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Sample records for reaction ir 1h

  1. Ir-Catalyzed enantioselective group transfer reactions.

    PubMed

    Schafer, Andrew G; Blakey, Simon B

    2015-10-01

    Recently, several novel iridium complexes have been shown to catalyse group transfer reactions in a highly selective fashion. Rhodium complexes, and in particular dirhodium tetracarboxylate salts, have proven to be a remarkably useful class of catalysts for these reactions through several decades of development. Recent results suggest that iridium may offer opportunities to address challenges in this chemistry and provide complementary reactivity patterns. This tutorial review outlines the recent developments in Ir-catalyzed enantioselective group transfer chemistry with highlights on examples which display this unique reactivity. PMID:26051004

  2. Competing reaction channels in IR-laser-induced unimolecular reactions

    SciTech Connect

    Berman, M.R.

    1981-01-01

    The competing reaction channels in the unimolecular decomposition of two molecules, formaldehyde and tetralin were studied. A TEA CO/sub 2/ laser was used as the excitation source in all experiments. The dissociation of D/sub 2/CO was studied by infrared multiphoton dissociation (MPD) and the small-molecule nature of formaldehyde with regard to MPD was explored. The effect of collisions in MPD were probed by the pressure dependence of the MPD yield and ir fluorescence from multiphoton excited D/sub 2/CO. MPD yield shows a near cubic dependence in pure D/sub 2/CO which is reduced to a 1.7 power dependence when 15 torr of NO is added. The peak amplitude of 5 ..mu..m ir fluorescence from D/sub 2/CO is proportional to the square of the D/sub 2/CO pressure in pure D/sub 2/CO or in the presence of 50 torr of Ar. Results are explained in terms of bottlenecks to excitation at the v = 1 level which are overcome by a combination of vibrational energy transfer and rotational relaxation. The radical/molecule branching ratio in D/sub 2/CO MPD was 0.10 +- 0.02 at a fluence of 125 J/cm/sup 2/ at 946.0 cm/sup -1/. The barrier height to molecular dissociation was calculated to be 3.6 +- 2.0 kcal/mole below the radical threshold or 85.0 +- 3.0 kcal/mole above the ground state of D/sub 2/CO. In H/sub 2/CO, this corresponds to 2.5 +- 2.0 kcal/mole below the radical threshold or 83.8 +- 3.0 kcal/mole above the ground state. Comparison with uv data indicate that RRKM theory is an acceptable description of formaldehyde dissociation in the 5 to 10 torr pressure range. The unimolecular decomposition of tetralin was studied by MPD and SiF/sub 4/ - sensitized pyrolysis. Both techniques induce decomposition without the interference of catalytic surfaces. Ethylene loss is identified as the lowest energy reaction channel. Dehydrogenation is found to result from step-wise H atom loss. Isomerization via disproportionation is also identified as a primary reaction channel.

  3. A classical approach in simple nuclear fusion reaction {sub 1}H{sup 2}+{sub 1}H{sup 3} using two-dimension granular molecular dynamics model

    SciTech Connect

    Viridi, S.; Kurniadi, R.; Waris, A.; Perkasa, Y. S.

    2012-06-06

    Molecular dynamics in 2-D accompanied by granular model provides an opportunity to investigate binding between nuclei particles and its properties that arises during collision in a fusion reaction. A fully classical approach is used to observe the influence of initial angle of nucleus orientation to the product yielded by the reaction. As an example, a simplest fusion reaction between {sub 1}H{sup 2} and {sub 1}H{sup 3} is observed. Several products of the fusion reaction have been obtained, even the unreported ones, including temporary {sub 2}He{sup 4} nucleus.

  4. A Classical Approach in Simple Nuclear Fusion Reaction 1H2 + 1H3 using Two-Dimension Granular Molecular Dynamics Model

    E-print Network

    Sparisoma Viridi; Rizal Kurniadi; Abdul Waris; Yudha Satya Perkasa

    2011-09-30

    Molecular dynamics in 2-D accompanied by granular model provides an opportunity to investigate binding between nuclei particles and its properties that arises during collision in a fusion reaction. A fully classical approach is used to observe the influence of initial angle of nucleus orientation to the product yielded by the reaction. As an example, a simplest fusion reaction between 1H2 and 1H3 is observed. Several products of the fusion reaction have been obtained, even the unreported ones, including temporary 2He4 nucleus.

  5. FT-IR and {sup 1}H NMR characterization of the products of an ethylene inverse diffusion flame

    SciTech Connect

    Santamaria, Alexander; Mondragon, Fanor; Molina, Alejandro; Marsh, Nathan D.; Eddings, Eric G.; Sarofim, Adel F.

    2006-07-15

    Knowledge of the chemical structure of young soot and its precursors is very useful in the understanding of the paths leading to soot particle inception. This paper presents analyses of the chemical functional groups, based on FT-IR and {sup 1}H NMR spectroscopy of the products obtained in an ethylene inverse diffusion flame. The trends in the data indicate that the soluble fraction of the soot becomes progressively more aromatic and less aliphatic as the height above the burner increases. Results from {sup 1}H NMR spectra of the chloroform-soluble soot samples taken at different heights above the burner corroborate the infrared results based on proton chemical shifts (Ha, H{alpha}, H{beta}, and H{gamma}). The results indicate that the aliphatic {beta} and {gamma} hydrogens suffered the most drastic reduction, while the aromatic character increased considerably with height, particularly in the first half of the flame. (author)

  6. Experimental (FT-IR, FT-Raman, 1H, 13C NMR) and theoretical study of alkali metal syringates

    NASA Astrophysics Data System (ADS)

    ?wis?ocka, Renata

    2013-07-01

    In this work the influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the syringic acid (4-hydroxy-3,5-dimethoxybenzoic acid) was studied. This paper presents spectroscopic vibrations (FT-IR, FT-Raman) and NMR (1H and 13C) study of the series of alkali metal syringates from lithium to cesium syringates. Characteristic shifts of band wavenumbers and changes in band intensities along the metal series were observed. Optimized geometrical structures of the studied compounds were calculated by the B3LYP method using the 6-311++G?? basis set. Aromaticity indices, atomic charges, dipole moments and energies were also calculated. The theoretical wavenumbers and intensities of IR and NMR spectra were obtained. The calculated parameters were compared to experimental characteristics of studied compounds.

  7. Experimental (FT-IR, FT-Raman, 1H, 13C NMR) and theoretical study of alkali metal syringates.

    PubMed

    ?wis?ocka, Renata

    2013-07-01

    In this work the influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the syringic acid (4-hydroxy-3,5-dimethoxybenzoic acid) was studied. This paper presents spectroscopic vibrations (FT-IR, FT-Raman) and NMR ((1)H and (13)C) study of the series of alkali metal syringates from lithium to cesium syringates. Characteristic shifts of band wavenumbers and changes in band intensities along the metal series were observed. Optimized geometrical structures of the studied compounds were calculated by the B3LYP method using the 6-311++G(**) basis set. Aromaticity indices, atomic charges, dipole moments and energies were also calculated. The theoretical wavenumbers and intensities of IR and NMR spectra were obtained. The calculated parameters were compared to experimental characteristics of studied compounds. PMID:23664591

  8. Experimental (FT-IR, FT-Raman, 1H, 13C NMR) and theoretical study of alkali metal 2-aminobenzoates

    NASA Astrophysics Data System (ADS)

    Samsonowicz, M.; ?wis?ocka, R.; Regulska, E.; Lewandowski, W.

    2008-09-01

    The influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the 2-aminobenzoic acid was studied by the methods of molecular spectroscopy. The vibrational (FT-IR, FT-Raman) and NMR ( 1H and 13C) spectra for 2-aminobenzoic acid and its alkali metal salts were recorded. The assignment of vibrational spectra was done on the basis of literature data, theoretical calculations and our previous experience. Characteristic shifts of bands and changes in intensities of bands along the metal series were observed. The changes of chemical shifts of protons ( 1H NMR) and carbons ( 13C NMR) in the series of studied alkali metal 2-aminobenzoates were observed too. Optimized geometrical structures of studied compounds were calculated by B3LYP method using 6-311++G ?? basis set. Geometric aromaticity indices, dipole moments and energies were also calculated. The theoretical wavenumbers and intensities of IR and Raman spectra were obtained. The calculated parameters were compared to experimental characteristic of studied compounds.

  9. L-glutamine: Dynamical properties investigation by means of INS, IR, RAMAN, 1H NMR and DFT techniques

    NASA Astrophysics Data System (ADS)

    Pawlukoj?, A.; Ho?derna-Natkaniec, K.; Bator, G.; Natkaniec, I.

    2014-10-01

    Vibrational spectra of L-glutamine in the solid state were studied using the inelastic neutron scattering (INS), infrared (IR), Raman and 1H NMR spectroscopy techniques. DFT calculation using CASTEP code with the periodic boundary conditions was used to determine and describe the normal modes in the vibrational spectra of pure L-glutamine. An excellent agreement between the calculated and experimental INS, IR and Raman data has been found. Bands assigned to the stretching vibrations of the NH3+ group in hydrogen bonds are observed at 2400, 2618 and 2619 cm-1, while the NH3+ torsion vibration mode is observed at 441 cm-1. The band at 2041 cm-1 is assigned to combinations of the NH3+ bending symmetry vibration and the CO2- rocking vibration and can be used as an "indicator band" for the identification of the NH3+ groups in amino acid. For the L-glutamine an activation energy needed for the NH3+ group reorientation was obtained as 7.4 kcal/mol. It was found, that the combination three spectroscopic methods (INS, IR and Raman) with calculations for the crystal state proved to be an effective tool to investigate dynamical properties of amino acid crystals.

  10. Conformational studies of DL-lactaldehyde by 1H-NMR, Raman and i.r. spectroscopy

    NASA Astrophysics Data System (ADS)

    Takahashi, Hiroaki; Kobayashi, Yoko; Kaneko, Norio

    1H-NMR, Raman and i.r. spectra of DL-lactaldehyde reveal that this compound crystallizes in three different crystal forms. All of them consist of hemiacetal dimers having the same 1,4-dioxane ring skeleton but with different configurations (e,e), (e,a) and (a,a) with respect to the two OH groups attached to the ring (e and a denote equatorial and axial, respectively). In addition to these three species, the monomer and at least one five-membered ring dimer, though both in negligibly small amount, exist in equilibrium solution. The most easily obtainable species in the crystalline state has the centrosymmetric configuration (a,a) which is least populated in solution. The existence of the crystal form which consists of non-centrosymmetric dimers having the (e,a) configuration is in contrast to simple carbohydrates such as glycolaldehyde, glyceraldehyde and 1,3-dihydroxyacetone which crystallize only as centrosymmetric dimers.

  11. IR, 1H NMR, mass, XRD and TGA/DTA investigations on the ciprofloxacin/iodine charge-transfer complex

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; El-Hawary, W. F.; Moussa, Mohamed A. A.

    2011-05-01

    The charge-transfer complex (CTC) of ciprofloxacin drug (CIP) as a donor with iodine (I 2) as a sigma acceptor has been studied spectrophotometrically in CHCl 3. At maximum absorption bands, the stoichiometry of CIP:iodine system was found to be 1:1 ratio according to molar ratio method. The essential spectroscopic data like formation constant ( KCT), molar extinction coefficient ( ?CT), standard free energy (? G°), oscillator strength ( f), transition dipole moment ( ?), resonance energy ( RN) and ionization potential ( ID) were estimated. The spectroscopic techniques such as IR, 1H NMR, mass and UV-vis spectra and elemental analyses (CHN) as well as TG-DTG and DTA investigations were used to characterize the chelating behavior of CIP/iodine charge-transfer complex. The iodine CT interaction was associated with a presence of intermolecular hydrogen bond. The X-ray investigation was carried out to investigate the iodine doping in the synthetic CT complex.

  12. Simultaneous 19F-1H medium resolution NMR spectroscopy for online reaction monitoring

    NASA Astrophysics Data System (ADS)

    Zientek, Nicolai; Laurain, Clément; Meyer, Klas; Kraume, Matthias; Guthausen, Gisela; Maiwald, Michael

    2014-12-01

    Medium resolution nuclear magnetic resonance (MR-NMR) spectroscopy is currently a fast developing field, which has an enormous potential to become an important analytical tool for reaction monitoring, in hyphenated techniques, and for systematic investigations of complex mixtures. The recent developments of innovative MR-NMR spectrometers are therefore remarkable due to their possible applications in quality control, education, and process monitoring. MR-NMR spectroscopy can beneficially be applied for fast, non-invasive, and volume integrating analyses under rough environmental conditions. Within this study, a simple 1/16? fluorinated ethylene propylene (FEP) tube with an ID of 0.04? (1.02 mm) was used as a flow cell in combination with a 5 mm glass Dewar tube inserted into a benchtop MR-NMR spectrometer with a 1H Larmor frequency of 43.32 MHz and 40.68 MHz for 19F. For the first time, quasi-simultaneous proton and fluorine NMR spectra were recorded with a series of alternating 19F and 1H single scan spectra along the reaction time coordinate of a homogeneously catalysed esterification model reaction containing fluorinated compounds. The results were compared to quantitative NMR spectra from a hyphenated 500 MHz online NMR instrument for validation. Automation of handling, pre-processing, and analysis of NMR data becomes increasingly important for process monitoring applications of online NMR spectroscopy and for its technical and practical acceptance. Thus, NMR spectra were automatically baseline corrected and phased using the minimum entropy method. Data analysis schemes were designed such that they are based on simple direct integration or first principle line fitting, with the aim that the analysis directly revealed molar concentrations from the spectra. Finally, the performance of 1/16? FEP tube set-up with an ID of 1.02 mm was characterised regarding the limit of detection (LOQ (1H) = 0.335 mol L-1 and LOQ (19F) = 0.130 mol L-1 for trifluoroethanol in D2O (single scan)) and maximum quantitative flow rates up to 0.3 mL min-1. Thus, a series of single scan 19F and 1H NMR spectra acquired with this simple set-up already presents a valuable basis for quantitative reaction monitoring.

  13. Discovering [superscript 13]C NMR, [superscript 1]H NMR, and IR Spectroscopy in the General Chemistry Laboratory through a Sequence of Guided-Inquiry Exercises

    ERIC Educational Resources Information Center

    Iler, H. Darrell; Justice, David; Brauer, Shari; Landis, Amanda

    2012-01-01

    This sequence of three guided-inquiry labs is designed for a second-semester general chemistry course and challenges students to discover basic theoretical principles associated with [superscript 13]C NMR, [superscript 1]H NMR, and IR spectroscopy. Students learn to identify and explain basic concepts of magnetic resonance and vibrational…

  14. 1H(d,2p)n reaction at 2 GeV deuteron energy

    NASA Astrophysics Data System (ADS)

    Erohuml, J.; Fodor, Z.; Koncz, P.; Seres, Z.; Perdrisat, C. F.; Punjabi, V.; Boudard, A.; Bonin, B.; Garçon, M.; Lombard, R.; Mayer, B.; Terrien, Y.; Tomasi, E.; Boivin, M.; Yonnet, J.; Bhang, H. C.; Youn, M.; Belostotsky, S. L.; Grebenuk, O. G.; Nikulin, V. N.; Kudin, L. G.

    1994-12-01

    The 1H(d,2p)n deuteron breakup reaction was measured at 2 GeV deuteron energy in a kinematically complete experiment. Fivefold differential cross sections are given in a wide range of kinematical variables and analyzed in terms of impulse approximation and NN rescattering. The deuteron momentum density was determined and deviations were found depending on the value of the four-momentum transfer ||t|| in the scattering process. At low ||t|| the momentum densities are in good agreement with the impulse approximation whereas large discrepancies were found above q~=200 MeV/c when the four-momentum transfer was large. Various possible origins of the anomalous behavior at high q values are discussed.

  15. Induced Polarization in the $^2$H($?,\\vec n$)$^1$H Reaction at Low Energy

    E-print Network

    R. Schiavilla

    2005-05-25

    The induced polarization, $P^\\prime_y$, of the neutron in the deuteron photo-disintegration from threshold up to 30 MeV is calculated using a variety of different, latest-generation potentials--Argonne $v_{18}$, Bonn 2000, and Nijmegen I-- and a realistic model for the nuclear electromagnetic current operator, including one- and two-body terms. The model dependence of the theoretical predictions is found to be very small. These predictions are systematically larger in magnitude than the measured $P^\\prime_y$ values, and corroborate the conclusions of an earlier, and much older, study. There is considerable scatter in the available experimental data. New and more accurate measurements of the induced polarization in the $^2$H($\\gamma,\\vec n$)$^1$H reaction are needed in order to establish unequivocally whether there is a discrepancy between theory and experiment.

  16. IR spectra and structure of 1-H-isoindole-1,3(2H)-dione (phthalimide), cis-hexahydro-1-H-isoindole-1,3(2H)-dione (hexahydrophthalimide) and of their nitranions

    NASA Astrophysics Data System (ADS)

    Binev, I. G.; Stamboliyska, B. A.; Binev, Y. I.; Velcheva, E. A.; Tsenov, J. A.

    1999-12-01

    The spectral and structural changes, accompanying the conversions of 1-H-isoindole-1,3(2H)-dione (phthalimide) and its cis-hexahydro derivative into the corresponding nitranions have been observed through IR spectra. These conversions lead to a strong decrease in carbonyl stretching frequencies ?COs by 74 cm -1 and ?COas by 134 cm -1 (mean values), a two-fold increase in the ?CO spliting, etc. According to ab initio MO calculations, greater parts of anionic charges are delocalized within carbonyl groups. The alkali-metal derivatives of the imides studied mainly exist in the dimethyl sulphoxide as free solvated ions.

  17. FT-IR, 1H, 13C NMR, ESI-MS and semiempirical investigation of the structures of Monensin phenyl urethane complexes with the sodium cation.

    PubMed

    Huczy?ski, Adam

    2013-06-01

    In this paper three forms of phenyl urethane of Monensin i.e. its acid form (H-MU) and its 1:1 complex with NaClO4 (H-MU-Na) and its sodium salt (Na-MU) were obtained and their structures were studied by FT-IR, (1)H and (13)C NMR, ESI MS and PM5 methods. The FT-IR data of Na-MU complexes demonstrate that the C=O urethane group is not engaged in the complexation of the sodium cation. However spectroscopic studies of H-MU-Na complex show that the structure in which this C=O urethane groups participate in the complexation is also present, but it is in the minority. The PM5 semiempirical calculations allow visualisation of all structures and determination of the hydrogen bond parameters. PMID:23578536

  18. Elucidation of solution state complexation in wet-granulated oven-dried ibuprofen and beta-cyclodextrin: FT-IR and 1H-NMR studies.

    PubMed

    Ghorab, M K; Adeyeye, M C

    2001-08-01

    The effect of oven-dried wet granulation on the complexation of beta-cyclodextrin with ibuprofen (IBU) in solution was investigated using Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance (1H NMR), and molecular modeling. Granulation was carried out using 5 mL of three different granulating solvents; water, ethanol (95% v/v), and isopropanol and the granules were oven-dried at 60 degrees C for 2 h. The granules were compared to oven-dried physical mixture and conventionally prepared complex. Phase solubility study was performed to investigate the stability of the granulation-formed complexes in solution. FT-IR was used to examine the complexation in the granules while 1H NMR, and molecular modeling studies were carried out to determine the mechanism of complexation in the water-prepared granules. The solubility studies suggested a 1:1 complex between IBU and betaCD. It also showed that the stability of the complex in solution was in the following order with respect to the granulating solvents: ethanol > water > isopropanol. The FT-IR study revealed a shift in the carboxylic acid stretching band and decrease in the intensities of the C-H bending bands of the isopropyl group and the out-of-plane aromatic ring, of IBU, in granules compared to the oven-dried physical mixture. This indicated that granules might have some extent of solid state complexation that could further enhance dissolution and the IBU-betaCD solution state complexation. 1H NMR showed that water prepared oven-dried granules had a different 1H NMR spectrum compared to similarly made oven-dried physical mixture, indicative of complexation in the former. The 1H NMR and the molecular modeling studies together revealed that solution state complexation from the granules occurred by inclusion of the isopropyl group together with part of the aromatic ring of IBU into the betaCD cavity probably through its wider side. These results indicate that granulation process induced faster complexation in solution which enhances the solubility and the dissolution rate of poorly soluble drugs. The extent of complexation in the granules was dependent on the type of solvent used. PMID:11485173

  19. Studying a Ligand Substitution Reaction with Variable Temperature 1H NMR Spectroscopy: An Experiment for Undergraduate Inoganic Chemistry Students

    NASA Astrophysics Data System (ADS)

    Orvis, Jeffery A.; Dimetry, Basant; Winge, Jeffery; Corbin Mullis, T.

    2003-07-01

    The study of ligand substitution reactions of transition metal complexes is often a significant component of undergraduate courses in inorganic chemistry. In the laboratory, many undergraduates have studied the aquation of [Co(NH3)5Cl]2+at elevated temperatures, taking aliquots of the reaction mixture, and obtaining a series of UV vis spectra. Recently, an improved synthesis of a similar complex, trans-[Co(NH3)4Cl2]+ was reported. This complex undergoes aquation in less than an hour at room temperature, much faster than [Co(NH3)5Cl]2+, and is readily monitored by 1H NMR spectroscopy. This reaction forms the basis of an instructive, multi-week laboratory experience in inorganic synthesis, followed by an analysis of a reaction mechanism using a classical activation parameter determination.

  20. FT-IR, FT-Raman, dispersive Raman, NMR spectroscopic studies and NBO analysis of 2-Bromo-1H-Benzimidazol by density functional method

    NASA Astrophysics Data System (ADS)

    Sas, E. B.; Kurt, M.; Karabacak, M.; Poiyamozhi, A.; Sundaraganesan, N.

    2015-02-01

    In this study, geometrical optimization, FT-IR (4000-400 cm-1), FT-Raman (4000-40 cm-1), dispersive Raman (4000-40 cm-1) spectroscopic analysis, electronic structure and 1H and 13C nuclear magnetic resonance (NMR) studies of 2-Bromo-1H-Benzimidazol (abbreviated as 2Br1HB) were undertaken by utilizing DFT/B3LYP with 6-311+G(d,p) basis set. The results of the calculations were applied to simulate spectra of the title compound, which show good agreement with observed spectra. Complete vibrational assignments, analysis and correlations of the fundamental modes for 2Br1HB compound were carried out. Stability of the molecule arising from hyperconjugative interactions, charge delocalization was analyzed using natural bond orbital (NBO) analysis. The molecule orbital contributions were studied by using the total density of states (TDOS), partial density of states (PDOS), and overlap population density of states (OPDOS). The electronic properties like HOMO-LUMO energies and molecular electrostatic potential (MEP) analysis were reported. The calculated HOMO and LUMO energies shows that charge transfer interactions take place within the molecule. Mulliken population analysis on atomic charges was also calculated. Good correlation between the experimental 1H and 13C NMR chemical shifts in DMSO solution and calculated gauge-including atomic orbital (GIAO) shielding tensors were found.

  1. Communication: Enhanced oxygen reduction reaction and its underlying mechanism in Pd-Ir-Co trimetallic alloys

    SciTech Connect

    Ham, Hyung Chul; Hwang, Gyeong S.; Manogaran, Dhivya; Lee, Kang Hee; Jin, Seon-ah; You, Dae Jong; Pak, Chanho; Kwon, Kyungjung

    2013-11-28

    Based on a combined density functional theory and experimental study, we present that the electrochemical activity of Pd{sub 3}Co alloy catalysts toward oxygen reduction reaction (ORR) can be enhanced by adding a small amount of Ir. While Ir tends to favorably exist in the subsurface layers, the underlying Ir atoms are found to cause a substantial modification in the surface electronic structure. As a consequence, we find that the activation barriers of O/OH hydrogenation reactions are noticeably lowered, which would be mainly responsible for the enhanced ORR activity. Furthermore, our study suggests that the presence of Ir in the near-surface region can suppress Co out-diffusion from the Pd{sub 3}Co substrate, thereby improving the durability of Pd-Ir-Co catalysts. We also discuss the relative roles played by Ir and Co in enhancing the ORR activity relative to monometallic Pd catalysts.

  2. Communication: Enhanced oxygen reduction reaction and its underlying mechanism in Pd-Ir-Co trimetallic alloys

    NASA Astrophysics Data System (ADS)

    Ham, Hyung Chul; Manogaran, Dhivya; Lee, Kang Hee; Kwon, Kyungjung; Jin, Seon-ah; You, Dae Jong; Pak, Chanho; Hwang, Gyeong S.

    2013-11-01

    Based on a combined density functional theory and experimental study, we present that the electrochemical activity of Pd3Co alloy catalysts toward oxygen reduction reaction (ORR) can be enhanced by adding a small amount of Ir. While Ir tends to favorably exist in the subsurface layers, the underlying Ir atoms are found to cause a substantial modification in the surface electronic structure. As a consequence, we find that the activation barriers of O/OH hydrogenation reactions are noticeably lowered, which would be mainly responsible for the enhanced ORR activity. Furthermore, our study suggests that the presence of Ir in the near-surface region can suppress Co out-diffusion from the Pd3Co substrate, thereby improving the durability of Pd-Ir-Co catalysts. We also discuss the relative roles played by Ir and Co in enhancing the ORR activity relative to monometallic Pd catalysts.

  3. Investigation of the Exclusive {sup 3}He(e,e{sup '}pn){sup 1}H Reaction

    SciTech Connect

    Middleton, D. G.; Grabmayr, P.; Hehl, T.; Heim, J.; Martin, I.; Moschini, F.; Annand, J. R. M.; Glazier, D. I.; MacGregor, I. J. D.; McGeorge, J. C.; Monstad, K.; Rosner, G.; Watts, D. P.; Antelo, M. Ases; Ayerbe, C.; Baumann, D.; Bermuth, J.; Bernauer, J.; Boehm, R.; Ding, M.

    2009-10-09

    Cross sections for the {sup 3}He(e,e{sup '}pn){sup 1}H reaction were measured for the first time at energy transfers of 220 and 270 MeV for several momentum transfers ranging from 300 to 450 MeV/c. Cross sections are presented as a function of the momentum of the recoil proton and the momentum transfer. Continuum Faddeev calculations using the Argonne V18 and Bonn-B nucleon-nucleon potentials overestimate the measured cross sections by a factor 5 at low recoil proton momentum with the discrepancy becoming smaller at higher recoil proton momentum.

  4. Conformational analysis, spectroscopic study (FT-IR, FT-Raman, UV, 1H and 13C NMR), molecular orbital energy and NLO properties of 5-iodosalicylic acid

    NASA Astrophysics Data System (ADS)

    Karaca, Caglar; Atac, Ahmet; Karabacak, Mehmet

    2015-02-01

    In this study, 5-iodosalicylic acid (5-ISA, C7H5IO3) is structurally characterized by FT-IR, FT-Raman, NMR and UV spectroscopies. There are eight conformers, Cn, n = 1-8 for this molecule therefore the molecular geometry for these eight conformers in the ground state are calculated by using the ab-initio density functional theory (DFT) B3LYP method approach with the aug-cc-pVDZ-PP basis set for iodine and the aug-cc-pVDZ basis set for the other elements. The computational results identified that the most stable conformer of 5-ISA is the C1 form. The vibrational spectra are calculated DFT method invoking the same basis sets and fundamental vibrations are assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method with PQS program. Total density of state (TDOS) and partial density of state (PDOS) and also overlap population density of state (COOP or OPDOS) diagrams analysis for C1 conformer were calculated using the same method. The energy and oscillator strength are calculated by time-dependent density functional theory (TD-DFT) results complement with the experimental findings. Besides, charge transfer occurring in the molecule between HOMO and LUMO energies, frontier energy gap, molecular electrostatic potential (MEP) are calculated and presented. The NMR chemical shifts (1H and 13C) spectra are recorded and calculated using the gauge independent atomic orbital (GIAO) method. Mulliken atomic charges of the title molecule are also calculated, interpreted and compared with salicylic acid. The optimized bond lengths, bond angles and calculated NMR and UV, vibrational wavenumbers showed the best agreement with the experimental results.

  5. Conformational analysis, spectroscopic study (FT-IR, FT-Raman, UV, 1H and 13C NMR), molecular orbital energy and NLO properties of 5-iodosalicylic acid.

    PubMed

    Karaca, Caglar; Atac, Ahmet; Karabacak, Mehmet

    2015-02-01

    In this study, 5-iodosalicylic acid (5-ISA, C7H5IO3) is structurally characterized by FT-IR, FT-Raman, NMR and UV spectroscopies. There are eight conformers, Cn, n=1-8 for this molecule therefore the molecular geometry for these eight conformers in the ground state are calculated by using the ab-initio density functional theory (DFT) B3LYP method approach with the aug-cc-pVDZ-PP basis set for iodine and the aug-cc-pVDZ basis set for the other elements. The computational results identified that the most stable conformer of 5-ISA is the C1 form. The vibrational spectra are calculated DFT method invoking the same basis sets and fundamental vibrations are assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method with PQS program. Total density of state (TDOS) and partial density of state (PDOS) and also overlap population density of state (COOP or OPDOS) diagrams analysis for C1 conformer were calculated using the same method. The energy and oscillator strength are calculated by time-dependent density functional theory (TD-DFT) results complement with the experimental findings. Besides, charge transfer occurring in the molecule between HOMO and LUMO energies, frontier energy gap, molecular electrostatic potential (MEP) are calculated and presented. The NMR chemical shifts ((1)H and (13)C) spectra are recorded and calculated using the gauge independent atomic orbital (GIAO) method. Mulliken atomic charges of the title molecule are also calculated, interpreted and compared with salicylic acid. The optimized bond lengths, bond angles and calculated NMR and UV, vibrational wavenumbers showed the best agreement with the experimental results. PMID:25448933

  6. Structural and Electrocatalytic Properties of PtIrCo/C Catalysts for Oxygen Reduction Reaction

    SciTech Connect

    Loukrakpam, Rameshwori; Wanjala, Bridgid N.; Yin, Jun; Fang, Bin; Luo, Jin; Shao, Minhua; Protsailo, Lesia; Kawamura, Tetsuo; Chen, Yongsheng; Petkov, Valeri; Zhong, Chuan-Jian

    2015-10-15

    This paper describes the results of an investigation of the synthesis of PtIrCo nanoparticles (2-3 nm) for electrocatalytic oxygen reduction reaction. The carbon-supported PtIrCo catalysts (PtIrCo/C) were thermally treated at temperatures ranging from 400 to 900 C. The size, composition, and atomic-scale structures of the PtIrCo/C catalysts were characterized for establishing their correlation with the electrocatalytic activity toward oxygen reduction reaction. The specific activity was found to increase by a factor of 3-5 for the PtIrCo/C catalysts in comparison with Pt/C catalysts. A correlation was identified between the specific activity and the nanoparticle's fcc-type lattice parameter. The specific activity increases whereas the fcc-type lattice parameter decreases with the thermal treatment temperature. This correlation was further substantiated by analyzing the interatomic spatial parameters in the trimetallic nanoparticles based on X-ray absorption fine structure spectroscopic and high-energy XRD experiments. Implications of these findings, along with the durability of the catalysts, to the design of active electrocatalysts were also discussed.

  7. High Catalytic Activity of Amorphous Ir-Pi for Oxygen Evolution Reaction.

    PubMed

    Irshad, Ahamed; Munichandraiah, Nookala

    2015-07-29

    Large-scale production of hydrogen gas by water electrolysis is hindered by the sluggish kinetics of oxygen evolution reaction (OER) at the anode. The development of a highly active and stable catalyst for OER is a challenging task. Electrochemically prepared amorphous metal-based catalysts have gained wide attention after the recent discovery of a cobalt-phosphate (Co-Pi) catalyst. Herein, an amorphous iridium-phosphate (Ir-Pi) is investigated as an oxygen evolution catalyst. The catalyst is prepared by the anodic polarization of carbon paper electrodes in neutral phosphate buffer solutions containing IrCl3. The Ir-Pi film deposited on the substrate has significant amounts of phosphate and Ir centers in an oxidation state higher than +4. Phosphate plays a significant role in the deposition of the catalyst and also in its activity toward OER. The onset potential of OER on the Ir-Pi is about 150 mV lower in comparison with the Co-Pi under identical experimental conditions. Thus, Ir-Pi is a promising catalyst for electrochemical oxidation of water. PMID:26132593

  8. BIGINELLI REACTION IN AQUEOUS MEDIUM: A GREENER AND SUSTAINABLE APPROACH TO SUBSTITUTED 3,4-DIHYDROPYRIMIDIN-2(1H)-ONES

    EPA Science Inventory

    An environmentally benign aqueous Biginelli protocol for the synthesis of substituted 3,4-dihydropyrimidin-2(1H)-ones using polystyrenesulfonic acid (PSSA) as a catalyst has been achieved. These microwave-assisted reactions proceed efficiently in water in the absence of organic s...

  9. Synthesis of Functionalized Chromeno[2,3-b]pyrrol-4(1H)-ones by Silver-Catalyzed Cascade Reactions of Chromones/Thiochromones and Isocyanoacetates.

    PubMed

    Qi, Xueyu; Xiang, Haoyue; Yang, Chunhao

    2015-11-20

    A novel and convenient approach to the synthesis of chromeno[2,3-b]pyrrol-4(1H)-ones has been developed. Furthermore, the method involves a facile silver-catalyzed cascade cyclization reaction including an intramolecular C-O bond formation. The silver salt acts as a key promoter. PMID:26562216

  10. Unexpected Synthesis of 5,6-Dihydropyridin-2(1H)-ones by a Domino Ugi/Aldol/Hydrolysis Reaction Starting from Baylis-Hillman Phosphonium Salts.

    PubMed

    Zeng, Xiao-Hua; Wang, Hong-Mei; Ding, Ming-Wu

    2015-05-01

    A one-pot synthetic approach to 5,6-dihydropyridin-2(1H)-ones has been developed using a domino process involving Ugi, aldol, and hydrolysis reactions, starting with Baylis-Hillman phosphonium salts, primary amines, isocyanides, and arylglyoxals. PMID:25875533

  11. Separation of the longitudinal and transverse cross sections in the {sup 1}H(e,e{prime} K{sup +}){Lambda} and {sup 1}H(e,e{prime} K{sup +}){Sigma}{sup 0} reactions

    SciTech Connect

    R.M. Mohring; David Abbott; Abdellah Ahmidouch; Thomas Amatuni; Pawel Ambrozewicz; Tatiana Angelescu; Christopher Armstrong; John Arrington; Ketevi Assamagan; Steven Avery; Kevin Bailey; Kevin Beard; S Beedoe; Elizabeth Beise; Herbert Breuer; Roger Carlini; Jinseok Cha; C. Chang; Nicholas Chant; Evaristo Cisbani; Glenn Collins; William Cummings; Samuel Danagoulian; Raffaele De Leo; Fraser Duncan; James Dunne; Dipangkar Dutta; T Eden; Rolf Ent; Laurent Eyraud; Lars Ewell; John Finn; H. Terry Fortune; Valera Frolov; Salvatore Frullani; Christophe Furget; Franco Garibaldi; David Gaskell; Donald Geesaman; Paul Gueye; Kenneth Gustafsson; Jens-Ole Hansen; Mark Harvey; Wendy Hinton; Ed Hungerford; Mauro Iodice; Ceasar Jackson; Cynthia Keppel; Wooyoung Kim; Kouichi Kino; Douglas Koltenuk; Serge Kox; Laird Kramer; Antonio Leone; Allison Lung; David Mack; Richard Madey; M Maeda; Stanislaw Majewski; Pete Markowitz; T Mart; C Martoff; David Meekins; A. Mihul; Joseph Mitchell; Hamlet Mkrtchyan; Sekazi Mtingwa; Maria-Ioana Niculescu; R. Perrino; David Potterveld; John Price; Brian Raue; Jean Sebastien Real; Joerg Reinhold; Philip Roos; Teijiro Saito; Geoff Savage; Reyad Sawafta; Ralph Segel; Stepan Stepanyan; Paul Stoler; Vardan Tadevosyan; Liguang Tang; Liliana Teodorescu; Tatsuo Terasawa; Hiroaki Tsubota; Guido Urciuoli; Jochen Volmer; William Vulcan; T. Welch; Robert Williams; Stephen Wood; Chen Yan; Benjamin Zeidman

    2003-05-19

    We report measurements of cross sections for the reaction {sup 1}H(e,e{prime} K{sup +})Y, for both the {Lambda} and {Sigma}{sup 0} hyperon states, at an invariant mass of W = 1.84 GeV and four-momentum transfers 0.5 < Q{sup 2} < 2 (GeV/c){sup 2}. Data were taken for three values of virtual photon polarization {epsilon}, allowing the decomposition of the cross sections into longitudinal and transverse components. The {Lambda} data are a revised analysis of prior work, whereas the {Sigma}{sup 0} results have not been previously reported.

  12. The spectroscopic (FT-IR, FT-Raman, l3C, 1H NMR and UV) and NBO analyses of 4-bromo-1-(ethoxycarbonyl)piperidine-4-carboxylic acid

    NASA Astrophysics Data System (ADS)

    Vitnik, Vesna D.; Vitnik, Željko J.

    2015-03-01

    In this work, we will report a combined experimental and theoretical study on molecular and vibrational structure of 4-bromo-1-(ethoxycarbonyl)piperidine-4-carboxylic acid (BEPA). BEPA has been characterized by FT-IR, FT-Raman, 1H NMR, 13C NMR and UV spectroscopy. The FT-IR and FT-Raman spectra of BEPA were recorded in the solid phase. The optimized geometry was calculated by B3LYP and M06-2X methods using 6-311G(d,p) basis set. The FT-IR and FT-Raman spectra of BEPA were calculated at the same level and were interpreted in terms of Potential Energy Distribution (PED) analysis. The scaled theoretical wavenumber showed very good agreement with the experimental values. The 1H and l3C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the Gauge-Independent Atomic Orbital (GIAO) method. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using Natural Bond Orbital (NBO) analysis. Density plots over the highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbitals (LUMO) energy surface directly identifies the donor and acceptor atoms in the molecule. It also provides information about the charge transfer within the molecule. To obtain chemical reactivity of the molecule, the molecular electrostatic potential (MEP) surface map is plotted over the optimized geometry of the molecule.

  13. Three Component Reaction: An Efficient Synthesis and Reactions of 3,4-Dihydropyrimidin-2(1H)-Ones and Thiones Using New Natural Catalyst

    PubMed Central

    Elmaghraby, A. M.; Mousa, I. A.; Harb, A. A.; Mahgoub, M. Y.

    2013-01-01

    Synthesis of 3,4-dihydropyrimidin-2(1H)-one and 3,4-dihydropyrimidin-2(1H)-thione derivatives from aldehydes, 1,3-dicarbonyl derivatives and urea or thiourea using granite and quartz as new, natural and reusable catalysts. Some of the 3,4-dihydropyrimidin-2(1H)-thione derivatives were used to prepare new heterocyclic compounds. The antimicrobial activity of selected examples of the synthesized compounds was tested and showed moderate activity. PMID:24052868

  14. Spectroscopic (FT-IR, FT-Raman, UV absorption, 1H and 13C NMR) and theoretical (in B3LYP/6-311++G** level) studies on alkali metal salts of caffeic acid.

    PubMed

    ?wis?ocka, Renata

    2013-01-01

    The effect of some metals on the electronic system of benzoic and nicotinic acids has recently been investigated by IR, Raman and UV spectroscopy [1-3]. Benzoic and nicotinic acids are regarded model systems representing a wide group of aromatic ligands which are incorporated into enzymes. In this work the FT-IR (in solid state and in solution), FT-Raman, UV absorption and (1)H and (13)C NMR spectra of caffeic acid (3,4-dihydroxycinnamic acid) and its salts with lithium, sodium, potassium, rubidium and caesium were registered, assigned and analyzed. The effect of alkali metals on the electronic system of ligands was discussed. Studies of differences in the number and position of bands from the IR, Raman, UV absorption spectra and chemical shifts from NMR spectra allowed to conclude on the distribution of electronic charge in the molecules, the delocalization energy of ? electrons and the reactivity of ligands in metal complexes. Optimized geometrical structures of studied compounds were calculated by B3LYP method using 6-311++G** basis set. Bond lengths, angles and dipole moments for the optimized structures of caffeic acid and lithium, sodium, potassium caffeinates were also calculated. The theoretical wavenumbers and intensities of IR spectra were obtained. The calculated parameters were compared to the experimental characteristics of investigated compounds. Microbial activity of studied compounds was tested against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Proteus vulgaris. PMID:22369898

  15. Spectroscopic (FT-IR, FT-Raman, UV absorption, 1H and 13C NMR) and theoretical (in B3LYP/6-311++G** level) studies on alkali metal salts of caffeic acid

    NASA Astrophysics Data System (ADS)

    ?wis?ocka, Renata

    The effect of some metals on the electronic system of benzoic and nicotinic acids has recently been investigated by IR, Raman and UV spectroscopy [1-3]. Benzoic and nicotinic acids are regarded model systems representing a wide group of aromatic ligands which are incorporated into enzymes. In this work the FT-IR (in solid state and in solution), FT-Raman, UV absorption and 1H and 13C NMR spectra of caffeic acid (3,4-dihydroxycinnamic acid) and its salts with lithium, sodium, potassium, rubidium and caesium were registered, assigned and analyzed. The effect of alkali metals on the electronic system of ligands was discussed. Studies of differences in the number and position of bands from the IR, Raman, UV absorption spectra and chemical shifts from NMR spectra allowed to conclude on the distribution of electronic charge in the molecules, the delocalization energy of ? electrons and the reactivity of ligands in metal complexes. Optimized geometrical structures of studied compounds were calculated by B3LYP method using 6-311++G** basis set. Bond lengths, angles and dipole moments for the optimized structures of caffeic acid and lithium, sodium, potassium caffeinates were also calculated. The theoretical wavenumbers and intensities of IR spectra were obtained. The calculated parameters were compared to the experimental characteristics of investigated compounds. Microbial activity of studied compounds was tested against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Proteus vulgaris.

  16. 2-Carbaborane-3-phenyl-1H-indoles – Synthesis via McMurry Reaction and COX Inhibition Activity

    PubMed Central

    Neumann, Wilma; Scholz, Matthias; Lönnecke, Peter; Crews, Brenda; Marnett, Lawrence J.; Pietzsch, Jens; Kniess, Torsten

    2013-01-01

    Cyclooxygenase-2 (COX-2) inhibitors have been in the focus of medicinal chemistry for years and many compounds exhibiting high selectivity and affinity were developed. As carbaboranes represent interesting pharmacophores as phenyl mimetics in drug development, this paper presents the synthesis of carbaboranyl derivatives of COX-2-selective 2,3-disubstituted indoles. Despite the lability of carbaboranes under reducing conditions, 2-carbaborane-3-phenyl-1H-indoles could be synthesized by McMurry cyclization of the corresponding amides. While the meta-carbaboranyl-substituted derivatives (3a-c) lacked COX inhibition activity, the ortho-carbaboranyl analog (3d) was active but showed a selectivity shift towards COX-1. PMID:23303738

  17. Vibrational (FT-IR and FT-Raman), electronic (UV-Vis), NMR (1H and 13C) spectra and reactivity analyses of 4,5-dimethyl-o-phenylenediamine

    NASA Astrophysics Data System (ADS)

    Atac, Ahmet; Karaca, Caglar; Gunnaz, Salih; Karabacak, Mehmet

    2014-09-01

    The structure of 4,5-dimethyl-o-phenylenediamine (C8H12N2, DMPDA) was investigated on the basis of spectroscopic data and theoretical calculations. The sterochemical structure was determined by FT-IR, FT-Raman, UV, 1H and 13C NMR spectra. An experimental study and a theoretical analysis were associated by using the B3LYP method with Gaussian09 package program. FT-IR and FT-Raman spectra were recorded in the region of 4000-400 cm-1 and 4000-10 cm-1, respectively. The vibrational spectra were calculated by DFT method and the fundamental vibrations were assigned on the basis of the total energy distribution (TED), calculated with scaled quantum mechanics (SQM) method with Parallel Quantum Solutions (PQS) program. The UV absorption spectrum of the compound that dissolved in ethanol solution were recorded in the range of 190-400 nm. Total density of state (TDOS) and partial density of state (PDOS) of the DMPDA in terms of HOMOs and LUMOs were calculated and analyzed. Chemical shifts were reported in ppm relative to tetramethylsilane (TMS) for 1H and 13C NMR spectra. The compound was dissolved in dimethyl sulfoxide (DMSO). Also, 1H and 13C chemical shifts calculated using the gauge independent atomic orbital (GIAO) method. Mullikan atomic charges and other thermo-dynamical parameters were investigated with the help of B3LYP (DFT) method using 6-311++G** basis set. On the basis of the thermodynamic properties of the title compound at different temperatures have been carried out, revealing the correlations between heat capacity (C), entropy (S), enthalpy changes (H) and temperatures. The optimized bond lengths, bond angles, chemical shifts and vibrational wavenumbers showed the best agreement with the experimental results.

  18. Vibrational (FT-IR and FT-Raman), electronic (UV-Vis), NMR (1H and 13C) spectra and reactivity analyses of 4,5-dimethyl-o-phenylenediamine.

    PubMed

    Atac, Ahmet; Karaca, Caglar; Gunnaz, Salih; Karabacak, Mehmet

    2014-09-15

    The structure of 4,5-dimethyl-o-phenylenediamine (C8H12N2, DMPDA) was investigated on the basis of spectroscopic data and theoretical calculations. The sterochemical structure was determined by FT-IR, FT-Raman, UV, 1H and 13C NMR spectra. An experimental study and a theoretical analysis were associated by using the B3LYP method with Gaussian09 package program. FT-IR and FT-Raman spectra were recorded in the region of 4000-400 cm(-1) and 4000-10 cm(-1), respectively. The vibrational spectra were calculated by DFT method and the fundamental vibrations were assigned on the basis of the total energy distribution (TED), calculated with scaled quantum mechanics (SQM) method with Parallel Quantum Solutions (PQS) program. The UV absorption spectrum of the compound that dissolved in ethanol solution were recorded in the range of 190-400 nm. Total density of state (TDOS) and partial density of state (PDOS) of the DMPDA in terms of HOMOs and LUMOs were calculated and analyzed. Chemical shifts were reported in ppm relative to tetramethylsilane (TMS) for 1H and 13C NMR spectra. The compound was dissolved in dimethyl sulfoxide (DMSO). Also, 1H and 13C chemical shifts calculated using the gauge independent atomic orbital (GIAO) method. Mullikan atomic charges and other thermo-dynamical parameters were investigated with the help of B3LYP (DFT) method using 6-311++G** basis set. On the basis of the thermodynamic properties of the title compound at different temperatures have been carried out, revealing the correlations between heat capacity (C), entropy (S), enthalpy changes (H) and temperatures. The optimized bond lengths, bond angles, chemical shifts and vibrational wavenumbers showed the best agreement with the experimental results. PMID:24813280

  19. Quantum mechanical and spectroscopic (FT-IR, FT-Raman, 1H NMR and UV) investigations of 2-(phenoxymethyl)benzimidazole

    NASA Astrophysics Data System (ADS)

    Mary, Y. Shyma; Jojo, P. J.; Panicker, C. Yohannan; Van Alsenoy, Christian; Ataei, Sanaz; Yildiz, Ilkay

    The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 2-(phenoxymethyl)benzimidazole have been investigated experimentally and theoretically using Gaussian09 software package. The energy and oscillator strength calculated by time dependent density functional theory results almost compliments with experimental findings. Gauge-including atomic orbital 1H NMR chemical shifts calculations were carried out and compared with experimental data. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. Molecular Electrostatic Potential was performed by the DFT method and the infrared intensities and Raman activities have also been reported. Mulliken’s net charges have been calculated and compared with the atomic natural charges. First hyperpolarizability is calculated in order to find its role in non-linear optics.

  20. FT-IR, HOMO-LUMO, NBO, MEP analysis and molecular docking study of 3-Methyl-4-{(E)-[4-(methylsulfanyl)-benzylidene]amino}1H-1,2,4-triazole-5(4H)-thione.

    PubMed

    Panicker, C Yohannan; Varghese, Hema Tresa; Manjula, P S; Sarojini, B K; Narayana, B; War, Javeed Ahamad; Srivastava, S K; Van Alsenoy, C; Al-Saadi, Abdulaziz A

    2015-12-01

    FT-IR spectrum of 3-Methyl-4-{(E)-[4-(methylsulfanyl)-benzylidene]amino}1H-1,2,4-triazole-5(4H)-thione was recorded and analysed. The vibrational wavenumbers were computed and at HF and DFT levels of theory. The data obtained from wavenumber calculations are used to assign the vibrational bands obtained in the IR spectrum. The NH stretching wavenumber is red shifted in the IR spectrum from the computed value, which indicates the weakening of the NH bond. The geometrical parameters of the title compound are in agreement with the XRD results. NBO analysis, HOMO-LUMO, first and second order hyperpolarizability and molecular electrostatic potential results are also reported. From the MEP map it is evident that the negative regions are localized over the sulphur atoms and N3 atom of triazole ring and the maximum positive region is localized on NH group, indicating a possible site for nucleophilic attack. Prediction of Activity Spectra analysis of the title compound predicts anti-tuberculostic activity with probability to be active value of 0.543. Molecular docking studies reveal that the triazole nitrogen atoms and the thione sulphur atom play vital role in bonding and results draw us to the conclusion that the compound might exhibit anti-tuberculostic activity. PMID:26142174

  1. Study of the A(e,e'$\\pi^+$) Reaction on $^1$H, $^2$H, $^{12}$C, $^{27}$Al, $^{63}$Cu and $^{197}$Au

    SciTech Connect

    Qian, X; Clasie, B; Arrington, J; Asaturyan, R; Benmokhtar, F; Boeglin, W; Bosted, P; Bruell, A; Christy, M E; Chudakov, E; Dalton, M M; Daniel, A; Day, D; Dutta, D; El Fassi, L; Ent, R; Fenker, H C; Ferrer, J; Fomin, N; Gao, H; Garrow, K; Gaskell, D; Gray, C; Huber, G M; Jones, M K; Kalantarians, N; Keppel, C E; Kramer, K; Li, Y; Liang, Y; Lung, A F; Malace, S; Markowitz, P; Matsumura, A; Meekins, D G; Mertens, T; Miyoshi, T; Mkrtchyan, H; Monson, R; Navasardyan, T; Niculescu, G; Niculescu, I; Okayasu, Y; Opper, A K; Perdrisat, C; Punjabi, V; Rauf, A W; Rodriquez, V M; Rohe, D; Seely, J; Segbefia, E; Smith, G R; Sumihama, M; Tadevosyan, V; Tang, L; Villano, A; Vulcan, W F; Wesselmann, F R; Wood, S A; Yuan, L; Zheng, X

    2010-05-01

    Cross sections for the p($e,e'\\pi^{+}$)n process on $^1$H, $^2$H, $^{12}$C, $^{27}$Al, $^{63}$Cu and $^{197}$Au targets were measured at the Thomas Jefferson National Accelerator Facility (Jefferson Lab) in order to extract the nuclear transparencies. Data were taken for four-momentum transfers ranging from $Q^2$=1.1 to 4.8 GeV$^2$ for a fixed center of mass energy of $W$=2.14 GeV. The ratio of $\\sigma_L$ and $\\sigma_T$ was extracted from the measured cross sections for $^1$H, $^2$H, $^{12}$C and $^{63}$Cu targets at $Q^2$ = 2.15 and 4.0 GeV$^2$ allowing for additional studies of the reaction mechanism. The experimental setup and the analysis of the data are described in detail including systematic studies needed to obtain the results. The results for the nuclear transparency and the differential cross sections as a function of the pion momentum at the different values of $Q^2$ are presented. Global features of the data are discussed and the data are compared with the results of model calculations for the p($e,e'\\pi^{+}$)n reaction from nuclear targets.

  2. Spectroscopic (FT-IR, FT-Raman, 1H, 13C NMR, UV/VIS), thermogravimetric and antimicrobial studies of Ca(II), Mn(II), Cu(II), Zn(II) and Cd(II) complexes of ferulic acid

    NASA Astrophysics Data System (ADS)

    Kalinowska, M.; Piekut, J.; Bruss, A.; Follet, C.; Sienkiewicz-Gromiuk, J.; ?wis?ocka, R.; Rz?czy?ska, Z.; Lewandowski, W.

    2014-03-01

    The molecular structure of Mn(II), Cu(II), Zn(II), Cd(II) and Ca(II) ferulates (4-hydroxy-3-methoxycinnamates) was studied. The selected metal ferulates were synthesized. Their composition was established by means of elementary and thermogravimetric analysis. The following spectroscopic methods were used: infrared (FT-IR), Raman (FT-Raman), nuclear magnetic resonance (13C, 1H NMR) and ultraviolet-visible (UV/VIS). On the basis of obtained results the electronic charge distribution in studied metal complexes in comparison with ferulic acid molecule was discussed. The microbiological study of ferulic acid and ferulates toward Escherichia coli, Bacillus subtilis, Candida albicans, Pseudomonas aeruginosa, Staphylococcus aureus and Proteus vulgaris was done.

  3. Platinum-monolayer Electrocatalysts: Palladium Interlayer on IrCo Alloy Core Improves Activity in Oxygen-reduction Reaction

    SciTech Connect

    Gong, K.; Chen, W.-F.; Sasaki, K.; Su, D.; Vukmirovic, M.B.; Zhou, W.; Izzo, E.L.; Perez-Acosta, C.; Hirunsit, P.; Balbuena, P.B.; Adzic, R.R.

    2010-11-15

    We describe the synthesis and electrocatalytic properties of a new low-Pt electrocatalyst consisting of an IrCo core, a Pd interlayer, and a surface Pt monolayer, emphasizing the interlayer's role in improving electrocatalytic activity for the oxygen-reduction reaction on Pt in HClO{sub 4} solution. We prepared the IrCo alloys by decomposing, at 800 C, hexacyanometalate, KCoIr(CN){sub 6}, adsorbed on the carbon surfaces. The synthesis of Ir{sub 3}Co/C involved heating a mix of metal salts and carbon in hydrogen at 500 C. Thereafter, we placed a palladium and/or platinum monolayer on them via the galvanic displacement of an underpotentially deposited copper monolayer. The electrocatalysts were characterized using structural- and electrochemical-techniques. For PtML/PdML/IrCo/C, we observed a Pt mass activity of 1.18 A/mg{sub (Pt)} and the platinum-group-metals mass of 0.16 A/mg{sub (Pt, Pd, Ir)}. In comparison, without a Pd interlayer, i.e., Pt{sub ML}/IrCo/C, the activities of 0.15 A/mg{sub (Pt)} and 0.036 A/mg{sub (Pt, Pd, Ir)} were considerably lower. We consider that the palladium interlayer plays an essential role in achieving high catalytic activity by adjusting the electronic interaction of the platinum monolayer with the IrCo core, so that it accelerates the kinetics of adsorption and desorption of the intermediates of oxygen reduction. A similar trend was observed for Pt{sub ML}/Pd{sub ML} and Pt{sub ML} deposited on Ir{sub 3}Co/C alloy core. We used density functional theory to interpret the observed phenomena.

  4. Spectroscopic investigation (FT-IR and FT-Raman), vibrational assignments, HOMO-LUMO, NBO, MEP analysis and molecular docking study of 2-(4-hydroxyphenyl)-4,5-dimethyl-1H-imidazole 3-oxide

    NASA Astrophysics Data System (ADS)

    Benzon, K. B.; Varghese, Hema Tresa; Panicker, C. Yohannan; Pradhan, Kiran; Tiwary, Bipransh Kumar; Nanda, Ashis Kumar; Alsenoy, C. Van

    2015-07-01

    In this work, the vibrational spectral analysis was carried out using FT-IR and FT-Raman spectroscopy of 2-(4-hydroxyphenyl)-4,5-dimethyl-1H-imidazole 3-oxide. The computations were performed at DFT levels of theory to get the optimized geometry and vibrational frequencies of the normal modes of the title compound using Gaussian09 software. The complete vibrational assignments of frequencies were made on the basis of potential energy distribution. The calculated HOMO and LUMO energies show the chemical activity of the molecule. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The hyperpolarizability values are reported and the first hyperpolarizability of the title compound is 19.61 times that of standard NLO material urea. From the MEP plot, the negative charge covers the nitro group and the positive region is over the hydroxyl group and N-H part of the imidazole ring. The calculated 1H NMR results are in good agreement with experimental data. Molecular docking study is also reported.

  5. Quantum mechanical calculations and spectroscopic (FT-IR, FT-Raman and UV) investigations, molecular orbital, NLO, NBO, NLMO and MESP analysis of 4-[5-(4-methylphenyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl] benzene-1-sulfonamide

    NASA Astrophysics Data System (ADS)

    Govindasamy, P.; Gunasekaran, S.

    2015-02-01

    The molecular structural parameters and vibrational frequencies of the fundamental modes of 4-[5-(4-methylphenyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl] benzene-1-sulfonamide(abbreviated as 4MPTFM1HPB1SA) have been obtained using Density functional theory (DFT) technique in the B3LYP approximation with 6-311G(d,p) and 6-311++G(d,p) basis sets. Detailed vibrational assignments of the observed FT-IR and FT-Raman bands have been proposed on the basis of potential energy distribution (PED). The difference between the observed and the calculated wavenumbers values are very small. The theoretically predicted FT-IR and FT-Raman spectra of the title molecule have been constructed. The molecular electrostatic potential has been mapped primarily for predicting sites and relative reactivities toward electrophilic and nucleophilic attack. The intramolecular contacts have been interpreted using Natural Bond Orbital (NBO) and Natural Localized Molecular Orbital (NLMO) analysis. Important non-linear properties such as electric dipolemoment and first hyperpolarizability of 4MPTFM1HPB1SA have been computed using B3LYP quantum chemical calculation. The absorption wavelength, energy and oscillator's strength are calculated by TD-DFT and 4MPTFM1HPB1SA is approach complement with the experimental findings. The temperature dependence of thermodynamic properties has been analyzed. The Natural charges, Frontier molecular orbitals (FMOs), chemical hardness (?), chemical potential (?), Electro negativity (?) and electrophilicity values (?) are calculated and reported.

  6. Kinetic study of the reaction CH (X 2Pi) + H2 yields CH2 (X 3B1) + H in the temperature range 372 to 675 K

    NASA Technical Reports Server (NTRS)

    Zabarnick, S.; Fleming, J. W.; Lin, M. C.

    1986-01-01

    The kinetics of the reversible reaction CH (X 2Pi) + H2 yields CH2 (X 3B1) + H at 372-675 K and total pressure 100 torr (mainly Ar) is investigated experimentally. The ground-state CH radicals are produced by photolysis of CHBr3 using 10-mJ 266-nm laser pulses (repetition rate 10 Hz) and monitored by measuring the fluorescence induced by a 429.8-nm dye laser, in the apparatus described by Berman et al. (1982) and Berman and Lin (1984). The results are presented in tables and graphs and characterized. The absolute rate constants for the forward and reverse reactions are determined, and their temperature dependence is given by Arrhenius expressions and formulas obtained in transition-state-theory calculations. The heat of formation of CH2 at 0 K is estimated (assuming that the recombination reaction CH2 + H has zero activation energy) as 92.6 + or - 0.5 kcal/mol.

  7. Monomeric and dimeric structures analysis and spectroscopic characterization of 3,5-difluorophenylboronic acid with experimental (FT-IR, FT-Raman, 1H and 13C NMR, UV) techniques and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Karabacak, Mehmet; Kose, Etem; Atac, Ahmet; Asiri, Abdullah M.; Kurt, Mustafa

    2014-01-01

    The spectroscopic properties of 3,5-difluorophenylboronic acid (3,5-DFPBA, C6H3F2B(OH)2) were investigated by FT-IR, FT-Raman UV-Vis, 1H and 13C NMR spectroscopic techniques. FT-IR (4000-400 cm-1) and FT-Raman spectra (3500-10 cm-1) in the solid phase and 1H and 13C NMR spectra in DMSO solution were recorded. The UV spectra that dissolved in ethanol and water were recorded in the range of 200-400 nm for each solution. The structural and spectroscopic data of the molecule have been obtained for possible three conformers from DFT (B3LYP) with 6-311++G(d,p) basis set calculations. The geometry of the molecule was fully optimized, vibrational spectra were calculated and fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method and PQS program. Hydrogen-bonded dimer of title molecule, optimized by counterpoise correction, was also studied B3LYP at the 6-311++G(d,p) level and the effects of molecular association through O-H⋯O hydrogen bonding have been discussed. 1H and 13C NMR chemical shifts were calculated by using the gauge-invariant atomic orbital (GIAO) method. The electronic properties, such as excitation energies, oscillator strength, wavelengths, HOMO and LUMO energies, were performed by time-dependent density functional theory (TD-DFT) results complements with the experimental findings. Total and partial density of state (TDOS and PDOS) and also overlap population density of state (OPDOS) diagrams analysis were presented. The effects due to the substitutions of boric acid group and halogen were investigated. The results of the calculations were applied to simulate spectra of the title compound, which show excellent agreement with observed spectra. Besides, frontier molecular orbitals (FMO), molecular electrostatic potential (MEP), nonlinear optical properties (NLO) and thermodynamic features were performed.

  8. Longitudinal and Transverse Cross Sections in the {sup 1}H ({ital e},thinspthinsp {ital e}{sup {prime}}{ital K}{sup +}){Lambda} Reaction

    SciTech Connect

    Niculescu, G.; Gueye, P.; Ahmidouch, A.; Assamagan, K.; Avery, S.; Baker, O.K.; Beard, K.; Cha, J.; Eden, T.; Harvey, M.; Hinton, W.; Keppel, C.; Madey, R.; Niculescu, I.; Savage, G.; Tang, L.; Williams, R.; Mohring, R.M.; Beise, E.; Breuer, H.; Chang, C.C.; Chant, N.; Collins, G.; Duncan, F.; Ewell, L.; Gustafsson, K.K.; Lung, A.; Roos, P.; Abbott, D.; Baker, O.K.; Carlini, R.; Dunne, J.; Ent, R.; Keppel, C.; Mack, D.; Majewski, S.; Mitchell, J.; Tang, L.; Vulcan, W.; Wood, S.; Yan, C.; Ahmidouch, A.; Madey, R.; Amatuni, T.A.; Mkrtchyan, H.; Stepanyan, S.; Tadevosian, V.; Ambrozewicz, P.; Martoff, C.J.; Angelescu, T.; Mihul, A.; Teodorescu, L.; Armstrong, C.S.; Finn, M.; Meekins, D.; Bailey, K.; Cummings, W.; Geesaman, D.F.; Hansen, J.; Potterveld, D.; Reinhold, J.; Zeidman, B.; Beedoe, S.; Danagoulian, S.; Jackson, C.; Mtingwa, S.; Sawafta, R.; Volmer, J.; Cisbani, E.; De Leo, R.; Frullani, S.; Garibaldi, F.; Iodice, M.; Leone, T.; Lolos, G.; Perrino, R.; Urciuoli, G.M.; Dutta, D.; Segel, R.; Eyraud, L.; Furget, C.; Kox, S.; Real, J.

    1998-08-01

    The {sup 1}H( e,thinspe{sup {prime}}K{sup +}){Lambda} reaction was studied as a function of the squared four-momentum transfer, Q{sup 2} , and the virtual photon polarization, {var_epsilon} . For each of four Q{sup 2} settings, 0.52, 0.75, 1.00, and 2.00 (GeV/c){sup 2} , the longitudinal and transverse virtual photon cross sections were extracted in measurements at three virtual photon polarizations. The Q{sup 2} dependence of the {sigma}{sub L}/{sigma}{sub T} ratio differs significantly from current theoretical predictions. This, combined with the precision of the measurement, implies a need for revision of existing calculations. {copyright} {ital 1998} {ital The American Physical Society }

  9. Aza-Diels–Alder reaction between N-aryl-1-oxo-1H-isoindolium ions and tert-enamides: Steric effects on reaction outcome

    PubMed Central

    Chou, Ting-Yi; ALJaroudi, Zainab; Ellis, Bobby D; Cameron, T Stanley

    2014-01-01

    Summary The synthesis of 5-substituted 6,6a-dihydroisoindolo[2,1-a]quinolin-11(5H)-ones via [4 + 2] imino-Diels–Alder cyclization from N-aryl-3-hydroxyisoindolinones and N-vinyl lactams under Lewis acid-catalysed anhydrous conditions is reported. Reactions of N-(2-substituted-aryl)-3-hydroxyisoindolinones with N-vinylpyrrolidone under identical conditions resulted in the formation of 2-(2-substitued-aryl)-3-(2-(2-oxopyrrolidin-1-yl)vinyl)isoindolin-1-one analogues indicating steric hinderance as the cause of deviation. The probable mechanism of the reaction based on the results from X-ray crystallography and molecular modelling is discussed. PMID:24778740

  10. H2O2-promoted reactions of aliphatic primary amines with 1,3-diketones for the synthesis of 1H-pyrrol-3(2H)-ones at ambient temperature in water.

    PubMed

    Sun, Xi; Li, Pinhua; Zhang, Xiuli; Wang, Lei

    2014-04-18

    A green organic reaction of aliphatic primary amines with 1,3-diketones promoted by 30% aqueous H2O2 has been developed. It provides an inexpensive, regioselective, and efficient approach to 1H-pyrrol-3(2H)-ones with high yields from the simple and readily available starting materials in one pot via multicomponent tandem cyclization reactions and C-C cleavage under very mild and environmentally friendly reaction conditions. PMID:24702671

  11. Crystal structure, FT-IR, FT-Raman, 1H NMR and computational study of ethyl 2-{[(Z)3-(4-chlorophenyl)-3-hydroxy-2-propene-1-thione] amino} acetate

    NASA Astrophysics Data System (ADS)

    Prasanth, S.; Varughese, Mary; Joseph, Nirmala; Mathew, Paulson; Manojkumar, T. K.; Sudarsanakumar, C.

    2015-02-01

    The molecular structure of a thioamide derivative ethyl 2-{[(Z)3-(4-chlorophenyl)-3-hydroxy-2-propene-1-thione] amino} acetate was determined by X-ray diffraction. The proton NMR (1H NMR), Fourier Transform Infra-Red (FT-IR) and Fourier Transform Raman (FT-Raman) spectra of the compound were recorded and analyzed. The conjugated enol form of the compound was crystallized in the monoclinic space group P21/c, with unit cell dimensions a = 12.514(2) Å, b = 5.403(5) Å, c = 21.233(3) Å, ? = 94.597(4)°. The structure was solved by direct methods and refined to the R value of 0.0462. The thioamide moiety in the compound adopts the Z-conformation and the Csbnd N bond shows a high rotational barrier. The geometry in the gas phase was optimized by B3LYP and RHF quantum mechanical calculations using Gaussian 09 programme and the vibrational frequencies were calculated. The experimental and theoretical data are in good agreement.

  12. Spectroscopic (FT-IR, FT-Raman, 1H- and 13C-NMR), theoretical and microbiological study of trans o-coumaric acid and alkali metal o-coumarates.

    PubMed

    Kowczyk-Sadowy, Ma?gorzata; ?wis?ocka, Renata; Lewandowska, Hanna; Piekut, Jolanta; Lewandowski, W?odzimierz

    2015-01-01

    This work is a continuation of research on a correlation between the molecular structure and electronic charge distribution of phenolic compounds and their biological activity. The influence of lithium, sodium, potassium, rubidium and cesium cations on the electronic system of trans o-coumaric (2-hydroxy-cinnamic) acid was studied. We investigated the relationship between the molecular structure of the tested compounds and their antimicrobial activity. Complementary molecular spectroscopic techniques such as infrared (FT-IR), Raman (FT-Raman), ultraviolet-visible (UV-VIS) and nuclear magnetic resonance (1H- and 13C-NMR) were applied. Structures of the molecules were optimized and their structural characteristics were calculated by the density functional theory (DFT) using the B3LYP method with 6-311++G** as a basis set. Geometric and magnetic aromaticity indices, atomic charges, dipole moments and energies were also calculated. Theoretical parameters were compared to the experimental characteristics of investigated compounds. Correlations between certain vibrational bands and some metal parameters, such as electronegativity, ionization energy, atomic and ionic radius, were found. The microbial activity of studied compounds was tested against Escherichia coli, Bacillus subtilis, Pseudomonas aeruginosa, Staphylococcus aureus, Proteus vulgaris and Candida albicans. PMID:25689641

  13. Impact of IrRu Oxygen Evolution Reaction Catalysts on Pt Nanostructured Thin Films under Start-Up/Shutdown Cycling

    SciTech Connect

    Cullen, David A; More, Karren Leslie; Atanasoska, Liliana; Atanasoski, Radoslav

    2014-01-01

    Electron microscopy and X-ray photoelectron spectroscopy (XPS) methods have been utilized to study the role of oxygen evolution reaction (OER) catalysts in mitigating degradation arising from start-up/shutdown events. Pt nanostructured thin films (NSTF) were coated with a Ru0.1Ir0.9 OER catalyst at loadings ranging from 1 to 10 g/cm2 and submitted to 5,000 potential cycles within a membrane electrode assembly. Analysis of the as-deposited catalyst showed that Ir and Ru coating is primarily metallic, and further evidence is provided to support the previously reported interaction between Ru and the perylene-red support. Aberration-corrected scanning transmission electron microscopy and energy dispersive X-ray spectroscopy were used to observe the impact of the OER catalysts on Pt dissolution and migration through the membrane. Elemental mapping showed a high percentage of the Ir catalyst was maintained on the NSTF whisker surfaces following testing. The presence of the OER catalysts greatly reduced the smoothing of the Pt NSTF whiskers, which has been correlated with Pt dissolution and losses in electrochemically active surface area. The dissolution of both Ir and Pt led to the formation of IrPt nanoparticle clusters in the membrane close to the cathode, as well as the formation of a Pt band deeper in the membrane.

  14. Helium diffusion coefficient measurements in R7T7 nuclear glass by 3He(d,?) 1H nuclear reaction analysis

    NASA Astrophysics Data System (ADS)

    Chamssedine, F.; Sauvage, T.; Peuget, S.; Fares, T.; Martin, G.

    2010-05-01

    The immobilization of fission products and minor actinides by vitrification is the reference process for industrial management of high-level radioactive wastes generated by spent fuel reprocessing. Radiation damage and radiogenic helium accumulation must be specifically studied to evaluate the effects of minor actinide alpha decay on the glass long-term behavior under repository conditions. A specific experimental study was conducted for a comprehensive evaluation of the behavior of helium and its diffusion mechanisms in borosilicate nuclear waste glass. Helium production was simulated by external implantation with 3He ions at a concentration (?1 at.%) 30 times higher than obtained after 10,000 years of storage. Helium diffusion coefficients as a function of temperature were extracted from the depth profiles after annealing. The 3He(d,?) 1H nuclear reaction analysis (NRA) technique was successfully adopted for low-temperature in situ measurements of depth profiles. Its high depth resolution revealed helium mobility at temperatures as low as 253 K and the presence of a trapped helium fraction. The diffusion coefficients of un-trapped helium atoms follow an Arrhenius law between 253 K and 323 K. An activation energy of 0.55 ± 0.03 eV was determined, which is consistent with a process controlled by diffusion in the glass free volume.

