantitatively investigates the effects of geologic heterogeneity on the process of gas phase CO2 evolution in shallow aquifers through an extensive set of experiments conducted in a column that was packed with layers of various test...

  15. Generation, Detection and characterization of Gas-Phase Transition Metal containing Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Steimle, Timothy [Arizona State Univ., Tempe, AZ (United States)

    2015-12-15

    The objective of this project was to generate, detect, and characterize small, gas-phase, metal containing molecules. In addition to being relevant to high temperature chemical environments (e.g. plasmas and combustion), gas-phase experiments on metal containing molecules serve as the most direct link to a molecular-level theoretical model for catalysis. Catalysis (i.e. the addition of a small about of recoverable material to control the rate and direction of a chemical reaction) is critical to the petroleum and pharmaceutical industries as well as environmental remediation. Currently, the majority of catalytic materials are based on very expensive metals such as platinum (Pt), palladium (Pd), iridium (Ir,) rhenium (Re), and rhodium (Rh). For example, the catalyst used for converting linear hydrocarbon molecules (e.g. hexane) to cyclic molecules (e.g. cyclohexane) is a mixture of Pt and Re suspended on alumina. It enables straight chain alkanes to be converted into branched-chain alkanes, cyclohexanes and aromatic hydrocarbons which are used, amongst other things, to enhance the octane number of petrol. A second example is the heterogeneous catalysis used in automobile exhaust systems to: a) decrease nitrogen oxide; b) reduce carbon monoxide; and c) oxidize unburned hydrocarbons. The exhaust is vented through a high-surface area chamber lined with Pt, Pd, and Rh. For example, the carbon monoxide is catalytically converted to carbon dioxide by reaction with oxygen. The research results from this work have been published in readily accessible journals1-28. The ground and excited electronic state properties of small metal containing molecules that we determine were: a) electronic state distributions and lifetimes, b) vibrational frequencies, c) bond lengths and angles, d) hyperfine interactions, e) permanent electric dipole moments, mel, and f) magnetic dipoles, μm. In general terms, μel, gives insight into the charge distribution and mm into

  16. Raman spectroscopic study of some chalcopyrite-xanthate flotation products

    CSIR Research Space (South Africa)

    Andreev, GN

    2003-12-16

    Full Text Available of normal vibrations of the corresponding individual compounds. The latter facilitated the Raman spectroscopic elucidation of the reaction products formed on the chalcopyrite surface in real industrial flotation conditions with a sodium isopropyl xanthate...

  17. A gas phase work station for the Brazilian National Synchrotron Laboratory

    International Nuclear Information System (INIS)

    Souza, G.G.B. de

    1988-01-01

    A gas phase work station which has been proposed to the Brazilian National Synchrotron Laboratory is described with emphasis on the broad spectrum of physical and chemical processes which can be studied with the incorporated instrumentation. (A.C.A.S.) [pt

  18. Gas-phase salt bridge interactions between glutamic acid and arginine

    NARCIS (Netherlands)

    Jaeqx, S.; Oomens, J.; Rijs, A.M.

    2013-01-01

    The gas-phase side chain-side chain (SC-SC) interaction and possible proton transfer between glutamic acid (Glu) and arginine (Arg) residues are studied under low-temperature conditions in an overall neutral peptide. Conformation-specific IR spectra, obtained with the free electron laser FELIX, in

  19. Operando Spectroscopy of the Gas-Phase Aldol Condensation of Propanal over Solid Base Catalysts

    NARCIS (Netherlands)

    Hernández-giménez, Ana M.; Ruiz-martínez, Javier; Puértolas, Begoña; Pérez-ramírez, Javier; Bruijnincx, Pieter C. A.; Weckhuysen, Bert M.

    2017-01-01

    The gas-phase aldol condensation of propanal, taken as model for the aldehyde components in bio-oils, has been studied with a combined operando set-up allowing to perform FT-IR & UV–Vis diffuse reflectance spectroscopy (DRS) with on-line mass spectrometry (MS). The selected solid base catalysts, a

  20. Gas-phase photoemission with soft x-rays: cross sections and angular distributions

    International Nuclear Information System (INIS)

    Shirley, D.A.; Kobrin, P.H.; Truesdale, C.M.; Lindle, D.W.; Ferrett, T.A.; Heimann, P.A.; Becker, U.; Kerkhoff, H.G.; Southworth, S.H.

    1983-09-01

    A summary is presented of typical gas-phase photoemission studies based on synchrotron radiation in the 50-5000 eV range, using beam lines at the Stanford Synchrotron Radiation Laboratory. Three topics are addressed: atomic inner-shell photoelectron cross sections and asymmetries, correlation peaks in rare gases, and core-level shape resonances in molecules

  1. Particle in a Disk: A Spectroscopic and Computational Laboratory Exercise Studying the Polycyclic Aromatic Hydrocarbon Corannulene

    Science.gov (United States)

    Frey, E. Ramsey; Sygula, Andrzej; Hammer, Nathan I.

    2014-01-01

    This laboratory exercise introduces undergraduate chemistry majors to the spectroscopic and theoretical study of the polycyclic aromatic hydrocarbon (PAH), corannulene. Students explore the spectroscopic properties of corannulene using UV-vis and Raman vibrational spectroscopies. They compare their experimental results to simulated vibrational…

  2. FTIR spectroscopic studies of bacterial cellular responses to environmental factors, plant-bacterial interactions and signalling

    OpenAIRE

    Kamnev, Alexander A.

    2008-01-01

    Modern spectroscopic techniques are highly useful in studying diverse processes in microbial cells related to or incited by environmental factors. Spectroscopic data for whole cells, supramolecular structures or isolated cellular constituents can reflect structural and/or compositional changes occurring in the course of cellular metabolic responses to the effects of pollutants, environmental conditions (stress factors); nutrients, signalling molecules (communication factors), etc. This inform...

  3. Multiple Multidentate Halogen Bonding in Solution, in the Solid State, and in the (Calculated) Gas Phase.

    Science.gov (United States)

    Jungbauer, Stefan H; Schindler, Severin; Herdtweck, Eberhardt; Keller, Sandro; Huber, Stefan M

    2015-09-21

    The binding properties of neutral halogen-bond donors (XB donors) bearing two multidentate Lewis acidic motifs toward halides were investigated. Employing polyfluorinated and polyiodinated terphenyl and quaterphenyl derivatives as anion receptors, we obtained X-ray crystallographic data of the adducts of three structurally related XB donors with tetraalkylammonium chloride, bromide, and iodide. The stability of these XB complexes in solution was determined by isothermal titration calorimetry (ITC), and the results were compared to X-ray analyses as well as to calculated binding patterns in the gas phase. Density functional theory (DFT) calculations on the gas-phase complexes indicated that the experimentally observed distortion of the XB donors during multiple multidentate binding can be reproduced in 1:1 complexes with halides, whereas adducts with two halides show a symmetric binding pattern in the gas phase that is markedly different from the solid state structures. Overall, this study demonstrates the limitations in the transferability of binding data between solid state, solution, and gas phase in the study of complex multidentate XB donors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Biofilm structure and mass transfer in a gas phase trickle-bed biofilter.

    Science.gov (United States)

    Zhu, X; Suidan, M T; Alonso, C; Yu, T; Kim, B J; Kim, B R

    2001-01-01

    Mass transport phenomena occurring in the biofilms of gas phase trickle-bed biofilters are investigated in this study. The effect of biofilm structure on mass transfer mechanisms is examined using experimental observation from the operating of biofilters, microelectrode techniques and microscopic examination. Since the biofilms of biofilters used for waste gas treatment are not completely saturated with water, there is not a distinguishable liquid layer outside the biofilm. Results suggest that due to this characteristic, gas phase substrates (such as oxygen or volatile organic compounds) may not be limited by the aqueous phase because transport of the compound into the biofilm can occur directly through non-wetted areas. On the other hand, for substrates that are present only in the liquid phase, such as nitrate, the mass transfer limitation is more serious because of the limited liquid supply. Microscopic observations show that a layered structure with void spaces exists within the biofilm. Oxygen concentration distributions along the depth of the biofilms are examined using an oxygen microelectrode. Results indicate that there are some high dissolved oxygen zones inside the biofilm, which suggests the existence of passages for oxygen transfer into the deeper sections of the biofilm in a gas phase trickle-bed biofilter. Both the low gas-liquid mass transfer resistance and the resulting internal structure contribute to the high oxygen penetration within the biofilms in gas phase trickle-bed biofilters.

  5. A spectroscopic study of uranium species formed in chloride melts

    International Nuclear Information System (INIS)

    Volkovich, Vladimir A.; Bhatt, Anand I.; May, Iain; Griffiths, Trevor R.; Thied, Robert C.

    2002-01-01

    The chlorination of uranium metal or uranium oxides in chloride melts offers an acceptable process for the head-end of pyrochemical reprocessing of spent nuclear fuels. The reactions of uranium metal and ceramic uranium dioxide with chlorine and with hydrogen chloride were studied in the alkali metal chloride melts, NaCl-KCl at 973K, NaCl-CsCl between 873 and 923K and LiCl-KCl at 873K. The uranium species formed therein were characterized from their electronic absorption spectra measured in situ. The kinetic parameters of the reactions depend on melt composition, temperature and chlorinating agent used. The reaction of uranium dioxide with oxygen in the presence of alkali metal chlorides results in the formation of alkali metal uranates. A spectroscopic study, between 723 and 973K, on their formation and their solutions was undertaken in LiCl, LiCl-KCl eutectic and NaCl-CsCl eutectic melts. The dissolution of uranium dioxide in LiCl-KCl eutectic at 923K containing added aluminium trichloride in the presence of oxygen has also been investigated. In this case, the reaction leads to the formation of uranyl chloride species. (author)

  6. Spectroscopic Studies of Molecular Systems relevant in Astrobiology

    Science.gov (United States)

    Fornaro, Teresa

    2016-01-01

    In the Astrobiology context, the study of the physico-chemical interactions involving "building blocks of life" in plausible prebiotic and space-like conditions is fundamental to shed light on the processes that led to emergence of life on Earth as well as to molecular chemical evolution in space. In this PhD Thesis, such issues have been addressed both experimentally and computationally by employing vibrational spectroscopy, which has shown to be an effective tool to investigate the variety of intermolecular interactions that play a key role in self-assembling mechanisms of nucleic acid components and their binding to mineral surfaces. In particular, in order to dissect the contributions of the different interactions to the overall spectroscopic signals and shed light on the intricate experimental data, feasible computational protocols have been developed for the characterization of the spectroscopic properties of such complex systems. This study has been carried out through a multi-step strategy, starting the investigation from the spectroscopic properties of the isolated nucleobases, then studying the perturbation induced by the interaction with another molecule (molecular dimers), towards condensed phases like the molecular solid, up to the case of nucleic acid components adsorbed on minerals. A proper modeling of these weakly bound molecular systems has required, firstly, a validation of dispersion-corrected Density Functional Theory methods for simulating anharmonic vibrational properties. The isolated nucleobases and some of their dimers have been used as benchmark set for identifying a general, reliable and effective computational procedure based on fully anharmonic quantum mechanical computations of the vibrational wavenumbers and infrared intensities within the generalized second order vibrational perturbation theory (GVPT2) approach, combined with the cost-effective dispersion-corrected density functional B3LYP-D3, in conjunction with basis sets of

  7. Deliberate and Accidental Gas-Phase Alkali Doping of Chalcogenide Semiconductors: Cu(In,Ga)Se2.

    Science.gov (United States)

    Colombara, Diego; Berner, Ulrich; Ciccioli, Andrea; Malaquias, João C; Bertram, Tobias; Crossay, Alexandre; Schöneich, Michael; Meadows, Helene J; Regesch, David; Delsante, Simona; Gigli, Guido; Valle, Nathalie; Guillot, Jérome; El Adib, Brahime; Grysan, Patrick; Dale, Phillip J

    2017-02-24

    Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se 2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gas-phase alkali transport in the kesterite sulfide (Cu 2 ZnSnS 4 ) system (re)open the way to a novel gas-phase doping strategy. However, the current understanding of gas-phase alkali transport is very limited. This work (i) shows that CIGSe device efficiency can be improved from 2% to 8% by gas-phase sodium incorporation alone, (ii) identifies the most likely routes for gas-phase alkali transport based on mass spectrometric studies, (iii) provides thermochemical computations to rationalize the observations and (iv) critically discusses the subject literature with the aim to better understand the chemical basis of the phenomenon. These results suggest that accidental alkali metal doping occurs all the time, that a controlled vapor pressure of alkali metal could be applied during growth to dope the semiconductor, and that it may have to be accounted for during the currently used solid state doping routes. It is concluded that alkali gas-phase transport occurs through a plurality of routes and cannot be attributed to one single source.

  8. Atomic and molecular physics in the gas phase

    International Nuclear Information System (INIS)

    Toburen, L.H.

    1990-09-01

    The spatial and temporal distributions of energy deposition by high-linear-energy-transfer radiation play an important role in the subsequent chemical and biological processes leading to radiation damage. Because the spatial structures of energy deposition events are of the same dimensions as molecular structures in the mammalian cell, direct measurements of energy deposition distributions appropriate to radiation biology are infeasible. This has led to the development of models of energy transport based on a knowledge of atomic and molecular interactions process that enable one to simulate energy transfer on an atomic scale. Such models require a detailed understanding of the interactions of ions and electrons with biologically relevant material. During the past 20 years there has been a great deal of progress in our understanding of these interactions; much of it coming from studies in the gas phase. These studies provide information on the systematics of interaction cross sections leading to a knowledge of the regions of energy deposition where molecular and phase effects are important and that guide developments in appropriate theory. In this report studies of the doubly differential cross sections, crucial to the development of stochastic energy deposition calculations and track structure simulation, will be reviewed. Areas of understanding are discussed and directions for future work addressed. Particular attention is given to experimental and theoretical findings that have changed the traditional view of secondary electron production for charged particle interactions with atomic and molecular targets

  9. Nonplanar property study of antifungal agent tolnaftate-spectroscopic approach

    Science.gov (United States)

    Arul Dhas, D.; Hubert Joe, I.; Roy, S. D. D.; Balachandran, S.

    2011-09-01

    Vibrational analysis of the thionocarbamate fungicide tolnaftate which is antidermatophytic, antitrichophytic and antimycotic agent, primarily inhibits the ergosterol biosynthesis in the fungus, was carried out using NIR FT-Raman and FTIR spectroscopic techniques. The equilibrium geometry, various bonding features, harmonic vibrational wavenumbers and torsional potential energy surface (PES) scan studies have been computed using density functional theory method. The detailed interpretation of the vibrational spectra has been carried out with the aid of VEDA.4 program. Vibrational spectra, natural bonding orbital (NBO) analysis and optimized molecular structure show the clear evidence for electronic interaction of thionocarbamate group with aromatic ring. Predicted electronic absorption spectrum from TD-DFT calculation has been compared with the UV-vis spectrum. The Mulliken population analysis on atomic charges and the HOMO-LUMO energy were also calculated. Vibrational analysis reveals that the simultaneous IR and Raman activation of the C-C stretching mode in the phenyl and naphthalene ring provide evidence for the charge transfer interaction between the donor and acceptor groups and is responsible for its bioactivity as a fungicide.

  10. Molecular docking, spectroscopic studies and quantum calculations on nootropic drug.

    Science.gov (United States)

    Uma Maheswari, J; Muthu, S; Sundius, Tom

    2014-04-05

    A systematic vibrational spectroscopic assignment and analysis of piracetam [(2-oxo-1-pyrrolidineacetamide)] have been carried out using FT-IR and FT-Raman spectral data. The vibrational analysis was aided by an electronic structure calculation based on the hybrid density functional method B3LYP using a 6-311G++(d,p) basis set. Molecular equilibrium geometries, electronic energies, IR and Raman intensities, and harmonic vibrational frequencies have been computed. The assignments are based on the experimental IR and Raman spectra, and a complete assignment of the observed spectra has been proposed. The UV-visible spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies and the maximum absorption wavelengths λmax were determined by the time-dependent DFT (TD-DFT) method. The geometrical parameters, vibrational frequencies and absorption wavelengths were compared with the experimental data. The complete vibrational assignments are performed on the basis of the potential energy distributions (PED) of the vibrational modes in terms of natural internal coordinates. The simulated FT-IR, FT-Raman, and UV spectra of the title compound have been constructed. Molecular docking studies have been carried out in the active site of piracetam by using Argus Lab. In addition, the potential energy surface, HOMO and LUMO energies, first-order hyperpolarizability and the molecular electrostatic potential have been computed. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Near-Infrared Spectroscopic Study of Chlorite Minerals

    Directory of Open Access Journals (Sweden)

    Min Yang

    2018-01-01

    Full Text Available The mineral chemistry of twenty chlorite samples from the United States Geological Survey (USGS spectral library and two other regions, having a wide range of Fe and Mg contents and relatively constant Al and Si contents, was studied via infrared (IR spectroscopy, near-infrared (NIR spectroscopy, and X-ray fluorescence (XRF analysis. Five absorption features of the twenty samples near 4525, 4440, 4361, 4270, and 4182 cm−1 were observed, and two diagnostic features at 4440 and 4280 cm−1 were recognized. Assignments of the two diagnostic features were made for two combination bands (ν+δAlAlO−OH and ν+δSiAlO−OH by regression with IR fundamental absorptions. Furthermore, the determinant factors of the NIR band position were found by comparing the band positions with relative components. The results showed that Fe/(Fe + Mg values are negatively correlated with the two NIR combination bands. The findings provide an interpretation of the NIR band formation and demonstrate a simple way to use NIR spectroscopy to discriminate between chlorites with different components. More importantly, spectroscopic detection of mineral chemical variations in chlorites provides geologists with a tool with which to collect information on hydrothermal alteration zones from hyperspectral-resolution remote sensing data.

  12. Spectroscopic and electrochemical study of polynuclear clusters from ruthenium acetate

    International Nuclear Information System (INIS)

    Cipriano, C.

    1989-01-01

    The chemistry of the trinuclear clusters [Ru sub(3) O (CH sub(3) CO sub(2)) sub(4) L sub(3)] where L = imidazole, pyridine or pyrazine type of ligands, was investigated based on spectroscopic and electrochemical techniques. These complexes are of great interest from the point of view of their electronic and redox properties, providing multisite species for electron transfer processes. They were isolated in solid state, and characterized by means of elementary analyses and infrared spectra. The electrochemical behaviour in acetonitrile solution was typically reversible; the cyclic voltammograms exhibited a series of four or five mono electronic waves ascribed to the sucessive Ru sup(IV) Ru sup(III) Ru sup(III) / Ru sup(III) Ru sup(III) Ru sup(III)/ --- Ru sup(II) Ru sup(II) Ru sup(II) redox couples. The differences between the successive redox potentials were about 1 V, indicating strong metal-metal interaction in the trinuclear Ru sub(3) centre. The E values were strongly sensitive to the nature of the N-heterocyclic ligand, increasing with the pi-acceptor properties of the pyridine and pyrazine derivatives, but in a much less pronounced way in the case of the imidazole derivatives. Resonance Raman studies for the pyrazine cluster showed selective intensification of the vibrational modes of the Ru-pyrazine chromophore, and the trinuclear centre, using excitation wavelengths coinciding with the metal-to-pyrazine and metal-metal bands, respectively. (author)

  13. Spectroscopic study on a thermoelectron-enhanced microplasma jet

    International Nuclear Information System (INIS)

    Ito, Tsuyohito; Nishiyama, Hiroyuki; Terashima, Kazuo; Sugimoto, Kyozo; Yoshikawa, Hirohisa; Takahashi, Hideaki; Sakurai, Takeki

    2004-01-01

    An Ar thermoelectron-enhanced microplasma (TEMP) jet was characterized by spectroscopic study. The 1s 5 lowest metastable densities at the core of the plasma and very close to the substrate, about 4 mm apart from the torch, were obtained successfully using laser absorption spectroscopy (LAS) and laser induced evanescent-mode fluorescence spectroscopy (LIEF). For TEMP generated with 450 MHz, 5 W and 60 Torr, these densities were estimated to be about 3 x 10 12 cm -3 and about 10 10 cm -3 , by the LAS and LIEF methods, respectively. Moreover, gaseous temperature was also estimated as about 700 K by the LAS method. Depopulation of the 1s 5 metastable atoms might be caused primarily by gaseous diffusion between the torch and the substrate. Finally, we report a device with a TEMP generator at the top of a flexible fibre called the 'plasma fibre', which allows plasma processing in any location, as with laser processing using an optical fibre. This article was due to be published in issue 23 of 2003. To access this special issue, please follow this link: http://www.iop.org/EJ/toc/0022-3727/36/23

  14. Moessbauer spectroscopic studies of hemoglobin and its isolated subunits

    International Nuclear Information System (INIS)

    Hoy, G.R.; Cook, D.C.; Berger, R.L.; Friedman, F.K.

    1986-01-01

    Samples of 90% enriched 57Fe hemoglobin and its isolated subunits have been prepared. Moessbauer spectroscopic measurements have been made on three such samples. Sample one contained contributions of oxyhemoglobin, deoxyhemoglobin, and carbonmonoxyhemoglobin. This sample was studied from a temperature of 90 K down to 230 mK. Measurements were also made at 4.2 K using a small applied magnetic field of 1.0 T. In general, the measured quadrupole splittings and isomer shifts for each component agreed with previous measurements on single component samples in the literature, and thus demonstrated that chemically enriched hemoglobin has not been altered. The second and third samples were isolated alpha and beta subunits, respectively. We have found measurable Moessbauer spectral differences between the HbO 2 sites in the alpha subunit sample and the beta subunit sample. The measured Moessbauer spectral areas indicate that the iron ion has the largest mean-square displacement at the deoxy Hb sites as compared to that at the oxy- and carbonmonoxy Hb sites. The mean-square displacement at the HbO 2 sites is the smallest

  15. Gas Phase Sulfur, Chlorine and Potassium Chemistry in Biomass Combustion

    DEFF Research Database (Denmark)

    Løj, Lusi Hindiyarti

    2007-01-01

    Gas Phase Sulfur, Chlorine and Alkali Metal Chemistry in Biomass Combustion Concern about aerosols formation, deposits, corrosion, and gaseous emissions during biomass combustion, especially straw, continues to be a driving force for investigation on S, Cl, K-containing species under combustions...... conditions. These trace species contained in the biomass structure will be released to the gas phase during combustion and contribute to the problems generated during the process. The investigation during this PhD project is done to stepwise improve the understanding in the chemistry and reduce...... the uncertainties. In the present work, the detailed kinetic model for gas phase sulfur, chlorine, alkali metal, and their interaction has been updated. The K/O/H/Cl chemistry, S chemistry, and their interaction can reasonably predict a range of experimental data. In general, understanding of the interaction...

  16. Nucleation and dissociation of nano-particles in gas phase

    International Nuclear Information System (INIS)

    Feiden, P.

    2007-09-01

    This work deals with the study of nano-particles formation in gas phase and their dissociation pathways after an optical excitation. The clusters formation decomposes in two steps: a seed is formed (nucleation phase) and sticks atoms during its propagation in a sodium atomic vapor (growth phase). Those two steps have been observed separately for homogeneous Na n and heterogeneous Na n X particles (X = (NaOH) 2 or (Na 2 O) 2 ). The growth mechanism is well interpreted by a Monte Carlo simulation taking into account an accretion mechanism with hard-sphere cross section. The homogeneous nucleation mechanism has been highlighted by a direct comparison with the Classical Nucleation Theory predictions. The clusters fragmentation of ionic Na + (NaOH) p et Na + (NaF) p particles is studied in the second part. The way clusters fragment with size when they are excited optically is compared with theoretical previsions: this highlights the existence of an energetic barrier for special size of clusters. Finally, the fragmentation of doubly charged Na + Na + (NaOH) p clusters shows a competition between the fission into two single charged fragments and the unimolecular evaporation of a neutral fragment. (author)

  17. In search of the X{sub 2}BO and X{sub 2}BS (X = H, F) free radicals: Ab initio studies of their spectroscopic signatures

    Energy Technology Data Exchange (ETDEWEB)

    Clouthier, Dennis J., E-mail: dclaser@uky.edu [Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055 (United States)

    2014-12-28

    The F{sub 2}BO free radical is a known, although little studied, species but similar X{sub 2}BY (X = H, D, F; Y = O, S) molecules are largely unknown. High level ab initio methods have been used to predict the molecular structures, vibrational frequencies (in cm{sup −1}), and relative energies of the ground and first two excited electronic states of these free radicals, as an aid to their eventual spectroscopic identification. The chosen theoretical methods and basis sets were tested on F{sub 2}BO and found to give good agreement with the known experimental quantities. In particular, complete basis set extrapolations of coupled-cluster single and doubles with perturbative triple excitations/aug-cc-pVXZ (X = 3, 4, 5) energies gave excellent electronic term values, due to small changes in geometry between states and the lack of significant multireference character in the wavefunctions. The radicals are found to have planar C{sub 2v} geometries in the X{sup ~2}B{sub 2} ground state, the low-lying A{sup ~2}B{sub 1} first excited state, and the higher B{sup ~2}A{sub 1} state. Some of these radicals have very small ground state dipole moments hindering microwave measurements. Infrared studies in matrices or in the gas phase may be possible although the fundamentals of H{sub 2}BO and H{sub 2}BS are quite weak. The most promising method of identifying these species in the gas phase appears to be absorption or laser-induced fluorescence spectroscopy through the allowed B{sup ~}-X{sup ~} transitions which occur in the visible-near UV region of the electromagnetic spectrum. The ab initio results have been used to calculate the Franck-Condon profiles of the absorption and emission spectra, and the rotational structure of the B{sup ~}-X{sup ~}0{sub 0}{sup 0} bands has been simulated. The calculated single vibronic level emission spectra provide a unique, readily recognizable fingerprint of each particular radical, facilitating the experimental identification of new X{sub 2}BY

  18. The Stability of CI02 as a Product of Gas Phase Decontamination Treatments

    International Nuclear Information System (INIS)

    Simmons, D. W.

    1994-01-01

    The gas phase decontamination project is investigating the use of chlorine trifluoride (ClF 3 ) to fluorinate nonvolatile uranium deposits to produce uranium hexafluoride (UF 6 ) gas. The potential existence of chlorine dioxide (ClO 2 ) during gas phase decontamination with ClF 3 has been the subject of recent safety discussions. Some of the laboratory data collected during feasibility studies of the gas phase process has been evaluated for the presence of ClO 2 in the product gas stream. The preliminary evidence to date can be summarized as follows: (1) ClO 2 was not detected in the flow loop in the absence of ClF 3 ; (2) ClO 2 was not detected in the static reactors in the absence of both ClF 3 and ClF; and (3) ClO 2 was detected in a static reactor in the absence of all fluorinating gases. The experimental evidence suggests that ClO 2 will not exist in the presence of ClF 3 , ClF, or UF 6 . The data analyzed to date is insufficient to determine the stability of ClO 2 in the presence of ClO 2 F. Thermodynamic calculations of the ClF 3 + H 2 O system support the experimental evidence, and suggest that ClO 2 will not exist in the presence of ClO 2 F. Additional experimental efforts are needed to provide a better understanding of the gas phase ClF 3 treatments and the product gases. However, preliminary evidence to date suggests that ClO 2 should not be present as a product during the normal operations of the gas phase decontamination project

  19. The Stability of CI02 as a Product of Gas Phase Decontamination Treatments

    Energy Technology Data Exchange (ETDEWEB)

    D. W. Simmons

    1994-09-01

    The gas phase decontamination project is investigating the use of chlorine trifluoride (ClF{sub 3}) to fluorinate nonvolatile uranium deposits to produce uranium hexafluoride (UF{sub 6}) gas. The potential existence of chlorine dioxide (ClO{sub 2}) during gas phase decontamination with ClF{sub 3} has been the subject of recent safety discussions. Some of the laboratory data collected during feasibility studies of the gas phase process has been evaluated for the presence of ClO{sub 2} in the product gas stream. The preliminary evidence to date can be summarized as follows: (1) ClO{sub 2} was not detected in the flow loop in the absence of ClF{sub 3}; (2) ClO{sub 2} was not detected in the static reactors in the absence of both ClF{sub 3} and ClF; and (3) ClO{sub 2} was detected in a static reactor in the absence of all fluorinating gases. The experimental evidence suggests that ClO{sub 2} will not exist in the presence of ClF{sub 3}, ClF, or UF{sub 6}. The data analyzed to date is insufficient to determine the stability of ClO{sub 2} in the presence of ClO{sub 2}F. Thermodynamic calculations of the ClF{sub 3} + H{sub 2}O system support the experimental evidence, and suggest that ClO{sub 2} will not exist in the presence of ClO{sub 2}F. Additional experimental efforts are needed to provide a better understanding of the gas phase ClF{sub 3} treatments and the product gases. However, preliminary evidence to date suggests that ClO{sub 2} should not be present as a product during the normal operations of the gas phase decontamination project.

  20. Gas-phase photocatalysis in μ-reactors

    DEFF Research Database (Denmark)

    Vesborg, Peter Christian Kjærgaard; Olsen, Jakob Lind; Henriksen, Toke Riishøj

    2010-01-01

    Gas-phase photocatalysis experiments may benefit from the high sensitivity and good time response in product detection offered by μ-reactors. We demonstrate this by carrying out CO oxidation and methanol oxidation over commercial TiO2 photocatalysts in our recently developed high-sensitivity reac......Gas-phase photocatalysis experiments may benefit from the high sensitivity and good time response in product detection offered by μ-reactors. We demonstrate this by carrying out CO oxidation and methanol oxidation over commercial TiO2 photocatalysts in our recently developed high...

  1. Post-flame gas-phase sulfation of potassium chloride

    DEFF Research Database (Denmark)

    Li, Bo; Sun, Zhiwei; Li, Zhongshan

    2013-01-01

    The sulfation of KCl during biomass combustion has implications for operation and emissions: it reduces the rates of deposition and corrosion, it increases the formation of aerosols, and it leads to higher concentrations of HCl and lower concentrations of SO2 in the gas phase. Rigorously homogene......The sulfation of KCl during biomass combustion has implications for operation and emissions: it reduces the rates of deposition and corrosion, it increases the formation of aerosols, and it leads to higher concentrations of HCl and lower concentrations of SO2 in the gas phase. Rigorously...

  2. Device to remove hydrogen isotopes from a gas phase

    International Nuclear Information System (INIS)

    Morlock, G.; Wiesemes, J.; Bachner, D.

    1977-01-01

    The device described here guarantees the selective removal of hydrogen isotopes from gas phases in order to prevent the occurence of explosive H 2 gas mixtures, or to separate off radioactive tritium in nuclear plants from the gas phase. It consists of a closed container whose walls are selectively penetrable by hydrogen isotopes. It is simultaneously filled compactly and presssure-resistant with a metal bulk (e.g. powder, sponges or the like of titanium or other hydrogen isotope binding metal). Walling and bulk are maintained at suitable working temperatures by means of a system according to the Peltier effect. The whole thing is safeguarded by protective walling. (RB) [de

  3. Reactive intermediates in the gas phase generation and monitoring

    CERN Document Server

    Setser, D W

    2013-01-01

    Reactive Intermediates in the Gas Phase: Generation and Monitoring covers methods for reactive intermediates in the gas phase. The book discusses the generation and measurement of atom and radical concentrations in flow systems; the high temperature flow tubes, generation and measurement of refractory species; and the electronically excited long-lived states of atoms and diatomic molecules in flow systems. The text also describes the production and detection of reactive species with lasers in static systems; the production of small positive ions in a mass spectrometer; and the discharge-excite

  4. Electrochemical and spectroscopic study on thiolation of polyaniline

    International Nuclear Information System (INIS)

    Blomquist, Maija; Bobacka, Johan; Ivaska, Ari; Levon, Kalle

    2013-01-01

    Highlights: ► We have thiolated and characterized polyaniline films in order to verify that the thiolation process has taken place. ► Such extensive characterization of thiolation of polyaniline has not previously been reported. ► Thiolation alters the electrochemical properties of polyaniline and the process should be understood. ► Through thiolation many reactive groups may covalently be bound to the polymer backbone. ► Possibility of covalent binding makes polyaniline films an attractive substrate for, e.g., biosensors. -- Abstract: Polyaniline (PANI) is a conducting polymer, easily synthesized and lucrative for many electrochemical applications like ion-selective sensors and biosensors. Thiolated molecules, including biological ones, can be bound by nucleophilic attachment to the polyaniline backbone. These covalently bound thiols add functionality to PANI, but also cause changes in the electrochemical properties of PANI. Polyaniline studied in this work was electropolymerized on glassy carbon electrodes. 2-Mercaptoethanol (MCE) and 6-(ferrocenyl)hexanethiol (FCHT) were used as the thiols to form functionalized films. The films were characterized by cyclic voltammetry (CV), ex situ FTIR and Raman spectroscopies, electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS). The goal of this work was to confirm the thiolation by spectroscopic methods and to study the impact of thiolation on the electrochemical properties of PANI. Our study showed that thiolated PANI has different electrochemical properties than PANI. Although the thiolation partially reduced the PANI backbone it still remained conductive after the thiolation. Detailed understanding of the thiolation process can be very useful for future applications of PANI

  5. Raman spectroscopic studies of optically trapped red blood cells

    International Nuclear Information System (INIS)

    Dasgupta, R.; Gupta, P.K.

    2010-01-01

    Raman spectroscopic studies were performed on optically trapped red blood cells (RBCs) collected from healthy volunteers and patients suffering from malaria (Plasmodium vivax infection) using near infrared (785 nm) laser source. The results show significant alteration in the spectra averaged over ∼ 50 non-parasitized RBCs per sample. As compared to RBCs from healthy donors, in cells collected from malaria patients, a significant decrease in the intensity of the low spin (oxygenated-haemoglobin) marker Raman band at 1223 cm -1 (υ 13 or υ 42 ) along with a concomitant increase in the high spin (deoxygenated-haemoglobin) marker bands at 1210 cm -1 (υ 5 + υ 18 ) and 1546 cm -1 (υ 11 ) was observed. The changes primarily suggest a reduced haemoglobin-oxygen affinity for the non-parasitized red cells in malaria patients. The possible causes include up regulation of intra-erythrocytic 2,3-diphosphoglycerate and/or ineffective erythropoiesis resulted from the disease. During the above study we also observed that significant photo-damage may results to the intracellular haemoglobin (Hb) if higher laser power is used. For a laser power above ∼ 5 mW the observed increase in intensity of the Raman bands at 975 cm -1 (υ 46 ), 1244 cm -1 (υ 42 ) and 1366 cm -1 (υ 4 ) with increasing exposure time suggests photo-denaturation of Hb and the concomitant decrease in intensity of the Raman band at 1544 cm -1 (υ 11 ) suggests photo induced methaemoglobin formation. The photo damage of intracellular haemoglobin by the above processes was also observed to result in intracellular heme aggregation. (author)

  6. The spectroscopic study of building composites containing natural sorbents.

    Science.gov (United States)

    Król, M; Mozgawa, W

    2011-08-15

    This work presents the results of FT-IR spectroscopic studies of heavy metal cations (Ag(+), Pb(2+), Zn(2+), Cd(2+) and Cr(3+)) immobilization from aqueous solutions on natural sorbents. The sorption has been conducted on sodium forms of zeolite (clinoptilolite) and clay minerals (mixtures containing mainly montmorillonite and kaolinite) which have been separated from natural Polish deposit. In the next part of the work both sorbents were used to obtain new building composites. It was proven those heavy metal cations' sorption causes changes in IR spectra of the zeolite and clay minerals. These alterations are dependent on the way the cations were sorbed. In the case of zeolite, variations of the bands corresponding to the characteristic ring vibrations have been observed. These rings occur in pseudomolecular complexes 4-4-1 (built of alumino- and silicooxygen tetrahedra) which constitute the secondary building units (SBU) and form spatial framework of the zeolite. The most significant changes have been determined in the region of pseudolattice vibrations (650-700 cm(-1)). In the instance of clay minerals, changes in the spectra occur at two ranges: 1200-800 cm(-1)--the range of the bands assigned to asymmetric Si-O(Si,Al) and bending Al-OH vibrations and 3800-3000 cm(-1)--the range of the bands originating from OH(-) groups stretching vibrations. Next results indicate possibilities of applying the used natural sorbents for the obtainment of new building materials having favourable composition and valuable properties. The zeolite was used for obtaining autoclaved materials with an addition of CaO, and the clay minerals for ceramic sintered materials with an addition of quartz and clinoptilolite were produced. FT-IR studies were also conducted on the obtained materials. Copyright © 2010 Elsevier B.V. All rights reserved.

  7. Gas-phase synthesis and structure of monomeric ZnOH: a model species for metalloenzymes and catalytic surfaces.

    Science.gov (United States)

    Zack, Lindsay N; Sun, Ming; Bucchino, Matthew P; Clouthier, Dennis J; Ziurys, Lucy M

    2012-02-16

    Monomeric ZnOH has been studied for the first time using millimeter and microwave gas-phase spectroscopy. ZnOH is important in surface processes and at the active site of the enzyme carbonic anhydrase. In the millimeter-wave direct-absorption experiments, ZnOH was synthesized by reacting zinc vapor, produced in a Broida-type oven, with water. In the Fourier-transform microwave measurements, ZnOH was produced in a supersonic jet expansion of CH(3)OH and zinc vapor, created by laser ablation. Multiple rotational transitions of six ZnOH isotopologues in their X(2)A' ground states were measured over the frequency range of 22-482 GHz, and splittings due to fine and hyperfine structure were resolved. An asymmetric top pattern was observed in the spectra, showing that ZnOH is bent, indicative of covalent bonding. From these data, spectroscopic constants and an accurate structure were determined. The Zn-O bond length was found to be similar to that in carbonic anhydrase and other model enzyme systems.

  8. A Spectroscopic and Photometric Study of Gravitational Microlensing Events

    Science.gov (United States)

    Kane, Stephen R.

    2000-08-01

    Gravitational microlensing has generated a great deal of scientific interest over recent years. This has been largely due to the realization of its wide-reaching applications, such as the search for dark matter, the detection of planets, and the study of Galactic structure. A significant observational advance has been that most microlensing events can be identified in real-time while the source is still being lensed. More than 400 microlensing events have now been detected towards the Galactic bulge and Magellanic Clouds by the microlensing survey teams EROS, MACHO, OGLE, DUO, and MOA. The real-time detection of these events allows detailed follow-up observations with much denser sampling, both photometrically and spectroscopically. The research undertaken in this project on photometric studies of gravitational microlensing events has been performed as a member of the PLANET (Probing Lensing Anomalies NETwork) collaboration. This is a worldwide collaboration formed in the early part of 1995 to study microlensing anomalies - departures from an achromatic point source, point lens light curve - through rapidly-sampled, multi-band, photometry. PLANET has demonstrated that it can achieve 1% photometry under ideal circumstances, making PLANET observations sensitive to detection of Earth-mass planets which require characterization of 1%--2% deviations from a standard microlensing light curve. The photometric work in this project involved over 5 months using the 1.0 m telescope at Canopus Observatory in Australia, and 3 separate observing runs using the 0.9 m telescope at the Cerro Tololo Inter-American Observatory (CTIO) in Chile. Methods were developed to reduce the vast amount of photometric data using the image analysis software MIDAS and the photometry package DoPHOT. Modelling routines were then written to analyse a selection of the resulting light curves in order to detect any deviation from an achromatic point source - point lens light curve. The photometric

  9. Optical and spectroscopic study of erbium doped calcium borotellurite glasses

    Science.gov (United States)

    Gomes, J. F.; Lima, A. M. O.; Sandrini, M.; Medina, A. N.; Steimacher, A.; Pedrochi, F.; Barboza, M. J.

    2017-04-01

    In this study, 10CaF2 - (29.9-0.4x)CaO - (60-0.6x)B2O3 - xTeO2 - 0,1Er2O3 (x = 10, 16, 22, 30 and 50 mol %) glasses were synthesized, and their optical and spectroscopic properties were investigated. X-ray diffraction, density, glass transition temperature (Tg), crystallization temperature (Tx), refraction index, luminescence, radiative lifetime and optical absorption measurements were carried out. Molar volume (Vm), thermal stability (Tx-Tg), electronic polarizability (αm), optical bang gap energy (Eg) and Judd-Ofelt (JO) parameters Ωt (2,4,6) were also calculated. The results are discussed in terms of tellurium oxide content. The increase of TeO2 in the glasses composition increases density, refractive index and electronic polarizability. The optical band gap energy decreases varying from 3.37 to 2.71 eV for the glasses with 10 and 50 mol% of TeO2, respectively. The optical absorption coefficient spectra show characteristic bands of Er3+ ions. Furthermore, these spectra in NIR region show a decrease of hydroxyl groups as a function of TeO2 addition. Luminescence intensity and radiative lifetimes at 1530 nm show an increasing with the TeO2 content. The JO parameters of Er:CaBTeX glasses follow the trend Ω2 > Ω4 > Ω6 and the quality factor values (Ω4/Ω6) were between 1.37 and 3.07. By comparing the measured lifetime with the calculated radiative decay time, quantum efficiency was calculated. The luminescence emission intensity at 1530 nm decreases with the increase of temperature. The lifetime values show a slight trend to decrease with the temperature increase, from 300 to 420 K, for all the samples.

  10. Opportunities from the nanoworld : Gas phase nanoparticles

    NARCIS (Netherlands)

    Palasantzas, G.; Koch, S. A.; Vystavel, T.; De Hosson, J. Th. M.

    2008-01-01

    In this paper we present studies related to coalescence and oxidation of transition metal nanoparticles with sizes ranging between 2 and 10 nm. For cobalt and iron exposure to air leads to thin oxide shell formation (thickness

  11. SVOC partitioning between the gas phase and settled dust indoors

    DEFF Research Database (Denmark)

    Weschler, Charles J.; Nazaroff, W. W.

    2010-01-01

    Semivolatile organic compounds (SVOCs) are a major class of indoor pollutants. Understanding SVOC partitioning between the gas phase and settled dust is important for characterizing the fate of these species indoors and the pathways by which humans are exposed to them. Such knowledge also helps...

  12. Gas-Phase IR Spectroscopy of Deprotonated Amino Acids

    NARCIS (Netherlands)

    Oomens, J.; Steill, J. D.; Redlich, B.

    2009-01-01

    Gas-phase infrared multiple photon dissociation (IRMPD) spectra have been recorded for the conjugate bases of a series of amino acids (Asp, Cys, Glu, Phe, Set, Trp, Tyr). The spectra are dominated by strong symmetric and antisymmetric carboxylate stretching modes around 1300 and 1600 cm(-1),

  13. Gas phase toluene isopropylation over high silica mordenite

    Indian Academy of Sciences (India)

    Mordenite (HM) catalysts with three different Si/Al ratios were compared for their activity and selectivities in gas phase toluene isopropylation with isopropanol. Catalyst with Si/Al ratio 44.9 offered better cumene selectivity, hence, it was chosen for detailed kinetic investigations. The influence of various process parameters ...

  14. Gas phase reactivity of thermal metal clusters

    International Nuclear Information System (INIS)

    Castleman, A.W. Jr.; Harms, A.C.; Leuchtner, R.E.

    1991-01-01

    Reaction kinetics of metal cluster ions under well defined thermal conditions were studied using a flow tube reactor in combination with laser vaporization. Aluminum anions and cations were reacted with oxygen, and several species which are predicted jellium shell closings, were found to have special stability. Metal alloy cluster anions comprised of Al, V and Nb were also seen to react with oxygen. Alloy clusters with an even number of electrons reacted more slowly than odd electron species, and certain clusters appeared to be exceptionally unreactive. Copper cation clusters were observed to associate with carbon monoxide with reactivities that approach bulk behavior at surprisingly small cluster size. These reactions demonstrate how the rate of reaction changes with cluster size. (orig.)

  15. Gas phase reactivity of thermal metal clusters

    Science.gov (United States)

    Castleman, A. W., Jr.; Harms, A. C.; Leuchtner, R. E.

    1991-03-01

    Reaction kinetics of metal cluster ions under well defined thermal conditions were studied using a flow tube reactor in combination with laser vaporization. Aluminum anions and cations were reacted with oxygen, and several species which are predicted jellium shell closings, were found to have special stability. Metal alloy cluster anions comprised of Al, V and Nb were also seen to react with oxygen. Alloy clusters with an even number of electrons reacted more slowly than odd electron species, and certain clusters appeared to be exceptionally unreactive. Copper cation clusters were observed to associate with carbon monoxide with reactivities that approach bulk behavior at surprisingly small cluster size. These reactions demonstrate how the rate of reaction changes with cluster size.

  16. Spectroscopic and theoretical studies of dalbergin and Methyldalbergin

    Science.gov (United States)

    Shweta; Khan, Eram; Tandon, Poonam; Bharti, Purnima; Kumar, Padam; Maurya, Rakesh

    2018-03-01

    Molecular structure and vibrational analysis of methyldalbergin (MDLBG) and dalbergin (DLBG) are presented using vibrational spectroscopy (infrared and Raman) and quantum chemical calculations. Difference in the Osbnd H stretching vibration wavenumber of two conformers of DLBG was observed as in one conformer this bond is making an intramolecular H-bond while in other it is free. The spectral calculations, ground state geometry and electronic structure calculations were performed based on the density functional theory (DFT) using the standard B3LYP/6-311++G(d,p) methodology. FT-Raman and FT-IR spectra were recorded in the solid phase, and interpreted in terms of potential energy distribution analysis. The UV-visible absorption spectrum was examined in DMSO solvent and compared with one calculated in gas phase as well as in solvent environment using TD-DFT/6-311G++(d,p) basis set. HOMO-LUMO energy gap results show chemical reactivity of conformers of DLBG and MDLBG.

  17. Spectroscopic studies of uranium species for environmental decontamination applications

    Science.gov (United States)

    Eng, Charlotte

    After the Cold War, Department of Energy began to concentrate its efforts on cleanup of former nuclear material processing facilities, especially uranium-contaminated groundwater and soil. This research aims to study uranium association to both organic and inorganic compounds found in the contaminated environment in the hopes that the information gathered can be applied to the development and optimization of cost-effective remediation techniques. Spectroscopic and electrochemical methods will be employed to examine the behavior of uranium in given conditions to further our understanding of its impact on the environment. Uranium found in groundwater and soil bind with various ligands, especially organic ligands present in the environment due to natural sources (e.g. metabolic by-products or degradation of plants and animals) or man-made sources (e.g. chelating agents used in operating or cleanup of uranium processing facilities). We selected reasonable analogs of naturally occurring matter and studied their structure, chemical and electrochemical behavior and found that the structure of uranyl complexes depends heavily on the nature of the ligand and environmental factors such as pH. Association of uranium-organic complexes with anaerobic bacteria, Clostridium sp. was studied to establish if the bacteria can effectively bioreduce uranium while going through normal bacterial activity. It was found that the nature of the organic ligand affected the bioavailability and toxicity of the uranium on the bacteria. In addition, we have found that the type of iron corrosion products and uranyl species present on the surface of corroded steel depended on various environmental factors, which subsequently affected the removal rate of uranium by a citric acid/hydrogen peroxide/deionized water cleaning process. The method was found to remove uranium from only the topmost corrosion layers and residual uranium could be found (a) deeper in the corrosion layers where it is occluded by

  18. Spectroscopic Tools for Quantitative Studies of DNA Structure and Dynamics

    DEFF Research Database (Denmark)

    Preus, Søren

    The main objective of this thesis is to develop quantitative fluorescence-based, spectroscopic tools for probing the 3D structure and dynamics of DNA and RNA. The thesis is founded on six peer-reviewed papers covering mainly the development, characterization and use of fluorescent nucleobase...... analogues. In addition, four software packages is presented for the simulation and quantitative analysis of time-resolved and steady-state UV-Vis absorption and fluorescence experiments....

  19. Ion-beam spectroscopic studies of the 69As nucleus

    International Nuclear Information System (INIS)

    Badica, T.; Cojocaru, V.; Olariu, A.; Petre, M.; Popescu, I. V.; Gheboianu, A.

    2009-01-01

    Excited state of the neutron deficient 69 As nucleus were investigated in the 58 Ni( 14 N,2pn) reaction by ion-beam γ spectroscopic methods (excitation functions, γγ-coincidences, angular distributions and linear polarization gated with neutrons). A new more complete level scheme of 69 As has been proposed with spin-parity values. The structure of the nucleus is discussed in the framework of the interaction boson-fermion model (IBFM). (authors)

  20. Solar photocatalytic gas-phase degradation of n-decane--a comparative study using cellulose acetate monoliths coated with P25 or sol-gel TiO₂ films.

    Science.gov (United States)

    Miranda, Sandra M; Lopes, Filipe V S; Rodrigues-Silva, Caio; Martins, Susana D S; Silva, Adrián M T; Faria, Joaquim L; Boaventura, Rui A R; Vilar, Vítor J P

    2015-01-01

    Cellulose acetate monoliths (CAM) were used as the substrate for the deposition of TiO2 films to produce honeycombed photoactive structures to fill a tubular photoreactor equipped with a compound parabolic collector. By using such a setup, an efficient single-pass gas-phase conversion was achieved in the degradation of n-decane, a model volatile organic compound. The CAM three-dimensional, gas-permeable transparent structure with a rugged surface enables a good adhesion of the catalytic coating. It also provides a rigid structure for packing the tubular photoreactor, and maximizing the illuminated catalyst surface. The efficiency of the photocatalytic oxidation (PCO) process on n-decane degradation was evaluated under different operating conditions, such as feeding concentration (73 and 146 ppm), gas stream flow rate (73, 150, and 300 mL min(-1)), relative humidity (3 and 25 %), and UV irradiance (18.9, 29.1, and 38.4 WUV m(-2)). The results show that n-decane degradation by neat photolysis is negligible, but mineralization efficiencies of 86 and 82 % were achieved with P25-CAM and SG-CAM, respectively, for parent pollutant conversions above 95 %, under steady-state conditions. A mass transfer model, considering the mass balance to the plug-flow packed photoreactor, and PCO reaction given by a Langmuir-Hinshelwood bimolecular non-competitive two types of sites equation, was able to predict well the PCO kinetics under steady-state conditions, considering all the operational parameters tested. Overall, the performance of P25-CAM was superior taking into account mineralization efficiency, cost of preparation, surface roughness, and robustness of the deposited film.

  1. Toward the first study of chemical reaction dynamics of Mu with vibrational-state-selected reactants in the gas phase: The Mu+H2*(v=1) reaction by stimulated Raman pumping

    International Nuclear Information System (INIS)

    Bakule, Pavel; Sukhorukov, Oleksandr; Matsuda, Yasuyuki; Pratt, Francis; Gumplinger, Peter; Momose, Takamasa; Torikai, Eiko; Fleming, Donald

    2009-01-01

    Stimulated Raman pumping (SRP) is used to produce H 2 in its first vibrational state, in order to measure, for the first time, the Mu+H 2 *(v=1)→MuH+H reaction rate at room temperature, as a prototypical example of new directions in gas-phase muonium chemistry, utilizing the pulsed muon beam and a new dedicated laser system at the RIKEN/RAL Laboratory. Reported here is a preliminary result but the final results are expected to provide definitive new tests of reaction rate theory on the highly accurate H 3 potential energy surface. The major difficulty in this experiment, compared to the standard SRP process, is to ensure a homogeneous excitation over a volume of several cm 3 and of sufficient intensity to ensure a measurable Mu relaxation rate. The techniques used to accomplish this are described. The experiment utilizes the 2nd harmonic output of a Nd:YAG laser (532 nm) with pulse energies up to 500 mJ at a repetition rate of 25 Hz. Different optical setups have been constructed and tested in order to optimize the number of laser-pumped H 2 molecules and their overlap with the stopping profile of the muon beam in the reaction cell (total volume ∼100x40x4mm 3 ). The first result of this experiment gives a measured relaxation rate due to laser excitation of λ*=0.085±0.051μs -1 , consistent with theory but limited by both low statistics and particularly a high background relaxation rate.

  2. Uptake of Organic Gas Phase Species by 1-Methylnaphthalene

    Science.gov (United States)

    Zhang, H.; Xia, J.; Davidovits, P.; Jayne, J. T.; Kolb, C. E.; Worsnop, D. R.

    2002-12-01

    Using a droplet train apparatus, the mass accommodation coefficients (α) on 1-methylnapthalene of gas phase m-xylene, ethylbenzene, butylbenzene, α-pinene, γ-terpinene, and 2-methyl-2-hexanol were measured as a function of temperature (265 K to 296 K). 1-methylnapthalene was selected as a surrogate for hydrophobic and aromatic hydrocarbons found in tropospheric aerosols. The mass accommodation coefficients (α) of all the molecules obtained from these measurements exhibit negative temperature dependence. The upper and lower values of α at 265 K and 296 K respectively are: for m-xylene 0.44 and 0.26; for ethylbenzene 0.37 and 0.22; for butylbenzene 0.47 and 0.31; for α-pinene 0.47 and 0.096; for γ-terpinene 0.39 and 0.12; for 2-methyl-2-hexanol 0.44 and 0.26. The uptake measurements also yielded values for the product HDl1/2 for most of the molecules studied (H = Henry's law constant, Dl = liquid phase diffusion coefficient). Using calculated values of Dl the Henry's law constant is obtained, and expressed in the form ln H (M/atm) = -A + B/T. The A and B values for the molecules studied are listed in Table 1. Table 1: A and B values for the Henry's law constant H expressed as ln H (M/atm) = -A + B/T \\ m-xylene: A=7.20, B=4060\\ethylbenzene: A=5.81, B=3660\\butylbenzene: A=16.95, B=7330α-pinene: A=15.69, B=6360\\2-methyl-2-hexanol: A=9.95, B=4760

  3. Vibrational Spectra of Discrete UO22+ Halide Complexes in the Gas Phase

    International Nuclear Information System (INIS)

    Groenewold, G.S.; Van Stipdonk, Michael J.; Oomens, Jos; De Jong, Wibe A.; Gresham, Garold L.; Mcilwain, Michael

    2010-01-01

    The intrinsic binding of halide ions to the metal center in the uranyl molecule is a topic of ongoing research interest in both the actinide separations and theoretical communities. Investigations of structure in the condensed phases is frequently obfuscated by solvent interactions that can alter ligand binding and spectroscopic properties. The approach taken in this study is to move the uranyl halide complexes into the gas phase where they are free from solvent interactions, and then interrogate their vibrational spectroscopy using infrared multiple photon dissociation (IRMPD). The spectra of cationic coordination complexes having the composition (UO 2 (X)(ACO) 3 ) + (where X = F, Cl, Br and I; ACO = acetone) were acquired using electrospray for ion formation, and monitoring the ion signal from the photoelimination of ACO ligands. The studies showed that the asymmetric ν 3 UO 2 frequency was insensitive to halide identity as X was varied from Cl to I, suggesting that in these pseudo-octahedral complexes, changing the nucleophilicity of the halide did not appreciably alter its binding in the complex. The ν 3 peak in the spectrum of the F-containing complex was 9 cm -1 lower indicating stronger coordination in this complex. Similarly the ACO carbonyl stretches showed that the C=O frequency was relatively insensitive to the identity of the halide, although a modest shift to higher wavenumber was seen for the complexes with the more nucleophilic anions, consistent with the idea that they loosen solvent binding. Surprisingly, the ν 1 stretch was activated when the softer anions Cl, Br and I were present in the complexes. IR studies of the anionic complexes (UO 2 X 3 ) - (where X = Cl - , Br - and I - ) compared the ν 3 UO 2 modes versus halide, and showed that the ν 3 values decreased with increasing anion nucleophilicity. This observation was consistent with DFT calculations that indicated that (UO 2 X 2 ) - -X, and (UO 2 X 2 )·-X - dissociation energies

  4. CHAOS. III. GAS-PHASE ABUNDANCES IN NGC 5457

    Energy Technology Data Exchange (ETDEWEB)

    Croxall, Kevin V.; Pogge, Richard W. [Department of Astronomy, The Ohio State University, 140 West 18th Avenue, Columbus, OH 43210 (United States); Berg, Danielle A. [Center for Gravitation, Cosmology and Astrophysics, Department of Physics, University of Wisconsin Milwaukee, 1900 East Kenwood Boulevard, Milwaukee, WI 53211 (United States); Skillman, Evan D. [Minnesota Institute for Astrophysics, University of Minnesota, 116 Church Street SE, Minneapolis, MN 55455 (United States); Moustakas, John [Department of Physics and Astronomy, Siena College, 515 Loudon Road, Loudonville, NY 12211 (United States)

    2016-10-10

    We present Large Binocular Telescope observations of 109 H ii regions in NGC 5457 (M101) obtained with the Multi-Object Double Spectrograph. We have robust measurements of one or more temperature-sensitive auroral emission lines for 74 H ii regions, permitting the measurement of “direct” gas-phase abundances. Comparing the temperatures derived from the different ionic species, we find: (1) strong correlations of T [N ii] with T [S iii] and T [O iii], consistent with little or no intrinsic scatter; (2) a correlation of T [S iii] with T [O iii], but with significant intrinsic dispersion; (3) overall agreement between T [N ii], T [S ii], and T [O ii], as expected, but with significant outliers; (4) the correlations of T [N ii] with T [S iii] and T [O iii] match the predictions of photoionization modeling while the correlation of T [S iii] with T [O iii] is offset from the prediction of photoionization modeling. Based on these observations, which include significantly more observations of lower excitation H ii regions, missing in many analyses, we inspect the commonly used ionization correction factors (ICFs) for unobserved ionic species and propose new empirical ICFs for S and Ar. We have discovered an unexpected population of H ii regions with a significant offset to low values in Ne/O, which defies explanation. We derive radial gradients in O/H and N/O which agree with previous studies. Our large observational database allows us to examine the dispersion in abundances, and we find intrinsic dispersions of 0.074 ± 0.009 in O/H and 0.095 ± 0.009 in N/O (at a given radius). We stress that this measurement of the intrinsic dispersion comes exclusively from direct abundance measurements of H ii regions in NGC 5457.

  5. Dissociative electron attachment to the gas-phase nucleobase hypoxanthine

    Energy Technology Data Exchange (ETDEWEB)

    Dawley, M. Michele [Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Tanzer, Katrin; Denifl, Stephan, E-mail: Stephan.Denifl@uibk.ac.at, E-mail: Sylwia.Ptasinska.1@nd.edu [Institut für Ionenphysik und Angewandte Physik, and Center for Molecular Biosciences Innsbruck (CMBI), Leopold-Franzens Universität Innsbruck, Technikerstr. 25, A-6020 Innsbruck (Austria); Carmichael, Ian [Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Ptasińska, Sylwia, E-mail: Stephan.Denifl@uibk.ac.at, E-mail: Sylwia.Ptasinska.1@nd.edu [Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Department of Physics, University of Notre Dame, Notre Dame, Indiana 46556 (United States)

    2015-06-07

    We present high-resolution measurements of the dissociative electron attachment (DEA) to isolated gas-phase hypoxanthine (C{sub 5}H{sub 4}N{sub 4}O, Hyp), a tRNA purine base. The anion mass spectra and individual ion efficiency curves from Hyp were measured as a function of electron energy below 9 eV. The mass spectra at 1 and 6 eV exhibit the highest anion yields, indicating possible common precursor ions that decay into the detectable anionic fragments. The (Hyp − H) anion (C{sub 5}H{sub 3}N{sub 4}O{sup −}) exhibits a sharp resonant peak at 1 eV, which we tentatively assign to a dipole-bound state of the keto-N1H,N9H tautomer in which dehydrogenation occurs at either the N1 or N9 position based upon our quantum chemical computations (B3LYP/6-311+G(d,p) and U(MP2-aug-cc-pVDZ+)) and prior studies with adenine. This closed-shell dehydrogenated anion is the dominant fragment formed upon electron attachment, as with other nucleobases. Seven other anions were also observed including (Hyp − NH){sup −}, C{sub 4}H{sub 3}N{sub 4}{sup −}/C{sub 4}HN{sub 3}O{sup −}, C{sub 4}H{sub 2}N{sub 3}{sup −}, C{sub 3}NO{sup −}/HC(HCN)CN{sup −}, OCN{sup −}, CN{sup −}, and O{sup −}. Most of these anions exhibit broad but weak resonances between 4 and 8 eV similar to many analogous anions from adenine. The DEA to Hyp involves significant fragmentation, which is relevant to understanding radiation damage of biomolecules.

  6. Kinetics of the gas-phase tritium oxidation reaction

    International Nuclear Information System (INIS)

    Failor, R.A.

    1989-01-01

    Homogeneous gas-phase kinetics of tritium oxidation (2T 2 + O 2 →2T 2 O) have been studied with a model that accounts explicitly for radiolysis of the major species and the kinetics of the subsequent reactions of ionic, excited-state, and neutral species. Results from model calculations are given for 10 -4 -1.0 mol% T 2 in O 2 (298 K, 1 atm). As the reaction evolves three different mechanisms control T 2 O production, each with a different overall rate expression and a different order with respect to the T 2 concentration. The effects of self-radiolysis of pure T 2 on the tritium oxidation reaction were calculated. Tritium atoms, the primary product of T 2 self-radiolysis, altered the oxidation mechanism only during the first few seconds following the initiation of the T 2 -O 2 reaction. Ozone, an important intermediate in T 2 oxidation, was monitored in-situ by U.V. absorption spectroscopy for 0.01-1.0 mol% T 2 an 1 atm O 2 . The shape of the experimental ozone time profile agreed with the model predictions. As predicted, the measured initial rate of ozone production varied linearly with initial T 2 concentration ([T 2 ] 0.6 o ), but at an initial rate one-third the predicted value. The steady-state ozone concentration ([O 3 ]ss) was predicted to be dependent on [T 2 ] 0.3 o , but the measured value was [T 2 ] 0.6 o , resulting in four times higher [O 3 ]ss than predicted for a 1.0% T 2 -O 2 mixture. Adding H 2 to the T 2 -O 2 mixture, to provide insight into the differences between the radiolytic and chemical behavior of the tritium, produced a greater decrease in [O 3 ]ss than predicted. Adjusting the reaction cell surface-to-volume ratio showed implications of minor surface removal of ozone

  7. Transport and spectroscopic studies of liquid and polymer electrolytes

    Science.gov (United States)

    Bopege, Dharshani Nimali

    trifluoromethanesulfonate, LiCF3SO3, abbreviated here as lithium triflate(LiTf). The molar absorption coefficients of nus(SO3), deltas(CF3), and deltas(SO3) vibrational modes of triflate anion in the LiTf-2-pentanone system were found to be 6708+/-89, 5182+/-62, and 189+/-2 kg mol-1 cm-1, respectively using Beer-Lambert law. Our results show that there is strong absorption by nu s(SO3) mode and weak absorption by deltas(CF 3) mode. Also, the absorptivity of each mode is independent of the ionic association with Li ions. This work allows for the direct quantitative comparison of calculated concentrations in different samples and different experimental conditions. In addition, this dissertation reports the temperature-dependent vibrational spectroscopic studies of pure poly(ethylene oxide) and LiTf-poly(ethylene oxide) complexes. A significant portion of this dissertation focuses on crystallographic studies of ketone-salt (LiTf:2-pentanone and NaTf:2-hexanone) and amine-acid (diethyleneamine: H3PO4, N,N'-dimethylethylenediamine:H 3PO4, and piperazine:H3PO4) systems. Here, sodium trifluoromethanesulfonate, NaCF3SO3 is abbreviated as NaTf. As model compounds, these systems provide valuable information about ion-ion interactions, which are helpful for understanding complex polymer systems. During this study, five crystal structures were solved using single X-ray diffractometry, and their vibrational modes were studied in the mid-infrared region. In the secondary amine/phosphoric acid systems, the nature of hydrogen-bonding network was examined.

  8. The nuclear liquid-gas phase transition: Present status and future perspectives

    International Nuclear Information System (INIS)

    Pochodzalla, J.; Imme, G.; Maddalena, V.

    1996-07-01

    More than two decades ago, the van der Waals behavior of the nucleon -nucleon force inspired the idea of a liquid-gas phase transition in nuclear matter. Heavy-ion reactions at relativistic energies offer the unique possibility for studying this phase transition in a finite, hadronic system. A general overview of this subject is given emphasizing the most recent results on nuclear calorimetry. (orig.)

  9. Heterogeneity-enhanced gas phase formation in shallow aquifers during leakage of CO2-saturated water from geologic sequestration sites

    Science.gov (United States)

    Plampin, Michael R.; Lassen, Rune N.; Sakaki, Toshihiro; Porter, Mark L.; Pawar, Rajesh J.; Jensen, Karsten H.; Illangasekare, Tissa H.

    2014-12-01

    A primary concern for geologic carbon storage is the potential for leakage of stored carbon dioxide (CO2) into the shallow subsurface where it could degrade the quality of groundwater and surface water. In order to predict and mitigate the potentially negative impacts of CO2 leakage, it is important to understand the physical processes that CO2 will undergo as it moves through naturally heterogeneous porous media formations. Previous studies have shown that heterogeneity can enhance the evolution of gas phase CO2 in some cases, but the conditions under which this occurs have not yet been quantitatively defined, nor tested through laboratory experiments. This study quantitatively investigates the effects of geologic heterogeneity on the process of gas phase CO2 evolution in shallow aquifers through an extensive set of experiments conducted in a column that was packed with layers of various test sands. Soil moisture sensors were utilized to observe the formation of gas phase near the porous media interfaces. Results indicate that the conditions under which heterogeneity controls gas phase evolution can be successfully predicted through analysis of simple parameters, including the dissolved CO2 concentration in the flowing water, the distance between the heterogeneity and the leakage location, and some fundamental properties of the porous media. Results also show that interfaces where a less permeable material overlies a more permeable material affect gas phase evolution more significantly than interfaces with the opposite layering.

  10. The Gas-Phase Formation of Methyl Formate in Hot Molecular Cores

    Science.gov (United States)

    Horn, Anne; Møllendal, Harald; Sekiguchi, Osamu; Uggerud, Einar; Roberts, Helen; Herbst, Eric; Viggiano, A. A.; Fridgen, Travis D.

    2004-08-01

    Methyl formate, HCOOCH3, is a well-known interstellar molecule prominent in the spectra of hot molecular cores. The current view of its formation is that it occurs in the gas phase from precursor methanol, which is synthesized on the surfaces of grain mantles during a previous colder era and evaporates while temperatures increase during the process of high-mass star formation. The specific reaction sequence thought to form methyl formate, the ion-molecule reaction between protonated methanol and formaldehyde followed by dissociative recombination of the protonated ion [HCO(H)OCH3]+, has not been studied in detail in the laboratory. We present here the results of both a quantum chemical study of the ion-molecule reaction between [CH3OH2]+ and H2CO as well as new experimental work on the system. In addition, we report theoretical and experimental studies for a variety of other possible gas-phase reactions leading to ion precursors of methyl formate. The studied chemical processes leading to methyl formate are included in a chemical model of hot cores. Our results show that none of these gas-phase processes produces enough methyl formate to explain its observed abundance.

  11. Quantum mechanical computations and spectroscopy: from small rigid molecules in the gas phase to large flexible molecules in solution.

    Science.gov (United States)

    Barone, Vincenzo; Improta, Roberto; Rega, Nadia

    2008-05-01

    Interpretation of structural properties and dynamic behavior of molecules in solution is of fundamental importance to understand their stability, chemical reactivity, and catalytic action. While information can be gained, in principle, by a variety of spectroscopic techniques, the interpretation of the rich indirect information that can be inferred from the analysis of experimental spectra is seldom straightforward because of the subtle interplay of several different effects, whose specific role is not easy to separate and evaluate. In such a complex scenario, theoretical studies can be very helpful at two different levels: (i) supporting and complementing experimental results to determine the structure of the target molecule starting from its spectral properties; (ii) dissecting and evaluating the role of different effects in determining the observed spectroscopic properties. This is the reason why computational spectroscopy is rapidly evolving from a highly specialized research field into a versatile and widespread tool for the assignment of experimental spectra and their interpretation in terms of chemical physical effects. In such a situation, it becomes important that both computationally and experimentally oriented chemists are aware that new methodological advances and integrated computational strategies are available, providing reliable estimates of fundamental spectral parameters not only for relatively small molecules in the gas phase but also for large and flexible molecules in condensed phases. In this Account, we review the most significant methodological contributions from our research group in this field, and by exploiting some recent results of their application to the computation of IR, UV-vis, NMR, and EPR spectral parameters, we discuss the microscopic mechanisms underlying solvent and vibrational effects on the spectral parameters. After reporting some recent achievements for the study of excited states by first principle quantum mechanical

  12. Treatment of reduced sulphur compounds and SO2 by Gas Phase Advanced Oxidation

    DEFF Research Database (Denmark)

    Meusinger, Carl; Bluhme, Anders Brostrøm; Ingemar, Jonas L.

    2017-01-01

    Reduced sulphur compounds (RSCs) emitted from pig farms are a major problem for agriculture, due to their health and environmental impacts and foul odour. This study investigates the removal of RSCs, including H2S, and their oxidation product SO2 using Gas Phase Advanced Oxidation (GPAO). GPAO...... is a novel air cleaning technique which utilises accelerated atmospheric chemistry to oxidise pollutants before removing their oxidation products as particles. Removal efficiencies of 24.5% and 3.9% were found for 461 ppb of H2S and 714 ppb of SO2 in a laboratory system (volumetric flow Q = 75 m3/h......). A numerical model of the reactor system was developed to explore the basic features of the system; its output was in fair agreement with the experiment. The model verified the role of OH radicals in initiating the oxidation chemistry. All sulphur removed from the gas phase was detected as particulate matter...

  13. Thermodynamic analysis of fuels in gas phase: ethanol, gasoline and ethanol - gasoline predicted by DFT method.

    Science.gov (United States)

    Neto, A F G; Lopes, F S; Carvalho, E V; Huda, M N; Neto, A M J C; Machado, N T

    2015-10-01

    This paper presents a theoretical study using density functional theory to calculate thermodynamics properties of major molecules compounds at gas phase of fuels like gasoline, ethanol, and gasoline-ethanol mixture in thermal equilibrium on temperature range up to 1500 K. We simulated a composition of gasoline mixture with ethanol for a thorough study of thermal energy, enthalpy, Gibbs free energy, entropy, heat capacity at constant pressure with respect to temperature in order to study the influence caused by ethanol as an additive to gasoline. We used semi-empirical computational methods as well in order to know the efficiency of other methods to simulate fuels through this methodology. In addition, the ethanol influence through the changes in percentage fractions of chemical energy released in combustion reaction and the variations on thermal properties for autoignition temperatures of fuels was analyzed. We verified how ethanol reduces the chemical energy released by gasoline combustion and how at low temperatures the gas phase fuels in thermal equilibrium have similar thermodynamic behavior. Theoretical results were compared with experimental data, when available, and showed agreement. Graphical Abstract Thermodynamic analysis of fuels in gas phase.

  14. The coupling effect of gas-phase chemistry and surface reactions on oxygen permeation and fuel conversion in ITM reactors

    KAUST Repository

    Hong, Jongsup

    2015-08-01

    © 2015 Elsevier B.V. The effect of the coupling between heterogeneous catalytic reactions supported by an ion transport membrane (ITM) and gas-phase chemistry on fuel conversion and oxygen permeation in ITM reactors is examined. In ITM reactors, thermochemical reactions take place in the gas-phase and on the membrane surface, both of which interact with oxygen permeation. However, this coupling between gas-phase and surface chemistry has not been examined in detail. In this study, a parametric analysis using numerical simulations is conducted to investigate this coupling and its impact on fuel conversion and oxygen permeation rates. A thermochemical model that incorporates heterogeneous chemistry on the membrane surface and detailed chemical kinetics in the gas-phase is used. Results show that fuel conversion and oxygen permeation are strongly influenced by the simultaneous action of both chemistries. It is shown that the coupling somewhat suppresses the gas-phase kinetics and reduces fuel conversion, both attributed to extensive thermal energy transfer towards the membrane which conducts it to the air side and radiates to the reactor walls. The reaction pathway and products, in the form of syngas and C2 hydrocarbons, are also affected. In addition, the operating regimes of ITM reactors in which heterogeneous- or/and homogeneous-phase reactions predominantly contribute to fuel conversion and oxygen permeation are elucidated.

  15. Reactions of newly formed fission products in the gas phase

    International Nuclear Information System (INIS)

    Strickert, R.G.

    1976-01-01

    A dynamic gas-flow system was constructed which stopped fission products in the gas phase and rapidly separated (in less than 2 sec) volatile compounds from non-volatile ones. The filter assembly designed and used was shown to stop essentially all non-volatile fission products. Between 5 percent and 20 percent of tellurium fission-product isotopes reacted with several hydrocarbon gases to form volatile compounds, which passed through the filter. With carbon monoxide gas, volatile tellurium compound(s) (probably TeCO) were also formed with similar efficiencies. The upper limits for the yields of volatile compounds formed between CO and tin and antimony fission products were shown to be less than 0.3 percent, so tellurium nuclides, not their precursors, reacted with CO. It was found that CO reacted preferentially with independently produced tellurium atoms; the reaction efficiency of beta-produced atoms was only 27 +- 3 percent of that of the independently formed atoms. The selectivity, which was independent of the over-all reaction efficiency, was shown to be due to reaction of independently formed atoms in the gas phase. The gas phase reactions are believed to occur mainly at thermal energies because of the independence of the yield upon argon moderator mole-fraction (up to 80 percent). It was shown in some experiments that about one-half of the TeCO decomposed in passing through a filter and that an appreciable fraction (approximately 20 percent) of the tellurium atoms deposited on the filter reacted agin with CO. Other tellurium atoms on the filter surface (those formed by beta decay and those formed independently but not reacting in the gas phase) also reacted with CO, but probably somewhat less efficiently than atoms formed by TeCO decomposition. No evidence was found for formation of TeCO as a direct result of beta-decay

  16. Gas phase fractionation method using porous ceramic membrane

    Science.gov (United States)

    Peterson, Reid A.; Hill, Jr., Charles G.; Anderson, Marc A.

    1996-01-01

    Flaw-free porous ceramic membranes fabricated from metal sols and coated onto a porous support are advantageously used in gas phase fractionation methods. Mean pore diameters of less than 40 .ANG., preferably 5-20 .ANG. and most preferably about 15 .ANG., are permeable at lower pressures than existing membranes. Condensation of gases in small pores and non-Knudsen membrane transport mechanisms are employed to facilitate and increase membrane permeability and permselectivity.

  17. Gas Phase Hydrogenation of Levulinic Acid to gamma-Valerolactone

    NARCIS (Netherlands)

    Bonrath, Werner; Castelijns, Anna Maria Cornelia Francisca; de Vries, Johannes Gerardus; Guit, Rudolf Philippus Maria; Schuetz, Jan; Sereinig, Natascha; Vaessen, Henricus Wilhelmus Leonardus Marie

    The gas phase hydrogenation of levulinic acid to gamma-valerolactone over copper and ruthenium based catalysts in a continuous fixed-bed reactor system was investigated. Among the catalysts a copper oxide based one [50-75 % CuO, 20-25 % SiO2, 1-5 % graphite, 0.1-1 % CuCO3/Cu(OH)(2)] gave

  18. Understanding Gas-Phase Ammonia Chemistry in Protoplanetary Disks

    Science.gov (United States)

    Chambers, Lauren; Oberg, Karin I.; Cleeves, Lauren Ilsedore

    2017-01-01

    Protoplanetary disks are dynamic regions of gas and dust around young stars, the remnants of star formation, that evolve and coagulate over millions of years in order to ultimately form planets. The chemical composition of protoplanetary disks is affected by both the chemical and physical conditions in which they develop, including the initial molecular abundances in the birth cloud, the spectrum and intensity of radiation from the host star and nearby systems, and mixing and turbulence within the disk. A more complete understanding of the chemical evolution of disks enables a more complete understanding of the chemical composition of planets that may form within them, and of their capability to support life. One element known to be essential for life on Earth is nitrogen, which often is present in the form of ammonia (NH3). Recent observations by Salinas et al. (2016) reveal a theoretical discrepancy in the gas-phase and ice-phase ammonia abundances in protoplanetary disks; while observations of comets and protostars estimate the ice-phase NH3/H2O ratio in disks to be 5%, Salinas reports a gas-phase NH3/H2O ratio of ~7-84% in the disk surrounding TW Hydra, a young nearby star. Through computational chemical modeling of the TW Hydra disk using a reaction network of over 5000 chemical reactions, I am investigating the possible sources of excess gas-phase NH3 by determining the primary reaction pathways of NH3 production; the downstream chemical effects of ionization by ultraviolet photons, X-rays, and cosmic rays; and the effects of altering the initial abundances of key molecules such as N and N2. Beyond providing a theoretical explanation for the NH3 ice/gas discrepancy, this new model may lead to fuller understanding of the gas-phase formation processes of all nitrogen hydrides (NHx), and thus fuller understanding of the nitrogen-bearing molecules that are fundamental for life as we know it.

  19. Improved machine learning method for analysis of gas phase chemistry of peptides

    Directory of Open Access Journals (Sweden)

    Ahn Natalie

    2008-12-01

    Full Text Available Abstract Background Accurate peptide identification is important to high-throughput proteomics analyses that use mass spectrometry. Search programs compare fragmentation spectra (MS/MS of peptides from complex digests with theoretically derived spectra from a database of protein sequences. Improved discrimination is achieved with theoretical spectra that are based on simulating gas phase chemistry of the peptides, but the limited understanding of those processes affects the accuracy of predictions from theoretical spectra. Results We employed a robust data mining strategy using new feature annotation functions of MAE software, which revealed under-prediction of the frequency of occurrence in fragmentation of the second peptide bond. We applied methods of exploratory data analysis to pre-process the information in the MS/MS spectra, including data normalization and attribute selection, to reduce the attributes to a smaller, less correlated set for machine learning studies. We then compared our rule building machine learning program, DataSqueezer, with commonly used association rules and decision tree algorithms. All used machine learning algorithms produced similar results that were consistent with expected properties for a second gas phase mechanism at the second peptide bond. Conclusion The results provide compelling evidence that we have identified underlying chemical properties in the data that suggest the existence of an additional gas phase mechanism for the second peptide bond. Thus, the methods described in this study provide a valuable approach for analyses of this kind in the future.

  20. Spectroscopic study on the stability of morin in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Bark, Ki Min [Dept. of Chemical Education and Research Institute of Life Science, Gyeongsang National University, Chinju (Korea, Republic of); Im, Seo Eun; Seo, Jung Ja; Park, Ok Hyun; Park, Hyoung Ryun [Dept. of Chemistry, Chonnam National University, Gwangju (Korea, Republic of); Park, Chul Ho [Dept. of Cosmetic Science, Nambu University, Gwangju (Korea, Republic of)

    2015-02-15

    Morin (3,2,4,5,7-pentahydroxyflavone) is a flavonol conjugated to a resorcinol moiety at the C-2 position, different from many other flavonoids. The UV–vis spectrum of morin in neat water reveals two major absorption bands with maxima at 265 and 387 nm. The substance is stable in acidic solution and neat water. However, its absorption maximum at 387 nm continuously shifts to longer wavelengths and new peaks appeared at wavelengths of 312 nm with increasing pH of the solution. The shape of the absorption spectrum of morin depends on the storage time at a given pH, indicating the occurrence of other successive chemical reactions. The fluorescence spectroscopic results also prove that new conjugated double bonds are formed in the deaerated basic solution at the initial state and decompose with time. This behavior indicates that morin is very unstable, and therefore its decomposition occurs by a sequence of multistep reactions in basic solution. Probable reaction pathways for the reaction are suggested based on the spectroscopic results.

  1. Gas phase decontamination of gaseous diffusion process equipment

    International Nuclear Information System (INIS)

    Bundy, R.D.; Munday, E.B.; Simmons, D.W.; Neiswander, D.W.