  15. Temperature Dependent Kinetics of the OH/HO2/O3 Chain Reaction by Time-Resolved IR Laser Absorption Spectroscopy

    E-print Network

    Nizkorodov, Sergey

    Temperature Dependent Kinetics of the OH/HO2/O3 Chain Reaction by Time-Resolved IR Laser Absorption) in the mid-latitudes. Indeed, the HOx chain reaction is estimated to be responsible for nearly half-tube apparatus, with the HOx chain reaction monitored as a function of time (i.e., the distance for a well

  16. Mechanisms and reaction pathways for simultaneous oxidation of NOx and SO? by ozone determined by in situ IR measurements.

    PubMed

    Sun, Chenglang; Zhao, Nan; Zhuang, Zhuokai; Wang, Haiqiang; Liu, Yue; Weng, Xiaole; Wu, Zhongbiao

    2014-06-15

    Ozone (O3) oxidation combined with wet scrubbing is a promising method for the simultaneous removal of SO2 and NOx in flue gas. In this study, the O3 oxidation processes of NO and SO2, as well as their coexistence, were investigated using an in situ IR spectrometer. Experimental results showed that the O3 concentration and the reaction temperature played critical roles in the O3 oxidation process of NO. Around 80°C, when inlet molar ratio of O3/NO was less than 1, NO was mainly oxidized to NO2, while when the ratio was greater than 1, NO would be further oxidized to NO3, N2O5, and HNO3. NO3 was the key intermediate product for the formation of N2O5 and HNO3. However, the subsequent reactions of NO3 were temperature dependence. With the increase of reaction temperature above 100°C, the concentration of NO2 increased whereas the concentrations of N2O5 and HNO3 decreased. The oxidation of SO2 by O3 was negligible and SO2 had little influence on the oxidation of NO in the simultaneous oxidation of NO and SO2. Finally, based on the in situ IR results, the oxidation mechanism is discussed and the reaction pathways are proposed. PMID:24801895

  17. Preignition reactions of AP-HTPB propellants studied by IR spectrometry. [Ammonium Perchlorate-Hydroxyl Terminated PolyButadiene

    NASA Technical Reports Server (NTRS)

    Law, R. J.; Baer, A. D.; Ryan, N. W.

    1977-01-01

    IR absorption spectrometry was used to follow the disappearance of NH and CH bonds during the pyrolysis of a polymer film containing 30 weight percent ammonium perchlorate (AP). The remaining 70 weight percent consisted of a mixture of 92.5 weight percent hydroxyl-terminated polybutadiene (HTPB) and 7.5 weight percent isophrone diisocyanate (IPDI). The results indicate that polymer decomposition is induced by products of AP decomposition, and that about 2.5 CH bonds disappear for each NH bond that disappears. The diffusion process occurring in the later stages of the reaction is analyzed in an attempt to account for the unexpectedly low activation energy.

  18. New types of anodes for the oxygen evolution reaction in acidic solution: IrO/sub 2//TiO/sub 2//Ti

    SciTech Connect

    Matsumoto, Y.; Tazawa, T.; Muroi, N.; Sato, E.I.

    1986-11-01

    New type of electrodes of IrO/sub 2//TiO/sub 2//Ti, where the TiO/sub 2/ films are prepared by the anodic oxidation accompanied by sparking and are porous, were tested as the anode for the oxygen evolution reaction in acidic solution. The IrO/sub 2//TiO/sub 2//Ti electrodes were prepared by thermal decomposition of IrCl/sub 4/ aqueous solution on the TiO/sub 2/ films. The resistivities of the electrodes themselves became zero by the thermal decomposition process to form IrO/sub 2/, if the TiO/sub 2/ films were prepared by the anodic oxidation accompanied by sufficient sparking. It was found that the catalytic activities of the IrO/sub 2//TiO/sub 2//Ti electrodes are higher than that of the IrO/sub 2//Ti electrode. The electrodes prepared at a calcination temperature lower than about 500/sup 0/C dissolved in the long-term test, although their surface areas were very large. The IrO/sub 2//TiO/sub 2//Ti electrodes prepared at 550/sup 0/ are very superior in their catalytic activity and their stability in the long-term test for the oxygen evolution reaction. The surface difference between the IRO/sub 2//TiO/sub 2//Ti and the IrO/sub 2//Ti electrodes is also discussed.

  19. Adsorption and oxidation of formaldehyde on a polycrystalline Pt film electrode: An in situ IR spectroscopy search for adsorbed reaction intermediates

    PubMed Central

    Behm, R Jürgen

    2014-01-01

    Summary As part of a mechanistic study of the electrooxidation of C1 molecules we have systematically investigated the dissociative adsorption/oxidation of formaldehyde on a polycrystalline Pt film electrode under experimental conditions optimizing the chance for detecting weakly adsorbed reaction intermediates. Employing in situ IR spectroscopy in an attenuated total reflection configuration (ATR-FTIRS) with p-polarized IR radiation to further improve the signal-to-noise ratio, and using low reaction temperatures (3 °C) and deuterium substitution to slow down the reaction kinetics and to stabilize weakly adsorbed reaction intermediates, we could detect an IR absorption band at 1660 cm?1 characteristic for adsorbed formyl intermediates. This assignment is supported by an isotope shift in wave number. Effects of temperature, potential and deuterium substitution on the formation and disappearance of different adsorbed species (COad, adsorbed formate, adsorbed formyl), are monitored and quantified. Consequences on the mechanism for dissociative adsorption and oxidation of formaldehyde are discussed. PMID:24991512

  20. Synthesis of novel polysubstituted N-benzyl-1H-pyrroles via a cascade reaction of alkynyl Fischer carbenes with ?-imino glycine methyl esters.

    PubMed

    de la Cruz, Fabiola N; López, Julio; Jiménez-Halla, J Óscar C; Flores-Álamo, Marcos; Tamaríz, Joaquín; Delgado, Francisco; Vázquez, Miguel A

    2015-12-28

    An efficient and simple synthesis of novel and densely substituted N-benzyl-1H-pyrroles 6a-r is described by a 1,4-addition/isomerization/ring closure/demetalation cascade process of alkynyl Fischer carbene complexes 1a-f and 2a and ?-imino glycine methyl esters 3a, b, d, g, h, and k promoted with LDA. PMID:26488365

  1. Time-Resolved O3 Chemical Chain Reaction Kinetics Via High-Resolution IR Laser Absorption Methods

    NASA Technical Reports Server (NTRS)

    Kulcke, Axel; Blackmon, Brad; Chapman, William B.; Kim, In Koo; Nesbitt, David J.

    1998-01-01

    Excimer laser photolysis in combination with time-resolved IR laser absorption detection of OH radicals has been used to study O3/OH(v = 0)/HO2 chain reaction kinetics at 298 K, (i.e.,(k(sub 1) is OH + 03 yields H02 + 02 and (k(sub 2) is H02 + 03 yields OH + 202). From time-resolved detection of OH radicals with high-resolution near IR laser absorption methods, the chain induction kinetics have been measured at up to an order of magnitude higher ozone concentrations ([03] less than or equal to 10(exp 17) molecules/cu cm) than accessible in previous studies. This greater dynamic range permits the full evolution of the chain induction, propagation, and termination process to be temporally isolated and measured in real time. An exact solution for time-dependent OH evolution under pseudo- first-order chain reaction conditions is presented, which correctly predicts new kinetic signatures not included in previous OH + 03 kinetic analyses. Specifically, the solutions predict an initial exponential loss (chain "induction") of the OH radical to a steady-state level ([OH](sub ss)), with this fast initial decay determined by the sum of both chain rate constants, k(sub ind) = k(sub 1) + k(sub 2). By monitoring the chain induction feature, this sum of the rate constants is determined to be k(sub ind) = 8.4(8) x 10(exp -14) cu cm/molecule/s for room temperature reagents. This is significantly higher than the values currently recommended for use in atmospheric models, but in excellent agreement with previous results from Ravishankara et al.

  2. Charged pion form factor between $Q^2$=0.60 and 2.45 GeV$^2$. I. Measurements of the cross section for the ${^1}$H($e,e'?^+$)$n$ reaction

    E-print Network

    H. P. Blok; T. Horn; G. M. Huber; E. J. Beise; D. Gaskell; D. J. Mack; V. Tadevosyan; J. Volmer; D. Abbott; K. Aniol; H. Anklin; C. Armstrong; J. Arrington; K. Assamagan; S. Avery; O. K. Baker; B. Barrett; C. Bochna; W. Boeglin; E. J. Brash; H. Breuer; C. C. Chang; N. Chant; M. E. Christy; J. Dunne; T. Eden; R. Ent; H. Fenker; E. Gibson; R. Gilman; K. Gustafsson; W. Hinton; R. J. Holt; H. Jackson; S. Jin; M. K. Jones; C. E. Keppel; P. H. Kim; W. Kim; P. M. King; A. Klein; D. Koltenuk; V. Kovaltchouk; M. Liang; J. Liu; G. J. Lolos; A. Lung; D. J. Margaziotis; P. Markowitz; A. Matsumura; D. McKee; D. Meekins; J. Mitchell; T. Miyoshi; H. Mkrtchyan; B. Mueller; G. Niculescu; I. Niculescu; Y. Okayasu; L. Pentchev; C. Perdrisat; D. Pitz; D. Potterveld; V. Punjabi; L. M. Qin; P. Reimer; J. Reinhold; J. Roche; P. G. Roos; A. Sarty; I. K. Shin; G. R. Smith; S. Stepanyan; L. G. Tang; V. Tvaskis; R. L. J. van der Meer; K. Vansyoc; D. Van Westrum; S. Vidakovic; W. Vulcan; G. Warren; S. A. Wood; C. Xu; C. Yan; W. -X. Zhao; X. Zheng; B. Zihlmann

    2008-09-18

    Cross sections for the reaction ${^1}$H($e,e'\\pi^+$)$n$ were measured in Hall C at Thomas Jefferson National Accelerator Facility (JLab) using the CEBAF high-intensity, continous electron beam in order to determine the charged pion form factor. Data were taken for central four-momentum transfers ranging from $Q^2$=0.60 to 2.45 GeV$^2$ at an invariant mass of the virtual photon-nucleon system of $W$=1.95 and 2.22 GeV. The measured cross sections were separated into the four structure functions $\\sigma_L$, $\\sigma_T$, $\\sigma_{LT}$, and $\\sigma_{TT}$. The various parts of the experimental setup and the analysis steps are described in detail, including the calibrations and systematic studies, which were needed to obtain high precision results. The different types of systematic uncertainties are also discussed. The results for the separated cross sections as a function of the Mandelstam variable $t$ at the different values of $Q^2$ are presented. Some global features of the data are discussed, and the data are compared with the results of some model calculations for the reaction ${^1}$H($e,e'\\pi^+$)$n$.

  3. Charged pion form factor between Q2=0.60 and 2.45 GeV2. I. Measurements of the cross section for the 1H(e,e'?+)n reaction

    NASA Astrophysics Data System (ADS)

    Blok, H. P.; Horn, T.; Huber, G. M.; Beise, E. J.; Gaskell, D.; Mack, D. J.; Tadevosyan, V.; Volmer, J.; Abbott, D.; Aniol, K.; Anklin, H.; Armstrong, C.; Arrington, J.; Assamagan, K.; Avery, S.; Baker, O. K.; Barrett, B.; Bochna, C.; Boeglin, W.; Brash, E. J.; Breuer, H.; Chang, C. C.; Chant, N.; Christy, M. E.; Dunne, J.; Eden, T.; Ent, R.; Fenker, H.; Gibson, E.; Gilman, R.; Gustafsson, K.; Hinton, W.; Holt, R. J.; Jackson, H.; Jin, S.; Jones, M. K.; Keppel, C. E.; Kim, P. H.; Kim, W.; King, P. M.; Klein, A.; Koltenuk, D.; Kovaltchouk, V.; Liang, M.; Liu, J.; Lolos, G. J.; Lung, A.; Margaziotis, D. J.; Markowitz, P.; Matsumura, A.; McKee, D.; Meekins, D.; Mitchell, J.; Miyoshi, T.; Mkrtchyan, H.; Mueller, B.; Niculescu, G.; Niculescu, I.; Okayasu, Y.; Pentchev, L.; Perdrisat, C.; Pitz, D.; Potterveld, D.; Punjabi, V.; Qin, L. M.; Reimer, P.; Reinhold, J.; Roche, J.; Roos, P. G.; Sarty, A.; Shin, I. K.; Smith, G. R.; Stepanyan, S.; Tang, L. G.; Tvaskis, V.; van der Meer, R. L. J.; Vansyoc, K.; Westrum, D. Van; Vidakovic, S.; Vulcan, W.; Warren, G.; Wood, S. A.; Xu, C.; Yan, C.; Zhao, W.-X.; Zheng, X.; Zihlmann, B.

    2008-10-01

    Cross sections for the reaction 1H(e,e'?+)n were measured in Hall C at Thomas Jefferson National Accelerator Facility (JLab) using the high-intensity Continuous Electron Beam Accelerator Facility (CEBAF) to determine the charged pion form factor. Data were taken for central four-momentum transfers ranging from Q2=0.60 to 2.45 GeV2 at an invariant mass of the virtual photon-nucleon system of W=1.95 and 2.22 GeV. The measured cross sections were separated into the four structure functions ?L,?T,?LT, and ?TT. The various parts of the experimental setup and the analysis steps are described in detail, including the calibrations and systematic studies, which were needed to obtain high-precision results. The different types of systematic uncertainties are also discussed. The results for the separated cross sections as a function of the Mandelstam variable t at the different values of Q2 are presented. Some global features of the data are discussed, and the data are compared with the results of some model calculations for the reaction 1H(e,e'?+)n.

  4. Investigation of photoneutron reactions on {sup 192}Os and {sup 191,193}Ir at energies of relevance for the astrophysical p process

    SciTech Connect

    Hasper, J.; Zilges, A.; Galaviz, D.; Mueller, S.; Sauerwein, A.; Savran, D.; Schnorrenberger, L.; Sonnabend, K.

    2009-05-15

    We have investigated the photoneutron reactions on the isotopes {sup 192}Os and {sup 191,193}Ir for astrophysically relevant photon energies just above the neutron separation energy. The experiments were performed using the photoactivation technique at the superconducting Darmstadt linear electron accelerator (S-DALINAC). The measurements extend the existing experimental database on photoneutron reactions in this mass region and serve as an important test for the state-of-the-art statistical model calculations commonly used for the prediction of stellar reaction rates.

  5. Effect of Bronsted Acids and Bases, and Lewis Acid (Sn(2+)) on the Regiochemistry of the Reaction of Amines with Trifluoromethyl-?-diketones: Reaction of 3-Aminopyrrole to Selectively Produce Regioisomeric 1H-Pyrrolo[3,2-b]pyridines.

    PubMed

    De Rosa, Michael; Arnold, David; Hartline, Douglas; Truong, Linda; Verner, Roman; Wang, Tianwei; Westin, Christian

    2015-12-18

    Reaction of 3-aminopyrrole (as its salt) with trifluoromethyl-?-diketones gave ?-1H-pyrrolo[3,2-b]pyridines via reaction at the less reactive carbonyl group. The trifluoromethyl group increased the electrophilicity of the adjacent carbonyl group and decreased the basicity of the hydroxyl group of the CF3 amino alcohol formed. This amino alcohol was formed faster, but its subsequent dehydration to the ?-enaminone was slow resulting in the preferential formation of the ?-regioisomer. Reaction of 4,4,4-trifluoro-1-phenyl-1,3-butadione with 3-aminopyrrole was carried out using a series of 6 amine buffers. Yields of the ?-1H-pyrrolo[3,2-b]pyridine increased as the pKa of the amine buffer decreased. Surprisingly the yield went down at higher pKas. There was a change in mechanism as the reaction mixture became more basic. With strong amines trifluoromethyl-?-diketones were present mainly or completely as the enolate. Under reductive conditions (3-nitropyrrole/Sn/AcOH/trifluoromethyl-?-diketone) the ?-1H-pyrrolo[3,2-b]pyridine was the major product as a result of Lewis acid catalysis by Sn(2+). Similar ?-regiochemistry was observed when the reaction of the 3-aminopyrrole salt with trifluoromethyl-?-diketones was carried out in the presence of base and tin(II) acetate. PMID:26575797

  6. Capture and dissociation in the complex-forming CH(v = 0,1) + D2 ? CHD + D, CD2 + H, CD + HD reactions and comparison with CH(v = 0,1) + H2.

    PubMed

    González, Miguel; Mayneris-Perxachs, Jordi; Saracibar, Amaia; Garcia, Ernesto

    2011-08-14

    Rate coefficients for the CH(v = 0,1) + D(2) reaction have been determined for all possible channels (T: 200-1200 K), using the quasiclassical trajectory method and a suitable treatment of the zero point energy. Calculations have also been performed on the CH(v = 1) + H(2) reaction and the CH(v = 1) + D(2) ? CH(v = 0) + D(2) process. Most of the results can be understood considering the key role played by the deep minimum of the potential energy surface (PES), the barrierless character of the PES, the energy of the reaction channels, and the kinematics. The good agreement found between theory and experiment for the rate coefficients of the capture process of CH(v = 0) + D(2), the total reactivity of CH(v = 1) + D(2), H(2), as well as the good agreement observed for the related CH(v = 0) + H(2) system (capture and abstraction), gives confidence on the theoretical rate coefficients obtained for the capture processes of CH(v = 1) + D(2), H(2), the individual reactive processes of CH(v = 1) + D(2), H(2), the abstraction and abstraction-exchange reactions for CH(v = 0) + D(2), and the inelastic process mentioned above, for which there are no experimental data available, and that can be useful in combustion chemistry and astrochemistry. PMID:21698329

  7. Hybrid quantum chemical studies for the methanol formation reaction assisted by the proton transfer mechanism in supercritical water: CH3Cl+nH2O-->CH3OH+HCl+(n-1)H2O

    NASA Astrophysics Data System (ADS)

    Hori, T.; Takahashi, H.; Nitta, T.

    2003-10-01

    The proton transfer along the chain of hydrogen bonds is involved in many chemical reactions in aqueous solution and known to play a decisive role. We have performed the hybrid quantum chemical simulations for the methanol formation reaction catalyzed by the proton transfer mechanism [CH3Cl+nH2O?CH3OH+HCl+(n-1)H2O, n=3] in supercritical water (SCW) to investigate the role of water solvent on the reaction. In the simulation, the electronic state of the chemically active solutes (CH3Cl+3H2O) has been determined quantum mechanically, while the static water solvent has been represented by a classical model. The activation free energy for the water-catalytic reaction in SCW has been found to be 9.6 kcal/mol, which is much lower than that in the gas phase (29.2 kcal/mol). The fractional charge analysis has revealed that the notable charge separation in the solute complex takes place at the transition state (TS) and the resulting huge dipole gives rise to the considerable stabilization of the TS as compared to the reactant. It has been shown that the reaction assisted by the proton transfer mechanism is energetically much favored than the ionic SN2 reaction (CH3Cl+OH-?CH3OH+Cl-, 18.8 kcal/mol). The present calculations suggest that the proton migrations through the chain of hydrogen bonds can be regarded as a probable candidate responsible for the anomalous reactivities observed in SCW.

  8. Synthesis, NMR, FT-IR, X-ray structural characterization, DFT analysis and isomerism aspects of 5-(2,6-dichlorobenzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione

    NASA Astrophysics Data System (ADS)

    Barakat, Assem; Al-Najjar, Hany J.; Al-Majid, Abdullah Mohammed; Soliman, Saied M.; Mabkhot, Yahia Nasser; Shaik, Mohammed Rafi; Ghabbour, Hazem A.; Fun, Hoong-Kun

    2015-08-01

    The synthesis and spectral characterization of the 5-(2,6-dichlorobenzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione;3 was reported. The solid state molecular structure of 3 was studied using X-ray crystallography. The relative stabilities of the seven possible isomers of 3 were calculated by DFT/B3LYP method using 6-311G(d,p) basis set. The calculated total energies and thermodynamic parameters were used to predict the relative stabilities of these isomers. The effect of solvent polarity on the relative stability of these isomers was studied at the same level of theory using PCM. It was found that the keto form, (T0), is the most stable isomer both in the gaseous state and solution. In solution, the calculated total energies of all isomers are decreased indicating that all isomers are stabilized by the solvent effect. The vibrational spectra of the most stable isomer, 3(T0) are calculated using the same level of theory and the results are compared with the experimentally measured FTIR spectra. Good correlation was obtained between the experimental and calculated vibrational frequencies (R2 = 0.9992). The electronic spectra of 3(T0) in gas phase as well as in solutions were calculated using the TD-DFT method. All the predicted electronic transitions showed very little spectral shifts and increase in the intensity of absorption due to solvent effect. Also the 1H- and 13C-NMR chemical shifts of the stable isomer were calculated and the results were correlated with the experimental data. Good correlations between the experimental and calculated chemical shifts were obtained.

  9. Influence of aging and salting on protein secondary structures and water distribution in uncooked and cooked pork. A combined FT-IR microspectroscopy and 1H NMR relaxometry study.

    PubMed

    Wu, Zhiyun; Bertram, Hanne Christine; Kohler, Achim; Böcker, Ulrike; Ofstad, Ragni; Andersen, Henrik J

    2006-11-01

    Fourier transform infrared (FT-IR) microspectroscopy and low-field (LF) proton NMR transverse relaxation measurements were used to study the changes in protein secondary structure and water distribution as a consequence of aging (1 day and 14 days) followed by salting (3%, 6%, and 9% NaCl) and cooking (65 degrees C). An enhanced water uptake and increased proton NMR relaxation times after salting were observed in aged meat (14 days) compared with nonaged meat (1 day). FT-IR bands revealed that salting induced an increase in native beta-sheet structure while aging triggered an increase in native alpha-helical structure before cooking, which could explain the effects of aging and salting on water distribution and water uptake. Moreover, the decrease in T2 relaxation times and loss of water upon cooking were attributed to an increase in aggregated beta-sheet structures and a simultaneous decrease in native protein structures. Finally, aging increased the cooking loss and subsequently decreased the final yield, which corresponded to a further decrease in T2 relaxation times in aged meat upon cooking. However, salting weakened the effect of aging on the final yield, which is consistent with the increased T2 relaxation times upon salting for aged meat after cooking and the weaker effect of aging on protein secondary structural changes for samples treated with high salt concentration. The present study reveals that changes in water distribution during aging, salting, and cooking are not only due to the accepted causal connection, i.e., proteolytic degradation of myofibrillar structures, change in electrostatic repulsion, and dissolution and denaturation of proteins, but also dynamic changes in specific protein secondary structures. PMID:17061838

  10. Visible-light-induced, Ir-catalyzed reactions of N-methyl-N-((trimethylsilyl)methyl)aniline with cyclic ?,?-unsaturated carbonyl compounds

    PubMed Central

    Lenhart, Dominik

    2014-01-01

    Summary N-Methyl-N-((trimethylsilyl)methyl)aniline was employed as reagent in visible-light-induced, iridium-catalyzed addition reactions to cyclic ?,?-unsaturated carbonyl compounds. Typical reaction conditions included the use of one equivalent of the reaction substrate, 1.5 equivalents of the aniline and 2.5 mol % (in MeOH) or 1.0 mol % (in CH2Cl2) [Ir(ppy)2(dtbbpy)]BF4 as the catalyst. Two major reaction products were obtained in combined yields of 30–67%. One product resulted from aminomethyl radical addition, the other product was a tricyclic compound, which is likely formed by attack of the intermediately formed ?-carbonyl radical at the phenyl ring. For five-membered ?,?-unsaturated lactone and lactam substrates, the latter products were the only products isolated. For the six-membered lactones and lactams and for cyclopentenone the simple addition products prevailed. PMID:24778745

  11. Visible-light-induced, Ir-catalyzed reactions of N-methyl-N-((trimethylsilyl)methyl)aniline with cyclic ?,?-unsaturated carbonyl compounds.

    PubMed

    Lenhart, Dominik; Bach, Thorsten

    2014-01-01

    N-Methyl-N-((trimethylsilyl)methyl)aniline was employed as reagent in visible-light-induced, iridium-catalyzed addition reactions to cyclic ?,?-unsaturated carbonyl compounds. Typical reaction conditions included the use of one equivalent of the reaction substrate, 1.5 equivalents of the aniline and 2.5 mol % (in MeOH) or 1.0 mol % (in CH2Cl2) [Ir(ppy)2(dtbbpy)]BF4 as the catalyst. Two major reaction products were obtained in combined yields of 30-67%. One product resulted from aminomethyl radical addition, the other product was a tricyclic compound, which is likely formed by attack of the intermediately formed ?-carbonyl radical at the phenyl ring. For five-membered ?,?-unsaturated lactone and lactam substrates, the latter products were the only products isolated. For the six-membered lactones and lactams and for cyclopentenone the simple addition products prevailed. PMID:24778745

  12. FT-IR, NBO, HOMO-LUMO, MEP analysis and molecular docking study of 1-[3-(4-Fluorophenyl)-5-phenyl-4,5-dihydro-1H-pyrazol-1-yl]ethanone.

    PubMed

    Mary, Y Sheena; Panicker, C Yohannan; Sapnakumari, M; Narayana, B; Sarojini, B K; Al-Saadi, Abdulaziz A; Van Alsenoy, Christian; War, Javeed Ahmad

    2015-02-01

    The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 1-[3-(4-fluorophenyl)-5-phenyl-4,5-dihydro-1H-pyrazol-1-yl]ethanone have been investigated experimentally and theoretically. The geometrical parameters are in agreement with XRD data. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. From the MEP it is evident that the negative charge covers the carbonyl group and the positive region is over the remaining groups. The more electronegativity in the carbonyl group makes it the most reactive part in the molecule. First hyperpolarizability is calculated in order to find its role in nonlinear optics. From the molecular docking studies, it is evident that the fluorine atom attached to benzene ring and ethanone attached to the pyrazoline ring are crucial for binding and the compound might exhibit inhibitory activity against TPII and may act as anti-neoplastic agent. PMID:25448949

  13. Molecular structure, FT-IR, vibrational assignments, HOMO-LUMO analysis and molecular docking study of 1-[5-(4-Bromophenyl)-3-(4-fluorophenyl)-4,5-dihydro-1H-pyrazol-1-yl]ethanone.

    PubMed

    Mary, Y Sheena; Panicker, C Yohannan; Sapnakumari, M; Narayana, B; Sarojini, B K; Al-Saadi, Abdulaziz A; Van Alsenoy, Christian; War, Javeed Ahmad; Fun, H K

    2015-02-01

    The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 1-[5-(4-bromophenyl)-3-(4-fluorophenyl)-4,5-dihydro-1H-pyrazol-1-yl]ethanone have been investigated experimentally and theoretically using Gaussian09 software package. The title compound was optimized using the HF/6-31G(d) (6D, 7F), B3LYP/6-31G (6D, 7F) and B3LYP/6-311++G(d,p) (5D, 7F) calculations. The B3LYP/6-311++G(d,p) (5D, 7F) results and in agreement with experimental infrared bands. The geometrical parameters are in agreement with XRD data. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. Molecular electrostatic potential was also performed. From the MEP it is evident that the negative charge covers the C=O group and the positive region is over the rings. First hyperpolarizability is calculated in order to find its role in nonlinear optics. Molecular docking studies suggest that the compound might exhibit inhibitory activity against TPII and may act as anti-neoplastic agent. PMID:25448948

  14. Stereochemistry of seven-membered heterocycles. communication 16. dipole moments, IR, /sup 1/H, and /sup 13/C nmr spectra, and conformations of 4-methyl-, 4-phenyl-, and isomeric 4,7-dimethyl-2,2-pentamethylene-1,3-dioxa-5,6-benzocycloheptenes

    SciTech Connect

    Klimovitskii, E.N.; Arbuzov, B.A.; Enikeev, K.M.; Il'yasov, A.V.; Sergeeva, G.N.

    1985-12-10

    In order to study the effect of the substituents at the benzyl carbon atoms on the conformational composition, the authors investigated the dynamic /sup 1/H and /sup 13/C NMR spectra of groups II-IV, the IR spectra of II, IV, and V and the dipole moments of IV and V. The measurements showed that the conformational mobility of 4-methyl-, 4-phenyl-, and trans-4,7-dimethyl-2,2-pentamethylene-1,3-dioxa-5,6-benzocycloheptenes is a consequence of the cyclohexane ring with rigid twist conformation of the heterocycle. The NMR signals of the benzyl protons of the heterocycle were assigned. The corresponding cis isomer exists as a conformational mixture of chair and twist forms.

  15. Spectroscopic (FT-IR, FT-Raman and 1H and 13C NMR) and theoretical in MP2/6-311++G(d,p) and B3LYP/6-311++G(d,p) levels study of benzenesulfonic acid and alkali metal benzenesulfonates

    NASA Astrophysics Data System (ADS)

    ?widerski, G.; Kalinowska, M.; ?wis?ocka, R.; Wojtulewski, S.; Lewandowski, W.

    The FT-IR, FT-Raman and NMR (1H and 13C) spectra of benzenesulfonic acid as well as lithium, sodium, potassium, rubidium and caesium benzenesulfonates were registered, assigned and compared. The molecular structures of ligand and alkali metal salts were discussed. On the basis of quantum mechanical calculations in MP2/6-311++G(d,p) and B3LYP/6-311++G(d,p) levels the geometric parameters, infrared spectra, NMR spectra, the magnetic and geometric aromaticity indices for acid and alkali metal benzenesulfonates and benzoates were obtained. The effect of alkali metal ions on the electronic charge distribution of benzenesulfonic acid was studied and compared with the alkali metal benzoates and benzoic acid.

  16. Spectroscopic (FT-IR, FT-Raman and 1H and 13C NMR) and theoretical in MP2/6-311++G(d,p) and B3LYP/6-311++G(d,p) levels study of benzenesulfonic acid and alkali metal benzenesulfonates.

    PubMed

    ?widerski, G; Kalinowska, M; ?wis?ocka, R; Wojtulewski, S; Lewandowski, W

    2013-01-01

    The FT-IR, FT-Raman and NMR ((1)H and (13)C) spectra of benzenesulfonic acid as well as lithium, sodium, potassium, rubidium and caesium benzenesulfonates were registered, assigned and compared. The molecular structures of ligand and alkali metal salts were discussed. On the basis of quantum mechanical calculations in MP2/6-311++G(d,p) and B3LYP/6-311++G(d,p) levels the geometric parameters, infrared spectra, NMR spectra, the magnetic and geometric aromaticity indices for acid and alkali metal benzenesulfonates and benzoates were obtained. The effect of alkali metal ions on the electronic charge distribution of benzenesulfonic acid was studied and compared with the alkali metal benzoates and benzoic acid. PMID:22406243

  17. Charged pion form factor between $Q^2$=0.60 and 2.45 GeV$^2$. I. Measurements of the cross section for the ${^1}$H($e,e'\\pi^+$)$n$ reaction.

    SciTech Connect

    Blok, Henk; Horn, Tanja; Huber, Garth; Beise, Elizabeth; Gaskell, David; Mack, David; Tadevosyan, Vardan; Volmer, Jochen; Abbott, David; Aniol, Konrad; Anklin, Heinz; Armstrong, Christopher; Arrington, John; Assamagan, Ketevi; Avery, Steven; Baker, O.; Barrett, Robert; Bochna, Christopher; Boeglin, Werner; Brash, Edward; Breuer, Herbert; Chang, C.; Chang, C.C.; Chant, Nicholas; Christy, Michael; Dunne, James; Eden, Thomas; Ent, Rolf; Fenker, Howard; Gibson, Edward; Gilman, Ronald; Gustafsson, Kenneth; Hinton, Wendy; Holt, Roy; Jackson, Harold; uk Jin, Seong; Jones, Mark; Keppel, Cynthia; Kim, pyunghun; Kim, Wooyoung; King, Paul; Klein, Andreas; Koltenuk, Douglas; Kovaltchouk, Vitali; Liang, Meihua; Liu, Jinghua; Lolos, George; Lung, Allison; Margaziotis, Demetrius; Markowitz, Pete; Matsumura, Akihiko; McKee, David; Meekins, David; Mitchell, Joseph; Miyoshi, Toshinobu; Mkrtchyan, Hamlet; Mueller, Robert; Niculescu, Gabriel; Niculescu, Maria-Ioana; Okayasu, Yuichi; Pentchev, Lubomir; Perdrisat, Charles; Pitz, David; Potterveld, David; Punjabi, Vina; Qin, Liming; Reimer, Paul; Reinhold, Joerg; Roche, Julie; Roos, Philip; Sarty, Adam; Shin, Ilkyoung; Smith, Gregory; Stepanyan, Stepan; Tang, Liguang; Tvaskis, Vladas; van der Meer, Rob; Vansyoc, Kelley; Van Westrum, Derek; Vidakovic, Sandra; Vulcan, William; Warren, Glen; Wood, Stephen; Xu, C.; Yan, Chen; Zhao, Wenxia; Zheng, Xiaochao; Zihlmann, Benedikt

    2008-10-01

    DOI: http://dx.doi.org/10.1103/PhysRevC.78.045202
    Cross sections for the reaction 1H(e,e'pi+)n were measured in Hall C at Thomas Jefferson National Accelerator Facility (JLab) using the high-intensity Continuous Electron Beam Accelerator Facility (CEBAF) to determine the charged pion form factor. Data were taken for central four-momentum transfers ranging from Q2=0.60 to 2.45 GeV2 at an invariant mass of the virtual photon-nucleon system of W=1.95 and 2.22 GeV. The measured cross sections were separated into the four structure functions sigmaL,sigmaT,sigmaLT, and sigmaTT. The various parts of the experimental setup and the analysis steps are described in detail, including the calibrations and systematic studies, which were needed to obtain high-precision results. The different types of systematic uncertainties are also discussed. The results for the separated cross sections as a function of the Mandelstam variable t at the different values of Q2 are presented. Some global featu

  18. Cross sections and tensor analyzing powers A{sub yy} of the reaction {sup 1}H(d-vector, pp)n in 'symmetric constant relative energy' geometries at E{sub d}=19 MeV

    SciTech Connect

    Ley, J.; Dueweke, C.; Emmerich, R.; Imig, A.; Paetz gen Schieck, H.; Golak, J.; Witala, H.; Epelbaum, E.; Deltuva, A.; Fonseca, A.C.; Gloeckle, W.; Meissner, U.-G.; Nogga, A.; Sauer, P.U.

    2006-06-15

    We measured the cross sections and tensor analyzing powers of the {sup 1}H(d-vector,pp)n breakup reaction at E{sub d}=19 MeV in four symmetric constant relative energy (SCRE) configurations. The data are compared with theoretical predictions from four different approaches: the first based on high-precision (semi)phenomenological potentials alone or, the second, combined with model three-nucleon forces, and the third based on chiral forces up to next-to-next-to-leading order (NNLO) in the chiral expansion. In these cases the Coulomb interaction is not included. In addition, a fourth approach consists in a comparison with predictions based on CD Bonn including the {delta} excitation and the Coulomb force. In all cases the measured cross sections are significantly below the theoretical values, whereas the magnitudes of the tensor analyzing powers agree within the error bars in three of the four cases. The apparent discrepancies in the breakup cross sections are similar to the known differences for the space-star breakup. This adds to the data base of unsolved low-energy discrepancies (puzzles)

  19. Cross sections and tensor analyzing powers A_yy of the reaction ^1H(|vec|d,pp)n in SCRE geometries at E_d=19 MeV

    SciTech Connect

    J. Ley; C. Dueweke; A. Emmerich; A. Imig; H. Paez gen. Schieck; J. Golak; H. Witala; Evgeny Epelbaum; A. Deltuva; A. C. Fonseca; W. Gloeckle; Ulf-G. Meissner; A. Nogga; P. U. Sauer

    2006-02-01

    We measured the cross sections and tensor analyzing powers of the 1H({approx}d,pp)n breakup reaction at Ed=19 MeV in four symmetric constant relative energy (SCRE) configurations. The data are compared with theoretical predictions from three different approaches: one based on high precision (semi)phenomenological potentials alone or combined with model three-nucleon forces, another on chiral forces up to next-to-next-to-leading order (NNLO) in the chiral expansion. In both cases, the Coulomb interaction is not included. In addition, a comparison to predictions based on CD Bonn including the Lambda excitation and the Coulomb force is presented. In all cases the measured cross sections are significantly below the theoretical values whereas the magnitude of the tensor analyzing powers agree within the error bars in three of the four cases. The apparent discrepancies in the breakup cross sections are similar to the known differences for the space-star breakup. This adds to the data base of unsolved low-energy discrepancies.

  20. Measurement of the 187Re({\\alpha},n)190Ir reaction cross section at sub-Coulomb energies using the Cologne Clover Counting Setup

    E-print Network

    Scholz, P; Hennig, A; Netterdon, L; Becker, H W; Endres, J; Mayer, J; Giesen, U; Rogalla, D; Schlüter, F; Pickstone, S G; Zell, K O; Zilges, A

    2015-01-01

    Uncertainties in adopted models of particle+nucleus optical-model potentials directly influence the accuracy in the theoretical predictions of reaction rates as they are needed for reaction-network calculations in, for instance, {\\gamma}-process nucleosynthesis. The improvement of the {\\alpha}+nucleus optical-model potential is hampered by the lack of experimental data at astrophysically relevant energies especially for heavier nuclei. Measuring the Re187({\\alpha},n)Ir190 reaction cross section at sub-Coulomb energies extends the scarce experimental data available in this mass region and helps understanding the energy dependence of the imaginary part of the {\\alpha}+nucleus optical-model potential at low energies. Applying the activation method, after the irradiation of natural rhenium targets with {\\alpha}-particle energies of 12.4 to 14.1 MeV, the reaction yield and thus the reaction cross section were determined via {\\gamma}-ray spectroscopy by using the Cologne Clover Counting Setup and the method of {\\ga...

  1. A study of the reactions of ethanol on CeO{sub 2} and Pd/CeO{sub 2} by steady state reactions, temperature programmed desorption, and in situ FT-IR

    SciTech Connect

    Yee, A.; Morrison, S.J.; Idriss, H.

    1999-09-10

    The reaction of ethanol on unreduced and H{sub 2}-reduced CeO{sub 2} and 1 wt% Pd/CeO{sub 2} has been investigated by steady state reactions, temperature programmed desorption (TPD), and in situ Fourier transform infrared (FT-IR) spectroscopy. Steady state reactions have shown a zero reaction order dependency for diatomic oxygen at and above 20%, while the addition of Pd to CeO{sub 2} decreases the apparent activation energy of the reaction from 75 kJ/mol on CeO{sub 2} alone to 40 kJ/mol (Pd/CeO{sub 2}). TPD experiments following ethanol adsorption on both CeO{sub 2} and Pd/CeO{sub 2} have shown desorption profiles corresponding to unreacted ethanol and various reaction and decomposition products (acetaldehyde, acetone, CO, CO{sub 2}, and methane). Ethanol conversion to reaction products was increased by the addition of Pd, from 15 to 30% on CeO{sub 2} and H{sub 2}-reduced CeO{sub 2}, to 71 and 63% on Pd/CeO{sub 2} and H{sub 2}-reduced Pd/CeO{sub 2}, respectively.

  2. U1h Superstructure

    SciTech Connect

    Glen Sykes

    2000-11-01

    The U1H Shaft Project is a design build subcontract to supply the U. S. Department of Energy (DOE) a 1,045 ft. deep, 20 ft. diameter, concrete lined shaft for unspecified purposes. The subcontract awarded to Atkinson Construction by Bechtel Nevada to design and construct the shaft for the DOE has been split into phases with portions of the work being released as dictated by available funding. The first portion released included the design for the shaft, permanent hoist, headframe, and collar arrangement. The second release consisted of constructing the shaft collar to a depth of 110 ft., the service entry, utility trenches, and installation of the temporary sinking plant. The temporary sinking plant included the installation of the sinking headframe, the sinking hoist, two deck winches, the shaft form, the sinking work deck, and temporary utilities required to sink the shaft. Both the design and collar construction were completed on schedule. The third release consisted of excavating and lining the shaft to the station depth of approximately 950 feet. Work is currently proceeding on this production sinking phase. At a depth of approximately 600 feet, Atkinson has surpassed production expectation and is more than 3 months ahead of schedule. Atkinson has employed the use of a Bobcat 331 excavator as the primary means of excavation. the shaft is being excavated entirely in an alluvial deposit with varying degrees of calcium carbonate cementation. Several more work packages are expected to be released in the near future. The remaining work packages include, construction of the shaft station a depth of 975 ft. and construction of the shaft sump to a depth of 1,045 ft., installation of the loading pocket and station steel and equipment, installation of the shaft steel and guides, installation of the shaft utilities, and installation of the permanent headframe, hoist, collar utilities, and facilities.

  3. Molecular structure, spectral investigation (1H NMR, 13C NMR, UV-Visible, FT-IR, FT-Raman), NBO, intramolecular hydrogen bonding, chemical reactivity and first hyperpolarizability analysis of formononetin [7-hydroxy-3(4-methoxyphenyl)chromone]: A quantum chemical study

    NASA Astrophysics Data System (ADS)

    Srivastava, Anubha; Mishra, Rashmi; Kumar, Sudhir; Dev, Kapil; Tandon, Poonam; Maurya, Rakesh

    2015-03-01

    Formononetin [7-hydroxy-3(4-methoxyphenyl)chromone or 4?-methoxy daidzein] is a soy isoflavonoid that is found abundantly in traditional Chinese medicine Astragalus mongholicus (Bunge) and Trifolium pretense L. (red clover), and in an Indian medicinal plant, Butea (B.) monosperma. Crude extract of B.monosperma is used for rapid healing of fracture in Indian traditional medicine. In this study, a combined theoretical and experimental approach is used to study the properties of formononetin. The optimized geometry was calculated by B3LYP method using 6-311++G(d,p) as a large basis set. The FT-Raman and FT-IR spectra were recorded in the solid phase, and interpreted in terms of potential energy distribution (PED) analysis. Density functional theory (DFT) is applied to explore the nonlinear optical properties of the molecule. Good consistency is found between the calculated results and observed data for the electronic absorption, IR and Raman spectra. The solvent effects have been calculated using time-dependent density functional theory in combination with the integral equation formalism polarized continuum model, and the results are in good agreement with observed measurements. The double well potential energy curve of the molecule about the respective bonds, have been plotted, as obtained from DFT/6-31G basis set. The computational results diagnose the most stable conformer of formononetin. The HOMO-LUMO energy gap of possible conformers has been calculated for comparing their chemical activity. Chemical reactivity has been measured by reactivity descriptors and molecular electrostatic potential surface (MEP). The 1H and 13C NMR chemical shifts of the molecule were calculated by the Gauge including atomic orbital (GIAO) method. Furthermore, the role of CHsbnd O intramolecular hydrogen bond in the stability of molecule is investigated on the basis of the results of topological properties of AIM theory and NBO analysis. The calculated first hyperpolarizability shows that the molecule is an attractive molecule for future applications in non-linear optics.

  4. Two bisthienylethene-Ir(iii) complexes showing acid/base-induced structural transformation and on-off luminescence switching in solution.

    PubMed

    Cao, Deng-Ke; Hu, Jiong-Sheng; Li, Min-Qiang; Gong, Dan-Ping; Li, Xiao-Xiong; Ward, Michael D

    2015-12-28

    Complexes [Ir(dfppy)2(pbdtiH)](PF6)·2CHCl3 (1-H) and [Ir(dfppy)2(pbdti)] (1) were synthesized by the reaction of bisthienylethene pbdtiH and an [Ir(dfppy)2Cl]2 dimer under neutral and basic conditions, respectively. Thus, the {Ir(dfppy)2}(+) unit is coordinated by pbdtiH in 1-H, and by pbdti(-) in 1, which are confirmed by their crystal structures. The structures of 1-H and 1 could be interconverted in solution, upon alternately adding NEt3 and TFA, thus resulting in reversible luminescence switching between the on-state of 1-H and the off-state of 1 at room temperature. In addition, both 1-H and 1 show solid-state luminescence, with a broad emission at 534 nm and 525 nm, respectively. The free pbdtiH ligand shows photochromic behavior in CH2Cl2 solution. However, no photochromism has been observed in 1-H and 1, indicating that the coordination of the pbdtiH/pbdti(-) ligand to the {Ir(dfppy)2}(+) unit could suppress their photochromic behaviors. PMID:26586364

  5. Measurement of the 187Re(?,n)190Ir reaction cross section at sub-Coulomb energies using the Cologne Clover Counting Setup

    E-print Network

    P. Scholz; A. Endres; A. Hennig; L. Netterdon; H. W. Becker; J. Endres; J. Mayer; U. Giesen; D. Rogalla; F. Schlüter; S. G. Pickstone; K. O. Zell; A. Zilges

    2015-01-07

    Uncertainties in adopted models of particle+nucleus optical-model potentials directly influence the accuracy in the theoretical predictions of reaction rates as they are needed for reaction-network calculations in, for instance, {\\gamma}-process nucleosynthesis. The improvement of the {\\alpha}+nucleus optical-model potential is hampered by the lack of experimental data at astrophysically relevant energies especially for heavier nuclei. Measuring the Re187({\\alpha},n)Ir190 reaction cross section at sub-Coulomb energies extends the scarce experimental data available in this mass region and helps understanding the energy dependence of the imaginary part of the {\\alpha}+nucleus optical-model potential at low energies. Applying the activation method, after the irradiation of natural rhenium targets with {\\alpha}-particle energies of 12.4 to 14.1 MeV, the reaction yield and thus the reaction cross section were determined via {\\gamma}-ray spectroscopy by using the Cologne Clover Counting Setup and the method of {\\gamma}{\\gamma} coincidences. Cross-section values at five energies close to the astrophysically relevant energy region were measured. Statistical model calculations revealed discrepancies between the experimental values and predictions based on widely used {\\alpha}+nucleus optical-model potentials. However, an excellent reproduction of the measured cross-section values could be achieved from calculations based on the so-called Sauerwein-Rauscher {\\alpha}+nucleus optical-model potential. The results obtained indicate that the energy dependence of the imaginary part of the {\\alpha}+nucleus optical-model potential can be described by an exponential decrease. Successful reproductions of measured cross sections at low energies for {\\alpha}-induced reactions in the mass range 141{\\leq}A{\\leq}187 confirm the global character of the Sauerwein-Rauscher potential.

  6. Measurement of the 187Re(? ,n )190Ir reaction cross section at sub-Coulomb energies using the Cologne Clover Counting Setup

    NASA Astrophysics Data System (ADS)

    Scholz, P.; Endres, A.; Hennig, A.; Netterdon, L.; Becker, H. W.; Endres, J.; Mayer, J.; Giesen, U.; Rogalla, D.; Schlüter, F.; Pickstone, S. G.; Zell, K. O.; Zilges, A.

    2014-12-01

    Background: Uncertainties in adopted models of particle+nucleu s optical-model potentials directly influence the accuracy in the theoretical predictions of reaction rates as they are needed for reaction-network calculations in, for instance, ? -process nucleosynthesis. The improvement of the ? +nucleu s optical-model potential is hampered by the lack of experimental data at astrophysically relevant energies especially for heavier nuclei. Purpose: Measuring the 187Re(? ,n )190Ir reaction cross section at sub-Coulomb energies extends the scarce experimental data available in this mass region and helps understanding the energy dependence of the imaginary part of the ? +nucleus optical-model potential at low energies. Method: Applying the activation method, after the irradiation of natural rhenium targets with ? -particle energies of 12.4 to 14.1 MeV, the reaction yield and thus the reaction cross section were determined via ? -ray spectroscopy by using the Cologne Clover Counting Setup and the method of ? ? coincidences. Results: Cross-section values at five energies close to the astrophysically relevant energy region were measured. Statistical model calculations revealed discrepancies between the experimental values and predictions based on widely used ? +nucleus optical-model potentials. However, an excellent reproduction of the measured cross-section values could be achieved from calculations based on the so-called Sauerwein-Rauscher ? +nucleus optical-model potential. Conclusion: The results obtained indicate that the energy dependence of the imaginary part of the ? +nucleus optical-model potential can be described by an exponential decrease. Successful reproductions of measured cross sections at low energies for ? -induced reactions in the mass range 141 ?A ?187 confirm the global character of the Sauerwein-Rauscher potential.

  7. Improvement of Anode Oxidation Reaction of a Fuel Cell Using Ammonium Formate with Pt-Ir Catalysts

    NASA Astrophysics Data System (ADS)

    Ohyama, Kazutoshi; Sugino, Takashi; Nitta, Tomohiro; Kimura, Chiharu; Aoki, Hidemitsu

    We have first attempted to develop high performance and safe fuel cells using ammonium formate as solid (powder) fuel. This solid fuel has potential to realize safe portability compared with liquid fuel such as methanol from the viewpoint of toxicity and flammability. In order to make use of some advantages of ammonium formate, we have investigated oxidation characteristics of ammonium formate toward Pt electrode. From cyclic voltammograms, ammonium formate has high activity to be oxidized with a Pt electrode. We have found that oxidation of ammonium formate can be improved by additional Ir catalysts with Pt catalysts. There is a high potentiality that ammonium formate is useful as solid (powder) fuel for polymer electrolyte membrane (PEM) fuel cells. This new fuel will be driving force to develop safe fuel cells for PEM.

  8. Teaching 1H NMR Spectrometry Using Computer Modeling.

    ERIC Educational Resources Information Center

    Habata, Yoichi; Akabori, Sadatoshi

    2001-01-01

    Molecular modeling by computer is used to display stereochemistry, molecular orbitals, structure of transition states, and progress of reactions. Describes new ideas for teaching 1H NMR spectroscopy using computer modeling. (Contains 12 references.) (ASK)

  9. Two different products from the reaction of 1-aryl-5-chloro-3-methyl-1H-pyrazole-4-carbaldehyde with cyclohexylamine when the aryl substituent is phenyl or pyridin-2-yl: hydrogen-bonded sheets versus dimers.

    PubMed

    Orrego Hernandez, Jessica; Portilla, Jaime; Cobo, Justo; Glidewell, Christopher

    2015-05-01

    Cyclohexylamine reacts with 5-chloro-3-methyl-1-(pyridin-2-yl)-1H-pyrazole-4-carbaldehyde to give 5-cyclohexylamino-3-methyl-1-(pyridin-2-yl)-1H-pyrazole-4-carbaldehyde, C16H20N4O, (I), formed by nucleophilic substitution, but with 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde the product is (Z)-4-[(cyclohexylamino)methylidene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one, C17H21N3O, (II), formed by condensation followed by hydrolysis. Compound (II) crystallizes with Z' = 2, and in one of the two independent molecular types the cyclohexylamine unit is disordered over two sets of atomic sites having occupancies of 0.65?(3) and 0.35?(3). The vinylogous amide portion in each compound shows evidence of electronic polarization, such that in each the O atom carries a partial negative charge and the N atom of the cyclohexylamine portion carries a partial positive charge. The molecules of (I) contain an intramolecular N-H...N hydrogen bond, and they are linked by C-H...O hydrogen bonds to form sheets. Each of the two independent molecules of (II) contains an intramolecular N-H...O hydrogen bond and each molecular type forms a centrosymmetric dimer containing one R2(2)(4) ring and two inversion-related S(6) rings. PMID:25940891

  10. VOLUME 81, NUMBER 9 P H Y S I C A L R E V I E W L E T T E R S 31 AUGUST 1998 Longitudinal and Transverse Cross Sections in the 1H e, e000K1 L Reaction

    E-print Network

    Maryland at College Park, University of

    . Mitchell,3 H. Mkrtchyan,5 S. Mtingwa,10 I. Niculescu,1 R. Perrino,12 D. Potterveld,9 J. W. Price,16 B. A and Transverse Cross Sections in the 1H e, e000K1 L Reaction G. Niculescu,1 R. M. Mohring,2 P. Gueye,1 D. Abbott. Urciuoli,12 J. Volmer,11 W. Vulcan,3 P. Welch,17 R. Williams,1 S. Wood,3 C. Yan,3 and B. Zeidman9 1 Hampton

  11. Tetrahydroindeno[1',2':4,5]pyrrolo[1,2-a]imidazol-5(1H)-ones as novel neonicotinoid insecticides: reaction selectivity and substituent effects on the activity level.

    PubMed

    Chen, Nanyang; Meng, Xiaoqing; Zhu, Fengjuan; Cheng, Jiagao; Shao, Xusheng; Li, Zhong

    2015-02-11

    Tetraheterocyclic tetrahydroindeno[1',2':4,5]pyrrolo[1,2-a]imidazol-5(1H)-one derivatives as novel neonicotinoid candidates were designed and prepared by selective etherification, chlorination and esterification of ninhydrin-heterocyclic ketene aminals adducts. Some of the designed compounds showed excellent insecticidal activity against cowpea aphids (Aphis craccivora), brown planthopper (Nilaparvata lugens), and armyworm (Mythimna separata). In particular, the activity against armyworm (Mythimna separata) improved a lot in contrast with that of imidacloprid and cycloxaprid. The research here provides a novel neonicotinoid chemotype for further development. PMID:25611859

  12. Unexpected reactions of 2,5-dimethylthiopene (2,5-Me{sub 2}t) in Cp{sup *}Ir({eta}{sup 5}-2,5-Me{sub 2}T){sup 2+}, Cp{sup *}Ir({eta}{sup 4}-2,5-Me{sub 2}T), and Cp{sup *}Ir(C,S-2,5-Me{sub 2}T) with cobaltocene

    SciTech Connect

    Chen, J.; Daniels, L.M.; Angelica, R.J.

    1996-02-20

    The reaction of Cp{sup *}Ir({eta}{sup 5}-2,5-Me{sub 2}T){sup 2+} (1) (Cp{sup *} = {eta}{sup 5}-C{sub 5}Me{sub 5}) with the reducing agent Cp{sub 2}Co yields Cp{sup *}Ir({eta}{sup 4}-2,5-Me{sub 2}T) (2) and Cp{sup *}Ir(C,S-2,5-Me{sub 2}T) (3), as well as the unexpected Cp{sup *}Ir({eta}{sup 4}-2,5-Me{sub 2}T{center_dot}C{sub 5}H{sub 4}) (4), which can also be prepared by reacting 1 with Cp{sup -}. An X-ray diffraction study of 4 shows the {eta}{sup 4}-2,5-Me{sub 2}T{center_dot}C{sub 5}H{sub 5} ligand to be a ring-opened 2,5-Me{sub 2}T allyl thiolate conjugated to a cyclopentadienylidene unit. The reduced products 2 and 3 react with Cp{sub 2}Co to give a ferrole-type product Cp{sup *}[IrC(Me)=CHCH=C(Me)]CoCp in which the planar iridacyclopentadiene ring is {pi}-bonded to the cobalt, as established by a structural investigation. The Cp{sup *}Co analog of 5 is prepared by the reaction of 2 or 3 with Cp{sup *}Co(CH{sub 2}=CH{sub 2}){sub 2}. These studies demonstrate that cobaltocene and Cp{sup *}Co(CH{sub 2}=CH{sub 2}){sub 2} readily desulfurize the 2,5-dimethylthiophene ligand in 2 and 3, which supports a previously proposed mechanism for the thiophene hydrodesulfurization. 37 refs., 2 figs., 5 tabs.

  13. Preparation, GIAO NMR Calculations and Acidic Properties of Some Novel 4,5-dihydro-1H-1,2,4-triazol-5-one Derivatives with Their Antioxidant Activities

    PubMed Central

    Yüksek, Haydar; Alkan, Muzaffer; Cakmak, Ismail; Ocak, Zafer; Bahçeci, ?ule; Calapo?lu, Mustafa; Elmasta?, Mahfuz; Kolomuç, Ali; Aksu, Havva

    2008-01-01

    Six novel 3-alkyl(aryl)-4-(p-nitrobenzoylamino)-4,5-dihydro-1H-1,2,4-triazol-5- ones (2a-f) were synthesized by the reactions of 3-alkyl(aryl)-4-amino-4,5-dihydro-1H- 1,2,4-triazol-5-ones (1a-f) with p-nitrobenzoyl chloride and characterized by elemental analyses and IR, 1H-NMR, 13C-NMR and UV spectral data. The newly synthesized compounds 2 were titrated potentiometrically with tetrabutylammonium hydroxide in four non-aqueous solvents such as acetone, isopropyl alcohol, tert-butyl alcohol and N,N-dimethylformamide, and the half-neutralization potential values and the corresponding pKa values were determined for all cases. Thus, the effects of solvents and molecular structure upon acidity were investigated. In addition, isotropic 1H and 13C nuclear magnetic shielding constants of compounds 2 were obtained by the gauge-including-atomic-orbital (GIAO) method at the B3LYP density functional level. The geometry of each compound has been optimized using the 6-311G basis set. Theoretical values were compared to the experimental data. Furthermore, these new compounds and five recently reported 3-alkyl-4-(2-furoylamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones (3a–c,e,f) were screened for their antioxidant activities. PMID:19325716

  14. Synthesis and Evaluation of Novel Iminosugars as Potential Male Contraceptive Agents; and the Chemistry of 2,3-Dihydropyridin-4-(1H)-ones and Related Enaminones in Multicomponent Reactions

    E-print Network

    Gu, Xingxian

    2010-04-26

    . The methylmalonate reaction products were cyclized under acidic conditions to form bicyclic lactams (octahydroquinoline-3- carboxylates and cyclopenta[b]pyridine-3-carboxylates). Oxidation of the octahydroquinoline-3-carboxylates furnished 2,5-dioxo-1... of the aduct 2.3.4 Oxidation of 2,5-dioxo-octahydroquinoline-3-carboxylates 2.3.5 Synthesis of N-substituted 2,5-dioxo-octahydroquinoline-3- carbonitriles 2.4 Concluding remarks Chapter 3 Experimental Data 3.1 Material and methods 3...

  15. Synthesis, characterization and theoretical studies of 5-(benzylthio)-1-cylopentyl-1H-tetrazole

    NASA Astrophysics Data System (ADS)

    Saglam, S.; Disli, A.; Erdogdu, Y.; Marchewka, M. K.; Kanagathara, N.; Bay, B.; Güllüo?lu, M. T.

    2015-01-01

    In this study, 5-(benzylthio)-1-cylopentyl-1H-tetrazole (5B1C1HT) have been synthesized. Boiling points of the obtained compound have been determined and it has been characterized by FT-IR, 1H NMR, 13C-APT and LC-MS spectroscopy techniques. The FT-IR, 1H NMR and 13C-APT spectral measurements of the 5B1C1HT compound and complete assignment of the vibrational bands observed in spectra has been discussed. The spectra were interpreted with the aid of normal coordinate analysis following full structure optimization and force field calculations based on Density Functional Theory (DFT) at 6-311++G**, cc-pVDZ and cc-pVTZ basis sets. The optimized geometry with 6-311++G** basis sets were used to determine the total energy distribution, harmonic vibrational frequencies, IR intensities.

  16. Vector correlations study of the reaction N(2D)+H2(X1?g+)?NH(a1?)+H(2S) with different collision energies and reagent vibration excitations

    NASA Astrophysics Data System (ADS)

    Li, Yong-Qing; Zhang, Yong-Jia; Zhao, Jin-Feng; Zhao, Mei-Yu; Ding, Yong

    2015-11-01

    Vector correlations of the reaction are studied based on a recent DMBE-SEC PES for the first excited state of NH2 [J. Phys. Chem. A 114 9644 (2010)] by using a quasi-classical trajectory method. The effects of collision energy and the reagent initial vibrational excitation on cross section and product polarization are investigated for v = 0–5 and j = 0 states in a wide collision energy range (10–50 kcal/mol). The integral cross section could be increased by H2 vibration excitation remarkably based on the DMBE-SEC PES. The different phenomena of differential cross sections with different collision energies and reagent vibration excitations are explained. Particularly, the NH molecules are scattered mainly in the backward hemisphere at low vibration quantum number and evolve from backward to forward direction with increasing vibration quantum number, which could be explained by the fact that the vibrational excitation enlarges the H–H distance in the entrance channel, thus enhancing the probability of collision between N atom and H atom. A further study on product polarization demonstrates that the collision energy and vibrational excitation of the reagent remarkably influence the distributions of P(?r), P(?r), and P(?r, ?r). Project supported by the National Natural Science Foundation of China (Grant Nos. 11474141 and 11404080), the Special Fund Based Research New Technology of Methanol conversion and Coal Instead of Oil, the China Postdoctoral Science Foundation (Grant No. 2014M550158) , the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry of China (Grant No. 2014-1685), and the Program for Liaoning Excellent Talents in University, China (Grant Nos. LJQ2015040 and LJQ2014001).

  17. Hydroxyl radical reaction rate coefficients as a function of temperature and IR absorption cross sections for CF3CH=CH2 (HFO-1243zf), potential replacement of CF3CH2F (HFC-134a).

    PubMed

    González, Sergio; Jiménez, Elena; Ballesteros, Bernabé; Martínez, Ernesto; Albaladejo, José

    2015-04-01

    CF3CH=CH2 (hydrofluoroolefin, HFO-1243zf) is a potential replacement of high global-warming potential (GWP) hydrofluorocarbon (HFC-134a, CF3CFH2). Both the atmospheric lifetime and the radiative efficiency of HFO-1243zf are parameters needed for estimating the GWP of this species. Therefore, the aim of this work is (i) to estimate the atmospheric lifetime of HFO-1243zf from the reported OH rate coefficients, k OH, determined under tropospheric conditions and (ii) to calculate its radiative efficiency from the reported IR absorption cross sections. The OH rate coefficient at 298 K also allows the estimation of the photochemical ozone creation potential (?(POCP)). The pulsed laser photolysis coupled to a laser-induced fluorescence technique was used to determine k OH for the reaction of OH radicals with HFO-1243zf as a function of pressure (50-650 Torr of He) and temperature (263-358 K). Gas-phase IR spectra of HFO-1243zf were recorded at room temperature using a Fourier transform IR spectrometer between 500 and 4,000 cm(-1). At all temperatures, k OH did not depend on bath gas concentration (i.e., on the total pressure between 50 and 650 Torr of He). A slight but noticeable T dependence of k OH was observed in the temperature range investigated. The observed behavior is well described by the following Arrhenius expression: k OH(T)?=?(7.65?±?0.26)?×?10(-13) exp [(165?±?10)?/?T]?cm(3) molecule(-1) s(-1). Negligible IR absorption of HFO-1243zf was observed at wavenumbers greater than 1,700 cm(-1). Therefore, IR absorption cross sections, [Formula: see text], were determined in the 500-1,700 cm(-1) range. Integrated [Formula: see text] were determined between 650 and 1,800 cm(-1) for comparison purposes. The main diurnal removal pathway for HFO-1243zf is the reaction with OH radicals, which accounts for 64% of the overall loss by homogeneous reactions at 298 K. Globally, the lifetime due to OH reaction (? OH) was estimated to be 8.7 days under the assumption of a well-mixed atmosphere. Assuming other removal pathways, the atmospheric lifetime (?) was estimated to be ?6 days. Considering the estimated ? OH and the measured IR absorption cross sections of HFO-1243zf in the atmospheric window (720-1,250 cm(-1)), its lifetime corrected radiative efficiency was calculated to be 0.019 W m(-2) ppbv(-1). GWP100 years for the HFO investigated, 0.29, is negligible compared to that of HFC-134a, the HFC to be potentially replaced (GWP100 years?=?1,300, Hodnebrog et al. (Rev Geophys 51:300-378, 2013)). ? POCP for HFO-1243zf was estimated to be around 1 order of magnitude lower than that for ethylene. In conclusion, HFO-1243zf is fast degraded in the atmosphere, and it does not appreciably contribute to global warming and local/regional air pollution. Therefore, HFO-1243zf can be a suitable replacement for HFC-134a in air conditioning units. PMID:25138554

  18. FT-IR, FT-Raman, molecular structure, first order hyperpolarizability, HOMO and LUMO analysis, MEP and NBO analysis of 3-(adamantan-1-yl)-4-(prop-2-en-1-yl)-1H-1,2,4-triazole-5(4H)-thione, a potential bioactive agent.

    PubMed

    Rosline Sebastian, S H; Attia, Mohamed I; Almutairi, Maha S; El-Emam, Ali A; Panicker, C Yohannan; Van Alsenoy, Christian

    2014-11-11

    The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 3-(adamantan-1-yl)-4-(prop-2-en-1-yl)-1H-1,2,4-triazole-5(4H)-thione have been investigated experimentally and theoretically using Gaussian09 software package. Potential energy distribution of normal modes vibrations was done using GAR2PED program. The HOMO and LUMO analysis are used to determine the charge transfer within the molecule. The stability of the molecule arising from hyperconjugative interaction and charge delocalization has been analyzed using NBO analysis. The calculated geometrical parameters are in agreement with the XRD data. The calculated first hyperpolarizability is high and the title compound is an attractive candidate for further studies in nonlinear optical applications. To estimate the chemical reactivity of the molecule, the molecular electrostatic potential is calculated for the optimized geometry of the molecule. PMID:24878436

  19. Intermolecular C-H activation with an Ir-METAMORPhos piano-stool complex--multiple reaction steps at a reactive ligand.

    PubMed

    Oldenhof, S; Lutz, M; van der Vlugt, J I; Reek, J N H

    2015-10-21

    Substrate activation by means of a reactive ligand is a topic of much interest. Herein we describe a stoichiometric anti-Markovnikov C-N bond formation involving ligand reactivity in multiple steps along the reaction coordinate, including ligand assisted substrate (de)protonation and C-N bond formation, as illustrated by a combined experimental, spectroscopic and computational study. This affords a highly unusual four-membered iridacycle bearing an exo-cyclic C=C double bond. PMID:26329519

  20. IR Windstreaks

    NASA Technical Reports Server (NTRS)

    2005-01-01

    [figure removed for brevity, see original site]

    Windstreaks are features caused by the interaction of wind and topographic landforms. The raised rims and bowls of impact craters causes a complex interaction such that the wind vortex in the lee of the crater can both scour away the surface dust and deposit it back in the center of the lee. If you look closely, you will see evidence of this in a darker 'rim' enclosing a brighter interior.

    This infrared image shows windstreaks in the region between Gordii Dorsum and Amazonis Mensa.

    Image information: IR instrument. Latitude -15.8, Longitude 215 East (145 West). 97 meter/pixel resolution.

    Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with Project policies at a later time.

    NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The Thermal Emission Imaging System (THEMIS) was developed by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. The THEMIS investigation is led by Dr. Philip Christensen at Arizona State University. Lockheed Martin Astronautics, Denver, is the prime contractor for the Odyssey project, and developed and built the orbiter. Mission operations are conducted jointly from Lockheed Martin and from JPL, a division of the California Institute of Technology in Pasadena.

  1. Synthesis, molecular structure and spectral analysis of ethyl 4-formyl-3,5-dimethyl-1H-pyrrole-2-carboxylate thiosemicarbazone: A combined DFT and AIM approach

    NASA Astrophysics Data System (ADS)

    Singh, R. N.; Kumar, Amit; Tiwari, R. K.; Rawat, Poonam; Verma, Divya; Baboo, Vikas

    2012-05-01

    A new ethyl 4-formyl-3,5-dimethyl-1H-pyrrole-2-carboxylate thiosemicarbazone (EFDMPCT) has been synthesized and characterized by elemental analysis and FT-IR, 1H NMR, UV-Visible, DART-mass spectroscopy. Quantum chemical calculations have been performed by DFT level of theory using B3LYP functional and 6-31G (d,p) as basis set. The calculated 1H NMR chemical shifts using gauge including atomic orbitals (GIAO) approach are in good agreement with the observed chemical shifts. The electronic transitions within molecule have been interpreted using the time dependent density functional theory (TD-DFT). The calculated and experimental wavenumbers analyses confirm the existence of dimer. Topological parameters electron density, Laplacian of electron density, kinetic electron energy density, potential electron density and the total electron energy density at the bond critical points (BCP) analyzed using 'Atoms in Molecules' AIM theory reveals intra and inter molecular hydrogen bonding other weaker interactions in detail. The calculated intermolecular hydrogen bond energy of dimer is -12.2176 kcal/mol using AIM calculation. The results of AIM ellipticity confirm the existence of resonance assisted hydrogen bonds in dimer. The calculated thermodynamic parameters show that reaction is exothermic and non-spontaneous at room temperature. The local reactivity descriptors find the reactive sites within molecules have been calculated.

  2. Diels-Alder reactions: The effects of catalyst on the addition reaction

    NASA Astrophysics Data System (ADS)

    Yilmaz, Özgür; Kus, Nermin Simsek; Tunç, Tuncay; Sahin, Ertan

    2015-10-01

    The reaction between 2,3-dimethyl-1,3-butadiene and dimethyl 7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate is efficiently achieved with small amounts of catalyst, i.e. phenol, AcOH, nafion, and ?-cyclodextrin. Exo-diastereoselective cycloaddition reactions were observed both without catalyst and different catalysts for 48 days. As a result, different products (tricyclicmolecule 5, retro-Diels-Alder product 6, and oxidation product 7) were obtained with different catalysts. In addition, we synthesized Diels-Alders product 8 and tricyclocyclitol 10 via Diels-Alder reaction. The structures of these products were characterized by 1H NMR, 13C NMR, MS and IR spectroscopy.

  3. Global sampling of the photochemical reaction paths of bromoform by ultrafast deep-UV through near-IR transient absorption and ab initio multiconfigurational calculations

    NASA Astrophysics Data System (ADS)

    Pal, S. K.; Mereshchenko, A. S.; Butaeva, E. V.; El-Khoury, P. Z.; Tarnovsky, A. N.

    2013-03-01

    Ultrafast deep-ultraviolet through near infrared (210-950 nm) transient absorption spectroscopy complemented by ab initio multiconfigurational calculations offers a global description of the photochemical reaction pathways of bromoform following 255-nm excitation in methylcyclohexane and acetonitrile solutions. Photoexcitation of CHBr3 leads to the ground-state iso-CHBr3 product in a large quantum yield (˜35%), formed through two different mechanisms: concerted excited-state isomerization and cage-induced isomerization through the recombination of the nascent radical pair. These two processes take place on different time scales of tens of femtoseconds and several picoseconds, respectively. The novel ultrafast direct isomerization pathway proposed herein is consistent with the occurrence of a conical intersection between the first excited singlet state of CHBr3 and the ground electronic state of iso-CHBr3. Complete active space self-consistent field calculations characterize this singularity in the vicinity of a second order saddle point on the ground state which connects the two isomer forms. For cage-induced isomerization, both the formation of the nascent radical pair and its subsequent collapse into ground-state iso-CHBr3 are directly monitored through the deep-ultraviolet absorption signatures of the radical species. In both mechanisms, the optically active (i.e., those with largest Franck-Condon factors) C-Br-Br bending and Br-Br stretching modes of ground-state iso-CHBr3 have the largest projection on the reaction coordinate, enabling us to trace the structural changes accompanying vibrational relaxation of the non-equilibrated isomers through transient absorption dynamics. The iso-CHBr3 photoproduct is stable in methylcyclohexane, but undergoes either facile thermal isomerization to the parent CHBr3 structure through a cyclic transition state stabilized by the polar acetonitrile medium (˜300-ps lifetime), and hydrolysis in the presence of water.