    1994-01-01

    D ampersand D of the process facilities at the gaseous diffusion plants (GDPs) will be an enormous task. The EBASCO estimate places the cost of D ampersand D of the GDP at the K-25 Site at approximately $7.5 billion. Of this sum, nearly $4 billion is associated with the construction and operation of decontamination facilities and the dismantlement and transport of contaminated process equipment to these facilities. In situ long-term low-temperature (LTLT) gas phase decontamination is being developed and demonstrated at the K-25 site as a technology that has the potential to substantially lower these costs while reducing criticality and safeguards concerns and worker exposure to hazardous and radioactive materials. The objective of gas phase decontamination is to employ a gaseous reagent to fluorinate nonvolatile uranium deposits to form volatile LJF6, which can be recovered by chemical trapping or freezing. The LTLT process permits the decontamination of the inside of gas-tight GDP process equipment at room temperature by substituting a long exposure to subatmospheric C1F for higher reaction rates at higher temperatures. This paper outlines the concept for applying LTLT gas phase decontamination, reports encouraging laboratory experiments, and presents the status of the design of a prototype mobile system. Plans for demonstrating the LTLT process on full-size gaseous diffusion equipment are also outlined briefly

  2. Investigation of gas-phase decontamination of internally radioactively contaminated gaseous diffusion process equipment and piping

    International Nuclear Information System (INIS)

    Bundy, R.D.; Munday, E.B.

    1991-01-01

    Construction of the gaseous diffusion plants (GDPs) was begun during World War 2 to produce enriched uranium for defense purposes. These plants, which utilized UF 6 gas, were used primarily for this purpose through 1964. From 1959 through 1968, production shifted primarily to uranium enrichment to supply the nuclear power industry. Additional UF 6 -handling facilities were built in feed and fuel-processing plants associated with the uranium enrichment process. Two of the five process buildings at Oak ridge were shut down in 1964. Uranium enrichment activities at Oak Ridge were discontinued altogether in 1985. In 1987, the Department of Energy (DOE) decided to proceed with a permanent shutdown of the Oak Ridge Gaseous Diffusion Plant (ORGDP). DOE intends to begin decommissioning and decontamination (D ampersand D) of ORGDP early in the next century. The remaining two GDPs are expected to be shut down during the next 10 to 40 years and will also require D ampersand D, as will the other UF 6 -handling facilities. This paper presents an investigation of gas- phase decontamination of internally radioactively contaminated gaseous diffusion process equipment and piping using powerful fluorinating reagents that convert nonvolatile uranium compounds to volatile UF 6 . These reagents include ClF 3 , F 2 , and other compounds. The scope of D ampersand D at the GDPs, previous work of gas-phase decontamination, four concepts for using gas-phase decontamination, plans for further study of gas-phase decontamination, and the current status of this work are discussed. 13 refs., 15 figs

  3. Conformational Preferences of Glycerol in the Gas Phase and in Water

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Keun Hong [Korea Military Academy, Seoul (Korea, Republic of); Byun, Byung Jin; Kang, Young Kee [Chungbuk National University, Cheongju (Korea, Republic of)

    2012-03-15

    The conformational study of glycerol has been carried out using the M06-2X/cc-pVTZ level of theory in the gas phase and the SMD M06-2X/cc-pVTZ level of theory in water in order to understand its conformational preferences and solvation effects. Most of the preferred conformers of glycerol have two C{sub 5} hydrogen bonds in the gas phase, as found by the analysis of calorimetric data. It has been known that the solvation drove the hydrogen bonds of glycerol to be weaker and its potential surface to be fatter and that glycerol exists as an ensemble of many feasible local minima in water. The calculated populations of glycerol in the gas phase and in water are consistent with the observed values, which are better than the previously calculated ones at the G2(MP2), CBS-QB3, and SM5.42 HF/6-31G(d) levels of theory

  4. Statistical parameter characteristics of gas-phase fluctuations for gas-liquid intermittent flow

    Energy Technology Data Exchange (ETDEWEB)

    Matsui, G.; Monji, H.; Takaguchi, M. [Univ. of Tsukuba (Japan)

    1995-09-01

    This study deals with theoretical analysis on the general behaviour of statistical parameters of gas-phase fluctuations and comparison of statistical parameter characteristics for the real void fraction fluctuations measured with those for the wave form modified the real fluctuations. In order to investigate the details of the relation between the behavior of the statistical parameters in real intermittent flow and analytical results obtained from information on the real flow, the distributions of statistical parameters for general fundamental wave form of gas-phase fluctuations are discussed in detail. By modifying the real gas-phase fluctuations to a trapezoidaly wave, the experimental results can be directly compared with the analytical results. The analytical results for intermittent flow show that the wave form parameter, and the total amplitude of void fraction fluctuations, affects strongly on the statistical parameter characteristics. The comparison with experiment using nitrogen gas-water intermittent flow suggests that the parameters of skewness and excess may be better as indicators of flow pattern. That is, the macroscopic nature of intermittent flow can be grasped by the skewness and the excess, and the detailed flow structure may be described by the mean and the standard deviation.

  5. Statistical parameter characteristics of gas-phase fluctuations for gas-liquid intermittent flow

    International Nuclear Information System (INIS)

    Matsui, G.; Monji, H.; Takaguchi, M.

    1995-01-01

    This study deals with theoretical analysis on the general behaviour of statistical parameters of gas-phase fluctuations and comparison of statistical parameter characteristics for the real void fraction fluctuations measured with those for the wave form modified the real fluctuations. In order to investigate the details of the relation between the behavior of the statistical parameters in real intermittent flow and analytical results obtained from information on the real flow, the distributions of statistical parameters for general fundamental wave form of gas-phase fluctuations are discussed in detail. By modifying the real gas-phase fluctuations to a trapezoidaly wave, the experimental results can be directly compared with the analytical results. The analytical results for intermittent flow show that the wave form parameter, and the total amplitude of void fraction fluctuations, affects strongly on the statistical parameter characteristics. The comparison with experiment using nitrogen gas-water intermittent flow suggests that the parameters of skewness and excess may be better as indicators of flow pattern. That is, the macroscopic nature of intermittent flow can be grasped by the skewness and the excess, and the detailed flow structure may be described by the mean and the standard deviation

  6. Gas-phase advanced oxidation as an integrated air pollution control technique

    Directory of Open Access Journals (Sweden)

    Getachew A. Adnew

    2016-03-01

    Full Text Available Gas-phase advanced oxidation (GPAO is an emerging air cleaning technology based on the natural self-cleaning processes that occur in the Earth’s atmosphere. The technology uses ozone, UV-C lamps and water vapor to generate gas-phase hydroxyl radicals that initiate oxidation of a wide range of pollutants. In this study four types of GPAO systems are presented: a laboratory scale prototype, a shipping container prototype, a modular prototype, and commercial scale GPAO installations. The GPAO systems treat volatile organic compounds, reduced sulfur compounds, amines, ozone, nitrogen oxides, particles and odor. While the method covers a wide range of pollutants, effective treatment becomes difficult when temperature is outside the range of 0 to 80 °C, for anoxic gas streams and for pollution loads exceeding ca. 1000 ppm. Air residence time in the system and the rate of reaction of a given pollutant with hydroxyl radicals determine the removal efficiency of GPAO. For gas phase compounds and odors including VOCs (e.g. C6H6 and C3H8 and reduced sulfur compounds (e.g. H2S and CH3SH, removal efficiencies exceed 80%. The method is energy efficient relative to many established technologies and is applicable to pollutants emitted from diverse sources including food processing, foundries, water treatment, biofuel generation, and petrochemical industries.

  7. Spectroscopic ellipsometry study of FePt nanoparticle films

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.J.; Lo, C.C.H. [Ames Laboratory, Iowa State University, Ames, IA 50011 (United States); Yu, A.C.C. [Sony Corporation, Sendai Technology Center, 3-4-1 Sakuragi, Miyagi 985-0842 (Japan); Fan, M. [School of Materials Science and Technology, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States)

    2006-12-15

    The optical properties of a FePt nanoparticle film were investigated using spectroscopic ellipsometry. The FePt nanoparticle film of thickness about 15 nm was prepared by deposition of FePt nanoparticles directly on a Si substrate. The nanoparticle film was annealed at 600 C in vacuum for two hours before the measurements. The optical properties of the FePt nanoparticle film showed distinctively different spectra from those obtained from the bulk and thin film FePt samples, in particular in the low photon energy range (below 3.5 eV) where the nanoparticle film exhibited a relatively flat refractive index and a substantially lower extinction coefficient than the bulk and epitaxial thin film samples. (copyright 2006 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  8. A spectroscopic study of uranium(VI) interaction with magnetite

    International Nuclear Information System (INIS)

    El Aamrani, S.; Gimenez, J.; Rovira, M.; Seco, F.; Grive, M.; Bruno, J.; Duro, L.; Pablo, J. de

    2007-01-01

    The uranium sorbed onto commercial magnetite has been characterized by using two different spectroscopic techniques such as X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS). Magnetite samples have been put in contact with uranium(VI) solutions in conditions in which a high uranium uptake is expected. After several days, the magnetite surface has been analysed by XPS and EXAFS. The XPS results obtained are not conclusive regarding the uranium oxidation state in the magnetite surface. On the other hand, the results obtained with the EXAFS technique show that the uranium-magnetite sample spectrum has characteristics from both the UO 2 and schoepite spectra, e.g. a relatively high coordination number of equatorial oxygens and two axial oxygens, respectively. These results would indicate that the uranium sorbed onto magnetite would be a mixture of uranium(IV) and uranium(VI)

  9. Study of single-nucleon spectroscopic characteristics in light nuclei

    International Nuclear Information System (INIS)

    Zhusupova, K.A.

    1998-01-01

    Single-nucleon characteristics of 1 p-shell nuclei are investigated in the thesis. These characteristics are necessary for describing nuclear processes leaded to separation of target nuclei or to addition of one nucleon to it. Multi-particle shell model and three-body cluster model (for 6 L i and 9 Be) are used. It is shown that shell model explains well spectroscopic S-factors for stripping and pick-up reactions of nucleon. Three body α2 N-model reproduces well S-factors and momentum distribution extracted from (e, e p) reactions for separation of proton from ground state of 6 L i nucleus accompanied by appearance of ground and high exited states of 5 He nucleolus. The classification and explanation for small value nucleon partial widths for high lying states for odd nuclei 1 p-shell with isospin T=3/2 are given. (author)

  10. Spectroscopic and computational studies of ionic clusters as models of solvation and atmospheric reactions

    Science.gov (United States)

    Kuwata, Keith T.

    Ionic clusters are useful as model systems for the study of fundamental processes in solution and in the atmosphere. Their structure and reactivity can be studied in detail using vibrational predissociation spectroscopy, in conjunction with high level ab initio calculations. This thesis presents the applications of infrared spectroscopy and computation to a variety of gas-phase cluster systems. A crucial component of the process of stratospheric ozone depletion is the action of polar stratospheric clouds (PSCs) to convert the reservoir species HCl and chlorine nitrate (ClONO2) to photochemically labile compounds. Quantum chemistry was used to explore one possible mechanism by which this activation is effected: Cl- + ClONO2 /to Cl2 + NO3- eqno(1)Correlated ab initio calculations predicted that the direct reaction of chloride ion with ClONO2 is facile, which was confirmed in an experimental kinetics study. In the reaction a weakly bound intermediate Cl2-NO3- is formed, with ~70% of the charge localized on the nitrate moiety. This enables the Cl2-NO3- cluster to be well solvated even in bulk solution, allowing (1) to be facile on PSCs. Quantum chemistry was also applied to the hydration of nitrosonium ion (NO+), an important process in the ionosphere. The calculations, in conjunction with an infrared spectroscopy experiment, revealed the structure of the gas-phase clusters NO+(H2O)n. The large degree of covalent interaction between NO+ and the lone pairs of the H2O ligands is contrasted with the weak electrostatic bonding between iodide ion and H2O. Finally, the competition between ion solvation and solvent self-association is explored for the gas-phase clusters Cl/-(H2O)n and Cl-(NH3)n. For the case of water, vibrational predissociation spectroscopy reveals less hydrogen bonding among H2O ligands than predicted by ab initio calculations. Nevertheless, for n /ge 5, cluster structure is dominated by water-water interactions, with Cl- only partially solvated by the

  11. Synergistic effects of liquid and gas phase discharges using pulsed high voltage for dyes degradation in the presence of oxygen.

    Science.gov (United States)

    Yang, Bin; Zhou, Minghua; Lei, Lecheng

    2005-07-01

    The technology of combined liquid and gas phase discharges (LGD) using pulsed high voltage for dyes degradation was developed in this study. Apparent synergistic effects for Acid orange II (AO) degradation in the presence of oxygen were observed. The enhancement of AO degradation rate was around 302%. Furthermore, higher energy efficiency was obtained comparing with individual liquid phase discharge (LD) or gas phase discharge process (GD). The AO degradation in the presence of oxygen by LGD proceeded through the direct ozone oxidation and the ozone decomposition induced by LD. Important operating parameters such as electrode distance, applied voltage, pulse repetition rate, and types of dyes were further investigated.

  12. Noncovalent Halogen Bonding as a Mechanism for Gas-Phase Clustering

    DEFF Research Database (Denmark)

    Wegeberg, Christina; Donald, William A.; McKenzie, Christine

    2017-01-01

    in the crystalline phases of PhIO2 and its derivatives serve as models for the structures of larger gas-phase clusters, and calculations on simple model gas-phase dimer and trimer clusters result in similar motifs. This is the first account of halogen bonding playing an extensive role in gas-phase associations....

  13. Facility at CIRUS reactor for thermal neutron induced prompt γ-ray spectroscopic studies

    International Nuclear Information System (INIS)

    Biswas, D.C.; Danu, L.S.; Mukhopadhyay, S.; Kinage, L.A.; Prashanth, P.N.; Goswami, A.; Sahu, A.K.; Shaikh, A.M.; Chatterjee, A.; Choudhury, R.K.; Kailas, S.

    2013-01-01

    A facility for prompt γ-ray spectroscopic studies using thermal neutrons from a radial beam line of Canada India Research Utility Services (CIRUS) reactor, Bhabha Atomic Research Centre (BARC), has been developed. To carry out on-line spectroscopy experiments, two clover germanium detectors were used for the measurement of prompt γ rays. For the first time, the prompt γ–γ coincidence technique has been used to study the thermal neutron induced fission fragment spectroscopy (FFS) in 235 U(n th , f). Using this facility, experiments have also been carried out for on-line γ-ray spectroscopic studies in 113 Cd(n th , γ) reaction

  14. Electrochemical and spectroscopic studies of uranium(IV), -(V), and -(VI) in carbonate-bicarbonate buffers

    International Nuclear Information System (INIS)

    Wester, D.W.; Sullivan, J.C.

    1980-01-01

    Recently a need for more detailed knowledge of the chemistry of actinide ions in basic media has arisen in connection with deducing their chemistry in the environment. In this work the results of polarographic, cyclic voltammetric, and spectroscopic studies of U(IV), -(V), and -(VI) in carbonate and bicarbonate media are reported. Polarographic studies were in excellent agreement with those reported previously. Cyclic voltammetric scans confirmed the irreversible reduction to U(V) in both solutions, but disproportionation of the U(V) was observed only in the bicarbonate solutions. The oxidation of U(V) in carbonate was followed spectroscopically for the first time. Reduction in bicarbonate produced U(IV), the spectrum of which is now reported and the oxidation of which was also followed spectroscopically for the first time

  15. Dielectric and impedance spectroscopic studies of neodymium gallate

    Energy Technology Data Exchange (ETDEWEB)

    Sakhya, Anup Pradhan, E-mail: npshakya31@gmail.com [Department of Physics, Bose Institute, 93/1 Acharya Prafulla Chandra Road, Kolkata 700009 (India); Dutta, Alo [Department of Condensed Matter Physics and Material Sciences, S. N. Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata 700098 (India); Sinha, T.P. [Department of Physics, Bose Institute, 93/1 Acharya Prafulla Chandra Road, Kolkata 700009 (India)

    2016-05-01

    The AC electrical properties of a polycrystalline neodymium gallate, NdGaO{sub 3} (NGO), synthesized by the sol–gel method have been investigated by employing impedance spectroscopy in the frequency range from 42 Hz to 5 MHz and in the temperature range from 323 K to 593 K. The X-ray diffraction analysis shows that the compound crystallizes in the orthorhombic phase with Pbnm space group at room temperature. Two relaxation processes with different relaxation times are observed from the impedance as well as modulus spectroscopic measurements, which have been attributed to the grain and the grain boundary effects at different temperatures in NGO. The complex impedance data are analyzed by an electrical equivalent circuit consisting of a resistance and a constant phase element in parallel. It has been observed that the value of the capacitance and the resistance associated with the grain boundary is higher than those associated with the grain. The temperature dependent electrical conductivity shows the negative temperature coefficient of resistance. The frequency dependent conductivity spectra are found to follow the power law.

  16. Vibrational Spectroscopic Studies of Tenofovir Using Density Functional Theory Method

    Directory of Open Access Journals (Sweden)

    G. R. Ramkumaar

    2013-01-01

    Full Text Available A systematic vibrational spectroscopic assignment and analysis of tenofovir has been carried out by using FTIR and FT-Raman spectral data. The vibrational analysis was aided by electronic structure calculations—hybrid density functional methods (B3LYP/6-311++G(d,p, B3LYP/6-31G(d,p, and B3PW91/6-31G(d,p. Molecular equilibrium geometries, electronic energies, IR intensities, and harmonic vibrational frequencies have been computed. The assignments proposed based on the experimental IR and Raman spectra have been reviewed and complete assignment of the observed spectra have been proposed. UV-visible spectrum of the compound was also recorded and the electronic properties such as HOMO and LUMO energies and were determined by time-dependent DFT (TD-DFT method. The geometrical, thermodynamical parameters, and absorption wavelengths were compared with the experimental data. The B3LYP/6-311++G(d,p-, B3LYP/6-31G(d,p-, and B3PW91/6-31G(d,p-based NMR calculation procedure was also done. It was used to assign the 13C and 1H NMR chemical shift of tenofovir.

  17. Gas-phase spectroscopy of ferric heme-NO complexes

    DEFF Research Database (Denmark)

    Wyer, J.A.; Jørgensen, Anders; Pedersen, Bjarke

    2013-01-01

    and significantly blue-shifted compared to ferric heme nitrosyl proteins (maxima between 408 and 422 nm). This is in stark contrast to the Q-band absorption where the protein microenvironment is nearly innocent in perturbing the electronic structure of the porphyrin macrocycle. Photodissociation is primarily...... maxima of heme and its complexes with amino acids and NO. Not so innocent: Weakly bound complexes between ferric heme and NO were synthesised in the gas phase, and their absorption measured from photodissociation yields. Opposite absorption trends in the Soret-band are seen upon NO addition to heme ions...

  18. The nuclear liquid gas phase transition and phase coexistence

    International Nuclear Information System (INIS)

    Chomaz, Ph.

    2001-01-01

    In this talk we will review the different signals of liquid gas phase transition in nuclei. From the theoretical side we will first discuss the foundations of the concept of equilibrium, phase transition and critical behaviors in infinite and finite systems. From the experimental point of view we will first recall the evidences for some strong modification of the behavior of hot nuclei. Then we will review quantitative detailed analysis aiming to evidence phase transition, to define its order and phase diagram. Finally, we will present a critical discussion of the present status of phase transitions in nuclei and we will draw some lines for future development of this field. (author)

  19. The nuclear liquid gas phase transition and phase coexistence

    Energy Technology Data Exchange (ETDEWEB)

    Chomaz, Ph

    2001-07-01

    In this talk we will review the different signals of liquid gas phase transition in nuclei. From the theoretical side we will first discuss the foundations of the concept of equilibrium, phase transition and critical behaviors in infinite and finite systems. From the experimental point of view we will first recall the evidences for some strong modification of the behavior of hot nuclei. Then we will review quantitative detailed analysis aiming to evidence phase transition, to define its order and phase diagram. Finally, we will present a critical discussion of the present status of phase transitions in nuclei and we will draw some lines for future development of this field. (author)

  20. Angular intensity of a gas-phase field ionization source

    International Nuclear Information System (INIS)

    Orloff, J.; Swanson, L.W.

    1979-01-01

    Angular intensities of 1 μA sr -1 have been measured for a gas-phase field ionization source in an optical column under practical operating conditions. The source, which was differentially pumped and cooled to 77 K, utilized a -oriented iridium emitter and precooled hydrogen gas at 10 -2 Torr. The ion beam was collimated with an electrostatic lens and detected below an aperture subtending 0.164 msr. A transmitted current of approx.10 -10 A was measured at voltages corresponding to a field of approx. =2.2 V/A at the emitter

  1. Elastic properties and spectroscopic studies of Na 2 O–ZnO–B 2 O 3 ...

    Indian Academy of Sciences (India)

    Elastic properties, 11B MAS–NMR and IR spectroscopic studies have been employed to study the structure of Na2O–ZnO–B2O3 glasses. Sound velocities and elastic moduli such as longitudinal, Young's, bulk and shear modulus have been measured at a frequency of 10 MHz as a function of ZnO concentration.

  2. Supramolecular architecture of 5-bromo-7-methoxy-1-methyl-1H-benzoimidazole.3H2O: Synthesis, spectroscopic investigations, DFT computation, MD simulations and docking studies

    Science.gov (United States)

    Murthy, P. Krishna; Smitha, M.; Sheena Mary, Y.; Armaković, Stevan; Armaković, Sanja J.; Rao, R. Sreenivasa; Suchetan, P. A.; Giri, L.; Pavithran, Rani; Van Alsenoy, C.

    2017-12-01

    Crystal and molecular structure of newly synthesized compound 5-bromo-7-methoxy-1-methyl-1H-benzoimidazole (BMMBI) has been authenticated by single crystal X-ray diffraction, FT-IR, FT-Raman, 1H NMR, 13C NMR and UV-Visible spectroscopic techniques; compile both experimental and theoretical results which are performed by DFT/B3LYP/6-311++G(d,p) method at ground state in gas phase. Visualize nature and type of intermolecular interactions and crucial role of these interactions in supra-molecular architecture has been investigated by use of a set of graphical tools 3D-Hirshfeld surfaces and 2D-fingerprint plots analysis. The title compound stabilized by strong intermolecular hydrogen bonds N⋯Hsbnd O and O⋯Hsbnd O, which are envisaged by dark red spots on dnorm mapped surfaces and weak Br⋯Br contacts envisaged by red spot on dnorm mapped surface. The detailed fundamental vibrational assignments of wavenumbers were aid by with help of Potential Energy distribution (PED) analysis by using GAR2PED program and shows good agreement with experimental values. Besides frontier orbitals analysis, global reactivity descriptors, natural bond orbitals and Mullikan charges analysis were performed by same basic set at ground state in gas phase. Potential reactive sites of the title compound have been identified by ALIE, Fukui functions and MEP, which are mapped to the electron density surfaces. Stability of BMMBI have been investigated from autoxidation process and pronounced interaction with water (hydrolysis) by using bond dissociation energies (BDE) and radial distribution functions (RDF), respectively after MD simulations. In order to identify molecule's most important reactive spots we have used a combination of DFT calculations and MD simulations. Reactivity study encompassed calculations of a set of quantities such as: HOMO-LUMO gap, MEP and ALIE surfaces, Fukui functions, bond dissociation energies and radial distribution functions. To confirm the potential

  3. Preconceptual design of the gas-phase decontamination demonstration cart

    International Nuclear Information System (INIS)

    Munday, E.B.

    1993-12-01

    Removal of uranium deposits from the interior surfaces of gaseous diffusion equipment will be a major portion of the overall multibillion dollar effort to decontaminate and decommission the gaseous diffusion plants. Long-term low-temperature (LTLT) gas-phase decontamination is being developed at the K-25 Site as an in situ decontamination process that is expected to significantly lower the decontamination costs, reduce worker exposure to radioactive materials, and reduce safeguard concerns. This report documents the preconceptual design of the process equipment that is necessary to conduct a full-scale demonstration of the LTLT method in accordance with the process steps listed above. The process equipment and method proposed in this report are not intended to represent a full-scale production campaign design and operation, since the gas evacuation, gas charging, and off-gas handling systems that would be cost effective in a production campaign are not cost effective for a first-time demonstration. However, the design presented here is expected to be applicable to special decontamination projects beyond the demonstration, which could include the Deposit Recovery Program. The equipment will therefore be sized to a 200 ft size 1 converter (plus a substantial conservative design margin), which is the largest item of interest for gas phase decontamination in the Deposit Recovery Program. The decontamination equipment will allow recovery of the UF 6 , which is generated from the reaction of ClF 3 with the uranium deposits, by use of NaF traps

  4. High-Pressure Catalytic Reactions of C6 Hydrocarbons on PlatinumSingle-Crystals and nanoparticles: A Sum Frequency Generation VibrationalSpectroscopic and Kinetic Study

    Energy Technology Data Exchange (ETDEWEB)

    Bratlie, Kaitlin [Univ. of California, Berkeley, CA (United States)

    2007-01-01

    Catalytic reactions of cyclohexene, benzene, n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene on platinum catalysts were monitored in situ via sum frequency generation (SFG) vibrational spectroscopy and gas chromatography (GC). SFG is a surface specific vibrational spectroscopic tool capable of monitoring submonolayer coverages under reaction conditions without gas-phase interference. SFG was used to identify the surface intermediates present during catalytic processes on Pt(111) and Pt(100) single-crystals and on cubic and cuboctahedra Pt nanoparticles in the Torr pressure regime and at high temperatures (300K-450K). At low pressures (<10-6 Torr), cyclohexene hydrogenated and dehydrogenates to form cyclohexyl (C6H11) and π-allyl C6H9, respectively, on Pt(100). Increasing pressures to 1.5 Torr form cyclohexyl, π-allyl C6H9, and 1,4-cyclohexadiene, illustrating the necessity to investigate catalytic reactions at high-pressures. Simultaneously, GC was used to acquire turnover rates that were correlated to reactive intermediates observed spectroscopically. Benzene hydrogenation on Pt(111) and Pt(100) illustrated structure sensitivity via both vibrational spectroscopy and kinetics. Both cyclohexane and cyclohexene were produced on Pt(111), while only cyclohexane was formed on Pt(100). Additionally, π-allyl c-C6H9 was found only on Pt(100), indicating that cyclohexene rapidly dehydrogenates on the (100) surface. The structure insensitive production of cyclohexane was found to exhibit a compensation effect and was analyzed using the selective energy transfer (SET) model. The SET model suggests that the Pt-H system donates energy to the E2u mode of free benzene, which leads to catalysis. Linear C6 (n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene) hydrocarbons were also investigated in the presence and absence of excess hydrogen on Pt

  5. Enantioselective supramolecular devices in the gas phase. Resorcin[4]arene as a model system

    Directory of Open Access Journals (Sweden)

    Caterina Fraschetti

    2012-04-01

    Full Text Available This review describes the state-of-art in the field of the gas-phase reactivity of diastereomeric complexes formed between a chiral artificial receptor and a biologically active molecule. The presented experimental approach is a ligand-displacement reaction carried out in a nano ESI-FT-ICR instrument, supported by a thermodynamic MS-study and molecular-mechanics and molecular-dynamics (MM/MD computational techniques. The noncovalent ion–molecule complexes are ideal for the study of chiral recognition in the absence of complicating solvent and counterion effects.

  6. New set-up for high-quality soft-X-ray absorption spectroscopy of large organic molecules in the gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Holch, Florian; Huebner, Dominique [Universitaet Wuerzburg, Experimentelle Physik VII, Am and Roentgen Reasearch Center for Complex Materials (RCCM) Hubland, 97074 Wuerzburg (Germany); Fink, Rainer [Universitaet Erlangen-Nuernberg, ICMM and CENEM, Egerlandstrasse 3, 91058 Erlangen (Germany); Schoell, Achim, E-mail: achim.schoell@physik.uni-wuerzburg.de [Universitaet Wuerzburg, Experimentelle Physik VII, Am and Roentgen Reasearch Center for Complex Materials (RCCM) Hubland, 97074 Wuerzburg (Germany); Umbach, Eberhard [Karlsruhe Institute of Technology, 76021 Karlsruhe (Germany)

    2011-11-15

    Highlights: {yields} We present a new set-up for x-ray absorption (NEXAFS) on large molecules in the gas-phase. {yields} The cell has a confined volume and can be heated. {yields} The spectra can be acquired fast, are of very high quality with respect tosignal-to-noise ratio and energy resolution. {yields} This allowsthe analysis of spectroscopic details (e.g. solid state effects by comparing gas- and condensed phase data). - Abstract: We present a new experimental set-up for the investigation of large (>128 amu) organic molecules in the gas-phase by means of near-edge X-ray absorption fine structure spectroscopy in the soft X-ray range. Our approach uses a gas cell, which is sealed off against the surrounding vacuum and which can be heated above the sublimation temperature of the respective molecular compound. Using a confined volume rather than a molecular beam yields short acquisition times and intense signals due to the high molecular density, which can be tuned by the container temperature. In turn, the resulting spectra are of very high quality with respect to signal-to-noise ratio and energy resolution, which are the essential aspects for the analysis of fine spectroscopic details. Using the examples of ANQ, NTCDA, and PTCDA, specific challenges of gas phase measurements on large organic molecules with high sublimation temperatures are addressed in detail with respect to the presented set-up and possible ways to tackle them are outlined.

  7. Gas phase precursors to anthropogenic secondary organic aerosol: detailed observations of 1,3,5-trimethylbenzene photooxidation

    Directory of Open Access Journals (Sweden)

    K. P. Wyche

    2009-01-01

    Full Text Available A series of photooxidation experiments were conducted in an atmospheric simulation chamber in order to investigate the oxidation mechanism and secondary organic aerosol (SOA formation potential of the model anthropogenic gas phase precursor, 1,3,5-trimethylbenzene. Alongside specific aerosol measurements, comprehensive gas phase measurements, primarily by Chemical Ionisation Reaction Time-of-Flight Mass Spectrometry (CIR-TOF-MS, were carried out to provide detailed insight into the composition and behaviour of the organic components of the gas phase matrix during SOA formation. An array of gas phase organic compounds was measured during the oxidation process, including several previously unmeasured primary bicyclic compounds possessing various functional groups. Analysis of results obtained during this study implies that these peroxide bicyclic species along with a series of ring opening products and organic acids contribute to SOA growth. The effect of varying the VOC/NOx ratio on SOA formation was explored, as was the effect of acid seeding. It was found that low NOx conditions favour more rapid aerosol formation and a higher aerosol yield, a result that implies a role for organic peroxides in the nucleation process and SOA growth.

  8. Source characterization and exposure modeling of gas-phase polycyclic aromatic hydrocarbon (PAH) concentrations in Southern California

    Science.gov (United States)

    Masri, Shahir; Li, Lianfa; Dang, Andy; Chung, Judith H.; Chen, Jiu-Chiuan; Fan, Zhi-Hua (Tina); Wu, Jun

    2018-03-01

    Airborne exposures to polycyclic aromatic hydrocarbons (PAHs) are associated with adverse health outcomes. Because personal air measurements of PAHs are labor intensive and costly, spatial PAH exposure models are useful for epidemiological studies. However, few studies provide adequate spatial coverage to reflect intra-urban variability of ambient PAHs. In this study, we collected 39-40 weekly gas-phase PAH samples in southern California twice in summer and twice in winter, 2009, in order to characterize PAH source contributions and develop spatial models that can estimate gas-phase PAH concentrations at a high resolution. A spatial mixed regression model was constructed, including such variables as roadway, traffic, land-use, vegetation index, commercial cooking facilities, meteorology, and population density. Cross validation of the model resulted in an R2 of 0.66 for summer and 0.77 for winter. Results showed higher total PAH concentrations in winter. Pyrogenic sources, such as fossil fuels and diesel exhaust, were the most dominant contributors to total PAHs. PAH sources varied by season, with a higher fossil fuel and wood burning contribution in winter. Spatial autocorrelation accounted for a substantial amount of the variance in total PAH concentrations for both winter (56%) and summer (19%). In summer, other key variables explaining the variance included meteorological factors (9%), population density (15%), and roadway length (21%). In winter, the variance was also explained by traffic density (16%). In this study, source characterization confirmed the dominance of traffic and other fossil fuel sources to total measured gas-phase PAH concentrations while a spatial exposure model identified key predictors of PAH concentrations. Gas-phase PAH source characterization and exposure estimation is of high utility to epidemiologist and policy makers interested in understanding the health impacts of gas-phase PAHs and strategies to reduce emissions.

  9. Gas-Phase Photocatalytic Oxidation of Dimethylamine: The Reaction Pathway and Kinetics

    Directory of Open Access Journals (Sweden)

    Anna Kachina

    2007-01-01

    Full Text Available Gas-phase photocatalytic oxidation (PCO and thermal catalytic oxidation (TCO of dimethylamine (DMA on titanium dioxide was studied in a continuous flow simple tubular reactor. Volatile PCO products of DMA included ammonia, formamide, carbon dioxide, and water. Ammonia was further oxidized in minor amounts to nitrous oxide and nitrogen dioxide. Effective at 573 K, TCO resulted in the formation of ammonia, hydrogen cyanide, carbon monoxide, carbon dioxide, and water. The PCO kinetic data fit well to the monomolecular Langmuir-Hinshelwood model, whereas TCO kinetic behaviour matched the first-order process. No deactivation of the photocatalyst during the multiple long-run experiments was observed.

  10. Zwitterionic states in gas-phase polypeptide ions revealed by 157-nm ultra-violet photodissociation

    DEFF Research Database (Denmark)

    Kjeldsen, Frank; Silivra, Oleg A; Zubarev, Roman A

    2006-01-01

    carboxylic groups relative to competing COOH losses (45 Da) from neutral carboxylic groups. Loss of CO2 is a strong indication of the presence of a zwitterionic [(+)...(-)...(+)] salt bridge in the gas-phase polypeptide cation. This method provides a tool for studying, for example, the nature of binding...... of the fragment formation should be taken into account. Cations of Trp-cage proteins exist preferentially as zwitterions, with the deprotonation position divided between the Asp9 residue and the C terminus in the ratio 3:2. The majority of dications of the same molecule are not zwitterions. Furthermore, 157-nm...

  11. Wettability in the liquid Cu-Ag alloy – fireproof material – gas phase system

    Directory of Open Access Journals (Sweden)

    G. Siwiec

    2013-07-01

    Full Text Available In the present paper, results of wettability studies on the liquid metal – fireproof material – gas phase system using copper and Cu-Ag alloys as well as typical fireproof materials, i.e. aluminium oxide, magnesium oxide and graphite, are presented. Contact angle measurements were conducted at 1 373–1 573 K by means of a high-temperature microscope coupled with a camera and a computer equipped with a program for recording and analysing images. For the measurements, the sessile drop method was used.

  12. Solvation of ions in the gas-phase: a molecular dynamics simulation

    Science.gov (United States)

    Cabarcos, Orlando M.; Lisy, James M.

    1996-07-01

    Molecular dynamics simulations have been performed on the collision between a cesium ion and a cluster of twenty methanol molecules. This process, generating a solvated ion, was studied over a range (1 to 25 eV) of eight collision energies. Preliminary analysis of this gas phase solvation has included the distribution of final ion cluster sizes, fragmentation patterns, solvation timescales and energetics. Two distinct patterns have emerged: a ballistic penetration of the neutral cluster at the higher collision energies and an evaporative evolution of the cluster ion at lower collision energies.

  13. A tetrapositive metal ion in the gas phase: Thorium(IV) coordinated by neutral tridentate ligands

    International Nuclear Information System (INIS)

    Gong, Yu; Tian, Guoxin; Rao, Linfeng; Gibson, John K.; Hu, Han-Shi; Li, Jun

    2013-01-01

    Sheltering thorium ions: A Th 4+ ion supported by three neutral tetramethyl-3-oxaglutaramide ligands (L=TMOGA) is produced in the gas phase by electrospray ionization. The thorium in chiral Th(L) 3 4+ is coordinated by nine oxygen atoms. Quantum chemical studies revealed a decrease in Th-O binding energies and bond orders and an increase in bond lengths, as the number of coordinating ligands increases. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. A tetrapositive metal ion in the gas phase: Thorium(IV) coordinated by neutral tridentate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Gong, Yu; Tian, Guoxin; Rao, Linfeng; Gibson, John K. [Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA (United States); Hu, Han-Shi [Department of Chemistry and Laboratory of Organic Optoelectronics and Molecular Engineering of the Ministry of Education, Tsinghua University (China); Li, Jun [Department of Chemistry and Laboratory of Organic Optoelectronics and Molecular Engineering of the Ministry of Education, Tsinghua University (China); William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory (United States)

    2013-07-01

    Sheltering thorium ions: A Th{sup 4+} ion supported by three neutral tetramethyl-3-oxaglutaramide ligands (L=TMOGA) is produced in the gas phase by electrospray ionization. The thorium in chiral Th(L){sub 3}{sup 4+} is coordinated by nine oxygen atoms. Quantum chemical studies revealed a decrease in Th-O binding energies and bond orders and an increase in bond lengths, as the number of coordinating ligands increases. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Gas Phase Vibrational Spectroscopy of Weakly Volatil Safe Taggants Using a Synchrotron Source

    Science.gov (United States)

    Cuisset, Arnaud; Hindle, Francis; Mouret, Gael; Gruet, Sebastien; Pirali, Olivier; Roy, Pascale

    2013-06-01

    The high performances of the AILES beamline of SOLEIL allow to study at medium resolution (0.5 cm^{-1}) the gas phase THz vibrational spectra of weakly volatil compounds. Between 2008 and 2010 we recorded and analyzed the THz/Far-IR spectra of phosphorous based nerve agents thanks to sufficient vapour pressures from liquid samples at room temperature. Recently, we extended these experiments towards the vibrational spectroscopy of vapour pressures from solid samples. This project is quite challenging since we target lower volatile compounds, and so requires very high sensitive spectrometers. Moreover a specially designed heated multipass-cell have been developped for the gas phase study of very weak vapor pressures. Thanks to skills acquired during initial studies and recent experiments performed on AILES with solid PAHs, we have recorded and assigned the gas phase vibrational fingerprints from the THz to the NIR spectral domain (10-4000 cm-1) of a set of targeted nitro-derivatives. The study was focused onto the para, ortho-mononitrotoluene (p-NT, o-NT), the 1,4 Dinitrobenzene (1,4 DNB), the 2,3-dimethyl-2,3-dinitrobutane (DMNB), and 2,4 and 2,6-dinitrotoluene (2,4-2,6 DNT), which are safe taggants widely used for the detection of commercial explosives. These taggants are usually added to plastic explosives in order to facilitate their vapour detection. Therefore, there is a continuous interest for their detection and identification in realistic conditions via optical methods. A first step consists in the recording of their gas phase vibrational spectra. These expected spectra focused onto molecules involved into defence and security domains are not yet available to date and will be very useful for the scientific community. This work is supported by the contract ANR-11-ASTR-035-01. A. Cuisset, G. Mouret, O. Pirali, P. Roy, F. Cazier, H. Nouali, J. Demaison, J. Phys. Chem. B, 2008, 112:, 12516-12525 I. Smirnova, A. Cuisset, R. Bocquet, F. Hindle, G. Mouret, O

  16. Gas-phase hydrosilylation of cyclohexene in an experimental radiation-chemical accelerator apparatus

    International Nuclear Information System (INIS)

    Pecherkin, A.S.; Sidorov, V.I.; Chernyshev, E.A.