  4. Characterization of heroin samples by 1H NMR and 2D DOSY 1H NMR.

    PubMed

    Balayssac, Stéphane; Retailleau, Emmanuel; Bertrand, Geneviève; Escot, Marie-Pierre; Martino, Robert; Malet-Martino, Myriam; Gilard, Véronique

    2014-01-01

    Twenty-four samples of heroin from different illicit drug seizures were analyzed using proton Nuclear Magnetic Resonance ((1)H NMR) and two-dimensional diffusion-ordered spectroscopy (2D DOSY) (1)H NMR. A careful assignment and quantification of (1)H signals enabled a comprehensive characterization of the substances present in the samples investigated: heroin, its main related impurities (6-acetylmorphine, acetylcodeine, morphine, noscapine and papaverine) and cutting agents (caffeine and acetaminophen in nearly all samples as well as lactose, lidocaine, mannitol, piracetam in one sample only), and hence to establish their spectral signatures. The good agreement between the amounts of heroin, noscapine, caffeine and acetaminophen determined by (1)H NMR and gas chromatography, the reference method in forensic laboratories, demonstrates the validity of the (1)H NMR technique. In this paper, 2D DOSY (1)H NMR offers a new approach for a whole characterization of the various components of these complex mixtures. PMID:24378299

  5. Construction of two Cd(II) complexes by flexible adipic acid plus 2-((benzoimidazol-yl)methyl)-1H-tetrazole ligand

    NASA Astrophysics Data System (ADS)

    Duan, Wanlu; Zhang, Yuhong; Wang, Xiuxiu; Meng, Xiangru

    2015-10-01

    Two new complexes with the formulas [Cd(bimt)(adi)]n (1) and {[Cd(bimt)(adi)0.5Br]·H2O}n (2) were synthesized through reactions of 2-((benzoimidazol-yl)methyl)-1H-tetrazole (bimt) with Cd(II) salts in the presence of adipic acid (H2adi). Single crystal X-ray analysis reveals that complex 1 shows a 1D chain structure in which adipate ligand coordinates to Cd(II) ions with ?3-bridging mode. Complex 2 displays a 2D layer structure with 4-connected (44·62) topology in which adipate ligand coordinates to Cd(II) ions with ?2-bridging mode. These results reveal that the versatile coordination modes of adipate ligands play an important role in controlling the structures of the complexes. In addition, their IR spectra, element analyses, PXRD patterns and luminescent properties are investigated.

  6. Time-Resolved Quantitative Measurement of OH HO2 and CH2O in Fuel Oxidation Reactions by High Resolution IR Absorption Spectroscopy.

    SciTech Connect

    Huang, Haifeng; Rotavera, Brandon; Taatjes, Craig A.

    2014-08-01

    Combined with a Herriott-type multi-pass slow flow reactor, high-resolution differential direct absorption spectroscopy has been used to probe, in situ and quantitatively, hydroxyl (OH), hydroperoxy (HO 2 ) and formaldehyde (CH 2 O) molecules in fuel oxidation reactions in the reactor, with a time resolution of about 1 micro-second. While OH and CH 2 O are probed in the mid-infrared (MIR) region near 2870nm and 3574nm respectively, HO 2 can be probed in both regions: near-infrared (NIR) at 1509nm and MIR at 2870nm. Typical sensitivities are on the order of 10 10 - 10 11 molecule cm -3 for OH at 2870nm, 10 11 molecule cm -3 for HO 2 at 1509nm, and 10 11 molecule cm -3 for CH 2 O at 3574nm. Measurements of multiple important intermediates (OH and HO 2 ) and product (CH 2 O) facilitate to understand and further validate chemical mechanisms of fuel oxidation chemistry.

  7. Dynamics of the reactions of O(1D) with CD3OH and CH3OD studied with time-resolved Fourier-transform IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Huang, Chong-Kai; Xu, Zhen-Feng; Nakajima, Masakazu; Nguyen, Hue M. T.; Lin, M. C.; Tsuchiya, Soji; Lee, Yuan-Pern

    2012-10-01

    We investigated the reactivity of O(1D) towards two types of hydrogen atoms in CH3OH. The reaction was initiated on irradiation of a flowing mixture of O3 and CD3OH or CH3OD at 248 nm. Relative vibration-rotational populations of OH and OD (1 ? v ? 4) states were determined from their infrared emission recorded with a step-scan time-resolved Fourier-transform spectrometer. In O(1D) + CD3OH, the rotational distribution of OD is nearly Boltzmann, whereas that of OH is bimodal; the product ratio [OH]/[OD] is 1.56 ± 0.36. In O(1D) + CH3OD, the rotational distribution of OH is nearly Boltzmann, whereas that of OD is bimodal; the product ratio [OH]/[OD] is 0.59 ± 0.14. Quantum-chemical calculations of the potential energy and microcanonical rate coefficients of various channels indicate that the abstraction channels are unimportant and O(1D) inserts into the C-H and O-H bonds of CH3OH to form HOCH2OH and CH3OOH, respectively. The observed three channels of OH are consistent with those produced via decomposition of the newly formed OH or the original OH moiety in HOCH2OH or decomposition of CH3OOH. The former decomposition channel of HOCH2OH produces vibrationally more excited OH because of incomplete intramolecular vibrational relaxation, and decomposition of CH3COOH produces OH with greater rotational excitation, likely due to a large torque angle during dissociation. The predicted [OH]/[OD] ratios are 1.31 and 0.61 for O(1D) + CD3OH and CH3OD, respectively, at collision energy of 26 kJ mol-1, in satisfactory agreement with the experimental results. These predicted product ratios vary weakly with collision energy.

  8. 1H Cramps Based on Trev

    NASA Astrophysics Data System (ADS)

    Buszko, M. L.; Bronnimann, C. E.; Maciel, G. E.

    Line-narrowing effects of the 1H TREV-8 pulse sequence applied to solids rotating at the magic angle have been examined. Polycrystalline samples of adipic, malonic, and fumaric acids, adamantane, a barley seed, and a pyridine-saturated coal sample were examined. The TREV-based 1H CRAMPS technique is seen to provide reasonably effective line narrowing for both "soft" solids (adamantane) and rigid solids (carboxylic acids), enabling 1H chemical-shift fine structure to be observed. For adamantane, the 1H linewidth is reduced from about 13 kHz (static) to 40 Hz (CRAMPS) at a 840 Hz MAS rate and a pulse spacing (?) of 7.8 ?s. The line-narrowing efficiency increases for larger ? values, but does not approach the efficiency of BR-24. However, unlike the case for BR-24 or other multiple-pulse line-narrowing sequences based on the formation of solid echoes, the line-narrowing efficiency of TREV-8 is sustained for large offsets; this feature, along with a relatively large bandwidth, may be an important factor when the sequence is implemented in 19F CRAMPS and in solid-sample imaging studies. TREV-CRAMPS may also be useful for samples in which the somewhat inferior line-narrowing behavior may be masked by line-broadening effects not based on homonuclear dipolar interactions.

  9. Catalytic Activity of Platinum Monolayer on Iridium and Rhenium Alloy Nanoparticles for the Oxygen Reduction Reaction

    SciTech Connect

    Karan, Hiroko I.; Sasaki, Kotaro; Kuttiyiel, Kurian; Farberow, Carrie A.; Mavrikakis, Manos; Adzic, Radoslav R.

    2012-05-04

    A new type of electrocatalyst with a core?shell structure that consists of a platinum monolayer shell placed on an iridium? rhenium nanoparticle core or platinum and palladium bilayer shell deposited on that core has been prepared and tested for electrocatalytic activity for the oxygen reduction reaction. Carbon-supported iridium? rhenium alloy nanoparticles with several different molar ratios of Ir to Re were prepared by reducing metal chlorides dispersed on Vulcan carbon with hydrogen gas at 400 °C for 1 h. These catalysts showed specific electrocatalytic activity for oxygen reduction reaction comparable to that of platinum. The activities of PtML/PdML/Ir2Re1, PtML/Pd2layers/Ir2Re1, and PtML/Pd2layers/Ir7Re3 catalysts were, in fact, better than that of conventional platinum electrocatalysts, and their mass activities exceeded the 2015 DOE target. Our density functional theory calculations revealed that the molar ratio of Ir to Re affects the binding strength of adsorbed OH and, thereby, the O2 reduction activity of the catalysts. The maximum specific activity was found for an intermediate OH binding energy with the corresponding catalyst on the top of the volcano plot. The monolayer concept facilitates the use of much less platinum than in other approaches. The results with the PtML/PdML/Ir2Re electrocatalyst indicate that it is a promising alternative to conventional Pt electrocatalysts in low-temperature fuel cells.

  10. Ir(III)-Based Phosphors with Bipyrazolate Ancillaries; Rational Design, Photophysics, and Applications in Organic Light-Emitting Diodes.

    PubMed

    Liao, Jia-Ling; Chi, Yun; Sie, Zong-Ting; Ku, Chia-Hao; Chang, Chih-Hao; Fox, Mark A; Low, Paul J; Tseng, Meu-Rurng; Lee, Gene-Hsiang

    2015-11-16

    A series of three charge-neutral Ir(III) complexes bearing both neutral chelating ligands 4,4'-di-t-butyl-2,2'-bipyridine (dtbbpy) and monoanionic cyclometalated ligands derived from 2-phenylpyridine (ppyH), together with either two monoanionic ligands (i.e., chloride and monodentate pyrazolate) or a single dianionic chelate derived from 5,5'-di(trifluoromethyl)-3,3'-bipyrazole (bipzH2) or 5,5'-(1-methylethylidene)-bis-(3-trifluoromethyl-1H-pyrazole) (mepzH2), was successfully synthesized. These complexes are derived from a common, structurally characterized, Ir(III) intermediate complex [Ir(dtbbpy) (ppy)Cl2] (1), from treatment of IrCl3·3H2O with equal amount of the diimine (N^N) and precursor of the cyclometalated (C^N) ligands in a form of one-pot reaction. Treatment of 1 with various functional pyrazoles afforded [Ir(dtbbpy) (ppy) (pz)Cl] (2), [Ir(dtbbpy) (ppy) (bipz)] (3), and [Ir(dtbbpy) (ppy) (mepz)] (4), which display intense room-temperature emission with ?max spanning the region between 532 and 593 nm in both fluid and solid states. The Ir(III) complexes, 3 and 4, showcase rare examples of three distinctive chelates (i.e., neutral, anionic, and dianionic) assembled around the central Ir(III) cation. Hybrid density functional theory (DFT; B3LYP) electronic structure calculations on 1-4 reveal the lowest unoccupied molecular orbital to be ?*(bpy) in character for all complexes and highest occupied molecular orbital (HOMO) offering d(Ir)-?(phenyl) character for 1, 2, and 4 and ?(bipz) character for 3. The different HOMO composition of 3 and 4 is also predicted by calculations using pure DFT (BLYP) and wave function (MP2) methods. On the basis of time-dependent DFT calculations, the emissive processes are dominated by the phenyl group-to-bipyridine, ligand(ppy)-to-ligand(bpy) charge transfer admixed with metal-to-ligand transition for all Ir(III) complexes. Organic light emitting diodes were successfully fabricated. A double emitting layer design was adopted in the device architecture using Ir(III) metal complexes 3 and 4, attaining peak external quantum efficiencies, luminance efficiencies, and power efficiencies of 18.1% (59.0 cd/A and 38.6 lm/W) and 16.6% (53.3 cd/A and 33.5 lm/W), respectively. PMID:26529058

  11. Radicals and Hydroxy Radical Reactions in Troposphere

    E-print Network

    Schofield, Jeremy

    { Continuous conversion between OH and NO 2 #12; Classi#12;cation of OH reactions 1. Addition reactions atom #15; Example: CH 4 +OH ! CH 3 #1; +H 2 O #15; Both addition reactions and H abstraction can occurRadicals and Hydroxy Radical Reactions in Troposphere Examples of ground state radicals: 1. H atom

  12. ALBERMARLE PAMLICO IR 2002

    EPA Science Inventory

    The 2002 Albermarle Pamlico Implementation Review (IR) highlights recent successes and challenges with the estuary program. Various components within the IR include: CCMP implementation, outlining priority management actions, public involvement, stakeholder contribution, and limi...

  13. Syntheses of vanadyl and zinc(II) complexes of 1-hydroxy-4,5,6-substituted 2(1H)-pyrimidinones and their insulin-mimetic activities.

    PubMed

    Yamaguchi, Mika; Wakasugi, Kei; Saito, Ryota; Adachi, Yusuke; Yoshikawa, Yutaka; Sakurai, Hiromu; Katoh, Akira

    2006-02-01

    Control of the glucose level in the blood plasma has been achieved in vitro and in vivo by administration of vanadium and zinc in form of inorganic salts. It has been shown that elements are poorly absorbed in their inorganic forms and required high doses which have been associated with undesirable side effects. Many researchers, therefore, have focused on metal complexes that were prepared from VOSO(4) or ZnSO(4) and low-molecular-weight bidentate ligands. Seven kinds of 1-hydroxy-4,6-disubstituted and 1-hydroxy-4,5,6-trisubstituted-2(1H)-pyrimidinones were synthesized by reaction of N-benzyloxyurea and beta-diketones and subsequent removal of the protecting group. Six kinds of 1-hydroxy-4-(substituted)amino-2(1H)-pyrimidinones were synthesized by the substitution reaction of 1-benzyloxy-4-(1',2',4'-triazol-1'-yl)-2(1H)-pyrimidinone with various alkyl amines or amino acids. Treatment with VOSO(4) and ZnSO(4) or Zn(OAc)(2) afforded vanadyl(IV) and zinc(II) complexes which were characterized by means of (1)H NMR, IR, EPR, and UV-vis spectroscopies, and combustion analysis. The in vitro insulin-mimetic activity of these complexes was evaluated from 50% inhibitory concentrations (IC(50)) on free fatty acid (FFA) release from isolated rat adipocytes treated with epinephrine. Vanadyl complexes of 4,6-disubstituted-2(1H)-pyrimidinones showed higher insulin-mimetic activities than those of 4,5,6-trisubstituted ones. On the other hand, Zn(II) complexes showed lower insulin-mimetic activities than VOSO(4) and ZnSO(4) as positive controls. It was found that the balance of the hydrophilicity and/or hydrophobicity is important for higher insulin-mimetic activity. The in vivo insulin-mimetic activity was evaluated with streptozotocin (STZ)-induced diabetic rats. Blood glucose levels were lowered from hyperglycemic to normal levels after the treatment with bis(1,2-dihydro-4,6-dimethyl-2-oxo-1-pyrimidinolato)oxovanadium(IV) by daily intraperitoneal injections. The improvement in glucose tolerance was also confirmed by an oral glucose tolerance test. PMID:16387366

  14. Synthesis of hexahydro-1H-isoindole derivatives from arylacyl bromides via homoallenic bromohydrins.

    PubMed

    Lin, Mei-Huey; Li, Yi-Syuan; Kuo, Chung-Kai; Chen, Chung-Hao; Huang, Yen-Chih; Liang, Kung-Yu; Chen, Yu-Chun; Tsai, Chang-Hsien; Chuang, Tsung-Hsun

    2015-02-20

    A procedure has been developed for the concise synthesis of hexahydro-1H-isoindole derivatives starting from phenacyl bromides. The approach employs a sequence involving an initial indium-mediated allenylation reaction of an arylacyl bromide with propargyl bromide. This process is followed by FeBr3-mediated SN2'-type substitution reaction of the formed homoallenic bromohydrin to produce a 2,5-dibromo-4-aryl-1,3-pentadiene, which then is subjected to a sequential, one-pot N-alkylation reaction with N-allyl-N-(p-tosyl)amine and a highly diastereoselective intramolecular Diels-Alder reaction of the formed ene-diene to generate the target hexahydro-1H-isoindole. PMID:25640074

  15. Aromatic derivatives of 2,3-dihydro-1H-1,5-benzodiazepine

    SciTech Connect

    Orlov, V.D.; Desenko, S.M.; Kiroga, Kh.

    1987-09-01

    The formation of 2,2,4-trisubstituted 2,3-dihydro-1H-1,5-benzodiazepines in the reactions of acetylarenes with 4-ethoxy- and 3,5-dimethyl-1,2-phenylenediamine was studied. The effect of the substituents on the individual stages of the reactions is discussed. A quantum-chemical calculation of the relative nucleophilicity of 1,2-phenylenediamine, 2,3-diaminopyridine, and 3,4-diaminofurazan was undertaken.

  16. IOT Overview: IR Instruments

    NASA Astrophysics Data System (ADS)

    Mason, E.

    In this instrument review chapter the calibration plans of ESO IR instruments are presented and briefly reviewed focusing, in particular, on the case of ISAAC, which has been the first IR instrument at VLT and whose calibration plan served as prototype for the coming instruments.

  17. IR Hot Wave

    SciTech Connect

    Graham, T. B.

    2010-04-01

    The IR Hot Wave{trademark} furnace is a breakthrough heat treatment system for manufacturing metal components. Near-infrared (IR) radiant energy combines with IR convective heating for heat treating. Heat treatment is an essential process in the manufacture of most components. The controlled heating and cooling of a metal or metal alloy alters its physical, mechanical, and sometimes chemical properties without changing the object's shape. The IR Hot Wave{trademark} furnace offers the simplest, quickest, most efficient, and cost-effective heat treatment option for metals and metal alloys. Compared with other heat treatment alternatives, the IR Hot Wave{trademark} system: (1) is 3 to 15 times faster; (2) is 2 to 3 times more energy efficient; (3) is 20% to 50% more cost-effective; (4) has a {+-}1 C thermal profile compared to a {+-}10 C thermal profile for conventional gas furnaces; and (5) has a 25% to 50% smaller footprint.

  18. Synthesis, Spectral investigation (1H, 13C) and Anti-microbial Screening of benzophenone imines.

    PubMed

    Khosa, Muhammad Kaleem; Jamal, Muhammad Asghar; Saif, Muhammad Jawad; Muneer, Majid; Rehman, Fazalur; Farman, Muhammad; Shoaib, Hafiz Muhammad; Shahid, Muhammad; Hameed, Shabnam

    2015-11-01

    New series of benzophenone imines with general formula Ph2-C=NR; R = Benzyl, 4-Fluorobenzyl, Naphthyl, Phenyl, 4-Nitrophenyl were synthesized by condensation of dichlorodiphenylmethane and different aromatic primary amines (1:1) Those imines were characterized by different physiochemical and spectroscopic techniques like melting point, elemental analysis, FT-IR, multinuclear NMR ((1)H, (13)C). After characterization, imines were subjected to anti-microbial activities. All compounds showed promising activity against different bacterial strains like Escherichia coli, Bacillussubtilis, Pasturellam ultocida and Staphylococcus aureus as well as fungal strains like Alternata alternaria, Ganoderma lucidium, Penicillium notatum and Trichoderma harzianum using Amoxicillin and Flucanazole as a standard drugs respectively. PMID:26639485

  19. IRS Updates IRS2Go Smartphone App The IRS recently released IRS2Go 5.0, an update to the only official IRS smartphone

    E-print Network

    IRS Updates IRS2Go Smartphone App The IRS recently released IRS2Go 5.0, an update to the only. You can check the status of your federal tax refund through IRS2Go. Enter your Social Security number qualify. This tool within IRS2Go will help you find the nearest volunteer tax help site. You can enter

  20. IR Kuiper Belt Constraints

    E-print Network

    Vigdor L. Teplitz; S. Alan Stern; John D. Anderson; Doris Rosenbaum; Randall J. Scalise; Paul Wentzler

    1998-11-20

    We compute the temperature and IR signal of particles of radius $a$ and albedo $\\alpha$ at heliocentric distance $R$, taking into account the emissivity effect, and give an interpolating formula for the result. We compare with analyses of COBE DIRBE data by others (including recent detection of the cosmic IR background) for various values of heliocentric distance, $R$, particle radius, $a$, and particle albedo, $\\alpha$. We then apply these results to a recently-developed picture of the Kuiper belt as a two-sector disk with a nearby, low-density sector (40Kuiper belt IR spectra for various parameter values.

  1. Practical choice of 1H- 1H decoupling schemes in through-bond 1H-{X} HMQC experiments at ultra-fast MAS

    NASA Astrophysics Data System (ADS)

    Nishiyama, Yusuke; Lu, Xingyu; Trébosc, Julien; Lafon, Olivier; Gan, Zhehong; Madhu, P. K.; Amoureux, Jean-Paul

    2012-01-01

    Three 1H- 1H homonuclear dipolar decoupling schemes for 1H indirect detection measurements at very fast MAS are compared. The sequences require the following conditions: (i) being operable at very fast MAS, (ii) a long T2' value, (iii) a large scaling factor, (iv) a small number of adjustable parameters, (v) an acquisition window, (vi) a low rf-power requirement, and (vii) a z-rotation feature. To satisfy these conditions a modified sequence named TIlted Magic-Echo Sandwich with zero degree sandwich pulse (TIMES 0) is introduced. The basic elements of TIMES 0 consist of one sampling window and two phase-ramped irradiations, which realize alternating positive and negative 360° rotations of 1H magnetization around an effective field tilted with an angle ? from the B0 axis. The TIMES 0 sequence benefits from very large chemical shift scaling factors at ultra-fast MAS that reach ?cs = 0.90 for ? = 25° at ?r = 80 kHz MAS and only four adjustable parameters, resulting in easy setup. Long ?T2' values, where T2' is a irreversible proton transverse relaxation time, greatly enhance the sensitivity in 1H-{ 13C} through-bond J-HMQC (Heteronuclear Multiple-Quantum Coherence) measurements with 1H- 1H decoupling during magnetization transfer periods. Although similar sensitivity can be obtained with through-space D-HMQC sequences, in which 13C- 1H dipolar interactions are recoupled, J-HMQC experiments incorporating 1H- 1H decoupling benefit from lower t1-noise, more uniform excitation of both CH, CH 2 and CH 3 moieties, and easier identification of through-bond connectivities.

  2. CHARLOTTE HARBOR IR, 2002

    EPA Science Inventory

    The 2002 Charlotte Harbor Implementation Review (IR) summarizes the progress and challenges ahead for the Charlotte Harbor National Estuary Program (CHNEP). The implementation review report requires seven components: Status of CCMP implementation (programmatic progress); Environm...

  3. Synthesis, characterization, antimicrobial, DNA-cleavage and antioxidant activities of 3-((5-chloro-2-phenyl-1H-indol-3-ylimino)methyl)quinoline-2(1H)-thione and its metal complexes

    NASA Astrophysics Data System (ADS)

    Vivekanand, B.; Mahendra Raj, K.; Mruthyunjayaswamy, B. H. M.

    2015-01-01

    Schiff base 3-((5-chloro-2-phenyl-1H-indol-3-ylimino)methyl)quinoline-2(1H)-thione and its Cu(II), Co(II), Ni(II), Zn(II) and Fe(III), complexes have been synthesized and characterized by elemental analysis, UV-Visible, IR, 1H NMR, 13C NMR and mass spectra, molar conductance, magnetic susceptibility, ESR and TGA data. The ligand and its metal complexes have been screened for their antibacterial activity against Staphylococcus aureus and Pseudomonas aeruginosa, antifungal activity against Aspergillus niger and Aspergillus flavus in minimum inhibition concentration (MIC) by cup plate method respectively, antioxidant activity using 1,1-diphenyl-2-picryl hydrazyl (DPPH), which was compared with that of standard drugs vitamin-C and vitamin-E and DNA cleavage activity using calf-thymus DNA.

  4. Tautomeric 2-arylquinolin-4(1 H)-one derivatives- spectroscopic, X-ray and quantum chemical structural studies

    NASA Astrophysics Data System (ADS)

    Mphahlele, Malose J.; El-Nahas, Ahmed M.

    2004-01-01

    A convenient method for the synthesis of 2-aryl-1-methylquinolin-4(1 H)-ones is described. Spectroscopic and X-ray crystallographic techniques as well as quantum chemical calculations have been used to probe the structure of potentially tautomeric 2-arylquinolin-4(1 H)-ones in solution phase, gas phase and solid state. The exclusive NH-4-oxo nature of the title compounds in solution phase (NMR) and solid state (IR and X-ray) is also corroborated by comparison of their spectroscopic data with those of the corresponding 2-aryl-1-methylquinolin-4(1 H)-one and 2-aryl-4-methoxyquinoline derivatives. Results from mass spectrometric analysis confirm the coexistence of the 4-quinolinone and 4-hydroxyquinoline isomers in the gas phase and this is supported by quantum chemical computations.

  5. Selective syntheses of leuconolam, leuconoxine, and mersicarpine alkaloids from a common intermediate through regiocontrolled cyclizations by Staudinger reactions† †Electronic supplementary information (ESI) available: Experimental details and procedures, compound characterization data, copies of 1H and 13C NMR spectra for new compounds. See DOI: 10.1039/c4qo00312h Click here for additional data file.

    PubMed Central

    Li, Zining; Geng, Qian; Lv, Zhe; Pritchett, Beau P.; Baba, Katsuaki; Numajiri, Yoshitaka

    2015-01-01

    Selective syntheses of leuconolam, leuconoxine, and mersicarpine alkaloids bearing distinctive core structures were achieved through Staudinger reactions using a common intermediate. In the key cyclization step, water functioned like a switch to control which core structure to produce. The chemistry allowed for selective syntheses of the group of alkaloids from a simple intermediate through straightforward chemical operations. PMID:25717379

  6. Measurement of (1)H-(15)N and (1)H-(13)C residual dipolar couplings in nucleic acids from TROSY intensities.

    PubMed

    Ying, Jinfa; Wang, Jinbu; Grishaev, Alex; Yu, Ping; Wang, Yun-Xing; Bax, Ad

    2011-09-01

    Analogous to the recently introduced ARTSY method for measurement of one-bond (1)H-(15)N residual dipolar couplings (RDCs) in large perdeuterated proteins, we introduce methods for measurement of base (13)C-(1)H and (15)N-(1)H RDCs in protonated nucleic acids. Measurements are based on quantitative analysis of intensities in (1)H-(15)N and (13)C-(1)H TROSY-HSQC spectra, and are illustrated for a 71-nucleotide adenine riboswitch. Results compare favorably with those of conventional frequency-based measurements in terms of completeness and convenience of use. The ARTSY method derives the size of the coupling from the ratio of intensities observed in two TROSY-HSQC spectra recorded with different dephasing delays, thereby minimizing potential resonance overlap problems. Precision of the RDC measurements is limited by the signal-to-noise ratio, S/N, achievable in the 2D TROSY-HSQC reference spectrum, and is approximately given by 30/(S/N) Hz for (15)N-(1)H and 65/(S/N) Hz for (13)C-(1)H. The signal-to-noise ratio of both (1)H-(15)N and (1)H-(13)C spectra greatly benefits when water magnetization during the experiments is not perturbed, such that rapid magnetization transfer from bulk water to the nucleic acid, mediated by rapid amino and hydroxyl hydrogen exchange coupled with (1)H-(1)H NOE transfer, allows for fast repetition of the experiment. RDCs in the mutated helix 1 of the riboswitch are compatible with nucleotide-specifically modeled, idealized A-form geometry and a static orientation relative to the helix 2/3 pair, which differs by ca 6° relative to the X-ray structure of the native riboswitch. PMID:21947918

  7. BUZZARDS BAY IR, 2002

    EPA Science Inventory

    The 2002 Buzzards Bay Implementation Review (IR) summarizes the progress and challenges ahead for the Buzzards Bay Project. Major new completed actions during the past two years include: designation of Buzzards Bay as a no discharge area in August 2000; full support by the Massac...

  8. Smart oxygen diffusion barrier based on IrAl alloy

    SciTech Connect

    Hosoda, Hideki; Watanabe, Sadao; Hanada, Shuji

    1999-07-01

    Ir should be used as an effective oxygen diffusion barrier (ODB) for ultrahigh temperature structural materials since Ir exhibits extremely low oxygen diffusivity. Oxidation resistance of Ir is, however, not good due to formation of gaseous oxide, IrO{sub 3}, over 1,390K. In this study, the improvement of oxidation resistance was aimed through alloy design of alloying with Al. IrAl is expected to form a self-healing multifunctional layered structure composed of Ir layer as ODB and Al{sub 2}O{sub 2} layer as a protective oxide (PO) on the Ir layer. Ar arc-melted IrAl alloy was crushed into powder, followed by hot pressing and heat treatment to remove Ir formed by eutectic reaction. Oxidation behavior was measured using thermogravimetry (TG) and differential thermal analysis (DTA) under the conditions of (1) dynamic heating of 0.167K/s and (2) isotherms at 1,273K to 1,673K in O{sub 2} environment. It was found that oxidation resistance is much improved by alloying with Al and that the designed structure (PO/ODB) is formed on the IrAl substrate. Compressive mechanical properties were investigated from RT to 1873K: both the strength as a function of normalized temperature and specific strength are higher than those of pure Ir, NiAl, TiAl and Ni{sub 3}Al. IrAl is promising as an advanced smart coating material equipping good oxidation resistance as well as high temperature strength.

  9. Novel 1H low field nuclear magnetic resonance applications for the field of biodiesel

    PubMed Central

    2013-01-01

    Background Biodiesel production has increased dramatically over the last decade, raising the need for new rapid and non-destructive analytical tools and technologies. 1H Low Field Nuclear Magnetic Resonance (LF-NMR) applications, which offer great potential to the field of biodiesel, have been developed by the Phyto Lipid Biotechnology Lab research team in the last few years. Results Supervised and un-supervised chemometric tools are suggested for screening new alternative biodiesel feedstocks according to oil content and viscosity. The tools allowed assignment into viscosity groups of biodiesel-petrodiesel samples whose viscosity is unknown, and uncovered biodiesel samples that have residues of unreacted acylglycerol and/or methanol, and poorly separated and cleaned glycerol and water. In the case of composite materials, relaxation time distribution, and cross-correlation methods were successfully applied to differentiate components. Continuous distributed methods were also applied to calculate the yield of the transesterification reaction, and thus monitor the progress of the common and in-situ transesterification reactions, offering a tool for optimization of reaction parameters. Conclusions Comprehensive applied tools are detailed for the characterization of new alternative biodiesel resources in their whole conformation, monitoring of the biodiesel transesterification reaction, and quality evaluation of the final product, using a non-invasive and non-destructive technology that is new to the biodiesel research area. A new integrated computational-experimental approach for analysis of 1H LF-NMR relaxometry data is also presented, suggesting improved solution stability and peak resolution. PMID:23590829

  10. Regioselective sulfonylation at O-2 of cyclomaltoheptaose with 1-(p-tolylsulfonyl)-(1H)-1,2,4-triazole.

    PubMed

    Law, Ho; Baussanne, Isabelle; García Fernández, José M; Defaye, Jacques

    2003-02-14

    2(I)-O-p-Tolylsulfonylcyclomaltoheptaose was obtained in 42% yield by reaction of 1-(p-tolylsulfonyl)-(1H)-1,2,4-triazole on NaH-deprotonated cyclomaltoheptaose in DMF and further converted into the corresponding mono-2(I),3(I)-manno-epoxide. PMID:12559748

  11. Permeable membrane/mass spectrometric measurement of solvent /sup 1/H//sup 2/H, /sup 12/C//sup 13/C, and /sup 16/O//sup 18/O kinetic isotope effects associated with alpha-chymotrypsin deacylation: evidence for reaction mechanism plasticity

    SciTech Connect

    Mishra, A.K.; Klapper, M.H.

    1986-11-18

    We have measured, by permeable membrane/mass spectrometry, the /sup 16/O//sup 18/O, /sup 12/C//sup 13/C, and solvent H/sup 2/O/D/sup 2/O kinetic isotope effects (kie) associated with acyl-alpha-chymotrypsin hydrolysis and transesterification. The hydrolysis of alpha-chymotrypsinyl 2-furoate has a /sup 12/C//sup 13/C kie of approximately 1.06. Transesterification of the same acyl enzyme shows /sup 16/O//sup 18/O, /sup 12/C//sup 13/C, and solvent H/sup 2/O/D/sup 2/O kinetic isotope effects of 1.015 (0.003), 1.01-1.02, and 2.226 (0.007), respectively. From the temperature independence of the /sup 16/O//sup 18/O transesterification kinetic isotope effect and kinetic data reported elsewhere, we conclude that there are two active forms of acylchymotrypsin. We also propose that formation of the tetrahedral intermediate is the rate-limiting step in both hydrolysis and transesterification and that the position of the transition state in the transesterification is closer to the starting enzyme ester while that for the hydrolytic reaction is closer to the tetrahedral intermediate. These results are discussed in terms of reaction mechanism plasticity.

  12. Localised IR spectroscopy of hemoglobin

    E-print Network

    Yarrow, Fiona

    2010-01-01

    IR absorption spectroscopy of hemoglobin was performed using an IR optical parametric oscillator laser and a commercial atomic force microscope in a novel experimental arrangement based on the use of a bottom-up excitation alignment. This experimental approach enables detection of protein samples with a resolution that is much higher than that of standard IR spectroscopy. Presented here are AFM based IR absorption spectra of micron sized hemoglobin features

  13. New N?-alkylidene/cycloalkylidene derivatives of 5-methyl-3-phenyl-1H-indole-2-carbohydrazide: synthesis, crystal structure, and quantum mechanical calculations

    NASA Astrophysics Data System (ADS)

    Kaynak, F. Betül; Öztürk, Devrim; Özbey, Süheyla; Çapan, Gültaze

    2005-04-01

    The condensation products of 5-methyl-3-phenyl-1 H-indole-2-carbohydrazide ( 1) with 2-butanone, 3-pentanone and cyclopentanone were prepared. The adducts ( 2a- c) were characterized by microanalysis, UV, IR, 1H NMR, 13C NMR and EI mass spectrometry. 1H NMR spectra of 2a and 2b revealed rotational restriction about the C-N bond in solution (DMSO-d 6) and displayed double resonances associated with the CH 3 and CH 2CH 3 residues of the alkylidene moieties. A variable temperature 1H NMR experiment was run on 2a to overcome the rotational barriers and thus determine the coalescence temperature but no coalescence was observed up to 77 °C. The structural analysis of 2a and 2c were also carried out by single crystal X-ray diffraction and confirmed by theoretical calculations (semiempirical PM3 and ab initio RHF/6-31G(d)).

  14. Theoretical Investigation of Iridium (II) Sulfides Ir2(?-S)2(PH3)4 AND Ir2(?-S)2(PPh3)4 

    E-print Network

    Kritikou, Stella

    2014-02-27

    Density functional theory results of the electronic structure of an iridium sulfide, Ir_(2)S_(2)(PPh_(3))_(4) (2), are presented here, along with a discussion of the reaction mechanism of dihydrogen activation on this sulfide. This Ir (II...

  15. IR Spot Weld Inspect

    Energy Science and Technology Software Center (ESTSC)

    2014-01-01

    In automotive industry, destructive inspection of spot welds is still the mandatory quality assurance method due to the lack of efficient non-destructive evaluation (NDE) tools. However, it is costly and time-consuming. Recently at ORNL, a new NDE prototype system for spot weld inspection using infrared (IR) thermography has been developed to address this problem. This software contains all the key functions that ensure the NDE system to work properly: system input/output control, image acquisition, datamore »analysis, weld quality database generation and weld quality prediction, etc.« less

  16. IR Spot Weld Inspect

    SciTech Connect

    2014-01-01

    In automotive industry, destructive inspection of spot welds is still the mandatory quality assurance method due to the lack of efficient non-destructive evaluation (NDE) tools. However, it is costly and time-consuming. Recently at ORNL, a new NDE prototype system for spot weld inspection using infrared (IR) thermography has been developed to address this problem. This software contains all the key functions that ensure the NDE system to work properly: system input/output control, image acquisition, data analysis, weld quality database generation and weld quality prediction, etc.

  17. Derivatives of 1,5-diamino-1H-tetrazole: a new family of energetic heterocyclic-based salts.

    PubMed

    Gálvez-Ruiz, Juan Carlos; Holl, Gerhard; Karaghiosoff, Konstantin; Klapötke, Thomas M; Löhnwitz, Karolin; Mayer, Peter; Nöth, Heinrich; Polborn, Kurt; Rohbogner, Christoph J; Suter, Max; Weigand, Jan J

    2005-06-13

    1,5-Diamino-1H-tetrazole (2, DAT) can easily be protonated by reaction with strong mineral acids, yielding the poorly investigated 1,5-diaminotetrazolium nitrate (2a) and perchlorate (2b). A new synthesis for 2 is introduced that avoids lead azide as a hazardous byproduct. The reaction of 1,5-diamino-1H-tetrazole with iodomethane (7a) followed by the metathesis of the iodide (7a) with silver nitrate (7b), silver dinitramide (7c), or silver azide (7d) leads to a new family of heterocyclic-based salts. In all cases, stable salts were obtained and fully characterized by vibrational (IR, Raman) spectroscopy, multinuclear NMR spectroscopy, mass spectrometry, elemental analysis, X-ray structure determination, and initial safety testing (impact and friction sensitivity). Most of the salts exhibit good thermal stabilities, and both the perchlorate (2b) and the dinitramide (7c) have melting points well below 100 degrees C, yet high decomposition onsets, defining them as new (7c), highly energetic ionic liquids. Preliminary sensitivity testing of the crystalline compounds indicates rather low impact sensitivities for all compounds, the highest being that of the perchlorate (2b) and the dinitramide (7c) with a value of 7 J. In contrast, the friction sensitivities of the perchlorate (2b, 60 N) and the dinitramide (7c, 24 N) are relatively high. The enthalpies of combustion (Delta(c)H degrees ) of 7b-d were determined experimentally using oxygen bomb calorimetry: Delta(c)H degrees (7b) = -2456 cal g(-)(1), Delta(c)H degrees (7c) = -2135 cal g(-)(1), and Delta(c)H degrees (7d) = -3594 cal g(-)(1). The standard enthalpies of formation (Delta(f)H degrees ) of 7b-d were obtained on the basis of quantum chemical computations using the G2 (G3) method: Delta(f)H degrees (7b) = 41.7 (41.2) kcal mol(-)(1), Delta(f)H degrees (7c) = 92.1 (91.1) kcal mol(-)(1), and Delta(f)H degrees (7d) = 161.6 (161.5) kcal mol(-)(1). The detonation velocities (D) and detonation pressures (P) of 2b and 7b-d were calculated using the empirical equations of Kamlet and Jacobs: D(2b) = 8383 m s(-)(1), P(2b) = 32.2 GPa; D(7b) = 7682 m s(-)(1), P(7b) = 23.4 GPa; D(7c) = 8827 m s(-)(1), P(7c) = 33.6 GPa; and D(7d) = 7405 m s(-)(1), P(7d) = 20.8 GPa. For all compounds, a structure determination by single-crystal X-ray diffraction was performed. 2a and 2b crystallize in the monoclinic space groups C2/c and P2(1)/n, respectively. The salts of 7 crystallize in the orthorhombic space groups Pna2(1) (7a, 7d) and Fdd2 (7b). The hydrogen-bonded ring motifs are discussed in the formalism of graph-set analysis of hydrogen-bond patterns and compared in the case of 2a, 2b, and 7b. PMID:15934752

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

    USGS Publications Warehouse

    Revesz, Kinga; Coplen, Tyler B.

    2008-01-01

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

  19. Synthesis, structural, theoretical studies and biological activities of 3-(arylamino)-2-phenyl-1H-inden-1-one derivative

    NASA Astrophysics Data System (ADS)

    El-Sheshtawy, Hamdy S.; Abou Baker, Ahmed M.

    2014-06-01

    Five derivatives of 2-phenyl-1H-indene-1-one have been prepared and fully characterized. Spectroscopic techniques such as FT-IR, 1H NMR, mass spectrometry, and elemental analysis were used to investigate the chemical structures and physical properties of the prepared compounds. The optimized structures and the distribution of the frontier molecular orbital were obtained using density functional theory (DFT) at B3LYP/6-311++G(d,p) level of theory. Additionally, the UV spectral properties of the indene compounds were corroborated by frontier orbital (HOMO and LUMO) calculations. Intramolecular charge transfer (ICT) peak has been observed in the UV spectra of the compounds and theoretically confirmed by the HOMO and LUMO analysis. The potential use of these compounds as antibacterial agents was investigated. The results show that indene-1-one derivatives have an antibacterial activity for both gram-negative (Pseudomonas aeruginosa) and gram-positive (Methicillin Resistant Staphylococcus aureus) bacteria.

  20. Osmium(IV) complexes with 1H- and 2H-indazoles: Tautomer identity versus spectroscopic properties and antiproliferative activity

    PubMed Central

    Büchel, Gabriel E.; Stepanenko, Iryna N.; Hejl, Michaela; Jakupec, Michael A.; Keppler, Bernhard K.; Heffeter, Petra; Berger, Walter; Arion, Vladimir B.

    2012-01-01

    A one-pot synthesis of osmium(IV) complexes with two different tautomers of indazole, 1H-indazole and 2H-indazole, namely (H2ind)[OsIVCl5(2H-ind)] (1) and (H2ind)[OsIVCl5(1H-ind)] (2) is reported. Both compounds have been comprehensively characterized by NMR spectroscopy, ESI (electrospray ionization) mass spectrometry, electronic absorption spectroscopy, IR spectroscopy, cyclic voltammetry and tested for antiproliferative activity in vitro in three human cancer cell lines, CH1 (ovarian carcinoma), A549 (non-small cell lung cancer) and SW480 (colon carcinoma), as well as in vivo in a Hep3B SCID mouse xeno-transplantation model. 2H-Indazole tautomer stabilization in 1 has been confirmed by X-ray diffraction. PMID:22687494

  1. Synthesis, structure and reactivity of [Ir(dippe)(l-Cl)]2, [Ir(dippe)2][Ir(dippe)Cl2] and [Ir(dippe)2]Cl

    E-print Network

    Jones, William D.

    Synthesis, structure and reactivity of [Ir(dippe)(l-Cl)]2, [Ir(dippe)2][Ir(dippe)Cl2] and [Ir 2004 Abstract [Ir(COD)(l-Cl)]2 reacts with two equivalents of 1,2-bis(diisopropylphosphino)ethane (dippe) to produce [Ir(dippe)(l-Cl)]2 (1a) in yields that are dependent upon the solvent. Its single

  2. Isomer dependence in the assembly and lability of silver(I) trifluoromethanesulfonate complexes of the heteroditopic ligands, 2-, 3-, and 4-[di(1H-pyrazolyl)methyl]phenyl(di-p-tolyl)phosphine.

    PubMed

    Gardinier, James R; Hewage, Jeewantha S; Lindeman, Sergey V

    2014-11-17

    Three isomers of a new heteroditopic ligand that contains a di(1H-pyrazolyl)methyl (-CHpz2) moiety connected to a di(p-tolyl)phosphine group via a para-, meta-, or ortho-phenylene spacer (pL, mL, and oL, respectively) have been synthesized by using a palladium(0)-catalyzed coupling reaction between HP(p-tolyl)2 and the appropriate isomer of (IC6H4)CHpz2. The 1:1 complexes of silver(I) trifluoromethanesulfonate, Ag(OTf), were prepared to examine the nature of ligand coordination and the type of supramolecular isomer (monomeric, cyclic oligomeric, or polymeric) that would be obtained. The single crystal X-ray diffraction studies showed that [Ag(pL)](OTf), 1, and [Ag(mL)](OTf), 2, possessed cyclic dimeric dications, whereas [Ag(oL)](OTf), 3, was a coordination polymer. The polymeric chain in 3 could be disrupted by reaction with triphenylphosphine, and the resulting complex, [Ag(oL)(PPh3)](OTf), 4, possessed a monometallic cation where the ligand was bound to silver in a chelating ?(2)P,N- coordination mode. The solution structures of 1-4 were probed via a combination of IR, variable-temperature multinuclear ((1)H, (13)C, (31)P) NMR spectroscopy, as well as by electron spray ionization (ESI)(+) mass spectrometry. A related complex [Ag(m-IC6H4CHpz2)2](OTf), 5, was also prepared, and its solid-state and solution spectroscopic properties were studied for comparison purposes. These studies suggest that the cyclic structures of 1 and 2 are likely preserved but are dynamic in solution at room temperature. Moreover, both 3 and 4 have dynamic solution structures where 3 is likely extensively dissociated in CH3CN or acetone rather than being polymeric as in the solid state. PMID:25375040

  3. New insights into the solvent-assisted excited-state double proton transfer of 2-(1H-pyrazol-5-yl)pyridine with alcoholic partners: A TDDFT investigation

    NASA Astrophysics Data System (ADS)

    Li, Hui; Shi, Ying; Yin, Hang; Wang, Ye; Cong, Lin; Jin, Mingxing; Ding, Dajun

    2015-04-01

    Excited-state double proton transfer (ESDPT) in the hydrogen-bonded 2-(1H-pyrazol-5-yl)pyridine with propyl alcoholic partner (PPP) was theoretically investigated by time-dependent density functional theory (TDDFT) method. Great changes have taken place for the calculated geometric structures, the electron density features and vibrational spectrum of PPP system in S0 and S1 state. Our results have demonstrated that ESDPT reaction happens within the system upon photoexcitation. We also found that the ESDPT process is facilitated by the electronically excited state intermolecular hydrogen bond strengthening. Particularly, after the photoexcitation from HOMO(?) to the LUMO(??), the rearrangement of electronic density distribution of frontier molecular orbitals (MOs) on pyridine and the pyrazol moieties exhibits a very important positive factor for the ESDPT. Furthermore, by the investigation of the stretching vibrations of Nsbnd H and Osbnd H groups, the infrared (IR) spectroscopic results provide us not only a theoretical evidence of ESDPT, but also a considerable clue to characterize the nature of intermolecular reaction. In addition, efforts have also been devoted towards calculating the absorption peak, which shows good consistency with the experimental result of the studied system.

  4. Synthesis, experimental and theoretical studies on its crystal structure and FT-IR spectrum of new thiosemicarbazone compound E-2-(4-isopropylbenzylidene)thiosemicarbazone

    NASA Astrophysics Data System (ADS)

    Khalaji, Aliakbar Dehno; Mehrani, Sepideh; Eigner, Vaclav; Dusek, Michal

    2013-09-01

    The title compound E-2-(4-isopropylbenzylidene)thiosemicarbazone (1) derived from the reaction of 4-isopropylbenzaldehyde and thiosemicarbazide in ethanol solution has been synthesized and characterized by elemental analyses, FT-IR and 1H NMR spectroscopy and single-crystal X-ray diffraction. Its optimized geometry together with the theoretical assignment of the vibrational frequencies of the title compound has been computed by using density functional theory (DFT) method. In the gas phase the four conformers of the title compound were found and it was found that the conformer Sn1 is the most stable one. The title compound crystallizes in the monoclinic space group P21/c with unit cell parameters: a = 14.4054(4), b = 5.6832(10), c = 14.4337(3) Å, ? = 93.306(2)°, V = 1179.70(5) Å3 and Z = 4.

  5. Localized double-quantum-filtered 1H NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Thomas, M. A.; Hetherington, H. P.; Meyerhoff, D. J.; Twieg, D. B.

    The image-guided in vivo spectroscopic (ISIS) pulse sequence has been combined with a double-quantum-filter scheme in order to obtain localized and water-suppressed 1H NMR spectra of J-coupled metabolites. The coherence-transfer efficiency associated with the DQ filter for AX and A 3X spin systems is described. Phantom results of carnosine, alanine, and ethanol in aqueous solution are presented. For comparison, the 1H NMR spectrum of alanine in aqueous solution with the binomial (1331, 2662) spin-echo sequence is also shown.

  6. Modified triglyceride oil through reactions with phenyltriazolinedione

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The synthesis of a modified triglyceride oil was achieved through the reactions with 4-phenyl-1,2-4-triazoline-3,5-dione (PTAD). 1H NMR was used for structure determination and to monitor the reactions. Several reaction products were produced, and their relative yields depended on the stoichiometry ...

  7. Probing degradation in complex engineering silicones by 1H multiple quantum NMR

    SciTech Connect

    Maxwell, R S; Chinn, S C; Giuliani, J; Herberg, J L

    2007-09-05

    Static {sup 1}H Multiple Quantum Nuclear Magnetic Resonance (MQ NMR) has recently been shown to provide detailed insight into the network structure of pristine silicon based polymer systems. The MQ NMR method characterizes the residual dipolar couplings of the silicon chains that depend on the average molecular weight between physical or chemical constraints. Recently, we have employed MQ NMR methods to characterize the changes in network structure in a series of complex silicone materials subject to numerous degradation mechanisms, including thermal, radiative, and desiccative. For thermal degradation, MQ NMR shows that a combination of crosslinking due to post-curing reactions as well as random chain scissioning reactions occurs. For radiative degradation, the primary mechanisms are via crosslinking both in the network and at the interface between the polymer and the inorganic filler. For samples stored in highly desiccating environments, MQ NMR shows that the average segmental dynamics are slowed due to increased interactions between the filler and the network polymer chains.

  8. Metabolite Characterization in Peritoneal Dialysis Effluent Using High-resolution 1H and 1H-13C NMR Spectroscopy

    E-print Network

    Guleria, Anupam; Rawat, Atul; Khetrapal, C L; Prasad, Narayan; Kumar, Dinesh

    2014-01-01

    Metabolite analysis of peritoneal dialysis (PD) effluent may provide information regarding onset and progression of complications associated with prolonged PD therapy. In this context, the NMR detectable small metabolites of PD effluent samples were characterized using high resolution 1H and 1H-13C NMR spectroscopy. The various spectra were recorded (at 800 MHz proton frequency) on PD effluent samples obtained after 4 hour (intraperitoneal) dwell time from patients with end stage renal failure (ESRF) and continuing normally on PD therapy. Inspite of devastating spectral feature of PD effluent due to the presence of intense resonances from glucose and lactate, we were able to identify about 53 small endogenous metabolites (including many complex coupled spin systems) and more than 90 % of the total CH cross peaks of 1H-13C HSQC spectrum were identified specific to various metabolites of PD effluent. We foresee that the characteristic fingerprints of various metabolites of control PD effluent samples will be us...

  9. Applications of 1H-NMR to Biodiesel Research

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Biodiesel is an alternative diesel fuel derived from vegetable oils, animal fats, or used cooking oils. It is produced by reacting these materials with an alcohol in the presence of a catalyst to give the corresponding mono-alkyl esters. 1H-NMR is a routine analytical method that has been used for...

  10. Diagnostic Performance 1 H after Simulation Training Predicts Learning

    ERIC Educational Resources Information Center

    Consoli, Anna; Fraser, Kristin; Ma, Irene; Sobczak, Matthew; Wright, Bruce; McLaughlin, Kevin

    2013-01-01

    Although simulation training improves post-training performance, it is unclear how well performance soon after simulation training predicts longer term outcomes (i.e., learning). Here our objective was to assess the predictive value of performance 1 h post-training of performance 6 weeks later. We trained 84 first year medical students a simulated…

  11. Proton-detected 3D 1H/13C/1H correlation experiment for structural analysis in rigid solids under ultrafast-MAS above 60 kHz

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Nishiyama, Yusuke; Ramamoorthy, Ayyalusamy

    2015-10-01

    A proton-detected 3D 1H/13C/1H chemical shift correlation experiment is proposed for the assignment of chemical shift resonances, identification of 13C-1H connectivities, and proximities of 13C-1H and 1H-1H nuclei under ultrafast magic-angle-spinning (ultrafast-MAS) conditions. Ultrafast-MAS is used to suppress all anisotropic interactions including 1H-1H dipolar couplings, while the finite-pulse radio frequency driven dipolar recoupling (fp-RFDR) pulse sequence is used to recouple dipolar couplings among protons and the insensitive nuclei enhanced by polarization transfer technique is used to transfer magnetization between heteronuclear spins. The 3D experiment eliminates signals from non-carbon-bonded protons and non-proton-bonded carbons to enhance spectral resolution. The 2D (F1/F3) 1H/1H and 2D 13C/1H (F2/F3) chemical shift correlation spectra extracted from the 3D spectrum enable the identification of 1H-1H proximity and 13C-1H connectivity. In addition, the 2D (F1/F2) 1H/13C chemical shift correlation spectrum, incorporated with proton magnetization exchange via the fp-RFDR recoupling of 1H-1H dipolar couplings, enables the measurement of proximities between 13C and even the remote non-carbon-bonded protons. The 3D experiment also gives three-spin proximities of 1H-1H-13C chains. Experimental results obtained from powder samples of L-alanine and L-histidine ? H2O ? HCl demonstrate the efficiency of the 3D experiment.

  12. A Practical Method for Stereospecific Assignments of ?- and ?-Methylene Hydrogens via Estimation of Vicinal 1H- 1H Coupling Constants

    NASA Astrophysics Data System (ADS)

    Cai, M. L.; Liu, J. H.; Gong, Y. X.; Krishnamoorthi, R.

    1995-05-01

    Stereospecific assignments are made for ?- and ?-methylene hydrogens in a protein by means of estimation of vicinal 1H-1H spin-spin coupling constants from a short-mixing-time TOCSY experiment. 3J?? coupling constants, as measured from a P.E. COSY map, are shown to be well correlated with ?-? cross-peak intensities of a short-mixing-time (10 ms) TOCSY map. The procedure is illustrated by application to a trypsin-inhibitor protein (Mr 7 Kd). Thus, ?-methylene hydrogens of isoleucine residues have been stereospecifically assigned on the basis of 3J??1H-1H coupling patterns and intraresidue cross-peak intensities in a NOESY map; ?-hydrogens of other residues, such as lysine and arginine, have been stereospecifically assigned solely on the basis of cross-peak intensity patterns resulting from coupling of two ?-hydrogens to two ?-hydrogens, and in conjunction with stereospecific assignments of ?-methylene hydrogens. However, intraresidue NOE intensities are needed if one or two pairs of coupling constants cannot be estimated because of cross peaks either overlapping or occurring proximal to the diagonal. The ?-methylene hydrogens have been stereospecifically assigned on the basis of coupling between two ?-hydrogens and two ?-hydrogens, in combination with stereospecific assignments of ?-hydrogens. Stereospecific assignments of side chains should contribute to the overall precision and accuracy of NMR-determined three-dimensional solution structures of proteins.

  13. 4D prediction of protein (1)H chemical shifts.

    PubMed

    Lehtivarjo, Juuso; Hassinen, Tommi; Korhonen, Samuli-Petrus; Peräkylä, Mikael; Laatikainen, Reino

    2009-12-01

    A 4D approach for protein (1)H chemical shift prediction was explored. The 4th dimension is the molecular flexibility, mapped using molecular dynamics simulations. The chemical shifts were predicted with a principal component model based on atom coordinates from a database of 40 protein structures. When compared to the corresponding non-dynamic (3D) model, the 4th dimension improved prediction by 6-7%. The prediction method achieved RMS errors of 0.29 and 0.50 ppm for Halpha and HN shifts, respectively. However, for individual proteins the RMS errors were 0.17-0.34 and 0.34-0.65 ppm for the Halpha and HN shifts, respectively. X-ray structures gave better predictions than the corresponding NMR structures, indicating that chemical shifts contain invaluable information about local structures. The (1)H chemical shift prediction tool 4DSPOT is available from http://www.uku.fi/kemia/4dspot . PMID:19876601

  14. [1H-NMR spectroscopy of a patient with pachygyria].

    PubMed

    Fuwa, S; Kaminaga, T; Kobayashi, M; Sasaki, Y; Furui, S; Abe, T

    1998-07-01

    1H-NMR spectroscopy was performed on a 6-month-old boy with pachygyria. A MRI study demonstrated an abnormally thick cortex localized in the right occipital lobe. 1H-NMR spectrums were collected from the lesion and the contralateral cortex that appeared normal on MRI. The N-acetylaspartate (NAA)/Cre (creatine) ratio was markedly lower in the abnormal cortex than in the contralateral cortex and the occipital cortex. NAA localizes to neurons, axons, dendrites and synaptic connections and increases with maturation of neurons. Its decrease is considered to represent the decrease in the number of these structures and/or disturbance of neuronal maturation. We conclude that NAA/Cre can be an important index that reflects the pathogenesis of pachygyria. PMID:9695632

  15. Ralf Siebenmorgen IR instrument from Antarctica (thermal) IR instruments from Antarctica

    E-print Network

    Siebenmorgen, Ralf

    Ralf Siebenmorgen IR instrument from Antarctica (thermal) IR instruments from Antarctica: what can Antarctica Atmospheric optical thickness spectrum #12;Ralf Siebenmorgen IR instrument from Antarctica Siebenmorgen IR instrument from Antarctica Paranal Dome C (30m) Atmospheric transmission #12;Ralf Siebenmorgen

  16. Nd(III) and Dy(III) coordination compounds based on 1H-tetrazolate-5-acetic acid ligands: Synthesis, crystal structures and catalytic properties

    SciTech Connect

    Li Qiaoyun; Chen Dianyu; He Minghua; Yang Gaowen; Shen Lei; Zhai Chun; Shen Wei; Gu Kun; Zhao Jingjing

    2012-06-15

    Reactions of 1H-tetrazolate-5-acetic acid(H{sub 2}tza) with Nd(NO{sub 3}){sub 3}{center_dot}6H{sub 2}O or Dy(NO{sub 3}){sub 3}{center_dot}6H{sub 2}O with the presence of KOH under solvothermal conditions, produced two new coordination compounds, [M{sub 2}(tza){sub 3}(H{sub 2}O){sub 6}]{center_dot}2H{sub 2}O [M=Nd(1), Dy(2)]. Both compounds were structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Compounds 1 and 2 reveal 1D structures via bridging tza as linker. Furthermore, the compounds 1 and 2 showed a specific and good catalytic behavior for the polymerization of styrene, and the polymerization showed controlled characteristics. - Graphical Abstract: Two new coordination compounds, [M{sub 2}(tza){sub 3}(H{sub 2}O){sub 6}]{center_dot}2H{sub 2}O [M=Nd(1), Dy(2)] have been synthesis. 1 and 2 reveal 1D structures via bridging tza as linker, and showed a specific and good catalytic behavior for the polymerization of styrene. Highlights: Black-Right-Pointing-Pointer we have reported two novel compounds formed by H{sub 2}tza and Nd(III) or Dy(III). Black-Right-Pointing-Pointer Compounds 1 and 2 were found to have catalysis property for the photo-polymerization of styrene. Black-Right-Pointing-Pointer The high molecular weight polymers with narrow molecular weight distributions were obtained.

  17. Molecular structure of 2-chloromethyl-1H-benzimidazole hydrochloride: Single crystal, spectral, biological studies, and DFT calculations

    NASA Astrophysics Data System (ADS)

    Abdel Ghani, Nour T.; Mansour, Ahmed M.

    2012-02-01

    In the present work, structural studies on 2-chloromethyl-1H-benzimidazole hydrochloride have been performed extensively by X-ray crystallography, 1H NMR, FT-IR, UV/vis, and elemental analysis. The title compound crystallizes in a monoclinic space group P21/c with a = 7.1982 (3) Å, b = 9.4513 (5) Å, c = 14.0485 (7) Å and ? = 102.440 (3)° forming an infinite chain structure parallel to " b" axis through the intermolecular hydrogen bond. Optimized geometrical structure, harmonic vibrational frequencies, natural bonding orbital (NBO) and frontier molecular orbitals (FMO) were obtained by DFT/B3LYP method combined with 6-31G(d) basis set. TD-DFT calculations help to assign the electronic transitions. The 1H NMR chemical shifts were computed at the B3LYP/6-311 + G(2d,p) level of theory in different solvents by applying GIAO method using the polarizable continuum model (PCM). The title compound was screened for its antibacterial activity referring to Tetracycline as a standard antibacterial agent.

  18. Le IR, c'est mort. Vive le IR

    E-print Network

    Salo, Dorothea

    2008-07-31

    The institutional repository is dead -- long live the institutional repository! Despite their rocky beginnings, IRs are finally finding their niche and surging forward. What were their initial mistakes, and how can further ...

  19. CHHC and [superscript 1]H–[superscript 1]H magnetization exchange: Analysis by experimental solid-state NMR and 11-spin density-matrix simulations

    E-print Network

    Aluas, Mihaela

    A protocol is presented for correcting the effect of non-specific cross-polarization in CHHC solid-state MAS NMR experiments, thus allowing the recovery of the [superscript 1]H–[superscript 1]H magnetization exchange ...

  20. Synthesis, optimization and structural characterization of a chitosan-glucose derivative obtained by the Maillard reaction.

    PubMed

    Gullón, Beatriz; Montenegro, María I; Ruiz-Matute, Ana I; Cardelle-Cobas, Alejandra; Corzo, Nieves; Pintado, Manuela E

    2016-02-10

    Chitosan (Chit) was submitted to the Maillard reaction (MR) by co-heating a solution with glucose (Glc). Different reaction conditions as temperature (40, 60 and 80°C), Glc concentration (0.5%, 1%, and 2%, w/v), and reaction time (72, 52 and 24h) were evaluated. Assessment of the reaction extent was monitored by measuring changes in UV absorbance, browning and fluorescence. Under the best conditions, 2% (w/v) of Chit, 2% (w/v) of Glc at 60°C and 32h of reaction time, a chitosan-glucose (Chit-Glc) derivative was purified and submitted to structural characterization to confirm its formation. Analysis of its molecular weight (MW) and the degree of substitution (DS) was carried out by HPLC-Size Exclusion Chromatography (SEC) and a colloid titration method, respectively. FT-IR and (1)H NMR were also used to analyze the functional groups and evaluate the introduction of Glc into the Chit molecule. According to our objectives, the results obtained in this work allowed to better understand the key parameters influencing the MR with Chit as well as to confirm the successful introduction of Glc into the Chit molecule obtaining a Chit-Glc derivative with a DS of 64.76±4.40% and a MW of 210.37kDa. PMID:26686142

  1. Ultrafast 2D IR microscopy.

    PubMed

    Baiz, Carlos R; Schach, Denise; Tokmakoff, Andrei

    2014-07-28

    We describe a microscope for measuring two-dimensional infrared (2D IR) spectra of heterogeneous samples with ?m-scale spatial resolution, sub-picosecond time resolution, and the molecular structure information of 2D IR, enabling the measurement of vibrational dynamics through correlations in frequency, time, and space. The setup is based on a fully collinear "one beam" geometry in which all pulses propagate along the same optics. Polarization, chopping, and phase cycling are used to isolate the 2D IR signals of interest. In addition, we demonstrate the use of vibrational lifetime as a contrast agent for imaging microscopic variations in molecular environments. PMID:25089490

  2. Formation of octahedral iridium(III) dihydrides from the reaction of ortho-chelated aryliridium(I) compounds with dihydrogen

    SciTech Connect

    van der Zeijden, A.A.H.; van Koten, G.; Lujik, R.; Grove, D.M.

    1988-07-01

    The reaction of Ir/sup I/(CH/sub 2/NMe/sub 2/)-2-R/sup 1/-4-R/sup 2/-6)(COD) (COD = cyclooacta-1,5-diene) with dihydrogen in CD/sub 2/Cl/sub 2/ was monitored by /sup 1/H NMR. At -20/sup 0/C quantitative formation of the novel dihydride complexes Ir/sup III/H/sub 2/(C/sub 6/H/sub 2/(CH/sub 2/NMe/sub 2/)-2-R/sup 1/-4-R/sup 2/-6)(COD) (R/sup 1/ = H, R/sup 2/ = CH/sub 2/NMe/sub 2/ (10), Me (11); R/sup 2/ = H, R/sup 1/ = H (12), Me (13), CH/sub 2/NMe/sub 2/ (14); R/sup 1/ = R/sup 2/ = CH/sub 2/NMe/sub 2/ (15)) occurs. Further reactions, the type of which depends on the bulkiness of the R/sup 1/ and R/sup 2/ groups, occur when these solutions are warmed to 0/sup 0/C. Complexes 12-14 (R/sup 2/ = H) lose H/sub 2/ to re-form Ir/sup I/(C/sub 6/H/sub 3/(CH/sub 2/NMe/sub 2/)-2-R/sup 1/-4)(COD). In contrast, complexes 10, 11, and 15 (R/sup 2/ = alkyl) react further by means of C(aryl)-H reductive elimination. For complex 15 (R/sup 1/ = CH/sub 2/NMe/sub 2/) this results in quantitative formation of 1,3,5-(Me/sub 2/NCH/sub 2/)/sub 3/C/sub 6/H/sub 3/ and IrH(COD). In Ir/sup III/H/sub 2/(C/sub 6/H/sub 3/(CH/sub 2/NMe/sub 2/)-2-R-6)(COD) (R = alkyl (10 and 11)), C(aryl)-H reductive elimination is followed by re-addition of another C(aryl)-H bond, which upon subsequent reductive elimination of H/sub 2/, yields the rearranged iridium(I) complexes Ir/sup I/(C/sub 6/H/sub 3/(CH/sub 2/NMe/sub 2/)-2-R-4)(COD). Since the rearrangement of Ir/sup I/(C/sub 6/H/sub 3/-(CH/sub 2/NMe/sub 2/)-2-R-6)(COD) to Ir/sup I/(C/sub 6/H/sub 3/(CH/sub 2/NMe/sub 2/)-2-R-4)(COD) can also be induced thermally at 60/sup 0/C, it is therefore being catalyzed by dihydrogen at 0/sup 0/C. None of these reactions with dihydrogen is attended by hydrogenation of the COD ligand.

  3. Optical/IR from ground

    NASA Technical Reports Server (NTRS)

    Strom, Stephen; Sargent, Wallace L. W.; Wolff, Sidney; Ahearn, Michael F.; Angel, J. Roger; Beckwith, Steven V. W.; Carney, Bruce W.; Conti, Peter S.; Edwards, Suzan; Grasdalen, Gary

    1991-01-01

    Optical/infrared (O/IR) astronomy in the 1990's is reviewed. The following subject areas are included: research environment; science opportunities; technical development of the 1980's and opportunities for the 1990's; and ground-based O/IR astronomy outside the U.S. Recommendations are presented for: (1) large scale programs (Priority 1: a coordinated program for large O/IR telescopes); (2) medium scale programs (Priority 1: a coordinated program for high angular resolution; Priority 2: a new generation of 4-m class telescopes); (3) small scale programs (Priority 1: near-IR and optical all-sky surveys; Priority 2: a National Astrometric Facility); and (4) infrastructure issues (develop, purchase, and distribute optical CCDs and infrared arrays; a program to support large optics technology; a new generation of large filled aperture telescopes; a program to archive and disseminate astronomical databases; and a program for training new instrumentalists)

  4. Synthesis and x-ray structural characterization of binuclear iridium(I) and rhodium(I) hydroxypyridinate complexes. 1. Complete assignment of the /sup 1/H NMR spectra by two-dimensional and NOE techniques. The nature of inside and outside /sup 1/H chemical shift differences

    SciTech Connect

    Rodman, G.S.; Mann, K.R.

    1988-09-21

    Six new d/sup 8/-d/sup 8/ complexes, (Ir(COD)(..mu..-hp))/sub 2/, (Ir(COD)(..mu..-mhp))/sub 2/, (Ir(COD)(..mu..-chp))/sub 2/, (Ir(COD)(..mu..-2hq))/sub 2/, (Rh(COD)(..mu..-hp))/sub 2/, and (Rh(COD)(..mu..-mhp))/sub 2/ (hp = 2-hydroxyphridinate, mhp = 6-methyl-2-hydroxypyridinate, chp = 6-chloro-2-hydroxypyridinate, 2hq = 2-hydroxyquinolate, COD = 1,5-cyclooctadiene), were synthesized and characterized by /sup 1/H NMR, /sup 13/C NMR, and IR spectroscopy and FAB mass spectrometry. X-ray crystallographic analyses of the isostructural (M(COD)(..mu..-mhp))/sub 2/ (M = Ir and Rh) complexes confirmed the binuclear nature of the complexes. The complete assignment of the /sup 1/H NMR spectrum of (Ir(COD)(..mu..-hp))/sub 2/ (and by analogy, the spectra of the other five complexes) was carried out with selective decoupling, nuclear Overhauser effect (NOE), and two-dimensional NMR techniques. The NOE observed between hp proton H5 and COD proton H15 allowed the precise assignment of all 12 COD resonances. Olefinic proton H12 (trans to N and outside) resonates downfield of olefinic proton H11 (trans to N and inside). Olefininc proton H15 (trans to O and outside) resonates upfield of olefinic proton H16 (trans to O and inside). The endo methylene protons resonate upfield of the exo methylene protons. The inside/outside chemical shift differences observed for these compounds are ascribed to steric and magnetic anisotropy effects. The crystallographic data are presented. The molecular structure of the complexes is discussed in detail. 39 references, 5 figures, 9 tables.

  5. Integrated uncooled array IR sensors

    NASA Astrophysics Data System (ADS)

    Pevtsov, Eugeny P.; Elkin, Eugeny G.; Pospelova, Marina A.

    1997-08-01

    Technologies enabling low-dissipation designs for uncooled array IR sensors are offered. The technique involves the etching of special buffer layers from under a 1-micrometers membrane followed by deposition of an IR-sensitive film and electrode structure. The electrical and physical properties of plumbum-zirconate-titanate, barium titanate, tetraaminodiphenyl, polyvinylidene fluoride pyroelectric films are compared. A circuit for sensing pyroelectric signals in a CCD is considered.

  6. Direct NMR detection of the unstable "red product" from the reaction between nitroprusside and 2-mercaptosuccinic acid.

    PubMed

    Gao, Yin; Mossing, Brendan; Wu, Gang

    2015-12-21

    The reaction between nitroprusside (NP, [Fe(II)(CN)5NO](2-)) and organic thiolates (RS(-)) in aqueous solution has long been known to produce an unstable red intermediate thus often being referred to as the "red product" (RP) in the literature. While RP has always been formulated as [Fe(II)(CN)5N(O)SR](3-), it is rather difficult to study it in aqueous solution because it is not only unstable but also exhibits rapid ligand exchange. All previous studies of RP have relied on UV-vis, IR, kinetics measurements, and analysis of decomposed products. Herein we report the first comprehensive multinuclear ((1)H, (13)C, (15)N, and (17)O) NMR characterization of the RP produced from the reaction between NP and 2-mercaptosuccinic acid (MSA). The NMR chemical shifts obtained for the RP are compared with those from the free ligand (S-nitrosothiol, RS-N[double bond, length as m-dash]O) prepared in situ by the reaction of MSA with NaNO2. We also showed that useful thermodynamic and kinetic properties of RP formation can be readily obtained from (1)H NMR studies. PMID:26575643

  7. Determination of relative orientation between (1)H CSA tensors from a 3D solid-state NMR experiment mediated through (1)H/(1)H RFDR mixing under ultrafast MAS.

    PubMed

    Pandey, Manoj Kumar; Nishiyama, Yusuke

    2015-09-01

    To obtain piercing insights into inter and intramolecular H-bonding, and ?-electron interactions measurement of (1)H chemical shift anisotropy (CSA) tensors is gradually becoming an obvious choice. While the magnitude of CSA tensors provides unique information about the local electronic environment surrounding the nucleus, the relative orientation between these tensors can offer further insights into the spatial arrangement of interacting nuclei in their respective three-dimensional (3D) space. In this regard, we present a 3D anisotropic/anisotropic/isotropic proton chemical shift (CSA/CSA/CS) correlation experiment mediated through (1)H/(1)H radio frequency-driven recoupling (RFDR) which enhances spin diffusion through recoupled (1)H-(1)H dipolar couplings under ultrafast magic angle spinning (MAS) frequency (70kHz). Relative orientation between two interacting 1H CSA tensors is obtained by fitting two-interacting (1)H CSA tensors by fitting two-dimensional (2D) (1)H/(1)H CSA/CSA spectral slices through extensive numerical simulations. To recouple (1)H CSAs in the indirect frequency dimensions of a 3D experiment we have employed ?-encoded radio frequency (RF) pulse sequence based on R-symmetry (R188(7)) with a series of phase-alternated 2700(°)-90180(°) composite-180° pulses on citric acid sample. Due to robustness of applied (1)H CSA recoupling sequence towards the presence of RF field inhomogeneity, we have successfully achieved an excellent (1)H/(1)H CSA/CSA cross-correlation efficiency between H-bonded sites of citric acid. PMID:26065628

  8. Effect of Exercise on the Creatine Resonances in 1H MR Spectra of Human Skeletal Muscle

    NASA Astrophysics Data System (ADS)

    Kreis, R.; Jung, B.; Slotboom, J.; Felblinger, J.; Boesch, C.

    1999-04-01

    1H MR spectra of human muscles were recorded before, during, and after fatiguing exercise. In contrast to expectations, it was found that the spectral contributions of creatine/phosphocreatine (Cr/PCr) were subject to change as a function of exercise. In particular, the dipolar-coupled methylene protons of Cr/PCr were found to be reduced in intensity in proportion to the co-registered PCr levels. Recovery after exercise and behavior under ischemic conditions provide further evidence to suggest that the contributions of the CH2protons of Cr/PCr to1H MR spectra of human musclein vivoreflect PCr rather than Cr levels. Variation of experimental parameters showed that this effect is not due to a trivial change in relaxation times. At present it can only be speculated about why the Cr resonances have reduced NMR visibility. If temporary binding to macromolecules should be involved, the free Cr concentration-important for equilibrium calculations of the creatine kinase reaction-might be different from what was previously assumed.

  9. Development of Ir-base refractory superalloys

    SciTech Connect

    Yamabe, Y.; Koizumi, Y.; Murakami, H.; Ro, Y.; Maruko, T.; Harada, H.

    1996-07-15

    In the present study the authors propose a new class of superalloys: refractory superalloys. This new concept is defined as alloys with {gamma}-fcc and {gamma}{prime}-L1{sub 2} phases coherent structures similar to Ni-base superalloys, and yet with considerably higher melting points. Ir, having a melting point of 2,443 C, is selected as the base metal for the refractory superalloys since Ir has {gamma}-fcc structure and can be equilibrated with {gamma}{prime}-L1{sub 2} structure according to binary phase diagrams, e.g., in Ir-Nb, Ir-Ti, Ir-Ta, Ir-Hf, Ir-Zr and Ir-V systems. Hence the authors designed Ir-base refractory superalloys and tested their mechanical properties and oxidation resistance at up to 1,800 C. The Ir-Nb and Ir-Ti alloys are reported in this paper.

  10. 2-Methyl-5-nitro-1H-benzimidazole monohydrate

    PubMed Central

    Ghalib, Raza Murad; Hashim, Rokiah; Sulaiman, Othman; Quah, Ching Kheng; Fun, Hoong-Kun

    2011-01-01

    In the title compound, C8H7N3O2·H2O, the 2-methyl-5-nitro-1H-benzimidazole mol­ecule, excluding the methyl H atoms, is approximately planar, with a maximum deviation of 0.137?(1)?Å. The crystal structure is stabilized by water mol­ecules via N—H?O(water), O(water)—H?O and O(water)—H?N hydrogen bonds, forming sheets parallel to the (100) plane. A short inter­molecular contact between the benzene and imidazole rings, with a centroid–centroid distance of 3.6419?(10)?Å, indicates a ?–? inter­action. PMID:21754885

  11. Te-Te and Te-C bond cleavage reactions using a monovalent gallanediyl.

    PubMed

    Ganesamoorthy, Chelladurai; Bendt, Georg; Bläser, Dieter; Wölper, Christoph; Schulz, Stephan

    2015-03-21

    LGa (L = [(2,6-i-Pr2-C6H3)NC(Me)]2CH) reacts with elemental tellurium with formation of the Te-bridged compound [LGa-?-Te]2 1, whereas the reactions with Ph2Te2 and i-Pr2Te occurred with cleavage of the Te-Te and Te-C bond, respectively, and subsequent formation of LGa(TePh)2 2 and LGa(i-Pr)Tei-Pr 3. 1-3 were characterized by heteronuclear NMR ((1)H, (13)C, (125)Te) and IR spectroscopy and their solid state structures were determined by single crystal X-ray analyses. PMID:25680084

  12. Reactions of nitric oxide and nitrogen dioxide with coenzyme Q: involvement of the isoprenic chain.

    PubMed

    Astolfi, Paola; Charles, Laurence; Gigmes, Didier; Greci, Lucedio; Rizzoli, Corrado; Sorana, Federico; Stipa, Pierluigi

    2013-02-28

    The formation of a di-tert-alkyl nitroxide has been observed by Electron Spin Resonance during the exposure of coenzyme CoQ(10), in both the oxidized and reduced forms, to nitrogen dioxide (?NO(2)) or to nitric oxide (?NO) in the presence of oxygen. The same kind of nitroxide has been observed also with CoQ(1), CoQ(3) or with 1-phenyl-3-methyl-2-butene, chosen as model compounds. In all cases, the formation of the nitroxide may be justified only by admitting the involvement of the isoprenic chain of the coenzymes and in particular the addition of ?NO(2) to the double bond. A mechanism which accounts for the formation of the nitroxide as well as the other compounds observed in the reactions is proposed and confirmed by a spectroscopic investigation (FT-IR, (1)H NMR, X-ray analysis) and by ESI-MS. PMID:23334659

  13. An iron-based green approach to 1-h production of single-layer graphene oxide

    PubMed Central

    Peng, Li; Xu, Zhen; Liu, Zheng; Wei, Yangyang; Sun, Haiyan; Li, Zheng; Zhao, Xiaoli; Gao, Chao

    2015-01-01

    As a reliable and scalable precursor of graphene, graphene oxide (GO) is of great importance. However, the environmentally hazardous heavy metals and poisonous gases, explosion risk and long reaction times involved in the current synthesis methods of GO increase the production costs and hinder its real applications. Here we report an iron-based green strategy for the production of single-layer GO in 1?h. Using the strong oxidant K2FeO4, our approach not only avoids the introduction of polluting heavy metals and toxic gases in preparation and products but also enables the recycling of sulphuric acid, eliminating pollution. Our dried GO powder is highly soluble in water, in which it forms liquid crystals capable of being processed into macroscopic graphene fibres, films and aerogels. This green, safe, highly efficient and ultralow-cost approach paves the way to large-scale commercial applications of graphene. PMID:25607686

  14. 2-Chloro-4-(1H-pyrazol-1-yl)-5-(trifluoro­meth­yl)pyrimidine

    PubMed Central

    Bunker, Kevin D.; Moore, Curtis; Palmer, Cynthia L.; Rheingold, Arnold L.; Yanovsky, Alex

    2010-01-01

    The reaction of 2,4-dichloro-5-(trifluoro­meth­yl)pyrimidine with 1H-pyrazole gave two structural isomers in a 1:1 ratio that were separable by chromatography. The title compound, C8H4ClF3N4, was the first product to elute and was characterized in the present study to confirm that substitution by the pyrazolyl group had occurred at position 4. The mol­ecule (with the exception of the F atoms) is essentially planar, with a mean deviation of 0.034?Å from the least-squares plane through all non-H and non-F atoms. The bond angles in the pyrimidine ring show a pronounced alternating pattern with three angles, including those at the two N atoms being narrower, and the remaining three wider than 120°. PMID:21579519

  15. An iron-based green approach to 1-h production of single-layer graphene oxide.

    PubMed

    Peng, Li; Xu, Zhen; Liu, Zheng; Wei, Yangyang; Sun, Haiyan; Li, Zheng; Zhao, Xiaoli; Gao, Chao

    2015-01-01

    As a reliable and scalable precursor of graphene, graphene oxide (GO) is of great importance. However, the environmentally hazardous heavy metals and poisonous gases, explosion risk and long reaction times involved in the current synthesis methods of GO increase the production costs and hinder its real applications. Here we report an iron-based green strategy for the production of single-layer GO in 1?h. Using the strong oxidant K2FeO4, our approach not only avoids the introduction of polluting heavy metals and toxic gases in preparation and products but also enables the recycling of sulphuric acid, eliminating pollution. Our dried GO powder is highly soluble in water, in which it forms liquid crystals capable of being processed into macroscopic graphene fibres, films and aerogels. This green, safe, highly efficient and ultralow-cost approach paves the way to large-scale commercial applications of graphene. PMID:25607686

  16. Hydrate layers on ice particles and superheated ice: a {sup 1}H NMR microimaging study

    SciTech Connect

    Moudrakovski, I.L.; Ratcliffe, C.I.; McLaurin, G.E.; Simard, B.; Ripmeester, J.A.

    1999-07-01

    Recent observations on the interaction of methane gas with ice surfaces have led to the suggestion that the resulting hydrate layer prevents the encapsulated ice from melting at its usual temperature. This would require ice to exist in a superheated state. The authors have examined the product of the gas-solid reaction with {sup 1}H NMR imaging. The imaging experiments show that the hydrate-encapsulated ice is able to melt at its usual melting point. As a possible alternative model, the authors suggest that a considerable amount of ice inside the hydrate layer can be converted to hydrate and liquid water under isothermal and constant volume conditions, the hydrate layer acting as an insulating, semipermeable layer that insulates processes inside the hydrate layer from external bulk temperature and pressure measurements.

  17. Inhibition of Myeloperoxidase: Evaluation of 2H-Indazoles and 1H-Indazolones

    PubMed Central

    Roth, Aaron; Ott, Sean; Farber, Kelli M.; Palazzo, Teresa A.; Conrad, Wayne E.; Haddadin, Makhluf J.; Tantillo, Dean J.; Cross, Carroll E.; Eiserich, Jason P.; Kurth, Mark J.

    2014-01-01

    Myeloperoxidase (MPO) produces hypohalous acids as a key component of the innate immune response; however, release of these acids extracellularly results in inflammatory cell and tissue damage. The two-step, one-pot Davis-Beirut reaction was used to synthesize a library of 2H-indazoles and 1H-indazolones as putative inhibitors of MPO. A structure-activity relationship study was undertaken wherein compounds were evaluated utilizing taurine-chloramine and MPO-mediated H2O2 consumption assays. Docking studies as well as toxicophore and Lipinski analyses were performed. Fourteen compounds were found to be potent inhibitors with IC50 values <1 ?M, suggesting these compounds could be considered as potential modulators of pro-oxidative tissue injury pertubated by the inflammatory MPO:H2O2:HOCl/HOBr system. PMID:25438766

  18. Inhibition of myeloperoxidase: evaluation of 2H-indazoles and 1H-indazolones.

    PubMed

    Roth, Aaron; Ott, Sean; Farber, Kelli M; Palazzo, Teresa A; Conrad, Wayne E; Haddadin, Makhluf J; Tantillo, Dean J; Cross, Carroll E; Eiserich, Jason P; Kurth, Mark J

    2014-11-15

    Myeloperoxidase (MPO) produces hypohalous acids as a key component of the innate immune response; however, release of these acids extracellularly results in inflammatory cell and tissue damage. The two-step, one-pot Davis-Beirut reaction was used to synthesize a library of 2H-indazoles and 1H-indazolones as putative inhibitors of MPO. A structure-activity relationship study was undertaken wherein compounds were evaluated utilizing taurine-chloramine and MPO-mediated H2O2 consumption assays. Docking studies as well as toxicophore and Lipinski analyses were performed. Fourteen compounds were found to be potent inhibitors with IC50 values <1?M, suggesting these compounds could be considered as potential modulators of pro-oxidative tissue injury pertubated by the inflammatory MPO/H2O2/HOCl/HOBr system. PMID:25438766

  19. Microwave assisted one-pot catalyst free green synthesis of new methyl-7-amino-4-oxo-5-phenyl-2-thioxo-2,3,4,5-tetrahydro-1H-pyrano[2,3-d]pyrimidine-6-carboxylates as potent in vitro antibacterial and antifungal activity

    PubMed Central

    Bhat, Ajmal R.; Shalla, Aabid H.; Dongre, Rajendra S.

    2014-01-01

    An efficiently simple protocol for the synthesis of methyl 7 amino-4-oxo-5-phenyl-2-thioxo-2, 3, 4,5-tetrahydro-1H-pyrano[2,3-d]pyrimidine-6-carboxylates via one-pot three component condensation pathway is established via microwave irradiation using varied benzaldehyde derivatives, methylcyanoacetate and thio-barbituric acid in water as a green solvent. A variety of functionalized substrates were found to react under this methodology due to its easy operability and offers several advantages like, high yields (78–94%), short reaction time (3–6 min), safety and environment friendly without used any catalyst. The synthesized compounds (4a–4k) showed comparatively good in vitro antimicrobial and antifungal activities against different strains. The Compounds 4a, 4b, 4c, 4d 4e and 4f showed maximum antimicrobial activity against Staphylococcus aureus, Bacillus cereus (gram-positive bacteria), Escherichia coli, Klebshiella pneumonia, Pseudomonas aeruginosa (gram-negative bacteria). The synthesized compound 4f showed maximum antifungal activity against Aspergillus Niger and Penicillium chrysogenum strains. Streptomycin is used as standard for bacterial studies and Mycostatin as standards for fungal studies. Structure of all newly synthesized products was characterized on the basis of IR, 1H NMR, 13C NMR and mass spectral analysis.

  20. Synthesis of 5-substituted 3-amino-1H-pyrazole-4-carbonitriles as precursors for microwave assisted regiospecific syntheses of pyrazolo[1,5-a]pyrimidines.

    PubMed

    Al-Qalaf, Fawzia; Mandani, Faisal; Abdelkhalik, Mervat Mohammed; Bassam, Abeer Abdulrahman

    2009-01-01

    A simple route to 3-oxoalkanonitrile 5, aprecursor of the title compounds is described. Reaction of enaminones 2 with hydroxylamine hydrochloride in ethanol yielded aldoximes 3 that were converted readily into 5 in basic medium. This method has been successfully applied with a number of substrates and resulted in excellent yields of the products. Reacting 5 with trichloroacetonitrile afforded 3-amino-2-aroyl-4,4,4-trichloro-2-butenenitriles 6 that condensed with hydrazines to yield 3-amino-1H-pyrazole-4-carbonitrilederivatives 8. Substituted pyrazolo[1,5-a]pyridmidines have been prepared with regioselective condensation reactions of 8 with nonsymmetrical dielectrophiles. The structures of compounds obtained were deduced based on (1)H-NMR, (1)H-(15)N HMBC- measurements. PMID:19127239

  1. 60 MHz 1H NMR spectroscopy for the analysis of edible oils?

    PubMed Central

    Parker, T.; Limer, E.; Watson, A.D.; Defernez, M.; Williamson, D.; Kemsley, E. Kate

    2014-01-01

    We report the first results from a new 60 MHz 1H nuclear magnetic resonance (NMR) bench-top spectrometer, Pulsar, in a study simulating the adulteration of olive oil with hazelnut oil. There were qualitative differences between spectra from the two oil types. A single internal ratio of two isolated groups of peaks could detect hazelnut oil in olive oil at the level of ?13%w/w, whereas a whole-spectrum chemometric approach brought the limit of detection down to 11.2%w/w for a set of independent test samples. The Pulsar’s performance was compared to that of Fourier transform infrared (FTIR) spectroscopy. The Pulsar delivered comparable sensitivity and improved specificity, making it a superior screening tool. We also mapped NMR onto FTIR spectra using a correlation-matrix approach. Interpretation of this heat-map combined with the established annotations of the NMR spectra suggested a hitherto undocumented feature in the IR spectrum at ?1130 cm?1, attributable to a double-bond vibration. PMID:24850979

  2. Metabolomic insight into soy sauce through (1)H NMR spectroscopy.

    PubMed

    Ko, Bong-Kuk; Ahn, Hyuk-Jin; van den Berg, Frans; Lee, Cherl-Ho; Hong, Young-Shick

    2009-08-12

    Soy sauce, a well-known seasoning in Asia and throughout the world, consists of many metabolites that are produced during fermentation or aging and that have various health benefits. However, their comprehensive assessment has been limited due to targeted or instrumentally specific analysis. This paper presents for the first time a metabolic characterization of soy sauce, especially that aged up to 12 years, to obtain a global understanding of the metabolic variations through (1)H NMR spectroscopy coupled with multivariate pattern recognition techniques. Elevated amino acids and organic acids and the consumption of carbohydrate were associated with continuous involvement of microflora in aging for 12 years. In particular, continuous increases in the levels of betaine were found during aging for up to 12 years, demonstrating that microbial- or enzyme-related metabolites were also coupled with osmotolerant or halophilic bacteria present during aging. This work provides global insights into soy sauce through a (1)H NMR-based metabolomic approach that enhances the current understanding of the holistic metabolome and allows assessment of soy sauce quality. PMID:19591484

  3. Dynamics-based selective 2D 1H/1H chemical shift correlation spectroscopy under ultrafast MAS conditions

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-05-01

    Dynamics plays important roles in determining the physical, chemical, and functional properties of a variety of chemical and biological materials. However, a material (such as a polymer) generally has mobile and rigid regions in order to have high strength and toughness at the same time. Therefore, it is difficult to measure the role of mobile phase without being affected by the rigid components. Herein, we propose a highly sensitive solid-state NMR approach that utilizes a dipolar-coupling based filter (composed of 12 equally spaced 90° RF pulses) to selectively measure the correlation of 1H chemical shifts from the mobile regions of a material. It is interesting to find that the rotor-synchronized dipolar filter strength decreases with increasing inter-pulse delay between the 90° pulses, whereas the dipolar filter strength increases with increasing inter-pulse delay under static conditions. In this study, we also demonstrate the unique advantages of proton-detection under ultrafast magic-angle-spinning conditions to enhance the spectral resolution and sensitivity for studies on small molecules as well as multi-phase polymers. Our results further demonstrate the use of finite-pulse radio-frequency driven recoupling pulse sequence to efficiently recouple weak proton-proton dipolar couplings in the dynamic regions of a molecule and to facilitate the fast acquisition of 1H/1H correlation spectrum compared to the traditional 2D NOESY (Nuclear Overhauser effect spectroscopy) experiment. We believe that the proposed approach is beneficial to study mobile components in multi-phase systems, such as block copolymers, polymer blends, nanocomposites, heterogeneous amyloid mixture of oligomers and fibers, and other materials.

  4. Ultrafast 2D-IR spectroelectrochemistry of flavin mononucleotide

    NASA Astrophysics Data System (ADS)

    El Khoury, Youssef; Van Wilderen, Luuk J. G. W.; Bredenbeck, Jens

    2015-06-01

    We demonstrate the coupling of ultrafast two-dimensional infrared (2D-IR) spectroscopy to electrochemistry in solution and apply it to flavin mononucleotide, an important cofactor of redox proteins. For this purpose, we designed a spectroelectrochemical cell optimized for 2D-IR measurements in reflection and measured the time-dependent 2D-IR spectra of the oxidized and reduced forms of flavin mononucleotide. The data show anharmonic coupling and vibrational energy transfer between different vibrational modes in the two redox species. Such information is inaccessible with redox-controlled steady-state FTIR spectroscopy. The wide range of applications offered by 2D-IR spectroscopy, such as sub-picosecond structure determination, IR band assignment via energy transfer, disentangling reaction mixtures through band connectivity in the 2D spectra, and the measurement of solvation dynamics and chemical exchange can now be explored under controlled redox potential. The development of this technique furthermore opens new horizons for studying the dynamics of redox proteins.

  5. Facile solvothermal synthesis of abnormal growth of one-dimensional ZnO nanostructures by ring-opening reaction of polyvinylpyrrolidone

    NASA Astrophysics Data System (ADS)

    Xu, G.; Wang, X. L.; Liu, G. Z.

    2015-02-01

    Abnormal growth of one-dimensional (1-D) ZnO nanostructures (NSs) have been accomplished with the assistance of polyvinylpyrrolidone (PVP) under a super high alkaline alcoholic solvothermal condition. The products were characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and proton nuclear magnetic resonance (1H NMR) spectroscopy. The effect of synthetic conditions, such as reaction temperature and the addition of PVP, on the morphologies of ZnO products were investigated. The results show that PVP molecules had the significant role in the transformation of morphologies of ZnO NSs ranging from nanorods, nanoparticles to pyramids, as well as flower-like assembly features. The possible growth mechanism of ZnO pyramids was proposed based on ring-opening reaction of PVP.

  6. Synthesis, characterization and computational study on ethyl 4-(3-Furan-2yl-acryloyl)-3,5-dimethyl-1H-pyrrole-2-carboxylate

    NASA Astrophysics Data System (ADS)

    Singh, R. N.; Rawat, Poonam; Sahu, Sangeeta

    2014-11-01

    As part of study on pyrrole derivatives, we have synthesized a pyrrole chalcone derivative: ethyl 4-(3-Furan-2yl-acryloyl)-3,5-dimethyl-1H-pyrrole-2-carboxylate (EFADPC) by aldol condensation of ethyl 3, 5-dimethyl-4-actyl-1H-pyrrole-2-carboxylate with furan-2-carbaldehyde in the presence of strong hydroxyl base as catalyst. The product EFADPC has been confirmed by spectroscopic (FT-IR, 1H NMR, and UV-visible) analyses. Quantum chemical calculation also provides good correlation with experimental data. The molecular electrostatic potential surface (MEP), natural bond orbital interactions (NBO), electronic descriptors, quantum theory of atoms' in molecules (QTAIM) and experimental FT-IR spectrum have been used to predict the sites and nature of interactions which indicate that the dimer formation with multiple interactions through Nsbnd H···O and Csbnd H···O. The vibrational analysis shows red shifts in ?Nsbnd H and ?Cdbnd O as result of dimer formation. The binding energy of dimer is calculated as 13.82, 15.24 kcal/mol using DFT, QTAIM analysis, respectively. The result of ellipticity confirms the existence of resonance assisted hydrogen bonds (RAHB) in dimer. The MEP and local reactivity descriptors analyses have been performed and the results indicate that carbonyl carbon and ?-carbon of chalcone frame have been prone to nucleophilic attack and lead to large number of heterocyclic compounds such as oxirane, oxazoles, pyrazoles, pyridines, pyrimidines, and pyran.

  7. IR CCD staring imaging system

    NASA Astrophysics Data System (ADS)

    Zhou, Qibo

    1991-12-01

    An infrared staring imaging system in the 3 to 5 micrometers spectral band has been developed by SITP laboratories in China. The sensor utilized is a Pt-Si Schottky-barrier infrared CCD focal plane array. The digital video processing electronics is designed for 32 X 64, 64 X 64, and 128 X 128 pixel formats and contains the elimination of fixed pattern noise and the correction of response nonuniformity in real time and provides the high-quality IR image. The standard TV compatible and portable features are part of the design. In this paper, we describe the design and performance of this prototype system and present some experimental examples of IR imagery. The results demonstrate that the Pt-Si IR CCD imaging system has good performance, high reliability, low cost, and can be suitable for a variety of commercial applications.

  8. UVIS and IR Earth Flats

    NASA Astrophysics Data System (ADS)

    Pavlovsky, Cheryl

    2011-10-01

    This program is a continuation of 11914 {UVIS} and 11917 {IR} from Cycle 17. Sunlit earthflats are in program 12710. Visible-wavelength flat fields will be obtained by observing the dark side of the Earth during periods of full moon illumination. The observations will consist of full-frame streaked WFC3 UVIS imagery: per 15-min total exposure time in a single "dark-sky" orbit. Infrared-wavelength flat fields will be obtained by observing the dark side of the Earth during periods of full moon illumination. The observations will consist of full-frame streaked WFC3 IR imagery: per single "dark-sky" orbit, we anticipate achieving Poisson S/N > 100 per pixel in each of three to five exposures, depending on sample sequence {SPARS25 or SPARS50}. The Sunlit Earth is too bright for full frame IR illumination in these filters.

  9. The Use and Evaluation of Scaffolding, Student Centered-Learning, Behaviorism, and Constructivism to Teach Nuclear Magnetic Resonance and IR Spectroscopy in a Two-Semester Organic Chemistry Course

    ERIC Educational Resources Information Center

    Livengood, Kimberly; Lewallen, Denver W.; Leatherman, Jennifer; Maxwell, Janet L.

    2012-01-01

    Since 2002, infrared spectroscopy (IR) and nuclear magnetic resonance (NMR) spectrometry have been introduced at the beginning of the first-semester organic chemistry lab course at this university. Starting in 2008, each individual student was given 20 unique homework problems that consisted of multiple-choice [superscript 1]H NMR and IR problems…

  10. Detection of IR target by fusing multispectral IR data

    NASA Astrophysics Data System (ADS)

    Li, Liya; Qi, Meng; Gao, Xuhui

    2011-08-01

    Detection of the small target in clutter, usually regarded as singular points in the infrared image, is an important issue in infrared searching and tracking (IRST) system. Because of the far range of the target to the sensor, the stealth technology, the effects of inherent sensor noise and the phenomena of nature, the target is more difficult to be detected. Multispectral sensor system has been proved it could greatly improve detection of the small, hard-to-find targets by multispectral processing techniques (such as sensor or image fusion). Aiming at the problem of multispectral IR Target Detection, a kind method of the multispectral IR target detection is proposed, based on the existed detection systems. In this method, the image registration is done firstly to make the different sensors have a same scene. Then, a fusion rule, named as adaptive weighted voting theory, is developed to combine the target detection results from the different spectral sensors. The adaptive weighted voting theory can give the different weights, based on the different spectral IR characteristics, and these weights decide the detected target is identified as real target or background. The experimental results show that the proposed method can reduce the detection uncertainty and improve the detection performance. Compared with the single spectral detection results and the others fusion detection methods, it can decrease the lost alarm rate and the false alarm rate effectively. The proposed method has been employed in our IR surveillance system, and it is easy to be used in the various circumstances.

  11. Spectroscopic and quantum chemical studies on the structure of 2-arylquinoline-4(1 H)-thione derivatives

    NASA Astrophysics Data System (ADS)

    Mphahlele, Malose J.; El-Nahas, Ahmed M.; El-Gogary, Tarek M.

    2004-03-01

    The geometries of the title compounds were probed in solution, solid and gas states using spectroscopic methods, X-ray crystallography and quantum chemical techniques. The exclusive existence of the NH-4-thiones in solution (NMR and PCM-B3LYP(MP2)/6-31+G(d) calculations) and solid state (FT-IR and X-ray) is also corroborated by comparison of their spectroscopic data with those of the corresponding 2-aryl-1-methylquinoline-4(1 H)-thione derivatives. The co-existence of the quinoline-4-thione and quinoline-4-thiol (4-mercaptoquinoline) isomers in the gas phase is confirmed by mass spectrometry and the preponderance of the 4-thiol is supported by quantum chemical techniques (PM3, MP2 and B3LYP).

  12. Spectroscopic and structural study of some 2,5-hexanedione bis(salicyloylhydrazone) complexes: Crystal structures of its Ni(II) and Cu(II) complexes and N-(2,5-dimethyl-1H-pyrrol-1-yl)-2-hydroxy-benzamide

    NASA Astrophysics Data System (ADS)

    Jeragh, Bakir; El-Asmy, Ahmed A.

    2014-08-01

    The reaction between 2,5-hexanedione and salicylic acid hydrazide produced two compounds: 2,5-hexanedione bis(salicyloylhydrazone) [HDSH] (ethanol insoluble) and N-(2,5-dimethyl-1H-pyrrol-1-yl)-2-hydroxybenzamide [DPH] (ethanol soluble). HDSH formed complexes with Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and Pd(II) which are characterized by elemental analyses, spectra (IR, 1H NMR, ESR and MS), thermal and magnetic measurements. The crystals of [Ni(HDSH-2H)(EtOH)(H2O)] and [Cu(HDSH-2H)] were solved having octahedral and square-planar geometries, respectively. The other complexes have the formulae [Co(HDSH-2H)(H2O)2], [Cu(HDSH-H)2], [Zn(HDSH-2H)(H2O)2], [Cd2(HDSH-4H)(H2O)4], [Cd2(HDSH-2H)(H2O)4Cl2]; [Hg(HDSH-2H)] and [Pd2(HDSH-4H)(H2O)4]. The obtained complexes are stable in air and non-hygroscopic. The magnetic moments and electronic spectra of the complexes provide different geometries. The ESR spectra support the mononuclear geometry for [Cu(HDSH-2H)] and [Cu(HDSH-H)2]. The thermal decomposition of the complexes revealed the coordinated waters as well as the end product which is in most cases the metal oxide. The crystal structure of N-(2,5-dimethyl-1H-pyrrol-1-yl)-2-hydroxybenzamide is solved by X-ray technique.

  13. Theoretical studies of Ir5Th and Ir5Ce nanoscale precipitates in Ir

    SciTech Connect

    Morris, James R; Averill, Frank; Cooper, Valentino R

    2014-01-01

    Experimentally, it is known that very small amounts of thorium and/or cerium added to iridium metal form a precipitate, Ir5Th / Ir5Ce, which improves the high temperature mechanical properties of the resulting alloys. We demonstrate that there are low-energy configurations for nano-scale precipitates of these phases in Ir, and that these coherent arrangements may assist in producing improved mechanical properties. One precipitate/matrix orientation gives a particularly low interfacial energy, and a low lattice misfit. Nanolayer precipitates with this orientation are found to be likely to form, with little driving force to coarsen. The predicted morphology of the precipitates and their orientation with the matrix phase provide a potential experiment that could be used to test these predictions.

  14. MARYLAND COASTAL BAYS IR 2002

    EPA Science Inventory

    The Maryland Coastal Bays Program Implementation Review (IR) summarizes the progress and challenges ahead for the Program through examination of its activities in relation to the CCMP. During the CCMP planning phase the stakeholders prioritized the actions and determined the impl...

  15. Pirmoji ir antroji kauno trianguliacijos

    NASA Astrophysics Data System (ADS)

    Girkus, Romualdas; Urbanavi?ius, Valdas

    2010-01-01

    Miesto plan? sudarymo reikm?ms atramos punkt? tinklas tarpukariu Europos valstyb?se buvo formuojamas trianguliacijos metodu. Kauno pirm? kart? 1924 m. jis buvo suprojektuotas iš 36 punkt?, fiksuotas vietov?je ir išmatuotas inž. Z. Ba?elio. Sudarytas trianguliacijos tinklas ap?m? tuometin? Vilijampol?s, Aleksoto, Žaliakalnio, Naujamies?io ir Žem?j? Šan?i? teritorij?. Kaunas, tap?s laikin?ja sostine, spar?iai augo, d?l to pirmoji trianguliacija netenkino poreiki?: dauguma punkt? vietov?je nebuvo išsaugoti, miestas dvigubai išsipl?t?, d?l naudot? geodezini? prietais? nepakankamas buvo punkt? tikslumas. Naujas tinklas buvo suprojektuotas taip, kad vienam punktui vidutini\\vskai tekt? vienas kvadratinis kilometras miesto ploto ir b?t? užtikrintas ?tvirtint? punkt? 10 cm ribinis tikslumas. Kauno antrosios trianguliacijos realizavimo nuopelnai priskirtini Kauno savivaldyb?s Matavim? dalies specialistams - ved?jui J. Deksniui ir jo pavaduotojui J. Ašmonui.

  16. Busch Gardens IRS Tax Forms

    E-print Network

    Sin, Peter

    Highlights Busch Gardens IRS Tax Forms Notes from the Office Birthdays Grammar Word Gardens. Please reserve your spot on the van by signing up and paying $20 in cash, exact change, to Nate. Bus passes are first come, first serve, and they do NOT include the price of Busch Gardens tickets

  17. Fingerprinting zein by IR analysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Zein, the dominant protein in corn, is a coproduct of the ethanol production industry. The protein content and purity of commercially available zein can vary widely depending on the source and production method. Infrared Spectroscopy Analysis (IR) was used to differentiate between zein samples of ...

  18. Synthesis, Structure, and Reactivity of O-Donor Ir(III) Complexes: C-H Activation Studies with Benzene

    E-print Network

    Goddard III, William A.

    with Benzene Gaurav Bhalla, Xiang Yang Liu, Jonas Oxgaard, William A. Goddard, III, and Roy A. Periana. All the R-Ir-Py complexes undergo quantitative, intermolecular CH activation reactions with benzene to benzene to generate a discrete benzene complex, cis-R-Ir-PhH; and (D) rapid C-H cleavage. Kinetic isotope

  19. Collaborative Student Laboratory Exercise Using FT-IR Spectroscopy for the Kinetics Study of a Biotin Analogue

    ERIC Educational Resources Information Center

    Leong, Jhaque; Ackroyd, Nathan C.; Ho, Karen

    2014-01-01

    The synthesis of N-methoxycarbonyl-2-imidazolidone, an analogue of biotin, was conducted by organic chemistry students and confirmed using FT-IR and H NMR. Spectroscopy students used FT-IR to measure the rate of hydrolysis of the product and determined the rate constant for the reaction using the integrated rate law. From the magnitude of the rate…

  20. Structural and spectroscopic studies of bis(2-amino-6-methylpyrimidinium-4-(1H)-one) aquapentachloridoindate(III) monohydrate

    NASA Astrophysics Data System (ADS)

    Nbili, W.; Kaabi, K.; Ferretti, V.; Lefebvre, F.; Ben Nasr, C.

    2015-11-01

    Physico-chemical properties of a new organic indate(III) (C5H8N3O)2[InCl5(H2O)].H2O are discussed on the basis of its X-ray crystal structure investigation. The asymmetric unit includes two independent 2-amino-6-methylpyrimidinium-4-(1H)-one cations, one aquapentachloridoindate dianion, and one crystallization water molecule. The InIII ion is in a slightly distorted octahedral coordination geometry. In the crystal structure, the dimeric species formed by two metal complexes and two water molecules are connected to the 2-amino-6-methylpyrimidin-4-1H)-one cations through N-H⋯Cl hydrogen bonds to build 2D sheets parallel to the (b, a + c) plane. The 13C and 15N CP-MAS NMR spectra are in agreement with the X-ray structure. The vibrational absorption bands were identified by infrared spectroscopy. DFT calculations allowed attributions of NMR signals and of the IR bands.

  1. An Ir(IV)-containing polyoxometalate.

    PubMed

    Adonin, Sergey A; Izarova, Natalya V; Besson, Claire; Abramov, Pavel A; Santiago-Schübel, Beatrix; Kögerler, Paul; Fedin, Vladimir P; Sokolov, Maxim N

    2015-01-25

    [HIr(IV)W6O24](7-), representing the first Ir-containing Anderson-Evans-type polyanion and the first structurally characterized Ir(IV)-based polyoxometalate, has been isolated as its hydrated sodium salt and characterized by single-crystal X-ray diffraction, mass spectrometry, and IR, UV-Vis and EPR spectroscopy. Cyclic voltammetry indicates that the Ir(IV) ions in [HIrW6O24](7-) can undergo reversible one-electron reduction and oxidation, resulting in Ir(III) and Ir(V) derivatives. PMID:25469664

  2. Preliminary study of corrosion mechanisms of actinides alloys: calibration of FT-IR spectroscopy

    SciTech Connect

    Magnien, Veronique; Cadignan, Marx; Faivret, Olivier; Rosa, Gaelle

    2008-07-01

    In situ analyzes of gaseous atmospheres could be performed by FT-IR spectroscopy in order to study the corrosion reactions of actinides. Nevertheless experimental conditions and the nature of studied species have a strong effect on IR absorption laws. Thus a prior calibration of our set-up is required to obtain an accurate estimation of gas concentration. For this purpose, the behavior of several air pure gases has been investigated according to their concentration from IR spectra. Reproducible results revealed subsequent increases of the most significant peak areas with gas pressure and small deviations from Beer Lambert's law. This preliminary work allowed to determine precise absorption laws for each studied pure gas in our in situ experimental conditions. Besides our FT-IR set-up was well suitable to quantitative analysis of gaseous atmosphere during corrosion reactions. Finally the effect of foreign gas will be investigated through more complex air mixtures to obtain a complete calibration network. (authors)

  3. Isomeric luminescent Zn(II) coordination polymers based on pyridinecarboxylate and 5-methyl-1H-tetrazole ligands

    NASA Astrophysics Data System (ADS)

    An, Zhe; Gao, Jing; Zhu, Ling

    2013-12-01

    Two new metal-organic frameworks, namely [Zn(nic)(mtz)]n (1) and [Zn(isonic)(mtz)]n (2) (Hnic = nicotinic acid, Hisonic = isonicotinic acid, Hmtz = 5-methyl-1H-tetrazole), have been obtained through the solvothermal reactions of Zn(NO3)2, Htmz and Hnic or Hisonic. Single crystal X-ray diffraction analysis reveals that compound 1 features a 2D layered structure with sql topology, which is further extended into a 3D supramolecular framework via weak CH…? interactions, and compound 2 is 2-fold interpenetrated 3D framework with dia topology. Luminescent investigation shows that both of them emit blue luminescence at room temperature.

  4. High-field localized 1 H NMR spectroscopy in the anesthetized and in

    E-print Network

    High-field localized 1 H NMR spectroscopy in the anesthetized and in the awake monkey Josef Localized cerebral in vivo 1 H NMR spectroscopy (MRS) was performed in the anesthetized as well as the awake-ml volumes. D 2004 Elsevier Inc. All rights reserved. Keywords: In vivo 1 H NMR spectroscopy; Short

  5. 1H and 13C Solid-state NMR of G. barbadense (Pima) Cotton

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The interaction of water with cellulose and its influence on the nuclear spin dynamics in G. barbadense (Pima) cotton were investigated with 1H and 13C solid-state NMR techniques. 1H spin diffusion results from a Goldman-Shen experiment indicate that the water is multilayered. 1H MAS experiment...

  6. 1H and 13C Solid-state NMR of Gossypium barbadense (Pima) Cotton

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The interaction of water with cellulose and its influence on the nuclear spin dynamics in G. barbadense (Pima) cotton were investigated by 1H and 13C solid-state NMR techniques. 1H spin diffusion results from a Goldman-Shen experiment indicate that the water is multilayered. 1H MAS experiments pro...

  7. Vibrational spectroscopic, 1H NMR and quantum chemical computational study of 4-hydroxy-2-oxo-1,2-dihydroquinoline-8-carboxylic acid.

    PubMed

    Ulahannan, Rajeev T; Panicker, C Yohannan; Varghese, Hema Tresa; Van Alsenoy, C; Musiol, Robert; Jampilek, Josef; Anto, P L

    2014-01-01

    FT-IR, FT-Raman and (1)H NMR spectra of 4-hydroxy-2-oxo-1,2-dihydroquinoline-8-carboxylic acid were recorded and obtained data were confronted with the computed using Gaussian09 software package. DFT/B3LYP, B3PW91 calculations have been done using 6-31G* and SDD basis sets, to investigate the vibrational frequencies and geometrical parameters. The assignments of the normal modes are done by potential energy distribution (PED) calculations. The calculated first hyperpolarizability is comparable with the reported values of similar quinoline derivatives and is an attractive object for future studies of non-linear optics. The stability of the molecule arising from hyperconjugative interaction and charge delocalization has been analyzed using NBO analysis. MEP predicts the most reactive part in the molecule. The calculated (1)H NMR results are in good agreement with experimental data. PMID:24287054

  8. Preliminary 1H NMR study on archaeological waterlogged wood.

    PubMed

    Maccotta, Antonella; Fantazzini, Paola; Garavaglia, Carla; Donato, Ines D; Perzia, Patrizia; Brai, Maria; Morreale, Filippa

    2005-01-01

    Magnetic Resonance Relaxation (MRR) and Magnetic Resonance Imaging (MRI) are powerful tools to obtain detailed information on the pore space structure that one is unlikely to obtain in other ways. These techniques are particularly suitable for Cultural Heritage materials, because they use water 1H nuclei as a probe. Interaction with water is one of the main causes of deterioration of materials. Porous structure in wood, for example, favours the penetration of water, which can carry polluting substances and promote mould growth. A particular case is waterlogged wood from underwater discoveries and moist sites; in fact, these finds are very fragile because of chemical, physical and biological decay from the long contact with the water. When wood artefacts are brought to the surface and directly dried in air, there is the collapse of the cellular structures, and wood loses its original form and dimensions and cannot be used for study and museum exhibits. In this work we have undertaken the study of some wood finds coming from Ercolano's harbour by MRR and MRI under different conditions, and we have obtained a characterization of pore space in wood and images of the spatial distribution of the confined water in the wood. PMID:16485652

  9. 3-hydroxy-2(1H)-pyridinone chelating agents

    DOEpatents

    Raymond, Kenneth N. (Berkeley, CA); Xu, Jide (Berkeley, CA)

    1997-01-01

    Disclosed is a series of improved metal chelating agents, which are highly effective upon both injection and oral administration; several of the most effective are of low toxicity. These chelating agents incorporate within their structure 1-hydroxy-2-pyridinone (1,2-HOPO) and 3-hydroxy-2-pyridinone (3,2-HOPO) moieties with a substituted carbamoyl group ortho to the hydroxy or oxo groups of the hydroxypyridinone ring. The electron-withdrawing carbamoyl group increases the acidity of the hydroxypyridinones. In the metal complexes of said chelating agents, the amide protons form very strong hydrogen bonds with its adjacent HOPO oxygen donor, making these complexes very stable at physiological conditions. The terminal N-substituents provides a certain degree of lipophilicity to said 3,2-HOPO, increasing oral activity. Also disclosed is a method of making the chelating agents and a method of producing a known compound, 3-hydroxy-1-alkyl-2(1H)pyridinone, used as a precursor to the chelating agent, safely and in large quantities.

  10. 3-hydroxy-2(1H)-pyridinone chelating agents

    DOEpatents

    Raymond, K.N.; Xu, J.

    1997-04-29

    Disclosed is a series of improved metal chelating agents, which are highly effective upon both injection and oral administration; several of the most effective are of low toxicity. These chelating agents incorporate within their structure 1-hydroxy-2-pyridinone (1,2-HOPO) and 3-hydroxy-2-pyridinone (3,2-HOPO) moieties with a substituted carbamoyl group ortho to the hydroxy or oxo groups of the hydroxypyridinone ring. The electron-withdrawing carbamoyl group increases the acidity of the hydroxypyridinones. In the metal complexes of the chelating agents, the amide protons form very strong hydrogen bonds with its adjacent HOPO oxygen donor, making these complexes very stable at physiological conditions. The terminal N-substituents provides a certain degree of lipophilicity to the 3,2-HOPO, increasing oral activity. Also disclosed is a method of making the chelating agents and a method of producing a known compound, 3-hydroxy-1-alkyl-2(1H)pyridinone, used as a precursor to the chelating agent, safely and in large quantities. 2 figs.

  11. PREDICTION OF REGIONAL WIND POWER T.S. Nielsen1, H. Madsen1, H. Aa. Nielsen1, L. Landberg2, G. Giebel2

    E-print Network

    PREDICTION OF REGIONAL WIND POWER T.S. Nielsen1, H. Madsen1, H. Aa. Nielsen1, L. Landberg2, G the total wind power production in a larger region based on a combination of on-line measurements of power production from selected wind farms, power measure- ments for all wind turbines in the area and numerical

  12. Paenibacillin A, a new 2(1H)-pyrazinone ring-containing natural product from the endophytic bacterium Paenibacillus sp. Xy-2.

    PubMed

    Bian, Xiqing; Shao, Meili; Pan, Huaqi; Wang, Kaibo; Huang, Shengdong; Wu, Xin; Xue, Chunmei; Hua, Huiming; Pei, Yuehu; Bai, Jiao

    2016-01-01

    A new 2(1H)-pyrazinone ring-containing natural product, paenibacillin A (1), together with five known diketopiperazine derivatives 2-6 and two known isoflavones 7-8, was isolated from the culture of an endophytic bacterium Paenibacillus sp. Xy-2. The structure of compound 1 was elucidated by extensive spectral methods, including UV, IR, HR-ESI-MS, 1D and 2D NMR and ECD experiments. Compound 1 exhibited moderate cytotoxicity against HL-60 cell line with IC50 value of 50.48 ?M. PMID:25981853

  13. CBL-2201. Report on a new designer drug: Napht-1-yl 1-(5-fluoropentyl)-1H-indole-3-carboxylate.

    PubMed

    Kondrasenko, A A; Goncharov, E V; Dugaev, K P; Rubaylo, A I

    2015-12-01

    The (1)H, (13)C and (15)N nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR) and gas chromatography coupled to mass spectrometry (GC-MS) identification of a synthetic cannabinoid compound has been conducted. It was shown that this compound cannot be reliably distinguished from the closely related quinolin-8-yl indole-3-carboxylic acid derivative by an automatic search in MS library. Structural difference of the studied compound and known illicit compounds has been determined using 1D and 2D NMR spectroscopy. Analytical data for the identification of this compound were provided. PMID:26386336

  14. A new one-dimensional Zn(II) coordination polymer based on 2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole and benzene-1,2-dicarboxylate.

    PubMed

    Huang, Qiu Ying; Liu, Wei; Yang, Yi; Meng, Xiang Ru

    2015-11-01

    Multidentate N-heterocyclic compounds form a variety of metal complexes with many intriguing structures and interesting properties. The title coordination polymer, catena-poly[zinc(II)-bis{?-2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole}-?(2)N(3):N(3');N(3'):N(3)-zinc(II)-bis(?-benzene-1,2-dicarboxylato)-?(2)O(1):O(2);?(3)O(1),O(1'):O(2)], [Zn2(C8H4O4)2(C11H10N4)2]n, has been synthesized by the reaction of Zn(NO3)2 with 2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole (imb) and benzene-1,2-dicarboxylic acid (H2bdic) under hydrothermal conditions. There are two crystallographically distinct imb ligands [imb(A) and imb(B)] in the structure which adopt very similar coordination geometries. The imb(A) ligand bridges two symmetry-related Zn1 ions, yielding a binuclear [(Zn1)2{imb(A)}2] unit, and the imb(B) ligand bridges two symmetry-related Zn2 ions resulting in a binuclear [(Zn2)2{imb(B)}2] unit. The above-mentioned binuclear units are further connected alternately by pairs of bridging bdic(2-) ligands, forming an infinite one-dimensional chain. These one-dimensional chains are further connected through N-H...O hydrogen bonds, leading to a two-dimensional layered structure. In addition, the title polymer exhibits good fluorescence properties in the solid state at room temperature. PMID:26524177

  15. New electrocatalysts for unitized regenerative fuel cell: Pt-Ir alloy deposited on the proton exchange membrane surface by impregnation-reduction method.

    PubMed

    Wan, Chieh-Hao; Wu, Chun-Lin; Lin, Meng-Tsun; Shih, Chihhsiong

    2010-07-01

    In this paper, a modified technique to prepare Pt-Ir catalyst layer on the proton exchange membrane (PEM) surface using the impregnation-reduction (IR) method is proposed to improve the electrocatalytic activity as well as the life cycle of the bifunctional oxygen electrode (BOE). The resulted electrocatalysts were characterized by the Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Electron Probe Micro-Analysis (EPMA), and Transmission Electron Microscope (TEM). The electrocatalytic properties of the Pt-Ir layer on PEM surface for the oxygen reduction and water oxidation reactions as well as the life cycle of MEA were investigated. Experimental results showed that the Ir particles were dispersed densely in the platinum layer through the modified IR technique. The atomic ratio of Pt over Ir elements was 9:1, and the resulted thickness of the obtained Pt-Ir catalyst layer was about 1.0 microm. The Pt-Ir catalyst layer was composed of Pt layer doped with Ir nano-particles comprising nano Pt-Ir alloy phase. The large surface area of Ir core with Pt shell particles and the presence of nano Pt-Ir alloy phase led to a higher electrocatalytic activity of BOE. Due to the good binding between the Nafion membrane and the Pt-Ir alloy catalyst, as well as the composite structure of the resulted Pt-Ir, the life cycle of Unitized Regenerative Fuel Cell (URFC) is improved through this novel BOE. PMID:21128466

  16. Optimized IR synchrotron beamline design.

    PubMed

    Moreno, Thierry

    2015-09-01

    Synchrotron infrared beamlines are powerful tools on which to perform spectroscopy on microscopic length scales but require working with large bending-magnet source apertures in order to provide intense photon beams to the experiments. Many infrared beamlines use a single toroidal-shaped mirror to focus the source emission which generates, for large apertures, beams with significant geometrical aberrations resulting from the shape of the source and the beamline optics. In this paper, an optical layout optimized for synchrotron infrared beamlines, that removes almost totally the geometrical aberrations of the source, is presented and analyzed. This layout is already operational on the IR beamline of the Brazilian synchrotron. An infrared beamline design based on a SOLEIL bending-magnet source is given as an example, which could be useful for future IR beamline improvements at this facility. PMID:26289267

  17. Allergic Reactions

    MedlinePLUS

    ... allergic reaction is actually a result of a chain reaction that begins in your genes and is expressed ... Tips • Allergy symptoms are the result of a chain reaction that starts in your immune system. • If you ...

  18. IRS memorandum limits joint ventures.

    PubMed

    Herman, A W

    1992-08-01

    Based on a new memorandum, the Internal Revenue Service (IRS) will be looking at joint hospital/physician activities with greater attention to the nuances of public versus private benefit. As a result, hospitals face greater risk of losing their tax-exempt status in the maze of joint ventures, physician recruitment, and practice acquisition. To be successful, ventures will have to be backed by sound reasoning and thorough documentation. PMID:10145664

  19. The partial (1)H NMR spectra of Al-OH and molecular H(2)O in hydrous aluminosilicate glasses: Component-Resolved analysis of (27)Al-(1)H cross polarization and (1)H spin-echo MAS NMR spectra.

    PubMed

    Malfait, Wim J; Xue, Xianyu

    2010-01-01

    The Component-Resolved methodology was applied to (1)H spin-echo and (27)Al-(1)H cross polarization (CP) MAS NMR data of aluminosilicate glasses. The method was able to resolve two components with different T2 relaxation rates, hydroxyl groups (OH) and molecular water (H(2)O(mol)), from the spin-echo data and to determine partial spectra and the relative abundances of OH and H(2)O(mol). The algorithm resolved two to three components with different (27)Al-(1)H CP dynamics from the (27)Al-(1)H cross polarization data; the obtained partial NMR spectra for Al-OH are in excellent agreement with those obtained previously from the difference spectra between spectra with various contact times and confirm previous quantitative results and models for the Al-OH, Si-OH and H(2)O(mol) speciation (Malfait and Xue, 2010). PMID:20418075

  20. Ultrafast 2D IR Vibrational Echo Spectroscopy

    E-print Network

    Fayer, Michael D.

    Ultrafast 2D IR Vibrational Echo Spectroscopy JUNRONG ZHENG, KYUNGWON KWAK, AND M. D. FAYER The experimental technique and applications of ultrafast two- dimensional infrared (2D IR) vibrational echo systems. The form and time evolution of the 2D IR spectrum permits examination of processes that cannot

  1. What Nonlinear-IR Experiments Can Tell You about Water that the IR Spectrum Cannot

    E-print Network

    Fayer, Michael D.

    What Nonlinear-IR Experiments Can Tell You about Water that the IR Spectrum Cannot Ivan R. PileticVersity, Stanford, California 94305 Received April 12, 2006; E-mail: fayer@stanford.edu Infrared (IR) spectroscopy as qualitative depictions of the integrity of the hydrogen bond network.2-4 Here, we use nonlinear-IR

  2. A study of the physico-chemical properties of 1,3,5-trihydroxy-1,3,5-triazin-2,4,6[1 H,3 H,5 H]-trione

    NASA Astrophysics Data System (ADS)

    Taka?, M. Jadrijevi?-Mladar; Kos, I.; Biruš, M.; Butula, I.; Gabri?evi?, M.

    2006-01-01

    Acetyl ( Ia) and pivaloyl ( Ib) triesters of the 1 N,3 N,5 N-trihydroxy-1,3,5-triazin-2,4,6[1 H,3 H,5 H]-trione ( I) were synthesised. The spectrophotometric and potentiometric investigation of I revealed a weak acidic properties of triprotonic acid (p Ka1=5.23, p Ka2=6.32, and p Ka3=7.93). The MS and TGA analyses of I indicated on hydroxyisocyanate as possible degradation product. The chelating ability of I with Fe(III)-ion was preliminary explored. IR measurements of aqueous solutions of I in the presence of Fe(III) ion showed the possible chelating ability of all hydroxamic moieties. The chemical structures and properties of investigated compounds were derived from the results of IR, 1H and 13C NMR, UV and MS spectrometric data, as well as thermogravimetric and potentiometric analysis.

  3. Unusual behavior in the reactivity of 5-substituted-1H-tetrazoles in a resistively heated microreactor

    PubMed Central

    Gutmann, Bernhard; Glasnov, Toma N; Razzaq, Tahseen; Goessler, Walter; Roberge, Dominique M

    2011-01-01

    Summary The decomposition of 5-benzhydryl-1H-tetrazole in an N-methyl-2-pyrrolidone/acetic acid/water mixture was investigated under a variety of high-temperature reaction conditions. Employing a sealed Pyrex glass vial and batch microwave conditions at 240 °C, the tetrazole is comparatively stable and complete decomposition to diphenylmethane requires more than 8 h. Similar kinetic data were obtained in conductively heated flow devices with either stainless steel or Hastelloy coils in the same temperature region. In contrast, in a flow instrument that utilizes direct electric resistance heating of the reactor coil, tetrazole decomposition was dramatically accelerated with rate constants increased by two orders of magnitude. When 5-benzhydryl-1H-tetrazole was exposed to 220 °C in this type of flow reactor, decomposition to diphenylmethane was complete within 10 min. The mechanism and kinetic parameters of tetrazole decomposition under a variety of reaction conditions were investigated. A number of possible explanations for these highly unusual rate accelerations are presented. In addition, general aspects of reactor degradation, corrosion and contamination effects of importance to continuous flow chemistry are discussed. PMID:21647324

  4. New supersymmetric quartet of nuclei: {sup 192,193}Os-{sup 193,194}Ir

    SciTech Connect

    Bijker, R.; Frank, A.; Barea, J.; Graw, G.; Wirth, H.-F.; Hertenberger, R.; Jolie, J.

    2009-01-28

    We present evidence for the existence of a new supersymmetric quartet of nuclei in the A{approx}190 mass region. The analysis is based on new experimental information on the odd-odd nucleus {sup 194}Ir from transfer and neutron capture reactions. The new data allow the identification of a new supersymmetric quartet, consisting of the {sup 192,193}Os and {sup 193,194}Ir nuclei. We make explicit predictions for {sup 193}Os, and suggest that its spectroscopic properties be measured in dedicated experiments. Finally, we study correlations between different transfer reactions.

  5. 1H NMR spectra of humic and fulvic acids and their peracetic oxidation products

    NASA Astrophysics Data System (ADS)

    Ruggiero, P.; Interesse, F. S.; Cassidei, L.; Sciacovelli, O.

    1980-04-01

    1H NMR spectra of humic (HA) and fulvic (FA) acids and their oxidative degradation products are reported. The HA shows the presence of -( CH2) n - CH3 ( n > 6) chemical fragments belonging to n-alkanes and/or n-fatty acids physically adsorbed onto the macromolecule structure. These fragments are absent in the FA fraction. Both humic fractions reveal the presence of similar amounts of aromatic protons which partly undergo exchange phenomena. The importance of this experimental observation is discussed. Oxidative degradation seems to cause partial cleavage of aromatic rings, more pronounced in the FA than in the HA. The degraded FA shows a higher total acidity and a higher phenolic OH content than the degraded HA. Both degraded fractions display some sharp singlet signals at 1.9 and 3.9 ppm arising from protons belonging to repetitive chemical fragments probably formed during the oxidation reaction. Tentative assignments of these signals are given. A general analysis of the HA and FA degraded spectra seems to indicate that the chemical fragments which undergo peracetic oxidation are substantially similar. The extent of oxidation of the two humic fractions is different. The HA degradation products reveal the presence of oligomeric structures, whereas the degraded FA appears less resistant to the oxidizing agent.

  6. IR susceptibility of naval ships using ShipIR/NTCS

    NASA Astrophysics Data System (ADS)

    Vaitekunas, David A.

    2010-04-01

    Methods of analysing the signature and susceptibility of naval platforms to infrared detection are described. An unclassified ShipIR destroyer model is used to illustrate the primary sources of infrared signature and detection: the exhaust system, solar-heating, and operating climate. The basic detection algorithm used by the Naval Threat Countermeasure Simulator (NTCS) component of ShipIR is described and used to analyse the effectiveness of various stealth technologies: stack suppression, low solar absorptive (LSA) paints, and Active Hull Cooling (AHC). Standard marine climate statistics are used to determine a minimum (5%), average (50%) and maximum (95%) signature condition for each operating region. The change in detection range of two wave-band sensors (3-5?m, 8-12 ?m) operating at different altitudes (10m, 270m) in each of four climatic conditions is used to assess the effectiveness of each stealth solution, providing a more integral approach to infrared stealth design. These tools and methods form the basis on which future platform designs are being evaluated.

  7. Carbon nanotube IR detectors (SV)

    SciTech Connect

    Leonard, F. L.

    2012-03-01

    Sandia National Laboratories (Sandia) and Lockheed Martin Corporation (LMC) collaborated to (1) evaluate the potential of carbon nanotubes as channels in infrared (IR) photodetectors; (2) assemble and characterize carbon nanotube electronic devices and measure the photocurrent generated when exposed to infrared light;(3) compare the performance of the carbon nanotube devices with that of traditional devices; and (4) develop and numerically implement models of electronic transport and opto-electronic behavior of carbon nanotube infrared detectors. This work established a new paradigm for photodetectors.

  8. FTIR and 1H MAS NMR investigations on the correlation between the frequency of stretching vibration and the chemical shift of surface OH groups of solids

    NASA Astrophysics Data System (ADS)

    Brunner, Eike; Karge, H. G.; Pfeifer, H.

    1992-03-01

    The study of surface hydroxyl groups of solids, especially of zeolites, belongs to the 'classical' topics of IR spectroscopy since physico-chemical information may be derived from the wavenumber (nu) OH of the stretching vibration of the different hydroxyls. On the other hand, the last decade has seen the development of high resolution solid-state NMR spectroscopy and through the use of the so-called magic-angle-spinning technique (MAS) the signals of different hydroxyl species can be resolved in the 1H NMR spectra of solids. The chemical shift (delta) H describing the position of these lines may be used as well as (nu) OH to characterize quantitatively the strength of acidity of surface OH groups of solids. In a first comparison of (nu) OH with (delta) H for several types of surface OH groups, a linear correlation between them could be found. The aim of this paper was to prove the validity of this correlation for a wide variety of hydroxyls. The IR measurements were carried out on a Perkin-Elmer FTIR spectrometer 1800 at the Fritz Haber Institute of the Max Planck Society, Berlin, and the 1H MAS NMR spectra were recorded on a Bruker MSL- 300 at the University of Leipzig.

  9. Ir Spectra of Cold Protonated Methane

    NASA Astrophysics Data System (ADS)

    Asvany, Oskar; Yamada, Koichi MT; Brünken, Sandra; Potapov, Alexey; Schlemmer, Stephan

    2015-06-01

    High-resolution infrared spectra of mass selected protonated methane, CH_5^+, have been recorded in the C-H stretching region in a 22-pole ion trap experiment at low temperatures. The frequencies of the infrared OPO system (pump and signal) have been calibrated using a NIR frequency comb. As a result the ro-vibrational IR transition frequencies of CH_5^+ could be determined to an accuracy in the MHz regime. In this contribution we discuss different techniques of laser induced reactions which enabled recording spectra at different temperatures. The spectra simplify dramatically at a nominal trap temperature of 4~K. Nevertheless an assignment of these spectra is very difficult. We apply the idea of the Rydberg-Ritz combination principle to the complex spectra of protonated methane in order to get first hints at the energy level structure of this enigmatic molecule. O. Asvany, J. Krieg, and S. Schlemmer, Frequency comb assisted mid-infrared spectroscopy of cold molecular ions, Review of Scientific Instruments, 83 (2012), 076102. O. Asvany, S. Brünken, L. Kluge, and S. Schlemmer, COLTRAP: a 22-pole ion trapping machine for spectroscopy at 4 K, Applied Physics B: Lasers and Optics, 114 (2014), 203-211

  10. Syntheses of 3-[(Alkylamino)methylene]-6-methylpyridine-2,4(1H,3H)-diones, 3-Substituted 7-Methyl-2H-pyrano[3,2-c]pyridine-2,5(6H)-dione Fluorescence Probes, and Tetrahydro-1H,9H-2,10-dioxa-9-azaanthracen-1-ones

    PubMed Central

    Prior, Allan M.; Gunaratna, Medha J.; Kikuchi, Daisuke; Desper, John; Kim, Yunjeong; Chang, Kyeong-Ok; Maezawa, Izumi; Jin, Lee-Way; Hua, Duy H.

    2014-01-01

    Various condensation and ring-closing reactions were used for the syntheses of 3-[(alkylamino)methylene]-6-methylpyri-dine-2,4(1H,3H)-diones, bicyclic pyridinones, and tricyclic morpholinopyrones. For instance, 3-[(dialkylamino)methylene]-6-methylpyridine-2,4(1H,3H)-diones were synthesized from the condensation of dialkylamines and 3-formyl-4-hydroxy-6-methylpyridin-2(1H)-one. 3-Formyl-4-hydroxy-6-methylpyridin-2(1H)-one, derived from 3-formyl-4-hydroxy-6-methylpyridin-2(1H)-one, was used to construct a number of bicyclic pyridinones via a one-pot Knoevenagal and intramolecular lactonization reaction. Tricyclic morpholinopyrones were assembled from a dialkylation reaction involving a dinucleophile, 3-amino-4-hydroxy-6-methyl-2H-pyran-2-one, and a dielectrophile, trans-3,6-dibromocyclohexene. Depending on the reaction conditions, isomers of the tricyclic molecules can be selectively produced, and their chemical structures were unequivocally determined using single-crystal X-ray analyses and 2D COSY spectroscopy. The fluorescently active bicyclic pyridinone compounds show longer absorption (368–430 nm; maximum) and emission wavelengths (450–467 nm) than those of 7-amino-4-methylcoumarin (AMC; ?abs,max = 350 nm; ?em = 430 nm) suggesting these molecules, such as 3-(2-aminoacetyl)-7-methyl-2H-pyrano[3,2-c]pyridine-2,5(6H)-dione, can be employed as fluorescence activity based probes for tracing biological pathways. PMID:25177061

  11. Monitoring bound HA1(H1N1) and HA1(H5N1) on freely suspended graphene over plasmonic platforms with infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Banerjee, Amrita; Chakraborty, Sumit; Altan-Bonnet, Nihal; Grebel, Haim

    2013-09-01

    Infrared (IR) spectroscopy provides fingerprinting of the energy and orientation of molecular bonds. The IR signals are generally weak and require amplification. Here we present a new plasmonic platform, made of freely suspended graphene, which was coating periodic metal structures. Only monolayer thick films were needed for a fast signal recording. We demonstrated unique IR absorption signals of bound proteins: these were the hemagglutinin area (HA1) of swine influenza (H1N1) and the avian influenza (H5N1) viruses bound to their respective tri-saccharides ligand receptors. The simplicity and sensitivity of such approach may find applications in fast monitoring of binding events.

  12. Epitaxial cobalt oxide films on Ir(100)-the importance of crystallographic analyses.

    PubMed

    Heinz, K; Hammer, L

    2013-05-01

    Epitaxial cobalt oxide films on Ir(100) exhibit a rich scenario of different structural phases which are reviewed in this paper. The great majority of phases could be, as a rare case, crystallographically described by the joint application of atomically resolved STM and quantitative LEED, whereby structural surprises were more the rule than the exception. So, the oxide grows in the polar (111) orientation for both the Co3O4 and CoO stoichiometry on the bare Ir substrate in spite of the latter's square symmetry. Moreover, the film orientation can be tuned to non-polar (100) growth when one or several pseudomorphic Co layers are introduced as an interface between oxide and Ir substrate. By using the nanostructured Ir(100)-(5 × 1)-H phase as a template a nanostructured Co film can be formed whose oxidation leads to a nanostructured oxide. The nominally polar films circumvent the polarity problem by appropriate surface terminations. That of CoO(111) is, again as a surprise, realized by a switch from rocksalt-type to wurtzite-type stacking near the surface, by which the latter becomes metallic. The stepwise oxidation of a pseudomorphic Co layer on the bare Ir substrate leads to the sequential formation of rocksalt-type tetrahedral Co-O building blocks (with intermediate BN-type blocks) whereby the Co species more and more assume positions determined by the inner-oxidic binding. PMID:23535176

  13. Coprates Chasma Landslides in IR

    NASA Technical Reports Server (NTRS)

    2005-01-01

    [figure removed for brevity, see original site]

    Today's daytime IR image is of a portion of Coprates Chasma, part of Valles Marineris. As with yesterday's image, this image shows multiple large landslides.

    Image information: IR instrument. Latitude -8.2, Longitude 300.2 East (59.8 West). 100 meter/pixel resolution.

    Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with Project policies at a later time.

    NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The Thermal Emission Imaging System (THEMIS) was developed by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. The THEMIS investigation is led by Dr. Philip Christensen at Arizona State University. Lockheed Martin Astronautics, Denver, is the prime contractor for the Odyssey project, and developed and built the orbiter. Mission operations are conducted jointly from Lockheed Martin and from JPL, a division of the California Institute of Technology in Pasadena.

  14. Xanthe Terra Landslide in IR

    NASA Technical Reports Server (NTRS)

    2005-01-01

    [figure removed for brevity, see original site]

    This is a daytime IR image of a chaos region within Xanthe Terra. As with earlier images, the landslide in this image is caused by the failure of steep slopes releasing material to form the landslide deposit.

    Image information: IR instrument. Latitude 3.1, Longitude 309.7 East (50.3 West). 100 meter/pixel resolution.

    Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with Project policies at a later time.

    NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The Thermal Emission Imaging System (THEMIS) was developed by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. The THEMIS investigation is led by Dr. Philip Christensen at Arizona State University. Lockheed Martin Astronautics, Denver, is the prime contractor for the Odyssey project, and developed and built the orbiter. Mission operations are conducted jointly from Lockheed Martin and from JPL, a division of the California Institute of Technology in Pasadena.

  15. Efficient approach to 2-hydroxy-2,3-dihydrofuran derivatives and its application for the synthesis of novel 4-(1H-pyrazol-4-yl)pyridazines.

    PubMed

    Ma, Jun-Rui; Shu, Wen-Ming; Zheng, Kai-Lu; Ni, Fan; Yin, Guo-Dong; Wu, An-Xin

    2015-05-01

    A highly efficient method for the synthesis of 2-hydroxy-2,3-dihydrofuran derivatives from 1,4-enediones and phenacyl pyridinium halides via a domino reaction has been developed. This is a simple and beneficial strategy for the construction of 2-hydroxy-2,3-dihydrofuran compounds from readily available starting materials under mild conditions. Moreover, the application of this reaction provides a straightforward and practical route for the synthesis of the novel 4-(1H-pyrazol-4-yl)pyridazine skeleton. PMID:25821120

  16. A protic ionic liquid catalyzes CO? conversion at atmospheric pressure and room temperature: synthesis of quinazoline-2,4(1H,3H)-diones.

    PubMed

    Zhao, Yanfei; Yu, Bo; Yang, Zhenzhen; Zhang, Hongye; Hao, Leiduan; Gao, Xiang; Liu, Zhimin

    2014-06-01

    The chemical fixation of CO2 under mild reaction conditions is of significance from a sustainable chemistry viewpoint. Herein a CO2-reactive protic ionic liquid (PIL), [HDBU(+)][TFE(-)], was designed by neutralization of the superbase 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) with a weak proton donor trifluoroethanol (TFE). As a bifunctional catalyst for simultaneously activating CO2 and the substrate, this PIL displayed excellent performance in catalyzing the reactions of CO2 with 2-aminobenzonitriles at atmospheric pressure and room temperature, thus producing a series of quinazoline-2,4(1H,3H)-diones in excellent yields. PMID:24788820

  17. Synthesis, conformational, spectroscopic and chemical reactivity analysis of 2-cyano-3-(1H-pyrrol-2-yl)acrylohydrazide using experimental and quantum chemical approaches

    NASA Astrophysics Data System (ADS)

    Rawat, Poonam; Singh, R. N.

    2015-02-01

    This paper describes the synthesis, spectroscopic (1H and 13C NMR, UV-Visible, FT-IR and ESI Mass), conformational analysis, chemical reactivity and non-linear optical (NLO) properties of newly synthesized pyrrole derivative 2-cyano-3-(1H-pyrrol-2-yl)acrylohydrazide (2CPA) C8H8N4O using experimental and quantum chemical techniques. The presence of signal at ? 8.010 ppm due to vinyl proton as well as NH and NH2 protons signals at 11.054 and 2.499 ppm in experimental 1H NMR spectrum indicate that 2CPA contain sbnd CHdbnd CCNsbnd and sbnd NHsbnd NH2 frame. The combined experimental and theoretical symmetric (3194 cm-1) and asymmetric (3221 cm-1) stretching wavenumber analysis confirms free NH2 group in the solid phase FT-IR spectrum of the synthesized compound. The interaction energies of dimer formation using density functional theory (DFT) and Quantum theory of Atoms in Molecules (QTAIM) calculations are found to be 20.210, 19.683 kcal/mol, respectively. The maximum values of the electrophilic reactivity descriptors at C6 indicate that this site is more prone to nucleophilic attack and favoring the formation of heterocyclic derivatives. A natural bond orbital (NBOs) analysis has been carried out to investigate intramolecular charge transfer, conjugative and hyperconjugative interactions within molecule. The calculated first hyperpolarizability (?0) of 2CPA, indicates that investigated molecule will show non-linear optical response and might be used as non-linear optical (NLO) material.

  18. Structural and in vitro cytotoxicity studies on 1H-benzimidazol-2-ylmethyl-N-phenyl amine and its Pd(II) and Pt(II) complexes

    NASA Astrophysics Data System (ADS)

    Abdel Ghani, Nour T.; Mansour, Ahmed M.