    1992-01-01

    A process for the synthesis of methylcyclohexyldichlorosilane (a basic monomer for the production of organosilicon photoresists) has been investigated and perfected on an experimental apparatus with an ELV-2 electron accelerator; this synthesis involves gas-phase radiation-induced hydrosilylation of cyclohexene by methyldichlorosilane. Basic characteristics of the yield of the desired product under static conditions were determined. With the help of experiments on the synthesis of methylcyclohexyldichlorosilane in a flow- through mode, the technical features of the process of radiation-chemical hydrosilylation of cyclohexene on an accelerator apparatus were determined and studied, the optimal conditions for the synthesis were determined, and an experimental batch of the desired product was produced

  17. Probing Protein Structure and Folding in the Gas Phase by Electron Capture Dissociation

    Science.gov (United States)

    Schennach, Moritz; Breuker, Kathrin

    2015-07-01

    The established methods for the study of atom-detailed protein structure in the condensed phases, X-ray crystallography and nuclear magnetic resonance spectroscopy, have recently been complemented by new techniques by which nearly or fully desolvated protein structures are probed in gas-phase experiments. Electron capture dissociation (ECD) is unique among these as it provides residue-specific, although indirect, structural information. In this Critical Insight article, we discuss the development of ECD for the structural probing of gaseous protein ions, its potential, and limitations.

  18. Gas Phase Chromatography of some Group 4, 5, and 6 Halides

    Energy Technology Data Exchange (ETDEWEB)

    Sylwester, Eric Robert [Univ. of California, Berkeley, CA (United States)

    1998-10-01

    Gas phase chromatography using The Heavy Element Volatility Instrument (HEVI) and the On Line Gas Apparatus (OLGA III) was used to determine volatilities of ZrBr4, HfBr4, RfBr4, NbBr5, TaOBr3, HaCl5, WBr6, FrBr, and BiBr3. Short-lived isotopes of Zr, Hf, Rf, Nb, Ta, Ha, W, and Bi were produced via compound nucleus reactions at the 88-Inch Cyclotron at Lawrence Berkeley National Laboratory and transported to the experimental apparatus using a He gas transport system. The isotopes were halogenated, separated from the other reaction products, and their volatilities determined by isothermal gas phase chromatography. Adsorption Enthalpy (ΔHa) values for these compounds were calculated using a Monte Carlo simulation program modeling the gas phase chromatography column. All bromides showed lower volatility than molecules of similar molecular structures formed as chlorides, but followed similar trends by central element. Tantalum was observed to form the oxybromide, analogous to the formation of the oxychloride under the same conditions. For the group 4 elements, the following order in volatility and ΔHa was observed: RfBr4 > ZrBr4 > HfBr4. The ΔHa values determined for the group 4, 5, and 6 halides are in general agreement with other experimental data and theoretical predictions. Preliminary experiments were performed on Me-bromides. A new measurement of the half-life of 261Rf was performed. 261Rf was produced via the 248Cm(18O, 5n) reaction and observed with a half-life of 74-6+7 seconds, in excellent agreement with the previous measurement of 78-6+11 seconds. We recommend a new half-life of 75±7 seconds for 261Rf based on these two measurements. Preliminary studies in transforming HEVI from an isothermal (constant

  19. Position for determining gas-phase volatile organic compound concentrations in transuranic waste containers. Revision 2

    Energy Technology Data Exchange (ETDEWEB)

    Connolly, M.J.; Liekhus, K.J. [Lockheed Martin Idaho Technologies Co., Idaho Falls, ID (United States). Idaho National Engineering and Environmental Lab.; Djordjevic, S.M.; Loehr, C.A.; Spangler, L.R. [Benchmark Environmental Corp. (United States)

    1998-06-01

    In the conditional no-migration determination (NMD) for the test phase of the Waste Isolation Pilot Plant (WIPP), the US Environmental Protection Agency (EPA) imposed certain conditions on the US Department of Energy (DOE) regarding gas phase volatile organic compound (VOC) concentrations in the void space of transuranic (TRU) waste containers. Specifically, the EPA required the DOE to ensure that each waste container has no layer of confinement that contains flammable mixtures of gases or mixtures of gases that could become flammable when mixed with air. The EPA also required that sampling of the headspace of waste containers outside inner layers of confinement be representative of the entire void space of the container. The EPA stated that all layers of confinement in a container would have to be sampled until DOE can demonstrate to the EPA that sampling of all layers is either unnecessary or can be safely reduced. A test program was conducted at the Idaho National Engineering and Environmental Laboratory (INEEL) to demonstrate that the gas phase VOC concentration in the void space of each layer of confinement in vented drums can be estimated from measured drum headspace using a theoretical transport model and that sampling of each layer of confinement is unnecessary. This report summarizes the studies performed in the INEEL test program and extends them for the purpose of developing a methodology for determining gas phase VOC concentrations in both vented and unvented TRU waste containers. The methodology specifies conditions under which waste drum headspace gases can be said to be representative of drum gases as a whole and describes a method for predicting drum concentrations in situations where the headspace concentration is not representative. The methodology addresses the approach for determining the drum VOC gas content for two purposes: operational period drum handling and operational period no-migration calculations.

  20. Position for determining gas phase volatile organic compound concentrations in transuranic waste containers. Revision 1

    International Nuclear Information System (INIS)

    Connolly, M.J.; Liekhus, K.J.; Djordjevic, S.M.; Loehr, C.A.; Spangler, L.R.

    1995-08-01

    In the conditional no-migration determination (NMD) for the test phase of the Waste Isolation Pilot Plant (WIPP), the US Environmental Protection Agency (EPA) imposed certain conditions on the US Department of Energy (DOE) regarding gas phase volatile organic compound (VOC) concentrations in the void space of transuranic (TRU) waste containers. Specifically, the EPA required the DOE to ensure that each waste container has no layer of confinement that contains flammable mixtures of gases or mixtures of gases that could become flammable when mixed with air. The EPA also required that sampling of the headspace of waste containers outside inner layers of confinement be representative of the entire void space of the container. The EPA stated that all layers of confinement in a container would have to be sampled until DOE can demonstrate to the EPA that sampling of all layers is either unnecessary or can be safely reduced. A test program was conducted at the Idaho National Engineering Laboratory (INEL) to demonstrate that the gas phase VOC concentration in the void space of each layer of confinement in vented drums can be estimated from measured drum headspace using a theoretical transport model and that sampling of each layer of confinement is unnecessary. This report summarizes the studies performed in the INEL test program and extends them for the purpose of developing a methodology for determining gas phase VOC concentrations in both vented and unvented TRU waste containers. The methodology specifies conditions under which waste drum headspace gases can be said to be representative of drum gases as a whole and describes a method for predicting drum concentrations in situations where the headspace concentration is not representative. The methodology addresses the approach for determining the drum VOC gas content for two purposes: operational period drum handling and operational period no-migration calculations

  1. Photoisomerization action spectroscopy of the carbocyanine dye DTC+ in the gas phase.

    Science.gov (United States)

    Adamson, Brian D; Coughlan, Neville J A; da Silva, Gabriel; Bieske, Evan J

    2013-12-19

    Molecular photoisomerization plays a crucial role in diverse biological and technological contexts. Here, we combine ion mobility spectrometry and laser spectroscopy to characterize the photoisomerization of molecular cations in the gas phase. The target molecular ions, polymethine dye cations 3,3'-diethylthiacarbocyanine (DTC(+)), are propelled through helium buffer gas by an electric field and are photoisomerized by light from a tunable laser. Photoexcitation over the 450-570 nm range converts trans-DTC(+) to cis-DTC(+), noticeably modifying the ions' arrival time distribution. The photoisomerization action spectrum, which has a maximum at 535 nm, resembles the absorption spectrum of DTC(+) in solution but is shifted 25 nm to shorter wavelength. Comparisons between measured and calculated mobilities suggest that the photoisomer involves a twist about the second C-C bond in the methine chain (8,9-cis isomer) rather than a twist about the first methine C-C bond (2,8-cis isomer). It is postulated that the excited gas-phase ions internally convert from the S1 Franck-Condon region to the S0 manifold and explore the conformational landscape as they cool through He buffer gas collisions. Master equation simulations of the relaxation process in the S0 manifold suggest that the 8,9-cis isomer is preferred over the 2,8-cis isomer because it lies lower in energy and because it is separated from the trans isomer by a substantially higher barrier. The study demonstrates that the photoisomerization of molecular ions can be probed selectively in the gas phase, providing insights into photoisomerization mechanisms and information on the solvent-free absorption spectrum.

  2. The Gas-Phase Photophysics of Eosin Y and its Maleimide Conjugate.

    Science.gov (United States)

    Daly, Steven; Kulesza, Alexander; Knight, Geoffrey; MacAleese, Luke; Antoine, Rodolphe; Dugourd, Philippe

    2016-05-26

    The use of the xanthene family of dyes as fluorescent probes in a wide range of applications has provided impetus for the studying of their photophysical properties. In particular, recent advances in gas-phase techniques such as FRET that utilize such chromophores have placed a greater importance on the characterization of these properties in the gas phase. Additionally, the use of synthetic linker chains to graft the chromophores in a site-specific manner to their target system is ubiquitous. There is, however, often limited information on how the addition of such a linker chain may affect the photophysical properties of the chromophores, which is of fundamental importance for interpretation of experimental data reliant on grafted chromophores. Here, we present data on the optical spectroscopy of different protonation states of Eosin Y, a fluorescein derivative. We compare the photophysics of Eosin Y to its maleimide conjugate, and to the thioether product of the reaction of this conjugate with cysteamine. Comparison of the mass spectra following laser irradiation shows that very different relaxation takes place upon addition of the maleimide moiety but that the photophysics of the bare chromophore are restored upon addition of cysteamine. This radical change in the photophysics is interpreted in terms of charge-transfer states, whose energy relative to the S1 ← S0 transition of the chromophore is dependent on the conjugation of the maleimide moiety. We also show that the shape of the absorption band is unchanged in the gas-phase as compared to the solution-phase, showing a maximum with a shoulder toward the blue, and examination of isotope distributions of the isolated ions show that this shoulder cannot be due to the presence of dimers. Consideration of the fluorescence emission spectrum allows a tentative assignment of the shoulder to be due to a vibrational progression with a high Franck-Condon factor.

  3. Position for determining gas-phase volatile organic compound concentrations in transuranic waste containers. Revision 2

    International Nuclear Information System (INIS)

    Connolly, M.J.; Liekhus, K.J.

    1998-06-01

    In the conditional no-migration determination (NMD) for the test phase of the Waste Isolation Pilot Plant (WIPP), the US Environmental Protection Agency (EPA) imposed certain conditions on the US Department of Energy (DOE) regarding gas phase volatile organic compound (VOC) concentrations in the void space of transuranic (TRU) waste containers. Specifically, the EPA required the DOE to ensure that each waste container has no layer of confinement that contains flammable mixtures of gases or mixtures of gases that could become flammable when mixed with air. The EPA also required that sampling of the headspace of waste containers outside inner layers of confinement be representative of the entire void space of the container. The EPA stated that all layers of confinement in a container would have to be sampled until DOE can demonstrate to the EPA that sampling of all layers is either unnecessary or can be safely reduced. A test program was conducted at the Idaho National Engineering and Environmental Laboratory (INEEL) to demonstrate that the gas phase VOC concentration in the void space of each layer of confinement in vented drums can be estimated from measured drum headspace using a theoretical transport model and that sampling of each layer of confinement is unnecessary. This report summarizes the studies performed in the INEEL test program and extends them for the purpose of developing a methodology for determining gas phase VOC concentrations in both vented and unvented TRU waste containers. The methodology specifies conditions under which waste drum headspace gases can be said to be representative of drum gases as a whole and describes a method for predicting drum concentrations in situations where the headspace concentration is not representative. The methodology addresses the approach for determining the drum VOC gas content for two purposes: operational period drum handling and operational period no-migration calculations

  4. Regenerable Air Purification System for Gas-Phase Contaminant Control

    Science.gov (United States)

    Constantinescu, Ileana C.; Finn, John E.; LeVan, M. Douglas; Lung, Bernadette (Technical Monitor)

    2000-01-01

    Tests of a pre-prototype regenerable air purification system (RAPS) that uses water vapor to displace adsorbed contaminants from an adsorbent column have been performed at NASA Ames Research Center. A unit based on this design can be used for removing trace gas-phase contaminants from spacecraft cabin air or from polluted process streams including incinerator exhaust. During the normal operation mode, contaminants are removed from the air on the column. Regeneration of the column is performed on-line. During regeneration, contaminants are displaced and destroyed inside the closed oxidation loop. In this presentation we discuss initial experimental results for the performance of RAPS in the removal and treatment of several important spacecraft contaminant species from air.

  5. FLUIDDYNAMIC ASPECTS OF GAS-PHASE ETHYLENE POLYMERIZATION REACTOR DESIGN

    Directory of Open Access Journals (Sweden)

    Guardani R.

    1998-01-01

    Full Text Available The relative importance of design variables affecting the fluiddynamic behavior of a fluidized bed reactor for the gas-phase ethylene polymerization is discussed, based on mathematical modeling. The three-phase bubbling fluidized bed model is based on axially distributed properties for the bubble, cloud and emulsion phases, combined with correlations for population balance and entrainment. Under the operating conditions adopted in most industrial processes, the reactor performance is affected mainly by the reaction rate and solids entrainment. Simulation results indicate that an adequate design of the freeboard and particle collecting equipment is of primary importance in order to produce polymeric particles with the desired size distribution, as well as to keep entrainment and catalyst feed rates at adequate levels.

  6. Technical Procedures Management in Gas-Phase Detoxification Laboratory

    International Nuclear Information System (INIS)

    Cardona Garcia, A. I.; Sanchez Cabrero, B.

    2000-01-01

    The natural cycle of Volatile Organic Compounds (VOCs) has been disturbed by the industrial and socioeconomic activities of human beings. This imbalance in the environment has affected the ecosystems and the human health. Initiatives have been planned to mitigate these adverse effects. In order to minimize the hazardous effects, initiatives have been proposed for the treatment of gaseous emissions. The solar photo catalysis appears as a clear and renewable technology in front of the conventional ones.In CIEMAT this line is being investigated as the base of a future implementation at a pre industrial scale.Technical procedures are written in this document for testing Gas-Phase detoxification at lab scale in the Renewable Energy Department (DER) CIEMAT- Madrid to eliminate the VOCs by using the solar photo catalysis technology. (Author) 34 refs

  7. Gas-phase synthesis of magnetic metal/polymer nanocomposites

    Science.gov (United States)

    Starsich, Fabian H. L.; Hirt, Ann M.; Stark, Wendelin J.; Grass, Robert N.

    2014-12-01

    Highly magnetic metal Co nanoparticles were produced via reducing flame spray pyrolysis, and directly coated with an epoxy polymer in flight. The polymer content in the samples varied between 14 and 56 wt% of nominal content. A homogenous dispersion of Co nanoparticles in the resulting nanocomposites was visualized by electron microscopy. The size and crystallinity of the metallic fillers was not affected by the polymer, as shown by XRD and magnetic hysteresis measurements. The good control of the polymer content in the product nanocomposite was shown by elemental analysis. Further, the successful polymerization in the gas phase was demonstrated by electron microscopy and size measurements. The presented effective, dry and scalable one-step synthesis method for highly magnetic metal nanoparticle/polymer composites presented here may drastically decrease production costs and increase industrial yields.

  8. Statistical Physics of Nanoparticles in the Gas Phase

    CERN Document Server

    Hansen, Klavs

    2013-01-01

    Thermal processes are ubiquitous and an understanding of thermal phenomena is essential for a complete description of the physics of nanoparticles, both for the purpose of modeling the dynamics of the particles and for the correct interpretation of experimental data. This book has the twofold aim to present coherently the relevant results coming from the recent scientific literature and to guide the readers through the process of deriving results, enabling them to explore the limits of the mathematical approximations and test the power of the method. The book is focused on the fundamental properties of nanosystems in the gas phase. For this reason there is a strong emphasis on microcanonical physics. Each chapter is enriched with exercises and 3 Appendices provide additional useful materials.

  9. Advanced Laser-Based Techniques for Gas-Phase Diagnostics in Combustion and Aerospace Engineering.

    Science.gov (United States)

    Ehn, Andreas; Zhu, Jiajian; Li, Xuesong; Kiefer, Johannes

    2017-03-01

    Gaining information of species, temperature, and velocity distributions in turbulent combustion and high-speed reactive flows is challenging, particularly for conducting measurements without influencing the experimental object itself. The use of optical and spectroscopic techniques, and in particular laser-based diagnostics, has shown outstanding abilities for performing non-intrusive in situ diagnostics. The development of instrumentation, such as robust lasers with high pulse energy, ultra-short pulse duration, and high repetition rate along with digitized cameras exhibiting high sensitivity, large dynamic range, and frame rates on the order of MHz, has opened up for temporally and spatially resolved volumetric measurements of extreme dynamics and complexities. The aim of this article is to present selected important laser-based techniques for gas-phase diagnostics focusing on their applications in combustion and aerospace engineering. Applicable laser-based techniques for investigations of turbulent flows and combustion such as planar laser-induced fluorescence, Raman and Rayleigh scattering, coherent anti-Stokes Raman scattering, laser-induced grating scattering, particle image velocimetry, laser Doppler anemometry, and tomographic imaging are reviewed and described with some background physics. In addition, demands on instrumentation are further discussed to give insight in the possibilities that are offered by laser flow diagnostics.

  10. Surfactants from the gas phase may promote cloud droplet formation.

    Science.gov (United States)

    Sareen, Neha; Schwier, Allison N; Lathem, Terry L; Nenes, Athanasios; McNeill, V Faye

    2013-02-19

    Clouds, a key component of the climate system, form when water vapor condenses upon atmospheric particulates termed cloud condensation nuclei (CCN). Variations in CCN concentrations can profoundly impact cloud properties, with important effects on local and global climate. Organic matter constitutes a significant fraction of tropospheric aerosol mass, and can influence CCN activity by depressing surface tension, contributing solute, and influencing droplet activation kinetics by forming a barrier to water uptake. We present direct evidence that two ubiquitous atmospheric trace gases, methylglyoxal (MG) and acetaldehyde, known to be surface-active, can enhance aerosol CCN activity upon uptake. This effect is demonstrated by exposing acidified ammonium sulfate particles to 250 parts per billion (ppb) or 8 ppb gas-phase MG and/or acetaldehyde in an aerosol reaction chamber for up to 5 h. For the more atmospherically relevant experiments, i.e., the 8-ppb organic precursor concentrations, significant enhancements in CCN activity, up to 7.5% reduction in critical dry diameter for activation, are observed over a timescale of hours, without any detectable limitation in activation kinetics. This reduction in critical diameter enhances the apparent particle hygroscopicity up to 26%, which for ambient aerosol would lead to cloud droplet number concentration increases of 8-10% on average. The observed enhancements exceed what would be expected based on Köhler theory and bulk properties. Therefore, the effect may be attributed to the adsorption of MG and acetaldehyde to the gas-aerosol interface, leading to surface tension depression of the aerosol. We conclude that gas-phase surfactants may enhance CCN activity in the atmosphere.

  11. Spectroscopic [FT-IR and FT-Raman] and molecular modeling (MM) study of benzene sulfonamide molecule using quantum chemical calculations

    Science.gov (United States)

    Vinod, K. S.; Periandy, S.; Govindarajan, M.

    2016-07-01

    The spectroscopic and molecular modeling (MM) study includes, FT-IR, FT-Raman and 13C NMR and 1H NMR spectra of the Benzene sulfonamide were recorded for the analysis. The observed experimental and theoretical frequencies (IR and Raman) were assigned according to their distinctive region. The present study of this title molecule have been carried out by hybrid computational calculations of HF and DFT (B3LYP) methods with 6-311+G(d,p) and 6-311++G(d,p) basis sets and the corresponding results are tabulated. The structural modifications of the compound due to the substitutions of NH2 and SO2 were investigated. The minimum energy conformers of the compound were studied using conformational analysis. The alternations of the vibrational pattern of the base structure related to the substitutions were analyzed. The thermodynamic parameters (such as zero-point vibrational energy, thermal energy, specific heat capacity, rotational constants, entropy, and dipole moment) of Benzene sulfonamide have been calculated. The donor acceptor interactions of the compound and the corresponding UV transitions are found out using NBO analysis. The NMR spectra were simulated by using the gauge independent atomic orbital (GIAO) method with B3LYP methods and the 6-311++G(d,p) basis set and their spectra were simulated and the chemical shifts related to TMS were compared. A quantum computational study on the electronic and optical properties absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, were performed by HF and DFT methods. The energy gap of the present compound was calculated related to HOMO and LUMO energies which confirm the occurring of charge transformation between the base and ligand group. Besides frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) was performed. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the title compound at different temperatures were calculated in gas phase and

  12. Alterations in prostacyclin and thromboxane formation by chronic cigarette smoke exposure: temporal relationships and whole smoke vs. gas phase

    Energy Technology Data Exchange (ETDEWEB)

    Lubawy, W.C.; Culpepper, B.T.; Valentovic, M.A.

    1986-04-01

    Chronic cigarette smoke exposure in vivo causes decreased conversion of (/sup 14/C)arachidonic acid (AA) to prostacyclin (PGI2) by isolated aortic tissue and increased conversion to thromboxane (TXA2) by isolated platelets from rats. Alterations in the PGI2/TXA2 balance may be part of the mechanism through which smoking increases the risk of cardiovascular disease. To study the influence of smoke exposure duration on this response, male rats were exposed daily to 10 puffs of freshly generated cigarette smoke. Animals were killed after 1, 4, 14, 28 and 57 days of smoke exposure and 3, 7, 14 and 28 days after cessation of the 57-day of smoke-exposure regimen. Elevated carboxyhemoglobin levels during the smoke-exposure sessions verified smoke (gas phase) inhalation. Statistically significant alterations in prostacyclin synthesis preceded those of thromboxane. A decrease of 20-25% (P less than 0.05) in PGI2 production from (/sup 14/C)AA in isolated aortic tissue was found beginning 28 days after smoke was initiated and quickly rebounded when smoke exposure was terminated. Increased production of TXA2 from (/sup 14/C)AA by isolated platelets became statistically significant (P less than 0.05) on the 57th day and returned to normal 7-14 days after cessation of smoke exposure. To determine the effect of gas phase constituents on the PGI2/TXA2 balance a second series of experiments divided male and female Sprague-Dawley rats into sham, whole smoke and gas phase groups. Gas phase was produced by passing whole smoke through a Cambridge filter to remove particulate matter. Per cent COHb averaged 1.4 for sham, 7.8 for whole smoke and 9.4 for gas phase groups.

  13. Photochemical reactions of triplet benzophenone and anthraquinone molecules with amines in the gas phase

    International Nuclear Information System (INIS)

    Zalesskaya, G.A.; Sambor, E.G.; Belyi, N.N.

    2004-01-01

    The intermolecular photoinduced reactions between triplet ketone molecules and aliphatic amines and pyridine are studied by the quenching of delayed fluorescence of anthraquinone and benzophenone vapors by diethylamine, dibutylamine, cyclohexylamine, triethylamine, and pyridine. In the temperature range 423-573 K, the delayed fluorescence quenching rate constants k q are estimated from changes in the decay rate constant and the intensity of delayed fluorescence upon increasing pressure of bath gases. It is ascertained that, in the gas phase, the mixtures under study exhibit both a negative and a positive dependence of k q on temperature, which indicates that some photoinduced reactions do not have activation barriers. The rate constant k q is shown to increase with decreasing ionization potential of the electron donors. This points to the importance of interactions with charge transfer in the photoreaction of triplet ketone molecules with aliphatic amines and pyridine in the gas phase. The relationship between k q and the change in the free energy ΔG upon the photoinduced intermolecular electron transfer, which is the primary stage of the photochemical reaction, is studied. It is shown that the dependence k q (ΔG) for the donor-acceptor pairs under study is described well by the Marcus equation, in which the average vibrational energies of the donor and acceptor are taken into account for the estimate of ΔG

  14. LABORATORY GAS-PHASE DETECTION OF THE CYCLOPROPENYL CATION (c-C{sub 3}H{sub 3} {sup +})

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Dongfeng; Doney, Kirstin D.; Linnartz, Harold, E-mail: zhao@strw.leidenuniv.nl [Sackler Laboratory for Astrophysics, Leiden Observatory, University of Leiden, PO Box 9513, NL 2300 RA Leiden (Netherlands)

    2014-08-20

    The cyclopropenyl cation (c-C{sub 3}H{sub 3} {sup +}) is the smallest aromatic hydrocarbon molecule and considered to be a pivotal intermediate in ion-molecule reactions in space. An astronomical identification has been prohibited so far, because of a lack of gas-phase data. Here we report the first high resolution infrared laboratory gas-phase spectrum of the ν {sub 4} (C-H asymmetric stretching) fundamental band of c-C{sub 3}H{sub 3} {sup +}. The c-C{sub 3}H{sub 3} {sup +} cations are generated in supersonically expanding planar plasma by discharging a propyne/helium gas pulse, yielding a rotational temperature of ∼35 K. The absorption spectrum is recorded in the 3.19 μm region using sensitive continuous-wave cavity ring-down spectroscopy. The analysis of about 130 ro-vibrational transitions results in precise spectroscopic parameters. These constants allow for an accurate comparison with high-level theoretical predictions, and provide the relevant information needed to search for this astrochemically relevant carbo-cation in space.

  15. Spectroscopic studies of surface-gas interactions and catalyst restructuring at ambient pressure: mind the gap!

    International Nuclear Information System (INIS)

    Rupprechter, Guenther; Weilach, Christian

    2008-01-01

    Recent progress in the application of surface vibrational spectroscopy at ambient pressure allows us to monitor surface-gas interactions and heterogeneous catalytic reactions under conditions approaching those of technical catalysis. The surface specificity of photon-based methods such as polarization modulation infrared reflection absorption spectroscopy (PM-IRAS) and sum frequency generation (SFG) spectroscopy is utilized to monitor catalytically active surfaces while they function at high pressure and high temperature. Together with complementary information from high-pressure x-ray photoelectron spectroscopy (HP-XPS) and high-resolution transmission electron microscopy (HRTEM), reaction mechanisms can be deduced on a molecular level. Well defined model catalysts, prepared under ultrahigh vacuum (UHV), are typically employed in such studies, including smooth and stepped single crystals, thin oxide films, and oxide-supported nanoparticles. A number of studies on unsupported and supported noble metal (Pd, Rh) catalysts are presented, focusing on the transformation of the catalysts from the 'as-prepared' to the 'active state'. This often involves pronounced alterations in catalyst structure and composition, for example the creation of surface carbon phases, surface oxides or surface alloys, as well as nanoparticle restructuring. The reactivity studies include CH 3 OH, CH 4 and CO oxidation with gas phase analysis by gas chromatography and mass spectrometry. Differing results between studies under ultrahigh vacuum and ambient pressure, and between studies on single crystals and supported nanoparticles, demonstrate the importance of 'minding the gap' between idealized and realistic conditions

  16. Product analyses and kinetic studies on gas phase oxidation of the fuel additive ethyl tert-butyl ether and its products; Produktanalysen und Kinetikuntersuchungen der Gasphasenoxidation des Kraftstoffadditivs Ethyl-tert-butylether und seiner Produkte

    Energy Technology Data Exchange (ETDEWEB)

    Becker, K H; Thuener, L

    1997-04-01

    The widespread use of the additive ETBE in gasoline leads to an increased release of this compound into the atmosphere via evaporation or exhaust fumes. In order to determine the influence of this additive on trace gas cycles it is first necessary to carry out studies on the degradation mechanisms and pertinent kinetic properties of this substance. The aim of the present study was to examine the degradation mechanisms of the fuel additive t-butyl ethyl ether under atmospheric conditions. The reactions of the main degradation products (t-butyl formiate and t-butyl acetate, together ca. 80%) were also studied in order to obtain as complete a picture of the degradation paths as possible. This was to permit an assessment of the influence of ETBE and its products on tropospheric trace gas cycles and ozone formation. [Deutsch] Bei haeufigem Zusatz von ETBE in Benzin wird diese Verbindung durch Verdampfung oder als Abgas verstaerkt in die Atmosphaere abgegeben. Um den Einfluss des Additivs auf die Spurengas-Kreislaeufe zu bestimmen, sind daher Untersuchungen noetig, um die Abbau-Mechanismen und die zugehoerigen kinetischen Daten zu ermitteln. Das Ziel dieser Arbeit ist die Untersuchung der Abbaumechanismen des Kraftstoffadditivs t-Butylethylether unter atmosphaerischen Bedingungen. Fuer eine moeglichst vollstaendige Analyse des Abbauweges werden auch die Reaktionen der Hauptabbauprodukte (t-Butylformiat und t-Butylacetat, zusammen etwa 80%) untersucht. Dadurch soll der Einfluss auf troposphaerische Spurengas-Kreislaeufe und auf die Ozonbildung von ETBE und seinen Produkten abgeschaetzt werden. (orig./SR)

  17. Low temperature FT-IR and molecular orbital study of N,N-dimethylglycine methyl ester: Proof for different ground conformational states in gas phase and in condensed media

    OpenAIRE

    Gómez-Zavaglia, A.; Fausto, R.

    2002-01-01

    N,N-dimethylglycine methyl ester (DMG-Me) was studied by FT-IR spectroscopy under several experimental conditions, including low temperature solid state and isolated in low temperature inert gas matrices, and by molecular orbital calculations. In agreement with the theoretical predictions, the experimental data show that in the gaseous phase the most stable conformer (ASC) has the ester group in cis configuration and the N–C–CO and Lp–N–C–C (Lp=lone electron pair) dihedral angles equal to 0° ...

  18. Thermodynamic-Controlled Gas Phase Process for the Synthesis of Nickel Nanoparticles of Adjustable Size and Morphology

    International Nuclear Information System (INIS)

    Kauffeldt, Elena; Kauffeldt, Thomas

    2006-01-01

    Gas phase processes are a successful route for the synthesis of nano materials. Nickel particles are used in applications ranging from catalysis to nano electronics and energy storage. The application field defines the required particle size, morphology, crystallinity and purity. Nickel tetracarbonyl is the most promising precursor for the synthesis of high purity nickel particles. Due to the toxicity of this precursor and to obtain an optimal process control we developed a two-step flow type process. Nickel carbonyl and nickel particles are synthesized in a sequence of reactions. The particles are formed in a hot wall reactor at temperatures below 400 deg. C in different gas compositions. Varying the process conditions enables the adjustment of the particle size in a range from 3 to 140 nm. The controllable crystalline habits are polycrystalline, single crystals or multiple twinned particles (MTP). Spectroscopic investigations show an excellent purity. We report about the process and first investigations of the properties of the synthesized nickel nanomaterial

  19. Gas-phase synthesis of semiconductor nanocrystals and its applications

    Science.gov (United States)

    Mandal, Rajib

    Luminescent nanomaterials is a newly emerging field that provides challenges not only to fundamental research but also to innovative technology in several areas such as electronics, photonics, nanotechnology, display, lighting, biomedical engineering and environmental control. These nanomaterials come in various forms, shapes and comprises of semiconductors, metals, oxides, and inorganic and organic polymers. Most importantly, these luminescent nanomaterials can have different properties owing to their size as compared to their bulk counterparts. Here we describe the use of plasmas in synthesis, modification, and deposition of semiconductor nanomaterials for luminescence applications. Nanocrystalline silicon is widely known as an efficient and tunable optical emitter and is attracting great interest for applications in several areas. To date, however, luminescent silicon nanocrystals (NCs) have been used exclusively in traditional rigid devices. For the field to advance towards new and versatile applications for nanocrystal-based devices, there is a need to investigate whether these NCs can be used in flexible and stretchable devices. We show how the optical and structural/morphological properties of plasma-synthesized silicon nanocrystals (Si NCs) change when they are deposited on stretchable substrates made of polydimethylsiloxane (PDMS). Synthesis of these NCs was performed in a nonthermal, low-pressure gas phase plasma reactor. To our knowledge, this is the first demonstration of direct deposition of NCs onto stretchable substrates. Additionally, in order to prevent oxidation and enhance the luminescence properties, a silicon nitride shell was grown around Si NCs. We have demonstrated surface nitridation of Si NCs in a single step process using non?thermal plasma in several schemes including a novel dual-plasma synthesis/shell growth process. These coated NCs exhibit SiNx shells with composition depending on process parameters. While measurements including

  20. Spectroscopic transport studies at the stellerator Wendelstein 7-AS

    International Nuclear Information System (INIS)

    Unger, E.

    1995-11-01

    The following topics were dealt with: Magnetic confinement experiments with toroidal geometry, foundations of particle transport theory, code calculations (SITAR), gaseous oscillation method for impurity transport study and results

  1. SPECTROSCOPIC STUDIES OF MATERIALS FOR ELECTROCHEMICAL ENERGY STORAGE

    Energy Technology Data Exchange (ETDEWEB)

    Greenbaum, Steven G.

    2014-03-01

    Several battery materials research projects were undertaken, suing NMR spectroscopy as a primary analytical tool. These include transport proerties of liquid and solid electrolytes and structural studies of Li ion electrodes.

  2. PHOSPHATO AND PHOSPHONATO ADDUCTS: SYNTHESIS AND SPECTROSCOPIC STUDY

    Directory of Open Access Journals (Sweden)

    Mouhamadou Birame Diop

    2014-05-01

    Full Text Available Two new adducts have been synthesized and studied by infrared and NMR spectroscopy. The suggested structures are discrete or of infinite chain type with a phosphate behaving as a bidentate ligand, a phosphonate acting as a monodentate ligand, the environments around the tin centre being tetrahedral or trigonal bipyramidal. In all the studied compounds, supramolecular architectures are obtained when hydrogen bonds are considered.

  3. Spectroscopic study of trivalent rare earth ions in calcium nitrate hydrate melt

    International Nuclear Information System (INIS)

    Fujii, Toshiyuki; Asano, Hideki; Kimura, Takaumi; Yamamoto, Takeshi; Uehara, Akihiro; Yamana, Hajimu

    2006-01-01

    Influence of the water content to chemical status of trivalent rare earth ions in calcium nitrate hydrate melt was studied by spectroscopic techniques. Fluorescence spectrometry for Eu(III) in Ca(NO 3 ) 2 .RH 2 O and electronic absorption spectrometry for Nd(III) in Ca(NO 3 ) 2 .RH 2 O were performed for analyzing the changing coordination symmetries through the changes in their hypersensitive transitions. Raman spectroscopic study and EXAFS study were performed for Y(NO 3 ) 3 solutions and Y(III) in Ca(NO 3 ) 2 .RH 2 O for analyzing the oxygen bonding to Y(III). Luminescence lifetime study of Eu(III) and Dy(III) in Ca(NO 3 ) 2 .RH 2 O was performed for evaluating the hydration number changes. Results of these spectroscopic studies indicated that, with the decrease of water content (R), the hydration number decreases while the interaction between trivalent rare earth ion and nitrate ion increases. It was also revealed that the symmetry of the coordination sphere gets distorted gradually by this interaction

  4. Molecular interactions in ethyl acetate-chlorobenzene binary solution: Dielectric, spectroscopic studies and quantum chemical calculations

    Science.gov (United States)

    Karthick, N. K.; Kumbharkhane, A. C.; Joshi, Y. S.; Mahendraprabu, A.; Shanmugam, R.; Elangovan, A.; Arivazhagan, G.

    2017-05-01

    Dielectric studies using Time Domain Reflectometry method has been carried out on the binary solution of Ethyl acetate (EA) with Chlorobenzene (CBZ) over the entire composition range. Spectroscopic (FTIR and 13C NMR) signatures of neat EA, CBZ and their equimolar binary solution have also been recorded. The results of the spectroscopic studies favour the presence of (CBZ) Csbnd H ⋯ Odbnd C (EA), (EA) methylene Csbnd H ⋯ π electrons (CBZ) and (EA) methyl Csbnd H ⋯ Cl (CBZ) contacts which have been validated using quantum chemical calculations. Dimerization of CBZ has been identified. Presence of β-clusters has been identified in all the solutions. Although EA and CBZ molecules have nearly equal molar volumes, CBZ molecules experience larger hindrance for the rotation than EA molecules. Very small excess dielectric constant (εE) values may be correlated with weak heteromolecular forces and/or closed heteromolecular association.

  5. Mapping the conformational free energy of aspartic acid in the gas phase and in aqueous solution.

    Science.gov (United States)

    Comitani, Federico; Rossi, Kevin; Ceriotti, Michele; Sanz, M Eugenia; Molteni, Carla

    2017-04-14

    The conformational free energy landscape of aspartic acid, a proteogenic amino acid involved in a wide variety of biological functions, was investigated as an example of the complexity that multiple rotatable bonds produce even in relatively simple molecules. To efficiently explore such a landscape, this molecule was studied in the neutral and zwitterionic forms, in the gas phase and in water solution, by means of molecular dynamics and the enhanced sampling method metadynamics with classical force-fields. Multi-dimensional free energy landscapes were reduced to bi-dimensional maps through the non-linear dimensionality reduction algorithm sketch-map to identify the energetically stable conformers and their interconnection paths. Quantum chemical calculations were then performed on the minimum free energy structures. Our procedure returned the low energy conformations observed experimentally in the gas phase with rotational spectroscopy [M. E. Sanz et al., Phys. Chem. Chem. Phys. 12, 3573 (2010)]. Moreover, it provided information on higher energy conformers not accessible to experiments and on the conformers in water. The comparison between different force-fields and quantum chemical data highlighted the importance of the underlying potential energy surface to accurately capture energy rankings. The combination of force-field based metadynamics, sketch-map analysis, and quantum chemical calculations was able to produce an exhaustive conformational exploration in a range of significant free energies that complements the experimental data. Similar protocols can be applied to larger peptides with complex conformational landscapes and would greatly benefit from the next generation of accurate force-fields.

  6. Gas-phase ion-molecule reactions and high-pressure mass spectrometer, 1

    International Nuclear Information System (INIS)

    Hiraoka, Kenzo

    1977-01-01

    The reasons for the fact that the research in gas-phase ion-molecule reactions, to which wide interest is shown, have greatly contributed to the physical and chemical fields are that, first it is essential in understanding general phenomena concerning ions, second, it can furnish many unique informations in the dynamics of chemical reactions, and third, usefulness of '' chemical ionization'' methods has been established as its application to chemical analysis. In this review, the history and trend of studies and equipments in gas-phase ion-molecule reactions are surveyed. The survey includes the chemical ionization mass spectrometer for simultaneously measuring the positive and negative ions utilizing a quadrupole mass spectrometer presented by Hunt and others, flowing afterglow method derived from the flowing method which traces neutral chemical species mainly optically, ion cyclotron resonance mass spectrometer, trapped ion mass spectrometer and others. Number of reports referred to ion-molecule reactions issued during the last one year well exceeds the total number of reports concerning mass spectrometers presented before 1955. This truly shows how active the research and development are in this field. (Wakatsuki, Y.)

  7. Oxo-exchange of gas-phase uranyl, neptunyl, and plutonyl with water and methanol.

    Science.gov (United States)

    Lucena, Ana F; Odoh, Samuel O; Zhao, Jing; Marçalo, Joaquim; Schreckenbach, Georg; Gibson, John K

    2014-02-17

    A challenge in actinide chemistry is activation of the strong bonds in the actinyl ions, AnO2(+) and AnO2(2+), where An = U, Np, or Pu. Actinyl activation in oxo-exchange with water in solution is well established, but the exchange mechanisms are unknown. Gas-phase actinyl oxo-exchange is a means to probe these processes in detail for simple systems, which are amenable to computational modeling. Gas-phase exchange reactions of UO2(+), NpO2(+), PuO2(+), and UO2(2+) with water and methanol were studied by experiment and density functional theory (DFT); reported for the first time are experimental results for UO2(2+) and for methanol exchange, as well as exchange rate constants. Key findings are faster exchange of UO2(2+) versus UO2(+) and faster exchange with methanol versus water; faster exchange of UO2(+) versus PuO2(+) was quantified. Computed potential energy profiles (PEPs) are in accord with the observed kinetics, validating the utility of DFT to model these exchange processes. The seemingly enigmatic result of faster exchange for uranyl, which has the strongest oxo-bonds, may reflect reduced covalency in uranyl as compared with plutonyl.

  8. Properties of clusters in the gas phase: V. Complexes of neutral molecules onto negative ions

    International Nuclear Information System (INIS)

    Keesee, R.G.; Lee, N.; Castleman, A.W. Jr.