    2011-10-01

    [MLCl 2]· zH 2O (L = (1H-benzimidazol-2-ylmethyl)-N-phenyl amine; M = Pd, z = 0; M = Pt, z = 1) and [PdL(OH 2) 2]·2X·zH 2O (X = Br, I, NO 3, z = 0; X = SCN, z = 1) complexes were synthesized as potential anticancer compounds and characterized by elemental analysis, spectral and thermal methods. FT-IR and 1H NMR studies revealed that the benzimidazole L is coordinated to the metal ions via the pyridine-type nitrogen (N py) of the benzimidazole ring and secondary amino group (NH sec). Quantum mechanical calculations of energies, geometries, vibrational wavenumbers, and 1H NMR of the benzimidazole L and its complexes were carried out by density functional theory using B3LYP functional combined with 6-31G(d) and LANL2DZ basis sets. Natural bond orbitals (NBOs) and frontier molecular orbitals were performed at B3LYP/LANL2DZ level of theory. The synthesized ligand, in comparison to its metal complexes was screened for its antibacterial activity. The benzimidazole L is more toxic against the bacterium Staphylococcus aureus (MIC = 58 ?g/mL) than the standard tetracycline (MIC = 82 ?g/mL). The complexes showed cytotoxicity against breast cancer, Colon Carcinoma, and human heptacellular Carcinoma cells. The platinum complex ( 6) displays cytotoxicity (IC 50 = 12.4 ?M) against breast cancer compared with that reported for cis-platin 9.91 ?M.

  19. A mixed experimental and DFT study on ethyl 4-[3-(4-dimethylamino-phenyl)-acryloyl]-3,5-dimethyl-1H-pyrrole-2-carboxylate

    NASA Astrophysics Data System (ADS)

    Singh, R. N.; Rawat, Poonam; Sahu, Sangeeta

    2014-05-01

    A new pyrrole containing chalcone, ethyl 4-[3-(4-dimethylamino-phenyl)-acryloyl]-3,5-dimethyl-1H-pyrrole-2-carboxylate (EDPADPC) derived from ethyl 4-acetyl-3,5-dimethyl-1H-pyrrole-2-carboxylate and 4-dimethylamino-benzaldehyde has been characterized by spectroscopic techniques (1H NMR, UV-Visible, FT-IR) and results have been compared by means of theoretical findings. A combined experimental and theoretical vibrational analysis identified red shifts in vNH and vCO indicating the formation of dimer in the solid state. The binding energy of dimer has been evaluated as 9.89 kcal/mol and the strength and nature of hydrogen bonding have also been analyzed in detail. The DFT derived reactivity descriptors indicate that EDPADPC is suitable for the formation of new heterocyclic compounds. The first hyperpolarizability (?0) of EDPADPC has been computed and found to be 62.0226 × 10-30 indicating its use as non-linear optical (NLO) material.

  20. IR Thermography NDE of ISS Radiator Panels

    NASA Technical Reports Server (NTRS)

    Koshti, Ajay; Winfree, William; Morton, Richard; Wilson, Walter; Reynolds, Gary

    2010-01-01

    The presentation covers an active and a passive infrared (IR) thermography for detection of delaminations in the radiator panels used for the International Space Station (ISS) program. The passive radiator IR data was taken by a NASA astronaut in an extravehicular activity (EVA) using a modified FLIR EVA hand-held camera. The IR data could be successfully analyzed to detect gross facesheet disbonds. The technique used the internal hot fluid tube as the heat source in analyzing the IR data. Some non-flight ISS radiators were inspected using an active technique of IR flash thermography to detect disbond of face sheet with honeycomb core, and debonds in facesheet overlap areas. The surface temperature and radiated heat emission from flight radiators is stable during acquisition of the IR video data. This data was analyzed to detect locations of unexpected surface temperature gradients. The flash thermography data was analyzed using derivative analysis and contrast evolutions. Results of the inspection are provided.

  1. Molecular Insight in Structure and Activity of Highly Efficient, Low-Ir Ir-Ni Oxide Catalysts for Electrochemical Water Splitting (OER).

    PubMed

    Reier, Tobias; Pawolek, Zarina; Cherevko, Serhiy; Bruns, Michael; Jones, Travis; Teschner, Detre; Selve, Sören; Bergmann, Arno; Nong, Hong Nhan; Schlögl, Robert; Mayrhofer, Karl J J; Strasser, Peter

    2015-10-14

    Mixed bimetallic oxides offer great opportunities for a systematic tuning of electrocatalytic activity and stability. Here, we demonstrate the power of this strategy using well-defined thermally prepared Ir-Ni mixed oxide thin film catalysts for the electrochemical oxygen evolution reaction (OER) under highly corrosive conditions such as in acidic proton exchange membrane (PEM) electrolyzers and photoelectrochemical cells (PEC). Variation of the Ir to Ni ratio resulted in a volcano type OER activity curve with an unprecedented 20-fold improvement in Ir mass-based activity over pure Ir oxide. In situ spectroscopic probing of metal dissolution indicated that, against common views, activity and stability are not directly anticorrelated. To uncover activity and stability controlling parameters, the Ir-Ni mixed thin oxide film catalysts were characterized by a wide array of spectroscopic, microscopic, scattering, and electrochemical techniques in conjunction with DFT theoretical computations. By means of an intuitive model for the formation of the catalytically active state of the bimetallic Ir-Ni oxide surface, we identify the coverage of reactive surface hydroxyl groups as a suitable descriptor for the OER activity and relate it to controllable synthetic parameters. Overall, our study highlights a novel, highly active oxygen evolution catalyst; moreover, it provides novel important insights into the structure and performance of bimetallic oxide OER electrocatalysts in corrosive acidic environments. PMID:26355767

  2. Theoretical and experimental IR, Raman and NMR spectra in studying the electronic structure of 2-nitrobenzoates

    NASA Astrophysics Data System (ADS)

    ?wis?ocka, R.; Samsonowicz, M.; Regulska, E.; Lewandowski, W.

    2007-05-01

    The influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the 2-nitrobenzoic acid (2-NBA) was studied. Optimized geometrical structures of studied compounds were calculated by HF, B3PW91, B3LYP methods using 6-311++G ?? basis set. The theoretical IR and NMR spectra were obtained. The vibrational (FT-IR, FT-Raman) and NMR ( 1H and 13C) spectra for 2-nitrobenzoic acid salts of alkali metals were also recorded. The assignment of vibrational spectra was done. Characteristic shifts of band wavenumbers and changes in band intensities along the metal series were observed. Good correlation between the wavenumbers of the vibrational bands in the IR and Raman spectra for 2-nitrobenzoates (2-NB) and ionic potential, electronegativity, atomic mass and affinity of metals were found. The chemical shifts of protons and carbons ( 1H, 13C NMR) in the series of studied alkali metal 2-nitrobenzoates were observed too. The calculated parameters were compared to experimental characteristic of studied compounds.

  3. Comparative field evaluation of repellent formulations containing deet and IR3535 against mosquitoes in Queensland, Australia.

    PubMed

    Frances, S P; MacKenzie, D O; Rowcliffe, K L; Corcoran, S K

    2009-12-01

    Field trials comparing repellent formulations containing IR3535 (ethyl butylacetylaminopropionate) and deet (N,N-diethyl-3-methylbenzamide) against mosquitoes in Queensland, Australia, were conducted. Two repellents were compared: Avon Bug Guard, containing 7.5% IR3535; and Australian Defense Force (ADF) deet, containing 35% deet in a gel. Two tests were conducted, one in February-March 2006, and the second in February 2007. In the 1st test, the predominant mosquito species collected were Mansonia uniformis (58.9% of collection) and Culex annulirostris (33.4%), and in the 2nd test, the predominant species was Aedes vigilax (85.7% of collection). In the 1st test, Avon Bug Guard provided >95% protection against all mosquitoes for only 1 h, and ADF deet provided the same level of protection for 5 h. In the 2nd field test, Avon Bug Guard provided only 85% protection against all mosquitoes 1 h after repellent application, while ADF deet provided 5 h of protection. The study showed that ADF deet provided significantly better protection against mosquitoes than Avon Bug Guard (IR3535). PMID:20099600

  4. Crystallographic identification of an unexpected by-product in an Ullman's reaction toward biphenyls: 1-(4-hexyloxy-3-hydroxyphenyl)ethanone.

    PubMed

    Manzano, Veronica E; Baggio, Ricardo; Cukiernik, Fabio D

    2015-11-01

    The synthesis of 3,3'-diacetoxy-4,4'-bis(hexyloxy)biphenyl following the nickel-modified Ullmann reaction yielded a by-product which was identified successfully by crystallographic analysis as 1-(4-hexyloxy-3-hydroxyphenyl)ethanone, C14H20O3. This unexpected nonbiphenyl by-product exhibited IR, (1)H NMR, (13)C NMR and COSY (correlation spectroscopy) spectra fully consistent with the proposed structure. The compound crystallized in the orthorombic Pbca space group, with two independent formula units in the asymmetric unit (one of which was slightly disordered), and showed a supramolecular architecture in which molecules linked by hydroxy-ethanone O-H...O interactions are organized in columns separated by the aliphatic tails. PMID:26524178

  5. Integrating IR detector imaging systems

    NASA Technical Reports Server (NTRS)

    Bailey, G. C. (inventor)

    1984-01-01

    An integrating IR detector array for imaging is provided in a hybrid circuit with InSb mesa diodes in a linear array, a single J-FET preamplifier for readout, and a silicon integrated circuit multiplexer. Thin film conductors in a fan out pattern deposited on an Al2O3 substrate connect the diodes to the multiplexer, and thick film conductors also connect the reset switch and preamplifier to the multiplexer. Two phase clock pulses are applied with a logic return signal to the multiplexer through triax comprised of three thin film conductors deposited between layers. A lens focuses a scanned image onto the diode array for horizontal read out while a scanning mirror provides vertical scan.

  6. Characterization of reaction intermediates by ion spectroscopy.

    PubMed

    Roithová, Jana

    2012-01-21

    In the last decade, we have experienced massive progress in spectroscopic methods for mass-selected ions. The aim of this tutorial review is to present action spectroscopy as a powerful tool for the investigation of ionic reaction intermediates. Examples span from ultraviolet and infrared photodissociation spectroscopy of model reaction intermediates to applications of infrared multiphoton dissociation spectroscopy (IRMPD) to intermediates directly sampled from reaction mixtures. The first example of double resonance IR-UV spectroscopy of model intermediates in an organometallic reaction is also mentioned. PMID:21792393

  7. Competition between vinylidene rearrangement and 1,2-insertion of carbon-disubstituted internal alkynes at a Cp*Ir(iii) complex.

    PubMed

    Ikeda, Yousuke; Kodama, Shintaro; Tsuchida, Noriko; Ishii, Youichi

    2015-10-28

    Competition between vinylidene rearrangement/1,1-insertion and 1,2-alkyne insertion into the Ir-Ar bond of [Cp*Ir(ppy-F4)](+) was observed on reaction with diarylacetylenes. The former process afforded the iridacycle 2via the subsequent 1,4-Ir migration, whereas the latter led to the pyridoisoquinolinium complex 4. Detailed analysis revealed that 4 isomerizes to 2 by heating at 50 °C. PMID:26328544

  8. A validated 1 H NMR method for the determination of the

    E-print Network

    Buschmann, Michael

    A validated 1 H NMR method for the determination of the degree of deacetylation of chitosan M for the determination of the degree of deacetylation (DDA) of chitosan by 1 H NMR spectroscopy has been formally validated. Chitosans with DDA ranging from 48 to 100% have been used for the validation. The method is found

  9. 4(1H)-Pyridone and 4(1H)-Quinolone Derivatives as Antimalarials with Erythrocytic, Exoerythrocytic, and Transmission Blocking Activities

    PubMed Central

    Monastyrskyi, Andrii; Kyle, Dennis E.; Manetsch, Roman

    2015-01-01

    Infectious diseases are the second leading cause of deaths in the world with malaria being responsible for approximately the same amount of deaths as cancer in 2012. Despite the success in malaria prevention and control measures decreasing the disease mortality rate by 45% since 2000, the development of single-dose therapeutics with radical cure potential is required to completely eradicate this deadly condition. Targeting multiple stages of the malaria parasite is becoming a primary requirement for new candidates in antimalarial drug discovery and development. Recently, 4(1H)-pyridone, 4(1H)-quinolone, 1,2,3,4-tetrahydroacridone, and phenoxyethoxy-4(1H)-quinolone chemotypes have been shown to be antimalarials with blood stage activity, liver stage activity, and transmission blocking activity. Advancements in structure-activity relationship and structure-property relationship studies, biological evaluation in vitro and in vivo, as well as pharmacokinetics of the 4(1H)-pyridone and 4(1H)-quinolone chemotypes will be discussed. PMID:25116582

  10. Synthesis and fungicidal activity of novel 3-(substituted/unsubstituted phenylselenonyl)-1-ribosyl/deoxyribosyl-1H-1,2,4-triazole.

    PubMed

    Singh, Pravin K

    2012-06-13

    Reaction of potassium 1H-1,2,4-triazole-3-selenolate (I) with acetylated ribose/deoxyribose (IIa,b) in the presence of montmorillonite K 10 as a solid adsorbent furnished potassium 1-acetylated ribosyl/deoxyribosyl-1H-1,2,4-triazole-3-selenolate (IIIa,b) with excellent yield under microwave irradiation in solvent-free conditions. This eliminates a series of complex isolation procedures and often minimizes the use of a large amount of expensive, toxic, and hazardous solvents after each step. This procedure reduces reaction time and cost and enhances yield. Reaction of compound (IIIa,b) with substituted/unsubstituted aryl diazonium chloride (IVa-e) at 0-5 °C gave pure 3-(substituted/unsubstituted phenyl selanyl)-1-acetylribosyl/deoxyribosyl-1H-1,2,4-triazole (Va-j). Oxidation of compound (Va-j) with oxone followed by alkaline hydrolysis furnished quantitatively and analytically pure 3-(substituted/unsubstituted phenylselenonyl)-1-ribosyl/deoxyribosyl-1H-1,2,4-triazole (VIIa-j). Compounds VIa-j and VIIa-j were evaluated in vitro for their fungitoxicities against Fusarium oxysporum and Penicillium citrinum. All the compounds were found to be antifungal active. Some of the compounds displayed activities comparable with that of the commercial fungicide Dithane M-45 and griseofulvin. Structure-activity relationships for the screened compounds were discussed. The fact that both of these fungi have developed resistance to several fungicide groups made them optimal candidates as target organisms for ongoing research about the potential application of 1,2,4-triazole and analogue compounds as reduced-risk fungicides. PMID:22563913

  11. 0 (IR + ) = span f e ' 0k : S k e

    E-print Network

    Tabacco, Anita

    and 0 e V B 0 (IR + ) = span f e ' 0k : S Ÿ k Ÿ e L \\Gamma 1g := span 0 e \\Phi 0 : (7­spline case (see Proposition 9.1 and also [15]). As before, we set 0 V j (IR + ) := T j ( 0 V 0 (IR + )) and 0 e V j (IR + ) := f T j ( 0 e V 0 (IR + )): Let us define 0 P 0 : L p (IR + ) \\Gamma! 0 V 0 (IR

  12. The IR Luminosity Functions of Rich Clusters

    E-print Network

    Lei Bai; George H. Rieke; Marcia J. Rieke; Daniel Christlein; Ann I. Zabludoff

    2008-12-02

    We present MIPS observations of the cluster A3266. About 100 spectroscopic cluster members have been detected at 24 micron. The IR luminosity function in A3266 is very similar to that in the Coma cluster down to the detection limit L_IR~10^43 ergs/s, suggesting a universal form of the bright end IR LF for local rich clusters with M~10^15 M_sun. The shape of the bright end of the A3266-Coma composite IR LF is not significantly different from that of nearby field galaxies, but the fraction of IR-bright galaxies (SFR > 0.2M_sun/yr) in both clusters increases with cluster-centric radius. The decrease of the blue galaxy fraction toward the high density cores only accounts for part of the trend; the fraction of red galaxies with moderate SFRs (0.2 IR bright galaxies, nearby rich clusters are distinguished from the field by a lower star-forming galaxy fraction, but not by a change in L*_IR. The composite IR LF of Coma and A3266 shows strong evolution when compared with the composite IR LF of two z~0.8 clusters, MS 1054 and RX J0152, with L*_IR \\propto (1+z)^{3.2+/-0.7},Phi*_IR \\propto (1+z)^{1.7+/-1.0}. This L*_IR evolution is indistinguishable from that in the field, and the Phi*_IR evolution is stronger, but still consistent with that in the field. The similarity of the evolution of bright-end IR LF in very different cluster and field environments suggests either this evolution is driven by the mechanism that works in both environments, or clusters continually replenish their star-forming galaxies from the field, yielding an evolution in the IR LF that is similar to the field. The mass-normalized integrated star formation rates (SFRs) of clusters within 0.5R_200 also evolve strongly with redshift, as (1+z)^5.3.

  13. Synthesis of alginate derivative via the Ugi reaction and its characterization.

    PubMed

    Yan, Huiqiong; Chen, Xiuqiong; Li, Jiacheng; Feng, Yuhong; Shi, Zaifeng; Wang, Xianghui; Lin, Qiang

    2016-01-20

    In this research, the systematic evaluation of fundamental properties of the alginate derivative (Ugi-Alg) synthesized by the Ugi reaction is presented. The structure of Ugi-Alg with the degree of substitution of 23.24% was confirmed by FT-IR and (1)H NMR spectrometers. The X-ray diffraction (XRD) results indicate the amorphous structure and the crystal structure change of Ugi-Alg, which is possibly ascribed to the destruction of inter- and intra-molecular hydrogen bonding interactions during the Ugi reaction. From thermal gravimetric analysis (TGA) and fluorescence spectrophotometer, Ugi-Alg shows high thermal stability and good amphiphilic functionality with the critical aggregation concentration of 0.07g/L in 0.15mol/L aqueous NaCl solution. Transmission electron microscope (TEM) image and dynamic light scattering (DLS) reveal that stable Ugi-Alg self-aggregated micelle with the average size of 162.3nm and ? potential at about -31.7mV could form in the aqueous media, which presents tremendous potential in pharmacology and tissue engineering. PMID:26572410

  14. (Phenoxyimidazolyl-salicylaldimine)iron complexes: synthesis, properties and iron catalysed ethylene reactions.

    PubMed

    Yankey, Margaret; Obuah, Collins; Guzei, Ilia A; Osei-Twum, Emmanuel; Hearne, Giovanni; Darkwa, James

    2014-10-01

    The reaction of 2-{[2-(1H-imidazol-4-yl)-ethylimino]-methyl}-phenol (L1), 2,4-di-tert-butyl-6-{[2-(1H-imidazol-4-yl)-ethylimino]-methyl}-phenol (L2) or 4-tert-butyl-2-{[2-(1H-imidazol-4-yl)-ethylimino]-methyl}-phenol (L3) with iron(ii) precursors produced either iron(ii) or iron(iii) complexes, depending on the nature of the anions in the iron(ii) precursor and the ligand. When the anion is chloride and the ligand L1, the product is [(L1)2Fe][FeCl4] (1), but when the anion is triflate (OTf(-)) and the ligand is L2, the product is [(L2)2Fe][OTf]2 (2). With iron(ii) halides and tert-butyl groups on the phenoxy ligands L2 and L3, the iron(iii) complexes [(L2)FeX2] {where X = Cl (3), Br (4) and I = (5)} and [(L3)FeCl2] (6) were formed. Complexes 1-6 were characterised by a combination of elemental analyses, IR spectroscopy and mass spectrometry; and in selected cases (3 and 4) by single crystal X-ray crystallography. The crystal structures of 3 and 4 indicated that the iron(ii) precursors oxidised to iron(iii) in forming complexes 3-6; an observation that was corroborated by the magnetic properties and the (57)Fe Mössbauer spectra of 3 and 4. The iron(iii) complexes 3-6 were used as pre-catalysts for the oligomerisation and polymerisation of ethylene. Products of these ethylene reactions depended on the solvent used. In toluene ethylene oligomerised mainly to 1-butene and was followed by the 1-butene alkylating the solvent to form butyl-toluenes via a Friedel-Crafts alkylation reaction. In chlorobenzene, ethylene oligomerised mainly to a mixture of C4-C12 alkenes. Interestingly small amounts of butyl-chlorobenzenes and hexyl-chlorobenzenes were also formed via a Friedel-Crafts alkylation with butenes and hexenes from the oligomerisation of ethylene. PMID:25111396

  15. (1)H NMR-based DS determination of barley starch sulfates prepared in 1-allyl-3-methylimidazolium chloride.

    PubMed

    Kärkkäinen, Johanna; Wik, Tiia-Riikka; Niemelä, Matti; Lappalainen, Katja; Joensuu, Päivi; Lajunen, Marja

    2016-01-20

    The use of natural resources in a development of products and materials is currently increasing. Starch is one of the investigated resources due to its bioavailability, biodegradability, safety and affordability. In this study, native barley starch was sulfated using a SO3-pyridine complex. The reaction was carried out for the first time using 1-allyl-3-methylimidazolium chloride ionic liquid, an excellent solvent for the starch modification. Reaction conditions (temperature, time and amount of the reagent) were studied using an experimental design. Starch sulfates with the degree of substitution (DS) 1.37 were obtained when the reaction was carried out at 40°C for 75min with 4:1 molar ratio of SO3-pyridine complex:anhydroglucose unit. The determination of DS was based on (1)H NMR instead of elemental analysis, which showed overestimated DS values in this study. Starch sulfates were analyzed with FTIR and HPLC, which showed that products contained small and large sulfated molecules. PMID:26572405

  16. Structural investigations of a series of 1,6-aryl-7-hydroxy-2,3-dihydroimidazo[1,2-a]pyrimidin-5(1H)-ones with potential antinociceptive activity

    NASA Astrophysics Data System (ADS)

    Wysocki, Waldemar; Karczmarzyk, Zbigniew; Rz?dkowska, Marzena; Szaco?, El?bieta; Matosiuk, Dariusz; Urba?czyk-Lipkowska, Zofia; Kalicki, Przemys?aw

    2015-08-01

    The structural investigations of a series of new bioactive imidazo[1,2-a]pyrimidines 1-6 were undertaken using IR, 1H and 13C NMR spectroscopic analysis, X-ray crystal structure determinations and theoretical calculations. The compounds 1-6 were obtained by condensation of the respective 1-aryl-4,5-dihydro-1H-imidazol-2-amine hydrobromide and diethyl phenylmalonate in presence of sodium methoxide in methanol and for these compounds the equilibrium between possible O10-enol/O11-keto (a), O11-enol/O10-keto (b) and O10,O11-diketo (c) tautomeric forms were investigated in the gaseous phase, solution and crystalline state. Spectroscopic studies 1H, 13C NMR and IR allowed for the identification of the compounds 1-6 but they did not indicate explicitly their tautomeric forms present in solution and in the solid state. The X-ray analysis showed that the molecules of all investigated compounds exist as the O10-enol/O11-keto (a) tautomeric form in the crystalline state. The hydroxyl and carbonyl groups characteristic for existing tautomeric form are involved in a strong intra- and/or intermolecular Osbnd H⋯O and Osbnd H⋯N hydrogen bonds. The theoretical calculations at DFT/B3LYP/6-311++G(d,p) level showed that two tautomeric forms (a) and (c) can coexist both in gas phase and the solution with the population of them being in the relation (a) > (or ?) (c). The comparison of the experimentally recorded IR, 1H and 13C spectra with the corresponding spectra theoretically calculated for all possible tautomeric forms of 1-6 shows that the correlation of experimental and theoretical spectra can be used to a limited extent for the identification of tautomeric forms.

  17. Northern Polar Spring in IR

    NASA Technical Reports Server (NTRS)

    2004-01-01

    [figure removed for brevity, see original site]

    Released 12 March 2004

    The Odyssey spacecraft has completed a full Mars year of observations of the red planet. For the next several weeks the Image of the Day will look back over this first mars year. It will focus on four themes: 1) the poles - with the seasonal changes seen in the retreat and expansion of the caps; 2) craters - with a variety of morphologies relating to impact materials and later alteration, both infilling and exhumation; 3) channels - the clues to liquid surface flow; and 4) volcanic flow features. While some images have helped answer questions about the history of Mars, many have raised new questions that are still being investigated as Odyssey continues collecting data as it orbits Mars.

    Infrared images taken during the daytime exhibit both the morphological and thermophysical properties of the surface of Mars. Morphologic details are visible due to the effect of sun-facing slopes receiving more energy than antisun-facing slopes. This creates a warm (bright) slope and cool (dark) slope appearance that mimics the light and shadows of a visible wavelength image. Thermophysical properties are seen in that dust heats up more quickly than rocks. Thus dusty areas are bright and rocky areas are dark.

    This image was collected October 19, 2002 during the northern spring season. The top half of this daytime IR image shows the North Polar sand sea.

    Image information: IR instrument. Latitude 76.2, Longitude 226.8 East (133.2 West). 19 meter/pixel resolution.

    Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with Project policies at a later time.

    NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The Thermal Emission Imaging System (THEMIS) was developed by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. The THEMIS investigation is led by Dr. Philip Christensen at Arizona State University. Lockheed Martin Astronautics, Denver, is the prime contractor for the Odyssey project, and developed and built the orbiter. Mission operations are conducted jointly from Lockheed Martin and from JPL, a division of the California Institute of Technology in Pasadena.

  18. A common polymorphism in NR1H2 (LXRbeta) is associated with preeclampsia

    PubMed Central

    2011-01-01

    Background Preeclampsia is a frequent complication of pregnancy and a leading cause of perinatal mortality. Both genetic and environmental risk factors have been identified. Lipid metabolism, particularly cholesterol metabolism, is associated with this disease. Liver X receptors alpha (NR1H3, also known as LXRalpha) and beta (NR1H2, also known as LXRbeta) play a key role in lipid metabolism. They belong to the nuclear receptor superfamily and are activated by cholesterol derivatives. They have been implicated in preeclampsia because they modulate trophoblast invasion and regulate the expression of the endoglin (CD105) gene, a marker of preeclampsia. The aim of this study was to investigate associations between the NR1H3 and NR1H2 genes and preeclampsia. Methods We assessed associations between single nucleotide polymorphisms of NR1H3 (rs2279238 and rs7120118) and NR1H2 (rs35463555 and rs2695121) and the disease in 155 individuals with preeclampsia and 305 controls. Genotypes were determined by high-resolution melting analysis. We then used a logistic regression model to analyze the different alleles and genotypes for those polymorphisms as a function of case/control status. Results We found no association between NR1H3 SNPs and the disease, but the NR1H2 polymorphism rs2695121 was found to be strongly associated with preeclampsia (genotype C/C: adjusted odds ratio, 2.05; 95% CI, 1.04-4.05; p = 0.039 and genotype T/C: adjusted odds ratio, 1.85; 95% CI, 1.01-3.42; p = 0.049). Conclusions This study provides the first evidence of an association between the NR1H2 gene and preeclampsia, adding to our understanding of the links between cholesterol metabolism and this disease. PMID:22029530

  19. Which Oxidation State Leads to O-O Bond Formation in Cp*Ir(bpy)Cl-Catalyzed Water Oxidation, Ir(V), Ir(VI), or Ir(VII)?

    E-print Network

    Liao, Rongzhen

    Which Oxidation State Leads to O-O Bond Formation in Cp*Ir(bpy)Cl-Catalyzed Water Oxidation, Ir(V), Ir(VI), or Ir(VII)? Rong-Zhen Liao* and Per E. M. Siegbahn* Department of Organic Chemistry by the Cp*Ir(bpy)Cl (Cp* = pentamethylcyclopentadienyl, bpy = 2,2-bipyridine) complex. One

  20. Synthesis, crystal structures and theoretical calculations of new 1-[2-(5-chloro-2-benzoxazolinone-3-yl)acetyl]-3,5-diphenyl-4,5-dihydro-(1H)-pyrazoles

    NASA Astrophysics Data System (ADS)

    Gök?en, Umut Salg?n; Alpaslan, Yelda Bingöl; Kelekçi, Nesrin Gökhan; I??k, ?amil; Ekizo?lu, Melike

    2013-05-01

    1-[2-(5-Chloro-2-benzoxazolinone-3-yl)acetyl]-3-phenyl-5-(3-methoxyphenyl)-4,5-dihydro-(1H)-pyrazole (5a), 1-[2-(5-chloro-2-benzoxazolinone-3-yl)acetyl]-3-phenyl-5-(3,4-dimethoxyphenyl)-4,5-dihydro-(1H)-pyrazole (5b) and 1-[2-(5-chloro-2-benzoxazolinone-3-yl)acetyl]-3-(4-methylphenyl)-5-(2,3-dimethoxyphenyl)-4,5-dihydro-(1H)-pyrazole (5c) were synthesized. The crystal and molecular structures of the compounds 5a, 5b and 5c were determined by elemental analyses, IR, 1H NMR, ESI-MS and single-crystal X-ray diffraction. DFT method with 6-31G(d,p) basis set was used to calculate the optimized geometrical parameters, vibrational frequencies and chemical shift values. The calculated vibrational frequencies and chemical shift values were compared with experimental IR and 1H NMR values. The results represented that there was a good agreement between experimental and calculated values of the compounds 5a-5c. In addition, DFT calculations of the compounds, molecular electrostatic potentials (MEPs) and frontier molecular orbitals were performed at B3LYP/6-31G(d,p) level of theory. Furthermore, compounds were tested against three Gram-positive bacteria: Staphylococcus aureus ATCC 29213 (American Type Culture Collection), methicillin resistant S. aureus (MRSA) ATCC 43300 and Enterococcus faecalis ATCC 29212; two Gram negative bacteria: Escherichia coli ATCC 25922 and Pseudomonas aeruginosa ATCC 27853; and three fungi: Candida albicans ATCC 90028, Candida krusei ATCC 6258 and Candida parapsilosis ATCC 90018. In general, all of the compounds were found to be slightly active against tested microorganisms.

  1. Recent catalysis measurements at IRS

    NASA Astrophysics Data System (ADS)

    Massuti-Ballester, B.; Pidan, S.; Herdrich, G.; Fertig, M.

    2015-08-01

    At the Institute of Space Systems (IRS), experiments have been performed using the high enthalpy, inductively heated plasma generator (IPG) in plasma wind tunnel 3 (PWK3), in order to assess the catalytic behaviour of different materials. Utilising the Upwind Relaxation Algorithm for Non-equilibrium Flows of the University of Stuttgart (URANUS), a methodology for determining catalytic efficiencies by obtaining atomic recombination probabilities ? for high temperature materials, has been developed. This method eliminates the inherent uncertainties produced when using catalytic properties of previously tested materials to infer those of new materials. In this work, eight different candidates for the Thermal Protection System (TPS) of an entry vehicle have been studied, of which six are ceramic materials and the other two are metallic alloys. Thermochemical properties of these specimens are given for surface temperatures between 1000 and 2000 K in pure oxygen and pure nitrogen plasmas. The high enthalpies and relatively low pressure conditions in which these material samples have been tested in PWK3 are relevant for entry applications from Low Earth Orbit (LEO).

  2. 55 1 1 -H3(Cat-EDT-TTF)2(-H)[3

    E-print Network

    Katsumoto, Shingo

    55 1 1 () () [1­8] -H3(Cat-EDT-TTF)2(-H)[3] ( 1) -H () [5] 1 .-H3(Cat-EDT-TTF)2(-H)(a)(b) -D3(Cat-EDT-TTF)2(-D) -H ( 1) 2 ( 2 Cat-EDT-TTF+0.5 -1 [ODO]-1 ) 1(a) 1(b)S=1/2 - ( 3(a))185K -H ( 3(b))185K -H p~0 emu mol-1 singlet-triplet ( 3(b))-D #12;2 55 1 -H

  3. C-H Activation of Phenyl Imines and 2-Phenylpyridines with [Cp*MCl2]2 (M ) Ir, Rh): Regioselectivity, Kinetics, and

    E-print Network

    Jones, William D.

    C-H Activation of Phenyl Imines and 2-Phenylpyridines with [Cp*MCl2]2 (M ) Ir, Rh promoted C-H activation in a series of para-substituted phenyl imines has been examined using [Cp*MCl2]2 (M was solvent dependent for the reaction with [Cp*IrCl2]2 but independent of solvent for the reaction with [Cp

  4. Functionalized multi-walled carbon nanotubes in an aldol reaction

    NASA Astrophysics Data System (ADS)

    Chronopoulos, D. D.; Kokotos, C. G.; Karousis, N.; Kokotos, G.; Tagmatarchis, N.

    2015-01-01

    The covalent functionalization of multi-walled carbon nanotubes (MWCNTs) with a proline-based derivative is reported. Initially, MWCNTs were oxidized in order to introduce a large number of carboxylic units on their tips followed by N-tert-butoxycarbonyl-2,2'(ethylenedioxy)bis-(ethylamine) conjugation through an amide bond. Then, a proline derivative bearing a carboxylic terminal moiety at the 4-position was coupled furnishing proline-modified MWCNTs. This new hybrid material was fully characterized by spectroscopic and microscopy means and its catalytic activity in the asymmetric aldol reaction between acetone and 4-nitrobenzaldehyde was evaluated for the first time, showing to proceed almost quantitatively in aqueous media. Furthermore, several amino-modified MWCNTs were prepared and examined in the particular aldol reaction. These new hybrid materials exhibited an enhanced catalytic activity in water, contrasting with the pristine MWCNTs as well as the parent organic molecule, which failed to catalyze the reaction efficiently. Furthermore, the modified MWCNTs proved to catalyze the aldol reaction even after three repetitive cycles. Overall, a green approach for the aldol reaction is presented, where water can be employed as the solvent and modified MWCNTs can be used as catalysts, which can be successfully recovered and reused, while their catalytic activity is retained.The covalent functionalization of multi-walled carbon nanotubes (MWCNTs) with a proline-based derivative is reported. Initially, MWCNTs were oxidized in order to introduce a large number of carboxylic units on their tips followed by N-tert-butoxycarbonyl-2,2'(ethylenedioxy)bis-(ethylamine) conjugation through an amide bond. Then, a proline derivative bearing a carboxylic terminal moiety at the 4-position was coupled furnishing proline-modified MWCNTs. This new hybrid material was fully characterized by spectroscopic and microscopy means and its catalytic activity in the asymmetric aldol reaction between acetone and 4-nitrobenzaldehyde was evaluated for the first time, showing to proceed almost quantitatively in aqueous media. Furthermore, several amino-modified MWCNTs were prepared and examined in the particular aldol reaction. These new hybrid materials exhibited an enhanced catalytic activity in water, contrasting with the pristine MWCNTs as well as the parent organic molecule, which failed to catalyze the reaction efficiently. Furthermore, the modified MWCNTs proved to catalyze the aldol reaction even after three repetitive cycles. Overall, a green approach for the aldol reaction is presented, where water can be employed as the solvent and modified MWCNTs can be used as catalysts, which can be successfully recovered and reused, while their catalytic activity is retained. Electronic supplementary information (ESI) available: Experimental details for the synthesis of 5, 8 and 11; 1H & 13C NMR of compounds 8 and 11; ATR-IR spectra, thermographs and TEM imaging of hybrids 10 and 13. See DOI: 10.1039/c4nr06543c

  5. Irs2 and Irs4 synergize in non-LepRb neurons to control energy balance and glucose homeostasis?

    PubMed Central

    Sadagurski, Marianna; Dong, X. Charlie; Myers, Martin G.; White, Morris F.

    2013-01-01

    Insulin receptor substrates (Irs1, 2, 3 and Irs4) mediate the actions of insulin/IGF1 signaling. They have similar structure, but distinctly regulate development, growth, and metabolic homeostasis. Irs2 contributes to central metabolic sensing, partially by acting in leptin receptor (LepRb)-expressing neurons. Although Irs4 is largely restricted to the hypothalamus, its contribution to metabolic regulation is unclear because Irs4-null mice barely distinguishable from controls. We postulated that Irs2 and Irs4 synergize and complement each other in the brain. To examine this possibility, we investigated the metabolism of whole body Irs4?/y mice that lacked Irs2 in the CNS (bIrs2?/?·Irs4?/y) or only in LepRb-neurons (Lepr?IrsIrs4?/y). bIrs2?/?·Irs4?/y mice developed severe obesity and decreased energy expenditure, along with hyperglycemia and insulin resistance. Unexpectedly, the body weight and fed blood glucose levels of Lepr?IrsIrs4?/y mice were not different from Lepr?Irs2 mice, suggesting that the functions of Irs2 and Irs4 converge upon neurons that are distinct from those expressing LepRb. PMID:24567904

  6. IndustrialAffiliatesDay Far IR and Terahertz Photonics

    E-print Network

    Van Stryland, Eric

    IndustrialAffiliatesDay 2011 Far IR and Terahertz Photonics University of Central Florida CREOL................................................................................................................................. 3 Symposium on Far IR and THz PhotonicsHertz, Federico Capasso .... 5 Novel nanoarchitectural concepts for THz/IR based biosensing applications, Dwight

  7. Matrix laser IR-visible image converter

    SciTech Connect

    Lipatov, N I; Biryukov, A S

    2006-04-30

    A new type of a focal matrix IR-visible image converter is proposed. The pixel IR detectors of the matrix are tunable microcavities of VCSEL (vertical-cavity surface emitting laser) semiconductor microstructures. The image conversion is performed due to the displacements of highly reflecting cavity mirrors caused by thermoelastic stresses in their microsuspensions appearing upon absorption of IR radiation. Analysis of the possibilities of the converter shows that its sensitivity is 10{sup -3}-10{sup -2} K and the time response is 10{sup -4}-10{sup -3} s. These characteristics determine the practical application of the converter. (laser applications and other topics in quantum electronics)

  8. Novel molecular platform integrated iron chelation therapy for 1H-MRI detection of ?-galactosidase activity.

    PubMed

    Li, Xiaojin; Zhang, Zhongwei; Yu, Zijun; Magnusson, Jennifer; Yu, Jian-Xin

    2013-04-01

    Targeting the increased Fe(3+) content in tumors, we propose a novel molecular platform integrated cancer iron chelation therapy for (1)H-magnetic resonance imaging (MRI) detection of ?-galactosidase (?-gal) activity. Following this idea, we have designed, synthesized, and characterized a series of ?-d-galactosides conjugated with various chelators and demonstrated the feasibility of this concept for assessing ?-gal activity in solution by (1)H-MRI T1 and T2 relaxation mapping. PMID:23391334

  9. 1H NMR quantitative determination of photosynthetic pigments from green beans (Phaseolus vulgaris L.).

    PubMed

    Valverde, Juan; This, Hervé

    2008-01-23

    Using 1H nuclear magnetic resonance spectroscopy (1D and 2D), the two types of photosynthetic pigments (chlorophylls, their derivatives, and carotenoids) of "green beans" (immature pods of Phaseolus vulgaris L.) were analyzed. Compared to other analytical methods (light spectroscopy or chromatography), 1H NMR spectroscopy is a fast analytical way that provides more information on chlorophyll derivatives (allomers and epimers) than ultraviolet-visible spectroscopy. Moreover, it gives a large amount of data without prior chromatographic separation. PMID:18081249

  10. Elaborated 1H NMR study for the ligitional behavior of two thiosemicarbazide derivatives towards some heavy metals (Sn(II), Sb(III), Pb(II) and Bi(III)), thermal, antibacterial and antifungal studies.

    PubMed

    el-Metwaly, Nashwa M; Refat, Moamen S

    2011-10-15

    A new series of heavy metal complexes are prepared. Sn(II), Sb(III), Pb(II) and Bi(III) are the metal ions used in complexation with two thiosemicarbazide ligands. The IR and (1)H NMR spectra of the free ligands display their presence in thiole-thione forms coincide with each other. The IR spectra of the complexes support the presence of 2:2 molar ratio (M:HL) with HL(1) ligand and 1:1 beside 1:2 with HL(2). The ligand coordinates as bi molecules in some complexes and displays two tautomer forms at the same complex molecule (1)H NMR spectra of Sn(II) and Sb(III) complexes were done and comes coincide with IR data. The electronic spectral analysis displays a lower shift appearance in n??* charge transfer band in most isolated complexes. As well as, a new band is shinned in visible region with Sb(III), Bi(III) complexes and Sn(II)-HL(2). This band is pointed to its use in spectrophotometric analysis for these metal ions. The TG analysis for all isolated compounds was briefly discussed. The molecular modeling parameters support the stability of thiole form of the free ligands in comparing with their thiones by a small difference. The antibacterial and antifungal activities were studied against some organisms and reveal the priority of most investigated complexes. PMID:21767980

  11. Alternative determination of blood alcohol concentration by (1)H NMR spectroscopy.

    PubMed

    Zailer, Elina; Diehl, Bernd W K

    2016-02-01

    A rapid, accurate and specific proton nuclear magnetic resonance ((1)H NMR) spectroscopic method is developed to determine ethanol in blood, known as the blood alcohol concentration (BAC). The limits of detection and quantification are 0.02g/L and 0.07g/L, respectively. The (1)H NMR spectra show linearity for whole blood and serum samples of a concentration range of 0.00-3.00g/L (R(2)>0.9995). The (1)H NMR method is applied and validated for whole blood as the sample media. Real driving under influence case samples are analyzed with the reference enzyme-based alcohol dehydrogenase and headspace gas chromatography techniques by the Forensic Medicine in Bonn. The reference results are compared with the (1)H NMR spectroscopic results. The validation and comparison indicate that (1)H NMR is suitable for the quantification of BAC in whole blood. This technique has the advantages of automated analysis with good measurement precision and fast sample throughput. A drop of blood (V=20?L) is adequate for an analysis leading to a possible simplification of the sample collection. Due to the non-destructive method, follow-up examinations by (1)H NMR spectroscopy or DNA determinations by different techniques (PCR, in situ hybridization) are possible in resolving legal disputes. PMID:26641708

  12. [(1)H] magnetic resonance spectroscopy of urine: diagnosis of a guanidinoacetate methyl transferase deficiency case.

    PubMed

    Tassini, Maria; Zannolli, Raffaella; Buoni, Sabrina; Engelke, Udo; Vivi, Antonio; Valensin, Gianni; Salomons, Gajja S; De Nicola, Anna; Strambi, Mirella; Monti, Lucia; Morava, Eva; Wevers, Ron A; Hayek, Joseph

    2010-01-01

    For the first time, the use of urine [(1)H] magnetic resonance spectroscopy has allowed the detection of 1 case of guanidinoacetate methyl transferase in a database sample of 1500 pediatric patients with a diagnosis of central nervous system impairment of unknown origin. The urine [(1)H] magnetic resonance spectroscopy of a 9-year-old child, having severe epilepsy and nonprogressive mental and motor retardation with no apparent cause, revealed a possible guanidinoacetic acid increase. The definitive assignment of guanidinoacetic acid was checked by addition of pure substance to the urine sample and by measuring [(1)H]-[(1)H] correlation spectroscopy. Diagnosis of guanidinoacetate methyl transferase deficiency was further confirmed by liquid chromatography-mass spectrometry, brain [(1)H] magnetic resonance spectroscopy, and mutational analysis of the guanidinoacetate methyl transferase gene. The replacement therapy was promptly started and, after 1 year, the child was seizure free. We conclude that for this case, urine [(1)H] magnetic resonance spectroscopy screening was able to diagnose guanidinoacetate methyl transferase deficiency. PMID:19461121

  13. Synthesis, spectroscopic studies and crystal structure of ( E)-2-(2,4-dihydroxybenzylidene)thiosemicarbazone and ( E)-2-[(1 H-indol-3-yl)methylene]thiosemicarbazone

    NASA Astrophysics Data System (ADS)

    Y?ld?z, Mustafa; Ünver, Hüseyin; Erdener, Di?dem; Kiraz, A?k?n; ?skeleli, Nazan Ocak

    2009-02-01

    Thiosemicarbazone Schiff bases ( 1 and 2) derived from 2,4-dihydroxybenzaldehyde, indoline-3-carbaldehyde and thiosemicarbazone have been synthesized and their structures were elucidated by elemental analysis, FT-IR, 1H NMR, 13C NMR and UV-visible spectroscopic techniques. The structures of compounds 1 and 2 have also been examined cyrstallographically. The title compounds 1 and 2 crystallize in the monoclinic space group C2/ c and triclinic space group P1¯, with unit cell parameters: a = 21.421(1) and 7.233(1), b = 4.131(1) and 11.166(1), c = 24.942(2) and 13.648(1) Å, V = 1856.1(2) and 1019.5(1) Å 3, D x = 1.512 and 1.422 g cm -3 and Z = 8 and 4, respectively.

  14. (1-Methyl-2-(thiophen-2-yl)-1H-benzo[d]imidazole) and its three copper complexes: Synthesis, characterization and fluorescence properties

    NASA Astrophysics Data System (ADS)

    Demir, Selçuk; Eren, Bilge; Ho?y?ska, Ma?gorzata

    2015-02-01

    (1-Methyl-2-(thiophen-2-yl)-1H-benzo[d]imidazole) (C12H10N2S) (L) ligand and its three copper complexes [(Cu2(L)2I2] (1), [(Cu(L)2X2] (X = Cl- (2), and NO3- (3)) were synthesized and characterized by elemental analysis and IR measurements. The structures of the complexes 1-3 were determined by single crystal X-ray diffraction. The complex molecules interact with each other's via weak Csbnd H⋯X hydrogen bonds (X = I for the complex 1, X = Cl for the complex 2 and X = O for the complex 3). Upon excitation with a wavelength of 350 nm at room temperature, free L and complex 1 emit fluorescence at 420 and 560 nm, respectively.

  15. Synthesis and anti-inflammatory evaluation of new 1,3,5-triaryl-4,5-dihydro-1H-pyrazole derivatives possessing an aminosulphonyl pharmacophore.

    PubMed

    Abdellatif, Khaled R A; Abdelgawad, Mohamed A; Elshemy, Heba A H; Alsayed, Shahinda S R; Kamel, Gehan

    2015-11-01

    A novel series of 2-pyrazoline derivatives 13a-l was synthesized via aldol condensation of 4-substituted acetophenones with appropriately substituted aldehydes followed by cyclization of the formed chalcones with 4-hydrazinobenzenesulfonamide hydrochloride. The chemical structures of the target pyrazoline derivatives were proved by means of IR, (1)H NMR, (13)C NMR, mass spectroscopy and elemental analyses data. All the synthesized compounds were evaluated for their cyclooxygenase selectivity, anti-inflammatory and ulcerogenic liability. While compounds 13e, 13h and 13i showed moderate COX-2 selectivity in vitro and good anti-inflammatory activity in vivo, compound 13i showed the highest anti-inflammatory activity that is very close in potency to the reference drug (celecoxib) with better gastric profile than celecoxib. PMID:25904239

  16. Finite-pulse radio frequency driven recoupling with phase cycling for 2D 1H/1H correlation at ultrafast MAS frequencies

    NASA Astrophysics Data System (ADS)

    Nishiyama, Yusuke; Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2014-06-01

    The first-order recoupling sequence radio frequency driven dipolar recoupling (RFDR) is commonly used in single-quantum/single-quantum homonuclear correlation 2D experiments under magic angle spinning (MAS) to determine homonuclear proximities. From previously reported analysis of the use of XY-based super-cycling schemes to enhance the efficiency of the finite-pulse-RFDR (fp-RFDR) pulse sequence, XY814 phase cycling was found to provide the optimum performance for 2D correlation experiments on low-? nuclei. In this study, we analyze the efficiency of different phase cycling schemes for proton-based fp-RFDR experiments. We demonstrate the advantages of using a short phase cycle, XY4, and its super-cycle XY414 that only recouples the zero-quantum homonuclear dipolar coupling, for the fp-RFDR sequence in 2D 1H/1H correlation experiments at ultrafast MAS frequencies. The dipolar recoupling efficiencies of XY4, XY414 and XY814 phase cycling schemes are compared based on results obtained from 2D 1H/1H correlation experiments, utilizing the fp-RFDR pulse sequence, on powder samples of U-13C,15N-L-alanine, N-acetyl-15N-L-valyl-15N-L-leucine, and glycine. Experimental results and spin dynamics simulations show that XY414 performs the best when a high RF power is used for the 180° pulse, whereas XY4 renders the best performance when a low RF power is used. The effects of RF field inhomogeneity and chemical shift offsets are also examined. Overall, our results suggest that a combination of fp-RFDR-XY414 employed in the recycle delay with a large RF-field to decrease the recycle delay, and fp-RFDR-XY4 in the mixing period with a moderate RF-field, is a robust and efficient method for 2D single-quantum/single-quantum 1H/1H correlation experiments at ultrafast MAS frequencies.

  17. Finite-pulse radio frequency driven recoupling with phase cycling for 2D (1)H/(1)H correlation at ultrafast MAS frequencies.

    PubMed

    Nishiyama, Yusuke; Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2014-06-01

    The first-order recoupling sequence radio frequency driven dipolar recoupling (RFDR) is commonly used in single-quantum/single-quantum homonuclear correlation 2D experiments under magic angle spinning (MAS) to determine homonuclear proximities. From previously reported analysis of the use of XY-based super-cycling schemes to enhance the efficiency of the finite-pulse-RFDR (fp-RFDR) pulse sequence, XY8(1)4 phase cycling was found to provide the optimum performance for 2D correlation experiments on low-? nuclei. In this study, we analyze the efficiency of different phase cycling schemes for proton-based fp-RFDR experiments. We demonstrate the advantages of using a short phase cycle, XY4, and its super-cycle XY4(1)4 that only recouples the zero-quantum homonuclear dipolar coupling, for the fp-RFDR sequence in 2D (1)H/(1)H correlation experiments at ultrafast MAS frequencies. The dipolar recoupling efficiencies of XY4, XY4(1)4 and XY8(1)4 phase cycling schemes are compared based on results obtained from 2D (1)H/(1)H correlation experiments, utilizing the fp-RFDR pulse sequence, on powder samples of U-(13)C,(15)N-l-alanine, N-acetyl-(15)N-l-valyl-(15)N-l-leucine, and glycine. Experimental results and spin dynamics simulations show that XY4(1)4 performs the best when a high RF power is used for the 180° pulse, whereas XY4 renders the best performance when a low RF power is used. The effects of RF field inhomogeneity and chemical shift offsets are also examined. Overall, our results suggest that a combination of fp-RFDR-XY4(1)4 employed in the recycle delay with a large RF-field to decrease the recycle delay, and fp-RFDR-XY4 in the mixing period with a moderate RF-field, is a robust and efficient method for 2D single-quantum/single-quantum (1)H/(1)H correlation experiments at ultrafast MAS frequencies. PMID:24713171

  18. Far-IR selected star formation regions

    NASA Technical Reports Server (NTRS)

    Jaffe, D. T.; Hildebrand, R. H.; Keene, J.; Harper, D. A.; Loewenstein, R. F.; Moran, J. M.

    1984-01-01

    Detailed far-IR observations and complemenary submillimeter, 5 GHz continuum and c(18)0 observations of a sample of far-IR selected luminous regions of star formation. The clouds and that the exciting stars lie deep within these condensations. The far-IR sources have diversely shaped 40 micron to 180 micron spectra even through their 60 micron to 100 micron color temperatures are similar. The radio and far-IR results together show that the exciting stars are in clusters containing either zero-age main sequence and pre-main sequence stars or consisting entirely of premain sequence objects. C(18)0 and submillimeter observations imply gas densities approximately .00005 - high enough to make t(sub dust) approximately t(sub gas).

  19. Lava Flows in IR Color

    NASA Technical Reports Server (NTRS)

    2004-01-01

    [figure removed for brevity, see original site]

    Released August 5, 2004 This image shows two representations of the same infra-red image covering a portion of the Solis Planum region, southeast of the Tharsis volcanoes. On the left is a grayscale image showing surface temperature, and on the right is a false-color composite made from 3 individual THEMIS bands. The false-color image is colorized using a technique called decorrelation stretch (DCS), which emphasizes the spectral differences between the bands to highlight compositional variations.

    Multiple layers of lava flows in this region show temperature differences, as well as some potential compositional differences. The temperature variations between these flows are likely caused by differences in their surface texture. The compositional variation could be due to differences in the make-up of the lava when it erupted onto the surface or might only reflect differences in the amount of dust covering these flows.

    Image information: IR instrument. Latitude -30.1, Longitude 275.9 East (84.1 West). 100 meter/pixel resolution.

    Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with Project policies at a later time.

    NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The Thermal Emission Imaging System (THEMIS) was developed by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. The THEMIS investigation is led by Dr. Philip Christensen at Arizona State University. Lockheed Martin Astronautics, Denver, is the prime contractor for the Odyssey project, and developed and built the orbiter. Mission operations are conducted jointly from Lockheed Martin and from JPL, a division of the California Institute of Technology in Pasadena.

  20. Gale Crater in IR Color

    NASA Technical Reports Server (NTRS)

    2004-01-01

    [figure removed for brevity, see original site]

    Released August 4, 2004 This image shows two representations of the same infra-red image of Gale Crater. On the left is a grayscale image showing surface temperature, and on the right is a false-color composite made from 3 individual THEMIS bands. The false-color image is colorized using a technique called decorrelation stretch (DCS), which emphasizes the spectral differences between the bands to highlight compositional variations.

    In the bottom of the crater, surrounding the central mound, there are extensive basaltic sand deposits. The basaltic sand spectral signature combined with the warm surface (due to the low albedo of basaltic sand) produces a very strong pink/magenta color. This color signature contrasts with the green/yellow color of soil and dust in the top of the image, and the cyan color due to the presence of water ice clouds at the bottom of the image. This migrating sand may be producing the erosional features seen on the central mound.

    Image information: IR instrument. Latitude -4.4, Longitude 137.4 East (222.6 West). 100 meter/pixel resolution.

    Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with Project policies at a later time.

    NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The Thermal Emission Imaging System (THEMIS) was developed by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. The THEMIS investigation is led by Dr. Philip Christensen at Arizona State University. Lockheed Martin Astronautics, Denver, is the prime contractor for the Odyssey project, and developed and built the orbiter. Mission operations are conducted jointly from Lockheed Martin and from JPL, a division of the California Institute of Technology in Pasadena.

  1. Basaltic Crater in Color IR

    NASA Technical Reports Server (NTRS)

    2004-01-01

    [figure removed for brevity, see original site]

    Released August 6, 2004 This image shows two representations of the same infra-red image near Nili Fosse in the the Isidis region of Mars. On the left is a grayscale image showing surface temperature, and on the right is a false-color composite made from 3 individual THEMIS bands. The false-color image is colorized using a technique called decorrelation stretch (DCS), which emphasizes the spectral differences between the bands to highlight compositional variations. In many cases craters trap sand in their topographic depressions, interrupting the sand's migration across the Martian surface. This image is particularly interesting because there appears to be more than 1 type of sand in the bottom of this crater and in the hummocky terrain near the bottom of the image. The pink/magenta areas are characteristic of a basaltic composition, but there are also orange areas that are likely caused by the presence of andesite. These two compositions, basalt and andesite, are some of the most common found on Mars.

    Image information: IR instrument. Latitude 24, Longitude 80.7 East (297.3 West). 100 meter/pixel resolution.

    Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with Project policies at a later time.

    NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The Thermal Emission Imaging System (THEMIS) was developed by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. The THEMIS investigation is led by Dr. Philip Christensen at Arizona State University. Lockheed Martin Astronautics, Denver, is the prime contractor for the Odyssey project, and developed and built the orbiter. Mission operations are conducted jointly from Lockheed Martin and from JPL, a division of the California Institute of Technology in Pasadena.

  2. IR Optimization, DID and anti-DID

    SciTech Connect

    Seryi, Andrei; Maruyama, Takashi; Parker, Brett; /Brookhaven

    2006-02-03

    In this paper, we discuss optimization of the larger crossing angle Interaction Region of the Linear Collider, where specially shaped transverse field of the Detector Integrated Dipole can be reversed and adjusted to optimize trajectories of the low energy pairs, so that their majority would be directed into the extraction exit hole. This decreases the backscattering and makes background in 14mrad IR to be similar to background in 2mrad IR.

  3. Determination of glucan phosphorylation using heteronuclear 1H, 13C double and 1H, 13C, 31P triple-resonance NMR spectra.

    PubMed

    Schmieder, Peter; Nitschke, Felix; Steup, Martin; Mallow, Keven; Specker, Edgar

    2013-10-01

    Phosphorylation and dephosphorylation of starch and glycogen are important for their physicochemical properties and also their physiological functions. It is therefore desirable to reliably determine the phosphorylation sites. Heteronuclear multidimensional NMR-spectroscopy is in principle a straightforward analytical approach even for complex carbohydrate molecules. With heterogeneous samples from natural sources, however, the task becomes more difficult because a full assignment of the resonances of the carbohydrates is impossible to obtain. Here, we show that the combination of heteronuclear (1) H,(13) C and (1) H,(13) C,(31) P techniques and information derived from spectra of a set of reference compounds can lead to an unambiguous determination of the phosphorylation sites even in heterogeneous samples. PMID:23913630

  4. Magnesium Silicate Dissolution Investigated by 29Si MAS, 1H-29Si CP MAS, 25Mg QCPMG, and 1H-25Mg CP QCPMG NMR

    SciTech Connect

    Davis, Michael C.; Brouwer, William J.; Wesolowski, David J.; Anovitz, Lawrence M.; Lipton, Andrew S.; Mueller, Karl T.

    2009-08-01

    Olivine has been the subject of frequent investigation in the earth sciences because of its simple structure and rapid dissolution kinetics. Several studies have observed a preferential release of magnesium with respect to silica during weathering under acidic conditions, which has been correlated to the formation of a silicon rich leached layer. While leached layer formation has been inferred through the changing solution chemistry, a thorough spectroscopic investigation of olivine reacted under acidic conditions has not been conducted. In particular, the fate of magnesium in the system is not understood and spectroscopic interrogations through nuclear magnetic resonance can elucidate the changing magnesium coordination and bonding environment. In this study, we combine analysis of the changing solution chemistry with advanced spectroscopic techniques (29Si MAS, 1H-29Si CP MAS, 25Mg QCPMG, and 1H-25Mg 2 CP QCPMG NMR) to probe leached layer formation and possible secondary phase precipitation during the dissolution of forsterite at 150 oC.

  5. Synthesis of two distinct pyrrole moiety-containing arenes from nitroanilines using Paal-Knorr followed by an indium-mediated reaction.

    PubMed

    Kim, Byeong Hyo; Bae, Seolhee; Go, Ahra; Lee, Hyunseung; Gong, Cheoloh; Lee, Byung Min

    2015-12-15

    Synthesis of arenes substituted with two differently substituted-pyrrole moieties was investigated. A Paal-Knorr condensation reaction of nitroanilines with 1,4-diketone to nitrophenyl-1H-pyrroles followed by an indium-mediated reduction-triggered coupling reaction with another kind of 1,4-diketone resulted in two distinct pyrrole-containing arenes, variously substituted 1-((1H-pyrrol-1-yl)phenyl)-1H-pyrroles, in reasonable yield. PMID:26593044

  6. Alzheimer Disease: Postmortem Neuropathologic Correlates of Antemortem 1H MR Spectroscopy Metabolite Measurements

    PubMed Central

    Kantarci, Kejal; Knopman, David S.; Dickson, Dennis W.; Parisi, Joseph E.; Whitwell, Jennifer L.; Weigand, Stephen D.; Josephs, Keith A.; Boeve, Bradley F.; Petersen, Ronald C.; Jack, Clifford R.

    2009-01-01

    Purpose To determine the neuropathologic correlates of antemortem hydrogen 1 (1H) magnetic resonance (MR) spectroscopy metabolite measurements in subjects with Alzheimer disease (AD)-type pathology. Materials and Methods This study was approved by the institutional review board and was compliant with HIPAA regulations. Informed consent was obtained from each subject. The authors identified 54 subjects who underwent antemortem 1H MR spectroscopy and were clinically healthy or had AD-type pathology with low to high likelihood of AD according to National Institute on Aging–Reagan neuropathologic criteria at autopsy. They investigated the associations between 1H MR spectroscopy metabolite measurements and Braak neurofibrillary tangle stage (Braak stage), neuritic plaque score, and AD likelihood, with adjustments for subject age, subject sex, and time between 1H MR spectroscopy and death. Results Decreases in N-acetylaspartate–to-creatine ratio, an index of neuronal integrity, and increases in myo-inositol–to-creatine ratio were associated with higher Braak stage, higher neuritic plaque score, and greater likelihood of AD. The N-acetylaspartate–to–myo-inositol ratio proved to be the strongest predictor of the pathologic likelihood of AD. The strongest association observed was that between N-acetylaspartate–to–myo-inositol ratio and Braak stage (RN2 = 0.47, P < .001). Conclusion Antemortem 1H MR spectroscopy metabolite changes correlated with AD-type pathology seen at autopsy. The study findings validated 1H MR spectroscopy metabolite measurements against the neuropathologic criteria for AD, and when combined with prior longitudinal 1H MR spectroscopy findings, indicate that these measurements could be used as biomarkers for disease progression in clinical trials. PMID:18566174

  7. Synthesis of Ir(III) complexes with Tp(Me2) and acac ligands and their reactivity with electrophiles.

    PubMed

    Morales-Cerón, Judith P; Salazar-Pereda, Verónica; Mendoza-Espinosa, Daniel; Alvarado-Rodríguez, José G; Cruz-Borbolla, Julián; Andrade-López, Noemí; Vásquez-Pérez, José M

    2015-08-21

    The reaction of the bis(ethylene) complex [Tp(Me2)Ir(C2H4)2] () (Tp(Me2) = hydrotris(3,5-dimethylpyrazolyl)borate) with an excess of 2,4-pentanedione (acetylacetone, Hacac) at 70 °C produced a mixture of the Ir(iii) complex [Tp(Me2)Ir(acac)(C2H5)] () as a major product (67% yield) and two other side complexes [Tp(Me2)Ir(acac)(H)] () and [Tp(Me2)Ir(C9H14O2)] () in 20 and 13% yields, respectively. According to the proposed reaction mechanism and DFT calculations, complexes and are generated from an 18e(-) intermediate [Tp(Me2)Ir(C2H4)(acac)(C2H3)] () which undergoes either hydrogen insertion or ?-hydride elimination followed by the subsequent loss of a molecule of ethylene. The lowest yielding complex which features a 2-iridafuran is presumably generated from an unusual thermal coupling between one vinylic and one acac moiety. The availability of the acidic ?-proton of the acac ligand was tested by the treatment of complex with Br2 and Cu(NO3)2 rendering the substitution complexes [Tp(3-Br,Me2)Ir(3-Br-acac)Br] () and [Tp(Me2)Ir(3-NO2-acac)(C2H5)] () in good yields. The series of heteroleptic iridium(iii) compounds display air and moisture stability and have been characterized by NMR, IR, and elemental analyses, and, in the case of , and , by single-crystal X-ray diffraction analyses. PMID:26148543

  8. Near-IR spectroscopy of OH/IR stars in the Galactic Centre

    E-print Network

    E. Vanhollebeke; J. A. D. L. Blommaert; M. Schultheis; B. Aringer; A. Lancon

    2006-04-28

    Context. Galactic Centre (GC) OH/IR stars can be, based on the expansion velocities of their circumstellar shells, divided into two groups which are kinematically different and therefore are believed to have evolved from different stellar populations. Aims. To study the metallicity distribution of the OH/IR stars population in the GC on basis of a theoretical relation between EW(Na), EW(Ca) and EW(CO) and the metallicity. Methods. For 70 OH/IR stars in the GC, we obtained near-IR spectra. The equivalent line widths of NaI, CaI, 12CO(2,0) and the curvature of the spectrum around 1.6 micron due to water absorption are determined. Results. The near-IR spectrum of OH/IR stars is influenced by several physical processes. OH/IR stars are variable stars suffering high mass-loss rates. The dust that is formed around the stars strongly influences the near-IR spectra and reduces the equivalent line widths of NaI, CaI. A similar effect is caused by the water content in the outer atmosphere of the OH/IR star. Because of these effects, it is not possible with our low resolution near-infrared spectroscopy to determine the metallicities of these stars.

  9. Near-IR/optical monitoring programme of the 'Arecibo sample of OH/IR stars'

    E-print Network

    Francisco Jiménez-Esteban; Dieter Engels; Pedro García-Lario

    2006-11-02

    We performed a near-IR/optical monitoring programme from 1999 to 2005 in order to study the variability properties of the 'Arecibo sample of OH/IR stars' (periods, amplitudes, and colour variations). Here we describe this multi-wavelength long-term monitoring programme. Data analysis is still in process. Our ultimate goal is to study in particular the oxygen-rich AGB stars with masses larger than 2 Solar Mass, which are probably rare among AGB stars discovered optically and/or in the near-IR, but are common in samples discovered in the mid- to far-IR.

  10. Synthesis, DFT calculations and cytotoxic investigation of platinum complexes with 3-thiolanespiro-5?-hydantoin and 4-thio-1H-tetrahydropyranespiro-5?-hydantoin

    NASA Astrophysics Data System (ADS)

    Bakalova, Adriana; Buyukliev, Rossen; Momekov, Georgi

    2015-07-01

    Two organic compounds - 3-thiolanespiro-5?-hydantoin, 4-thio-1H-tetrahydropyranespiro-5?-hydantoin and four new Pt(II) and Pt(IV) complexes with general formulas cis-[Pt(L)2Cl2] and cis-[Pt(L)2Cl4] were synthesized. The obtained compounds were characterized by elemental analysis, IR, 1H, 13C NMR spectroscopy. The hybrid DFT calculations were used for optimization of the structure geometries of the ligand (L1) and its Pt(II) complex (1). The calculated structural parameters such as bond lengths and angles are in good agreement with the experimental data for similar hydantoins and their platinum complexes. The obtained results showed that the geometry of the complex (1) is plane square and the bounding of the L1 with platinum ion is realized by sulfur atom from thiolane ring. The complexes were tested for cytotoxicity in vitro on four human tumor cell lines. The tested compounds exerted concentration-dependent cytotoxic effects against some of the tumor cell lines.

  11. Synthesis, spectroscopic characterization and crystal structure of 5-bromo-1-(2-cyano-pyridin-4-yl)-1 H-indazole-3-carboxylic acid diethylamide

    NASA Astrophysics Data System (ADS)

    Anuradha, G.; Vasuki, G.; Surendrareddy, G.; Veerareddy, A.; Dubey, P. K.

    2014-07-01

    The title compound 5-bromo-1-(2-cyano-pyridin-4-yl)-1 H-indazole-3-carboxylic acid diethylamide, C18H16BrN5O, is prepared from 5-bromoindazole-3-carboxylic acid methylester. N 1-arylation is carried out with 4-chloro-2-cyanopyridine and the resulting product is converted to diethylamide by reacting with thionyl chloride and diethylamine. The structure is identified from its FT-IR, 1H NMR, 13C NMR spectroscopy, elemental analysis data and unambiguously confirmed by single crystal X-ray diffraction studies. There are two symmetry independent molecules in the asymmetric unit with no significant differences in bond lengths and angles. The title compound crystallizes in the triclinic system, space group , with a = 11.2330(2); b = 11.6130(2); c = 15.4710(3) Å, ? = 92.515(1)°; ? = 109.956(1)°; ? = 107.199(1)°; V = 1788.45(6)Å3 and z = 4. An intramolecular C-H…N hydrogen bond forms an S(6) ring motif in one of the unique molecules. In the crystal, two molecules are linked about a center of inversion by C-H…O hydrogen bonded dimers generating an R {2/2}(16) ring motif. The crystal packing is stabilized by C-H…N, C-H…O hydrogen bonds and ?…? stacking interactions.

  12. Synthesis, structure, optical properties, antifungal and antibacterial activities of 2-(1-oxo-1H-2,3-dihydroisoindol-2-yl)-3-imidazolyl-L-lactamic acid

    NASA Astrophysics Data System (ADS)

    Jia, Ting; Zhang, Wei-Long; Chen, Yun; Cai, Shuang-Lian; Yi, Hai-Bo

    2013-10-01

    2-(1-oxo-1H-2,3-dihydroisoindol-2-yl)-3-imidazolyl-L-lactamic acid has been prepared conveniently by the condensation reaction of o-phthalaldehyde (OPA) with L-Histidine, and its single crystal structure has been characterized by X-ray crystallography method. The in vitro antifungal and antibacterial activities of the compound were investigated with the representative strains of Candida albicans, Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa. Its luminescent and nonlinear optical properties have also been investigated. Second-harmonic-generation (SHG) measurements indicate that compound 1 displays a weak SHG response of about 0.75 times that of KH2PO4.

  13. Synthesis of Highly Stable 1,3-Diaryl-1H-1,2,3-triazol-5-ylidenes and their Applications in Ruthenium-Catalyzed Olefin Metathesis

    PubMed Central

    Bouffard, Jean; Keitz, Benjamin K.; Tonner, Ralf; Lavallo, Vincent; Guisado-Barrios, Gregorio; Frenking, Gernot

    2011-01-01

    The formal cycloaddition between 1,3-diaza-2-azoniaallene salts and alkynes or alkyne equivalents provides an efficient synthesis of 1,3-diaryl-1H-1,2,3-triazolium salts, the direct precursors of 1,2,3-triazol-5-ylidenes. These N,N-diarylated mesoionic carbenes (MICs) exhibit enhanced stability in comparison to their alkylated counterparts. Experimental and computational results confirm that these MICs act as strongly electron-donating ligands. Their increased stability allows for the preparation of ruthenium olefin metathesis catalysts that are efficient in both ring-opening and ring-closing reactions. PMID:21572542

  14. Analyzing powers for {sup 1}H{searrow}({pi}{sup +},{pi}{sup +}{ital p}) at {ital T}{sub {pi}}=165 and 240 MeV

    SciTech Connect

    Raue, B.A.; Greco, T.A.; Khayat, M.G.; Adimi, F.; Brandt, B.v.; Breuer, H.; Chang, T.; Chant, N.S.; Chen, H.; Dooling, T.A.; Dvoredsky, A.P.; Flanders, B.S.; Gu, T.; Haas, J.P.; Hautle, P.; Huffman, J.; Kelly, J.J.; Klein, A.; Koch, K.; Konter, J.A.; Kovalev, A.I.; Kyle, G.S.; Lawrie, J.J.; Lin, Z.; Mango, S.; Markowitz, P.; Meier, R.; Payerle, T.; Ritt, S.; Roos, P.G.; Wang, M.

    1996-02-01

    We have measured the analyzing power for elastic scattering of {pi}{sup +} from a target of polarized {sup 1}H. Data were taken for incident pion beam energies of 165 and 240 MeV at several pion scattering angles. The current data generally agree with previously existing measurements of {ital A}{sub {ital y}} for this reaction and also with results of the SAID phase-shift analysis program. In most cases the new data are of higher precision than previously existing data. {copyright} {ital 1996 The American Physical Society.}

  15. Syntheses and structures of three novel coordination compounds assembled with 1,1?-(2,2?-oxybis(ethane-2,1-diyl))bis(1H-imidazole)

    NASA Astrophysics Data System (ADS)

    Qi, Yan; Che, Yunxia; Zheng, Jimin

    2008-11-01

    A new long flexible ligand, 1,1'-(2,2'-oxybis(ethane-2,1-diyl))bis(1H-imidazole) (L), has been prepared. The hydrothermal reactions of L with various metal ions (M(II) = Cu(II), Cd(II) and Ni(II)) yielded three new coordination compounds consisting of 0D, 1D and 2D structures. Compound 1 is a dinuclear M 2L 2 metallocycle. Compound 2 is a double-stranded chain running along b axis direction. Compound 3 affords highly undulated 2D (4, 4) layers. In addition, complex 2 exhibits strong blue photoluminescence.

  16. Specific control of BMP signaling and mesenchymal differentiation by cytoplasmic phosphatase PPM1H

    PubMed Central

    Shen, Tao; Sun, Chuang; Zhang, Zhengmao; Xu, Ningyi; Duan, Xueyan; Feng, Xin-Hua; Lin, Xia

    2014-01-01

    Bone morphogenetic proteins (BMPs) belong to the TGF-? superfamily of structurally related signaling proteins that regulate a wide array of cellular functions. The key step in BMP signal transduction is the BMP receptor-mediated phosphorylation of transcription factors Smad1, 5, and 8 (collectively Smad1/5/8), which leads to the subsequent activation of BMP-induced gene transcription in the nucleus. In this study, we describe the identification and characterization of PPM1H as a novel cytoplasm-localized Smad1/5/8-specific phosphatase. PPM1H directly interacts with Smad1/5/8 through its Smad-binding domain, and dephosphorylates phospho-Smad1/5/8 (P-Smad1/5/8) in the cytoplasm. Ectopic expression of PPM1H attenuates BMP signaling, whereas loss of PPM1H activity or expression greatly enhances BMP-dependent gene regulation and mesenchymal differentiation. In conclusion, this study suggests that PPM1H acts as a gatekeeper to prevent excessive BMP signaling through dephosphorylation and subsequent nuclear exclusion of P-Smad1/5/8 proteins. PMID:24732009

  17. Origins of linewidth in 1H magic-angle spinning NMR.

    PubMed

    Zorin, Vadim E; Brown, Steven P; Hodgkinson, Paul

    2006-10-14

    A detailed study of the factors determining the linewidth (and hence resolution) in 1H solid-state magic-angle spinning NMR is described. Although it has been known from the early days of magic-angle spinning (MAS) that resolution of spectra from abundant nuclear spins, such as 1H, increases approximately linearly with increasing sample rotation rate, the difficulty of describing the dynamics of extended networks of coupled spins has made it difficult to predict a priori the resolution expected for a given sample. Using recently developed, highly efficient methods of numerical simulation, together with experimental measurements on a variety of test systems, we propose a comprehensive picture of 1H resolution under MAS. The "homogeneous" component of the linewidth is shown to depend primarily on the ratio between an effective local coupling strength and the spin rate, modified by geometrical factors which loosely correspond to the "dimensionality" of the coupling network. The remaining "inhomogeneous" component of the natural linewidth is confirmed to have the same properties as in dilute-spin NMR. Variations in the NMR frequency due to chemical shift effects are shown to have minimal impact on 1H resolution. The implications of these results for solid-state NMR experiments involving 1H and other abundant-spin nuclei are discussed. PMID:17042610

  18. The synthesis and characterization of nonperipherally tetra terminal alkynyl substituted phthalocyanines and glycoconjugation via the click reaction.

    PubMed

    Kanat, Zeliha; Dinçer, Hatice

    2014-06-21

    In order to obtain nonperipherally tetra terminal alkynyl substituted phthalocyanines (Pcs), new 3-pent-4-ynyloxy phthalonitrile (3) was prepared by the nucleophilic displacement reaction of 3-nitrophthalonitrile (1) and 4-pentyn-1-ol (2) and then cyclotetramerization was attained in the presence of zinc acetate, cobalt acetate, and/or DBU in n-pentanol without protection/deprotection. For the first time, the glycoconjugation of the nonperipherally tetra terminal alkynyl substituted zinc phthalocyanine (ZnPc) (6) can be easily achieved via the click reaction in a high yield. The electronic absorption spectrum of the glucopyranosyl substituted ZnPc (10) derivative showed a red-shifted Q band at 751 nm in dichloromethane due to the protonation of the meso nitrogens of the Pc macrocycle. Deacylation yielded ZnPc (11) bearing glucose substituents at nonperipheral positions with an improved water-solubility and non-aggregation in DMSO. The chemical structures of the new compounds were characterized by (1)H NMR, (13)C NMR, FT-IR, UV-Vis, mass spectrometry and elemental analysis. Moreover, the phthalonitrile compound was characterized using X-ray. PMID:24763524

  19. Issue Number: IR-2015-22 Inside This Issue

    E-print Network

    Issue Number: IR-2015-22 Inside This Issue IRS Launches Directory of Federal Tax Return Preparers the launch of a new, online public directory of tax return preparers. This searchable directory on IRS on the services of a paid return preparer," said IRS Commissioner John Koskinen. "Taxpayers can also look

  20. MHPCC Web-based IR data library and simulation

    NASA Astrophysics Data System (ADS)

    Koligman, Michael; Quinn-Jacobs, David; Attili, Joseph B.

    1998-08-01

    The Maui High Performance Computing Center has recently established a remote IR Data Library and Web-based Simulation environment. This environment enables a large number of researchers to access, review, and process IR data sets via the internet. The IR data was collected with the ARPA-sponsored Airborne IR Measurement System (AIRMS) sensor under the completed AIRMS program.

  1. Amino­silanes derived from 1H-benzimidazole-2(3H)-thione

    PubMed Central

    Palomo-Molina, Juliana; García-Báez, Efrén V.; Contreras, Rosalinda; Pineda-Urbina, Kayim; Ramos-Organillo, Angel

    2015-01-01

    Two new mol­ecular structures, namely 1,3-bis­(tri­methyl­silyl)-1H-benzimidazole-2(3H)-thione, C13H22N2SSi2, (2), and 1-tri­methyl­silyl-1H-benzimidazole-2(3H)-thione, C10H14N2SSi, (3), are reported. Both systems were derived from 1H-benzimidazole-2(3H)-thione. Noncovalent C—H?? inter­actions between the centroid of the benzmidazole system and the SiMe3 groups form helicoidal arrangements in (2). Dimerization of (3) results in the formation of R 2 2(8) rings via N—H?S inter­actions, along with parallel ?–? inter­actions between imidazole and benzene rings. PMID:26322611

  2. Aminosilanes derived from 1H-benzimidazole-2(3H)-thione.

    PubMed

    Palomo-Molina, Juliana; García-Báez, Efrén V; Contreras, Rosalinda; Pineda-Urbina, Kayim; Ramos-Organillo, Angel

    2015-09-01

    Two new molecular structures, namely 1,3-bis(trimethylsilyl)-1H-benzimidazole-2(3H)-thione, C13H22N2SSi2, (2), and 1-trimethylsilyl-1H-benzimidazole-2(3H)-thione, C10H14N2SSi, (3), are reported. Both systems were derived from 1H-benzimidazole-2(3H)-thione. Noncovalent C-H···? interactions between the centroid of the benzmidazole system and the SiMe3 groups form helicoidal arrangements in (2). Dimerization of (3) results in the formation of R2(2)(8) rings via N-H···S interactions, along with parallel ?-? interactions between imidazole and benzene rings. PMID:26322611

  3. Multislice 1H magnetic resonance spectroscopic imaging: assessment of epilepsy, Alzheimer's disease, and amyotrophic lateral sclerosis

    NASA Astrophysics Data System (ADS)

    Weiner, Michael W.; Maudsley, Andrew A.; Schuff, Norbert; Soher, Brian J.; Vermathen, Peter P.; Fein, George; Laxer, Kenneth D.

    1998-07-01

    Proton magnetic resonance spectroscopic imaging (1H MRSI) with volume pre-selection (i.e. by PRESS) or multislice 1H MRSI was used to investigate changes in brain metabolites in Alzheimer's disease, epilepsy, and amyotrophic lateral sclerosis. Examples of results from several ongoing clinical studies are provided. Multislice 1H MRSI of the human brain, without volume pre-selection offers considerable advantages over previously available techniques. Furthermore, MRI tissue segmentation and completely automated spectra curve fitting greatly facilitate quantitative data analysis. Future efforts will be devoted to obtaining full brain coverage and data acquisition at short spin echo times (TE less than 30 ms) for the detection of metabolites with short T2 relaxation times.

  4. DFT calculation of 1J(119Sn,13C) and 2J(119Sn,1H) coupling constants in di- and trimethyltin(IV) compounds.

    PubMed

    Casella, Girolamo; Ferrante, Francesco; Saielli, Giacomo

    2008-06-01

    We have tested several computational protocols, at the nonrelativistic DFT level of theory, for the calculation of 1J(119Sn, 13C) and 2J(119Sn, 1H) spin-spin coupling constants in di- and trimethyltin(IV) derivatives with various ligands. Quite a good agreement with experimental data has been found with several hybrid functionals and a double-zeta basis set for a set of molecules comprising tetra-, penta-, and hexa-coordinated tin(IV). Then, some of the protocols have been applied to the calculation of the 2J(119Sn, 1H) of the aquodimethyltin(IV) ion and dimethyltin(IV) complex with D-ribonic acid and to the calculation of 1J(119Sn, 13C) and 2J(119Sn, 1H) of the dimethyltin(IV)-glycylglycine and glycylhistidine complexes in water solutions. Solvent effects have been considered in these cases by including explicit water molecules and/or the solvent reaction field, resulting in a good agreement with experimental data. The proposed protocols constitute a helpful tool for the structural determination of di- and triorganotin(IV) derivatives. PMID:18459719

  5. Iridium Interfacial Stack - IrIS

    NASA Technical Reports Server (NTRS)

    Spry, David

    2012-01-01

    Iridium Interfacial Stack (IrIS) is the sputter deposition of high-purity tantalum silicide (TaSi2-400 nm)/platinum (Pt-200 nm)/iridium (Ir-200 nm)/platinum (Pt-200 nm) in an ultra-high vacuum system followed by a 600 C anneal in nitrogen for 30 minutes. IrIS simultaneously acts as both a bond metal and a diffusion barrier. This bondable metallization that also acts as a diffusion barrier can prevent oxygen from air and gold from the wire-bond from infiltrating silicon carbide (SiC) monolithically integrated circuits (ICs) operating above 500 C in air for over 1,000 hours. This TaSi2/Pt/Ir/Pt metallization is easily bonded for electrical connection to off-chip circuitry and does not require extra anneals or masking steps. There are two ways that IrIS can be used in SiC ICs for applications above 500 C: it can be put directly on a SiC ohmic contact metal, such as Ti, or be used as a bond metal residing on top of an interconnect metal. For simplicity, only the use as a bond metal is discussed. The layer thickness ratio of TaSi2 to the first Pt layer deposited thereon should be 2:1. This will allow Si from the TaSi2 to react with the Pt to form Pt2Si during the 600 C anneal carried out after all layers have been deposited. The Ir layer does not readily form a silicide at 600 C, and thereby prevents the Si from migrating into the top-most Pt layer during future anneals and high-temperature IC operation. The second (i.e., top-most) deposited Pt layer needs to be about 200 nm to enable easy wire bonding. The thickness of 200 nm for Ir was chosen for initial experiments; further optimization of the Ir layer thickness may be possible via further experimentation. Ir itself is not easily wire-bonded because of its hardness and much higher melting point than Pt. Below the iridium layer, the TaSi2 and Pt react and form desired Pt2Si during the post-deposition anneal while above the iridium layer remains pure Pt as desired to facilitate easy and strong wire-bonding to the SiC chip circuitry.

  6. Near-IR imaging and imaging polarimetry of OMC 2

    NASA Technical Reports Server (NTRS)

    Rayner, John; Mclean, Ian; Aspin, Colin; Mccaughrean, Mark

    1989-01-01

    NIR and 2.2-micron imaging polarimetry of the molecular cloud region OMC 2, reveals a cluster of low- to intermediate-mass premain-sequence stars embedded in circumstellar disks. The 2.2-micron imaging polarimetry indicates that the compact NIR sources OMC 2 IRS1, IRS2, IRS3 and IRS4 N, are illumination centers for the surrounding extended emission. By application of Hubble's relation to the nebulae illuminated by IRS1, IRS2 and IRS4 N, the illuminating geometry is explained and the intrinsic NIR colors of these objects are estimated.

  7. Relativistic Force Field: Parametrization of (13)C-(1)H Nuclear Spin-Spin Coupling Constants.

    PubMed

    Kutateladze, Andrei G; Mukhina, Olga A

    2015-11-01

    Previously, we reported a reliable DU8 method for natural bond orbital (NBO)-aided parametric scaling of Fermi contacts to achieve fast and accurate prediction of proton-proton spin-spin coupling constants (SSCC) in (1)H NMR. As sophisticated NMR experiments for precise measurements of carbon-proton SSCCs are becoming more user-friendly and broadly utilized by the organic chemistry community to guide and inform the process of structure determination of complex organic compounds, we have now developed a fast and accurate method for computing (13)C-(1)H SSCCs. Fermi contacts computed with the DU8 basis set are scaled using selected NBO parameters in conjunction with empirical scaling coefficients. The method is optimized for inexpensive B3LYP/6-31G(d) geometries. The parametric scaling is based on a carefully selected training set of 274 ((3)J), 193 ((2)J), and 143 ((1)J) experimental (13)C-(1)H spin-spin coupling constants reported in the literature. The DU8 basis set, optimized for computing Fermi contacts, which by design had evolved from optimization of a collection of inexpensive 3-21G*, 4-21G, and 6-31G(d) bases, offers very short computational (wall) times even for relatively large organic molecules containing 15-20 carbon atoms. The most informative SSCCs for structure determination, i.e., (3)J, were computed with an accuracy of 0.41 Hz (rmsd). The new unified approach for computing (1)H-(1)H and (13)C-(1)H SSCCs is termed "DU8c". PMID:26414291

  8. 507 IR BAP J 504 IR BAP E Dlgation Ile de France Ouest et Nord

    E-print Network

    Pouyanne, Nicolas

    507 IR BAP J 504 IR BAP E Délégation Ile de France Ouest et Nord 29 mai 2015 Délégation Ile de France Ouest et Nord CONCOURS INTERNES Dates et lieux des réunions d'admissibilités LIEUX Délégation Ile de France Ouest et Nord Délégation Ile de France Ouest et Nord CONCOURS DATES 3 juin 2015 1er et 2

  9. 20 ArthurJ. Sedlaceketal. Fqr infrared (IR) absorption, a strong IR absorber (such as

    E-print Network

    BNL-69387 #12;20 ArthurJ. Sedlaceketal. .. Fqr infrared (IR) absorption, a strong IR absorber (such from the surface. Hence, infrared absorption is better suited to sensing gases, with a highly pioneered the application of lidar technology towards the no?~-conluct (meters to - 500 meters), in G

  10. Novel FT-IR Microspectroscopic Census of Simple Starch Granules for Octenyl Succinate Ester Modification

    SciTech Connect

    Bai, Y.; Shi, Y; Wetzel, D

    2009-01-01

    Fourier transform infrared (FT-IR) microspectroscopy was used to investigate reaction homogeneity of octenyl succinic anhydride modification on waxy maize starch and detect uniformity of blends of modified and native starches. For the first time, the level and uniformity of chemical substitution on individual starch granules were analyzed by FT-IR microspectroscopy. More than 100 starch granules of each sample were analyzed one by one by FT-IR microspectroscopy. In comparison to the native starch, modified starch had two additional bands at 1723 and 1563 cm{sup -1}, indicative of ester formation in the modified starch. For the 3% modification level, the degree of substitution (DS) was low (0.019) and the distribution of the ester group was not uniform among starch granules. For the modified starch with DS of 0.073, 99% of individual starch granules had a large carbonyl band area, indicating that most granules were modified to a sufficient extent that the presence of their carbonyl ester classified them individually as being modified. However, the octenyl succinate concentration varied between granules, suggesting that the reaction was not uniform. When modified starch (DS = 0.073) was blended with native starch (3:7, w/w) to achieve a mixture with an average DS of 0.019, FT-IR microspectroscopy was able to detect heterogeneity of octenyl succinate in the blend and determine the ratio of the modified starch to the native starch granules.

  11. miR-194 Promotes burn-induced hyperglycemia via attenuating IGF-IR expression.

    PubMed

    Yu, Yonghui; Chai, Jiake; Zhang, Haijun; Chu, Wanli; Liu, Lingying; Ma, Li; Duan, Hongjie; Li, Bailing; Li, Dawei

    2014-12-01

    Hyperglycemia is one of the most important clinical features of burn patients. Previous reports had demonstrated that miRNA was involved in regulating glucose metabolism in various diseases such as diabetes and obesity. Our current study discovered the relationship between miR-194 and hyperglycemia in burn rats via suppressing insulin-like growth factor 1 receptor (IGF-IR). We found that the fasting blood glucose was significantly increased in rats of the burn group, and protein expression of IGF-IR was attenuated in response to burn injury. Similar to the results of animal experiments, miR-194 expression was significantly elevated and IGF-IR protein level was suppressed in L6 cells treated with serum from burn rats compared with those treated by serum from sham rats. However, IGF-IR mRNA level was comparable between burn and sham rats, suggesting that IGF-IR may be downregulated at the translation level. Further experiments revealed that miR-194 was significantly increased in burn rats compared with sham rats using miRNA array and real-time polymerase chain reaction (PCR) assay. And IGF-IR protein expression was reduced in L6 cells transfected with miR-194 plasmid. Insulin-like growth factor 1 receptor expression was also repressed and fasting blood glucose was increased in rats injected with miR-194 plasmid. In general, we have identified a novel function of miR-194 in modulating burn-induced hyperglycemia via suppressing the expression of IGF-IR. PMID:25186839

  12. Detection of hydrogen dissolved in acrylonitrile butadiene rubber by 1H nuclear magnetic resonance

    NASA Astrophysics Data System (ADS)

    Nishimura, Shin; Fujiwara, Hirotada

    2012-01-01

    Rubber materials, which are used for hydrogen gas seal, can dissolve hydrogen during exposure in high-pressure hydrogen gas. Dissolved hydrogen molecules were detected by solid state 1H NMR of the unfilled vulcanized acrylonitrile butadiene rubber. Two signals were observed at 4.5 ppm and 4.8 ppm, which were assignable to dissolved hydrogen, in the 1H NMR spectrum of NBR after being exposed 100 MPa hydrogen gas for 24 h at room temperature. These signals were shifted from that of gaseous hydrogen molecules. Assignment of the signals was confirmed by quantitative estimation of dissolved hydrogen and peak area of the signals.

  13. Proton Fingerprints Portray Molecular Structures: Enhanced Description of the 1H NMR Spectra of Small Molecules

    PubMed Central

    Napolitano, José G.; Lankin, David C.; McAlpine, James B.; Niemitz, Matthias; Korhonen, Samuli-Petrus; Chen, Shao-Nong; Pauli, Guido F.

    2013-01-01

    The characteristic signals observed in NMR spectra encode essential information on the structure of small molecules. However, extracting all of this information from complex signal patterns is not trivial. This report demonstrates how computer-aided spectral analysis enables the complete interpretation of 1D 1H NMR data. The effectiveness of this approach is illustrated with a set of organic molecules, for which replicas of their 1H NMR spectra were generated. The potential impact of this methodology on organic chemistry research is discussed. PMID:24007197

  14. Synthesis and Herbicidal Activity of 5-Heterocycloxy-3-methyl-1-substituted-1H-pyrazoles.

    PubMed

    Kang, Jing; Yue, Xia Li; Chen, Chang Shui; Li, Jian Hong; Ma, Hong Ju

    2015-01-01

    With the objective of finding valuable herbicidal candidates, a series of new 5-heterocycloxy-3-methyl-1-substituted-1H-pyrazoles were synthesized and their herbicidal activities were evaluated. The bioassay results showed that some compounds exhibited excellent herbicidal activities at the concentration of 100 mg/L, and compound 5-chloro-2-((3-methyl-1-(2,2,2-trifluoroethyl)-1H-pyrazol-5-yl)oxy)pyrimidine showed bleaching activity to green weeds. In greenhouse conditions, this compound also showed excellent post-emergence herbicidal effect against Digitaria sanguinalis L. at the dosage of 750 g a. i. ha(-1). PMID:26712728

  15. Structural analysis of photodegraded lime wood by means of FT-IR and 2D IR correlation spectroscopy.

    PubMed

    Popescu, Carmen-Mihaela; Popescu, Maria-Cristina; Vasile, Cornelia

    2011-05-01

    In this study the weathering behavior of lime wood (Tillia cordata Mill.) has been examined using FT-IR and 2D IR correlation spectroscopy, which evidenced chemical changes induced by exposure to weathering conditions. It was showed that lignin is most sensitive component to the photodegradation processes as indicated by considerable decreases in the intensities of the characteristic aromatic lignin band at 1505cm(-1) and other associated bands. By 2D correlation spectroscopy has been demonstrated that the moment of CO from carboxyl and acetyl groups in hemicelluloses is changing first, followed by the CC of aromatic skeletal, CO in non-conjugated ketones, carboxyl groups and lactones, absorbed O-H and conjugated C-O groups in quinones. The carbonyl formation corresponded well with lignin degradation, indicating a close relationship between them. Comparing the rate of carbonyl formation and lignin decay clearly showed that the former is remarkably higher than the latter, indicating the formation of carbonyl bands at 1738cm(-1) probably resulted from not only lignin oxidation but also from reactions occurring in other components of the wood. Quinine formation is combined with the decay of aromatic structures and the formation of conjugated carbonyl groups. PMID:21349282

  16. Selective excitation enables assignment of proton resonances and 1H-1H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-01

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of 1H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as 13C or 15N. In this method, after the initial preparation of proton magnetization and cross-polarization to 13C nuclei, transverse magnetization of desired 13C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific 13C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of 1H-1H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

  17. Dynamics-based selective 2D {sup 1}H/{sup 1}H chemical shift correlation spectroscopy under ultrafast MAS conditions

    SciTech Connect

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-05-28

    Dynamics plays important roles in determining the physical, chemical, and functional properties of a variety of chemical and biological materials. However, a material (such as a polymer) generally has mobile and rigid regions in order to have high strength and toughness at the same time. Therefore, it is difficult to measure the role of mobile phase without being affected by the rigid components. Herein, we propose a highly sensitive solid-state NMR approach that utilizes a dipolar-coupling based filter (composed of 12 equally spaced 90° RF pulses) to selectively measure the correlation of {sup 1}H chemical shifts from the mobile regions of a material. It is interesting to find that the rotor-synchronized dipolar filter strength decreases with increasing inter-pulse delay between the 90° pulses, whereas the dipolar filter strength increases with increasing inter-pulse delay under static conditions. In this study, we also demonstrate the unique advantages of proton-detection under ultrafast magic-angle-spinning conditions to enhance the spectral resolution and sensitivity for studies on small molecules as well as multi-phase polymers. Our results further demonstrate the use of finite-pulse radio-frequency driven recoupling pulse sequence to efficiently recouple weak proton-proton dipolar couplings in the dynamic regions of a molecule and to facilitate the fast acquisition of {sup 1}H/{sup 1}H correlation spectrum compared to the traditional 2D NOESY (Nuclear Overhauser effect spectroscopy) experiment. We believe that the proposed approach is beneficial to study mobile components in multi-phase systems, such as block copolymers, polymer blends, nanocomposites, heterogeneous amyloid mixture of oligomers and fibers, and other materials.

  18. Response of ER -IR and ER -IR cells in the forebrain of female rats to mating stimuli

    E-print Network

    Response of ER -IR and ER -IR cells in the forebrain of female rats to mating stimuli Be´atrice Gre -, and mating-induced Fos-immunoreactivity (Fos-ir) in neurons in which mating stimulation reliably increases, or received 15 intromissions. In the rostral medial preoptic area, Fos-ir was induced by mounts alone

  19. Properties of the {pi}h{sub 11/2} band in the stable nucleus {sup 193}Ir

    SciTech Connect

    Fang, Y. D.; Zhang, Y. H.; Zhou, X. H.; Liu, M. L.; Wang, J. G.; Ma, F.; Guo, Y. X.; Fang, F.; Shi, Y.; Xu, F. R.; Gao, B. S.; Wang, S. C.; Li, S. C.; Yan, X. L.; He, L.; Wang, Z. G.; Wu, X. G.; He, C. Y.; Zheng, Y.; Wang, Z. M.

    2011-05-15

    Excited states in the stable nucleus {sup 193}Ir have been investigated through an in-beam {gamma}-ray spectroscopic technique following the {sup 192}Os({sup 7}Li, {alpha}2n) reaction at a beam energy of 44 MeV. A level scheme built on the {pi}h{sub 11/2} isomer has been extended to high-spin states using eleven newly observed {gamma} transitions. The {pi}h{sub 11/2} band is proposed to be formed by coupling an h{sub 11/2} proton to a core with large triaxial deformation. Three-quasiparticle states are suggested in {sup 193}Ir on referring to the similar states in {sup 187}Ir. The features of signature splitting in the {pi}h{sub 11/2} bands of {sup 187-193}Ir are discussed with the help of total Routhian surface calculations.

  20. Fiber Delivery of mid-IR lasers

    SciTech Connect

    Kriesel, J.M.; Gat, N.; Bernacki, Bruce E.; Myers, Tanya L.; Bledt, Carlos M.; Harrington, James P.

    2011-08-24

    Fiber optics for the visible to near infrared (NIR) wavelength regimes (i.e. = 0.42 {mu}m) have proven to be extremely useful for a myriad of applications such as telecommunications, illumination, and sensors because they enable convenient, compact, and remote delivery of laser beams. Similarly, there is a need for fiber optics operating at longer wavelengths. For example, systems operating in the mid-IR regime (i.e., = 314 {mu}m) are being developed to detect trace molecular species with far-reaching applications, such as detecting explosives on surfaces, pollutants in the environment, and biomarkers in the breath of a patient. Furthermore, with the increasing availability of quantum cascade lasers (QCLs) which are semiconductor lasers that operate in the mid-IR regime additional uses are rapidly being developed. Here, we describe the development of hollow-core fibers for delivery of high-quality mid-IR laser beams across a broad spectral range.

  1. IR signature management for the modern navy

    NASA Astrophysics Data System (ADS)

    Vaitekunas, David A.; Kim, Yoonsik

    2013-06-01

    A methodology for analysing the infrared (IR) signature and susceptibility of naval platforms using ShipIR/NTCS was presented by Vaitekunas (2010). This paper provides three key improvements: use of a larger climatic data set (N=100), a new target sub-image algorithm eliminating false detections from pixel-aliasing at the horizon, and a new seeker model interfacing with a line-by-line background clutter model. Existing commercial stealth technologies (exhaust stack suppression, low solar absorptive paints, extended hull film-cooling) are re-analysed using the new models and methods to produce a more rigorous and comprehensive analysis of their effectiveness based on the statistics of reduction in IR susceptibility. These methods and results combined with the cost of each stealth option should allow platform managers to select an appropriate level of infrared suppression and establish the design criteria for a new ship.

  2. Effect of vaccination of cattle with the low virulence Nc-Spain 1H isolate of Neospora caninum against a heterologous challenge in early and mid-gestation

    PubMed Central

    2013-01-01

    Live vaccines have emerged as one of the most potentially cost-effective measures for the control of bovine neosporosis. Previous studies have shown that Nc-Spain 1H is a naturally attenuated isolate of Neospora caninum and that immunisation with live Nc-Spain 1H tachyzoites generated a protective immune response in mice. The aim of this study was to evaluate the safety and efficacy of immunisation in cattle. N. caninum-seronegative heifers were immunised subcutaneously twice with 107 live Nc-Spain 1H tachyzoites prior to artificial insemination. No adverse reactions or negative effects on reproductive parameters were recorded following immunisation. In immunised and non-challenged heifers, no foetal deaths were observed, and none of the calves was congenitally infected. The efficacy against N. caninum-associated foetal death and vertical transmission was determined after challenge with high doses of the Nc-1 isolate at 70 and 135 days of gestation, respectively. After the challenge in early gestation, the immunisation induced a protection of 50% against foetal death. In addition, the microsatellite analysis performed in PCR-positive tissue samples from foetuses that died after challenge infection showed that the profiles corresponded to the challenge isolate Nc-1. A degree of protection against vertical transmission was observed after challenge at mid-gestation; calves from immunised heifers showed significantly lower pre-colostral Neospora-specific antibody titres than calves from the non-immunised/challenge group (P?1H vaccine isolate appeared to be safe and reduced the occurrence of N. caninum-associated abortion and vertical transmission in experimentally infected cattle. In light of these encouraging results, the next step for testing this live attenuated candidate should be the assessment of its efficacy and safety in naturally infected cattle. PMID:24180373

  3. Tunable mid IR plasmon in GZO nanocrystals

    NASA Astrophysics Data System (ADS)

    Hamza, M. K.; Bluet, J.-M.; Masenelli-Varlot, K.; Canut, B.; Boisron, O.; Melinon, P.; Masenelli, B.

    2015-07-01

    Degenerate metal oxide nanoparticles are promising systems to expand the significant achievements of plasmonics into the infrared (IR) range. Among the possible candidates, Ga-doped ZnO nanocrystals are particularly suited for mid IR, considering their wide range of possible doping levels and thus of plasmon tuning. In the present work, we report on the tunable mid IR plasmon induced in degenerate Ga-doped ZnO nanocrystals. The nanocrystals are produced by a plasma expansion and exhibit unprotected surfaces. Tuning the Ga concentration allows tuning the localized surface plasmon resonance. Moreover, the plasmon resonance is characterized by a large damping. By comparing the plasmon of nanocrystal assemblies to that of nanoparticles dispersed in an alumina matrix, we investigate the possible origins of such damping. We demonstrate that it partially results from the self-organization of the naked particles and also from intrinsic inhomogeneity of dopants.Degenerate metal oxide nanoparticles are promising systems to expand the significant achievements of plasmonics into the infrared (IR) range. Among the possible candidates, Ga-doped ZnO nanocrystals are particularly suited for mid IR, considering their wide range of possible doping levels and thus of plasmon tuning. In the present work, we report on the tunable mid IR plasmon induced in degenerate Ga-doped ZnO nanocrystals. The nanocrystals are produced by a plasma expansion and exhibit unprotected surfaces. Tuning the Ga concentration allows tuning the localized surface plasmon resonance. Moreover, the plasmon resonance is characterized by a large damping. By comparing the plasmon of nanocrystal assemblies to that of nanoparticles dispersed in an alumina matrix, we investigate the possible origins of such damping. We demonstrate that it partially results from the self-organization of the naked particles and also from intrinsic inhomogeneity of dopants. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03378k

  4. A flexible Au-Ir cell with quick assembly for hydrothermal experiments

    USGS Publications Warehouse

    Rosenbauer, R.J.; Bischoff, J.L.; Potter, J.M.

    1993-01-01

    The paper describes a new flexible reaction cell for high-temperature and high-pressure experiments in hydrothermal apparatus. The interior of the cell is all Au, except for two inert Ir gaskets. The design features an all Au cap that can be easily and rapidly assembled and disassembled. The capacity of the cell is approximately 240 mL, with a height of 20 cm and an o.d. of 6 cm. -Authors

  5. Compressive sensing in the EO/IR.

    PubMed

    Gehm, M E; Brady, D J

    2015-03-10

    We investigate the utility of compressive sensing (CS) to electro-optic and infrared (EO/IR) applications. We introduce the field through a discussion of historical antecedents and the development of the modern CS framework. Basic economic arguments (in the broadest sense) are presented regarding the applicability of CS to the EO/IR and used to draw conclusions regarding application areas where CS would be most viable. A number of experimental success stories are presented to demonstrate the overall feasibility of the approaches, and we conclude with a discussion of open challenges to practical adoption of CS methods. PMID:25968399

  6. On IR solutions in Horava gravity theories

    E-print Network

    Horatiu Nastase

    2009-04-30

    In this note we search for large distance solutions of Horava gravity. In the case of the "detailed balance" action, gravity solutions asymptote to IR only above the cosmological constant ($\\sim$horizon) scale. However, if one adds IR dominant terms $\\alpha R^{(3)}+\\beta \\Lambda_W$, one can recover general relativity solutions on usual scales in the real Universe, provided one fine-tunes the cosmological constant, reobtaining the usual cosmological constant problem. We comment on pp wave solutions, in order to gain insight into the relativistic properties of the theory.

  7. Interpretation of IR Spectra of Indolinospirobenzothiopyran

    NASA Astrophysics Data System (ADS)

    Gladkov, L. L.; Khamchukov, Yu. D.; Sychev, I. Yu.; Lyubimov, A. V.; Gladkova, G. A.

    2015-09-01

    The structures of four stereomers (enantiomers) of photochromic indolinospirobenzothiopyran (ISTP) in the closed form were studied by the DFT method. The most stable structure was found. IR spectra of ISTP in KBr pellets and as a film on single-crystalline KBr plates (in the region 400-4000 cm -1 ) and as a powder between polyethylene plates (100-400 cm -1 ) were measured. An interpretation of the obtained IR spectra was proposed. Specific features of normal modes of ISTP caused by the presence of the spiro center were revealed.

  8. Planar integrated plasmonic mid-IR spectrometer

    NASA Astrophysics Data System (ADS)

    Figuierdo, P.; Nath, J.; Medhi, G.; Muraviev, A.; Fredricksen, C. J.; Buchwald, W. R.; Cleary, J. W.; Peale, R. E.

    2011-10-01

    Mid-IR spectrometers with adequate resolution for chemical sensing and identification are typically large, heavy, and require sophisticated non-stationary optical components. Such spectrometers are limited to laboratory settings. We propose an alternative based on semiconductor micro-fabrication techniques. The device consists of several enabling parts: a compact broad-band IR source, photonic waveguides, a photon-to-surface-plasmon transformer, a surfaceplasmon sample-interaction region, and an array of silicon ring-resonators and detectors to analyze the spectrum. Design considerations and lessons learned from initial experiments are presented.

  9. Elevated Glutamatergic Compounds in Pregenual Anterior Cingulate in Pediatric Autism Spectrum Disorder Demonstrated by 1H MRS and 1H MRSI

    PubMed Central

    Bejjani, Anthony; O'Neill, Joseph; Kim, John A.; Frew, Andrew J.; Yee, Victor W.; Ly, Ronald; Kitchen, Christina; Salamon, Noriko; McCracken, James T.; Toga, Arthur W.; Alger, Jeffry R.; Levitt, Jennifer G.

    2012-01-01

    Recent research in autism spectrum disorder (ASD) has aroused interest in anterior cingulate cortex and in the neurometabolite glutamate. We report two studies of pregenual anterior cingulate cortex (pACC) in pediatric ASD. First, we acquired in vivo single-voxel proton magnetic resonance spectroscopy (1H MRS) in 8 children with ASD and 10 typically developing controls who were well matched for age, but with fewer males and higher IQ. In the ASD group in midline pACC, we found mean 17.7% elevation of glutamate + glutamine (Glx) (p<0.05) and 21.2% (p<0.001) decrement in creatine + phosphocreatine (Cr). We then performed a larger (26 subjects with ASD, 16 controls) follow-up study in samples now matched for age, gender, and IQ using proton magnetic resonance spectroscopic imaging (1H MRSI). Higher spatial resolution enabled bilateral pACC acquisition. Significant effects were restricted to right pACC where Glx (9.5%, p<0.05), Cr (6.7%, p<0.05), and N-acetyl-aspartate + N-acetyl-aspartyl-glutamate (10.2%, p<0.01) in the ASD sample were elevated above control. These two independent studies suggest hyperglutamatergia and other neurometabolic abnormalities in pACC in ASD, with possible right-lateralization. The hyperglutamatergic state may reflect an imbalance of excitation over inhibition in the brain as proposed in recent neurodevelopmental models of ASD. PMID:22848344

  10. Magnesium silicate dissolution investigated by 29Si MAS, 1H-29Si CPMAS, 25Mg QCPMG, and 1H-25Mg CP QCPMG NMR.

    PubMed

    Davis, Michael C; Brouwer, William J; Wesolowski, David J; Anovitz, Lawrence M; Lipton, Andrew S; Mueller, Karl T

    2009-08-28

    Olivine-(Mg,Fe)(2)SiO(4)-has been the subject of frequent investigation in the earth sciences because of its simple structure and rapid dissolution kinetics. Several studies have observed a preferential release of the divalent cation with respect to silicon during weathering under acidic conditions, which has been correlated to the formation of a silicon-rich leached layer. While leached layer formation has been inferred through the changing solution chemistry, a thorough spectroscopic investigation of olivine reacted under acidic conditions has not been conducted. The pure magnesium end member of the olivine series (forsterite-Mg(2)SiO(4)) was chosen for detailed investigations in this study because paramagnetic iron hinders NMR investigations by providing an extra mode of relaxation for neighboring nuclei, causing lineshapes to become significantly broadened and unobservable in the NMR spectrum. For reacting forsterite, spectroscopic interrogations using nuclear magnetic resonance (NMR) can elucidate the changing magnesium coordination and bonding environment. In this study, we combine analysis of the changing solution chemistry with advanced NMR techniques ((29)Si MAS, (1)H-(29)Si CP MAS, (25)Mg QCPMG, and (1)H-(25)Mg CP QCPMG NMR) to probe leached layer formation and secondary phase precipitation during the dissolution of forsterite at 150 degrees C. PMID:19652836

  11. Molecular orbital calculations of /sup 13/C-/sup 13/C and /sup 1/H-/sup 1/H nuclear spin-spin coupling constants

    SciTech Connect

    Severson, M.L.

    1984-01-01

    Theoretical studies are presented for the conformational dependencies of vicinal /sup 13/C-/sup 13/C coupling constants within a variety of saturated and unsaturated molecular frameworks. Using the molecular orbital approach of Blizzard and Santry, it is shown that three distinct patterns of dihedral angle versus /sup 3/H/sub CC/sup contract/ coupling are produced, depending upon the degree of double bonding present within the direct coupling path. By means of calculations that involve modifying the various exchange integrals, two of these coupling patterns are found to depend on sigma-..pi.. exchange. A rationalization of the origin of these coupling patterns is presented. In all systems studied, the orbital and dipolar contributions to the vicinal coupling constant are calculated to be negligible compared to the Fermi contact mechanism except in conjugated systems. The FP/INDO molecular orbital method is employed in the investigation of substitutent effects on /sup 1/H-/sup 1/H coupling constants in substituted ethanes, ethylenes, and benzenes. Substituent effects are simulated by varying the (1/2)(I + A) INDO parameters on two different types of pseudoatoms, one essentially a pseudo-hydrogen and the other involving 2s and 2p orbitals on two centers. A review of the theory of nuclear spin-spin coupling is presented.

  12. Myocardial Metabolic Abnormality in a Primary Left Atrial Rhabdomyosarcoma: Localized 1H MR Spectroscopy

    PubMed Central

    Kim, Tae Hoon; Jeong, Gwang Woo; Kim, Tae Su; Kim, Yun Hyeon

    2015-01-01

    We report a 73-year-old woman with primary left atrial rhabdomyosarcoma and its 1H MR spectroscopy (MRS) findings. The tumor showed a 2.8 cm sized lesion in the posteroinferior atrial wall on MRI. 1H MR spectra were acquired using a point-resolved spectroscopy (PRESS) sequence with electrocardiographic (ECG) gating and respiratory motion. The use of 1H-MRS allowed the quantification of triglyceride (TG) peak groups at 0.9 and 1.3 ppm, and unsaturated group of lipids at 2.1 ppm, creatine (Cr) at 3.0 ppm, and choline (Cho) at 3.2 ppm. The percentages of the myocardial metabolites based on water-peak in the interventricular septum were TG 18.4%, Cr 1.6%, Cho 3.3% and unsaturated group 4.0%, whereas the rhabdomyosarcoma showed TG 118.8%, unsaturated group 5.1%, Cr 1.3%, Cho 3.5% and the olefinic components of fatty acid at 5.4 ppm 24.5%. This case demonstrates that 1H-MRS is potentially useful to diagnose the rhabdomyosarcoma by quantifying the myocardial metabolites which are important biomarkers for heart function and diseases. PMID:26557276

  13. Bulk magnetization and 1H NMR spectra of magnetically heterogeneous model systems

    SciTech Connect

    Levin, E. M.; Bud' ko, S. L.

    2011-04-28

    Bulk magnetization and {sup 1}H static and magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of two magnetically heterogeneous model systems based on laponite (LAP) layered silicate or polystyrene (PS) with low and high proton concentration, respectively, and ferrimagnetic Fe{sub 2}O{sub 3} nano- or micro-particles have been studied. In LAP+Fe{sub 2}O{sub 3}, a major contribution to the NMR signal broadening is due to the dipolar coupling between the magnetic moments of protons and magnetic particles. In PS+Fe{sub 2}O{sub 3}, due to the higher proton concentration in polystyrene and stronger proton–proton dipolar coupling, an additional broadening is observed, i.e. {sup 1}H MAS NMR spectra of magnetically heterogeneous systems are sensitive to both proton–magnetic particles and proton–proton dipolar couplings. An increase of the volume magnetization by ?1 emu/cm{sup 3} affects the {sup 1}H NMR signal width in a way that is similar to an increase of the proton concentration by ?2×10{sup 22}/cm{sup 3}. {sup 1}H MAS NMR spectra, along with bulk magnetization measurements, allow the accurate determination of the hydrogen concentration in magnetically heterogeneous systems.

  14. 1 H-1B Dept Questionnaire.docx; Jan 2012 INTERNATIONAL SERVICES OFFICE UNIVERSITY OF ROCHESTER

    E-print Network

    Cantlon, Jessica F.

    ;2 H-1B Dept Questionnaire.docx; Jan 2012 9. Does the H-1B employee possess sufficient proficiency, and the job being performed by the foreign national. H- 1B work authorization is granted by USCIS1 H-1B Dept Questionnaire.docx; Jan 2012 INTERNATIONAL SERVICES OFFICE UNIVERSITY OF ROCHESTER 213

  15. Dihydride chain formation on a Si(1 0 0)-2 × 1-H surface

    NASA Astrophysics Data System (ADS)

    Fujimori, Masaaki; Suwa, Yuji; Heike, Seiji; Terada, Yasuhiko; Hashizume, Tomihiro

    2004-10-01

    Characteristic dihydride chain formation was observed on a Si(1 0 0)-2 × 1-H surface. The dihydride chains are formed only at SB step edges and are accompanied with a structure transformation from a rebonded to non-rebonded structure at the edges. The mechanism of the dihydride chain migration is suggested based on experimental observations and theoretical calculations.

  16. Transversity and Collins Functions: from e+ e- --> h1 h2 X to SIDIS Processes

    E-print Network

    M. Anselmino; M. Boglione; U. D'Alesio; A. Kotzinian; F. Murgia; A. Prokudin; C. Turk

    2007-07-09

    We present [1] the first simultaneous extraction of the transversity distribution and the Collins fragmentation function, obtained through a combined analysis of experimental data on azimuthal asymmetries in semi-inclusive deep inelastic scattering (SIDIS), from the HERMES and COMPASS Collaborations, and in e+ e- --> h1 h2 X processes, from the Belle Collaboration.

  17. Mutation screen reveals novel variants and expands the phenotypes associated with DYNC1H1.

    PubMed

    Strickland, Alleene V; Schabhüttl, Maria; Offenbacher, Hans; Synofzik, Matthis; Hauser, Natalie S; Brunner-Krainz, Michaela; Gruber-Sedlmayr, Ursula; Moore, Steven A; Windhager, Reinhard; Bender, Benjamin; Harms, Matthew; Klebe, Stephan; Young, Peter; Kennerson, Marina; Garcia, Avencia Sanchez Mejias; Gonzalez, Michael A; Züchner, Stephan; Schule, Rebecca; Shy, Michael E; Auer-Grumbach, Michaela

    2015-09-01

    Dynein, cytoplasmic 1, heavy chain 1 (DYNC1H1) encodes a necessary subunit of the cytoplasmic dynein complex, which traffics cargo along microtubules. Dominant DYNC1H1 mutations are implicated in neural diseases, including spinal muscular atrophy with lower extremity dominance (SMA-LED), intellectual disability with neuronal migration defects, malformations of cortical development, and Charcot-Marie-Tooth disease, type 2O. We hypothesized that additional variants could be found in these and novel motoneuron and related diseases. Therefore, we analyzed our database of 1024 whole exome sequencing samples of motoneuron and related diseases for novel single nucleotide variations. We filtered these results for significant variants, which were further screened using segregation analysis in available family members. Analysis revealed six novel, rare, and highly conserved variants. Three of these are likely pathogenic and encompass a broad phenotypic spectrum with distinct disease clusters. Our findings suggest that DYNC1H1 variants can cause not only lower, but also upper motor neuron disease. It thus adds DYNC1H1 to the growing list of spastic paraplegia related genes in microtubule-dependent motor protein pathways. PMID:26100331

  18. Synthesis of stereospecifically deuterated desoxypodophyllotoxins and 1H-nmr assignment of desoxypodophyllotoxin

    NASA Technical Reports Server (NTRS)

    Pullockaran, A. J.; Kingston, D. G.; Lewis, N. G.

    1989-01-01

    [4 beta- 2H1]Desoxypodophyllotoxin [3], [4 alpha- 2H1]desoxypodophyllotoxin [4], and [4, 4- 2 H2]desoxypodophyllotoxin [9] were prepared from podophyllotoxin [1] via its chloride [5]. A complete assignment of the 1H-nmr spectrum of desoxypodophyllotoxin [2] was made on the basis of the spectra of the deuterated compounds [3] and [4].

  19. Molecular Structures from [superscript 1]H NMR Spectra: Education Aided by Internet Programs

    ERIC Educational Resources Information Center

    Debska, Barbara; Guzowska-Swider, Barbara

    2007-01-01

    The article presents the way in which freeware Internet programs can be applied to teach [superscript 1]H NMR spectroscopy. The computer programs described in this article are part of the educational curriculum that explores spectroscopy and spectra interpretation. (Contains 6 figures.)

  20. Happenings Fall 2012 1 H A P P E N I N G S

    E-print Network

    Dudek, Daniel M.

    engineering science/ engineering physics programs places us fifth in the nation in a list that includes peerHappenings Fall 2012 1 H A P P E N I N G S Engineering Science and Mechanics ESM GRADUATE PROGRAM..................................................................................14 Scholarships and Graduate Degrees..............................18 Staff News

  1. Aminosilanes derived from 1H-benzimidazole-2(3H)-thione

    SciTech Connect

    Palomo-Molina, Juliana; García-Báez, Efrén V.; Pineda-Urbina, Kayim; Ramos-Organillo, Angel

    2015-08-12

    In two trimethylsilyl-substituted 1H-benzimidazole-2(3H)-thiones, noncovalent C—H?? interactions between the centroid of the benzmidazole system and the SiMe{sub 3} groups form helicoidal arrangements in one, and dimerization results in the formation of R{sub s} {sup 2}(8) rings via N—H?S interactions, along with parallel ?–? interactions between imidazole and benzene rings, in the second compound. Two new molecular structures, namely 1,3-bis(trimethylsilyl)-1H-benzimidazole-2(3H)-thione, C{sub 13}H{sub 22}N{sub 2}SSi{sub 2}, (2), and 1-trimethylsilyl-1H-benzimidazole-2(3H)-thione, C{sub 10}H{sub 14}N{sub 2}SSi, (3), are reported. Both systems were derived from 1H-benzimidazole-2(3H)-thione. Noncovalent C—H?? interactions between the centroid of the benzmidazole system and the SiMe{sub 3} groups form helicoidal arrangements in (2). Dimerization of (3) results in the formation of R{sub 2}{sup 2}(8) rings via N—H?S interactions, along with parallel ?–? interactions between imidazole and benzene rings.

  2. NMR resonance splitting of urea in stretched hydrogels: Proton exchange and 1H/2H isotopologues

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

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

  3. The identification and stereochemical study of tetracycline antibiotics by 1H nuclear magnetic resonance spectroscopy.

    PubMed

    Casy, A F; Yasin, A

    1983-01-01

    The 1H NMR spectra of seven tetracycline antibiotics of clinical importance are reported and assigned as solutes in DMSO-d6 and other solvents. The data are analysed in terms of analytical utility and the provision of evidence of solute stereochemistry. PMID:16867798

  4. GPS Time Synchronization System for K2K1 H. G. Berns and R. J. Wilkes

    E-print Network

    Berns, Hans-Gerd

    GPS Time Synchronization System for K2K1 H. G. Berns and R. J. Wilkes Department of Physics System (GPS) provides a means for satisfying this requirement at very low cost. In addition to low- resolution time data (day of year, hour, minute, second), commercial GPS receivers output a 1 pulse per sec

  5. GPS Time Synchronization System for K2K 1 H. G. Berns and R. J. Wilkes

    E-print Network

    Berns, Hans-Gerd

    GPS Time Synchronization System for K2K 1 H. G. Berns and R. J. Wilkes Department of Physics System (GPS) provides a means for satisfying this requirement at very low cost. In addition to low­resolution time data (day of year, hour, minute, second), commercial GPS receivers output a 1 pulse per sec (1PPS

  6. Structural and computational features of four highly polar quinolin-2(1H)-ylidene derivatives: Equilibrium preference for enaminothione, enamine, and enaminone tautomeric structures

    NASA Astrophysics Data System (ADS)

    Nesterov, Volodymyr V.; Yang, Li; Nesterov, Vladimir N.; Richmond, Michael G.

    2013-12-01

    The coupling of the active methylene compounds 2-cyanothioacetamide, malononitrile, and ethyl cyanoacetate with quinoline-N-oxide and 6-methoxyquinoline-N-oxide has been investigated, and the compounds (2Z)-2-cyano-2-quinolin-2(1H)-ylidene-ethanethioamide (1a), 6-methoxyquinolin-2(1H)-ylidene-propanedinitrile (1b), ethyl (2Z)-cyano-6-methoxyquinolin-2(1H)-ylidene-ethanoate (1c), and (2Z)-2-cyano-2-(6-methoxyquinolin)-2(1H)-ylidene-ethanethioamide (1d) have been isolated. Compounds 1a-d have been characterized by a combination of IR and NMR spectroscopies, combustion and X-ray diffraction analyses. The solid-state structure of each molecule is found to be almost planar and contains a hydrogen atom attached to the quinoline nitrogen. The observed pattern of exocyclic bond lengths signifies the existence of strong conjugation between quinoline fragment and the electron-withdrawing substituent situated at C-1. The CS bond distance of 1.708(1) and 1.704(1) Å in 1a and 1d, respectively, is intermediate in length between CS and CS bond distances. The CO bond distance in 1c displays a similar elongation [1.237(2) Å] relative to the CO bond distance in non-conjugated organic carbonyl compounds. All four structures exhibit an exocyclic CC bond between the heterocycle and the electron-withdrawing substituent that is elongated to 1.400 Å, a feature consistent with significant CC bond contribution. Strong intramolecular H-bonds in 1a, 1c, and 1d help promote molecular conjugation of the heterocycle and exocyclic appendage defined by the atoms HNCCCS/O into flat six-membered rings. In the crystals of 1a and 1b, the molecules are aligned in head-to-head stacks, while in the crystalline lattice of 1c and 1d the molecules exhibit a motif involving head-to-tail stacks. Intermolecular H-bonds link molecules 1a, 1b, and 1d into centrosymmetric dimers, while in the crystal of 1c weak intermolecular CH⋯N H-bonds orient molecules into zigzag chains. The bonding in 1a-d has been examined by electronic structure calculations, and these data are discussed with respect to the X-ray diffraction structures and the equilibrium preference for the enaminothione (1a and 1d), enamine (1b), and enaminone (1c) tautomers.

  7. Mechanism of Efficient Anti-Markovnikov Olefin Hydroarylation Catalyzed by Homogeneous Ir(III) Complexes

    SciTech Connect

    Bhalla, Gaurav; Bischof, Steven M; Ganesh, Somesh K; Liu, Xiang Y; Jones, C J; Borzenko, Andrey; Tenn, William J; Ess, Daniel H; Hashiguchi, Brian G; Lokare, Kapil S; Leung, Chin Hin; Oxgaard, Jonas; Goddard, William A; Periana, Roy A

    2011-01-01

    The mechanism of the hydroarylation reaction between unactivated olefins (ethylene, propylene, and styrene) and benzene catalyzed by [(R)Ir(?-acac-O,O,C{sup 3})-(acac-O,O){sub 2}]{sub 2} and [R-Ir(acac-O,O){sub 2}(L)] (R = acetylacetonato, CH{sub 3}, CH{sub 2}CH{sub 3}, Ph, or CH{sub 2}CH{sub 2}Ph, and L = H{sub 2}O or pyridine) Ir(III) complexes was studied by experimental methods. The system is selective for generating the anti-Markovnikov product of linear alkylarenes (61:39 for benzene + propylene and 98:2 for benzene + styrene). The reaction mechanism was found to follow a rate law with first-order dependence on benzene and catalyst, but a non-linear dependence on olefin. {sup 13}C-labelling studies with CH{sub 3}{sup 13}CH{sub 2}-Ir-Py showed that reversible ?-hydride elimination is facile, but unproductive, giving exclusively saturated alkylarene products. The migration of the {sup 13}C-label from the ? to ?-positions was found to be slower than the C–H activation of benzene (and thus formation of ethane and Ph-d{sub 5}-Ir-Py). Kinetic analysis under steady state conditions gave a ratio of the rate constants for CH activation and ?-hydride elimination (k{sub CH}: k{sub ?}) of ~0.5. The comparable magnitude of these rates suggests a common rate determining transition state/intermediate, which has been shown previously with B3LYP density functional theory (DFT) calculations. Overall, the mechanism of hydroarylation proceeds through a series of pre-equilibrium dissociative steps involving rupture of the dinuclear species or the loss of L from Ph-Ir-L to the solvento, 16-electron species, Ph-Ir(acac-O,O){sub 2}-Sol (where Sol refers to coordinated solvent). This species then undergoes trans to cisisomerization of the acetylacetonato ligand to yield the pseudo octahedral species cis-Ph-Ir-Sol, which is followed by olefin insertion (the regioselective and rate determining step), and then activation of the C–H bond of an incoming benzene to generate the product and regenerate the catalyst.

  8. MTR and In-vivo 1H-MRS studies on mouse brain with parkinson's disease

    NASA Astrophysics Data System (ADS)

    Yoon, Moon-Hyun; Kim, Hyeon-Jin; Chung, Jin-Yeung; Doo, Ah-Reum; Park, Hi-Joon; Kim, Seung-Nam; Choe, Bo-Young

    2012-12-01

    The aim of this study was to investigate whether the changes in the magnetization transfer ratio (MTR) histogram are related to specific characteristics of Parkinson's disease (PD) and to investigate whether the MTR histogram parameters are associated with neurochemical dysfunction by performing in vivo proton magnetic resonance spectroscopy (1H-MRS). MTR and in vivo 1H-MRS studies were performed on control mice (n = 10) and 1-methyl-1,2,3,6-tetrahydropyridine intoxicated mice (n = 10). All the MTR and in vivo 1H-MRS experiments were performed on a 9.4 T MRI/MRS system (Bruker Biospin, Germany) using a standard head coil. The protondensity fast spin echo (FSE) images and the T2-weighted spin echo (SE) images were acquired with no gap. Outer volume suppression (OVS), combined with the ultra-short echo-time stimulated echo acquisition mode (STEAM), was used for the localized in-vivo 1H-MRS. The quantitative analysis of metabolites was performed from the 1H spectra obtained in vivo on the striatum (ST) by using jMRUI (Lyon, France). The peak height of the MTR histograms in the PD model group was significantly lower than that in the control group (p < 0.05). The midbrain MTR values for volume were lower in the PD group than the control group(p < 0.05). The complex peak (Glx: glutamine+glutamate+ GABA)/creatine (Cr) ratio of the right ST in the PD group was significantly increased as compared to that of the control group. The present study revealed that the peak height of the MTR histogram was significantly decreased in the ST and substantia nigra, and a significant increase in the Gl x /Cr ratio was found in the ST of the PD group, as compared with that of the control group. These findings could reflect the early phase of neuronal dysfunction of neurotransmitters.

  9. Novel mutations expand the clinical spectrum of DYNC1H1-associated spinal muscular atrophy

    PubMed Central

    Scoto, Mariacristina; Rossor, Alexander M.; Harms, Matthew B.; Cirak, Sebahattin; Calissano, Mattia; Robb, Stephanie; Manzur, Adnan Y.; Martínez Arroyo, Amaia; Rodriguez Sanz, Aida; Mansour, Sahar; Fallon, Penny; Hadjikoumi, Irene; Klein, Andrea; Yang, Michele; De Visser, Marianne; Overweg-Plandsoen, W.C.G. (Truus); Baas, Frank; Taylor, J. Paul; Benatar, Michael; Connolly, Anne M.; Al-Lozi, Muhammad T.; Nixon, John; de Goede, Christian G.E.L.; Foley, A. Reghan; Mcwilliam, Catherine; Pitt, Matthew; Sewry, Caroline; Phadke, Rahul; Hafezparast, Majid; Chong, W.K. “Kling”; Mercuri, Eugenio; Baloh, Robert H.; Reilly, Mary M.

    2015-01-01

    Objective: To expand the clinical phenotype of autosomal dominant congenital spinal muscular atrophy with lower extremity predominance (SMA-LED) due to mutations in the dynein, cytoplasmic 1, heavy chain 1 (DYNC1H1) gene. Methods: Patients with a phenotype suggestive of a motor, non–length-dependent neuronopathy predominantly affecting the lower limbs were identified at participating neuromuscular centers and referred for targeted sequencing of DYNC1H1. Results: We report a cohort of 30 cases of SMA-LED from 16 families, carrying mutations in the tail and motor domains of DYNC1H1, including 10 novel mutations. These patients are characterized by congenital or childhood-onset lower limb wasting and weakness frequently associated with cognitive impairment. The clinical severity is variable, ranging from generalized arthrogryposis and inability to ambulate to exclusive and mild lower limb weakness. In many individuals with cognitive impairment (9/30 had cognitive impairment) who underwent brain MRI, there was an underlying structural malformation resulting in polymicrogyric appearance. The lower limb muscle MRI shows a distinctive pattern suggestive of denervation characterized by sparing and relative hypertrophy of the adductor longus and semitendinosus muscles at the thigh level, and diffuse involvement with relative sparing of the anterior-medial muscles at the calf level. Proximal muscle histopathology did not always show classic neurogenic features. Conclusion: Our report expands the clinical spectrum of DYNC1H1-related SMA-LED to include generalized arthrogryposis. In addition, we report that the neurogenic peripheral pathology and the CNS neuronal migration defects are often associated, reinforcing the importance of DYNC1H1 in both central and peripheral neuronal functions. PMID:25609763

  10. Mutations in the tail domain of DYNC1H1 cause dominant spinal muscular atrophy

    PubMed Central

    Harms, M.B.; Ori-McKenney, K.M.; Scoto, M.; Tuck, E.P.; Bell, S.; Ma, D.; Masi, S.; Allred, P.; Al-Lozi, M.; Reilly, M.M.; Miller, L.J.; Jani-Acsadi, A.; Pestronk, A.; Shy, M.E.; Muntoni, F.; Vallee, R.B.

    2012-01-01

    Objective: To identify the gene responsible for 14q32-linked dominant spinal muscular atrophy with lower extremity predominance (SMA-LED, OMIM 158600). Methods: Target exon capture and next generation sequencing was used to analyze the 73 genes in the 14q32 linkage interval in 3 SMA-LED family members. Candidate gene sequencing in additional dominant SMA families used PCR and pooled target capture methods. Patient fibroblasts were biochemically analyzed. Results: Regional exome sequencing of all candidate genes in the 14q32 interval in the original SMA-LED family identified only one missense mutation that segregated with disease state—a mutation in the tail domain of DYNC1H1 (I584L). Sequencing of DYNC1H1 in 32 additional probands with lower extremity predominant SMA found 2 additional heterozygous tail domain mutations (K671E and Y970C), confirming that multiple different mutations in the same domain can cause a similar phenotype. Biochemical analysis of dynein purified from patient-derived fibroblasts demonstrated that the I584L mutation dominantly disrupted dynein complex stability and function. Conclusions: We demonstrate that mutations in the tail domain of the heavy chain of cytoplasmic dynein (DYNC1H1) cause spinal muscular atrophy and provide experimental evidence that a human DYNC1H1 mutation disrupts dynein complex assembly and function. DYNC1H1 mutations were recently found in a family with Charcot-Marie-Tooth disease (type 2O) and in a child with mental retardation. Both of these phenotypes show partial overlap with the spinal muscular atrophy patients described here, indicating that dynein dysfunction is associated with a range of phenotypes in humans involving neuronal development and maintenance. PMID:22459677

  11. 1H Magnetic Resonance Spectroscopy Predicts Hepatocellular Carcinoma in a Subset of Patients With Liver Cirrhosis

    PubMed Central

    Wang, Dan; Li, Yuehua

    2015-01-01

    Abstract The goal of this study was to investigate the utility of 1H magnetic resonance spectroscopy (1H-MRS) to quantify the differences in liver metabolites. Magnetic resonance spectroscopy was used as a means of predicting the probability of developing hepatocellular carcinoma (HCC) in patients with liver cirrhosis secondary to chronic hepatitis B. This study included 20 healthy volunteers, 20 patients with liver cirrhosis secondary to chronic hepatitis B (cirrhosis group), and 20 patients with small HCC secondary to cirrhosis liver parenchyma (HCC group). All patients underwent routine MRI and 1H-MRS scanning. LCModel software was used to quantify Cho (Choline), Lip (lipid), and Cho/Lip in the 3 groups, and a one-way ANOVA was used to compare the differences in these metabolites between groups. Choline levels were significantly different between the control and HCC group and between the cirrhosis group and the HCC group (all P?1H-MRS followed by the analysis with LCModel can be used to measure changes in hepatic metabolite levels in patients with liver cirrhosis secondary to chronic hepatitis B and HCC. Thus, 1H-MRS may be helpful in monitoring HCC and liver cirrhosis development. PMID:26166077

  12. Knoevenagel Reaction of Unprotected Sugars

    NASA Astrophysics Data System (ADS)

    Scherrmann, Marie-Christine

    The Knoevenagel reaction of unprotected sugars was investigated in the 1950s using zinc chloride as promoter. The so-called Garcia Gonzalez reaction had been almost forgotten for 50 years, until the emergence of new water tolerant catalysts having Lewis acid behavior. The reaction was thus reinvestigated and optimal conditions have been found to prepare trihydroxylated furan derivatives from pentose or ?-tetrahydrofuranylfuran from hexoses with non-cyclic ?-keto ester or ?-diketones. Other valuable compounds such as ?-linked tetrahydrobenzofuranyl glycosides or hydroxyalkyl-3,3,6,6,-tetramethyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione can be obtained using cyclic ?-dicarbonylic derivatives. Apart from one report in the 1950s, the Knoevenagel reaction of unprotected carbohydrate in basic condition has been studied only in the mid-1980s to prepare C-glycosyl barbiturates from barbituric acids and, later on, from non-cyclic ?-diketones, ?-C-glycosidic ketones. The efficient method exploited to prepare such compounds has found an industrial development in cosmetics.

  13. Rapamycin reverses insulin resistance (IR) in high-glucose medium without causing IR in normoglycemic medium.

    PubMed

    Leontieva, O V; Demidenko, Z N; Blagosklonny, M V

    2014-01-01

    Mammalian target of rapamycin (mTOR) is involved in insulin resistance (IR) and diabetic retinopathy. In retinal pigment epithelial (RPE) cells, insulin activates the mTOR pathway, inducing hypoxia-inducible factor-1? (HIF-1?) and HIF-dependent transcription in serum-free minimum essential medium Eagle (MEM). Serendipitously, we found that insulin failed to induce the HIF-1?-dependent response, when RPE cells were cultured in Dulbecco's modification of Eagle's medium (DMEM). Whereas concentration of glucose in MEM corresponds to normal glucose levels in blood (5.5 mM), its concentration in DMEM corresponds to severe diabetic hyperglycemia (25 mM). Addition of glucose to MEM also caused IR. Glucose-mediated IR was characterized by basal activation of mTORC1 and its poor inducibility by insulin. Basal levels of phosphorylated S6 kinase (S6K), S6 and insulin receptor substrate 1 (IRS1) S635/639 were high, whereas their inducibilities were decreased. Insulin-induced Akt phosphorylation was decreased and restored by rapamycin and an inhibitor of S6K. IR was associated with de-phosphorylation of IRS1 at S1011, which was reversed by rapamycin. Both short (16-40 h) and chronic (2 weeks) treatment with rapamycin reversed IR. Furthermore, rapamycin did not impair Akt activation in RPE cells cultured in normoglycemic media. In contrast, Torin 1 blocked Akt activation by insulin. We conclude that by activating mTOR/S6K glucose causes feedback IR, preventable by rapamycin. Rapamycin does not cause IR in RPE cells regardless of the duration of treatment. We confirmed that rapamycin also did not impair phosphorylation of Akt at T308 and S473 in normal myoblast C2C12 cells. Our work provides insights in glucose-induced IR and suggests therapeutic approaches to treat patients with IR and severe hyperglycemia and to prevent diabetic complications such as retinopathy. Also our results prompt to reconsider physiological relevance of numerous data and paradigms on IR given that most cell lines are cultured with grossly super-physiological levels of glucose. PMID:24810050

  14. LONG ISLAND SOUND STUDY 2002 CCMP IR

    EPA Science Inventory

    The Long Island Sound Study Implementation Review (IR) summarizes the progress and challenges ahead for the for the Long Island Sound Study (LISS) through examination of it activities in relation to the CCMP. The LISS CCMP identified six major areas requiring management action: 1...

  15. IR-4 Ornamental Horticulture Program Trial Report

    E-print Network

    Lieth, J. Heinrich

    was conducted first for the initial period indicated in the protocol. With cut-flower roses any impact impact branching, to determine if the branches are of suitable quality to serve as cut- flowers. Thus 10, representing information on the subsequent flush of flowers. #12;IR-4 Ornamental Horticulture

  16. IR laser-induced protein crystal transformation

    PubMed Central

    Kiefersauer, Reiner; Grandl, Brigitte; Krapp, Stephan; Huber, Robert

    2014-01-01

    A method and the design of instrumentation, and its preliminary practical realisation, including test experiments, with the object of inducing phase changes of biomolecular crystals by controlled dehydration through heating with infrared (IR) light are described. The aim is to generate and select crystalline phases through transformation in the solid state which have improved order (higher resolution in X-ray diffraction experiments) and reduced mosaic spread (more uniformly aligned mosaic blocks) for diffraction data collection and analysis. The crystal is heated by pulsed and/or constant IR laser irradiation. Loss of crystal water following heating and its reabsorption through equilibration with the environment is measured optically by a video system. Heating proved superior to traditional controlled dehydration by humidity change for the test cases CODH (carbon monoxide dehydrogenase) and CLK2 (a protein kinase). Heating with IR light is experimentally simple and offers an exploration of a much broader parameter space than the traditional method, as it allows the option of varying the rate of phase changes through modification of the IR pulse strength, width and repeat frequency. It impacts the crystal instantaneously, isotropically and homogeneously, and is therefore expected to cause less mechanical stress. PMID:24816092

  17. Wide-angle conformal IR transceiver

    NASA Astrophysics Data System (ADS)

    Liepmann, Till W.; Randall, Michael R.; Shapiro, Alan R.

    1993-08-01

    Accessing a large field-of-regard (FOR) from an aircraft-mounted infrared system imposes significant structural and aerodynamic penalties. A novel conformal infrared (IR) transceiver concept is presented which is currently under development. A trial design of this concept can access a 160 deg FOR without a gimbal mirror or 'fish eye' lens. A fiber optic bundle is used to allow a wide range of beamsteering technologies with small steering angles (i.e., +/- 5 degree(s)) to access the large FOR (+/- 80 deg) through a single, conformal aperture. The output lens size is less than a factor of three times larger than the input/output IR beam, yet provides near diffraction limited polychromatic collimation over the full FOR. The concept is applicable over a wide spectral band (ultraviolet to far IR), however, it is being developed for the mid-IR (2 - 6 micron) band. The challenging technical aspects of the fiber optics in this spectral band are discussed.

  18. Optimal Mixture Models in IR Victor Lavrenko

    E-print Network

    Edinburgh, University of

    Optimal Mixture Models in IR Victor Lavrenko Center for Intelligent Information Retrieval. We explore the use of Optimal Mixture Models to represent topics. We analyze two broad classes of mixture models: set-based and weighted. We provide an original proof that estimation of set-based models

  19. IR laser-induced protein crystal transformation

    SciTech Connect

    Kiefersauer, Reiner Grandl, Brigitte; Krapp, Stephan; Huber, Robert

    2014-05-01

    A novel method and the associated instrumentation for improving crystalline order (higher resolution of X-ray diffraction and reduced mosaicity) of protein crystals by precisely controlled heating is demonstrated. Crystal transformation is optically controlled by a video system. A method and the design of instrumentation, and its preliminary practical realisation, including test experiments, with the object of inducing phase changes of biomolecular crystals by controlled dehydration through heating with infrared (IR) light are described. The aim is to generate and select crystalline phases through transformation in the solid state which have improved order (higher resolution in X-ray diffraction experiments) and reduced mosaic spread (more uniformly aligned mosaic blocks) for diffraction data collection and analysis. The crystal is heated by pulsed and/or constant IR laser irradiation. Loss of crystal water following heating and its reabsorption through equilibration with the environment is measured optically by a video system. Heating proved superior to traditional controlled dehydration by humidity change for the test cases CODH (carbon monoxide dehydrogenase) and CLK2 (a protein kinase). Heating with IR light is experimentally simple and offers an exploration of a much broader parameter space than the traditional method, as it allows the option of varying the rate of phase changes through modification of the IR pulse strength, width and repeat frequency. It impacts the crystal instantaneously, isotropically and homogeneously, and is therefore expected to cause less mechanical stress.

  20. MID-IR IMAGING OF NATURAL FIBERS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fourier Transform Mid-IR microspectroscopy has been used to identify compounds in various tissues of bio-based fibers. Mapping techniques have provided the location of specific components within the cell walls and interstitial spaces of tissues and identified compounds removed during the retting of...

  1. Panel discussion: The future of IR astronomy

    NASA Technical Reports Server (NTRS)

    Caroff, Lawrence J.

    1995-01-01

    A panel discussion was held on the future of IR astronomy. The chairman gave a brief introduction to current planned programs for NASA and other space agencies, followed by short contributions from the six panel members on a variety of special topics. After that, a short question and answer session was held.