    1980-01-01

    Ion--molecules association reactions of the form A - (B)/sub n1/-+B=A - (B)/sub n/ were studied over a range of temperatures in the gas phase using high pressure mass spectrometry. Enthalpy and entropy changes were determined for the stepwise clustering reactions of (1) sulfur dioxide onto Cl - , I - , and NO 2 - with n ranging from one to three or four, and onto SO 2 - and SO 3 - with n equal to one; and (2) carbon dioxide onto Cl - , I - , NO 2 - , CO 3 - , and SO 3 - with n equal to one. From these data and earlier hydration results, the order of the magnitude of the enthalpy changes on the association of the first neutral for a series of negative ions was found to parallel the gas-phase basicity of those anions. For any given ion, the relative order of the addition enthalpies among the neutrals was found to be dependent on the polarizabilities of the neutrals and on the covalency in the ion-neutral bond. Dispersion of charge via covalent bonding was found to affect significantly the succeeding clustering steps

  9. Gas phase collision dynamics by means of pulse-radiolysis methods

    International Nuclear Information System (INIS)

    Hatano, Yoshihiko

    1989-01-01

    After a brief survey of recent advances in gas-phase collision dynamics studies using pulse radiolysis methods, the following two topics in our research programs are presented with emphasis on the superior advantages of the pulse radiolysis methods over the various methods of gas-phase collision dynamics, such as beam methods, swarm methods and flow methods. One of the topics is electron attachment to van der Waals molecules. The attachment rates of thermal electrons to O 2 and other molecules in dense gases have been measured in wide ranges of both gas temperatures and pressures, from which experimental evidence has been obtained for electron attachment to van der Waals molecules. The results have been compared with theories and discussed in terms of the effect of van der Waals interaction on the electron attachment resonance. The obtained conclusions have been related with investigations of electron attachment, solvation and localization in the condensed phase. The other is Penning ionization and its related processes. The rate constants for the de-excitation of He(2 1 P), He(2 3 S), Ne( 3 P 0 ), Ne( 3 P 1 ), Ne( 3 P 2 ), Ar( 1 P 1 ), Ar( 3 P 1 ), by atoms and molecules have been measured in the temperature range from 100 to 300 K, thus obtaining the collisional energy dependence of the de-excitation cross sections. The results are compared in detail with theories classified according to the excited rare gas atoms in the metastable and resonance states. (author)

  10. Optical Absorptions of Oxygenated Carbon Chain Cations in the Gas Phase

    Science.gov (United States)

    Hardy, F.-X.; Rice, C. A.; Chakraborty, A.; Fulara, J.; Maier, J. P.

    2016-06-01

    The gas-phase electronic spectra of linear OC4O+ and a planar C6H2O+ isomer were obtained at a rotational temperature of ≈10 K. Absorption measurements in a 6 K neon matrix were followed by gas-phase observations in a cryogenic radiofrequency ion trap. The origin bands of the 1{}2{{{\\Pi }}}u ≤ftarrow X{}2{{{\\Pi }}}g transition of OC4O+ and the 1{}2A{}2 ≤ftarrow X{}2B1 of HCCC(CO)CCH+ lie at 417.31 ± 0.01 nm and 523.49 ± 0.01 nm, respectively. These constitute the first electronic spectra of oxygenated carbon chain cations studied under conditions that are relevant to the diffuse interstellar bands (DIBs), as both have a visible transition. The recent analysis of the 579.5 nm DIB indicates that small carriers, five to seven heavy atoms, continue to be possible candidates (Huang & Oka 2015). Astronomical implications are discussed regarding this kind of oxygenated molecules.

  11. Mapping the conformational free energy of aspartic acid in the gas phase and in aqueous solution

    Science.gov (United States)

    Comitani, Federico; Rossi, Kevin; Ceriotti, Michele; Sanz, M. Eugenia; Molteni, Carla

    2017-04-01

    The conformational free energy landscape of aspartic acid, a proteogenic amino acid involved in a wide variety of biological functions, was investigated as an example of the complexity that multiple rotatable bonds produce even in relatively simple molecules. To efficiently explore such a landscape, this molecule was studied in the neutral and zwitterionic forms, in the gas phase and in water solution, by means of molecular dynamics and the enhanced sampling method metadynamics with classical force-fields. Multi-dimensional free energy landscapes were reduced to bi-dimensional maps through the non-linear dimensionality reduction algorithm sketch-map to identify the energetically stable conformers and their interconnection paths. Quantum chemical calculations were then performed on the minimum free energy structures. Our procedure returned the low energy conformations observed experimentally in the gas phase with rotational spectroscopy [M. E. Sanz et al., Phys. Chem. Chem. Phys. 12, 3573 (2010)]. Moreover, it provided information on higher energy conformers not accessible to experiments and on the conformers in water. The comparison between different force-fields and quantum chemical data highlighted the importance of the underlying potential energy surface to accurately capture energy rankings. The combination of force-field based metadynamics, sketch-map analysis, and quantum chemical calculations was able to produce an exhaustive conformational exploration in a range of significant free energies that complements the experimental data. Similar protocols can be applied to larger peptides with complex conformational landscapes and would greatly benefit from the next generation of accurate force-fields.

  12. Spectroscopic studies of irradiated glasses: Application in nuclear dosimetry

    International Nuclear Information System (INIS)

    Farah, Khaled

    2010-01-01

    The present work aims to study the effects of ionizing radiation on silicate glasses in order to develop a new dosimetry system simple, precise, stable and inexpensive. Indeed, changes in mechanical properties, optical and paramagnetic glasses when subjected to ionizing radiation. The prediction of long-term behavior, physical aging under irradiation, the glass is paramount. many studies have brought many ways to avoid obscuring glass windows used in nuclear reactors or hot cells and optical devices. Recently, much work has concentrated on the application of the color induced by irradiation for developing a recyclable glass in the glass industry is of great interest economically and environmentally.

  13. Comparative study of spectroscopic properties of the low-lying ...

    Indian Academy of Sciences (India)

    due to the substitutions by methyl (II), isopropyl (III) and fluoromethyl (IV) groups on nitrogen. Some theo- retical studies on PSB (I) have been earlier reported at different level of calculations. AM1/CISD, MP4, MRCI calculations have been carried out by Dobado and. Nonella,25 while MNDO-CI method has been applied.

  14. Moessbauer spectroscopic studies of magnetically ordered biological materials

    International Nuclear Information System (INIS)

    Dickson, D.P.E.

    1987-01-01

    This paper discusses recent work showing the application of Moessbauer spectroscopy to the study of the properties of the magnetically ordered materials which occur in a variety of biological systems. These materials display a diversity of behaviour which provides good examples of the various possibilities which can arise with iron-containing particles of different compositions and sizes. (orig.)

  15. Synthesis and Spectroscopic, Thermal and Crystal Structure Studies ...

    African Journals Online (AJOL)

    NICO

    Structure Studies of Hydrazinium Hydrogensuccinate .... SMART and SAINT software packages28 were used for ... were corrected for systematic errors using SADABS29 based on ... T. Premkumar, R. Selvakumar, N.P. Rath and S. Govindarajan,. 86. S. Afr. J. .... 6 D. Gajapathy, S. Govindarajan and K.C. Patil, Thermochim.

  16. Deformed shell model studies of spectroscopic properties of Zn and ...

    Indian Academy of Sciences (India)

    2014-04-05

    Apr 5, 2014 ... April 2014 physics pp. 757–767. Deformed shell model studies of ... experiments without isotopical enrichment thereby reducing the cost considerably. By taking a large mass of the sample because of its low cost, one can ...

  17. 57Fe Moessbauer spectroscopic studies on photosensitive nitrile hydratase (NHase)

    International Nuclear Information System (INIS)

    Kobayashi, Yoshio; Odaka, Masafumi

    2001-01-01

    57 Fe Moessbauer spectroscopy is a very useful technique for elucidating the chemical properties and biological changes of Fe species located at the reaction centers in various biological systems. We have applied 57 Fe Moessbauer spectroscopy to study the mechanism of photoactivation and the structural change caused by light irradiation of nitrile hydratase (NHase). (author)

  18. Spectroscopic studies of dynamically compacted monoclinic ZrO2

    NARCIS (Netherlands)

    Maczka, M.; Lutz, E.T.G.; Verbeek, H.J.; Oskam, K.; Meijerink, A.; Hanuza, J.; Stuivinga, M.E.C.

    1999-01-01

    The properties of dynamically compacted monoclinic zirconia have been studied by X-ray powder diffraction, IR, Raman, EPR and luminescence spectroscopy. Compaction introduces a large number of defects into the sample, which leads to a broadening of the X-ray lines, and IR and Raman bands. Besides,

  19. Structural, spectroscopic and electrochemical study of V substituted ...

    Indian Academy of Sciences (India)

    Administrator

    Electrochemical impedance studies showed that ionic conductivity is high for x = 0∙10 composition. a.c. and ... ground in an agate mortar in the presence of methanol for .... tion peaks are stabilized at 2∙41 V. The oxidation peaks are observed ...

  20. Synthesis and spectroscopic study of high quality alloy Cdx S ...

    Indian Academy of Sciences (India)

    Wintec

    In the present study, we report the synthesis of high quality CdxZn1–xS nanocrystals alloy at. 150°C with .... (XRD) using a Siemens model D 500, powder X-ray ... decays were analysed using IBH DAS6 software. 3. ... This alloying process is.

  1. Spectroscopic Studies of the Electron Donor-Acceptor Interaction of ...

    African Journals Online (AJOL)

    Conformity with Beer\\'s law was evident over the concentration range 0.8 – 8.0 mg/100 ml of chloroquine phosphate; thus making it possible for an accurate quantitative determination of the drug. Conclusion: The studied complexation phenomenon formed a basis for the quantitative determination of both pure samples and ...

  2. Thermophysical and spectroscopic studies of room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate in Tritons

    International Nuclear Information System (INIS)

    Chaudhary, Ganga Ram; Bansal, Shafila; Mehta, S.K.; Ahluwalia, A.S.

    2012-01-01

    Highlights: ► Thermophysical studies of new formulations of [BMIM][PF 6 ]+TX(45,100) have been made. ► Strong intermolecular interactions between [BMIM][PF 6 ] and TX (45, 100) is observed. ► Magnitude of interactions increases with the addition of oxyethylene groups in TX. ► With rise in temperature, intermolecular interactions increases. ► Spectroscopic studies show that interactions are via aromatic rings of RTIL and TX. - Abstract: The thermophysical properties viz. density ρ, speed of sound u, and specific conductivity κ of pure room temperature ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate) and its binary formulations with Triton X-45 and Triton X-100 have been studied over the entire composition range at different temperatures (293.15 to 323.15) K. Excess molar volume V E , deviation in isentropic compressibility ΔK S , partial molar excess volume V i E , deviation in partial molar isentropic compressibility ΔK S,i , deviation in specific conductivity Δκ have also been estimated and analysed. Spectroscopic properties (IR, 1 H and 13 C NMR) of these mixtures have been investigated in order to understand the structural and interactional behaviour of formulations studied. The magnitude of interactions between the two components increases with addition of number of oxyethylene groups in Tritons and with rise in temperature. Spectroscopic measurements indicate that interactions are mainly taking place through the five member ring of room temperature ionic liquid and six member ring of Tritons.

  3. Spectroscopic studies with the use of deep-inelastic heavy-ion reactions

    International Nuclear Information System (INIS)

    Broda, R

    2006-01-01

    Gamma spectroscopic studies exploiting deep-inelastic heavy-ion reactions in thick target experiments are reviewed. The description of physical motivation, history of early experiments, analysis of the N/Z equilibration process as well as the outline of the experimental method and data analysis are followed by the presentation of main results obtained in various regions of the nuclide chart. Brief comments on thin target spectroscopy experiments involving fragment detection and future outlook are summarized. (topical review)

  4. Isolation and spectroscopic studies of curcumin from Philippine Curcuma longa L

    International Nuclear Information System (INIS)

    Torres, Rosalinda C.; Bonifacio, Teresita S.; Herrera, Celia L.; Lanto, Eduardo A.

    1998-01-01

    Curcumin, the yellow coloring matter was isolated from the rhizomes of Philippine Curcuma longa L. (turmeric) by Soxhlet extraction with toluene followed by concentration and slow crystallization. The isolated curcumin was then subjected to chromatographic and spectroscopic studies with the Merck curcumin standard. The infra red and UV-vis spectra of both compounds were found to be almost identical indicating a high purity of the isolate. The % yield obtained was 2-3%. (Author)

  5. Spectroscopic and transport studies of Cu 2 ion doped in (40–x ...

    Indian Academy of Sciences (India)

    The preparation of (40 – )Li2O–LiF–60Bi2O3 glassy system and spectroscopic and transport studies of this system are reported. IR results show that this glass consists of [BiO3] units and indicate formation of Bi–F bonds with the addition of LiF. From the ESR spectra of Cu2+ ion, the effective values are found to vary ...

  6. Spectroscopic study of silicate glass structure. Application to the case of iron and magnesium

    International Nuclear Information System (INIS)

    Rossano, Stephanie

    2008-01-01

    During the last 10 years, I focused my research topics on silicate glass structure. More specifically I have been interested by two main components of natural and technological silicate glasses, Fe and Mg. Using solid state spectroscopic methods adapted to the disordered nature of glass coupled to molecular dynamics simulation and modeling or ab initio calculation, I have studied the environment of iron and magnesium and their impact on glass properties. Information on the distribution of environments in glasses have been extracted. (author)

  7. Spectroscopic Study of Electrical Glow Discharges in Gases

    Science.gov (United States)

    Reyes, P. G.; Evangelista, M.; Trujillo, C.; Castillo, F.; Rangel, J.

    2006-12-01

    The variation of the power of the light emitted in a Glow Discharge in Gases of low pressure (GDGLP) excited by a DC source was studied. A lack of dependency of the kind of gas used and the pressure it is located at was obtained. This is comparable to the potential drop which takes place in the discharge by inelastic collisions such as ionization, recombination, excitation, relaxation, etc.

  8. Spectroscopic studies on Titanium ion binding to the apo lactoferrin

    International Nuclear Information System (INIS)

    Moshtaghie, A.A.; Ani, M.; Arabi, M.H.

    2006-01-01

    Titanium is a relatively abundant element that has found growing applications in medical science and recently some of Titanium compounds are introduced as anticancer drugs. In spite of very limited data which exist on the Titanium metabolism, some proteins might be involved in the mechanism of action of Titanium up to our knowledge, there is not any report in the literature concerning binding of Titanium to apo lactoferrin. Binding of apo lactoferrin with Ti(IV)-citrate was studied by spectroflourimeterey and spectrophotometery techniques under physiological conditions. The spectroflourimeteric studies revealed a significant fluorescence quenching, that indicated binding of apo lactoferrin with Ti(IV). The same reaction was monitored through spectrophotometry technique; this represents a characteristic UV difference band at 267 nm, which is different from lac-Fe (III). Titration studies how that lactoferrin specifically binds two moles Ti(IV) as complex with citrate per mol protein. Spectroflourimeterey and spectrophotometery techniques indicated that Ti(IV) ions cause a reduction (13%-14%) in binding of Fe(III) to lactoferrin. In overall, we may come to this conclusion that this element might be involved in the iron metabolism

  9. Vibrational spectroscopic, structural and nonlinear optical activity studies on 6-aminonicotinamide: A DFT approach

    Energy Technology Data Exchange (ETDEWEB)

    Asath, R. Mohamed; Premkumar, S.; Mathavan, T.; Benial, A. Milton Franklin, E-mail: miltonfranklin@yahoo.com [Department of Physics, N.M.S.S.V.N College, Madurai-625019, Tamilnadu (India); Rekha, T. N. [PG & Research Department of Physics, Lady Doak College, Madurai 625002, Tamilnadu (India); Jawahar, A. [Department of Chemistry, N.M.S.S.V.N College, Madurai-625019, Tamilnadu (India)

    2016-05-23

    The conformational analysis was carried out for 6-aminonicotinamide (ANA) using potential energy surface scan method and the most stable optimized conformer was predicted. The theoretical vibrational frequencies were calculated for the optimized geometry using DFT/B3LYP cc-pVQZ basis set by Gaussian 09 Program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using VEDA 4.0 program. The Mulliken atomic charge values were calculated. In the Frontier molecular orbitals analysis, the molecular reactivity, kinetic stability, intermolecular charge transfer studies and the related molecular properties were calculated. The ultraviolet-visible spectrum was simulated for both in the gas phase and liquid phase (ethanol) and the π to π* electronic transition was predicted. The nonlinear optical (NLO) activity was studied by means of the first order hyperpolarizability value, which was 8.61 times greater than the urea and the natural bond orbital analysis was also performed to confirm the NLO activity of the molecule. Hence, the ANA molecule is a promising candidate for the NLO materials.

  10. Vibrational spectroscopic, structural and nonlinear optical activity studies on 6-aminonicotinamide: A DFT approach

    Science.gov (United States)

    Asath, R. Mohamed; Premkumar, S.; Rekha, T. N.; Jawahar, A.; Mathavan, T.; Benial, A. Milton Franklin

    2016-05-01

    The conformational analysis was carried out for 6-aminonicotinamide (ANA) using potential energy surface scan method and the most stable optimized conformer was predicted. The theoretical vibrational frequencies were calculated for the optimized geometry using DFT/B3LYP cc-pVQZ basis set by Gaussian 09 Program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using VEDA 4.0 program. The Mulliken atomic charge values were calculated. In the Frontier molecular orbitals analysis, the molecular reactivity, kinetic stability, intermolecular charge transfer studies and the related molecular properties were calculated. The ultraviolet-visible spectrum was simulated for both in the gas phase and liquid phase (ethanol) and the л to л* electronic transition was predicted. The nonlinear optical (NLO) activity was studied by means of the first order hyperpolarizability value, which was 8.61 times greater than the urea and the natural bond orbital analysis was also performed to confirm the NLO activity of the molecule. Hence, the ANA molecule is a promising candidate for the NLO materials.

  11. [Derivative spectrophotometric and NMR spectroscopic study in pharmaceutical science].

    Science.gov (United States)

    Kitamura, Keisuke

    2007-10-01

    This review starts with an introduction of derivative spectrophotometry followed by a description on the construction of a personal computer-assisted derivative spectrophotometric (DS) system. An acquisition system for inputting digitalized absorption spectra into personal computers and a BASIC program for calculating derivative spectra were developed. Then, applications of the system to drug analyses that are difficult with traditional absorption methods are described. Following this, studies on the interactions of drugs with biological macromolecules by the DS and NMR methods were discussed. An (1)H NMR study elucidated that the small unilamellar vesicle (SUV) has a single membrane made of a phosphatidylcholine bilayer, and that chlorpromazine interacts with both the outer and inner layers. (13)C NMR revealed a reduction of the dissociation constants of phenothiazine drugs due to their interaction with SUV. The partition coefficients of phenothiazine, benzodiazepine and steroid drugs in an SUV-water system and the effects of cholesterol or amino lipids content on these partition coefficients were examined by the DS method. The binding constants of phenothiazine drugs to bovine serum albumin (BSA) and the influence of Na(+), K(+), Cl(-), Br(-), and I(-) on these binding constants were determined by DS. It was found that I(-), Br(-), Cl(-) reduce the binding constants in this order, and that Na(+) and K(+) have no effect. A (19)F NMR study revealed that triflupromazine binds to BSA and human serum albumin in two regions including Site II with different populations, and that a nonsteroidal anti-inflammatory drug, niflumic acid, binds Sites Ia and Ib.

  12. Studies on spectroscopic and thermal behaviour of neodymium soaps

    International Nuclear Information System (INIS)

    Mehrotra, K.N.; Chauhan, M.; Shukla, R.K.

    1992-01-01

    The present work has been initiated with a view to study the nature of bonding, structure, thermal and micellar behaviour of neodymium soaps in non-aqueous media. The structure of these soaps in solid state has been investigated by infrared spectra and X-ray diffraction patterns, and spectrophotometric result confirms the nature of bonding and micellar behaviour of neodymium soaps. The results of TGA have been used to explain the order of reaction and to find out the values of energy of activation for the decomposition process. (author). 9 refs., 5 tabs

  13. Mechanism of the electrochemical oligomerization of thionaphteneindole: a spectroscopic study

    Science.gov (United States)

    Poggi, Gabriella; Casalbore Miceli, Giuseppe; Beggiato, Giancarlo; Emmi, Salvatore S.

    1997-10-01

    The UV, visible and NIR spectra recorded during electrolysis of TNI in CH 2Cl 2 have been studied as a function of electrolysis time and of the quantity of charge exchanged. Among the oligomeric species that might be responsible for the behaviour observed, particular attention has been devoted to dimers of TNI characterized by different charges, presence of unpaired electrons, and deprotonation of the amino hydrogens. A sample of these species has been described theoretically by means of the PM3 semiempirical hamiltonian and their spectra have been computed giving results in reasonable agreement with the observed transitions.

  14. Near-Infrared Spectroscopic Study of Chlorite Minerals

    OpenAIRE

    Min Yang; Meifang Ye; Haihui Han; Guangli Ren; Ling Han; Zhuan Zhang

    2018-01-01

    The mineral chemistry of twenty chlorite samples from the United States Geological Survey (USGS) spectral library and two other regions, having a wide range of Fe and Mg contents and relatively constant Al and Si contents, was studied via infrared (IR) spectroscopy, near-infrared (NIR) spectroscopy, and X-ray fluorescence (XRF) analysis. Five absorption features of the twenty samples near 4525, 4440, 4361, 4270, and 4182 cm−1 were observed, and two diagnostic features at 4440 and 4280 cm−1 we...

  15. Spectroscopic, structural and drug docking studies of carbocysteine

    Science.gov (United States)

    Manivannan, M.; Rajeshwaran, K.; Govindhan, R.; Karthikeyan, B.

    2017-09-01

    Carbocysteine or carbocisteine having the empirical formula C5H9NO4S,is one of the most therapeutically prescribed expectorant, sold under the brand name viz., Mucodyne (UK and India), Rhinathiol and Mucolite. In pediatric respiratory pathology, it can relieve the symptoms of obstructive pulmonary disease (COPD) and bronchiectasis. On the consideration of its extensive pharmaceutical usage and medicinal value, we have investigated its chemical structure and composition by employing various spectral techniques like 1H, 13C NMR, FT-IR,Raman, UV-Visible spectroscopy and powder X-ray diffraction method. Density Functional Theoretical (DFT) studies on its electronic structure is also carried out. Drug docking studies were carried out to ascertain the nature of molecular interaction with the biological protein system. Furthermore theoretical Raman spectrum of this molecule has been computed and compared with the experimental Raman spectrum. The forbidden energy gap between its frontier molecular orbitals, viz., HOMO-LUMO is calculated and correlated with its observed λmax value. Atomic orbitals which are mainly contributes to the frontier molecular orbitals were identified. Molecular electrostatic potential diagram has been mapped to explain its chemical activity. Based on the results, a suitable mechanism of its protein binding mode and drug action has been discussed.

  16. Impedance and modulus spectroscopic study of nano hydroxyapatite

    Science.gov (United States)

    Jogiya, B. V.; Jethava, H. O.; Tank, K. P.; Raviya, V. R.; Joshi, M. J.

    2016-05-01

    Hydroxyapatite (Ca10 (PO4)6 (OH)2, HAP) is the main inorganic component of the hard tissues in bones and also important material for orthopedic and dental implant applications. Nano HAP is of great interest due to its various bio-medical applications. In the present work the nano HAP was synthesized by using surfactant mediated approach. Structure and morphology of the synthesized nano HAP was examined by the Powder XRD and TEM. Impedance study was carried out on pelletized sample in a frequency range of 100Hz to 20MHz at room temperature. The variation of dielectric constant, dielectric loss, and a.c. conductivity with frequency of applied field was studied. The Nyquist plot as well as modulus plot was drawn. The Nyquist plot showed two semicircle arcs, which indicated the presence of grain and grain boundary effect in the sample. The typical behavior of the Nyquist plot was represented by equivalent circuit having two parallel RC combinations in series.

  17. Divalent thulium triflate. A structural and spectroscopic study

    Energy Technology Data Exchange (ETDEWEB)

    Xemard, Mathieu; Jaoul, Arnaud; Cordier, Marie; Nocton, Gregory [Univ. Paris-Saclay, Palaiseau (France). LCM, Ecole polytechnique, CNRS; Molton, Florian; Duboc, Carole [Grenoble Univ., Saint Martin d' Heres (France). Dept. de Chimie Moleculaire; Cador, Olivier; Le Guennic, Boris [Univ. de Rennes 1 (France). Inst. des Sciences Chimique de Rennes, UMR 6226 CNRS; Maury, Olivier [Univ. Claude Bernard Lyon 1 (France). Lab. de Chimie; Clavaguera, Carine [Univ. Paris-Saclay, Palaiseau (France). LCM, Ecole polytechnique, CNRS; Univ. Paris Sud, Univ. Paris-Saclay, Orsay (France). Lab. de Chimie Physique, CNRS

    2017-04-03

    The first molecular Tm{sup II} luminescence measurements are reported along with rare magnetic, X and Q bands EPR studies. Access to simple and soluble molecular divalent lanthanide complexes is highly sought for small-molecule activation studies and organic transformations using single-electron transfer processes. However, owing to their low stability and propensity to disproportionate, these complexes are hard to synthetize and their electronic properties are therefore almost unexplored. Herein we present the synthesis of [Tm(μ-OTf){sub 2}(dme){sub 2}]{sub n}, a rare and simple coordination compound of divalent thulium that can be seen as a promising starting material for the synthesis of more elaborated complexes. This reactive complex was structurally characterized by X-ray diffraction analysis and its electronic structure has been compared with that of its halide cousin TmI{sub 2}(dme){sub 3}. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Multinuclear nuclear magnetic resonance spectroscopic study of cartilage proteoglycans

    Energy Technology Data Exchange (ETDEWEB)

    Lerner, L.

    1985-01-01

    Hyaline cartilage is a composite material whose major function is to withstand compression while retaining flexibility. Its mechanical properties are affected by tissue hydration and ionic composition. Models of the mechanical behavior of cartilage have incorporated certain assumptions about the interactions of the major components of cartilage: collagen, proteoglycans, water, and cations. To determine the validity of these assumption, the authors have used nuclear magnetic resonance spectroscopy (NMR). Two approaches have been used: (a) natural abundance carbon-13 NMR; and (b) NMR of sodium-23, potassium-39, magnesium-25, and calcium-43. Evidence from studies in intact tissues are reinforced by extensive measurements on solutions of proteoglycans and other relevant macromolecules. Based on the measurements of NMR relaxation rates and lineshapes reported here, it is concluded that neither sodium nor potassium interact strongly with bovine nasal proteoglycan aggregates or their substituent glycosaminoglycan chains in solution. Proteoglycans do bind magnesium and calcium. Therefore there is a qualitative difference between monovalent and divalent cations, which is not taken into account by polyelectrolyte models or models for the ionic dependence of mechanical properties. Cation binding to heparin, which has a higher charge density than cartilage proteoglycans, was also studied. The results presented here establish that heparin binds sodium, magnesium, and calcium.

  19. Photoacoustic FTIR spectroscopic study of undisturbed nacre from red abalone

    Science.gov (United States)

    Verma, Devendra; Katti, Kalpana; Katti, Dinesh

    2006-07-01

    In this work, photoacoustic Fourier transform infrared (PA-FTIR) spectroscopy has been utilized to study interfacial interactions of undisturbed nacre and nacre powder from red abalone shell. The spectra of both undisturbed nacre and nacre powder showed characteristic bands of aragonite and proteins. Although nacre powder and undisturbed nacre are chemically identical, PA-FTIR spectrum of undisturbed nacre is found to be significantly different from that of nacre powder. A broad and strong band is observed at around 1485 cm -1 in nacre powder. The intensity of this band is notably reduced in undisturbed nacre. This result is explained on the basis of interfacial interactions between aragonite platelets and acidic proteins. It is also observed that band at around 1788 cm -1 originates from three overlapping bands 1797, 1787 and 1778 cm -1. The band at around 1787 cm -1 is assigned to C dbnd O stretching of carboxylate groups of acidic proteins. The other two bands at 1797 and 1778 cm -1, originate from aragonite and have been assigned to combination bands, ν 3 + ν 4a and ν 3 + ν 4b, respectively. For the study of stratification in undisturbed nacre, PA-FTIR spectra have been collected in step scan mode. The variation in spectra with depth can be attributed to changes in conformation of proteins as well as interfacial interactions.

  20. Spectroscopic studies on surface reactions between minerals and reagents in flotation systems

    International Nuclear Information System (INIS)

    Giesekke, E.W.

    1981-01-01

    A study of the adsorbed species at the interface between the minerals and the aqueous solution is reported in the hope that it will contribute to a better understanding of selective mineral flotation by various reagents. The results of infrared spectroscopic studies are cited from the author's investigation on the fluorite-sodium oleate and fluorite-linoleate systems. Electron-spectroscopic techniques, e.g., electron spectroscopy for chemical analysis (ESCA) have also been useful in the identification of adsorbed species on mineral surfaces. Some experimental data from the literature are discussed. These studies have the disadvantage that they are not in situ investigations of the interface between the mineral and the aqueous solution. The potential use of other spectroscopic techniques are discussed, photo-acoustic, Raman, and electron-spin-resonance spectroscopy being considered as possible alternatives. It is suggested that the relatively small surface areas of minerals used in flotation (i.e. smaller than 2m 2 .g- 1 ) impose severe restrictions on the use of such techniques

  1. DFT Study of dimers of dimethyl sulfoxide in gas phase

    Directory of Open Access Journals (Sweden)

    Reza Fazaeli

    2014-10-01

    Full Text Available Density functional (DFT calculations at M05-2x/aug-cc-pVDZ level were used to analyze the interactions between dimethyl sulfoxide (DMSO dimers. The structures obtained have been ana-lyzed with the Atoms in Molecules (AIMs and Natural Bond Orbital (NBO methodologies. Four minima were located on the potential energy surface of the dimers. Three types of interac-tions are observed, CH•••O, CH•••S hydrogen bonds and orthogonal interaction between the lone pair of the oxygen with the electron-deficient region of the sulfur atom. Stabilization energies of dimers including BSSE and ZPE are in the range 27–40 kJmol-1. The most stable conformers of dimers at DFT level is cyclic structure with antiparallel orientation of S=O groups pairing with three C–H∙∙∙O and a S∙∙∙O interactions.

  2. Raman spectroscopic study of plasma-treated salmon DNA

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Geon Joon; Kim, Yong Hee; Choi, Eun Ha [Plasma Bioscience Research Center, Kwangwoon University, Seoul 139-701 (Korea, Republic of); Kwon, Young-Wan [Department of Chemistry, Korea University, Seoul 136-701 (Korea, Republic of)

    2013-01-14

    In this research, we studied the effect of plasma treatment on the optical/structural properties of the deoxyribonucleic acid (DNA) extracted from salmon sperm. DNA-cetyltrimethylammonium (CTMA) films were obtained by complexation of DNA with CTMA. Circular dichroism (CD) and Raman spectra indicated that DNA retained its double helical structure in the solid film. The Raman spectra exhibited several vibration modes corresponding to the nuclear bases and the deoxyribose-phosphate backbones of the DNA, as well as the alkylchains of CTMA. Dielectric-barrier-discharge (DBD) plasma treatment induced structural modification and damage to the DNA, as observed by changes in the ultraviolet-visible absorption, CD, and Raman spectra. The optical emission spectra of the DBD plasma confirmed that DNA modification was induced by plasma ions such as reactive oxygen species and reactive nitrogen species.

  3. Activation of heterogenised rhodium carbonylation catalyst infrared spectroscopic study

    Energy Technology Data Exchange (ETDEWEB)

    Scurrell, M S

    1977-01-01

    In a study related to heterogeneous versions of homogeneous catalysts active in carbonylation of methanol to acetic acid, the catalyst consisted of 1Vertical Bar3< rhodium as rhodium trichloride supported on 13X zeolite and evacuated at 437/sup 0/K. Contacting the catalyst with carbon monoxide caused two bands, at 2025 and 2095 cm/sup -1/, to appear. Contact with a mixture of carbon monoxide and methyl iodide (the usual promoter) caused bands at 2085, 1710, 1440, and 1370 cm/sup -1/ to appear; the first two correspond to the bands at 2062 and 1711 cm/sup -1/ in homogeneous catalysts attributed to the formation of Rh(CH/sup 3/CO)(CO)X/sup 2/I/sup -/. Spectra.

  4. A spectroscopic study of interaction of cationic dyes with heparin

    Directory of Open Access Journals (Sweden)

    R. Nandini

    2010-01-01

    Full Text Available The interaction of two cationic dyes namely, acridine orange and pinacyanol chloride with an anionic polyelectrolyte, heparin, has been investigated by spectrophotometric method.The polymer induced metachromasy in the dyes resulting in the shift of the absorption maxima of the dyes towards shorter wavelengths. The stability of the complexes formed between acridine orange and heparin was found to be lesser than that formed between pinacyanol chloride and heparin. This fact was further confirmed by reversal studies using alcohols, urea and surfactants. The interaction of acridine orange with heparin has also been investigated fluorimetrically.The interaction parameters revealed that binding between acridine orange and heparin arises due to electrostatic interaction while that between pinacyanol chloride and heparin is found to involve both electrostatic and hydrophobic forces. The effect of the structure of the dye in inducing metachromasy has also been discussed.

  5. Tertiary phosphine complexes of rhenium: a spectroscopic study

    International Nuclear Information System (INIS)

    Fergusson, J.E.; Heveldt, P.F.

    1976-01-01

    Complexes of the type ReOX 3 L 2 , ReNX 2 L 3 , ReX 3 (NO)L 2 and ReX 2 (NO)L 3 have been studied using, UV visible, IR and H 1 , C 13 NMR spectroscopy. (X is a halogen, Cl, Br, I and L is a tertiary phosphine Et 3 P and Et 2 PhP). Evidence obtained on the blue cis isomer ReOCl 3 L 2 suggests that the halogens are arranged on a face of the octahedral complex. Assignments of ν(Re-X) and ν(Re-P) vibrations have been made. Three complexes of technetium, [TcCl 4 (Ph 3 P) 2 ], [TcCl 3 (Et 2 PhP) 3 ] and [TcCl 3 (NO)(Et 2 PhP) 2 ] have been isolated. (author)

  6. Moessbauer spectroscopic studies of iron-storage proteins

    Energy Technology Data Exchange (ETDEWEB)

    St. Pierre, T.G.

    1986-01-01

    /sup 57/Fe Moessbauer spectroscopy was used to study iron storage proteins. Various cryostats and a superconducting magnet were used to obtain sample environment temperatures from 1.3 to 200K and applied magnetic fields of up to 10T. The Moessbauer spectra of ferritins isolated from iron-overloaded human spleen, limpet (Patella vulgata), giant limpet (Patella laticostata) and chiton (Clavarizona hirtosa) hemolymph, and bacterial (Pseudomonas aeruginosa) cells are used to gain information on the magnetic ordering- and superparamagnetic transition temperatures of the microcrystalline cores of the proteins. Investigations were made about the cause of the difference in the magnetic anisotropy constants of the cores of iron-overloaded human spleen ferritin and hemosiderin. Livers taken from an iron-overloaded hornbill and artificially iron-loaded rats showed no component with a superparamagnetic transition temperature approaching that of the human spleen hemosiderin.

  7. Spectroscopic study of low-temperature hydrogen absorption in palladium

    Energy Technology Data Exchange (ETDEWEB)

    Ienaga, K., E-mail: ienaga@issp.u-tokyo.ac.jp; Takata, H.; Onishi, Y.; Inagaki, Y.; Kawae, T. [Department of Applied Quantum Physics, Faculty of Engineering, Kyushu University, Motooka, Nishi-Ku, Fukuoka 819-0395 (Japan); Tsujii, H. [Department of Physics, Faculty of Education, Kanazawa University, Kakuma-machi, Kanazawa 920-1192 (Japan); Kimura, T. [Department of Physics, Kyushu University, Hakozaki, Higashi-Ku, Fukuoka 812-8581 (Japan)

    2015-01-12

    We report real-time detection of hydrogen (H) absorption in metallic palladium (Pd) nano-contacts immersed in liquid H{sub 2} using inelastic electron spectroscopy (IES). After introduction of liquid H{sub 2}, the spectra exhibit the time evolution from the pure Pd to the Pd hydride, indicating that H atoms are absorbed in Pd nano-contacts even at the temperature where the thermal process is not expected. The IES time and bias voltage dependences show that H absorption develops by applying bias voltage 30 ∼ 50 mV, which can be explained by quantum tunneling. The results represent that IES is a powerful method to study the kinetics of high density H on solid surface.

  8. Phosphonic drugs: Experimental and theoretical spectroscopic studies of fosfomycin

    Science.gov (United States)

    Chruszcz-Lipska, Katarzyna; Zborowski, Krzysztof K.; Podstawka-Proniewicz, Edyta; Liu, Shaoxuan; Xu, Yizhuang; Proniewicz, Leonard M.

    2011-02-01

    pH and time-dependant changes of fosfomycin molecular structure in an aqueous solution are studied by Raman, NMR, and generalized 2D correlation spectroscopies. Interpretation of the experimental spectra is based on the assumption of formation of different species running on applied physicochemical conditions. Geometries of all possible structures were entirely optimized with the 6-311++G(2df,p) basis set at the B3LYP theoretical level using procedures implemented in the Gaussian '03 set of programs. Harmonic frequency calculations verified the nature of the studied structures and allowed to simulate obtained Raman spectra. The theoretical NMR shielding was calculated using the GIAO method at the same computational level. In addition, in some cases PCM model was used to monitor the influence of water molecules on the NMR spectra. It is shown that in the pH range of 1-2 of fosfomycin aqueous solution oxirane ring is open sequent to nucleophilic attack and forms 1,2-dihydroxyphosphonic acid with small content of its monodeprotonated species. On the other hand, in pH 7 and higher it appears either as 1,2-epoxypropylphosphonic or 1,2-dihydroxyphosphonic dianion depending upon whether hydrolysis took place or not. It is also discussed that Raman marker bands originating from the individual species of fosfomycin can be used to detect and/or to monitor this antibiotic in an aqueous medium (for example urine samples). Hence, depending upon the structure found in urine one can tell about metabolic processes of this antibiotic in the body.

  9. Vibrational spectroscopic studies of Isoleucine by quantum chemical calculations.

    Science.gov (United States)

    Moorthi, P P; Gunasekaran, S; Ramkumaar, G R

    2014-04-24

    In this work, we reported a combined experimental and theoretical study on molecular structure, vibrational spectra and NBO analysis of Isoleucine (2-Amino-3-methylpentanoic acid). The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments, thermodynamics properties, NBO analyses, NMR chemical shifts and ultraviolet-visible spectral interpretation of Isoleucine have been studied by performing MP2 and DFT/cc-pVDZ level of theory. The FTIR, FT-Raman spectra were recorded in the region 4000-400 cm(-1) and 3500-50 cm(-1) respectively. The UV-visible absorption spectra of the compound were recorded in the range of 200-800 nm. Computational calculations at MP2 and B3LYP level with basis set of cc-pVDZ is employed in complete assignments of Isoleucine molecule on the basis of the potential energy distribution (PED) of the vibrational modes, calculated using VEDA-4 program. The calculated wavenumbers are compared with the experimental values. The difference between the observed and calculated wavenumber values of most of the fundamentals is very small. (13)C and (1)H nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method and compared with experimental results. The formation of hydrogen bond was investigated in terms of the charge density by the NBO calculations. Based on the UV spectra and TD-DFT calculations, the electronic structure and the assignments of the absorption bands were carried out. Besides, molecular electrostatic potential (MEP) were investigated using theoretical calculations. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. NMR spectroscopic studies of membrane-bound biological systems

    International Nuclear Information System (INIS)

    Hohlweg, W.

    2013-01-01

    In the course of this thesis, biological NMR spectroscopy was employed in studying membrane-bound peptides and proteins, for which structural information is still comparatively hard to obtain. Initial work focused on various model peptides bound to membrane-mimicking micelles, studying the protonation state of arginine in a membrane environment. Strong evidence for a cation-π complex was found in TM7, a peptide which forms the seventh transmembrane helix of subunit a of the vacuolar-type H+-ATPase (V-ATPase). V-ATPase is a physiologically highly relevant proton pump, which is present in intracellular membranes of all eukaryotic organisms, as well as the plasma membrane of several specialized cells. Loss of functional V-ATPase is associated with human diseases such as osteopetrosis, distal renal tubular acidosis or the spreading of cancer. V-ATPase is considered a potential drug target in the treatment of osteoporosis and cancer, or in the development of novel contraceptives. Results from NMR solution structure determination, NMR titration experiments, paramagnetic relaxation enhancement experiments and tryptophan fluorescence spectroscopy confirm the existence of a buried cation-? complex formed between arginine residue R735, which is essential for proton transport, and neighbouring tryptophan and tyrosine residues. In vivo experiments in the yeast Saccharomyces cerevisiae using selective growth tests and fluorescence microscopy showed that formation of the cation-π complex is essential for V-ATPase function. Deletion of both aromatic residues, as well as only the one tryptophan residue leads to growth defects and inability to maintain vacuolar pH homeostasis. These findings shine new light on the still elusive mechanism of proton transport in V-ATPase, and show that arginine R735 may be directly involved in proton transfer across the membrane. (author) [de

  11. Raman spectroscopic study of ancient South African domestic clay pottery

    Science.gov (United States)

    Legodi, M. A.; de Waal, D.

    2007-01-01

    The technique of Raman spectroscopy was used to examine the composition of ancient African domestic clay pottery of South African origin. One sample from each of four archaeological sites including Rooiwal, Lydenburg, Makahane and Graskop was studied. Normal dispersive Raman spectroscopy was found to be the most effective analytical technique in this study. XRF, XRD and FT-IR spectroscopy were used as complementary techniques. All representative samples contained common features, which were characterised by kaolin (Al 2Si 2O 5(OH) 5), illite (KAl 4(Si 7AlO 20)(OH) 4), feldspar (K- and NaAlSi 3O 8), quartz (α-SiO 2), hematite (α-Fe 2O 3), montmorillonite (Mg 3(Si,Al) 4(OH) 2·4.5H 2O[Mg] 0.35), and calcium silicate (CaSiO 3). Gypsum (CaSO 4·2H 2O) and calcium carbonates (most likely calcite, CaCO 3) were detected by Raman spectroscopy in Lydenburg, Makahane and Graskop shards. Amorphous carbon (with accompanying phosphates) was observed in the Raman spectra of Lydenburg, Rooiwal and Makahane shards, while rutile (TiO 2) appeared only in Makahane shard. The Raman spectra of Lydenburg and Rooiwal shards further showed the presence of anhydrite (CaSO 4). The results showed that South African potters used a mixture of clays as raw materials. The firing temperature for most samples did not exceed 800 °C, which suggests the use of open fire. The reddish brown and grayish black colours were likely due to hematite and amorphous carbon, respectively.

  12. Spectroscopic study of the reaction between Br2 and dimethyl sulfide (DMS), and comparison with a parallel study made on Cl2 + DMS: possible atmospheric implications.

    Science.gov (United States)

    Beccaceci, Sonya; Ogden, J Steven; Dyke, John M

    2010-03-07

    The reaction between molecular bromine and dimethyl sulfide (DMS) has been studied both as a co-condensation reaction in low temperature matrices by infrared (IR) matrix isolation spectroscopy and in the gas-phase at low pressures by UV photoelectron spectroscopy (PES). The co-condensation reaction leads to the formation of the molecular van der Waals adduct DMS-Br(2). This was identified by IR spectroscopy supported by results of electronic structure calculations. Calculation of the minimum energy structures in important regions of the reaction surface and computed IR spectra of these structures, which could be compared with the experimental spectra, allowed the structure of the adduct (C(s)) to be determined. The low pressure (ca. 10(-5) mbar) gas-phase reaction was studied by UV-PES, but did not yield any observable products, indicating that a third body is necessary for the adduct to be stabilised. These results are compared with parallel co-condensation and gas-phase reactions between DMS and Cl(2). For this reaction, a similar van der Waals adduct DMS-Cl(2) is observed by IR spectroscopy in the co-condensation reactions, but in the gas-phase, this adduct converts to a covalently bound structure Me(2)SCl(2), observed in PES studies, which ultimately decomposes to monochlorodimethylsulfide and HCl. For these DMS + X(2) reactions, computed relative energies of minima and transition states on the potential energy surfaces are presented which provide an interpretation for the products observed from the two reactions studied. The implications of the results obtained to atmospheric chemistry are discussed.

  13. Spectroscopic studies on novel donor-acceptor and low band-gap polymeric semiconductors

    International Nuclear Information System (INIS)

    Cravino, A.

    2002-11-01

    Novel low band-gap conjugated polymeric semiconductors as well as conjugated electron donor chains carrying electron acceptor substituents were electrochemically prepared and investigated by means of different spectroscopic techniques. Using in situ FTIR and ESR spectroelectrochemistry, the spectroscopic features of injected positive charges are found to be different as opposed to the negative charge carriers on the same conjugated polymer. These results, for which the theoretical models so far developed do not account, demonstrate the different structure and delocalization of charge carriers with opposite signs. In addition, vibrational spectroscopy results proof the enhanced 'quinoid' character of low band-gap conjugated chains. Excited state spectroscopy was applied to study photoexcitations in conjugated polymers carrying tetracyanoanthraquinone type or fullerene moieties. This novel class of materials, hereafter called double-cable polymers, was found promising as alternative to the conjugated polymer:fullerene mixtures currently used for the preparation of 'bulk-heterojunction' polymeric solar cells. (author)

  14. Ir Spectroscopic Studies on Microsolvation of HCl by Water

    Science.gov (United States)

    Mani, Devendra; Schwan, Raffael; Fischer, Theo; Dey, Arghya; Kaufmann, Matin; Redlich, Britta; van der Meer, Lex; Schwaab, Gerhard; Havenith, Martina

    2016-06-01

    Acid dissociation reactions are at the heart of chemistry. These reactions are well understood at the macroscopic level. However, a microscopic level understanding is still in the early stages of development. Questions such as 'how many H_2O molecules are needed to dissociate one HCl molecule?' have been posed and explored both theoretically and experimentally.1-5 Most of the theoretical calculations predict that four H_2O molecules are sufficient to dissociate one HCl molecule, resulting in the formation of a solvent separated H_3O+(H_2O)3Cl- cluster.1-3 IR spectroscopy in helium nanodroplets has earlier been used to study this dissociation process.3-5 However, these studies were carried out in the region of O-H and H-Cl stretch, which is dominated by the spectral features of undissociated (HCl)m-(H_2O)n clusters. This contributed to the ambiguity in assigning the spectral features arising from the dissociated cluster.4,5 Recent predictions from Bowman's group, suggest the presence of a broad spectral feature (1300-1360 wn) for the H_3O+(H_2O)3Cl- cluster, corresponding to the umbrella motion of H_3O+ moiety.6 This region is expected to be free from the spectral features due to the undissociated clusters. In conjunction with the FELIX laboratory, we have performed experiments on the (HCl)m(H_2O)n (m=1-2, n≥4) clusters, aggregated in helium nanodroplets, in the 900-1700 wn region. Mass selective measurements on these clusters revealed the presence of a weak-broad feature which spans between 1000-1450 wn and depends on both HCl as well as H_2O concentration. Measurements are in progress for the different deuterated species. The details will be presented in the talk. References: 1) C.T. Lee et al., J. Chem. Phys., 104, 7081 (1996). 2) H. Forbert et al., J. Am. Chem. Soc., 133, 4062 (2011). 3) A. Gutberlet et al., Science, 324, 1545 (2009). 4) S. D. Flynn et al., J. Phys. Chem. Lett., 1, 2233 (2010). 5) M. Letzner et al., J. Chem. Phys., 139, 154304 (2013). 6) J. M

  15. Fourier Transform Infrared and Resonance Raman Spectroscopic Studies of Bacteriorhodopsin.

    Science.gov (United States)

    Earnest, Thomas Nixon

    Fourier transform infrared and resonance Raman spectroscopy were used to investigate the structure and function of the light-activated, transmembrane proton pump, bacteriorhodopsin, from the purple membrane of Halobacterium halobium. Bacteriorhodopsin (bR) is a 27,000 dalton integral membrane protein consisting of 248 amino acids with a retinylidene chromophore. Absorption of a photon leads to the translocation of one or two protons from the inside of the cell to the outside. Resonance Raman spectroscopy allows for the study of the configuration of retinal in bR and its photointermediates by the selective enhancement of vibrational modes of the chromophore. This technique was used to determine that the chromophore is attached to lysine-216 in both the bR _{570} and the M _{412} intermediates. In bR with tyrosine-64 selectively nitrated or aminated, the chromophore appears to have the same configuration in that bR _{570} (all- trans) and M _{412} (13- cis) states as it does in unmodified bR. Polarized Fourier transform infrared spectroscopy (FTIR) permits the study of the direction of transition dipole moments arising from molecular vibrations of the protein and the retinal chromophore. The orientation of alpha helical and beta sheet components was determined for bR with the average helical tilt found to lie mostly parallel to the membrane normal. The beta sheet structures also exhibit an IR linear dichroism for the amide I and amide II bands which suggest that the peptide backbone is mostly perpendicular to the membrane plane although it is difficult to determine whether the bands originate from sheet or turn components. The orientation of secondary structure components of the C-1 (residues 72-248) and C-2 (residues 1-71) fragments were also investigated to determine the structure of these putative membrane protein folding intermediates. Polarized, low temperature FTIR -difference spectroscopy was then used to investigate the structure of bR as it undergoes

  16. GAS-PHASE CHEMISTRY OF THE CYANATE ION, OCN−

    International Nuclear Information System (INIS)

    Cole, Callie A.; Wang, Zhe-Chen; Bierbaum, Veronica M.; Snow, Theodore P.

    2015-01-01

    Cyanate (OCN − ) is the only ion to date whose presence has been confirmed in the icy mantles that coat interstellar dust grains. Understanding the chemical behavior of cyanate at a fundamental level is therefore integral to the advancement of astrochemistry. We seek to unravel the chemistry of this intriguing anion through a combination of gas-phase experiments and theoretical explorations. Our approach is twofold: first, employing a flowing afterglow-selected ion flow tube apparatus, the reactions between OCN − and three of the most abundant atomic species in the interstellar medium, hydrogen, nitrogen, and oxygen, are examined. Hydrogen atoms readily react by associative detachment, but the remarkable stability of OCN − does not give rise to an observable reaction with either nitrogen or oxygen atoms. To explain these results, the potential energy surfaces of several reactions are investigated at the B3LYP/6-311++G(d,p) level of theory. Second, collision induced dissociation experiments involving deprotonated uracil, thymine, and cytosine in an ion trap mass spectrometer reveal an interesting connection between these pyrimidine nucleobase anions and OCN − . Theoretical calculations at the B3LYP/6-311++G(d,p) level of theory are performed to delineate the mechanisms of dissociation and explore the possible role of OCN − as a biomolecule precursor

  17. The Influence of Mixing in High Temperature Gas Phase Reactions

    DEFF Research Database (Denmark)

    Østberg, Martin

    1996-01-01

    by injection of NH3 with carrier gas into the flue gas. NH3 can react with NO and form N2, but a competing reaction path is the oxidation of NH3 to NO.The SNR process is briefly described and it is shown by chemical kinetic modelling that OH radicals under the present conditions will initiate the reaction......The objective of this thesis is to describe the mixing in high temperature gas phase reactions.The Selective Non-Catalytic Reduction of NOx (referred as the SNR process) using NH3 as reductant was chosen as reaction system. This in-furnace denitrification process is made at around 1200 - 1300 K...... diffusion. The SNR process is simulated using the mixing model and an empirical kinetic model based on laboratory experiments.A bench scale reactor set-up has been built using a natural gas burner to provide the main reaction gas. The set-up has been used to perform an experimental investigation...

  18. Gas phase reactions of nitrogen oxides with olefins

    Energy Technology Data Exchange (ETDEWEB)

    Altshuller, A P; Cohen, I

    1961-01-01

    The nature of the condensation products formed in the gas phase reactions of nitrogen dioxide and nitric oxide with pentene-1, 2-methylbutene-2, and 2-methylbutadiene-1,3 was investigated. The reactants were combined at partial pressures in the range of 0.1 to 2.5 mm with the total pressure at one atmosphere. The products were determined by infrared and ultraviolet spectroscopy and colorimetry. The condensates included primary and secondary nitro compounds and alkyl nitrates. Strong hydroxyl and single bond carbon to oxygen stretching vibrations indicate the presence of either nitroalcohols or simple aliphatic alcohols formed through oxidation reactions. Carbonyl stretching frequencies observable in some of the reactions support the conclusion that a portion of the reactants disappear by oxidation rather than by nitration processes. The available results do not indicate the presence of appreciable amounts of tert.-nitro compounds, conjugated nitro-olefins, or gem-dinitro-alkanes. The reactivities of the olefins with the nitrogen oxides are in the decreasing order: 2-methyl-butadiene-1,3, 2-methylbutene-2, pentene-1. 20 references.

  19. Precursor-Less Coating of Nanoparticles in the Gas Phase

    Directory of Open Access Journals (Sweden)

    Tobias V. Pfeiffer

    2015-03-01

    Full Text Available This article introduces a continuous, gas-phase method for depositing thin metallic coatings onto (nanoparticles using a type of physical vapor deposition (PVD at ambient pressure and temperature. An aerosol of core particles is mixed with a metal vapor cloud formed by spark ablation by passing the aerosol through the spark zone using a hollow electrode configuration. The mixing process rapidly quenches the vapor, which condenses onto the core particles at a timescale of several tens of milliseconds in a manner that can be modeled as bimodal coagulation. Gold was deposited onto core nanoparticles consisting of silver or polystyrene latex, and silver was deposited onto gold nanoparticles. The coating morphology depends on the relative surface energies of the core and coating materials, similar to the growth mechanisms known for thin films: a coating made of a substance having a high surface energy typically results in a patchy coverage, while a coating material with a low surface energy will normally “wet” the surface of a core particle. The coated particles remain gas-borne, allowing further processing.

  20. In-situ Spectroscopic Studies and Modelling of Crystallization Processes of Sulphuric Acid Catalysts

    DEFF Research Database (Denmark)

    Oehlers, C.; Fehrmann, Rasmus; Masters, Stephen Grenville

    1996-01-01

    Deactivation of commercial and prototype sulphuric acid catalysts has been investigated in-situ by ESR spectroscopy. The influence of support pore structure,and the chemical composition of the catalyst and the gas phase was dicussed.A statistical lattice model was applied to describe the crystall......Deactivation of commercial and prototype sulphuric acid catalysts has been investigated in-situ by ESR spectroscopy. The influence of support pore structure,and the chemical composition of the catalyst and the gas phase was dicussed.A statistical lattice model was applied to describe...

  1. Studies on selected polymeric materials using the photoacoustic spectroscopic technique

    International Nuclear Information System (INIS)

    Singh, Hukum

    2011-01-01

    Polymethylmethacrylate—graft—polybisphenol—A-carbonate (PMMA-G-PC) with 50% grafting is synthesized. The graft co-polymerization of methylmethacrylate (0.036 mol · lit −1 ) onto polybisphenol—A-carbonate (0.5 g) in the presence of a redox couple formed from potassium persulphate (40 mol · lit −1 ) and thio-urea (30 mmol · lit −1 ) in aqueous nitric acid (0.18 M, 100 ml) in air at (45±2) °C for 3.0 h. Condensation of (PMMA-G-PC) with N- [p-(carboxyl phenyl amino acetic acid)] hydrazide (PCPH) affords polybisphenol-A-carbonate-graft-polymethylmethacrylate hydrazide (PCGH). The photoacoustic (PA) spectra of (PCGH) are recorded in a wavelength range from 200 nm to 800 nm at a modulation frequency of 22 Hz, and compared with those of pure polybisphenol-A-carbonate (PC), (PMMA-G-PC) and (PCPH). In the present work, a non-destructive and non-contact analytical method, namely the photoacoustic technique, is successfully implemented for optical and thermal characterization of selected polymeric materials. The indigenous PA spectrometer used in the present study consists of a 300-W xenon arc lamp, a lock-in amplifier, a chopper, a (1/8)-m monochromator controlled by computer and a home-made PA cell. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  2. Moessbauer spectroscopic studies of alkylammonium iron(III) complexes

    International Nuclear Information System (INIS)

    Katada, M.; Kozawa, S.; Nakajima, Y.

    2006-01-01

    Alkylammonium iron(III) complexes, [(n-C n H 2n+1 )mNH 4-m ] 3 [Fe(CN) 6 ] were prepared and studied by Moessbauer spectroscopy, XRD, and DSC. In the complexes with m=2, the temperature dependences of the area intensity of Moessbauer are correlated to the motion of alkyl chains. The temperature dependence of the complex with n=4 was linear and smaller than that of other complexes. Especially in the complex with n=6, the deviation from the linear was the largest in the complexes observed. This result is attributed to the structural difference of the complex. The complexes with n≥8 consist of two-dimensional layer structure. The temperature dependence of the area intensity was similar to each other. This means that the motion of alkyl chain in these complexes are almost the same. The values of quadrupole splitting for the complexes were larger those that of the complexes (m=1). This indicates that the form of [Fe(CN) 6 ] 3- ion is affected by the differences of the number of alkyl groups. (author)

  3. Spectroscopic studies on the antioxidant activity of ellagic acid

    Science.gov (United States)

    Kilic, Ismail; Yeşiloğlu, Yeşim; Bayrak, Yüksel

    2014-09-01

    Ellagic acid (EA, C14H6O8) is a natural dietary polyphenol whose benefits in a variety of diseases shown in epidemiological and experimental studies involve anti-inflammation, anti-proliferation, anti-angiogenesis, anticarcinogenesis and anti-oxidation properties. In vitro radical scavenging and antioxidant capacity of EA were clarified using different analytical methodologies such as total antioxidant activity determination by ferric thiocyanate, hydrogen peroxide scavenging, 1,1-diphenyl-2-picryl-hydrazyl free radical (DPPH) scavenging, 2,2‧-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) radical scavenging activity and superoxide anion radical scavenging, ferrous ions (Fe2+) chelating activity and ferric ions (Fe3+) reducing ability. EA inhibited 71.2% lipid peroxidation of a linoleic acid emulsion at 45 μg/mL concentration. On the other hand, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), α-tocopherol and ascorbic acid displayed 69.8%, 66.8%, 64.5% and 59.7% inhibition on the peroxidation of linoleic acid emulsion at the same concentration, respectively. In addition, EA had an effective DPPH• scavenging, ABTSrad + scavenging, superoxide anion radical scavenging, hydrogen peroxide scavenging, ferric ions (Fe3+) reducing power and ferrous ions (Fe2+) chelating activities. Also, those various antioxidant activities were compared to BHA, BHT, α-tocopherol and ascorbic acid as references antioxidant compounds. These results suggested that EA can be used in the pharmacological, food industry and medicine because of these properties.

  4. A theoretical and spectroscopic study of conformational structures of piroxicam

    Science.gov (United States)

    Souza, Kely Ferreira de; Martins, José A.; Pessine, Francisco B. T.; Custodio, Rogério

    2010-02-01

    Piroxicam (PRX) has been widely studied in an attempt to elucidate the causes and mechanisms of its side effects, mainly the photo-toxicity. In this paper fluorescence spectra in non-protic solvents and different polarities were carried out along with theoretical calculations. Preliminary potential surfaces of the keto and enol forms were obtained at AM1 level of theory providing the most stable conformers, which had their structure re-optimized through the B3LYP/CEP-31G(d,p) method. From the optimized structures, the electronic spectra were calculated using the TD-DFT method in vacuum and including the solvent effect through the PCM method and a single water molecule near PRX. A new potential surface was constructed to the enol tautomer at DFT level and the most stable conformers were submitted to the QST2 calculations. The experimental data showed that in apolar media, the solution fluorescence is raised. Based on conformational analysis for the two tautomers, keto and enol, the results indicated that the PRX-enol is the main tautomer related to the drug fluorescence, which is reinforced by the spectra results, as well as the interconvertion barrier obtained from the QST2 calculations. The results suggest that the PRX one of the enol conformers presents great possibility of involvement in the photo-toxicity mechanisms.

  5. Borax methylene blue: a spectroscopic and staining study.

    Science.gov (United States)

    Donaldson, P T; Russo, A; Reynolds, C; Lillie, R D

    1978-07-01

    Borax methylene blue is quite stable at room temperatures of 22-25 C. At 30 C polychroming is slow; during 50 days in a water bath at this temperature the absorption peak moves from 665 to 656 nm. At 35 C, the absorption peak reaches 660 nm in 7 days, 654 nm in 14. At 60 C polychroming is rapid, the absorption peak reaching 640-620 nm in 3 days. When the pH of the borax methylene blue solutions, normally about 9.0, is adjusted to pH 6.5, the absorption peak remains at 665 nm even when incubated at 60 C for extended periods. When used as a blood stain 0.4 ml borax methylene blue (1% methylene blue in 1% borax), 4 ml acetone, 2 ml borax-acid phosphate buffer to bring the solution to pH 6.5, and distilled water to make 40 ml, with 0.2 ml 1% eosin added just before using, an excellent Nocht-Giemsa type stain is achieved after 30 minutes staining. The material plasmodia P. falciparum, P. vivax, and P. berghei stain moderate blue with dark red chromatin and green to black pigment granules. The study confirms Malachowski's 1891 results and explains Gautier's 1896-98 failure to duplicate it.

  6. HPLC assisted Raman spectroscopic studies on bladder cancer

    Science.gov (United States)

    Zha, W. L.; Cheng, Y.; Yu, W.; Zhang, X. B.; Shen, A. G.; Hu, J. M.

    2015-04-01

    We applied confocal Raman spectroscopy to investigate 12 normal bladder tissues and 30 tumor tissues, and then depicted the spectral differences between the normal and the tumor tissues and the potential canceration mechanism with the aid of the high-performance liquid chromatographic (HPLC) technique. Normal tissues were demonstrated to contain higher tryptophan, cholesterol and lipid content, while bladder tumor tissues were rich in nucleic acids, collagen and carotenoids. In particular, β-carotene, one of the major types of carotenoids, was found through HPLC analysis of the extract of bladder tissues. The statistical software SPSS was applied to classify the spectra of the two types of tissues according to their differences. The sensitivity and specificity of 96.7 and 66.7% were obtained, respectively. In addition, different layers of the bladder wall including mucosa (lumps), muscle and adipose bladder tissue were analyzed by Raman mapping technique in response to previous Raman studies of bladder tissues. All of these will play an important role as a directive tool for the future diagnosis of bladder cancer in vivo.

  7. Moessbauer spectroscopic study on inorganic compounds. Pt. 2

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, Masashi; Kitazawa, Takafumi; Nanba, Hiroshi; Yoshinaga, Tomohiro; Nakajima, Norio; Sumisawa, Yasuhiro; Takeda, Masuo [Toho Univ., Funabashi, Chiba (Japan). Faculty of Science; Sawahata, Hiroyuki; Ito, Yasuo

    1998-01-01

    {sup 166}Er and {sup 127}I Moessbauer spectra were observed. {sup 166}Er Moessbauer spectrum of Er metal and 9 compounds were measured by {sup 166}Ho/Y{sub 0.6}Ho{sub 0.4}H{sub 2} source at 12K and the parameters such as e{sup 2}qQ(mm s{sup -1}), Heff(T) and {tau}(ns) were determined. The relaxation time of ErCl{sub 3}{center_dot}6H{sub 2}O was 0.7ns, long, but that of ErCl{sub 3} was 10 ps, short time. {sup 127}I Moessbauer spectrum of PhI(O{sub 2}CR){sub 2} (R=CH{sub 3}, CHF{sub 2}, CH{sub 2}Cl, CHCl{sub 2}, CCl{sub 3}, CH{sub 2}Br, CHBr{sub 2} and CBr{sub 3}) were observed and compared with that of R`{sub 3}Sb(O{sub 2}CR){sub 2} was similar to that of PhI(O{sub 2}CR){sub 2}. The correlation coefficient between e{sup 2}qQ({sup 127}I) and Mulliken population of carboxylic hydrogen atom of R{sub 2}CO{sub 2}H was -0.87. The relation between the hypervalent bond of O-I-O and that of O-Sb-0 was shown by the equation: e{sup 2}qQ({sup 121}Sb)/mm s{sup -1} = -47.2 + 1.32 e{sup 2}qQ({sup 127}I)/mm s{sup -1}. Hypervalent iodine complex such as (PhI(py){sub 2}){sup 2+} salt and E-Sb-I (E=O, I, N and C) were studied, too. (S.Y.)

  8. Synchronous fluorescence spectroscopic study of solvatochromic curcumin dye

    Science.gov (United States)

    Patra, Digambara; Barakat, Christelle

    2011-09-01

    Curcumin, the main yellow bioactive component of turmeric, has recently acquired attention by chemists due its wide range of potential biological applications as an antioxidant, an anti-inflammatory, and an anti-carcinogenic agent. This molecule fluoresces weakly and poorly soluble in water. In this detailed study of curcumin in thirteen different solvents, both the absorption and fluorescence spectra of curcumin was found to be broad, however, a narrower and simple synchronous fluorescence spectrum of curcumin was obtained at Δ λ = 10-20 nm. Lippert-Mataga plot of curcumin in different solvents illustrated two sets of linearity which is consistent with the plot of Stokes' shift vs. the ET30. When Stokes's shift in wavenumber scale was replaced by synchronous fluorescence maximum in nanometer scale, the solvent polarity dependency measured by λSFSmax vs. Lippert-Mataga plot or ET30 values offered similar trends as measured via Stokes' shift for protic and aprotic solvents for curcumin. Better linear correlation of λSFSmax vs. π* scale of solvent polarity was found compared to λabsmax or λemmax or Stokes' shift measurements. In Stokes' shift measurement both absorption/excitation as well as emission (fluorescence) spectra are required to compute the Stokes' shift in wavenumber scale, but measurement could be done in a very fast and simple way by taking a single scan of SFS avoiding calculation and obtain information about polarity of the solvent. Curcumin decay properties in all the solvents could be fitted well to a double-exponential decay function.

  9. Spectroscopic studies of molybdenum complexes as models for nitrogenase

    International Nuclear Information System (INIS)

    Walker, T.P.

    1981-05-01

    Because biological nitrogen fixation requires Mo, there is an interest in inorganic Mo complexes which mimic the reactions of nitrogen-fixing enzymes. Two such complexes are the dimer Mo 2 O 4 (cysteine) 2 2- and trans-Mo(N 2 ) 2 (dppe) 2 (dppe = 1,2-bis(diphenylphosphino)ethane). The H 1 and C 13 NMR of solutions of Mo 2 O 4 (cys) 2 2- are described. It is shown that in aqueous solution the cysteine ligands assume at least three distinct configurations. A step-wise dissociation of the cysteine ligand is proposed to explain the data. The Extended X-ray Absorption Fine Structure (EXAFS) of trans-Mo(N 2 ) 2 (dppe) 2 is described and compared to the EXAFS of MoH 4 (dppe) 2 . The spectra are fitted to amplitude and phase parameters developed at Bell Laboratories. On the basis of this analysis, one can determine (1) that the dinitrogen complex contains nitrogen and the hydride complex does not and (2) the correct Mo-N distance. This is significant because the Mo inn both complexes is coordinated by four P atoms which dominate the EXAFS. A similar sort of interference is present in nitrogenase due to S coordination of the Mo in the enzyme. This model experiment indicates that, given adequate signal to noise ratios, the presence or absence of dinitrogen coordination to Mo in the enzyme may be determined by EXAFS using existing data analysis techniques. A new reaction between Mo 2 O 4 (cys) 2 2- and acetylene is described to the extent it is presently understood. A strong EPR signal is observed, suggesting the production of stable Mo(V) monomers. EXAFS studies support this suggestion. The Mo K-edge is described. The edge data suggests Mo(VI) is also produced in the reaction. Ultraviolet spectra suggest that cysteine is released in the course of the reaction

  10. 2-Ethynylpyridine dimers: IR spectroscopic and computational study

    Science.gov (United States)

    Bakarić, Danijela; Spanget-Larsen, Jens

    2018-04-01

    2-ethynylpyridine (2-EP) presents a multifunctional system capable of participation in hydrogen-bonded complexes utilizing hydrogen bond donating (tbnd Csbnd H, Aryl-H) and hydrogen bond accepting functions (N-atom, Ctbnd C and pyridine π-systems). In this work, IR spectroscopy and theoretical calculations are used to study possible 2-EP dimer structures as well as their distribution in an inert solvent such as tetrachloroethene. Experimentally, the tbnd Csbnd H stretching vibration of the 2-EP monomer absorbs close to 3300 cm-1, whereas a broad band with maximum around 3215 cm-1 emerges as the concentration rises, indicating the formation of hydrogen-bonded complexes involving the tbnd Csbnd H moiety. The Ctbnd C stretching vibration of monomer 2-EP close to 2120 cm-1 is, using derivative spectroscopy, resolved from the signals of the dimer complexes with maximum around 2112 cm-1. Quantum chemical calculations using the B3LYP + D3 model with counterpoise correction predict that the two most stable dimers are of the π-stacked variety, closely followed by dimers with intermolecular tbnd Csbnd H⋯N hydrogen bonding; the predicted red shifts of the tbnd Csbnd H stretching wavenumbers due to hydrogen bonding are in the range 54-120 cm-1. No species with obvious hydrogen bonding involving the Ctbnd C or pyridine π-systems as acceptors are predicted. Dimerization constant at 25 °C is estimated to be K2 = 0.13 ± 0.01 mol-1 dm3.

  11. Spectroscopic study of synthetic hydrothermal Fe3+-bearing beryl

    Science.gov (United States)

    Taran, Michail N.; Dyar, M. Darby; Khomenko, Vladimir M.

    2018-05-01

    A synthetic hydrothermal beryl Fe-4-51, investigated previously by Taran and Rossman (Am Miner 86:973-980, 2001), was additionally studied by microprobe, Mössbauer, optical absorption, Raman and IR spectroscopy. For comparison, polarized spectra of natural blue aquamarine and Cr3+, Fe3+-bearing alexandrite, both from Brazil, are also presented. Fe-4-51 is a nearly pure Fe3+-bearing beryl, with a homogeneous composition as shown by electron microprobe. Averaging over 22 points gives a formula of Be3.07(Al1.94,{Fe}_{{{0.07}}}^{{{3}+}})Σ=2.01Si5.95O18, with Fe3+ replacing Al3+ in the octahedral site of the structure. The Mössbauer spectrum is dominated by a broad disordered pattern with beryl-suitable parameters; for Fe2+, IS = 1.21 mm/s, QS = 2.71 mm/s, area ≈ 5% and for Fe3+, IS = 0.34 mm/s, QS = 0.71 mm/s, and area ≈ 67%—are distinguished overlying a broad disordered continuum. The optical absorption spectrum is typical of octahedral Fe3+. From it, the crystal field strength Dq is derived as 1520 cm-1 and the values of Racah parameters of interelectronic repulsion B and C are found to be 665 and 3415 cm-1, respectively. This rather low B value, compared with that of a free Fe3+ ion, 814 cm-1, suggests a comparatively high degree of covalency in the octahedral Fe3+-O bond. Infrared spectra show the presence of channel H2O of both I and II structural type in comparable quantities, about 0.5 and 1 mass%, respectively. Raman data show the expected five bands in the energy range from 300 to 1200 cm-1.

  12. [Spectroscopic studies on the interaction of nicotine and BSA].

    Science.gov (United States)

    Chen, Yun; Kong, Xiang-rong; Shen, Xinag-can; Liang, Hong

    2005-10-01

    The interaction of nicotine and bovine serum albumin(BSA) was investigated by fluorescence spectra and UV-vis spectra. The fluorescence spectrum showed that BSA fluorescence quench regularly with the addition of nicotine.The fluorescence quenching mechanisms were also studied in pH 5.0, pH 7.4 and pH 11.0 by Stern-Volmer equation, indicating dynamic quenching(pH 5.0) and static quenching(pH 7.4 and pH 11.0) respectively. Association constants (k) of nicotine and BSA at pH 7.4 and pH 11.0 at the temperatures of 20 and 37 degrees C were given by the Lineweaver-Buck equation, which are: k(20 degrees C) = 140.15 L x mol(-1) and k(37 degrees C) = 131.83 mol x L(-1) (pH 7.4), and k(20 degrees C) = 141.76 mol x L(-1), k(37 degrees C) = 27.79 mol x L(-1) (pH 11.0), suggesting that the association constant is effected by the temperature much more remarkably at pH 7.4 than that at pH 11.0 because of the different states of nicotine at different pHs. The UV-Vis spectra exhibit that the absorbance of BSA(210 nm) shifts to red and decreases gradually with the addition of nicotine, reflecting the transition of secondary structure of BSA, namely, the helix of BSA becomes looser. The UV-Vis second derivative spectra and synchronous spectra (delta wavelength = wavelength(em) - wavelength(ex) = 15 nm and delta wavelength = wavelength(em) - wavelength(ex) = 60 nm) imply the change of the microcircumstance of aromatic amino residues of BSA(Trp, Tyr and Phe) from hydrophobicity to hydrophilicity at high concentration of nicotine.

  13. Raman spectroscopic studies on exfoliated cells of oral and cervix

    Science.gov (United States)

    Hole, Arti; Sahu, Aditi; Shaikh, Rubina; Tyagi, Gunjan; Murali Krishna, C.

    2018-01-01

    Visual inspection followed by biopsy is the standard procedure for cancer diagnosis. Due to invasive nature of the current diagnostic methods, patients are often non-compliant. Hence, it is necessary to explore less invasive and rapid methods for early detection. Exfoliative cytology is a simple, rapid, and less invasive technique. It is thus well accepted by patients and is suitable for routine applications in population screening programs. Raman spectroscopy (RS) has been increasingly explored for disease diagnosis in the recent past. In vivo RS has previously shown promise in management of both oral and cervix cancers. In vivo applications require on-site instrumentation and stringent experimental conditions. Hence, RS of less invasive samples like exfoliated cells has been explored, as this facilitates collection at multiple screening centers followed by analysis at a centralized facility. In the present study, efficacy of Raman spectroscopy in classification of 15 normal and 29 abnormal oral exfoliated cells specimens and 28 normal and 38 abnormal cervix specimens were explored. Spectra were acquired by Raman microprobe (HE 785, Horiba-Jobin-Yvon, France) from several areas to span the pellet. Spectral acquisition parameters were: microscopic objective: 40X, power: 40 mW, acquisition time: 15 s and average: 3. PCA and PC-LDA of pre-processed spectra was carried out on a 4-model system of normal and tumor of both cervix and oral specimens. Leave-one-out-cross-validation findings indicate 73 % correct classification. Findings suggest RS of exfoliated cells may serve as a patient-friendly, non-invasive, rapid and objective method for management of cervix and oral cancers.

  14. Theoretical and spectroscopic studies of a tricyclic antidepressant, imipramine hydrochloride

    Science.gov (United States)

    Sagdinc, S. G.; Azkeskin, Caner; Eşme, A.

    2018-06-01

    Imipramine hydrochloride ([H-IMI]Cl), C19H24N2.HCl, is the prototypic tricyclic antidepressant (TCA) inhibitor of norepinephrine and serotonin neuronal reuptake. The molecular structure, molecular electrostatic potential (MEP), natural bond orbital (NBO) analysis, linear and non-linear optical (NLO) properties of [H-IMI]Cl have been investigated using the density functional theory (DFT) calculations with the B3LYP level at the 6‒311++G(d,p) basis set. The UV-Vis spectra for [H-IMI]Cl were experimentally studied in water and methanol. TD‒DFT calculations in water and methanol were employed to investigate the absorption wavelengths (λ), excitation energies (E), and oscillator strengths (f) for the UV-Vis analysis and the major contributions to the electronic transitions. From NBO analysis, the orbitals with the stabilization energy E(2) of 192.15 kcal/mol are π*(C5sbnd C18) as donor NBO and π*(C19sbnd C20) as acceptor NBO. The FT‒IR (4000‒400 cm-1) and FT‒Raman (3500-50 cm-1) spectra have been measured and analyzed. The assignment of bands observed vibrational spectra have been made by comparison of its calculated theoretical vibrational frequencies obtained using the DFT/B3LYP/6‒311++G(d,p) method. The detailed vibrational assignments were performed with the DFT calculation, and the potential energy distribution (PED) of [H-IMI]Cl was obtained by the Vibrational Energy Distribution Analysis 4 (VEDA4) program. The scaled frequencies resulted in good agreement with the observed spectral patterns.

  15. Synthesis, structural, spectroscopic and biological studies of Schiff base complexes

    Science.gov (United States)

    Diab, M. A.; El-Sonbati, A. Z.; Shoair, A. F.; Eldesoky, A. M.; El-Far, N. M.

    2017-08-01

    Schiff base ligand 4-((pyridin-2- yl)methyleneamino)-1,2-dihydro-2,3-dimethyl-1-phenylpyrazol-5-one (PDMP) and its complexes were prepared and characterized on the basis of elemental analysis, IR, mass spectra and thermogravimetric analysis. All results confirm that the complexes have 1:1 (M: PMDP) stoichiometric formula [M(PMDP)Cl2H2O ] (M = Cu(II), Co(II), Ni(II) and Mn(II)), [Cd(PMDP)Cl2] and the ligand behaves as a bi/tridentate forming five-membered chelating ring towards the metal ions, bonding through azomethine nitrogen/exocyclic carbonyl oxygen, azomethine pyridine nitrogen and exocyclic carbonyl oxygen. The shift in the band positions of the groups involved in coordination has been utilized to estimate the metal-nitrogen and/or oxygen bond lengths. The complexes of Co(II), Ni(II) and Cu(II) are paramagnetic and the magnetic as well as spectral data suggest octahedral geometry, whereas the Cd(II) complex is tetrahedral. The XRD studies show that both the ligand and its metal complexes (1 and 3) show polycrystalline with crystal structure. Molecular docking was used to predict the binding between PMDP ligand and the receptors. The corrosion inhibition of mild steel in 2 M HCl solution by PDMP was explored utilizing potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and (EFM) electrochemical frequency modulation method. Potentiodynamic polarization demonstrated that PDMP compound is mixed-type inhibitor. EIS spectra exhibit one capacitive loop and confirm the protective ability. The percentage of inhibition efficiency was found to increase with increasing the inhibitor concentration.

  16. A Moessbauer spectroscopic study of stannosilicate and ferrisilicate glasses

    International Nuclear Information System (INIS)

    Appleyard, P.G.

    2000-02-01

    Silicate glasses of variable composition, containing tin and iron have been studied using Moessbauer spectroscopy. The glass samples consisted of 3 basic groups; binary stannosilicate glasses, ternary stannosilicate glasses and ternary ferrisilicate glasses. The binary stannosilicate glasses were a simple x SnO + (1-x) SiO 2 composition, with x ranging from 16.5% to 67.7% mole. The ternary stannosilicate glasses followed a nominal compositional range of 0.5 SiO 2 + (0.5-x) SnO + x RO, where RO is modifier oxide. Several series of ternary stannosilicates were manufactured, with each series containing a different modifier type. The modifiers chosen were; group I metal oxides of Li, Na, K and Rb, group II metal oxides of Mg, Ca and Sr and group III metal oxide of Al. Two series of ternary ferrisilicate glasses were manufactured following nominal compositional ranges of (0.7-x) SiO 2 + x Fe 2 O 3 + 0.3 Na 2 O and 0.7 SiO 2 + xFe 2 O 3 + (0.3-x) Na 2 O. In the majority of the stannosilicate glasses, the Sn was shown to exist primarily in the Sn(II) valence state. The Moessbauer centre shift and quadrupole splitting of the Sn(II) were shown to possess a dependence on sample concentration, this being weak in the binary glasses, but large and distinct in the ternary glasses. The isomer shift and quadrupole splitting slowly decreased with increasing modifier concentration in the ternary glasses. The rate of this decrease was proportional to the Z/radius of the modifier ion. Variable temperature experiments on a large selection of the glasses revealed that the Sn(II) isomer shift and quadrupole splitting possessed positive and negative dependencies on temperature respectively. The increase in isomer shift is consistent with the effects of thermal expansion and an increase in pressure at the Sn site. The decrease in quadrupole splitting is also consistent with thermal expansion of the Sn-O bonds. The temperature dependence of the isomer shift was incorporated into the

  17. Homolytic iodination and nitration of some benzene derivatives in the gas phase

    International Nuclear Information System (INIS)

    Vonk, W.F.M.