  2. Gas-Phase IR Spectroscopy of Nucleobases.

    PubMed

    de Vries, Mattanjah S

    2015-01-01

    IR spectroscopy of nucleobases in the gas phase reflects simultaneous advances in both experimental and computational techniques. Important properties, such as excited state dynamics, depend in subtle ways on structure variations, which can be followed by their infrared signatures. Isomer specific spectroscopy is a particularly powerful tool for studying the effects of nucleobase tautomeric form and base pair hydrogen-bonding patterns. PMID:25663555

  3. IR-4 Ornamental Horticulture Program Trial Report

    E-print Network

    Lieth, J. Heinrich

    (s): 25887 (Cyclanilide), 25888 (Fascination), 25891 (MaxCel) and 25893 (ProVide) 1 Project Title: Efficacy and Phytotoxicity of Cyclanilide, Fascination, MaxCel and Provide for Increased Branching of Hydrangea (Hydrangea macrophylla `Angel Robe') IR4 PR#: 25887 (Cyclanilide), 25888 (Fascination), 25891 (MaxCel) and 25893 (Pro

  4. IR sensors and imagers in networked operations

    NASA Astrophysics Data System (ADS)

    Breiter, Rainer; Cabanski, Wolfgang

    2005-05-01

    "Network-centric Warfare" is a common slogan describing an overall concept of networked operation of sensors, information and weapons to gain command and control superiority. Referring to IR sensors, integration and fusion of different channels like day/night or SAR images or the ability to spread image data among various users are typical requirements. Looking for concrete implementations the German Army future infantryman IdZ is an example where a group of ten soldiers build a unit with every soldier equipped with a personal digital assistant (PDA) for information display, day photo camera and a high performance thermal imager for every unit. The challenge to allow networked operation among such a unit is bringing information together and distribution over a capable network. So also AIM's thermal reconnaissance and targeting sight HuntIR which was selected for the IdZ program provides this capabilities by an optional wireless interface. Besides the global approach of Network-centric Warfare network technology can also be an interesting solution for digital image data distribution and signal processing behind the FPA replacing analog video networks or specific point to point interfaces. The resulting architecture can provide capabilities of data fusion from e.g. IR dual-band or IR multicolor sensors. AIM has participated in a German/UK collaboration program to produce a demonstrator for day/IR video distribution via Gigabit Ethernet for vehicle applications. In this study Ethernet technology was chosen for network implementation and a set of electronics was developed for capturing video data of IR and day imagers and Gigabit Ethernet video distribution. The demonstrator setup follows the requirements of current and future vehicles having a set of day and night imager cameras and a crew station with several members. Replacing the analog video path by a digital video network also makes it easy to implement embedded training by simply feeding the network with simulation data. The paper addresses the special capabilities, requirements and design considerations of IR sensors and imagers in applications like thermal weapon sights and UAVs for networked operating infantry forces.

  5. NMR profiling of biomolecules at natural abundance using 2D 1H-15N and 1H-13C multiplicity-separated (MS) HSQC spectra

    NASA Astrophysics Data System (ADS)

    Chen, Kang; Freedberg, Darón I.; Keire, David A.

    2015-02-01

    2D NMR 1H-X (X = 15N or 13C) HSQC spectra contain cross-peaks for all XHn moieties. Multiplicity-edited1H-13C HSQC pulse sequences generate opposite signs between peaks of CH2 and CH/CH3 at a cost of lower signal-to-noise due to the 13C T2 relaxation during an additional 1/1JCH period. Such CHn-editing experiments are useful in assignment of chemical shifts and have been successfully applied to small molecules and small proteins (e.g. ubiquitin) dissolved in deuterated solvents where, generally, peak overlap is minimal. By contrast, for larger biomolecules, peak overlap in 2D HSQC spectra is unavoidable and peaks with opposite phases cancel each other out in the edited spectra. However, there is an increasing need for using NMR to profile biomolecules at natural abundance dissolved in water (e.g., protein therapeutics) where NMR experiments beyond 2D are impractical. Therefore, the existing 2D multiplicity-edited HSQC methods must be improved to acquire data on nuclei other than 13C (i.e.15N), to resolve more peaks, to reduce T2 losses and to accommodate water suppression approaches. To meet these needs, a multiplicity-separated1H-X HSQC (MS-HSQC) experiment was developed and tested on 500 and 700 MHz NMR spectrometers equipped with room temperature probes using RNase A (14 kDa) and retroviral capsid (26 kDa) proteins dissolved in 95% H2O/5% D2O. In this pulse sequence, the 1/1JXH editing-period is incorporated into the semi-constant time (semi-CT) X resonance chemical shift evolution period, which increases sensitivity, and importantly, the sum and the difference of the interleaved 1JXH-active and the 1JXH-inactive HSQC experiments yield two separate spectra for XH2 and XH/XH3. Furthermore we demonstrate improved water suppression using triple xyz-gradients instead of the more widely used z-gradient only water-suppression approach.

  6. Tax-deferred annuity plans: meeting the IRS audit challenge.

    PubMed

    Schussler, M

    1997-01-01

    A growing number of nonprofit organizations are being fined for violations of IRS regulations following IRS audits of their tax-deferred annuity (TDA) plans. To ensure that their organizations can withstand the scrutiny of an IRS audit, TDA plan administrators must ensure that plans meet IRS regulations and be prepared for IRS audits. Documentation--particularly of the TDA plan itself, and procedures related to salary reduction programs, compensation limits, excess deferrals and other excess contributions, loans, and distributions--must be comprehensive and in compliance with IRS regulations. PMID:10163893

  7. New honeycomb iridium(v) oxides: NaIrO3 and Sr3CaIr2O9.

    PubMed

    Wallace, David C; McQueen, Tyrel M

    2015-12-21

    We report the structures and physical properties of two new iridates, NaIrO3 and Sr3CaIr2O9, both of which contain continuous two-dimensional honeycomb connectivity. NaIrO3 is produced by room temperature oxidative deintercalation of sodium from Na2IrO3, and contains edge-sharing IrO6 octahedra that form a planar honeycomb lattice. Sr3CaIr2O9, produced via conventional solid-state synthesis, hosts a buckled honeycomb lattice with novel corner-sharing connectivity between IrO6 octahedra. Both of these new compounds are comprised of Ir(5+) (5d(4)) and exhibit negligible magnetic susceptibility. They are thus platforms to investigate the origin of the nonmagnetic behavior exhibited by Ir(5+) oxides, and provide the first examples of a J = 0 state on a honeycomb lattice. PMID:26505461

  8. Structure and elementary properties of the new Ir hollandite Rb{sub 0.17}IrO{sub 2}

    SciTech Connect

    Schoop, Leslie M.; Krizan, Jason W.; Gibson, Quinn D.; Cava, R.J.

    2014-01-15

    We report the synthesis and structural characterization of the new Ir holladite, Rb{sub 0.17}IrO{sub 2}. Rb{sub 0.17}IrO{sub 2} crystallizes in the tetragonal hollandite structure. In contrast to the previously reported monoclinic Ir hollandite K{sub 0.25}IrO{sub 2}, we do not observe a difference in Ir–O bond lengths in Rb{sub 0.17}IrO{sub 2} and thus find Ir in an average oxidation state of + 3.83. We also report and compare the electronic and magnetic properties of Rb{sub 0.17}IrO{sub 2} and K{sub 0.25}IrO{sub 2}, finding that they are both metallic and Pauli paramagnets further supporting that the electrons are delocalized in the Ir 5d states. - Graphical abstract: Crystal structure of Rb{sub 0.17}IrO{sub 2} (right), and the SEM image of Rb{sub 0.17}IrO{sub 2}, showing the growth of thin needles (left). Display Omitted - Highlights: • New iridium hollandite. • Naturally grows in very thin wires. • Elementary physical properties of Ir holladites reported for the first time metallic conductor and paramagnetic.

  9. Synthesis of cationic iridium(I) complexes of water-soluble phosphine ligands, [Ir(CO)(TPPMS){sub 3}]CF{sub 3}SO{sub 3}, [Ir(CO)(H{sub 2}O)(TPPTS){sub 2}]CF{sub 3}SO{sub 3}, and [Ir(CO){sub 2}(TPPMS){sub 3}]ClO{sub 4} (TPPMS = PPh{sub 2}(m-C{sub 6}H{sub 4}SO{sub 3}K), TPPTS = P(m-C{sub 6}H{sub 4}SO{sub 3}Na){sub 3})

    SciTech Connect

    Paterniti, D.P.; Francisco, L.W.; Atwood, J.D.

    1999-01-18

    Several new water-soluble iridium(I) complexes were synthesized and their reactivities with small molecules (H{sub 2} or CO) in polar solvents (DMSO or H{sub 2}O) examined. Reaction of H{sub 2} with [Ir(CO)(TPPMS){sub 3}]CF{sub 3}SO{sub 3} (TPPMS = P(C{sub 6}H{sub 5}){sub 2}(m-C{sub 6}H{sub 4}SO{sub 3}K)) in DMSO or H{sub 2}O produces [cis,mer-Ir(CO)(H){sub 2}(TPPMS){sub 3}]CF{sub 3}SO{sub 3}, while the reaction of CO with [Ir(CO)(TPPMS){sub 3}]-CF{sub 3}SO{sub 3} in water yields [Ir(CO){sub 2}(TPPMS){sub 3}]CF{sub 3}SO{sub 3}. Carbonylation of [Ir(CO){sub 2}(TPPMS){sub 3}]ClO{sub 4} in DMSO produces [Ir(CO){sub 3}(TPPMS){sub 2}]ClO{sub 4} and TPPMS; no reaction is observed in H{sub 2}O. Hydrogenation of [Ir(CO){sub 2}(TPPMS){sub 3}]ClO{sub 4} in DMSO or H{sub 2}O yields [cis,mer-Ir(CO)(H){sub 2}(TPPMS){sub 3}]ClO{sub 4}, while reaction of H{sub 2} with an aqueous solution of [Ir(CO)(H{sub 2}O)(TPPTS){sub 2}]CF{sub 3}SO{sub 3} produces [Ir(CO)(H{sub 2}O)(H){sub 2}(TPPTS){sub 2}]CF{sub 3}SO{sub 3}. Reaction of trans-Ir(CO)ClL{sub 2} (L = TPPMS or TPPTS) with excess L in H{sub 2}O produces [Ir(CO)L{sub 3}]Cl, while no reaction occurs in DMSO, [Ir(CO){sub 3}(TPPMS){sub 2}]Cl reacts irreversibly with TPPMS in H{sub 2}O to produce [Ir(CO){sub 2}-(TPPMS){sub 3}]Cl.

  10. Synergistic effects of Ir-Au/TiO2 catalysts in the total oxidation of propene: influence of the activation conditions.

    PubMed

    Aguilar-Tapia, Antonio; Zanella, Rodolfo; Calers, Christophe; Louis, Catherine; Delannoy, Laurent

    2015-11-14

    Iridium was added to the Au/TiO2 system to try to enhance its catalytic activity in the reaction of propene oxidation, performed under conditions close to those used in the studies of decomposition of volatile organic compounds (1200 ppm propene and 9 vol% O2 in He). Titania supported Ir-Au (Ir/Au = 1) was prepared by sequential deposition-precipitation with urea (DPU) of Ir then Au. The effect of the activation conditions (hydrogen or air at 400 °C) was investigated. The study of the activation conditions of Ir-Au/TiO2 showed that activation under hydrogen at 400 °C generated a catalyst more active than the monometallic ones, while Ir-Au/TiO2 activated in air remained as poorly active as Au/TiO2. TEM characterization showed the formation of metallic particles of similar size (2-3 nm) in both monometallic Au/TiO2 and bimetallic Ir-Au/TiO2. Characterization especially by DRIFTS using CO as a probe molecule suggests the presence of Ir-Au interaction, IrO2-Au(0) interaction when the sample is calcined and Ir(0)-Au(0) bimetallic particles when it is reduced. XPS and TPR characterization techniques showed that gold hinders to some extent the reoxidation of iridium in the reduced bimetallic Ir-Au/TiO2 catalyst. The enhanced catalytic activity of the reduced bimetallic Ir-Au/TiO2 catalyst is attributed to a surface Ir(0)-Au(0) synergism. PMID:25785784

  11. Antiferromagnet IrMn thickness dependence in exchange-biased perpendicular magnetic anisotropy based on CoFe/Pt/CoFe/[IrMn( tIrMn)] multilayers

    NASA Astrophysics Data System (ADS)

    Lee, S. S.; Choi, J. G.; Kim, S. W.; Rhee, J. R.; Hwang, D. G.

    2006-09-01

    The effect of the antiferromagnetic IrMn thickness upon the magnetic properties of CoFe/Pt/CoFe/[IrMn( tIrMn)] multilayers is studied. An oscillatory interlayer coupling (IEC) has been shown in pinned CoFe/Pt( tPt)/CoFe/IrMn multilayers with perpendicular anisotropy. The period of oscillation corresponds to about 2 monolayers of Pt. The oscillatory behavior of IEC depends on the nonmagnetic metallic Pt thickness and is thought to be related to the antiferromagnetic ordering induced by the IrMn layer. From the extraordinary Hall voltage amplitude (EHA) curves as function of IrMn thickness, we report that the oscillation dependence of IEC for the [CoFe/Pt/CoFe] multilayer system induced by IrMn with spacer-layer thickness is a important features of perpendicular exchange biased system.

  12. Synthesis of Phenyl-Adducted Cyclodextrin through the Click Reaction

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new derivative of ß-cyclodextrin (CD) has been made incorporating the phenyl group through the use of click reaction. The resulting product exhibits a self-association phenomenon through the formation of inclusion compound between the phenyl group and CD. The product has been characterized by 1H...

  13. Structural modifications of Tilia cordata wood during heat treatment investigated by FT-IR and 2D IR correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Popescu, Maria-Cristina; Froidevaux, Julien; Navi, Parviz; Popescu, Carmen-Mihaela

    2013-02-01

    It is known that heat treatment of wood combined with a low percent of relative humidity causes transformations in the chemical composition of it. The modifications and/or degradation of wood components occur by hydrolysis, oxidation, and decarboxylation reactions. The aim of this study was to give better insights on wood chemical modifications during wood heat treatment under low temperature at about 140 °C and 10% percentage of relative humidity, by infrared, principal component analysis and two dimensional infrared correlation spectroscopy. For this purpose, hardwood samples of lime (Tilia cordata) were investigated and analysed. The infrared spectra of treated samples were compared with the reference ones, the most important differences being observed in the "fingerprint" region. Due to the complexity of this region, which have contributions from all the wood constituents the chemical changes during hydro-thermal treatment were examined in detail using principal component analysis and 2D IR correlation spectroscopy. By hydro-thermal treatment of wood results the formation of acetic acid, which catalyse the hydrolysis reactions of hemicelluloses and amorphous cellulose. The cleavage of the ?-O-4 linkages and splitting of the aliphatic methoxyl chains from the aromatic lignin ring was also observed. For the first treatment interval, a higher extent of carbohydrates degradation was observed, then an increase of the extent of the lignin degradation also took place.

  14. 1H and 13C resonance designation of antimycin A1 by two-dimensional NMR spectroscopy

    USGS Publications Warehouse

    Abidi, S.L.; Adams, B.R.

    1987-01-01

    Complete 1H and 13C resonance assignments of antimycin A1 were accomplished by two-dimensional NMR techniques, viz. 1H homonuclear COSY correlation, heteronuclear 13C-1H chemical shift correlation and long-range heteronuclear 13C-1H COLOC correlation. Antimycin A1 was found to consist of two isomeric components in a 2:1 ratio based on NMR spectroscopic evidence. The structure of the major component was newly assigned as the 8-isopentanoic acid ester. The spectra of the minor component were consistent with the known structure of antimycin A1.

  15. Precipitation hardening of Ir-Nb and Ir-Zr alloys

    SciTech Connect

    Yamabe-Mitarai, Y.; Ro, Y.; Harada, H.; Maruko, T.

    1998-12-04

    The authors previously developed refractory superalloys based on platinum-group metals with fcc and L1{sub 2} two-phase coherent structures. The refractory superalloys are potentially useful at ultra-high temperature, at which Ni-based superalloys can not be used. From among the platinum-group metals, they selected Ir as the base material because its melting temperature (2447 C) is higher than that of Ni (1455 C) and because Ir, with an fcc structure, can be equilibrated with the L1{sub 2} structure phase. Preliminary results demonstrated the superior strength of Ir-based refractory superalloys above 1200 C. Those results also revealed that precipitation hardening occurs and is affected by the shape of the precipitate. The precipitate shape of Ir-based alloys heat-treated at 1200 C is affected by the lattice misfits between the matrix and precipitates. In this study, the authors investigated the precipitation hardening mechanism by observing dislocation structures in deformed samples of Ir-Nb and Ir-Zr alloys using bright-field imaging and dark-field weak-beam imaging techniques with a transmission electron microscope (TEM).

  16. C-H activation in Ir(III) and N-demethylation in Pt(II) complexes with mesoionic carbene ligands: examples of monometallic, homobimetallic and heterobimetallic complexes.

    PubMed

    Maity, Ramananda; Tichter, Tim; van der Meer, Margarethe; Sarkar, Biprajit

    2015-11-14

    Mononuclear Pt(II) and the first dinuclear Pt(II) complexes along with a cyclometalated heterobimetallic Ir(III)/Pd(II) complex bearing mesoionic carbene donor ligands are presented starting from the same bis-triazolium salt. The mononuclear Pt(II) complex possesses a free triazole moiety which is generated from the corresponding triazolium salt through an N-demethylation reaction, whereas the mononuclear Ir(III) complex features an unreacted triazolium unit. PMID:26443200

  17. An epoxy monomer derived from Tung oil fatty acids and its products cured by two synergistic reactions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new bio-based epoxy monomer containing conjugated double bonds, the glycidyl ester of eleostearic acid (GEEA), was synthesized from tung oil fatty acids. It was characterized using 1H-NMR, 13C-NMR and mass spectrometric analysis. Differential scanning calorimetry (DSC) and FT-IR spectroscopy were ...

  18. A compact and portable IR analyzer: progress of a MOEMS FT-IR system for mid-IR sensing

    NASA Astrophysics Data System (ADS)

    Kenda, Andreas; Lüttjohann, Stephan; Sandner, Thilo; Kraft, Martin; Tortschanoff, Andreas; Simon, Arno

    2011-06-01

    We show results on the progress in the development of MOEMS based FT spectrometers dedicated to operate in the mid-IR. Recent research is performed within an EC-FP7 project with the goal to show the feasibility of miniaturized high performance infrared spectroscopic chemical analyzers. Exploiting the high analyte selectivity of the mid-IR paired with the inherent sensitivity of an FT-IR spectrometer, such devices could be used in a wide range of applications, from air monitoring over in-line real-time process control to security monitoring. For practical applicability in these fields, appropriate detection limits and spectral quality standards have to be met. The presented system aims at a performance to measure in the range between 4000-700 cm-1 at a spectral resolution better than 10 cm-1, which would clearly outmatch previous MOEMS based spectrometer approaches. A further technological advantage is the rapid-scan capability. The MOEMS devices oscillate at 500 Hz. A spectrometer based on this device can acquire 1,000 scans per second in forward-backward mode. The interplay of all these components with the challenges in system integration will be described in detail and experimental results will be shown, presenting a significant step forward in smart spectroscopic sensors, microsystems technology and vibrational spectroscopy instrumentation.

  19. Sequential acquisition of multi-dimensional heteronuclear chemical shift correlation spectra with 1H detection

    NASA Astrophysics Data System (ADS)

    Bellstedt, Peter; Ihle, Yvonne; Wiedemann, Christoph; Kirschstein, Anika; Herbst, Christian; Görlach, Matthias; Ramachandran, Ramadurai

    2014-03-01

    RF pulse schemes for the simultaneous acquisition of heteronuclear multi-dimensional chemical shift correlation spectra, such as {HA(CA)NH & HA(CACO)NH}, {HA(CA)NH & H(N)CAHA} and {H(N)CAHA & H(CC)NH}, that are commonly employed in the study of moderately-sized protein molecules, have been implemented using dual sequential 1H acquisitions in the direct dimension. Such an approach is not only beneficial in terms of the reduction of experimental time as compared to data collection via two separate experiments but also facilitates the unambiguous sequential linking of the backbone amino acid residues. The potential of sequential 1H data acquisition procedure in the study of RNA is also demonstrated here.

  20. A mathematical force and moment model of a UH-1H helicopter for flight dynamics simulations

    NASA Technical Reports Server (NTRS)

    Talbot, P. D.; Corliss, L. D.

    1977-01-01

    A model of a UH-1H helicopter was developed to support flight simulations and for developmental work on an avionics system known as V/STOLAND system. Equations and numerical values of constants used to represent the helicopter are presented. Responses to stop inputs of the cyclic and collective controls are shown and compared with flight test data for a UH-1H. The model coefficients were adjusted in an attempt to get a consistant match with the flight time histories at hover and 60 knots. Response matching was obtained at 60 knots, but the matching at hover was not as successful. Pilot evaluations of the model, both fixed and moving base, were made.

  1. Shaft Sinking at the Nevada Test Site, U1h Shaft Project

    SciTech Connect

    B. Briggs; R. Musick

    2001-03-01

    The U1h Shaft Project is a design/build subcontract to construct one 6.1 meter (m) (20 feet (ft)) finished diameter shaft to a depth of 321.6 m (1,055 ft.) at the Nevada Test Site. Atkinson Construction was subcontracted by Bechtel Nevada to construct the U1h Shaft for the U.S. Department of Energy. The project consists of furnishing and installing the sinking plant, construction of the 321.6 m (1,055 ft.) of concrete lined shaft, development of a shaft station at a depth of 297.5 m (976 ft.), and construction of a loading pocket at the station. The outfitting of the shaft and installation of a new hoist may be incorporated into the project at a later date. This paper will describe the design phase, the excavation and lining operation, shaft station construction and the contractual challenges encountered on this project.

  2. New (1)h NMR procedure for the characterization of native and modified food-grade starches.

    PubMed

    Tizzotti, Morgan J; Sweedman, Michael C; Tang, Daniel; Schaefer, Christian; Gilbert, Robert G

    2011-07-13

    A novel, fast, and straightforward procedure is presented for the characterization of starch (the largest energy component in food) and modified starches (such as octenyl succinic anhydride (OSA)-modified starches used as a dispersing agent in the food industry). The method uses (1)H NMR to measure the degree of branching and also, for modified starches, the degree of chemical substitution. The substrate is dissolved in dimethyl-d(6) sulfoxide; addition of a very low amount of deuterated trifluoroacetic acid (d(1)-TFA) to the medium gives rise to a shift to high frequency of the exchangeable protons of the starch hydroxyl groups, leading to a clear and well-defined (1)H NMR spectrum, which provides an improved way to determine the degrees of both branching and chemical substitution. Measurements of the size and molecular weight distributions by multiple-detector size exclusion chromatography show that degradation by TFA does not affect the accuracy of the method. PMID:21608525

  3. The effect of chemical stability on the NIPAM gel dosimeter using 1H-NMR

    NASA Astrophysics Data System (ADS)

    Huang, You-Ruei; Hsieh, Ling-Ling; Chang, Yuan-Jen; Hsieh, Bor-Tsung

    2013-06-01

    Radiation-induced chemical changes in the N-isopropylacrylamide (NIPAM) gels used in three-dimensional dosimeters were investigated using 1H-NMR in this study. The experimental results show that the signal from C=C bonds of NIPAM and N,N'-Methylenediacrylamide (BIS) are 5.5 and 6.3 ppm, respectively. The double bonds from the NIPAM and BIS disappeared with half-dose (D50) were about 10.90 Gy ± 0.76 Gy and 10.09 Gy ± 0.29 Gy, respectively. This observation demonstrates that the polymerization rate of BIS is faster than that of the NIPAM monomer. The 1H-NMR can indicate the chemical structure changes of the polymer gel dosimeter after irradiation and successfully determine the D50 in the NIPAM gel dosimeter.

  4. Growth and characterization of 1H-Imidazolinium Hydrogen L-tartrate single crystals

    NASA Astrophysics Data System (ADS)

    Srinivasan, T. P.; Indirajith, R.; Gopalakrishnan, R.

    2010-02-01

    Single crystals of 1H-Imidazolinium Hydrogen L-tartrate (ImiLT) were grown by slow evaporation solution growth technique at ambient temperature in different solvents. The grown crystals were characterized by single-crystal XRD using MoK ? ( ?=0.71073 Å) radiation and the lattice parameters have been obtained. The Fourier transform infrared spectrum of 1H-Imidazolinium Hydrogen L-tartrate reveals the presence of carboxyl functional groups in the compound. The dielectric behaviour of ImiLT crystals was studied at different frequencies and temperatures. The optical transparency window in the UV-VIS region is found to be good for nonlinear optical applications. Thermogravimetric and Differential thermal analyses reveal that the compound decomposes beyond 204 °C. The theoretical factor group analysis predicts 138 internal modes of vibration and optical modes in the grown title compound. The SHG behaviour of the title compound was demonstrated using Q-switched Nd:YAG laser.

  5. The morphology of C–S–H: Lessons from {sup 1}H nuclear magnetic resonance relaxometry

    SciTech Connect

    Valori, A.; McDonald, P.J.; Scrivener, K.L.

    2013-07-15

    {sup 1}H nuclear magnetic resonance has been applied to cement pastes, and in particular calcium silicate hydrate (C–S–H), for the characterisation of porosity and pore water interactions for over three decades. However, there is now renewed interest in the method, given that it has been shown to be non-invasive, non-destructive and fully quantitative. It is possible to make measurements of pore size distribution, specific surface area, C–S–H density and water fraction and water dynamics over 6 orders of magnitude from nano- to milli-seconds. This information comes in easily applied experiments that are increasingly well understood, on widely available equipment. This contribution describes the basic experiments for a cement audience new to the field and reviews three decades of work. It concludes with a summary of the current state of understanding of cement pore morphology from the perspective of {sup 1}H NMR.

  6. Characterization of 1H NMR Signal in Human Cortical Bone for Magnetic Resonance Imaging

    PubMed Central

    Horch, R. Adam; Nyman, Jeffry S.; Gochberg, Daniel F.; Dortch, Richard D.; Does, Mark D.

    2010-01-01

    Recent advancements in magnetic resonance imaging (MRI) have enabled clinical imaging of human cortical bone (HCB), providing a potentially powerful new means for assessing bone health with molecular-scale sensitivities unavailable to conventional X-ray-based diagnostics. In HCB, MRI is sensitive to populations of protons (1H) partitioned among water and protein sources, which may be differentiated according to intrinsic nuclear magnetic resonance (NMR) properties such as chemical shift and transverse and longitudinal relaxation rates. Herein, these NMR properties were assessed in HCB donors from a broad age range, and four distinct 1H populations were consistently identified and attributed to five microanatomical sources. These findings show that modern HCB MRI contrast will be dominated by collagen-bound water, which can also be exploited to study HCB collagen via magnetization transfer. PMID:20806375

  7. Total (1)H NMR assignment of 3?-acetoxypregna-5,16-dien-20-one.

    PubMed

    Becerra-Martinez, Elvia; Ramírez-Gualito, Karla E; Pérez-Hernández, Nury; Joseph-Nathan, Pedro

    2015-12-01

    This work describes the total and unambiguous assignment of the 750MHz (1)H NMR spectrum of 3?-acetoxypregna-5,16-dien-20-one or 16-DPA (1), the well-known intermediate utilized in the synthesis of biological important commercial steroids. The task was accomplished by extracting the coupling constant values in the overlapped spectrum region by HSQC, and using these values in the (1)H iterative full spin analysis integrated in the PERCH NMR software. Comparison of the experimental vicinal coupling constants of 1 with the values calculated using Altona provides an excellent correlation. The same procedure, when applied to the published data of progesterone (2) and testosterone (3), afforded an acceptable correlation for 2 and a poor correlation for 3. In the last case, this suggested the reassignment of all four vicinal coupling constants for the methylene signals at the C-15 and C-16 positions, demonstrating the utility of this methodology. PMID:26476187

  8. Improved Carbohydrate Structure Generalization Scheme for (1)H and (13)C NMR Simulations.

    PubMed

    Kapaev, Roman R; Toukach, Philip V

    2015-07-21

    The improved Carbohydrate Structure Generalization Scheme has been developed for the simulation of (13)C and (1)H NMR spectra of oligo- and polysaccharides and their derivatives, including those containing noncarbohydrate constituents found in natural glycans. Besides adding the (1)H NMR calculations, we improved the accuracy and performance of prediction and optimized the mathematical model of the precision estimation. This new approach outperformed other methods of chemical shift simulation, including database-driven, neural net-based, and purely empirical methods and quantum-mechanical calculations at high theory levels. It can process structures with rarely occurring and noncarbohydrate constituents unsupported by the other methods. The algorithm is transparent to users and allows tracking used reference NMR data to original publications. It was implemented in the Glycan-Optimized Dual Empirical Spectrum Simulation (GODESS) web service, which is freely available at the platform of the Carbohydrate Structure Database (CSDB) project ( http://csdb.glycoscience.ru). PMID:26087011

  9. Evaluation of saffron (Crocus sativus L.) adulteration with plant adulterants by (1)H NMR metabolite fingerprinting.

    PubMed

    Petrakis, Eleftherios A; Cagliani, Laura R; Polissiou, Moschos G; Consonni, Roberto

    2015-04-15

    In the present work, a preliminary study for the detection of adulterated saffron and the identification of the adulterant used by means of (1)H NMR and chemometrics is reported. Authentic Greek saffron and four typical plant-derived materials utilised as bulking agents in saffron, i.e., Crocus sativus stamens, safflower, turmeric, and gardenia were investigated. A two-step approach, relied on the application of both OPLS-DA and O2PLS-DA models to the (1)H NMR data, was adopted to perform authentication and prediction of authentic and adulterated saffron. Taking into account the deficiency of established methodologies to detect saffron adulteration with plant adulterants, the method developed resulted reliable in assessing the type of adulteration and could be viable for dealing with extensive saffron frauds at a minimum level of 20% (w/w). PMID:25466103

  10. Quantitative 1H MRI and MRS Microscopy of Individual V79 Lung Tumor Spheroids

    NASA Astrophysics Data System (ADS)

    Minard, Kevin R.; Guo, Xiuling; Wind, Robert A.

    1998-08-01

    In this Communication1H MRI and MRS microscopy experiments of individual V79 lung tumor spheroids with diameters between 550 and 650 ?m are reported. The results have been used to determine theT1,T2, andDvalues as well as the concentrations of water, total choline, creatine/phosphocreatine, and mobile lipids in the viable rims and in the necrotic centers.

  11. Initial-Stage Dihydride Formation on Si(100)-2×1-H Surface

    NASA Astrophysics Data System (ADS)

    Fujimori, Masaaki; Heike, Seiji; Suwa, Yuji; Hashizume, Tomihiro

    2003-11-01

    Initial-stage dihydride formation on a Si(100)-2×1-H monohydride surface is investigated by scanning tunneling microscopy. The formation of dihydride species induces bond rearrangement from rebonded to nonrebonded structures at the so-called SB-type step edges. Dihydride chains along the dimer-row direction are then stabilized at a distance of a couple of dimer units away from the step edges. Possible mechanisms of dihydride-chain formation are discussed.

  12. Attenuated Blood-Brain Barrier Dysfunction by XQ-1H Following Ischemic Stroke in Hyperlipidemic Rats.

    PubMed

    Fang, Weirong; Sha, Lan; Kodithuwakku, Nandani Darshika; Wei, Jie; Zhang, Rui; Han, Dan; Mao, Lishun; Li, Yunman

    2015-08-01

    Following ischemic stroke, blood-brain barrier (BBB) is disrupted and is further aggravated with the corresponding incidence of hyperlipidemia. BBB breakdown promotes inflammation infiltration into the brain, which exacerbates cerebral ischemic injury as a result. Here, we report that 10-O-(N,N-dimethylaminoethyl)-ginkgolide B methanesulfonate (XQ-1H), a novel analog of ginkgolide B, alleviates BBB breakdown in hyperlipidemic rats and protects endothelial cells against inflammatory response. Middle cerebral artery occlusion (MCAO) modeled ischemic stroke in rats. Before surgery, these rats were fed a cholesterol-rich diet to induce an experimental hyperlipidemic condition. Additionally, lipopolysaccharide (LPS) incubation with rat brain microvessel endothelial cells (rBMECs) was applied to mimic hyperlipidemia-induced inflammatory injury of BBB. The results indicated more severe infarct size, increased BBB permeability, excessive secretion of pro-inflammatory cytokines, and exaggerated inflammation infiltration of the brain in hyperlipidemic rats following MCAO when compared to rats fed with normal diet. XQ-1H protected BBB integrity, lessoned brain edema and inflammation penetration, downregulated MMP-9 and VCMA-1 expressions, and extenuated ischemic infarction. XQ-1H alleviated LPS-induced inflammatory response in rBMECs, characterized by promoting cell viability, inhibiting TNF-?, IL-1?, and IL-6 releasing, and downregulating NF-?B inflammatory signal and downstream proteins, such as VCAM-1 and iNOS. In conclusion, the present study shows that XQ-1H stabilizes BBB function following ischemic stroke in hyperlipidemic rats, and the possible mechanisms may be related to inflammation inhibition. PMID:25128027

  13. Application of 1H-NMR Metabolomic Profiling for Reef-Building Corals

    PubMed Central

    Sogin, Emilia M.; Anderson, Paul; Williams, Philip; Chen, Chii-Shiarng; Gates, Ruth D.

    2014-01-01

    In light of global reef decline new methods to accurately, cheaply, and quickly evaluate coral metabolic states are needed to assess reef health. Metabolomic profiling can describe the response of individuals to disturbance (i.e., shifts in environmental conditions) across biological models and is a powerful approach for characterizing and comparing coral metabolism. For the first time, we assess the utility of a proton-nuclear magnetic resonance spectroscopy (1H-NMR)-based metabolomics approach in characterizing coral metabolite profiles by 1) investigating technical, intra-, and inter-sample variation, 2) evaluating the ability to recover targeted metabolite spikes, and 3) assessing the potential for this method to differentiate among coral species. Our results indicate 1H-NMR profiling of Porites compressa corals is highly reproducible and exhibits low levels of variability within and among colonies. The spiking experiments validate the sensitivity of our methods and showcase the capacity of orthogonal partial least squares discriminate analysis (OPLS-DA) to distinguish between profiles spiked with varying metabolite concentrations (0 mM, 0.1 mM, and 10 mM). Finally, 1H-NMR metabolomics coupled with OPLS-DA, revealed species-specific patterns in metabolite profiles among four reef-building corals (Pocillopora damicornis, Porites lobata, Montipora aequituberculata, and Seriatopora hystrix). Collectively, these data indicate that 1H-NMR metabolomic techniques can profile reef-building coral metabolomes and have the potential to provide an integrated picture of the coral phenotype in response to environmental change. PMID:25354140

  14. Automated annotation and quantification of metabolites in 1H NMR data of biological origin.

    PubMed

    Alm, Erik; Slagbrand, Tove; Aberg, K Magnus; Wahlström, Erik; Gustafsson, Ingela; Lindberg, Johan

    2012-04-01

    In (1)H NMR metabolomic datasets, there are often over a thousand peaks per spectrum, many of which change position drastically between samples. Automatic alignment, annotation, and quantification of all the metabolites of interest in such datasets have not been feasible. In this work we propose a fully automated annotation and quantification procedure which requires annotation of metabolites only in a single spectrum. The reference database built from that single spectrum can be used for any number of (1)H NMR datasets with a similar matrix. The procedure is based on the generalized fuzzy Hough transform (GFHT) for alignment and on Principal-components analysis (PCA) for peak selection and quantification. We show that we can establish quantities of 21 metabolites in several (1)H NMR datasets and that the procedure is extendable to include any number of metabolites that can be identified in a single spectrum. The procedure speeds up the quantification of previously known metabolites and also returns a table containing the intensities and locations of all the peaks that were found and aligned but not assigned to a known metabolite. This enables both biopattern analysis of known metabolites and data mining for new potential biomarkers among the unknowns. PMID:22362275

  15. [Study on three different species tibetan medicine sea buckthorn by 1H-NMR-based metabonomics].

    PubMed

    Su, Yong-Wen; Tan, Er; Zhang, Jing; You, Jia-Li; Liu, Yue; Liu, Chuan; Zhou, Xiang-Dong; Zhang, Yi

    2014-11-01

    The 1H-NMR fingerprints of three different species tibetan medicine sea buckthorn were established by 1H-HMR metabolomics to find out different motablism which could provide a new method for the quality evaluation of sea buckthorn. The obtained free induction decay (FID) signal will be imported into MestReNova software and into divide segments. The data will be normalized and processed by principal component analysis and.partial least squares discriminant analysis to perform pattern recognition. The results showed that 25 metabolites belonging to different chemical types were detected from sea buckthorn,including flavonoids, triterpenoids, amino acids, carbohydrates, fatty acids, etc. PCA and PLS-DA analysis showed three different varietiest of sea buckthorn that can be clearly separated by the content of L-quebrachitol, malic acid and some unidentified sugars, which can be used as the differences metabolites of three species of sea buckthorn. 1H-NMR-based metabonomies method had a holistic characteristic with sample preparation and handling. The results of this study can offer an important reference for the species identification and quality control of sea buckthorn. PMID:25775800

  16. Dissection of barley chromosomes 1H and 6H by the gametocidal system.

    PubMed

    Ishihara, Ayaka; Mizuno, Nobuyuki; Islam, Rafiqul A K M; Doležel, Jaroslav; Endo, Takashi R; Nasuda, Shuhei

    2014-01-01

    We dissected barley chromosomes 1H and 6H added to common wheat by the gametocidal system and identified structural changes of the chromosomes by fluorescence in situ hybridization and genomic in situ hybridization. We found five aberrations of chromosome 1H, all of which lacked the long arm: one small fragment with the subtelomeric HvT01 sequence, one terminal deletion, and three telocentric chromosomes of the short arm. We established 33 dissection lines carrying single aberrant 6H chromosomes, of which 15 were deletions, 16 were translocations and two were isochromosomes. We conducted PCR analysis of the aberrant barley chromosomes using 75 and 81 EST markers specific to chromosomes 1H and 6H, respectively. This enabled us to construct a cytological map of chromosome 6H and to compare it to the previously reported genetic map and also to the physical map, which were released by the International Barley Genome Sequencing Consortium. The marker orders on the three maps were largely in agreement. The cytological map had better resolution in the proximal region of chromosome 6H than the corresponding genetic map. We discuss some of the discrepancies in marker order between the three maps that might be due to intraspecific polymorphism and gene duplication, as well as to technical problems inherent in the physical mapping process. PMID:25832747

  17. Water 1H spin-lattice relaxation as a fingerprint of porous media.

    PubMed

    Borgia, G C; Fantazzini, P; Mesini, E

    1990-01-01

    The 1H spin-lattice relaxation curves of water in samples of natural porous media can be thought of as "fingerprints" of the porous samples. Also the whole of traditional petrophysical properties (permeability, irreducible water saturation, etc.) can be thought of as "fingerprints" of the porous samples. The characteristics of the pore space determine on one hand the relaxation curve shape, and on the other the petrophysical properties. The understanding of this correspondence can contribute to a better definition of the concept of the architecture of a porous medium. At this purpose we have obtained 1H spin-lattice relaxation curves from a collection of standard sandstone cores of known petrophysical properties and characterized by the same surface properties. The results corroborate the idea that the structure of relaxation curves contains information on the distance scale and on the architecture of the pore space, even if it is difficult to extract it without ambiguities. Different methods of curve fitting were performed and compared with the aim of getting the maximum information from the relaxation curves. Several aspects of this kind of investigation indicate the analogies between 1H response of water confined in porous media and in biological tissues. PMID:2392032

  18. {sup 1}H relaxation enhancement induced by nanoparticles in solutions: Influence of magnetic properties and diffusion

    SciTech Connect

    Kruk, D.; Korpa?a, A.; Institute of Physics, Jagiellonian University, Reymonta 4, 30-059 Kraków ; Taheri, S. Mehdizadeh; Förster, S.; Koz?owski, A.; Rössler, E. A.

    2014-05-07

    Magnetic nanoparticles that induce nuclear relaxation are the most promising materials to enhance the sensitivity in Magnetic Resonance Imaging. In order to provide a comprehensive understanding of the magnetic field dependence of the relaxation enhancement in solutions, Nuclear Magnetic Resonance {sup 1}H spin-lattice relaxation for decalin and toluene solutions of various Fe{sub 2}O{sub 3} nanoparticles was investigated. The relaxation experiments were performed in a frequency range of 10 kHz–20 MHz by applying Field Cycling method, and in the temperature range of 257–298 K, using nanoparticles differing in size and shape: spherical – 5 nm diameter, cubic – 6.5 nm diameter, and cubic – 9 nm diameter. The relaxation dispersion data were interpreted in terms of a theory of nuclear relaxation induced by magnetic crystals in solution. The approach was tested with respect to its applicability depending on the magnetic characteristics of the nanocrystals and the time-scale of translational diffusion of the solvent. The role of Curie relaxation and the contributions to the overall {sup 1}H spin-lattice relaxation associated with the electronic spin-lattice and spin-spin relaxation was thoroughly discussed. It was demonstrated that the approach leads to consistent results providing information on the magnetic (electronic) properties of the nanocrystals, i.e., effective electron spin and relaxation times. In addition, features of the {sup 1}H spin-lattice relaxation resulting from the electronic properties of the crystals and the solvent diffusion were explained.

  19. {sup 1}H NMR spectroscopic studies establish that heparanase is a retaining glycosidase

    SciTech Connect

    Wilson, Jennifer C.; Laloo, Andrew Elohim; Singh, Sanjesh; Ferro, Vito

    2014-01-03

    Highlights: •{sup 1}H and {sup 13}C NMR chemical shifts of fondaparinux were fully assigned by 1D and 2D NMR techniques. •Hydrolysis of fondaparinux by heparanase was monitored by {sup 1}H NMR spectroscopy. •Heparanase is established to be a retaining glycosidase. -- Abstract: Heparanase is an endo-?-glucuronidase that cleaves heparan sulfate side chains of proteoglycans in basement membranes and the extracellular matrix (ECM). Heparanase is implicated in several diverse pathological processes associated with ECM degradation such as metastasis, inflammation and angiogenesis and is thus an important target for anti-cancer and anti-inflammatory drug discovery. Heparanase has been classed as belonging to the clan A glycoside hydrolase family 79 based on sequence analysis, secondary structure predictions and mutagenic analysis, and thus it has been inferred that it is a retaining glycosidase. However, there has been no direct experimental evidence to support this conclusion. Herein we describe {sup 1}H NMR spectroscopic studies of the hydrolysis of the pentasaccharide substrate fondaparinux by heparanase, and provide conclusive evidence that heparanase hydrolyses its substrate with retention of configuration and is thus established as a retaining glycosidase. Knowledge of the mechanism of hydrolysis may have implications for future design of inhibitors for this important drug target.

  20. Crystallographic and magnetic properties of Pb2-xBixIr2O7-? (0 ? x ? 2)

    NASA Astrophysics Data System (ADS)

    Retuerto, M.; Sarkar, T.; Li, M.-R.; Ignatov, A.; Croft, M.; Hodges, J. P.; Thao Tran, T.; Shiv Halasyamani, P.; Greenblatt, M.

    2014-12-01

    The title series of compounds have been synthesized by solid state reaction and characterized by x-ray diffraction (PXD), neutron powder diffraction (PND), second harmonic generation (SHG), x-ray absorption spectroscopy (XAS) and magnetization measurements. The crystal structures have been refined from PND data in the centrosymmetric space group Fd\\bar{3}m with pyrochlore structure. No sign of a break of the centrosymmetry has been observed by SHG and no change of the structure to a polar space group in any component of the series, as it was previously reported for Pb2Ir2O7-? with non-centrosymmetric F\\bar{4}3m space group. We have determined by PND that the oxidation state of Ir is slightly decreasing from 5+-to-4+ in the Pb-rich to almost 4+ in the Bi-rich samples. This evolution is confirmed by XAS and also it explains the progression of the crystallographic parameters. All the samples are paramagnetic in the temperature range measured and the magnitude of the effective magnetic moment is enhanced with Bi content, correlated with the enhancement of Ir4+ compared to Ir5+; suggesting Ir5+ to be present in a trigonal antiprism crystal field splitting and therefore Ir4+ as the only magnetic cation.

  1. Room-temperature self-curing ene reactions involving soybean oil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A mixture of soybean oil with diethyl azodicarboxylate exhibits a remarkable self-curing and thickening behavior at room temperature due to the occurrence of crosslinking ene reactions. The kinetics and the reaction mechanisms have been studied with the help of model compounds, 1H and 13C NMR, and ...

  2. Theoretical IR spectra of ionized naphthalene

    NASA Technical Reports Server (NTRS)

    Pauzat, F.; Talbi, D.; Miller, M. D.; DeFrees, D. J.; Ellinger, Y.

    1992-01-01

    We report the results of a theoretical study of the effect of ionization on the IR spectrum of naphthalene, using ab initio molecular orbital theory. For that purpose we determined the structures, band frequencies, and intensities of neutral and positively ionized naphthalene. The calculated frequencies and intensities allowed an assignment of the most important bands appearing in the newly reported experimental spectrum of the positive ion. Agreement with the experimental spectrum is satisfactory enough to take into consideration the unexpected and important result that ionization significantly affects the intensities of most vibrations. A possible consequence on the interpretation of the IR interstellar emission, generally supposed to originate from polycyclic aromatic hydrocarbons (PAHs), is briefly presented.

  3. Infrared Measurements of Possible IR Filter Materials

    SciTech Connect

    Koller,D.; Ediss, G.; Mihaly, L.; Carr, G.

    2006-01-01

    A Fourier Transform Infrared Spectrometer (FTS) was used to obtain the transmission spectra of candidate materials for use as infrared (IR) filters in cryogenic receivers. The data cover the range from 50 cm-1 ({approx}1.5 THz), well below the peak of the 300 K black body spectrum, to 5000 cm-1 ({approx}150 THz), Z-cut quartz, Gore-Tex, Zitex G and Zitex A, High Density Polyethylene (HDPE), Teflon (PTFE), Fluorogold and Black Polyethylene were measured. The relative effectiveness of each material as a filter is determined by integrating the transmission spectrum multiplied by the Planck distribution to obtain a normalized attenuation for the mid-IR band. Measurements at both room temperature and 8 K are compared.

  4. Advances in handheld FT-IR instrumentation

    NASA Astrophysics Data System (ADS)

    Arnó, Josep; Cardillo, Len; Judge, Kevin; Frayer, Maxim; Frunzi, Michael; Hetherington, Paul; Levy, Dustin; Oberndorfer, Kyle; Perec, Walter; Sauer, Terry; Stein, John; Zuidema, Eric

    2012-06-01

    FT-IR spectroscopy is the technology of choice to identify solid and liquid phase unknown samples. The challenges of ConOps (Concepts of Operation) in emergency response and military field applications require a significant redesign of the stationary FT-IR bench-top instruments typically used in laboratories. Specifically, field portable units require high levels of resistance against mechanical shock and chemical attack, ease of use in restrictive gear, quick and easy interpretation of results, and reduced size. In the last 20 years, FT-IR instruments have been re-engineered to fit in small suitcases for field portable use and recently further miniaturized for handheld operation. This article introduces the advances resulting from a project designed to overcome the challenges associated with miniaturizing FT-IR instruments. The project team developed a disturbance-corrected permanently aligned cube corner interferometer for improved robustness and optimized opto-mechanical design to maximize optical throughput and signal-to-noise ratios. Thermal management and heat flow were thoroughly modeled and studied to isolate sensitive components from heat sources and provide the widest temperature operation range. Similarly, extensive research on mechanical designs and compensation techniques to protect against shock and vibration will be discussed. A user interface was carefully created for military and emergency response applications to provide actionable information in a visual, intuitive format. Similar to the HazMatID family of products, state-of-the-art algorithms were used to quickly identify the chemical composition of complex samples based on the spectral information. This article includes an overview of the design considerations, tests results, and performance validation of the mechanical ruggedness, spectral, and thermal performance.

  5. NEXT GENERATION IR MAGNETS FOR HADRON COLLIDERS.

    SciTech Connect

    GUPTA,R.; ANERELLA,M.; COZZOLINO,J.; ESCALLIER,J.; GANETIS,G.; HARRISON,M.; WANDERER,P.

    2002-08-04

    Brookhaven National Laboratory (BNL) is developing ''React & Wind'' designs and technology for building long high field accelerator magnets. This paper presents the R&D program for interaction region (IR) magnets made with ''Rutherford'' cable for the luminosity upgrade of the Large Hadron Collider (LHC). This paper will introduce a few new end design concepts that make the bend radius of the cable in the end independent of the coil aperture. These designs are suitable for building magnets with ''React & Wind'' technology.

  6. Planar integrated plasmonic mid-IR spectrometer

    NASA Astrophysics Data System (ADS)

    Fredricksen, Christopher J.; Cleary, Justin W.; Buchwald, Walter R.; Figueiredo, Pedro; Khalilzadeh-Rezaie, Farnood; Medhi, Gautam; Rezadad, Imen; Shahzad, Monas; Yesiltas, Mehmet; Nath, Janardan; Boroumand, Javaneh; Smith, Evan; Peale, Robert E.

    2012-06-01

    The convergence of silicon photonics and infrared plasmonics allows compact, chip-scale spectral sensors. We report on the development of a compact mid-IR spectrometer based on a broad-band IR source, dielectric waveguides, a transformer to convert between waveguide modes and surface plasmon polaritons (SPP), an interaction region where analyte molecules are interrogated by SPPs, an array of ring resonators to disperse the light into spectral components, and photodetectors. The mid-IR light source emits into a dielectric waveguide, leading to a region that allows coupling of the incident photons into SPPs. The SPPs propagate along a functionalized metal surface within an interaction region. Interactions between the propagating SPP and any analytes bound to the surface increase loss at those wavelengths that correspond to the analyte vibrational modes. After a suitable propagation length the SPP will be coupled back into a dielectric waveguide, where specific wavelength components will be out-coupled to detectors by an array of ring resonators. We have selected a 3.4 micron LED as the IR source, based on both cost and performance. Initial experiments with circular waveguides formed from GLSO glass include measurement of the loss per mm. Electrodynamic simulations have been performed to inform the eventual Si taper design of the proposed photonic/plasmonic transformer. The SPP propagation length necessary for a discernible change in the signal due to absorption in the interaction region has been estimated to be on the order of 1 mm, well within the bounds of calculated propagation lengths for SPPs on Au.

  7. Condensed imidazo-1,2,4-azines. 15. Reaction of 1,2-diaminobenzimidazole with 5-phenyl-2,3-dihydrofuran-2,3-dione

    SciTech Connect

    Kruglenko, V.P.; Gnidets, V.P.; Klyuev, N.A.; Povstyanoi, M.V.

    1987-10-01

    The reaction of 1,2-diaminobenzimidazole with 5-phenyl-2,3-dihydrofuran-2,3-dione in acetic acid gave a mixture of 2-benzoylmethyl-1,2,4-triazino (2,3-..cap alpha..)-benzimidazol-4H-3-one and 3-benzoylmethyl-1,2,4-triazino(2,3-..cap alpha..)benzimidazol-1H-2-one, the intramolecular cyclization of which gave isomeric 2-phenylfuro-(5,4-e)- and 2-phenylfuro(4,5-e)-1,2,4-triazino(2,3-..cap alpha..)benzimidazoles. Only the corresponding furo(4,5-e)-1,2,4-triazino(2,3-..cap alpha..)benzimidazole was isolated when the reaction was carried out in sulfuric acid. The IR spectra of KBr pellets of the compounds were recorded with a UR-20 spectrometer. The electronic absorption spectra of solutions in dioxane were obtained with a Specord UV-vis spectrophotometer. The mass spectra were recorded with a Varian MAT-311a spectrometer. The quantum-chemical calculations were made by the Pariser-Parr-Pople (PPP) method with the standard parametrization.

  8. Understanding the Effect of Monomeric Iridium(III/IV) Aquo Complexes on the Photoelectrochemistry of IrO(x)·nH2O-Catalyzed Water-Splitting Systems.

    PubMed

    Zhao, Yixin; Vargas-Barbosa, Nella M; Strayer, Megan E; McCool, Nicholas S; Pandelia, Maria-Erini; Saunders, Timothy P; Swierk, John R; Callejas, Juan F; Jensen, Lasse; Mallouk, Thomas E

    2015-07-15

    Soluble, monomeric Ir(III/IV) complexes strongly affect the photoelectrochemical performance of IrO(x)·nH2O-catalyzed photoanodes for the oxygen evolution reaction (OER). The synthesis of IrO(x)·nH2O colloids by alkaline hydrolysis of Ir(III) or Ir(IV) salts proceeds through monomeric intermediates that were characterized using electrochemical and spectroscopic methods and modeled in TDDFT calculations. In air-saturated solutions, the monomers exist in a mixture of Ir(III) and Ir(IV) oxidation states, where the most likely formulations at pH 13 are [Ir(OH)5(H2O)](2-) and [Ir(OH)6](2-), respectively. These monomeric anions strongly adsorb onto IrO(x)·nH2O colloids but can be removed by precipitation of the colloids with isopropanol. The monomeric anions strongly adsorb onto TiO2, and they promote the adsorption of ligand-free IrO(x)·nH2O colloids onto mesoporous titania photoanodes. However, the reversible adsorption/desorption of electroactive monomers effectively short-circuits the photoanode redox cycle and thus dramatically degrades the photoelectrochemical performance of the cell. The growth of a dense TiO2 barrier layer prevents access of soluble monomeric anions to the interface between the oxide semiconductor and the electrode back contact (a fluorinated tin oxide transparent conductor) and leads to improved photoanode performance. Purified IrO(x)·nH2O colloids, which contain no adsorbed monomer, give improved performance at the same electrodes. These results explain earlier observations that IrO(x)·nH2O catalysts can dramatically degrade the performance of metal oxide photoanodes for the OER reaction. PMID:26106904

  9. The chemical instability of Na{sub 2}IrO{sub 3} in air

    SciTech Connect

    Krizan, J.W. Roudebush, J.H.; Fox, G.M.; Cava, R.J.

    2014-04-01

    Highlights: • Na{sub 2}IrO{sub 3} decomposes rapidly in laboratory air. • The decomposition requires the simultaneous presence of CO{sub 2} and H{sub 2}O. • Decomposition results in a dramatic change in the magnetic properties. • Second 5 K feature in magnetic susceptibility not previously reported. - Abstract: We report that Na{sub 2}IrO{sub 3}, which has a layered honeycomb iridium oxide sublattice interleaved by Na planes, decomposes in laboratory air while maintaining the same basic crystal structure. The decomposition reaction was monitored by time-dependent powder X-ray diffraction under different ambient atmospheres, through which it was determined that it occurs only in the simultaneous presence of both CO{sub 2} and H{sub 2}O. A hydrated sodium carbonate is the primary decomposition product along with altered Na{sub 2}IrO{sub 3}. The diffraction signature of the altered Na{sub 2}IrO{sub 3} is quite similar to that of the pristine material, which makes the detection of decomposition difficult in a sample handled under ordinary laboratory conditions. The decomposed samples show a significantly decreased magnetic susceptibility and the disappearance of the low temperature antiferromagnetic transition considered to be characteristic of the phase. Samples that have never been exposed to air after synthesis display a previously unreported magnetic transition at 5 K.

  10. Identifying Defective IR Cameras through a Machine Learning Approach

    E-print Network

    Arvestad, Lars

    Identifying Defective IR Cameras through a Machine Learning Approach to Image Artifact Detection O IR Cameras through a Machine Learning Approach to Image Artifact Detection O S C A R D A N I E L;Abstract Title: Identifying Defective IR Cameras through a Machine Learning Approach to Image Artifact

  11. IR Imaging of SN1987A I. J. Danziger

    E-print Network

    De Buizer, James Michael

    IR Imaging of SN1987A I. J. Danziger , P. Bouchet , I. J. M. DeBuizer , E. Dwek and R. Arendt, Inc., Code 665, NASA Goddard Space Flight Center, Greenbelt, Maryland, USA Abstract. We present IR emphasis is placed on the recently resolved mid- IR images showing dust in the inner ring being heated

  12. Modeling IR Radiative Loss from Eppley PSP Pyranometers Frank Vignola

    E-print Network

    Oregon, University of

    Modeling IR Radiative Loss from Eppley PSP Pyranometers Frank Vignola University of Oregon Renewable Energy Laboratory ABSTRACT A method has been developed to estimate IR radiative losses using solar radiation and meteorological data without the need for pyrgeometer data. The modeled IR radiative losses

  13. The OH/IR star population in the Galactic center

    E-print Network

    Sjouwerman, Loránt

    The OH/IR star population in the Galactic center by Lor'ant Oliv'er Sjouwerman Technical Report No Space Observatory #12; Abstract The OH/IR stars, and M­type Mira variables, that form the topic of this thesis are in two important ways distinct from OH/IR stars found elsewhere in the Galaxy. Their location

  14. IR4IP Tutorial IPI Confex, March 2009

    E-print Network

    Roelleke, Thomas

    IR4IP Tutorial IPI Confex, March 2009 Erik Graf and Thomas Roelleke 1 / 18 Introduction IPI Confex, March 2009 Thomas Roelleke Queen Mary University of London 2 / 18 Outline 1 Structure of IR4IP Tutorial 2 Topics, Issues, and "Problems" in IR 3 Foundations 4 Historical Notes 5 Web or Enterprise Search

  15. Mobile Robotics I: Lab 3 Obstacle Avoidance with IR Sensors

    E-print Network

    Farritor, Shane

    Mobile Robotics I: Lab 3 Obstacle Avoidance with IR Sensors CEENBoTTM Mobile Robotics Platform 1.01 #12;. ( Blank ) #12;Mobile Robotics I ­ Obstacle Avoidance with IR Sensors Purpose the locomotion of your CEENBoT. Specifically, you will take advantage of the on-board infrared (IR) proximity

  16. ;ii.ir,+;r:.1 t.i

    E-print Network

    Bertoloni Meli, Domenico

    ;!i (: ;ii.ir,+;r:.1 t.i:::lr:i,L-::i .. :l . r:, i:.trr-..i l:.,.:!'r_ 'l- ..:::t -.t : . : ; -r..::;. .r- :r:, r" i :' i::irE j-; .,4, . "- '. :::lt-.- l ' .::-'] -o j:.l;;, r: I ':'.; .1. I - 1::-. I l .,-.: -: r r i+;, ^] ,i'.,r. ] . -. -'.'., I l :--, .,', I : :. ,,,--.::,. . ] ','; l:'i ll :--.::..:- i .l

  17. IR-drop Reduction Through Combinational Circuit Partitioning

    E-print Network

    Wang, Yu

    IR-drop Reduction Through Combinational Circuit Partitioning Hai Lin, Yu Wang, Rong Luo, Huazhong {linhai99, wangyuu99}@mails.tsinghua.edu.cn, {luorong, yanghz, wangh}@tsinghua.edu.cn Abstract. IR cur- rent reduction to reduce the IR-drop problem only focus on synchronous sequential logic circuits

  18. Arbitrage Rebate Compliance: Recent IRS Scrutiny of School Districts.

    ERIC Educational Resources Information Center

    Given, Lynda K.; Gurrola, George E.; Richardson, James R.

    2002-01-01

    Describes rules and procedures school districts must follow to comply with IRS arbitrage and rebate rules and exceptions on profits derived from investing yields of tax-exempt bonds in a higher yielding account. Describes consequences of noncompliance and seven ways to be prepared for an IRS audit--for example, answering the IRS promptly. (PKP)

  19. IR Cards: Inquiry-Based Introduction to Infrared Spectroscopy

    ERIC Educational Resources Information Center

    Bennett, Jacqueline; Forster, Tabetha

    2010-01-01

    As infrared spectroscopy (IR) is frequently used in undergraduate organic chemistry courses, an inductive introduction to IR spectroscopy that uses index cards printed with spectra, structures, and chemical names is described. Groups of students are given an alphabetized deck of these "IR cards" to sort into functional groups. The students then…

  20. 78 FR 913 - IRS Truncated Taxpayer Identification Numbers

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-01-07

    ... identifying number known as an IRS truncated taxpayer identification number, a TTIN. As an alternative to using a social security number (SSN), IRS individual taxpayer identification number (ITIN), or IRS adoption taxpayer identification number (ATIN), the filer of certain information returns may use a TTIN...

  1. A Fluorescent Molecular Probe for the Detection of Hydrogen Based on Oxidative Addition Reactions with Crabtree-Type Hydrogenation Catalysts.

    PubMed

    Kos, Pavlo; Plenio, Herbert

    2015-11-01

    A Crabtree-type Ir(I) complex tagged with a fluorescent dye (bodipy) was synthesized. The oxidative addition of H2 converts the weakly fluorescent Ir(I) complex (?=0.038) into a highly fluorescent Ir(III) species (?=0.51). This fluorogenic reaction can be utilized for the detection of H2 and to probe the oxidative addition step in the catalytic hydrogenation of olefins. PMID:26358887

  2. Kinematic structure of OH/IR stars

    NASA Astrophysics Data System (ADS)

    Sun, J.; Kwok, S.

    1987-10-01

    A kinematic model is constructed for 1612 MHz OH maser emssion in OH/IR stars. The spatial distributions of OH maser intensity are calculated from a model of spherically-symmetric uniformly-expanding circumstellar shell. By comparing VLA/VLBI maps of OH/IR stars with model results, the acceptable range of combination of physical parameters M/Ve, (nH2)max, (nH2)min, fOH = [nOH]/[nH2] are derived. The theoretical relations between OH shell radius R0 and mass loss rate Mand between OH maser luminosity LOH and Mare also obtained. These relations are in good agreement with empirical relations established by Bowers et al. (1983) and Baud et al. (1983). The ranges of (nH2)max and (nOH)min under different Mrequired for operating saturated 1612 MHz OH masers are also discussed. The authors find that the OH emission phase can last over 1000 years after the termination of the asymptotic giant branch and many protoplanetary nebulae may have the characteristics of OH/IR stars.

  3. Choices for Tissue Visualization with IR Microspectroscopy

    SciTech Connect

    Gough,K.; Rak, M.; Bookatz, A.; Del Bigio, M.; Mai, S.; Westaway, D.

    2005-01-01

    In this paper, we address some of the issues associated with infrared (IR) imaging, with reference to our work on brain tissue from the TgCRND8 mouse, a transgenic model of Alzheimer's disease (AD). AD is the most common cause of dementia in the aging population. One of the characteristic hallmarks of this chronic neurodegenerative disorder is the accumulation of plaques in the brain, usually visualized with histochemistry and immunostaining. Although these methods are extremely useful, they illustrate only certain aspects of the sample, require a great amount of tissue processing, and are highly dependent on experimental protocols and reagent quality. IR imaging provides information on multiple components, with a minimal amount of sample processing. However, in order to interpret the data successfully, the issues of spectral acquisition parameters, pre-processing, and spectral artifacts need to be considered. The methods commonly used to process the data, such as uni- and bi-variate spectral analysis, and multivariate methods, such as hierarchical cluster analysis, and some issues concerning the use of second derivatives of IR spectra are discussed.

  4. An uncooled capacitive sensor for IR detection

    NASA Astrophysics Data System (ADS)

    Siebke, Georg; Gerngroß, Kathrin; Holik, Peter; Schmitz, Sam; Rohloff, Markus; Tätzner, Simon; Steltenkamp, Siegfried

    2014-06-01

    The beetle Melanophila acuminata detects forest fires from distances as far as 80 miles away. To accomplish this, the beetle uses highly specific IR receptors with a diameter of approximately 15 ?m. These receptors are mechanoreceptors that detect deformations induced by the absorption of radiation. Although the detection mechanism is understood in principle, it is still unclear how the beetle reaches such high sensitivity. In this work, we present the biomimetic approach of an uncooled IR sensor based on the beetle's receptors. This sensor is based on a fluid-filled pressure cell and operates at room temperature. Upon absorbing IR radiation, the fluid heats up and expands. The expanding fluid deflects one electrode of a plate capacitor. By measuring the change in capacitance, the volume increase and the absorbed energy can be inferred. To prevent the risk of damage at high energy absorption, a compensation mechanism is presented in this work. The mechanism prevents large but slow volume changes inside the pressure cell by a microfluidic connection of the pressure cell with a compensation chamber. The channel and the compensation chamber act as a microfluidic low-pass filter and do not affect the overall sensitivity above an appropriate cut-off frequency. Using MEMS technology, we are able to incorporate the complete system into a silicon chip with an area of a few mm2. Here, we show a proof-of-concept and first measurements of the sensor.

  5. Use of FT-IR reflection-absorbance spectroscopy to study photochemical degradation of polymeric coatings on mirrors

    SciTech Connect

    Webb, J D; Schissel, P; Czanderna, A W; Smith, D M; Chughtai, A R

    1981-01-01

    A technique is presented for in situ study of degradative changes in polymeric coatings on metallic substrates. The technique uses a controlled environment chamber in conjunction with a Fourier-transform infrared (FT-IR) spectrophotometer. The chamber design permits collection of IR reflection-absorbance spectra from a sample undergoing exposure to controlled ultraviolet (uv) radiation, gas mixtures, and temperatures. Initial data presented confirm the ability of the technique to provide information regarding the bulk photochemistry of bisphenol-A polycarbonate coatings on gold and aluminum substrates. Refinements of this technique should allow a detailed kinetic study of degradative reactions at the polymer/metal interface.

  6. FT-IR and FT-Raman spectroscopic and DFT theoretical studies on 4-azabenzimidazole

    NASA Astrophysics Data System (ADS)

    Yurdakul, ?enay; Bado?lu, Serdar

    2012-04-01

    The Becke, three-parameter, Lee-Yang-Parr exchange-correlation functional have been used to study the geometry, relative energy, frequency and intensity of the vibrational bands of the 4-azabenzimidazole (4AB) tautomers and the most stable tautomer's homodimers. FT-IR and Raman spectra of the 4AB have been measured in the regions 4000-100 cm-1 and 3500-100 cm-1, respectively for the first time. The stability of 4AB tautomers were reported. All vibrational frequencies assigned in detail with the help of total energy distribution (TED) and isotopic shifts. The energy and atomic charges were discussed. Nsbnd H⋯N type intermolecular hydrogen bonding interactions were suggested for 4AB dimeric forms. 1H and 13C NMR properties have been calculated for the most stable two tautomeric forms using the gauge independent atomic orbital (GIAO) method.

  7. An in situ ATR-IR spectroscopy study of aluminas under aqueous phase reforming conditions.

    PubMed

    Koichumanova, K; Sai Sankar Gupta, K B; Lefferts, L; Mojet, B L; Seshan, K

    2015-10-01

    High temperature/pressure in situ Attenuated Total Reflection Infrared (ATR-IR) spectroscopy was used to investigate the phase transformation of support ?-Al2O3 into boehmite (AlO(OH)) under the hydrothermal conditions of aqueous phase reforming (APR). Activation energy barriers of boehmite formation in hot compressed water at temperatures between 150 and 180 °C were calculated to be 15.9 ± 4.8 kJ mol(-1) for ?-Al2O3 and 43.2 ± 4.3 kJ mol(-1) for Pt/?-Al2O3. The influence of Pt particles is suggested to slow down the phase transformation by selective blockage of the surface nucleation sites. The presence of ethylene glycol has also an inhibiting effect on the transformation due to the carbon deposits formed on the oxide surface. Post-mortem analysis using Raman spectroscopy, (1)H and (27)Al MAS NMR confirms the formation of boehmite. PMID:26305344

  8. 40 CFR 180.228 - S-Ethyl hexahydro-1H-aze-pine-1-carbothioate; tolerances for residues.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false S-Ethyl hexahydro-1H-aze-pine-1-carbothioate; tolerances for residues. 180.228 Section 180.228 Protection of Environment ENVIRONMENTAL... FOOD Specific Tolerances § 180.228 S-Ethyl hexahydro-1H-aze-pine-1-carbothioate; tolerances...

  9. 1H-NMR METABONOMICS ANALYSIS OF SERA DIFFERENTIATES BETWEEN MAMMARY TUMOR-BEARING MICE AND HEALTHY CONTROLS

    EPA Science Inventory

    Global analysis of 1H-NMR spectra of serum is an appealing approach for the rapid detection of cancer. To evaluate the usefulness of this method in distinguishing between mammary tumor-bearing mice and healthy controls, we conducted 1H-NMR metabonomic analyses on serum samples ob...

  10. Complete assignments of (1)H and (13)C NMR data of three new dihydrophenanthrofurans from Pleione yunnanensis.

    PubMed

    Dong, Hailing; Wang, Chunlan; Li, Yan; Guo, Shunxing; Yang, Junshan

    2010-03-01

    Three new dihydrophenanthrofurans, pleionesins A-C (1-3), together with two known dihydrophenanthrenes (4-5) were isolated from the tubers of Pleione yunnanensis (Rolfe). The complete (1)H and (13)C NMR spectra assignments of these compounds were carried out using 1D and 2D NMR experiments ((1)H, (13)C, selective 1D NOE, HSQC and HMBC). PMID:20066660

  11. Response to the Letter to the Editor regarding "Determination of the fatty acid profile by 1H-NMR spectroscopy."

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In expansion of previous work (G. Knothe, J.A. Kenar, Determination of the fatty acid profile by 1H-NMR spectroscopy, Eur. J. Lipid Sci. Technol. 2004, 106, 88-96), an additional approach is discussed for quantitating saturated fatty acids in the fatty acid profiles of common vegetable oils by 1H-NM...

  12. Toward single-shot pure-shift solution 1H NMR by trains of BIRD-based homonuclear decoupling

    E-print Network

    Frydman, Lucio

    Toward single-shot pure-shift solution 1H NMR by trains of BIRD-based homonuclear decoupling Adonis enhancement BIRD pulses a b s t r a c t Achieving homonuclear 1H decoupling remains one of the key challenges by heteronuclei. The present study relies on the latter approach, and explores the use of BIRD pulses

  13. Facile synthesis of Pd-Ir bimetallic octapods and nanocages through galvanic replacement and co-reduction, and their use for hydrazine decomposition.

    PubMed

    Liu, Maochang; Zheng, Yiqun; Xie, Shuifen; Li, Naixu; Lu, Ning; Wang, Jinguo; Kim, Moon J; Guo, Liejin; Xia, Younan

    2013-07-28

    This article describes a facile synthesis of Pd-Ir bimetallic nanostructures in the forms of core-shell octapods and alloyed nanocages. The success of this synthesis relies on the use of Pd nanocubes as the sacrificial templates and interplay of two different processes: the galvanic replacement between an Ir precursor and the Pd nanocubes and the co-reduction of Pd(2+) and Ir(3+) by ethylene glycol. The galvanic replacement played a dominant role in the initial stage, through which Pd atoms were dissolved from the side faces whereas Ir atoms were deposited at the corner sites to generate Pd-Ir core-shell octapods. As the concentration of Pd(2+) in the reaction mixture was increased, co-reduction of Pd(2+) and Ir(3+) occurred in the late stage of synthesis. The resultant Pd and Ir atoms were deposited onto the octapods while the Pd atoms in the interiors continued to be etched away due to the galvanic replacement, finally leading to the formation of Pd-Ir alloyed nanocages. The octapods and nanocages were then evaluated as catalysts for the selective generation of hydrogen from the decomposition of hydrous hydrazine. The nanocages exhibited better selectivity for hydrogen generation than octapods (66% versus 29%), which can be attributed to the presence of an alloyed, porous structure on the surface. PMID:23760572

  14. IR Spectroscopic signs of malignant neoplasms in the thyroid gland

    NASA Astrophysics Data System (ADS)

    Tolstorozhev, G. B.; Skornyakov, I. V.; Butra, V. A.