    1980-01-01

    Two gas phase reactions, involving the iodination and nitration of benzene derivatives, are described. The experimental techniques of the apparatus and the methods used are outlined. The kinetic H/D isotope effect in the gas phase nitration of benzene with NO 2 is determined. (C.F.)

  18. Spectroscopic studies of copper doped alkaline earth lead zinc phosphate glasses

    Energy Technology Data Exchange (ETDEWEB)

    Sastry, S. Sreehari, E-mail: sreeharisastry@yahoo.com [Department of Physics, Acharya Nagarjuna University, Nagarjunanagar 522510 (India); Rao, B. Rupa Venkateswara [Department of Physics, Acharya Nagarjuna University, Nagarjunanagar 522510 (India); Department of Physics, V.R. Siddhartha Engineering College, Vijayawada 52007 (India)

    2014-02-01

    In this paper spectroscopic investigation of Cu{sup 2+} doped alkaline earth lead zinc phosphate glasses was done through the spectroscopic techniques like X-ray diffraction, Ultra Violet (UV) absorption Spectroscopy, Electron Paramagnetic Resonance (EPR – X band), Fourier Transform Infra Red (FTIR) and Raman Spectroscopy. Alkaline earth lead zinc phosphate glasses containing 0.1% copper oxide (CuO) were prepared by the melt quenching technique. Spectroscopic studies indicated that there is a greater possibility for the copper ions to exist in Cu{sup 2+} state in these glasses. The optical absorption spectra indicated that the absorption peak of Cu{sup 2+} is a function of composition. The maxima absorption peak was reported at 862 nm for strontium lead zinc phosphate glass. Bonding parameters were calculated for the optical and EPR data. All these spectral results indicated clearly that there are certain structural changes in the present glass system with different alkaline earth contents. The IR and Raman spectra noticed the breaking of the P–O–P bonds and creating more number of new P–O–Cu bonds.

  19. Spectroscopic studies of copper doped alkaline earth lead zinc phosphate glasses

    International Nuclear Information System (INIS)

    Sastry, S. Sreehari; Rao, B. Rupa Venkateswara

    2014-01-01

    In this paper spectroscopic investigation of Cu 2+ doped alkaline earth lead zinc phosphate glasses was done through the spectroscopic techniques like X-ray diffraction, Ultra Violet (UV) absorption Spectroscopy, Electron Paramagnetic Resonance (EPR – X band), Fourier Transform Infra Red (FTIR) and Raman Spectroscopy. Alkaline earth lead zinc phosphate glasses containing 0.1% copper oxide (CuO) were prepared by the melt quenching technique. Spectroscopic studies indicated that there is a greater possibility for the copper ions to exist in Cu 2+ state in these glasses. The optical absorption spectra indicated that the absorption peak of Cu 2+ is a function of composition. The maxima absorption peak was reported at 862 nm for strontium lead zinc phosphate glass. Bonding parameters were calculated for the optical and EPR data. All these spectral results indicated clearly that there are certain structural changes in the present glass system with different alkaline earth contents. The IR and Raman spectra noticed the breaking of the P–O–P bonds and creating more number of new P–O–Cu bonds

  20. Comparisons between a gas-phase model of silane chemical vapor deposition and laser-diagnostic measurements

    International Nuclear Information System (INIS)

    Breiland, W.G.; Coltrin, M.E.; Ho, P.

    1986-01-01

    Theoretical modeling and experimental measurements have been used to study gas-phase chemistry in the chemical vapor deposition (CVD) of silicon from silane. Pulsed laser Raman spectroscopy was used to obtain temperature profiles and to obtain absolute density profiles of silane during deposition at atmospheric and 6-Torr total pressures for temperatures ranging from 500 to 800 0 C. Laser-excited fluorescence was used to obtain relative density profiles of Si 2 during deposition at 740 0 C in helium with 0-12 Torr added hydrogen. These measurements are compared to predictions from the theoretical model of Coltrin, Kee, and Miller. The predictions agree qualitatively with experiment. These studies indicate that fluid mechanics and gas-phase chemical kinetics are important considerations in understanding the chemical vapor deposition process

  1. Protonated Nitrous Oxide, NNOH(+): Fundamental Vibrational Frequencies and Spectroscopic Constants from Quartic Force Fields

    Science.gov (United States)

    Huang, Xinchuan; Fortenberry, Ryan C.; Lee, Timothy J.

    2013-01-01

    The interstellar presence of protonated nitrous oxide has been suspected for some time. Using established high-accuracy quantum chemical techniques, spectroscopic constants and fundamental vibrational frequencies are provided for the lower energy O-protonated isomer of this cation and its deuterated isotopologue. The vibrationally-averaged B0 and C0 rotational constants are within 6 MHz of their experimental values and the D(subJ) quartic distortion constants agree with experiment to within 3%. The known gas phase O-H stretch of NNOH(+) is 3330.91 cm(exp-1), and the vibrational configuration interaction computed result is 3330.9 cm(exp-1). Other spectroscopic constants are also provided, as are the rest of the fundamental vibrational frequencies for NNOH(+) and its deuterated isotopologue. This high-accuracy data should serve to better inform future observational or experimental studies of the rovibrational bands of protonated nitrous oxide in the ISM and the laboratory.

  2. Identification of Guest-Host Inclusion Complexes in the Gas Phase by Electrospray Ionization-Mass Spectrometry

    Science.gov (United States)

    Mendes, De´bora C.; Ramamurthy, Vaidhyanathan; Da Silva, Jose´ P.

    2015-01-01

    In this laboratory experiment, students follow a step-by-step procedure to prepare and study guest-host complexes in the gas phase using electrospray ionization-mass spectrometry (ESI-MS). Model systems are the complexes of hosts cucurbit[7]uril (CB7) and cucurbit[8]uril (CB8) with the guest 4-styrylpyridine (SP). Aqueous solutions of CB7 or CB8…

  3. The properties of gas-phase multiply charged ions

    International Nuclear Information System (INIS)

    Newson, K.A.

    1999-01-01

    This thesis presents the results of a series of experiments investigating the reactivity of gas-phase molecular dications with various neutral collision partners, at collision energies between 3 and 13 eV in the laboratory frame, using a crossed-beam apparatus. The experiment involves the measurement of product ion intensities, which are determined by means of time-of-flight mass spectrometry. The experimental apparatus and methodology, together with the areas of theory important to ion chemistry, are described in the thesis. The product ions of greatest interest are those ions formed by bond-forming (chemical) reactivity. The relative intensities of such product ions, and those ions formed as a result of electron-transfer reactions, are, when recorded as a function of the collision energy, a powerful probe of the reaction mechanism. Additionally, where appropriate, the reactions are examined for isotope effects by using the isotopic analogue of the neutral collision partner. The results of the experiments indicate that no intermolecular isotope effects are present in the reactions of CF 2 2+ and CF 3 2+ with H 2 and D 2 neutral targets. In addition, the observed collision energy dependence is symptomatic of the absence of a barrier to reaction. These observations suggest that the reactions proceed via an impulsive direct reaction mechanism. Such a conclusion casts doubt on the applicability of the Landau-Zener model of H - /D - transfer reactivity. Other results presented in this thesis include the first reported observation of a bond-forming reaction between a molecular dication (CF2 2+ ) and a polyatomic neutral species (NH 3 ). Finally, the branching ratio of the products of bond-forming reactions between CF 2 2+ with HD indicates the operation of a strong intramolecular isotope effect, favouring the formation of the deuterated product. This observation points to a reaction mechanism in which the bond-formation is preceded by electron-transfer. (author)

  4. Dissociative attachment reactions of electrons with gas phase superacids

    International Nuclear Information System (INIS)

    Liu, X.

    1992-01-01

    Using the flowing afterglow Langmuir probe (FALP) technique, dissociative attachment coefficients β for reactions of electrons with gas phase superacids HCo(PF 3 ) 4 , HRh(PF 3 ) 4 and carbonyl hydride complexes HMn(CO) 5 , HRe(CO) 5 have been determined under thermal conditions over the approximate temperature range 300∼550 K. The superacids react relatively slowly ( max ) with free electrons in a thermal plasma, and the values of β obtained this far do not show a correlation between acidity and β. The pioneer researchers in this field had speculated that any superacid would be a rapid attacher of electrons; it was found that this speculation is not true in general. The product distribution of electron attachment reaction to HCo(PF 3 ) 4 was found to be independent of temperature even though the β[HCo(PF 3 ) 4 ] increases with temperature. This proposes that the electron attachment process occurs well before the excited complex dissociates. In addition, the activation energy of HCo(PF 3 ) 4 for electron attachment has been derived from the Arrhenius plots. The carbonyl hydride complexes, HMn(CO) 5 and HRe(CO) 5 , react relatively rapidly (>1/4 of β max ) with free electrons in thermal plasma. This indicates that these reactions cannot be significantly endothermic. Observation of rapid attachment for these non-superacids shows that the Mn-CO and Re-CO bonds are weaker than the Mn-H and Re-H bonds, respectively. Comparisons between the carbonyl and trifluorophosphine cases implies that fast electron capture is related more to the CO ligand than to the transition-metal species

  5. Gas-Phase Combustion Synthesis of Aluminum Nitride Powder

    Science.gov (United States)

    Axelbaum, R. L.; Lottes, C. R.; Huertas, J. I.; Rosen, L. J.

    1996-01-01

    Due to its combined properties of high electrical resistivity and high thermal conductivity aluminum nitride (AlN) is a highly desirable material for electronics applications. Methods are being sought for synthesis of unagglomerated, nanometer-sized powders of this material, prepared in such a way that they can be consolidated into solid compacts having minimal oxygen content. A procedure for synthesizing these powders through gas-phase combustion is described. This novel approach involves reacting AlCl3, NH3, and Na vapors. Equilibrium thermodynamic calculations show that 100% yields can be obtained for these reactants with the products being AlN, NaCl, and H2. The NaCl by-product is used to coat the AlN particles in situ. The coating allows for control of AlN agglomeration and protects the powders from hydrolysis during post-flame handling. On the basis of thermodynamic and kinetic considerations, two different approaches were employed to produce the powder, in co-flow diffusion flame configurations. In the first approach, the three reactants were supplied in separate streams. In the second, the AlCl3 and NH3 were premixed with HCl and then reacted with Na vapor. X-ray diffraction (XRD) spectra of as-produced powders show only NaCl for the first case and NaCl and AlN for the second. After annealing at 775 C tinder dynamic vacuum, the salt was removed and XRD spectra of powders from both approaches show only AlN. Aluminum metal was also produced in the co-flow flame by reacting AlCl3 with Na. XRD spectra of as-produced powders show the products to be only NaCl and elemental aluminum.

  6. Binding Studies of Andrographolide with Human serum albumin: Molecular Docking, Chromatographic and Spectroscopic studies.

    Science.gov (United States)

    Godugu, Deepika; Rupula, Karuna; Beedu, Sashidhar Rao

    2018-02-11

    Andrographolide, sourced from Andrographis paniculata, is an established therapeutic agent with variety of pharmacological properties in treatment of various diseases. The present study is designed to evaluate the interaction and binding affinity of andrographolide with HSA by docking and spectral studies. The docking study for screening the interaction of andrographolide with HSA protein was carried out using Auto Dock Vina software and the binding score of andrographolide was -8.7 kcal mol-1 and formed one hydrogen bond with Arg 218 residue of HSA in sub-domains IIA region. The formation of HSA-andrographolide complex was characterized by spectroscopic methods - UV absorption, HPLC, CD and FTIR analysis. The UV spectral analysis revealed a decrease in the absorption peak of HSA due to its interaction with andrographolide. A new peak was observed at retention time 7.45 min by HPLC analysis and the Bmax was found to be 7.5 ± 0.4 mg protein with a Kd value of 1.89 mM, indicating interaction of andrographolide with HSA. The CD spectra results suggested, a marginal decrease in the negative ellipticity without any significant shift in peak, indicating the stabilization of the HSA-andrographolide complex. The FTIR analysis further confirmed, a shift of amide I groups from 1646 to 1637 cm-1 and a peak at 1016 cm-1 in andrographolide, was observed in the complex, indicating the interaction. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  7. Studies on the binding behavior of prodigiosin with bovine hemoglobin by multi-spectroscopic techniques

    Science.gov (United States)

    Tang, Jing; Yang, Chao; Zhou, Lin; Ma, Fei; Liu, Shuchao; Wei, Shaohua; Zhou, Jiahong; Zhou, Yanhuai

    2012-10-01

    In this article, the interaction mechanism of prodigiosin (PG) with bovine hemoglobin (BHb) is studied in detail using various spectroscopic technologies. UV-vis absorption and fluorescence spectra demonstrate the interaction process. The Stern-Volmer plot and the time-resolved fluorescence study suggest the quenching mechanism of fluorescence of BHb by PG is a static quenching procedure, and the hydrophobic interactions play a major role in binding of PG to BHb. Furthermore, synchronous fluorescence studies, Fourier transform infrared (FTIR) and circular dichroism (CD) spectra reveal that the conformation of BHb is changed after conjugation with PG.

  8. Spectroscopic Study of L Hypernuclei with Electron Beams at Jefferson Lab

    Energy Technology Data Exchange (ETDEWEB)

    Nakamura, Satoshi [Tohoku Univ., Sendai (Japan); Gogami, Toshiyuki [Tohoku Univ., Sendai (Japan); Tang, Liguang [Hampton Univ., Hampton, VA (United States); Thomas Jefferson National Accelerator Facility (TJNAF), Newport News, VA (United States)

    2017-07-01

    The missing mass spectroscopy of L hypernuclei with the (e, e'K^+) reaction was started from 2000 at Jefferson Lab. In this fifteen years, various hypernuclei (A = 7 - 52) including hyperon (L, S^0) productions have been studied with newly developed experimental techniques. The (e, e'K^+) reaction spectroscopy of L hypernuclei features its capability of absolute missing mass calibration and production of new species of hypernuclei which are the isospin partners of well studied hypernuclei by (K^-, pi-) and (pi^+, K^+) reactions. In this paper, we will review how we established the (e, e'K^+) spectroscopic study of hypernuclei.

  9. Preparation of sulfur/multiple pore size porous carbon composite via gas-phase loading method for lithium-sulfur batteries

    International Nuclear Information System (INIS)

    Li, Long-Yan; Chen, Yan-Xiao; Guo, Xiao-Dong; Zhong, Ben-He; Zhong, Yan-Jun

    2014-01-01

    A porous carbon with multiple pore size distribution was synthesized, and regarded as a carrier to obtain the sulfur/carbon (S/C) composite via a gas-phase loading method. We proposed this novel gas-phase loading method by using a specially designed fluid-bed reactor to encapsulate and sequester gas-phase sulfur molecules into the porous carbon in current study. The nitrogen Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM) and X-ray powder diffraction (XRD) characterizations were investigated on both the porous carbon and the sulfur/carbon composite. The results show that the gas-phase loading method contributes to the combination of sulfur molecules and matrix porous carbon. Furthermore, the sulfur/multiple pore size distribution carbon composite based on the gas-phase loading method demonstrate an excellent electrochemical property. The initial specific discharge capacity is 795.0 mAh g −1 at 800 mA g −1 , with a capacity retention of 86.3% after 100 cycles

  10. High-Resolution Photoionization, Photoelectron and Photodissociation Studies. Determination of Accurate Energetic and Spectroscopic Database for Combustion Radicals and Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Ng, Cheuk-Yiu [Univ. of California, Davis, CA (United States)

    2016-04-25

    The main goal of this research program was to obtain accurate thermochemical and spectroscopic data, such as ionization energies (IEs), 0 K bond dissociation energies, 0 K heats of formation, and spectroscopic constants for radicals and molecules and their ions of relevance to combustion chemistry. Two unique, generally applicable vacuum ultraviolet (VUV) laser photoion-photoelectron apparatuses have been developed in our group, which have used for high-resolution photoionization, photoelectron, and photodissociation studies for many small molecules of combustion relevance.

  11. Some insights into formamide formation through gas-phase reactions in the interstellar medium

    International Nuclear Information System (INIS)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

    2014-01-01

    We study the viability of different gas-phase ion-molecule reactions that could produce precursors of formamide in the interstellar medium. We analyze different reactions between cations containing a nitrogen atom (NH 3 + , NH 4 + , NH 3 OH + , and NH 2 OH + ) and neutral molecules having one carbonyl group (H 2 CO and HCOOH). First, we report a theoretical estimation of the reaction enthalpies for the proposed processes. Second, for more favorable reactions, from a thermodynamic point of view, we perform a theoretical study of the potential energy surface. In particular, the more exothermic processes correspond to the reactions of ionized and protonated hydroxylamine with formaldehyde. In addition, a neutral-neutral reaction has also been considered. The analysis of the potential energy surfaces corresponding to these reactions shows that these processes present a net activation barrier and that they cannot be considered as a source of formamide in space.

  12. Some Insights into Formamide Formation through Gas-phase Reactions in the Interstellar Medium

    Science.gov (United States)

    Redondo, Pilar; Barrientos, Carmen; Largo, Antonio

    2014-01-01

    We study the viability of different gas-phase ion-molecule reactions that could produce precursors of formamide in the interstellar medium. We analyze different reactions between cations containing a nitrogen atom (NH_{3}^{+}, NH_{4}^{+}, NH3OH+, and NH2OH+) and neutral molecules having one carbonyl group (H2CO and HCOOH). First, we report a theoretical estimation of the reaction enthalpies for the proposed processes. Second, for more favorable reactions, from a thermodynamic point of view, we perform a theoretical study of the potential energy surface. In particular, the more exothermic processes correspond to the reactions of ionized and protonated hydroxylamine with formaldehyde. In addition, a neutral-neutral reaction has also been considered. The analysis of the potential energy surfaces corresponding to these reactions shows that these processes present a net activation barrier and that they cannot be considered as a source of formamide in space.

  13. An improved stochastic algorithm for temperature-dependent homogeneous gas phase reactions

    CERN Document Server

    Kraft, M

    2003-01-01

    We propose an improved stochastic algorithm for temperature-dependent homogeneous gas phase reactions. By combining forward and reverse reaction rates, a significant gain in computational efficiency is achieved. Two modifications of modelling the temperature dependence (with and without conservation of enthalpy) are introduced and studied quantitatively. The algorithm is tested for the combustion of n-heptane, which is a reference fuel component for internal combustion engines. The convergence of the algorithm is studied by a series of numerical experiments and the computational cost of the stochastic algorithm is compared with the DAE code DASSL. If less accuracy is needed the stochastic algorithm is faster on short simulation time intervals. The new stochastic algorithm is significantly faster than the original direct simulation algorithm in all cases considered.

  14. Spectroscopic studies of 2-thenoyltrifluoro acetonate of uranyl salts doped with europium

    International Nuclear Information System (INIS)

    Nakagawa, F.T.; Luiz, J.E.M. de Sa; Felinto, M.C.F.C.; Brito, H.F.; Teotonio, E.E.S.

    2006-01-01

    Uranyl compounds present a great potential as luminescence materials. Some examples of applications are: in laser technology, cathode ray tube, X-rays diagnostic. In this work it was studied the synthesis, characterization and spectroscopic properties study of uranyl 2-thenoyl trifluoroacetonate and uranyl 2- thenoyl trifluoroacetonate doped with europium. The compounds were synthesized and characterized by infrared absorption spectroscopy, thermal analysis, scanning electronic microscopy, and electronic spectroscopy of emission and excitation. The Eu 3+ ion acted as an effective luminescent probe, however the process of energy transfer from UO 2 2+ to Eu 3+ ion has not been efficient. (author)

  15. Mössbauer spectroscopic study of cobalt hexacyanoferrate nanoparticles: Effect of hydrogenation

    Science.gov (United States)

    Kumar, Asheesh; Kanagare, A. B.; Meena, Sher Singh; Banerjee, S.; Kumar, P.; Sudarsan, V.

    2018-04-01

    This paper reports Mössbauer study of cobalt hexacyanoferrate (CoHCF) before and after hydrogenation. The CoHCF was synthesised by chemical precipitation method. The sample was characterized by using various techniques (XRD, TG, EDX and FTIR). The CoHCF paricles show fcc structure. The hydrogen storage property was measured at different temperature. The COHCF shows maximum 0.93 wt% hydrogen storage capacity at 223K. 57Fe Mössbauer spectroscopic study shows the effect of hydrogenation on the electronic structure in terms of electronic charge distribution and volume expansion. Isomer shift and quadrupole splitting values were found to be increased after hydrogenation.

  16. Gas Phase Emission Ratios From In-Use Diesel and CNG Curbside Passenger Buses in New York City

    Science.gov (United States)

    Herndon, S. C.; Shorter, J.; Canagaratna, M.; Jayne, J.; Nelson, D. D.; Wormhoudt, J. C.; Williams, P.; Silva, P. J.; Shi, Q.; Ghertner, A.; Zahniser, M.; Worsnop, D.; Kolb, C.; Lanni, T.; Drewnick, F.; Demerjian, K. L.

    2002-12-01

    The Aerodyne Mobile Laboratory simultaneously measured gas phase and particulate emissions from in use vehicles during two campaigns in New York City. The campaigns took place during two weeks in October, 2000 and four weeks in July-August, 2001. Passenger curbside buses were the primary focus of the study, but school buses and several other heavy duty diesel vehicles were also characterized. This paper describes the methodologies used to measure individual in use vehicles and presents the results of the gas phase measurements. Emission ratios for NO, NO2, SO2, N2O, CO, CH4 and H2CO relative to CO2 have been determined across several classes of buses. The gas phase concentrations were measured each second, using Tunable Infrared Laser Direct Absorption Spectroscopy (TILDAS). Some of the categories of buses into which the data has been sorted are; diesel (both 6V92 and Series 50) with and without the Continuous Regenerative Technology (CRT) retrofit, compressed natural gas powered(CNG) and hybrid diesel-electric buses. The New York Metropolitan Transit Authority (MTA) cooperated with this work, providing details about each of their buses followed. In addition to MTA buses, other New York City passenger bus operators were also measured. In September 2000, MTA began to switch to 30 ppm sulfur diesel fuel while it is believed the non MTA operators did not. The measured emission ratios show that low sulfur fuel greatly reduces the amount of SO2 per CO2. Roughly one third of the MTA fleet of diesel buses have been equipped with the CRT retrofit. The gas phase results of interest in this category show increased direct emission of NO2 and companion work (also submitted to the 12th CRC) show the impact the CRT refit has on particulate emissions. CNG buses show increased H2CO and CH4 emission ratios relative to diesel powered motors.

  17. Gas phase chemistry and removal of CH3I during a severe accident

    International Nuclear Information System (INIS)

    Karhu, A.

    2001-01-01

    The purpose of this literature review was to gather valuable information on the behavior of methyl iodide on the gas phase during a severe accident. The potential of transition metals, especially silver and copper, to remove organic iodides from the gas streams was also studied. Transition metals are one of the most interesting groups in the context of iodine mitigation. For example silver is known to react intensively with iodine compounds. Silver is also relatively inert material and it is thermally stable. Copper is known to react with some radioiodine species. However, it is not reactive toward methyl iodide. In addition, it is oxidized to copper oxide under atmospheric conditions. This may limit the industrial use of copper.(au)

  18. Zpif's law in the liquid gas phase transition of nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Y.G. [China Center of Advanced Science and Technology (CCAST), Beijing, BJ (China). World Lab.; Shanghai Institute of Nuclear Research, Chinese Academy of Sciences, P.O. Box 800-204, Shanghai 201800 (China)

    1999-12-01

    Zpif's law in the field of linguistics is tested in the nuclear disassembly within the framework of isospin dependent lattice gas model. It is found that the average cluster charge (or mass) of rank n in the charge (or mass) list shows exactly inversely to its rank, i.e., there exists Zpif's law, at the phase transition temperature. This novel criterion shall be helpful to search the nuclear liquid gas phase transition experimentally and theoretically. In addition, the finite size scaling of the effective phase transition temperature at which the Zpif's law appears is studied for several systems with different mass and the critical exponents of {nu} and {beta} are tentatively extracted. (orig.)

  19. Atmospheric-pressure dielectric barrier discharge with capillary injection for gas-phase nanoparticle synthesis

    International Nuclear Information System (INIS)

    Ghosh, Souvik; Liu, Tianqi; Bilici, Mihai; Cole, Jonathan; Huang, I-Min; Sankaran, R Mohan; Staack, David; Mariotti, Davide

    2015-01-01

    We present an atmospheric-pressure dielectric barrier discharge (DBD) reactor for gas-phase nanoparticle synthesis. Nickel nanoparticles are synthesized by homogenous nucleation from nickelocene vapor and characterized online by aerosol mobility measurements. The effects of residence time and precursor concentration on particle growth are studied. We find that narrower distributions of smaller particles are produced by decreasing the precursor concentration, in agreement with vapor nucleation theory, but larger particles and aggregates form at higher gas flow rates where the mean residence time should be reduced, suggesting a cooling effect that leads to enhanced particle nucleation. In comparison, incorporating a capillary gas injector to alter the velocity profile is found to significantly reduce particle size and agglomeration. These results suggest that capillary gas injection is a better approach to decreasing the mean residence time and narrowing the residence time distribution for nanoparticle growth by producing a sharp and narrow velocity profile. (paper)

  20. UPS and DFT investigation of the electronic structure of gas-phase trimesic acid

    Energy Technology Data Exchange (ETDEWEB)

    Reisberg, L., E-mail: rebban@ut.ee [Institute of Physics, University of Tartu, W. Oswaldi 1, EE-50411 Tartu (Estonia); Pärna, R. [Institute of Physics, University of Tartu, W. Oswaldi 1, EE-50411 Tartu (Estonia); MAX IV Laboratory, Lund University, Fotongatan 2, 225 94 Lund (Sweden); Kikas, A.; Kuusik, I.; Kisand, V. [Institute of Physics, University of Tartu, W. Oswaldi 1, EE-50411 Tartu (Estonia); Hirsimäki, M.; Valden, M. [Surface Science Laboratory, Optoelectronics Research Centre, Tampere University of Technology, FIN-33101 Tampere (Finland); Nõmmiste, E. [Institute of Physics, University of Tartu, W. Oswaldi 1, EE-50411 Tartu (Estonia)

    2016-11-15

    Highlights: • In the current study outer valence band electronic structure of benzene-1,3,5-tricarboxylic acid was interpreted. • Experimental and calculated trimesic acid (TMA) spectrum were compared to ones of benzene and benzoic acid. • It is shown that similarities between MO energies and shapes for benzene and TMA exists. • Addition of carboxyl groups to the benzene ring clearly correlates with increasing binding energy of HOMO. - Abstract: Benzene-1,3,5-tricarboxylic acid (trimesic acid, TMA) molecules in gas-phase have been investigated by using valence band photoemission. The photoelectron spectrum in the binding energy region from 9 to 22 eV is interpreted by using density functional theory calculations. The electronic structure of TMA is compared with benzene and benzoic acid in order to demonstrate changes in molecular orbital energies induced by addition of carboxyl groups to benzene ring.

  1. Relaxation rates of low-field gas-phase ^129Xe storage cells

    Science.gov (United States)

    Limes, Mark; Saam, Brian

    2010-10-01

    A study of longitudinal nuclear relaxation rates T1 of ^129Xe and Xe-N2 mixtures in a magnetic field of 3.8 mT is presented. In this regime, intrinsic spin relaxation is dominated by the intramolecular spin-rotation interaction due to persistent xenon dimers, a mechanism that can be quelled by introducing large amounts of N2 into the storage cell. Extrinsic spin relaxation is dominated by the wall-relaxation rate, which is the primary quantity of interest for the various low-field storage cells and coatings that we have tested. Previous group work has shown that extremely long gas-phase relaxation times T1 can be obtained, but only at large magnetic fields and low xenon densities. The current work is motivated by the practical benefits of retaining hyperpolarized ^129Xe for extended periods of time in a small magnetic field.

  2. Gas phase chemistry and removal of CH{sub 3}I during a severe accident

    Energy Technology Data Exchange (ETDEWEB)

    Karhu, A. [VTT. Energy, Esbo (Finland)

    2001-01-01

    The purpose of this literature review was to gather valuable information on the behavior of methyl iodide on the gas phase during a severe accident. The potential of transition metals, especially silver and copper, to remove organic iodides from the gas streams was also studied. Transition metals are one of the most interesting groups in the context of iodine mitigation. For example silver is known to react intensively with iodine compounds. Silver is also relatively inert material and it is thermally stable. Copper is known to react with some radioiodine species. However, it is not reactive toward methyl iodide. In addition, it is oxidized to copper oxide under atmospheric conditions. This may limit the industrial use of copper.(au)

  3. Effects of the liquid-gas phase transition and cluster formation on the symmetry energy

    International Nuclear Information System (INIS)

    Typel, S.; Wolter, H.H.; Roepke, G.; Blaschke, D.

    2014-01-01

    Various definitions of the symmetry energy are introduced for nuclei, dilute nuclear matter below saturation density and stellar matter, which is found in compact stars or core-collapse supernovae. The resulting differences are exemplified by calculations in a theoretical approach based on a generalized relativistic density functional for dense matter. It contains nucleonic clusters as explicit degrees of freedom with medium-dependent properties that are derived for light clusters from a quantum statistical approach. With such a model the dissolution of clusters at high densities can be described. The effects of the liquid-gas phase transition in nuclear matter and of cluster formation in stellar matter on the density dependence of the symmetry energy are studied for different temperatures. It is observed that correlations and the formation of inhomogeneous matter at low densities and temperatures causes an increase of the symmetry energy as compared to calculations assuming a uniform uncorrelated spatial distribution of constituent baryons and leptons. (orig.)

  4. The Northwest Infrared (NWIR) gas-phase spectral database of industrial and environmental chemicals: Recent updates

    Energy Technology Data Exchange (ETDEWEB)

    Brauer, Carolyn S.; Johnson, Timothy J.; Blake, Thomas A.; Sharpe, Steven W.; Sams, Robert L.; Tonkyn, Russell G.

    2014-05-22

    With continuing improvements in both standoff- and point-sensing techniques, there is an ongoing need for high-quality infrared spectral databases. The Northwest Infrared Database (NWIR) contains quantitative, gas-phase infrared spectra of nearly 500 pure chemical species that can be used for a variety of applications such as atmospheric monitoring, biomass burning studies, etc. The data, recorded at 0.1 cm-1 resolution, are pressure broadened to one atmosphere (N2) in order to mimic atmospheric conditions. Each spectrum is a composite composed of multiple individual measurements. Recent updates to the database include over 60 molecules that are known or suspected biomass-burning effluents. Examples from this set of measurements will be presented and experimental details will be discussed in the context of the utility of NWIR for environmental applications.

  5. Detection methods for atoms and radicals in the gas phase

    Science.gov (United States)

    Hack, W.

    This report lists atoms and free radicals in the gas phase which are of interest for environmental and flame chemistry and have been detected directly. The detection methods which have been used are discussed with respect to their range of application, specificity and sensitivity. In table 1, detection methods for the five atoms of group IV (C, Si, Ge, Sn, Pb) and about 60 radicals containing at least one atom of group IV are summarized (CH, Cd, Cf, CC1, CBr, Cn, Cs, CSe, CH2, CD2, Chf, Cdf, CHC1, CHBr, CF2, CC12, CBr2, CFC1, CFBr, CH3, CD3, CF3, CH2F, CH2C1, CH2Br, CHF2, CHC12, CHBr2, Hco, Fco, CH30, CD30, CH2OH, CH3S, Nco, CH4N, CH302, CF302; C2, C2N, C2H, C20, C2HO, C2H3, C2F3, C2H5, C2HsO, C2H4OH, CH3CO, CD3CO, C2H3O, C2H502, CH3COO2, C2H4N, C2H6N, C3; Si, SiF, SiF2, SiO, SiC, Si2; Ge, GeC, GeO, GeF, GeF2, GeCl2, Sn, SnF, SnO, SnF2, Pb, PbF, PbF2, PbO, PbS). In table 2 detection methods for about 25 other atoms and 60 radicals are listed: (H, D, O, O2, Oh, Od, HO2, DO2, F, Ci, Br, I, Fo, Cio, BrO, Io, FO2, C1O2, Li, Na, K, Rb, Cs, N, N3, Nh, Nd, Nf, Nci, NBr, NH2, ND2, Nhd, Nhf, NF2, NC12, N2H3, No, NO2, NO3, Hno, Dno, P, Ph, Pd, Pf, Pci, PH2, PD2, PF2, Po, As, AsO, AsS, Sb, Bi, S, S2, Sh, Sd, Sf, SF2, So, Hso, Dso, Sn, Se, Te, Se2, SeH, SeD, SeF, SeO, SeS, SeN, TeH, TeO, Bh, BH2, Bo, Bn, B02, Cd, Hg, UF5). The tables also cite some recent kinetic applications of the various methods.

  6. Electron-beam synthesis of fuel in the gas phase

    International Nuclear Information System (INIS)

    Ponomarev, A.V.; Holodkova, E.M.; Ershov, B.G.

    2011-01-01

    Complete text of publication follows. Tendencies of world development focus attention on a vegetative biomass as on the major raw resource for future chemistry and a fuel industry. The significant potential for perfection of biomass conversion processes is concentrated in the field of radiation-chemical methods. Both the mode of post-radiation distillation and mode of electron-beam distillation of biomass have been investigated as well as the mode of gas-phase synthesis of liquid engine fuel from of biomass distillation products. Synergistic action of radiation and temperature has been analyzed at use of the accelerated electron beams allowing to combine radiolysis with effective radiation heating of a material without use of additional heaters. At dose rate above 1 kGy/s the electron-beam irradiation results in intensive decomposition of a biomass and evaporation of formed fragments with obtaining of a liquid condensate (∼ 60 wt%), CO 2 and Co gases (13-18 wt%) and charcoal in the residue. Biomass distillation at radiation heating allows to increase almost three times an organic liquid yield in comparison with pyrolysis. The majority of liquid products from cellulose is represented by the furan derivatives considered among the very perspective components for alternative engine fuels. Distilled-off gases and vapors are diluted with gaseous C 1 -C 5 alkanes and again are exposed to an irradiation to produce liquid fuel from a biomass. This transformation is based on a method of electron-beam circulation conversion of gaseous C 1 -C 5 alkanes (Ponomarev, A.V., Radiat. Phys. Chem., 78, 48, 2009) which consists in formation and removal of liquid products with high degree of carbon skeleton branching. The isomers ratio in a liquid may be controlled by means of change of an irradiation condition and initial gas composition. The irradiation of gaseous alkanes together with vaporous products of biomass destruction allows to synthesize the fuel enriched by conventional

  7. Diesel-related hydrocarbons can dominate gas phase reactive carbon in megacities

    Directory of Open Access Journals (Sweden)

    R. E. Dunmore

    2015-09-01

    Full Text Available Hydrocarbons are key precursors to two priority air pollutants, ozone and particulate matter. Those with two to seven carbons have historically been straightforward to observe and have been successfully reduced in many developed cities through air quality policy interventions. Longer chain hydrocarbons released from diesel vehicles are not considered explicitly as part of air quality strategies and there are few direct measurements of their gaseous abundance in the atmosphere. This study describes the chemically comprehensive and continuous measurements of organic compounds in a developed megacity (London, which demonstrate that on a seasonal median basis, diesel-related hydrocarbons represent only 20–30 % of the total hydrocarbon mixing ratio but comprise more than 50 % of the atmospheric hydrocarbon mass and are a dominant local source of secondary organic aerosols. This study shows for the first time that 60 % of the winter primary hydrocarbon hydroxyl radical reactivity is from diesel-related hydrocarbons and using the maximum incremental reactivity scale, we predict that they contribute up to 50 % of the ozone production potential in London. Comparing real-world urban composition with regulatory emissions inventories in the UK and US highlights a previously unaccounted for, but very significant, under-reporting of diesel-related hydrocarbons; an underestimation of a factor ~4 for C9 species rising to a factor of over 70 for C12 during winter. These observations show that hydrocarbons from diesel vehicles can dominate gas phase reactive carbon in cities with high diesel fleet fractions. Future control of urban particulate matter and ozone in such locations requires a shift in policy focus onto gas phase hydrocarbons released from diesels as this vehicle type continues to displace gasoline world-wide.

  8. Reaction pathways for catalytic gas-phase oxidation of glycerol over mixed metal oxides

    Energy Technology Data Exchange (ETDEWEB)

    Suprun, W.; Glaeser, R.; Papp, H. [Leipzig Univ. (Germany). Inst. of Chemical Technology

    2011-07-01

    Glycerol as a main by-product from bio-diesel manufacture is a cheap raw material with large potential for chemical or biochemical transformations to value-added C3-chemicals. One possible way of glycerol utilization involves its catalytic oxidation to acrylic acid as an alternative to petrochemical routes. However, this catalytic conversion exhibits various problems such as harsh reaction conditions, severe catalyst coking and large amounts of undesired by-products. In this study, the reaction pathways for gas-phase conversion of glycerol over transition metal oxides (Mo, V und W) supported on TiO{sub 2} and SiO{sub 2} were investigated by two methods: (i) steady state experiments of glycerol oxidation and possible reactions intermediates, i.e., acrolein, 3-hydroxy propionaldehyde and acetaldehyde, and (ii) temperature-programmed surface reaction (TPSR) studies of glycerol conversion in the presence and in the absence of gas-phase oxygen. It is shown that the supported W-, V and Mo-oxides possess an ability to catalyze the oxidation of glycerol to acrylic acid. These investigations allowed us to gain a deeper insight into the reaction mechanism. Thus, based on the obtained results, three possible reactions pathways for the selective oxidation of glycerol to acrylic acid on the transition metal-containing catalysts are proposed. The major pathways in presence of molecular oxygen are a fast successive destructive oxidation of glycerol to CO{sub x} and the dehydration of glycerol to acrolein which is a rate-limiting step. (orig.)

  9. Raman Spectroscopic Studies of YBa2Cu3O7 Coated Conductors

    International Nuclear Information System (INIS)

    Choi, Mi Kyeung; Mnh, Nguyen Van; Bae, J. S.; Jo, William; Yang, In Sang; Ko, Rock Kil; Ha, Hong Soo; Park, Chan

    2005-01-01

    We present results of Raman spectroscopic studies of superconducting YBa 2 Cu 3 O 7 (YBCO) coated conductors. Raman scattering is used to characterize optical phonon modes, oxygen content, c-axis misalignment, and second phases of the YBCO coated conductors at a micro scale. A two-dimensional mapping of Raman spectra with transport properties has been performed to elucidate the effect of local propertied on current path and superconducting phase. The information taken from the local measurement will be useful for optimizing the process condition.

  10. Preparation and spectroscopic studies of PbS/nanoMCM-41 nanocomposite

    Directory of Open Access Journals (Sweden)

    A. Pourahmad

    2014-11-01

    Full Text Available The present work describes the preparation and characterization of nanosized PbS particles inside the mesopore channels of nanoMCM-41 silicate molecular sieves. The encapsulation of the lead sulfide was carried out at room temperature by ion-exchange method. Diffuse reflectance ultraviolet–visible spectroscopic studies showed a significant shift in the absorption band for the entrapped metal sulfide as compared to corresponding bulk sulfide. Thus, confirming the quantum confinement of the incorporated nanoparticles in nanoMCM-41.

  11. The interaction of new piroxicam analogues with lipid bilayers--a calorimetric and fluorescence spectroscopic study.

    Science.gov (United States)

    Maniewska, Jadwiga; Szczęśniak-Sięga, Berenika; Poła, Andrzej; Sroda-Pomianek, Kamila; Malinka, Wiesław; Michalak, Krystyna

    2014-01-01

    The purpose of the present paper was to assess the ability of new piroxicam analogues to interact with the lipid bilayers. The results of calorimetric and fluorescence spectroscopic experiments of two new synthesized analogues of piroxicam, named PR17 and PR18 on the phase behavior of phospholipid bilayers and fluorescence quenching of fluorescent probes (Laurdan and Prodan), which molecular location within membranes is known with certainty, are shown in present work. The presented results revealed that, depending on the details of chemical structure, the studied compounds penetrated the lipid bilayers.

  12. Mg co-ordination with potential carcinogenic molecule acrylamide: Spectroscopic, computational and cytotoxicity studies

    Science.gov (United States)

    Singh, Ranjana; Mishra, Vijay K.; Singh, Hemant K.; Sharma, Gunjan; Koch, Biplob; Singh, Bachcha; Singh, Ranjan K.

    2018-03-01

    Acrylamide (acr) is a potential toxic molecule produced in thermally processed food stuff. Acr-Mg complex has been synthesized chemically and characterized by spectroscopic techniques. The binding sites of acr with Mg were identified by experimental and computational methods. Both experimental and theoretical results suggest that Mg coordinated with the oxygen atom of Cdbnd O group of acr. In-vitro cytotoxicity studies revealed significant decrease in the toxic level of acr-Mg complex as compared to pure acr. The decrease in toxicity on complexation with Mg may be a useful step for future research to reduce the toxicity of acr.

  13. Spectroscopic techniques in the study of human tissues and their components. Part I: IR spectroscopy.

    Science.gov (United States)

    Olsztyńska-Janus, Sylwia; Szymborska-Małek, Katarzyna; Gąsior-Głogowska, Marlena; Walski, Tomasz; Komorowska, Małgorzata; Witkiewicz, Wojciech; Pezowicz, Celina; Kobielarz, Magdalena; Szotek, Sylwia

    2012-01-01

    Among the currently used methods of monitoring human tissues and their components many types of research are distinguished. These include spectroscopic techniques. The advantage of these techniques is the small amount of sample required, the rapid process of recording the spectra, and most importantly in the case of biological samples - preparation of tissues is not required. In this work, vibrational spectroscopy: ATR-FTIR and Raman spectroscopy will be used. Studies are carried out on tissues: tendons, blood vessels, skin, red blood cells and biological components: amino acids, proteins, DNA, plasma, and deposits.

  14. Synthesis, molecular structure, spectroscopic properties and stability of (Z)-N-methyl-C-2,4,6-trimethylphenylnitrone

    Science.gov (United States)

    Lasri, Jamal; Ismail, Ali I.; Haukka, Matti; Soliman, Saied M.

    2015-02-01

    New N-methyl-C-2,4,6-trimethylphenylnitrone 1 has been synthesized starting from N-methylhydroxylamine and mesitaldehyde. The product was fully characterized using different spectroscopic techniques; FTIR, NMR, UV-Vis, high resolution mass spectrometry and X-ray diffraction. The relative stability and percent of population of its two possible isomers (E and Z) were calculated using the B3LYP/6-311++G(d,p) method in gas phase and in solution. In agreement with the X-ray results, it was found that Z-isomer is the most stable one in both gas phase and solution. The molecular geometry, vibrational frequencies, gauge-including atomic orbital (GIAO), and chemical shift values were also calculated using the same level of theory. The TD-DFT results of the studied nitrone predicted a π-π∗ transition band at 285.1 nm (fosc = 0.3543) in the gas phase. The rest of the spectral bands undergo either hyperchromic or hypsochromic shifts in the presence of solvent. Polarizability and HOMO-LUMO gap values were used to predict the nonlinear optical properties (NLO) of the studied compound. NBO analysis has been used to determine the most accurate Lewis structure of the studied molecule.

  15. The influence of gas phase velocity fluctuations on primary atomization and droplet deformation

    Science.gov (United States)

    Kourmatzis, A.; Masri, A. R.

    2014-02-01

    The effects of grid-generated velocity fluctuations on the primary atomization and subsequent droplet deformation of a range of laminar liquid jets are examined using microscopic high-speed backlit imaging of the break-up zone and laser Doppler anemometry of the gas phase separately. This is done for fixed gas mean flow conditions in a miniature wind tunnel experiment utilizing a selection of fuels, turbulence-generating grids and two syringe sizes. The constant mean flow allows for an isolated study of velocity fluctuation effects on primary atomization in a close approximation to homogeneous decaying turbulence. The qualitative morphology of the primary break-up region is examined over a range of turbulence intensities, and spectral analysis is performed in order to ascertain the break-up frequency which, for a case of no grid, compares well with the existing literature. The addition of velocity fluctuations tends to randomize the break-up process. Slightly downstream of the break-up region, image processing is conducted in order to extract a number of metrics, which do not depend on droplet sphericity, and these include droplet aspect ratio and orientation, the latter quantity being somewhat unconventional in spray characterization. A turbulent Weber number which takes into account gas phase fluctuations is utilized to characterize the resulting droplet shapes, in addition to a mean Weber number . Above a a clear positive relationship exists between the mean aspect ratio of droplets and the turbulent Weber number where is varied by altering all relevant variables including the velocity root mean square, the initial droplet diameter, the surface tension and the density.

  16. Gas Phase Thz Spectroscopy of Organosulfide and Organophosphorous Compounds Using a Synchrotron Source

    Science.gov (United States)

    Cuisset, Arnaud; Smirnova, Irina; Bocquet, Robin; Hindle, Francis; Mouret, Gael; Sadovskii, Dmitrii A.; Pirali, Olivier; Roy, Pascale

    2011-06-01

    This study concerns the gas phase rovibrational spectroscopy of organosulfide and organophosphorous which are considered as non toxic model compounds in the analysis of chemical weapon materials, high pathogenic and mutagenic agents, and other environmentally interesting air-borne species. The coupling of the synchrotron radiation with multipass cells and the FTIR spectrometer allowed to obtain very conclusive results in term of sensitivity and resolution and improved the previous results obtained with classical sources. For DMSO, using an optical path of 150 m the spectra have been recorded at the ultimate resolution of 0.001 Cm-1 allowing to fully resolve the rotational structure of the lowest vibrational modes observed in the THz region. In the 290 - 420 Cm-1 region, the rovibrational spectrum of the "perpendicular" and "parallel" vibrational bands associated with, respectively, the asymmetric ν23 and symmetric ν11 bending modes of DMSO have been recorded with a resolution of 1.5× 10-3 Cm-1. The gas phase vibrational spectra of organophosphorous compounds were measured by FTIR spectroscopy using the vapor pressure of the compounds. Except for TBP, the room temperature vapor pressure was sufficient to detect all active vibrational modes from THz to NIR domain. Contrary to DMSO, the rotational patterns of alkyl phosphates and alkyl phosphonates could not be resolved; only a vibrational analysis may be performed. Nevertheless, the spectral fingerprints observed in the THz region allowed a clear discrimination between the molecules and between the different molecular conformations. A. Cuisset, G. Mouret, O. Pirali, P. Roy, F. Cazier, H. Nouali, J. Demaison, J. Phys. Chem. B, 2008, 112:, 12516-12525 A. Cuisset, L. Nanobashvili, I. Smirnova, R. Bocquet, F. Hindle, G. Mouret, O. Pirali, P. Roy and D. A. Sadovskií, Chem. Phys. Lett., 2010, 492: 30-34 I. Smirnova, A. Cuisset, R. Bocquet, F. Hindle, G. Mouret, O. Pirali, P. Roy, J. Phys. Chem. B, 2010, 114: 16936-16947.

  17. Molecular simulation of excess isotherm and excess enthalpy change in gas-phase adsorption.

    Science.gov (United States)

    Do, D D; Do, H D; Nicholson, D

    2009-01-29

    We present a new approach to calculating excess isotherm and differential enthalpy of adsorption on surfaces or in confined spaces by the Monte Carlo molecular simulation method. The approach is very general and, most importantly, is unambiguous in its application to any configuration of solid structure (crystalline, graphite layer or disordered porous glass), to any type of fluid (simple or complex molecule), and to any operating conditions (subcritical or supercritical). The behavior of the adsorbed phase is studied using the partial molar energy of the simulation box. However, to characterize adsorption for comparison with experimental data, the isotherm is best described by the excess amount, and the enthalpy of adsorption is defined as the change in the total enthalpy of the simulation box with the change in the excess amount, keeping the total number (gas + adsorbed phases) constant. The excess quantities (capacity and energy) require a choice of a reference gaseous phase, which is defined as the adsorptive gas phase occupying the accessible volume and having a density equal to the bulk gas density. The accessible volume is defined as the mean volume space accessible to the center of mass of the adsorbate under consideration. With this choice, the excess isotherm passes through a maximum but always remains positive. This is in stark contrast to the literature where helium void volume is used (which is always greater than the accessible volume) and the resulting excess can be negative. Our definition of enthalpy change is equivalent to the difference between the partial molar enthalpy of the gas phase and the partial molar enthalpy of the adsorbed phase. There is no need to assume ideal gas or negligible molar volume of the adsorbed phase as is traditionally done in the literature. We illustrate this new approach with adsorption of argon, nitrogen, and carbon dioxide under subcritical and supercritical conditions.

  18. Conformational preferences of γ-aminobutyric acid in the gas phase and in water

    Science.gov (United States)

    Song, Il Keun; Kang, Young Kee

    2012-09-01

    The conformational study of γ-aminobutyric acid (GABA) has been carried out at the M06-2X/cc-pVTZ level of theory in the gas phase and the SMD M06-2X/cc-pVTZ level of theory in water. In the gas phase, the folded conformation gG1 with gauche- and gauche+ conformations for the Cβsbnd Cα and Cγsbnd Cβ bonds, respectively, is found to be lowest in energy and enthalpy, which can be ascribed to the favored hyperconjugative n → π* interaction between the lone electron pair of the amine nitrogen atom and the Cdbnd O bond of the carboxylic group and the favored antiparallel dipole-dipole interaction between the Nsbnd H bond and the Cdbnd O bond. In addition, the intramolecular hydrogen bonds between the carboxylic group and the amine Nsbnd H group have contributed to stabilize some low-energy conformers. However, the most preferred conformation is found to be tG1 and more stable by 0.4 kcal/mol in ΔG than the conformer gG1, in which the favored entropic term due to the conformational flexibility and the other favored n → σ*, σ → σ*, and π → σ* interactions seem to play a role. The conformational preferences of the neutral GABA calculated by ΔG's are reasonably consistent with the populations deduced from FT microwave spectroscopy in supersonic jets combined with laser ablation. In water, the two folded conformers Gg and gG of the zwitterionic GABA are dominantly populated, each of which has the population of 47%, and the hydrogen bond between the ammonium Nsbnd H group and the lone electron pair of the Csbnd O- group seems to be crucial in stabilizing these conformers. Our calculated result that the folded conformers preferentially exist in water is consistent with the 1H NMR experiments in D2O.

  19. Gas phase enthalpies of formation of nitrobenzamides using combustion calorimetry and thermal analysis

    International Nuclear Information System (INIS)

    Ximello, Arturo; Flores, Henoc; Rojas, Aarón; Adriana Camarillo, E.; Patricia Amador, M.

    2014-01-01

    Graphical abstract: - Highlights: • Formation enthalpies of the nitrobenzamides were derived from combustion calorimetry. • Enthalpies of vaporisation and sublimation were calculated by thermogravimetry. • From gas phase enthalpies of formation the stability of the isomers is studied. • Stability of isomers is not driven by a steric hindrance between functional groups. - Abstract: The standard molar energies of combustion of 2-nitrobenzamide, 3-nitrobenzamide and 4-nitrobenzamide were determined with an isoperibolic, static-bomb, combustion calorimeter. From the combustion results, the standard molar enthalpies of combustion and formation for these compounds in the condensed phase at T = 298.15 K were derived. Subsequently, to determine the enthalpies of sublimation, the vapour pressure data as a function of the temperature for the compounds under investigation were estimated using thermogravimetry by applying Langmuir’s equation, and the enthalpies of vaporisation were derived. Standard enthalpies of fusion were measured by differential scanning calorimetry then added to those of vaporisation to obtain reliable results for the enthalpy of sublimation. From the combustion and sublimation data, the gas phase enthalpies of formation were determined to be (−138.9 ± 3.5) kJ · mol −1 , (−122.9 ± 2.9) kJ · mol −1 and (−108.5 ± 3.7) kJ · mol −1 for the ortho, meta and para isomers of nitrobenzamide, respectively. The meaning of these results with regard to the enthalpic stability of these molecular structures is discussed herein

  20. Infrared spectroscopic and voltammetric study of adsorbed CO on stepped surfaces of copper monocrystalline electrodes

    International Nuclear Information System (INIS)

    Koga, O.; Teruya, S.; Matsuda, K.; Minami, M.; Hoshi, N.; Hori, Y.

    2005-01-01

    Voltammetric and infrared (IR) spectroscopic measurements were carried out to study adsorbed CO on two series of copper single crystal electrodes n(111)-(111) and n(111)-(100) in 0.1M KH 2 PO 4 +0.1M K 2 HPO 4 at 0 o C. Reversible voltammetric waves were observed below -0.55V versus SHE for adsorption of CO which displaces preadsorbed phosphate anions. The electric charge of the redox waves is proportional to the step atom density for both single crystal series. This fact indicates that phosphate anions are specifically adsorbed on the step sites below -0.55V versus SHE. Voltammetric measurements indicated that (111) terrace of Cu is covered with adsorbed CO below -0.5V versus SHE. Nevertheless, no IR absorption band of adsorbed CO is detected from (111) terrace. Presence of adsorbed CO on (111) terrace is presumed which is not visible by the potential difference spectroscopy used in the present work. IR spectroscopic measurements showed that CO is reversibly adsorbed with an on-top manner on copper single crystal electrodes of n(111)-(111) and n(111)-(100) with approximately same wavenumber of C?O stretching vibration of 2070cm -1 . The IR band intensity is proportional to the step atom density. Thus CO is adsorbed on (111) or (100) steps on the single crystal surfaces. An analysis of the IR band intensity suggested that one CO molecule is adsorbed on every two or more Cu step atom of the monocrystalline surface. The spectroscopic data were compared with those reported for uhv system. The C-O stretching wavenumber of adsorbed CO in the electrode-electrolyte system is 30-40cm -1 lower than those in uhv system

  1. THE DISTANCE TO THE MASSIVE GALACTIC CLUSTER WESTERLUND 2 FROM A SPECTROSCOPIC AND HST PHOTOMETRIC STUDY

    International Nuclear Information System (INIS)

    Vargas Álvarez, Carlos A.; Kobulnicky, Henry A.; Bradley, David R.; Kannappan, Sheila J.; Norris, Mark A.; Cool, Richard J.; Miller, Brendan P.

    2013-01-01

    We present a spectroscopic and photometric determination of the distance to the young Galactic open cluster Westerlund 2 using WFPC2 imaging from the Hubble Space Telescope (HST) and ground-based optical spectroscopy. HST imaging in the F336W, F439W, F555W, and F814W filters resolved many sources previously undetected in ground-based observations and yielded photometry for 1136 stars. We identified 15 new O-type stars, along with two probable binary systems, including MSP 188 (O3 + O5.5). We fit reddened spectral energy distributions based on the Padova isochrones to the photometric data to determine individual reddening parameters R V and A V for O-type stars in Wd2. We find average values (R V ) = 3.77 ± 0.09 and (A V ) = 6.51 ± 0.38 mag, which result in a smaller distance than most other spectroscopic and photometric studies. After a statistical distance correction accounting for close unresolved binaries (factor of 1.08), our spectroscopic and photometric data on 29 O-type stars yield that Westerlund 2 has a distance (d) = 4.16 ± 0.07 (random) +0.26 (systematic) kpc. The cluster's age remains poorly constrained, with an upper limit of 3 Myr. Finally, we report evidence of a faint mid-IR polycyclic aromatic hydrocarbon ring surrounding the well-known binary candidate MSP 18, which appears to lie at the center of a secondary stellar grouping within Westerlund 2.

  2. THE DISTANCE TO THE MASSIVE GALACTIC CLUSTER WESTERLUND 2 FROM A SPECTROSCOPIC AND HST PHOTOMETRIC STUDY

    Energy Technology Data Exchange (ETDEWEB)

    Vargas Alvarez, Carlos A.; Kobulnicky, Henry A. [Department of Physics and Astronomy, University of Wyoming, Dept. 3905, Laramie, WY 82071 (United States); Bradley, David R.; Kannappan, Sheila J.; Norris, Mark A. [Department of Physics and Astronomy, University of North Carolina, Chapel Hill, CB 3255, Phillips Hall, Chapel Hill, NC 27599-3255 (United States); Cool, Richard J. [Observatories of the Carnegie Institution of Washington, 813 Santa Barbara Street, Pasadena, CA 91101 (United States); Miller, Brendan P., E-mail: cvargasa@uwyo.edu, E-mail: chipk@uwyo.edu, E-mail: davidbradley512@gmail.com, E-mail: sheila@physics.unc.edu, E-mail: manorris@physics.unc.edu, E-mail: rcool@obs.carnegiescience.edu, E-mail: mbrendan@umich.edu [Department of Astronomy, University of Michigan, 745 Dennison Building, 500 Church St., Ann Arbor, MI 48109 (United States)

    2013-05-15

    We present a spectroscopic and photometric determination of the distance to the young Galactic open cluster Westerlund 2 using WFPC2 imaging from the Hubble Space Telescope (HST) and ground-based optical spectroscopy. HST imaging in the F336W, F439W, F555W, and F814W filters resolved many sources previously undetected in ground-based observations and yielded photometry for 1136 stars. We identified 15 new O-type stars, along with two probable binary systems, including MSP 188 (O3 + O5.5). We fit reddened spectral energy distributions based on the Padova isochrones to the photometric data to determine individual reddening parameters R{sub V} and A{sub V} for O-type stars in Wd2. We find average values (R{sub V} ) = 3.77 {+-} 0.09 and (A{sub V} ) = 6.51 {+-} 0.38 mag, which result in a smaller distance than most other spectroscopic and photometric studies. After a statistical distance correction accounting for close unresolved binaries (factor of 1.08), our spectroscopic and photometric data on 29 O-type stars yield that Westerlund 2 has a distance (d) = 4.16 {+-} 0.07 (random) +0.26 (systematic) kpc. The cluster's age remains poorly constrained, with an upper limit of 3 Myr. Finally, we report evidence of a faint mid-IR polycyclic aromatic hydrocarbon ring surrounding the well-known binary candidate MSP 18, which appears to lie at the center of a secondary stellar grouping within Westerlund 2.

  3. Spectroscopic and structural study of the newly synthesized heteroligand complex of copper with creatinine and urea.

    Science.gov (United States)

    Gangopadhyay, Debraj; Singh, Sachin Kumar; Sharma, Poornima; Mishra, Hirdyesh; Unnikrishnan, V K; Singh, Bachcha; Singh, Ranjan K

    2016-02-05

    Study of copper complex of creatinine and urea is very important in life science and medicine. In this paper, spectroscopic and structural study of a newly synthesized heteroligand complex of copper with creatinine and urea has been discussed. Structural studies have been carried out using DFT calculations and spectroscopic analyses were carried out by FT-IR, Raman, UV-vis absorption and fluorescence techniques. The copper complex of creatinine and the heteroligand complex were found to have much increased water solubility as compared to pure creatinine. The analysis of FT-IR and Raman spectra helps to understand the coordination properties of the two ligands and to determine the probable structure of the heteroligand complex. The LIBS spectra of the heteroligand complex reveal that the complex is free from other metal impurities. UV-visible absorption spectra and the fluorescence emission spectra of the aqueous solution of Cu-Crn-urea heteroligand complex at different solute concentrations have been analyzed and the complex is found to be rigid and stable in its monomeric form at very low concentrations. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. MP CBM-Z V1.0: design for a new CBM-Z gas-phase chemical mechanism architecture for next generation processors

    OpenAIRE

    Wang, Hui; Lin, Junmin; Wu, Qizhong; Chen, Huansheng; Tang, Xiao; Wang, Zifa; Chen, Xueshun; Cheng, Huaqiong; Wang, Lanning

    2018-01-01

    Precise and rapid air quality simulation and forecasting are limited by the computation performance of the air quality model, and the gas-phase chemistry module is the most time-consuming function in the air quality model. In this study, we designed a new framework for the widely used Carbon Bond Mechanism Z (CBM-Z) gas-phase chemical kinetics kernel to adapt the Single Instruction Multiple Data (SIMD) technology in the next-generation processors for improving its calculation performance. The...

  5. Protein and Peptide Gas-phase Structure Investigation Using Collision Cross Section Measurements and Hydrogen Deuterium Exchange

    Science.gov (United States)

    Khakinejad, Mahdiar

    Protein and peptide gas-phase structure analysis provides the opportunity to study these species outside of their explicit environment where the interaction network with surrounding molecules makes the analysis difficult [1]. Although gas-phase structure analysis offers a unique opportunity to study the intrinsic behavior of these biomolecules [2-4], proteins and peptides exhibit very low vapor pressures [2]. Peptide and protein ions can be rendered in the gas-phase using electrospray ionization (ESI) [5]. There is a growing body of literature that shows proteins and peptides can maintain solution structures during the process of ESI and these structures can persist for a few hundred milliseconds [6-9]. Techniques for monitoring gas-phase protein and peptide ion structures are categorized as physical probes and chemical probes. Collision cross section (CCS) measurement, being a physical probe, is a powerful method to investigate gas-phase structure size [3, 7, 10-15]; however, CCS values alone do not establish a one to one relation with structure(i.e., the CCS value is an orientationally averaged value [15-18]. Here we propose the utility of gas-phase hydrogen deuterium exchange (HDX) as a second criterion of structure elucidation. The proposed approach incudes extensive MD simulations to sample biomolecular ion conformation space with the production of numerous, random in-silico structures. Subsequently a CCS can be calculated for these structures and theoretical CCS values are compared with experimental values to produce a pool of candidate structures. Utilizing a chemical reaction model based on the gas-phase HDX mechanism, the HDX kinetics behavior of these candidate structures are predicted and compared to experimental results to nominate the best in-silico structures which match (chemically and physically) with experimental observations. For the predictive approach to succeed, an extensive technique and method development is essential. To combine CCS

  6. The vibrational spectra of N-phenylpyrrole in the gas phase, in argon matrices and in single crystals

    International Nuclear Information System (INIS)

    Schweke, D.; Brauer, B.; Gerber, R.B.; Haas, Y.

    2007-01-01

    The infrared spectrum of N-phenylpyrrole (PP) was measured in the gas phase and in an argon matrix, and the Raman spectrum was obtained in a single crystal. The measured matrix shifts are found to be small: many bands are not split, and the shifts from the gas phase values are less than 1%. Splitting to two sub-bands is observed for some bands, indicating the presence of two major trapping sites, in agreement with previous predictions. The spectra are analyzed with the help of harmonic calculations on the free molecule and on its adduct with one or two argon atoms, and anharmonic frequency calculations on the free molecule. Harmonic frequencies were obtained at the MP2/cc-pVDZ and DFT-B3LYP/cc-pVDZ levels. Anharmonic frequencies were obtained by the correlation-corrected vibrational self-consistent field (CC-VSCF) method with a variant of the PM3 semiempirical electronic structure method, calibrated for much improved spectroscopic accuracy. The potential surfaces used in the CC-VSCF calculation obtained by adjusting standard PM3 surfaces so that they provide harmonic frequencies that are comparable to those obtained at the DFT-B3LYP/cc-pVDZ level. Agreement between the experimental and theoretical results is in general very good, allowing the assignments of most bands. The harmonic frequency calculations of PP-Ar clusters, at the MP2/cc-pVDZ level show that the environment can greatly affect the intensities of some of the transitions, which is in accord with experiment

  7. Spectroscopic studies on the interaction between ZnSe nanoparticles with bovine serum albumin

    International Nuclear Information System (INIS)

    Chen, Zhi; Wu, Dudu

    2012-01-01

    The interaction between ZnSe nanoparticles (NPs) and bovine serum albumin (BSA) was studied by UV–vis, fluorescence spectroscopic techniques. The results showed that the fluorescence of BSA was strongly quenched by ZnSe NPs and the quenching mechanism was discussed to be a static quenching procedure, which was proved by quenching constant (K q ). The recorded UV–vis data and the fluorescence data quenching by the ZnSe NPs showed that the interaction between them leads to the formation of ZnSe–BSA complex. Based on the synchronous fluorescence spectra, it was established that the conformational change of BSA was induced by the interaction of ZnSe with the tyrosine micro-region of the BSA molecules. Furthermore, the temperature effects on the structural and spectroscopic properties of individual ZnSe NPs and protein and their bioconjugates (ZnSe–BSA) were also researched. It was found that, compared to the monotonic decrease of the individual ZnSe NPs fluorescence intensity, the temperature dependence of the ZnSe–BSA emission had a much more complex behavior, which was highly sensitive to the conformational changes of the protein. - Highlights: ►Interaction between bovine serum albumin (BSA) and ZnSe nanoparticles was studied. ► UV–vis data and fluorescence data demonstrated the formation of ZnSe–BSA complex. ► Temperature dependence of ZnSe–BSA emission was sensitive to the conformational changes of protein.

  8. Thermal and spectroscopic studies on solid ibuprofen complexes of lighter trivalent lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Gálico, D.A.; Holanda, B.B.C.; Guerra, R.B.; Legendre, A.O.; Rinaldo, D. [UNESP – Univ Estadual Paulista, Faculdade de Ciências, Departamento de Química, São Paulo CEP 17033-260 (Brazil); Treu-Filho, O. [UNESP – Univ Estadual Paulista, Instituto de Química, São Paulo CEP 14800-900 (Brazil); Bannach, G., E-mail: gilbert@fc.unesp.br [UNESP – Univ Estadual Paulista, Faculdade de Ciências, Departamento de Química, São Paulo CEP 17033-260 (Brazil)

    2014-01-10

    Highlights: • Lighter trivalent lanthanide complexes of ibuprofen have been synthesized. • The TG-FTIR allowed the identification of propane as the gas evolved during the thermal decomposition of the neodymium compound. • The thermal analysis provided information about the composition, dehydration, thermal behavior and thermal decomposition of the samples. • The theoretical and experimental spectroscopic studies suggest that the carboxylate group of ibuprofen is coordinated to the metals by a bidentate bond. - Abstract: Solid-state compounds of general formula Ln(L){sub 3}, in which L is ibuprofen and Ln stands for trivalent La, Ce, Pr, Nd, Sm and Eu, have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), X-ray powder diffractometry (DRX), complexometry, Fourier-transformed infrared spectroscopy (FTIR) and thermogravimetry coupled to Fourier-transformed infrared spectroscopy (TG-FTIR) were used to characterize these compounds. The results provided information concerning the chemical composition, dehydration, coordination modes of the ligands, crystallinity of the samples, thermal behavior and thermal decomposition of the compounds. The theoretical and experimental spectroscopic studies suggest that ibuprofen coordinates through the carboxylate group as a chelating ligand.

  9. Confirming LBV Candidates Through Variability: A Photometric and Spectroscopic Monitoring Study

    Science.gov (United States)

    Stringfellow, Guy; Gvaramadze, Vasilii

    2013-02-01

    Luminous Blue Variable (LBV) stars represent an extremely rare class of luminous massive stars with high mass loss rates. The paucity ( 12) of confirmed Galactic LBV precludes determining a solid evolutionary connection between LBV and other intermediate (e.g. Ofpe/WN9, WNL) phases in the life of very massive stars. We've been conducting an optical/near-IR spectral survey of a large subset of central stars residing within newly discovered it Spitzer nebulae and have identified over two dozen new candidate LBVs (cLBVs) based on spectral similarity alone; confirming them as bona fide LBVs requires demonstrating 1-3 mag photometric and spectroscopic variability. This marks a significant advancement in the study of massive stars, far outweighing the return from many studies searching for LBVs and WRs the past several decades. Monitoring from semesters 2011B-2012A already has confirmed one new cLBV as a bona fide LBV. We propose to continue optical-IR photometric monitoring of these cLBVS with the 1.3m. Chiron, replacing the RC spectrograph on the 1.5m, now allows high-resolution optical spectroscopic monitoring of bright cLBVs, 11 of which are proposed herein. Spectra are important for understanding the physics driving photometric variability, properties of the wind, and allow analysis of line profiles.

  10. Thermal and spectroscopic studies on solid ibuprofen complexes of lighter trivalent lanthanides

    International Nuclear Information System (INIS)

    Gálico, D.A.; Holanda, B.B.C.; Guerra, R.B.; Legendre, A.O.; Rinaldo, D.; Treu-Filho, O.; Bannach, G.

    2014-01-01

    Highlights: • Lighter trivalent lanthanide complexes of ibuprofen have been synthesized. • The TG-FTIR allowed the identification of propane as the gas evolved during the thermal decomposition of the neodymium compound. • The thermal analysis provided information about the composition, dehydration, thermal behavior and thermal decomposition of the samples. • The theoretical and experimental spectroscopic studies suggest that the carboxylate group of ibuprofen is coordinated to the metals by a bidentate bond. - Abstract: Solid-state compounds of general formula Ln(L) 3 , in which L is ibuprofen and Ln stands for trivalent La, Ce, Pr, Nd, Sm and Eu, have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), X-ray powder diffractometry (DRX), complexometry, Fourier-transformed infrared spectroscopy (FTIR) and thermogravimetry coupled to Fourier-transformed infrared spectroscopy (TG-FTIR) were used to characterize these compounds. The results provided information concerning the chemical composition, dehydration, coordination modes of the ligands, crystallinity of the samples, thermal behavior and thermal decomposition of the compounds. The theoretical and experimental spectroscopic studies suggest that ibuprofen coordinates through the carboxylate group as a chelating ligand

  11. Infrared spectroscopy of gas-phase clusters using a free-electron laser

    International Nuclear Information System (INIS)

    Heijnsbergen, D. van; Helden, G. von; Meijer, G.

    2002-01-01

    Most clusters produced in the gas phase, especially those containing metals, remain largely uncharaterized, among these are transition metal - carbide, -oxide and -nitride clusters. A method for recording IR spectra of strongly bound gas-phase clusters is presented. It is based on a free-electron laser called Felix, characterized by wide wavelength tuning range, covering almost the full 'molecular finger print' region, high power and fluence which make it suited to excite gas-phase species i.e. gas -phase clusters. Neutral clusters were generated by laser vaporization technique, ions that were created after the interaction with the free-electron laser were analyzed in a flight mass spectrometer. Experiments were run with titanium carbide clusters and their IR spectra given. It was shown that this method is suited to strongly bound clusters with low ionization energies, a condition met for many pure metal clusters and metal compound clusters. (nevyjel)

  12. Defect formation in fluoropolymer films at their condensation from a gas phase

    Science.gov (United States)

    Luchnikov, P. A.

    2018-01-01

    The questions of radiation defects, factors of influence of electronic high-frequency discharge plasma components on the molecular structure and properties of the fluoropolymer vacuum films synthesized on a substrate from a gas phase are considered. It is established that at sedimentation of fluoropolymer coverings from a gas phase in high-frequency discharge plasma in films there are radiation defects in molecular and supramolecular structure because of the influence of active plasma components which significantly influence their main properties.

  13. Ultrafast electronic relaxation of excited state vitamin B12 in the gas phase

    International Nuclear Information System (INIS)

    Shafizadeh, Niloufar; Poisson, Lionel; Soep, Benoit

    2008-01-01

    The time evolution of electronically excited vitamin B 12 (cyanocobalamin) has been observed for the first time in the gas phase. It reveals an ultrafast decay to a state corresponding to metal excitation. This decay is interpreted as resulting from a ring to metal electron transfer. This opens the observation of the excited state of other complex biomimetic systems in the gas phase, the key to the characterisation of their complex evolution through excited electronic states

  14. A new method for determining gas phase heat of formation of aromatic energetic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Keshavarz, Mohammad H. [Department of Chemistry, Malek-ashtar University of Technology, Shahin-shahr P. O. Box 83145/115 (Iran); Tehrani, Masoud K. [Department of Physics, Malek-ashtar University of Technology, Shahin-shahr P. O. Box 83145/115 (Iran)

    2007-04-15

    A new correlation is introduced for desk calculation of gas phase heat of formation of aromatic energetic compounds that contain the elements of carbon, hydrogen, nitrogen and oxygen. Predicted gas phase heats of formation for 26 energetic compounds have a root mean square of deviation from experiment of 20.67 kJ/mol, which is in good agreement with respect to measured values of oxygen-lean and oxygen-rich aromatic energetic compounds. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

  15. Theoretical studies on CH+ ion molecule using configuration interaction method and its spectroscopic properties

    International Nuclear Information System (INIS)

    Machado, F.B.C.

    1985-01-01

    The use of the configuration (CI) method for the calculation of very accurate potential energy curves and dipole moment functions, and then their use in the comprehension of spectroscopic properties of diatomic molecules is presented. The spectroscopic properties of CH + and CD + such as: vibrational levels, spectroscopic constants, averaged dipole moments for all vibrational levels, radiative transition probabilities for emission and absorption, and radiative lifetimes are verificated. (M.J.C.) [pt

  16. A NEAR-INFRARED SPECTROSCOPIC STUDY OF YOUNG FIELD ULTRACOOL DWARFS

    Energy Technology Data Exchange (ETDEWEB)

    Allers, K. N. [Department of Physics and Astronomy, Bucknell University, Lewisburg, PA 17837 (United States); Liu, Michael C., E-mail: k.allers@bucknell.edu [Institute for Astronomy, University of Hawaii, 2680 Woodlawn Drive, Honolulu, HI 96822 (United States)

    2013-08-01

    We present a near-infrared (0.9-2.4 {mu}m) spectroscopic study of 73 field ultracool dwarfs having spectroscopic and/or kinematic evidence of youth ( Almost-Equal-To 10-300 Myr). Our sample is composed of 48 low-resolution (R Almost-Equal-To 100) spectra and 41 moderate-resolution spectra (R {approx}> 750-2000). First, we establish a method for spectral typing M5-L7 dwarfs at near-IR wavelengths that is independent of gravity. We find that both visual and index-based classification in the near-IR provides consistent spectral types with optical spectral types, though with a small systematic offset in the case of visual classification at J and K band. Second, we examine features in the spectra of {approx}10 Myr ultracool dwarfs to define a set of gravity-sensitive indices based on FeH, VO, K I, Na I, and H-band continuum shape. We then create an index-based method for classifying the gravities of M6-L5 dwarfs that provides consistent results with gravity classifications from optical spectroscopy. Our index-based classification can distinguish between young and dusty objects. Guided by the resulting classifications, we propose a set of low-gravity spectral standards for the near-IR. Finally, we estimate the ages corresponding to our gravity classifications.

  17. Ab initio study of the O4H(+) novel species: spectroscopic fingerprints to aid its observation.

    Science.gov (United States)

    Xavier, F George D; Hernández-Lamoneda, Rámon

    2015-06-28

    A detailed ab initio characterization of the structural, energetic and spectroscopic properties of the novel O4H(+) species is presented. The equilibrium structures and relative energies of all multiplet states have been determined systematically by analyzing static and dynamical correlation effects. The two and three body dissociation processes have been studied and indicate the presence of conical intersections in various states including the ground state. Comparison with available thermochemical data is very good, supporting the applied methodology. The reaction, H3(+) + O4→ O4H(+) + H2, was found to be exothermic ΔH = -19.4 kcal mol(-1) and therefore, it is proposed that the product in the singlet state could be formed in the interstellar medium (ISM) via collision processes. To aid in its laboratory or radioastronomy detection in the interstellar medium we determined spectroscopic fingerprints. It is estimated for the most stable geometry of O4H(+) dipole allowed electronic transitions in the visible region at 429 nm and 666 nm, an intense band at 1745 cm(-1) in the infrared and signals at 40.6, 81.2 and 139.2 GHz in the microwave region at 10, 50 and 150 K respectively, relevant for detection in the ISM.

  18. Spectroscopic study of honey from Apis mellifera from different regions in Mexico

    Science.gov (United States)

    Frausto-Reyes, C.; Casillas-Peñuelas, R.; Quintanar-Stephano, JL; Macías-López, E.; Bujdud-Pérez, JM; Medina-Ramírez, I.

    2017-05-01

    The objective of this study was to analyze by Raman and UV-Vis-NIR Spectroscopic techniques, Mexican honey from Apis Mellífera, using representative samples with different botanic origins (unifloral and multifloral) and diverse climates. Using Raman spectroscopy together with principal components analysis, the results obtained represent the possibility to use them for determination of floral origin of honey, independently of the region of sampling. For this, the effect of heat up the honey was analyzed in relation that it was possible to greatly reduce the fluorescence background in Raman spectra, which allowed the visualization of fructose and glucose peaks. Using UV-Vis-NIR, spectroscopy, a characteristic spectrum profile of transmittance was obtained for each honey type. In addition, to have an objective characterization of color, a CIE Yxy and CIE L*a*b* colorimetric register was realized for each honey type. Applying the principal component analysis and their correlation with chromaticity coordinates allowed classifying the honey samples in one plot as: cutoff wavelength, maximum transmittance, tones and lightness. The results show that it is possible to obtain a spectroscopic record of honeys with specific characteristics by reducing the effects of fluorescence.

  19. Glucose Oxidase Adsorption on Sequential Adsorbed Polyelectrolyte Films Studied by Spectroscopic Techniques

    Science.gov (United States)

    Tristán, Ferdinando; Solís, Araceli; Palestino, Gabriela; Gergely, Csilla; Cuisinier, Frédéric; Pérez, Elías

    2005-04-01

    The adsorption of Glucose Oxidase (GOX) on layers of poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) deposited on Sequentially Adsorbed Polyelectrolyte Films (SAPFs) were studied by three different spectroscopic techniques. These techniques are: Optical Wave Light Spectroscopy (OWLS) to measure surface density; Fluorescence Resonance Energy Transfer (FRET) to verify the adsorption of GOX on the surface; and Fourier Transform Infrared Spectroscopy in Attenuated Total Reflection mode (FTIR-HATR) to inspect local structure of polyelectrolytes and GOX. Two positive and two negative polyelectrolytes are used: Cationic poly(ethyleneimine) (PEI) and poly(allylamine hydrochloride) (PAH) and anionic poly(sodium 4-styrene sulfonate) (PSS) and poly(acrylic acid) (PAA). These spectroscopic techniques do not require any labeling for GOX or SAPFs, specifically GOX and PSS are naturally fluorescent and are used as a couple donor-acceptor for the FRET technique. The SAPFs are formed by a (PEI)-(PSS/PAH)2 film followed by (PAA/PAH)n bilayers. GOX is finally deposited on top of SAPFs at different values of n (n=1..5). Our results show that GOX is adsorbed on positive ended SAPFs forming a monolayer. Contrary, GOX adsorption is not observed on negative ended film polyelectrolyte. GOX stability was tested adding a positive and a negative polyelectrolyte after GOX adsorption. Protein is partially removed by PAH and PAA, with lesser force by PAA.

  20. Optical spectroscopy using gas-phase femtosecond laser filamentation.

    Science.gov (United States)

    Odhner, Johanan; Levis, Robert

    2014-01-01

    Femtosecond laser filamentation occurs as a dynamic balance between the self-focusing and plasma defocusing of a laser pulse to produce ultrashort radiation as brief as a few optical cycles. This unique source has many properties that make it attractive as a nonlinear optical tool for spectroscopy, such as propagation at high intensities over extended distances, self-shortening, white-light generation, and the formation of an underdense plasma. The plasma channel that constitutes a single filament and whose position in space can be controlled by its input parameters can span meters-long distances, whereas multifilamentation of a laser beam can be sustained up to hundreds of meters in the atmosphere. In this review, we briefly summarize the current understanding and use of laser filaments for spectroscopic investigations of molecules. A theoretical framework of filamentation is presented, along with recent experimental evidence supporting the established understanding of filamentation. Investigations carried out on vibrational and rotational spectroscopy, filament-induced breakdown, fluorescence spectroscopy, and backward lasing are discussed.