    2012-03-01

    We use Fourier transform IR spectroscopy to study thyroid tumor tissues which were removed during surgery. The IR spectra of the tissues with pathological foci are compared with data from histologic examination. In the region of N-H, C-H, and C = O stretching vibrations, the IR spectra of the tissues for thyroid cancer are different from the IR spectra of tissues without malignant formations. We identify the spectral signs of thyroid cancer. We show that IR analysis is promising for identification of thyroid pathology at the molecular level.

  15. Determining Transition State Geometries in Liquids Using 2D-IR

    SciTech Connect

    Harris, Charles; Cahoon, James F.; Sawyer, Karma R.; Schlegel, Jacob P.; Harris, Charles B.

    2007-12-11

    Many properties of chemical reactions are determined by the transition state connecting reactant and product, yet it is difficult to directly obtain any information about these short-lived structures in liquids. We show that two-dimensional infrared (2D-IR) spectroscopy can provide direct information about transition states by tracking the transformation of vibrational modes as a molecule crossed a transition state. We successfully monitored a simple chemical reaction, the fluxional rearrangement of Fe(CO)5, in which the exchange of axial and equatorial CO ligands causes an exchange of vibrational energy between the normal modes of the molecule. This energy transfer provides direct evidence regarding the time scale, transition state, and mechanism of the reaction.

  16. Comprehensive Exam in Analysis Spring 2009 Summary of the Problems (1) Let f : IR IR be a continuous function which satisfies the equation f(x+y) = f(x)f(y) for all x, y IR.

    E-print Network

    Li, Peter

    Comprehensive Exam in Analysis Spring 2009 ­ Summary of the Problems (1) Let f : IR IR be a continuous function which satisfies the equation f(x+y) = f(x)f(y) for all x, y IR. Prove the following statements: (a) If f is positive at one point of IR, then f is positive at every point of IR. (b) If f

  17. Mechanism of Au(III) reduction by chitosan: comprehensive study with 13C and 1H NMR analysis of chitosan degradation products.

    PubMed

    Pestov, Alexander; Nazirov, Alexander; Modin, Evgeny; Mironenko, Alexander; Bratskaya, Svetlana

    2015-03-01

    The mechanism of Au(III) reduction by chitosan has been proposed on the basis of comprehensive study of kinetics of Au(III) reduction and chitosan chain degradation using UV-vis spectroscopy and viscosimetry, and identification of reaction products using colloid titration and (13)C, (1)H NMR spectroscopy. We have shown that formation of gold nanoparticles in H[AuCl4]/chitosan solutions starts with hydrolysis of chitosan catalyzed by Au(III). The products of chitosan hydrolysis rather than chitosan itself act as the main reducing species. According to (13)C and (1)H NMR spectroscopy data, chitosan/Au(0) composites contain chitosan with reduced molecular weight and acetylation degree, whereas water-soluble by-products consist of chitosan oligomers with higher acetylation degree, derivatives of glucosamine acids, and formate ion. Chitosan degradation has significantly contributed to the decrease of its efficiency as a gold nanoparticles stabilizer. The gold particle size increased from 6.9 nm to 16.2 nm, when Au(III)/chitosan molar ratio changed from 1:80 to 1:10. PMID:25498610

  18. A copper(I) coordination polymer incorporation the corrosion inhibitor 1H-benzotriazole: poly[?3-benzotriazolato-?(3)N(1):N(2):N(3)-copper(I)].

    PubMed

    Liu, Jian-Jun; Li, Zuo-Yin; Yuan, Xiong; Wang, Yao; Huang, Chang-Cang

    2014-06-01

    The title complex, [Cu(C6H4N3)]n, was synthesized by the reaction of cupric nitrate, 1H-benzotriazole (BTAH) and aqueous ammonia under hydrothermal conditions. The asymmetric unit contains three crystallographically independent Cu(I) cations and two 1H-benzotriazolate ligands. Two of the Cu(I) cations, one with a linear two-coordinated geometry and one with a four-coordinated tetrahedral geometry, are located on sites with crystallographically imposed twofold symmetry. The third Cu(I) cation, with a planar three-coordinated geometry, is on a general position. Two Cu(I) cations are doubly bridged by two BTA(-) ligands to afford a noncentrosymmetric planar [Cu2(BTA)2] subunit, and two [Cu2(BTA)2] subunits are arranged in an antiparallel manner to form a centrosymmetric [Cu2(BTA)2]2 secondary building unit (SBU). The SBUs are connected in a crosswise manner via the sharing of four-coordinated Cu(I) cations, Cu-N bonding and bridging by two-coordinate Cu(I) cations, resulting in a one-dimensional chain along the c axis. These one-dimensional chains are further linked by C-H···? and weak van der Waals interactions to form a three-dimensional supramolecular architecture. PMID:24898965

  19. Optical alignment and testing of the Diffuse IR Background Experiment IR cryogenic telescope

    NASA Technical Reports Server (NTRS)

    Wood, H. John

    1989-01-01

    Diffuse Infrared Background Experiment (DIRBE) optical alignment and testing methods are discussed. Using strobe videography, vibration and performance testing of a 32 hz tuning-fork chopper was carried out. The Cosmic Background explorer satellite provides improved microwave and IR all-sky maps of the cosmic background radiation from a polar orbit. A liquid helium cryostat houses the DIRBE and the Far IR Absolute Spectrophotometer (FIRAS) instruments at a temperature of 2 K. Differential MicRowave Radiometers (DMRs) provide large scale maps of anisotropy of the 3 K background at wavelengths of 3.3, 5.7, and 9.6 mm. The DIRBE telescope is an IR photometric instrument with 10 wavelength bands between 1 and 300 microns, designed to measure radiation from the epoch of galaxy formation. Stringent stray light requirements mean that the DIRBE flight instrument has to be built and tested in a class 100 environment.

  20. Enhanced oxygen evolution activity of IrO2 and RuO2 (100) surfaces

    SciTech Connect

    Stoerzinger, Kelsey; Qiao, Liang; Biegalski, Michael D; Christen, Hans M; Shao-Horn, Yang

    2014-01-01

    The activities of the oxygen evolution reaction (OER) on IrO2 and RuO2 catalysts are among the highest known to date. However, the intrinsic OER activities of surfaces with defined crystallographic orientations are not well established experimentally. Here we report that the (100) surface of IrO2 and RuO2 is more active than the (110) surface that has been traditionally explored by density functional theory studies. The relation between the OER activity and density of coordinatively undersaturated metal sites exposed on each rutile crystallographic facet is discussed. The surface-orientation dependent activities can guide the design of high-surface-area catalysts with increased activity for electrolyzers, metal-air batteries, and photoelectrochemical water splitting applications.

  1. Identifying metabolites related to nitrogen mineralisation using 1H NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    . T McDonald, Noeleen; Graham, Stewart; Watson, Catherine; Gordon, Alan; Lalor, Stan; Laughlin, Ronnie; Elliott, Chris; . P Wall, David

    2015-04-01

    Exploring new analysis techniques to enhance our knowledge of the various metabolites within our soil systems is imperative. Principally, this knowledge would allow us to link key metabolites with functional influences on critical nutrient processes, such as the nitrogen (N) mineralisation in soils. Currently there are few studies that utilize proton nuclear magnetic resonance spectroscopy (1H NMR) to characterize multiple metabolites within a soil sample. The aim of this research study was to examine the effectiveness of 1H NMR for isolating multiple metabolites that are related to the mineralizable N (MN) capacity across a range of 35 Irish grassland soils. Soils were measured for MN using the standard seven day anaerobic incubation (AI-7). Additionally, soils were also analysed for a range of physio-chemical properties [e.g. total N, total C, mineral N, texture and soil organic matter (SOM)]. Proton NMR analysis was carried on these soils by extracting with 40% methanol:water, lyophilizing and reconstituting in deuterium oxide and recording the NMR spectra on a 400MHz Bruker AVANCE III spectrometer. Once the NMR data were spectrally processed and analysed using multivariate statistical analysis, seven metabolites were identified as having significant relationships with MN (glucose, trimethylamine, glutamic acid, serine, aspartic acid, 4-aminohippuirc acid and citric acid). Following quantification, glucose was shown to explain the largest percentage variability in MN (72%). These outcomes suggest that sources of labile carbon are essential in regulating N mineralisation and the capacity of plant available N derived from SOM-N pools in these soils. Although, smaller in concentration, the amino acids; 4-aminohippuirc acid, glutamic acid and serine also significantly (P<0.05) explained 43%, 27% and 19% of the variability in MN, respectively. This novel study highlights the effectiveness of using 1H NMR as a practical approach to profile multiple metabolites in soils simultaneously, and increasing the potential to identify those related to various soil processes.

  2. Advanced Fuel Cycle Initiative AFC-1D, AFC-1G and AFC-1H Irradiation Report

    SciTech Connect

    Debra J. Utterbeck; Gray Chang

    2005-09-01

    The U. S. Advanced Fuel Cycle Initiative (AFCI) seeks to develop and demonstrate the technologies needed to transmute the long-lived transuranic actinide isotopes contained in spent nuclear fuel into shorter-lived fission products, thereby dramatically decreasing the volume of material requiring disposition and the long-term radiotoxity and heat load of high-level waste sent to a geologic repository. The AFC-1 irradiation experiments on transmutation fuels are expected to provide irradiation performance data on non-fertile and low-fertile fuel forms specifically, irradiation growth and swelling, helium production, fission gas release, fission product and fuel constituent migration, fuel phase equilibria, and fuel-cladding chemical interaction. Contained in this report are the to-date physics evaluations performed on three of the AFC-1 experiments; AFC-1D, AFC-1G and AFC-1H. The AFC-1D irradiation experiment consists of metallic non-fertile fuel compositions with minor actinides for potential use in accelerator driven systems and AFC-1G and AFC-1H irradiation experiments are part of the fast neutron reactor fuel development effort. These experiments are high burnup analogs to previously irradiated experiments and are to be irradiated to = 20 atom % burnup. Results of the evaluations show that AFC-1D will remain in the ATR for approximately 100 additional effective full power days (EFPDs), and AFC-1G and AFC-1H for approximately 300 additional EFPDs in order to reach the desired programmatic burnup. The specific irradiation schedule for these tests will be determined based on future physics evaluations and all results will be documented in subsequent reports.

  3. Applications of high-resolution 1H solid-state NMR.

    PubMed

    Brown, Steven P

    2012-02-01

    This article reviews the large increase in applications of high-resolution (1)H magic-angle spinning (MAS) solid-state NMR, in particular two-dimensional heteronuclear and homonuclear (double-quantum and spin-diffusion NOESY-like exchange) experiments, in the last five years. These applications benefit from faster MAS frequencies (up to 80 kHz), higher magnetic fields (up to 1 GHz) and pulse sequence developments (e.g., homonuclear decoupling sequences applicable under moderate and fast MAS). (1)H solid-state NMR techniques are shown to provide unique structural insight for a diverse range of systems including pharmaceuticals, self-assembled supramolecular structures and silica-based inorganic-organic materials, such as microporous and mesoporous materials and heterogeneous organometallic catalysts, for which single-crystal diffraction structures cannot be obtained. The power of NMR crystallography approaches that combine experiment with first-principles calculations of NMR parameters (notably using the GIPAW approach) are demonstrated, e.g., to yield quantitative insight into hydrogen-bonding and aromatic CH-? interactions, as well as to generate trial three-dimensional packing arrangements. It is shown how temperature-dependent changes in the (1)H chemical shift, linewidth and DQ-filtered signal intensity can be analysed to determine the thermodynamics and kinetics of molecular level processes, such as the making and breaking of hydrogen bonds, with particular application to proton-conducting materials. Other applications to polymers and biopolymers, inorganic compounds and bioinorganic systems, paramagnetic compounds and proteins are presented. The potential of new technological advances such as DNP methods and new microcoil designs is described. PMID:22177472

  4. Identification of fucans from four species of sea cucumber by high temperature 1H NMR

    NASA Astrophysics Data System (ADS)

    Wu, Nian; Chen, Shiguo; Ye, Xingqian; Li, Guoyun; Yin, Li'ang; Xue, Changhu

    2014-10-01

    Acidic polysaccharide, which has various biological activities, is one of the most important components of sea cucumber. In the present study, crude polysaccharide was extracted from four species of sea cucumber from three different geographical zones, Pearsonothuria graeffei ( Pg) from Indo-Pacific, Holothuria vagabunda ( Hv) from Norwegian Coast, Stichopus tremulu ( St) from Western Indian Ocean, and Isostichopus badionotu ( Ib) from Western Atlantic. The polysaccharide extract was separated and purified with a cellulose DEAE anion-exchange column to obtain corresponding sea cucumber fucans (SC-Fucs). The chemical property of these SC-Fucs, including molecular weight, monosaccharide composition and sulfate content, was determined. Their structure was compared simply with fourier infrared spectrum analyzer and identified with high temperature 1H nuclear magnetic resonance spectrum analyzer (NMR) and room temperature 13C NMR. The results indicated that Fuc- Pg obtained from the torrid zone mainly contained 2,4-O-disulfated and non-sulfated fucose residue, whereas Fuc- Ib from the temperate zone contained non-, 2-O- and 2,4-O-disulfated fucose residue; Fuc- St from the frigid zone and Fuc- Hv from the torrid zone contained mainly non-sulfated fucose residue. The proton of SC-Fucs was better resolved via high temperature 1H NMR than via room temperature 1H NMR. The fingerprint of sea cucumber in different sea regions was established based on the index of anomer hydrogen signal in SC-Fucs. Further work will help to understand whether there exists a close relationship between the geographical area of sea cucumber and the sulfation pattern of SC-Fucs.

  5. 1H and (13)C NMR of multilamellar dispersions of polyunsaturated (22:6) phospholipids.

    PubMed Central

    Everts, S; Davis, J H

    2000-01-01

    The polyunsaturated fatty acid docosahexaenoic acid (DHA) makes up approximately 50% of the lipid chains in the retinal rod outer segment disk membranes and a large fraction of the lipid chains in the membranes of neuronal tissues. There is an extensive literature concerned with the dietary requirements for essential fatty acids and the importance of DHA to human health, but relatively little research has been done on the physical properties of this important molecule. Using (1)H and (13)C MAS NMR measurements of dispersions of 1-palmitoyl-2-docosahexaenoyl-phosphatidylcholine in excess phosphate buffer, we have unambiguously assigned most of the resonances in both the (1)H and (13)C NMR spectra. We were able to use cross-polarization spectroscopy to follow the transfer of polarization from specific (1)H nuclei not only to their directly bonded (13)C but also to those (13)C that are in close proximity, even though they are not directly bonded. Cross-peaks in two-dimensional cross-polarization spectra revealed a close association between the choline headgroup and at least part of the DHA chain but not with the palmitate chain. Finally, we examined the dynamics of the different parts of this lipid molecule, using rotating frame spin-lattice relaxation measurements, and found that methylene groups of both chains experience important motions with correlation times in the 10-micros range, with those for the palmitate chain being approximately 50% longer than those of the DHA chain. The choline headgroup and the chain terminal groups have significantly shorter correlation times, and that part of the dipolar interaction that is fluctuating at these correlation times is significantly smaller for these groups than it is for the palmitate and DHA chain methylenes. PMID:10920020

  6. Study the chemical composition and biological outcomes resulting from the interaction of the hormone adrenaline with heavy elements: Infrared, Raman, electronic, 1H NMR, XRD and SEM studies

    NASA Astrophysics Data System (ADS)

    Ibrahim, Omar B.; Mohamed, Mahmoud A.; Refat, Moamen S.

    2014-01-01

    Heavy metal adrenaline complexes formed from the reaction of adrenaline with Al3+, Zn2+, Sn2+, Sb3+, Pb2+and Bi3+ ions in methanolic solvent at 60 °C. The final reaction products have been isolated and characterization using elemental analyses (% of carbon, hydrogen and nitrogen), conductivity measurements, mid infrared, Raman laser, UV-Vis, 1H NMR spectra, X-ray powder diffraction, scanning electron microscopy and energy-dispersive X-ray spectroscopy (EDX). Upon the spectroscopic, conductivity and elemental analyses, the stoichiometric reactions indicated that the data obtained refer to 1:2 (M:L) for Zn2+, Sn2+, Pb2+and Bi3+ complexes [Zn(Adr)2(Cl)2], [Sn(Adr)2]Cl2, [Pb(Adr)2](NO3)2 and [Bi(Adr)2(Cl)2]Cl, while the molar ratio 1:3 (M:L) for Al3+ and Sb3+ with formulas [Al(Adr)3](NO3)3 and [Sb(Adr)3]Cl3. The infrared and Raman laser spectra interpreted the mode of interactions which associated through the two phenolic groups of catechol moiety. The adrenaline chelates have been screened for their in vitro antibacterial activity against four bacteria, Gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) and two strains of fungus (Aspergillus flavus and Candida albicans). The metal chelates were shown to possess more antibacterial and antifungal activities than the free adrenaline chelate.

  7. Carboxylic acid-grafted mesoporous material and its high catalytic activity in one-pot three-component coupling reaction

    SciTech Connect

    Gomes, Ruth; Bhaumik, Asim; Dutta, Saikat

    2014-11-01

    A new carboxylic acid functionalized mesoporous organic polymer has been synthesized via in situ radical polymerization of divinylbenzene and acrylic acid using a mesoporous silica as a seed during the polymerization process under solvothermal conditions. The mesoporous material MPDVAA-1 has been thoroughly characterized employing powder XRD, solid state {sup 13}C cross polarization magic angle spinning-nuclear magnetic resonance, FT-IR spectroscopy, N{sub 2} sorption, HR-TEM, and NH{sub 3} temperature programmed desorption-thermal conductivity detector (TPD-TCD) analysis to understand its porosity, chemical environment, bonding, and surface properties. The mesoporous polymer was used as a catalyst for a three comp onent Biginelli condensation between various aldehydes, ?-keto esters, and urea/thioureas to give 3,4-dihydropyrimidine-2(1H)-ones. The reactions were carried out under conventional heating as well as solvent-free microwave irradiation of solid components, and in both the cases, the mesoporous polymer MPDVAA-1 proved to be a powerful, robust, and reusable catalyst with high catalytic efficiency.

  8. Carboxylic acid-grafted mesoporous material and its high catalytic activity in one-pot three-component coupling reaction

    NASA Astrophysics Data System (ADS)

    Gomes, Ruth; Dutta, Saikat; Bhaumik, Asim

    2014-11-01

    A new carboxylic acid functionalized mesoporous organic polymer has been synthesized via in situ radical polymerization of divinylbenzene and acrylic acid using a mesoporous silica as a seed during the polymerization process under solvothermal conditions. The mesoporous material MPDVAA-1 has been thoroughly characterized employing powder XRD, solid state 13C cross polarization magic angle spinning-nuclear magnetic resonance, FT-IR spectroscopy, N2 sorption, HR-TEM, and NH3 temperature programmed desorption-thermal conductivity detector (TPD-TCD) analysis to understand its porosity, chemical environment, bonding, and surface properties. The mesoporous polymer was used as a catalyst for a three comp onent Biginelli condensation between various aldehydes, ?-keto esters, and urea/thioureas to give 3,4-dihydropyrimidine-2(1H)-ones. The reactions were carried out under conventional heating as well as solvent-free microwave irradiation of solid components, and in both the cases, the mesoporous polymer MPDVAA-1 proved to be a powerful, robust, and reusable catalyst with high catalytic efficiency.

  9. An investigation of slow charge separation in a Tyrosine M210 to Tryptophan mutant of the Rhodobacter sphaeroides reaction center

    E-print Network

    van Stokkum, Ivo

    /mid-infrared (mid-IR) probe spectroscopy at room temperature, with the aim to further characterize the primary that of the adjacent M209 amino acid. Introduction The purple bacterial reaction center (RC) is a transmembrane pigment

  10. V/STOL AND digital avionics system for UH-1H

    NASA Technical Reports Server (NTRS)

    Liden, S.

    1978-01-01

    A hardware and software system for the Bell UH-1H helicopter was developed that provides sophisticated navigation, guidance, control, display, and data acquisition capabilities for performing terminal area navigation, guidance and control research. Two Sperry 1819B general purpose digital computers were used. One contains the development software that performs all the specified system flight computations. The second computer is available to NASA for experimental programs that run simultaneously with the other computer programs and which may, at the push of a button, replace selected computer computations. Other features that provide research flexibility include keyboard selectable gains and parameters and software generated alphanumeric and CRT displays.

  11. 1H nuclear magnetic resonance study of hydrated water dynamics in perfluorosulfonic acid ionomer Nafion

    NASA Astrophysics Data System (ADS)

    Han, Jun Hee; Lee, Kyu Won; Jeon, G. W.; Lee, Cheol Eui; Park, W. K.; Choi, E. H.

    2015-01-01

    We have studied the dynamics of hydrated water molecules in the proton exchange membrane of Nafion by means of high-resolution 1H nuclear magnetic resonance (NMR) measurements. "Bound" and "free" states of hydrated water clusters as well as the exchange protons were identified from the NMR chemical shift measurements, and their activation energies were obtained from the temperature-dependent laboratory- and rotating-frame spin-lattice relaxation measurements. Besides, a peculiar motional transition in the ultralow frequency region was observed at 373 K for the "free" hydrated water from the rotating-frame NMR spin-lattice relaxation time measurements.

  12. Clinical Imaging of Tumor Metabolism with (1)H Magnetic Resonance Spectroscopy.

    PubMed

    Martín Noguerol, Teodoro; Sánchez-González, Javier; Martínez Barbero, José Pablo; García-Figueiras, Roberto; Baleato-González, Sandra; Luna, Antonio

    2016-02-01

    Magnetic resonance spectroscopy (MRS) is a noninvasive functional technique to evaluate the biochemical behavior of human tissues. This property has been widely used in assessment and therapy monitoring of brain tumors. MRS studies can be implemented outside the brain, with successful and promising results in the evaluation of prostate and breast cancer, although still with limited reproducibility. As a result of technical improvements, malignancies of the musculoskeletal system and abdominopelvic organs can benefit from the molecular information that MRS provides. The technical challenges and main applications in oncology of (1)H MRS in a clinical setting are the focus of this review. PMID:26613876

  13. 1H-NMR study of the spin dynamics of fine superparamagnetic nanoparticles

    SciTech Connect

    Bordonali, L.; Furukawa, Y.; Kraken, M.; Litterst, F.J.; Sangregorio, C.; Casula, M.F.; Lascialfari, A.

    2012-05-25

    We report a broadband 1H-NMR study of the temperature spin dynamics of nearly monodisperse dextran-coated ?-Fe2O3 magnetic nanoparticles. We observed a maximum in T1?1(T) that decreases in amplitude and shifts toward higher temperatures with increasing field. We suggest that this is related to the progressive superparamagnetic spin blocking of the ferrite core. The data can be explained by assuming a single electronic spin-spin correlation time and introducing a field-dependent distribution of anisotropy energy barriers.

  14. Ring-substituted 4-hydroxy-1H-quinolin-2-ones: preparation and biological activity.

    PubMed

    Jampilek, Josef; Musiol, Robert; Pesko, Matus; Kralova, Katarina; Vejsova, Marcela; Carroll, James; Coffey, Aidan; Finster, Jacek; Tabak, Dominik; Niedbala, Halina; Kozik, Violetta; Polanski, Jaroslaw; Csollei, Jozef; Dohnal, Jiri

    2009-01-01

    In the study, a series of twelve ring-substituted 4-hydroxy-1H-quinolin-2-one derivatives were prepared. The procedures for synthesis of the compounds are presented. The compounds were analyzed using RP-HPLC to determine lipophilicity and tested for their photosynthesis-inhibiting activity using spinach (Spinacia oleracea L.) chloroplasts. All the synthesized compounds were also evaluated for antifungal activity using in vitro screening with eight fungal strains. For all the compounds, the relationships between the lipophilicity and the chemical structure of the studied compounds are discussed, as well as their structure-activity relationships (SAR). PMID:19305366

  15. Structure determination of noncanonical RNA motifs guided by 1H NMR chemical shifts

    PubMed Central

    Sripakdeevong, Parin; Cevec, Mirko; Chang, Andrew T.; Erat, Michèle C.; Ziegeler, Melanie; Zhao, Qin; Fox, George E.; Gao, Xiaolian; Kennedy, Scott D.; Kierzek, Ryszard; Nikonowicz, Edward P.; Schwalbe, Harald; Sigel, Roland K. O.; Turner, Douglas H.; Das, Rhiju

    2014-01-01

    Structured non-coding RNAs underline fundamental cellular processes, but determining their 3D structures remains challenging. We demonstrate herein that integrating NMR 1H chemical shift data with Rosetta de novo modeling can consistently return high-resolution RNA structures. On a benchmark set of 23 noncanonical RNA motifs, including 11 blind targets, Chemical-Shift-ROSETTA for RNA (CS-ROSETTA-RNA) recovered the experimental structures with high accuracy (0.6 to 2.0 Å all-heavy-atom rmsd) in 18 cases. PMID:24584194

  16. Rapid identification of ergot derivatives by 1H-NMR spectroscopy.

    PubMed

    Casy, A F

    1994-01-01

    The 400 MHz 1H-NMR spectra of some therapeutically important ergot derivatives (three bases, four protonated bases and four dihydroergoline salts) are analysed in terms of the low field chemical shift region (above 5 ppm), common resonances of rings C and D (below 5 ppm) and C-8 substituent features. Attention is drawn to data of specific analytical value, and a scheme for the rapid identification of members of this group of ergots proposed. Features which provide evidence of the solute conformation of ring D, and isomerization to less active C-8 epimers are also emphasized. PMID:8161604

  17. Syntheses, crystal structures, and properties of EuRhIn, EuIr{sub 2}, and EuIrSn{sub 2}

    SciTech Connect

    Poettgen, R.; Hoffmann, R.D.; Moeller, M.H.; Kotzyba, G.; Kuennen, B.; Rosenhahn, C.; Mosel, B.D.

    1999-06-01

    The title compounds were prepared from the elements by reactions in sealed tantalum tubes in a high-frequency furnace. Their structures were refined from single crystal X-ray diffractometer data: Pnma, a = 744.4(1) pm, b = 434.15(9) pm, c = 845.5(1) pm, wR2 = 0.0433, 658 F{sup 2} values, 20 variables for EuRhIn, Rd3m, a = 756.5(1) pm, wR2 = 0.0349, 94 F{sup 2} values, 5 variables for EuIr{sub 2}, and Cmcm, a = 434.78(3) pm, b = 1124.0(1) pm, c = 751.20(5) pm, wR2 = 0.0561, 565 F{sup 2} values, 16 variables for EuIrSn{sub 2}. EuRhIn crystallizes with a TiNiSi type structure that consists of strongly puckered Rh{sub 3}In{sub 3} hexagons. The europium atoms fill the channels within the three-dimensional [RhIn] polyanion. EuRhIn orders ferromagnetically at 22.0(5) K with a saturation magnetic moment of 6.7(1) {mu}{sub B}/Eu at 4 k and 5.5 T. The divalent character of the europium atoms in EuRhIn was determined from temperature dependent susceptibility (7.9 {mu}{sub B}/Eu in the high-temperature part) and {sup 151}Eu Moessbauer spectroscopic experiments. The latter show an isomer shift of {delta} = {minus}8.30(2) mm/s at 78 K. At 4.2 K full magnetic hyperfine field splitting subjected to significant quadrupole splitting of {Delta}E{sub Q} = 8 mm/s is observed. EuRhIn is a metallic conductor with a room temperature value of 58 {micro}{Omega}cm for the specific resistivity. The structure of the Laves phase EuIr{sub 2} is confirmed on the basis of single crystal X-ray data. The iridium atoms form a tetrahedral network with Ir-Ir distances of 268 pm. EuIrSn{sub 2} adopts a MgCuAl{sub 2} type structure that may be described as an iridium-filled variant of a distorted CaIn{sub 2}-like sublattice of composition EuSn{sub 2}. The tin atoms in the distorted and puckered hexagonal network have shorter (303 and 322 pm) and longer (343 pm) tin-tin contacts. 40 refs., 9 figs., 5 tabs.

  18. 1H, 13C and 15N resonance assignments for the oxidized and reduced states of the N-terminal domain of DsbD from Escherichia coli.

    PubMed

    Mavridou, Despoina A I; Stelzl, Lukas S; Ferguson, Stuart J; Redfield, Christina

    2012-10-01

    Viability and pathogenicity of Gram-negative bacteria is linked to the cytochrome c maturation and the oxidative protein folding systems in the periplasm. The transmembrane reductant conductor DsbD is a unique protein which provides the necessary reducing power to both systems through thiol-disulfide exchange reactions in a complex network of protein-protein interactions. The N-terminal domain of DsbD (nDsbD) is the delivery point of the reducing power originating from cytoplasmic thioredoxin to a variety of periplasmic partners. Here we report (1)H, (13)C and (15)N assignments for resonances of nDsbD in its oxidized and reduced states. These assignments provide the starting point for detailed investigations of the interactions of nDsbD with its protein partners. PMID:22127524

  19. High-fidelity synthetic IR imaging model

    NASA Astrophysics Data System (ADS)

    Wegener, Michael; Drake, Richard

    2000-07-01

    This paper describes a High Fidelity Synthetic IR Imaging Model which attempts to generate accurate static images as would be seen by a defined IR sensor given the target type and the atmospheric conditions. The model attempts to be quite general in its accommodation of physical processes yet maintain radiometric accuracy. Its main application are to assist in the validation of real-time IR scene generation software, and as a tool which can be used for range performance studies of electro-optical systems. The software model allows facet modeling of targets including temperature profiles and material properties. LOWTRAN/MODTRAN is used to provide atmospheric data for transmittance and self-radiation. Optical systems are described in terms of their transmittance and point spread function, both as functions of wavelength, and a self radiation term having temperature and material properties. At each wavelength desired the model generates descriptions of the flux distribution falling on the focal plane of the sensor system. The flux from different sources is added together to form the total flux distribution on the focal plane. Pixels on the focal plane are modeled by groups of facets with associated material properties allowing the shape and wavelength sensitivity to be expressed. The raw pixel output is obtained by integrating the flux distribution over the component facets and across wavelengths. Following non-uniformity modeling a convolution is applied which models readout smearing. Bandlimited noise is then added. The model is also able to generate and apply a matched filter to the output image. The model is designed to use common commercial software tools such as Multigen for target modeling and Open GL for the rendering. The model currently executes on Silicon Graphics hardware.

  20. Orthogonal hydrogen/halogen bonding in 1-(2-methoxyphenyl)-1H-imidazole-2(3H)-thione-I2 adduct: An experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    El-Sheshtawy, Hamdy S.; Ibrahim, Mohamed M.; El-Mehasseb, Ibrahim; El-Kemary, Maged

    2015-05-01

    The molecular complex between 1-(2-methoxyphenyl)-1H-imidazole-2(3H)-thione (HmimOMe) and iodine (I2) was investigated. Single crystal of [(HmimOMe)radI2] adduct was grown by slow evaporation technique from chloroform at room temperature. Spectroscopic techniques such as FT-IR and Raman techniques, as well as elemental and thermal analysis were used to characterize the complex. The crystal structure shows that the formed adduct stabilized by two noncovalent interactions, namely, hydrogen bond (HB) and halogen bond (XB). Orthogonal HB/XB associated with iodine atom (I) was observed and fully characterized. The ability of iodine to behave as hydrogen bond acceptor and halogen bond donor was held responsible for the orthogonal HB/XB presence. In addition, the structure of HmimOMeradI2 was investigated theoretically using MP2/aug-cc-pVDZ level of theory. Natural bond orbital analysis (NBO) was used to investigate the molecular orbitals interactions and orbitals stabilization energies.

  1. Structural characterization of lignins isolated from Caragana sinica using FT-IR and NMR spectroscopy.

    PubMed

    Xiao, Ling-Ping; Shi, Zheng-Jun; Xu, Feng; Sun, Run-Cang; Mohanty, Amar K

    2011-09-01

    In order to efficiently explore and use woody biomass, six lignin fractions were isolated from dewaxed Caragana sinica via successive extraction with organic solvents and alkaline solutions. The lignin structures were characterized by Fourier transform infrared spectroscopy (FT-IR) and 1D and 2D Nuclear Magnetic Resonance (NMR). FT-IR spectra revealed that the "core" of the lignin structure did not significantly change during the treatment under the conditions given. The results of 1H and 13C NMR demonstrated that the lignin fraction L2, isolated with 70% ethanol containing 1% NaOH, was mainly composed of beta-O-4 ether bonds together with G and S units and trace p-hydroxyphenyl unit. Based on the 2D HSQC NMR spectrum, the ethanol organosolv lignin fraction L1, extracted with 70% ethanol, presents a predominance of beta-O-4' aryl ether linkages (61% of total side chains), and a low abundance of condensed carbon-carbon linked structures (such as beta-beta', beta-1', and beta-5') and a lower S/G ratio. Furthermore, a small percentage (ca. 9%) of the linkage side chain was found to be acylated at the gamma-carbon. PMID:22097829

  2. Iridium?Ruthenium Alloyed Nanoparticles for the Ethanol Oxidation Fuel Cell Reactions

    SciTech Connect

    Su D.; Du, W.; Deskins, N.A.; Teng, X.

    2012-06-01

    In this study, carbon supported Ir-Ru nanoparticles with average sizes ranging from 2.9 to 3.7 nm were prepared using a polyol method. The combined characterization techniques, that is, scanning transmission electron microscopy equipped with electron energy loss spectroscopy, high resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction, were used to determine an Ir-Ru alloy nanostructure. Both cyclic voltammetry and chronoamperometry (CA) results demonstrate that Ir{sub 77}Ru{sub 23}/C bears superior catalytic activities for the ethanol oxidation reaction compared to Ir/C and commercial Pt/C catalysts. In particular, the Ir{sub 77}Ru{sub 23}/C catalyst shows more than 21 times higher mass current density than that of Pt/C after 2 h reaction at a potential of 0.2 V vs Ag/AgCl in CA measurement. Density functional theory simulations also demonstrate the superiority of Ir-Ru alloys compared to Ir for the ethanol oxidation reaction.

  3. Standoff imaging of chemicals using IR spectroscopy

    SciTech Connect

    Senesac, Larry R; Thundat, Thomas George; Morales Rodriguez, Marissa E

    2011-01-01

    Here we report on a standoff spectroscopic technique for identifying chemical residues on surfaces. A hand-held infrared camera was used in conjunction with a wavelength tunable mid-IR quantum cascade laser (QCL) to create hyperspectral image arrays of a target with an explosive residue on its surface. Spectral signatures of the explosive residue (RDX) were extracted from the hyperspectral image arrays and compared with a reference spectrum. Identification of RDX was achieved for residue concentrations of 20 g per cm2 at a distance of 1.5 m, and for 5 g per cm2 at a distance of 15 cm.

  4. Stringy Horizons and UV/IR Mixing

    E-print Network

    Roy Ben-Israel; Amit Giveon; Nissan Itzhaki; Lior Liram

    2015-06-24

    The target-space interpretation of the exact (in $\\alpha'$) reflection coefficient for scattering from Euclidean black-hole horizons in classical string theory is studied. For concreteness, we focus on the solvable $SL(2, \\mathbb{R})_k/U(1)$ black hole. It is shown that it exhibits a fascinating UV/IR mixing, dramatically modifying the late-time behavior of general relativity. We speculate that this might play an important role in the black-hole information puzzle, as well as in clarifying features related with the non-locality of Little String Theory.

  5. Gated IR Images of Shocked Surfaces

    SciTech Connect

    S. S. Lutz; W. D. Turley; P. M. Rightley; L. E. Primas

    2001-06-01

    Gated infrared (IR) images have been taken of a series of shocked surface geometries in tin. Metal coupons machined with steps and flats were mounted directly to the high explosive. The explosive was point-initiated and 500-ns to 1-microsecond-wide gated images of the target were taken immediately following shock breakout using a Santa Barbara Focalplane InSb camera (SBF-134). Spatial distributions of surface radiance were extracted from the images of the shocked samples and found to be non-single-valued. Several geometries were modeled using CTH, a two-dimensional Eulerian hydrocode.

  6. Low Power Polysilicon Sources for IR Applications

    NASA Technical Reports Server (NTRS)

    Das, N. C.; Jhabvala, M.; Shu, P.

    1998-01-01

    We have designed and fabricated polysilicon thin film infrared (IR) sources by micromachining technology. These sources are made with a lightly doped middle region for light emission and heavy doping of the supporting legs. The sources are fabricated on a 10 mm thick, low temperature process parameters in the fabrication of these silicon dioxide layer. Different doping levels were used to achieve various source resistances. From the power requirement to reach the required light emission versus source resistance curve it is seen that there exists a resistance value which minimizes the necessary input power.

  7. Low docosahexaenoic acid status is associated with reduced indices in cortical integrity in the anterior cingulate of healthy male children: A 1H MRS Study

    PubMed Central

    McNamara, Robert K.; Jandacek, Ronald; Tso, Patrick; Weber, Wade; Chu, Wen-Jang; Strakowski, Stephen M.; Adler, Caleb M.; DelBello, Melissa P.

    2014-01-01

    Docosahexaenoic acid (DHA, 22:6n-3) is the principal omega-3 fatty acid in mammalian brain gray matter, and emerging preclinical evidence suggests that DHA has neurotrophic and neuroprotective properties. This study investigated relationships among DHA status, neurocognitive performance, and cortical metabolism measured with proton magnetic resonance spectroscopy (1H MRS) in healthy developing male children (aged 8–10 years, n = 38). Subjects were segregated into low-DHA (n = 19) and high-DHA (n = 19) status groups by a median split of erythrocyte DHA levels. Group differences in 1H MRS indices of cortical metabolism, including choline (Cho), creatine (Cr), glutamine + glutamate + ?-aminobutyric acid (Glx), myo-inositol (mI), and N-acetyl aspartate (NAA), were determined in the right and left dorsolateral prefrontal cortex (R/L-DLPFC, BA9) and bilateral anterior cingulate cortex (ACC, BA32/33). Group differences in neurocognitive performance were evaluated with the Kaufman Brief Intelligence Test and identical-pairs version of the continuous performance task (CPT-IP). Subjects in the low-DHA group consumed fish less frequently (P = 0.02), had slower reaction times on the CPT-IP (P = 0.007), and exhibited lower mI (P = 0.007), NAA (P = 0.007), Cho (P = 0.009), and Cr (P = 0.01) concentrations in the ACC compared with the high-DHA group. There were no group differences in ACC Glx or any metabolite in the L-DLPFC and R-DLPFC. These data indicate that low-DHA status is associated with reduced indices of metabolic function in the ACC and slower reaction time during sustained attention in developing male children. PMID:23582513

  8. Reactions of H+ (pyridine)m(H2O)n and H+

    E-print Network

    Meskhidze, Nicholas

    Reactions of H+ (pyridine)m(H2O)n and H+ (NH3)1(pyridine)m(H2O)n with NH3: experiments and kinetic of the inbound H+ (H2O)15 clusters (> 90%) remains un-reacted because of the low NH3 pressure in the collision cell. H+ (H2O)15 + NH3 H+ (NH3)1(H2O)14 + 1H2O -1 u relative PI (RA) H+ (NH3)1(H2O)13 + 2H2O -19 u

  9. Surface characterization of Kevlar fibers by FT-IR spectroscopy

    SciTech Connect

    Chatzi, E.G.

    1987-01-01

    The Kevlar-49 aramid fiber offers considerable potential for utilization in high-performance composite materials. However, it has poor adhesion to the polymer matrix resin. In order to improve the adhesion the surface of the fiber was characterized by using two nondestructive Fourier transform infrared (FT-IR) techniques. It was shown that the polymer chains in the skin are oriented parallel to the surface, while in the core they are almost radially oriented. This orientation as well as the fact that the functional groups are intermolecularly hydrogen-bonded might limit their availability for reacting with the polymer matrix. The author also characterized the water absorbed in both the skin and the core of the fiber and found the existence of three types of water: (a) weakly hydrogen-bonded between one NH and one carbonyl group, (b) between two carbonyl groups and (c) liquid-like water clustered in microvoids and other sites inside the fibers. It was also found that 30% of the NH groups of the Kevlar-49 fiber are accessible for deuterium exchange. These groups on one hand are available for reactions that would improve the adhesion, but on the other hand can hydrogen-bond with water, which would be detrimental for the mechanical properties of the composite.

  10. Metabolic characterization of natural and cultured Ophicordyceps sinensis from different origins by 1H NMR spectroscopy.

    PubMed

    Zhang, Jianshuang; Zhong, Xin; Li, Shaosong; Zhang, Guren; Liu, Xin

    2015-11-10

    Ophicordyceps sinensis is a well-known traditional Chinese medicine and cultured mycelium is a substitute for wild O. sinensis. Metabolic profiles of wild O. sinensis from three geographical locations and cultivated mycelia derived from three origins were investigated using (1)H nuclear magnetic resonance (NMR) analysis combined with multivariate statistical analysis. A total of 56 primary metabolites were identified and quantified from O. sinensis samples. The principle component analysis (PCA) showed significant differences between natural O. sinensis and fermentation mycelia. Seven metabolites responsible for differentiation were screened out by orthogonal partial least squares discriminant analysis (OPLS-DA). The concentrations of mannitol, trehalose, arginine, trans-4-hydroxyproline, alanine and glucitol were significantly different between wild and cultured groups. The variation in metabolic profiling among artificial mycelia was greater than that among wild O. sinensis. Furthermore, wild samples from different origins were clearly distinguished by the levels of mannitol, trehalose and some amino acids. This study indicates that (1)H NMR-based metabolomics is useful for fingerprinting and discriminating O. sinensis of different geographical regions and cultivated mycelia of different strains. The present study provided an efficient approach for investigating chemical compositions and evaluating the quality of medicine and health food derived from O. sinensis. PMID:26279370

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

    USGS Publications Warehouse

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

    1994-01-01

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

  12. Noninvasive (1)H and (23)Na nuclear magnetic resonance imaging of ancient Egyptian human mummified tissue.

    PubMed

    Münnemann, Kerstin; Böni, Thomas; Colacicco, Giovanni; Blümich, Bernhard; Rühli, Frank

    2007-11-01

    Historic mummies are a unique example of the human desire for immortality. Therefore, it is not surprising that modern diagnostic imaging has been widely applied to study them. Yet, magnetic resonance imaging (MRI) of such old remains has never been successfully achieved in a noninvasive way without rehydration. Furthermore, the impact of artificial mummification as done in ancient Egypt by natron (a blend of NaCl, Na(2)CO(3), NaHCO(3) and NaP(2)SO(4)) on human tissue with a particular focus on the sodium spatial distribution has never been addressed. Here, we show for the very first time completely noninvasive (1)H and (23)Na imaging of an ancient Egyptian mummified finger by nuclear magnetic resonance (NMR). Protons could be visualized by NMR only in the tissue close to surface and sodium primarily in the bone, while computer tomography images both, soft tissue and bone but does not distinguish between different chemical elements. The selective enrichment of sodium in the bone may by due to postmortem incorporation of (23)Na into the tissue by natron-based mummification because our reference measurement of a historical finger not subjected to artificial mummification showed no sodium signal at all. Our results demonstrate not only the general feasibility of nonclinical MRI to visualize historic dry human tissues but also shows the specific (1)H and (23)Na spatial distributions in such mummy tissue, which is particularly interesting for archeology and may open up a new application for MRI. PMID:17490843

  13. Spatially localized sup 1 H NMR spectra of metabolites in the human brain

    SciTech Connect

    Hanstock, C.C. ); Rothman, D.L.; Jue, T.; Shulman, R.G. ); Prichard, J.W. )

    1988-03-01

    Using a surface coil, the authors have obtained {sup 1}H NMR spectra from metabolites in the human brain. Localization was achieved by combining depth pulses with image-selected in vivo spectroscopy magnetic field gradient methods. {sup 1}H spectra in which total creatine (3.03 ppm) has a signal/noise ratio of 95:1 were obtained in 4 min from 14 ml of brain. A resonance at 2.02 ppm consisting predominantly of N-acetylaspartate was measured relative to the creatine peak in gray and white matter, and the ratio was lower in the white matter. The spin-spin relaxation times of N-acetylaspartate and creatine were measured in white and gray matter and while creatine relaxation times were the same in both, the N-acetylaspartate relaxation time was longer in white matter. Lactate was detected in the normoxic brain and the average of three measurements was {approx}0.5 mM from comparison with the creatine plus phosphocreatine peak, which was assumed to be 10.5 mM.

  14. Low Temperature 1H MAS NMR Spectroscopy Studies of Proton Motion in Zeolite

    SciTech Connect

    Huo, H.; Peng, L; Grey, C

    2009-01-01

    Low temperature {sup 1}H MAS NMR spectroscopy is used to study protonic motion in zeolite HZSM-5 in both samples that have been dried using procedures that are standard in the literature and samples that have been more carefully dehydrated. A significant enhancement of proton mobility is seen for the ''standard'' dehydrated HZSM-5 sample in comparison to that seen for the much drier sample. This is ascribed to a vehicle-hopping mechanism involving the residual water that is present in these zeolites. A gradual change of the framework structure is observed on cooling to approximately 213 K, as monitored via the change in {sup 1}H chemical shift values of the Broensted acid resonances and by X-ray diffraction. A more sudden change in structure is seen by differential scanning calorimetry and NMR at approximately 220?230 K, which is associated with changes in both the mobility and the modes of binding of the residual water to the Broensted acid sites and the zeolite framework.

  15. Antimalarial 4(1H)-pyridones bind to the Qi site of cytochrome bc1

    PubMed Central

    Capper, Michael J.; O’Neill, Paul M.; Fisher, Nicholas; Strange, Richard W.; Moss, Darren; Ward, Stephen A.; Berry, Neil G.; Lawrenson, Alexandre S.; Hasnain, S. Samar; Biagini, Giancarlo A.; Antonyuk, Svetlana V.

    2015-01-01

    Cytochrome bc1 is a proven drug target in the prevention and treatment of malaria. The rise in drug-resistant strains of Plasmodium falciparum, the organism responsible for malaria, has generated a global effort in designing new classes of drugs. Much of the design/redesign work on overcoming this resistance has been focused on compounds that are presumed to bind the Qo site (one of two potential binding sites within cytochrome bc1) using the known crystal structure of this large membrane-bound macromolecular complex via in silico modeling. Cocrystallization of the cytochrome bc1 complex with the 4(1H)-pyridone class of inhibitors, GSK932121 and GW844520, that have been shown to be potent antimalarial agents in vivo, revealed that these inhibitors do not bind at the Qo site but bind at the Qi site. The discovery that these compounds bind at the Qi site may provide a molecular explanation for the cardiotoxicity and eventual failure of GSK932121 in phase-1 clinical trial and highlight the need for direct experimental observation of a compound bound to a target site before chemical optimization and development for clinical trials. The binding of the 4(1H)-pyridone class of inhibitors to Qi also explains the ability of this class to overcome parasite Qo-based atovaquone resistance and provides critical structural information for future design of new selective compounds with improved safety profiles. PMID:25564664

  16. Antimalarial 4(1H)-pyridones bind to the Qi site of cytochrome bc1.

    PubMed

    Capper, Michael J; O'Neill, Paul M; Fisher, Nicholas; Strange, Richard W; Moss, Darren; Ward, Stephen A; Berry, Neil G; Lawrenson, Alexandre S; Hasnain, S Samar; Biagini, Giancarlo A; Antonyuk, Svetlana V

    2015-01-20

    Cytochrome bc1 is a proven drug target in the prevention and treatment of malaria. The rise in drug-resistant strains of Plasmodium falciparum, the organism responsible for malaria, has generated a global effort in designing new classes of drugs. Much of the design/redesign work on overcoming this resistance has been focused on compounds that are presumed to bind the Q(o) site (one of two potential binding sites within cytochrome bc1 using the known crystal structure of this large membrane-bound macromolecular complex via in silico modeling. Cocrystallization of the cytochrome bc1 complex with the 4(1H)-pyridone class of inhibitors, GSK932121 and GW844520, that have been shown to be potent antimalarial agents in vivo, revealed that these inhibitors do not bind at the Q(o) site but bind at the Q(i )site. The discovery that these compounds bind at the Q(i) site may provide a molecular explanation for the cardiotoxicity and eventual failure of GSK932121 in phase-1 clinical trial and highlight the need for direct experimental observation of a compound bound to a target site before chemical optimization and development for clinical trials. The binding of the 4(1H)-pyridone class of inhibitors to Q(i) also explains the ability of this class to overcome parasite Q(o)-based atovaquone resistance and provides critical structural information for future design of new selective compounds with improved safety profiles. PMID:25564664

  17. 1H NMR-based metabonomic analysis of urine from young spontaneously hypertensive rats.

    PubMed

    Akira, Kazuki; Masu, Shigenori; Imachi, Misako; Mitome, Hidemichi; Hashimoto, Miho; Hashimoto, Takao

    2008-02-13

    Spontaneously hypertensive rats (SHR) and their substrains are a useful model for studying essential hypertension which is a complex, polygenic, and multifactorial disorder. Their genetic and metabolic features are of great interest because they may provide insights into the mechanism of blood pressure regulation. We have compared urinary metabolic profiles of young SHR with those of their age-matched normotensive controls, Wistar Kyoto rats, using (1)H NMR-based metabonomics. Principal components analysis was applied to the NMR spectral data after data-reduced and normalized by the total integral or the creatinine integral. Consequently, a clear separation of urine samples between the two strains was observed in the principal components scores plot. The loadings plot from the data normalized by the creatinine integral showed that many metabolites such as citrate, alpha-ketoglutarate, and hippurate contributed to the separation, and the urinary levels of most metabolites used in this study, including these three, were lower in SHR than in Wistar Kyoto rats. These metabolic changes may be concerned with blood pressure regulation in SHR, although a relation to other strain differences cannot be ruled out. The present study suggests the usefulness of a (1)H NMR-based metabonomic approach using SHR in the field of hypertension research. PMID:18164575

  18. The molecular structure and vibrational, (1)H and (13)C NMR spectra of lidocaine hydrochloride monohydrate.

    PubMed

    Badawi, Hassan M; Förner, Wolfgang; Ali, Shaikh A

    2016-01-01

    The structure, vibrational and NMR spectra of the local anesthetic drug lidocaine hydrochloride monohydrate salt were investigated by B3LYP/6-311G(??) calculations. The lidocaine·HCl·H2O salt is predicted to have the gauche structure as the predominant form at ambient temperature with NCCN and CNCC torsional angles of 110° and -123° as compared to 10° and -64°, respectively in the base lidocaine. The repulsive interaction between the two N-H bonds destabilized the gauche structure of lidocaine·HCl·H2O salt. The analysis of the observed vibrational spectra is consistent with the presence of the lidocaine salt in only one gauche conformation at room temperature. The (1)H and (13)C NMR spectra of lidocaine·HCl·H2O were interpreted by experimental and DFT calculated chemical shifts of the lidocaine salt. The RMSD between experimental and theoretical (1)H and (13)C chemical shifts for lidocaine·HCl·H2O is 2.32 and 8.21ppm, respectively. PMID:26196935

  19. The molecular structure and vibrational, 1H and 13C NMR spectra of lidocaine hydrochloride monohydrate

    NASA Astrophysics Data System (ADS)

    Badawi, Hassan M.; Förner, Wolfgang; Ali, Shaikh A.

    2016-01-01

    The structure, vibrational and NMR spectra of the local anesthetic drug lidocaine hydrochloride monohydrate salt were investigated by B3LYP/6-311G?? calculations. The lidocaine·HCl·H2O salt is predicted to have the gauche structure as the predominant form at ambient temperature with NCCN and CNCC torsional angles of 110° and -123° as compared to 10° and -64°, respectively in the base lidocaine. The repulsive interaction between the two N-H bonds destabilized the gauche structure of lidocaine·HCl·H2O salt. The analysis of the observed vibrational spectra is consistent with the presence of the lidocaine salt in only one gauche conformation at room temperature. The 1H and 13C NMR spectra of lidocaine·HCl·H2O were interpreted by experimental and DFT calculated chemical shifts of the lidocaine salt. The RMSD between experimental and theoretical 1H and 13C chemical shifts for lidocaine·HCl·H2O is 2.32 and 8.21 ppm, respectively.

  20. Metabolomic Investigations of American Oysters Using 1H-NMR Spectroscopy

    PubMed Central

    Tikunov, Andrey P.; Johnson, Christopher B.; Lee, Haakil; Stoskopf, Michael K.; Macdonald, Jeffrey M.

    2010-01-01

    The Eastern oyster (Crassostrea virginica) is a useful, robust model marine organism for tissue metabolism studies. Its relatively few organs are easily delineated and there is sufficient understanding of their functions based on classical assays to support interpretation of advanced spectroscopic approaches. Here we apply high-resolution proton nuclear magnetic resonance (1H NMR)-based metabolomic analysis to C. virginica to investigate the differences in the metabolic profile of different organ groups, and magnetic resonance imaging (MRI) to non-invasively identify the well separated organs. Metabolites were identified in perchloric acid extracts of three portions of the oyster containing: (1) adductor muscle, (2) stomach and digestive gland, and (3) mantle and gills. Osmolytes dominated the metabolome in all three organ blocks with decreasing concentration as follows: betaine > taurine > proline > glycine > ß-alanine > hypotaurine. Mitochondrial metabolism appeared most pronounced in the adductor muscle with elevated levels of carnitine facilitating ß-oxidation, and ATP, and phosphoarginine synthesis, while glycogen was elevated in the mantle/gills and stomach/digestive gland. A biochemical schematic is presented that relates metabolites to biochemical pathways correlated with physiological organ functions. This study identifies metabolites and corresponding 1H NMR peak assignments for future NMR-based metabolomic studies in oysters. PMID:21116407

  1. Perspectives of 1H-NMR-based urinary metabonomics in Fabry disease.

    PubMed

    Beneduci, Amerigo; Cuccurullo, Manuela; Pontoni, Gabriele; Chidichimo, Giuseppe; Capasso, Giovambattista

    2010-01-01

    High resolution proton magnetic resonance spectroscopy (1H-NMR) of body fluids coupled with multivariate data analysis has led to a new science known as metabonomics. Metabonomics is a powerful tool for investigating any disturbance in the normal homeostasis of biochemical processes. In particular, urine metabonomics provides information on the metabolite phenotype of the human being and is therefore appropriate to study the status of the global system. Here we applied 1H-NMR-based urinary metabonomics in a perspective study of the inherited lysosomal storage disorder known as Fabry disease, starting from the metabolite profiling of urine samples of male and female naïve Fabry subjects. Here we show that the 2 groups of patients can be fairly clearly separated into 2 classes due to statistically significant differences in the urinary level of some metabolites. This preliminary study shows that metabonomics can potentially be used for characterizing the biochemical mechanisms underlying the disease and, hopefully, for early diagnosis of Fabry disease. PMID:21170883

  2. Toxicity assessment of Arisaematis Rhizoma in rats by a (1)H NMR-based metabolomics approach.

    PubMed

    Dong, Ge; Wang, Junsong; Guo, Pingping; Wei, Dandan; Yang, Minghua; Kong, Lingyi

    2015-02-01

    Arisaematis Rhizoma (AR), a famous traditional Chinese medicine, has been widely used in Asia over thousands of years. Documented with noticeable toxicity in ancient books, AR has been used to treat various diseases in the clinic. Therefore, it is important to assess the toxicity of AR dynamically and holistically. In this study, a (1)H NMR-based metabolomics approach complemented with serum chemistry and histopathology has been applied to investigate the toxicity of AR. Rats were intragastrically administered with AR (0, 0.5 and 1 g kg(-1) body weight) for 30 days, and serum and urine samples were collected. Their (1)H NMR profiles were analyzed by multivariate pattern recognition techniques to denote metabolic variations induced by AR, and 13 metabolites in urine and 6 metabolites in serum were significantly altered, which suggested that disturbances in energy metabolism, perturbation of the gut microflora environment, membrane damage, folate deficiency and injury of kidneys are produced by AR. Histopathology showed a slight vacuolization of the glomerular matrix and edema of renal tubular epithelial cells in kidneys of AR administered rats, which were evidenced by increased levels of blood urea nitrogen and creatinine in serum chemistry. Our results indicated that oral administration of crude AR was found to induce slight renal toxicity. Therefore, precautions should be made to monitor the potential nephrotoxicity of AR in clinical use. The metabolomics approach provided a promising tool for the study and better understanding of TCM-induced toxicity dynamically and holistically. PMID:25407163

  3. Novel S-Gal(®) analogs as (1)H MRI reporters for in vivo detection of ?-galactosidase.

    PubMed

    Gulaka, Praveen K; Yu, Jian-Xin; Liu, Li; Mason, Ralph P; Kodibagkar, Vikram D

    2013-07-01

    The quantitative assessment of gene expression and related enzyme activity in vivo could be important for the characterization of gene altering diseases and therapy. The development of imaging techniques, based on specific reporter molecules may enable routine non-invasive assessment of enzyme activity and gene expression in vivo. We recently reported the use of commercially available S-Gal(®) as a ?-galactosidase reporter for (1)H MRI, and the synthesis of several S-Gal(®) analogs with enhanced response to ?-galactosidase activity. We have now compared these analogs in vitro and have identified the optimal analog, C3-GD, based on strong T1 and T2 response to enzyme presence (?R1 and ?R2~1.8 times S-Gal(®)). Moreover, application is demonstrated in vivo in human breast tumor xenografts. MRI studies in MCF7-lacZ tumors implanted subcutaneously in athymic nude mice (n=6), showed significant reduction in T1 and T2 values (each~13%) 2h after intra-tumoral injection of C3-GD, whereas the MCF7 (wild type) tumors showed slight increase. Thus, C3-GD successfully detects ?-galactosidase activity in vivo and shows promise as a lacZ gene (1)H MR reporter molecule. PMID:23602729

  4. Two-dimensional /sup 1/H NMR studies on cyclophilin, a cytosolic cyclosporin A binding protein

    SciTech Connect

    Dalgarno, D.C.; Harding, M.W.; Lazarides, A.; Handschumacher, R.E.; Armitage, I.M.

    1986-05-01

    Cyclophilin (CyP) is a specific cytosolic cyclosporin A (CsA) binding protein (163 residues) that has been implicated in the pharmacological action of this potent immunosuppressant. One and two-dimensional /sup 1/H NMR methods are being employed to elucidate the solution structural properties of CyP particularly as they relate to the binding site of CsA. The focal point for these studies is the single Trp (residue number120) in CyP which, in the 1:1 CyP:CsA complex (K/sub d/approx.2 x 10/sup -7/M), shows a 2 fold enhancement in its intrinsic fluorescence. Using 2D /sup 1/H NMR methods, a low resolution structure has been derived for a very hydrophobic domain containing the Trp residue using interresidue n.O.e. data between assigned spin systems and a distance geometry algorithm. The structure of this hydrophobic domain will be discussed in relation to the predicted ..cap alpha../..beta.. secondary structure of this protein and comparisons made between its structure in the drug free and complexed form of the protein.

  5. Strategies for rapid in vivo 1H and hyperpolarized 13C MR spectroscopic imaging

    NASA Astrophysics Data System (ADS)

    Nelson, Sarah J.; Ozhinsky, Eugene; Li, Yan; Park, Il woo; Crane, Jason

    2013-04-01

    In vivo MRSI is an important imaging modality that has been shown in numerous research studies to give biologically relevant information for assessing the underlying mechanisms of disease and for monitoring response to therapy. The increasing availability of high field scanners and multichannel radiofrequency coils has provided the opportunity to acquire in vivo data with significant improvements in sensitivity and signal to noise ratio. These capabilities may be used to shorten acquisition time and provide increased coverage. The ability to acquire rapid, volumetric MRSI data is critical for examining heterogeneity in metabolic profiles and for relating serial changes in metabolism within the same individual during the course of the disease. In this review we discuss the implementation of strategies that use alternative k-space sampling trajectories and parallel imaging methods in order to speed up data acquisition. The impact of such methods is demonstrated using three recent examples of how these methods have been applied. These are to the acquisition of robust 3D 1H MRSI data within 5-10 min at a field strength of 3 T, to obtaining higher sensitivity for 1H MRSI at 7 T and to using ultrafast volumetric and dynamic 13C MRSI for monitoring the changes in signals that occur following the injection of hyperpolarized 13C agents.

  6. (1)H NMR Spectroscopy of Fecal Extracts Enables Detection of Advanced Colorectal Neoplasia.

    PubMed

    Amiot, Aurelien; Dona, Anthony C; Wijeyesekera, Anisha; Tournigand, Christophe; Baumgaertner, Isabelle; Lebaleur, Yann; Sobhani, Iradj; Holmes, Elaine

    2015-09-01

    Colorectal cancer (CRC) is a growing cause of mortality in developing countries, warranting investigation into its etiopathogenesis and earlier diagnosis. Here, we investigated the fecal metabolic phenotype of patients with advanced colorectal neoplasia and controls using (1)H-nuclear magnetic resonance (NMR) spectroscopy and multivariate modeling. The fecal microbiota composition was assessed by quantitative real-time PCR as well as Wif-1 methylation levels in stools, serum, and urine and correlated to the metabolic profile of each patient. The predictivity of the model was 0.507 (Q(2)Y), and the explained variance was 0.755 (R(2)Y). Patients with advanced colorectal neoplasia demonstrated increased fecal concentrations of four short-chain fatty acids (valerate, acetate, propionate, and butyrate) and decreased signals relating to ?-glucose, glutamine, and glutamate. The predictive accuracy of the multivariate (1)H NMR model was higher than that of the guaiac-fecal occult blood test and the Wif-1 methylation test for predicting advanced colorectal neoplasia. Correlation analysis between fecal metabolites and bacterial profiles revealed strong associations between Faecalibacterium prausnitzii and Clostridium leptum species with short-chain fatty acids concentration and inverse correlation between Faecalibacterium prausnitzii and glucose. These preliminary results suggest that fecal metabonomics may potentially have a future role in a noninvasive colorectal screening program and may contribute to our understanding of the role of these dysregulated molecules in the cross-talk between the host and its bacterial microbiota. PMID:26211820

  7. Conductivity and 1H NMR Studies on Pvp:. NH4Br Polymer Electrolyte

    NASA Astrophysics Data System (ADS)

    Vijaya, N.; Selvasekarapandian, S.; Malathi, J.; Iwai, Y.; Nithya, H.; Kawamura, J.

    2013-07-01

    Proton conducting polymer electrolytes based on Poly (N-vinyl pyrrrolidone) and Ammmonium Bromide (NH4Br) have been prepared in different compositions by solution casting technique. The prepared polymer electrolytes have been characterised by the experimental techniques such as XRD, DSC, AC Impedance Spectroscopy and 1H NMR. The XRD analysis reveals the amorphous nature of the polymer electrolyte. The DSC analysis shows that the glass transition temperature of the polymer complexes decreases upon addition of NH4Br salt indicating the interaction between the polymer and the salt. AC impedance analysis has been carried out to find the best composition possessing good electrical and mechanical stability. The maximum protonic conductivity at room temperature has been found to be 1.06×10-3 S cm-1 for 25 mol% salt doped electrolyte and the electrolyte obeys the Arrhenius behaviour. 1HNMR study has been carried out on the prepared polymer electrolytes to have a better understanding of the ion transport mechanism. 1H NMR study indicates that the NH4+ ion is responsible for the proton conduction.

  8. Authentication of beef versus horse meat using 60 MHz 1H NMR spectroscopy

    PubMed Central

    Jakes, W.; Gerdova, A.; Defernez, M.; Watson, A.D.; McCallum, C.; Limer, E.; Colquhoun, I.J.; Williamson, D.C.; Kemsley, E.K.

    2015-01-01

    This work reports a candidate screening protocol to distinguish beef from horse meat based upon comparison of triglyceride signatures obtained by 60 MHz 1H NMR spectroscopy. Using a simple chloroform-based extraction, we obtained classic low-field triglyceride spectra from typically a 10 min acquisition time. Peak integration was sufficient to differentiate samples of fresh beef (76 extractions) and horse (62 extractions) using Naïve Bayes classification. Principal component analysis gave a two-dimensional “authentic” beef region (p = 0.001) against which further spectra could be compared. This model was challenged using a subset of 23 freeze–thawed training samples. The outcomes indicated that storing samples by freezing does not adversely affect the analysis. Of a further collection of extractions from previously unseen samples, 90/91 beef spectra were classified as authentic, and 16/16 horse spectra as non-authentic. We conclude that 60 MHz 1H NMR represents a feasible high-throughput approach for screening raw meat. PMID:25577043

  9. On the use of 1H and 13C 1D NMR spectra as QSPR descriptors.

    PubMed

    Willighagen, E L; Denissen, H M G W; Wehrens, R; Buydens, L M C

    2006-01-01

    Recently, 1D NMR and IR spectra have been proposed as descriptors containing 3D information. And, as such, said to be suitable for making QSAR and QSPR models where 3D molecular geometries matter, for example, in binding affinities. This paper presents a study on the predictive power of 1D NMR spectra-based QSPR models using simulated proton and carbon 1D NMR spectra. It shows that the spectra-based models are outperformed by models based on theoretical molecular descriptors and that spectra-based models are not easy to interpret. We therefore conclude that the use of such NMR spectra offers no added value. PMID:16562976

  10. A new perovskite polytype in the high-pressure sequence of BaIrO(3).

    PubMed

    Cheng, Jin-Guang; Alonso, José Antonio; Suard, Emmanuelle; Zhou, Jian-Shi; Goodenough, John B

    2009-06-01

    The high-pressure sequence of the perovskite polytypes of BaIrO(3) has been investigated in the pressure range up to 10 GPa. At ambient pressure the so-called "9R" polytype has been prepared by solid-state reaction and slow cooling in air to yield an almost fully oxygen-stoichiometric BaIrO(2.96(1)) composition. The crystal structure has been refined from XRD data in the monoclinic C2/m space group with a = 10.0046(3) A, b = 5.75362(14) A, c = 15.1839(4) A, beta = 103.27(1) degrees ; it contains trimers of face-sharing octahedra (or Ir(3)O(12) trioctahedra) that are linked by their vertices to form columns parallel to the c-axis with a stacking of layers of corner sharing (c) and face sharing (h) IrO(6) octahedra along the sequence hhchhc. This structure is stable up to 3 GPa; at 4 GPa a new 5H polytype has been stabilized as a pure phase. The crystal structure has been solved by ab initio procedures from powder XRD data. It is monoclinic with a = 9.9511(2) A, b = 5.7503(1) A, c = 13.71003(3) A, beta = 118.404(2) degrees , and it was refined in the C2/m space group from NPD data collected at room temperature. This polytype can be described as a stacking of IrO(6) octahedra along the sequence hchcc. The structure contains chains of double dimer units of face-sharing octahedra; the twin dimers are connected to single layers of vertex-sharing octahedra, forming infinite chains along c. This is a unique stacking that, with this repetition length, has never been described before among the hexagonal polytypes of ABO(3) perovskites. The 5H polytype is stable in a narrow pressure range; at 5 GPa the 6H structure is formed, stable up to 10 GPa. The 6H-BaIrO(3) polytype is monoclinic, space group C2/c, with a = 5.7483(2) A, b = 9.9390(3) A, c = 14.3582(5) A, beta = 91.319(2) degrees . The structure consists of dimers of face-sharing octahedra separated by single corner-sharing octahedra, showing the sequence hcchcc along the c-axis. At 10 GPa the cubic 3C perovskite structure could be identified as a minority phase, with a = 4.0611(7) A, defined in the Pm3m space group. The precarious stability of the 5H polytype, as well as the novel pressure sequence displayed by BaIrO(3) that is distinct from the classical sequence 9R-4H-6H-3C exhibited by many transition metal oxides, for instance BaRuO(3), is a result of the particular stability of the "9R" ambient-pressure structure, which is reinforced by a strong Ir-Ir bond across the octahedral faces, and the Ir-Ir Coulombic repulsion across shared faces that destabilizes the 4H polytype relative to the 6H phase to allow stabilization of the hybrid 5H polytype in a narrow presure range. PMID:19469581

  11. Zea mays iRS1563: a comprehensive genome-scale metabolic reconstruction of maize metabolism.

    PubMed

    Saha, Rajib; Suthers, Patrick F; Maranas, Costas D

    2011-01-01

    The scope and breadth of genome-scale metabolic reconstructions have continued to expand over the last decade. Herein, we introduce a genome-scale model for a plant with direct applications to food and bioenergy production (i.e., maize). Maize annotation is still underway, which introduces significant challenges in the association of metabolic functions to genes. The developed model is designed to meet rigorous standards on gene-protein-reaction (GPR) associations, elementally and charged balanced reactions and a biomass reaction abstracting the relative contribution of all biomass constituents. The metabolic network contains 1,563 genes and 1,825 metabolites involved in 1,985 reactions from primary and secondary maize metabolism. For approximately 42% of the reactions direct literature evidence for the participation of the reaction in maize was found. As many as 445 reactions and 369 metabolites are unique to the maize model compared to the AraGEM model for A. thaliana. 674 metabolites and 893 reactions are present in Zea mays iRS1563 that are not accounted for in maize C4GEM. All reactions are elementally and charged balanced and localized into six different compartments (i.e., cytoplasm, mitochondrion, plastid, peroxisome, vacuole and extracellular). GPR associations are also established based on the functional annotation information and homology prediction accounting for monofunctional, multifunctional and multimeric proteins, isozymes and protein complexes. We describe results from performing flux balance analysis under different physiological conditions, (i.e., photosynthesis, photorespiration and respiration) of a C4 plant and also explore model predictions against experimental observations for two naturally occurring mutants (i.e., bm1 and bm3). The developed model corresponds to the largest and more complete to-date effort at cataloguing metabolism for a plant species. PMID:21755001

  12. Development of a tunable IR lidar system

    NASA Astrophysics Data System (ADS)

    Amoruso, S.; Amodeo, A.; Armenante, M.; Boselli, A.; Mona, L.; Pandolfi, M.; Pappalardo, G.; Velotta, R.; Spinelli, N.; Wang, X.

    2002-05-01

    A differential absorption lidar system (DIAL) based on a continuously tunable optical parametric amplifier (OPA) pumped by a Nd : YAG laser (200 mJ at ?=355 nm) operating at a maximum pulse repetition rate of 100 Hz has been developed. The system provides continuously tunable coherent radiation in the Visible-near IR range (0.4-2.5 ?m), allowing to perform DIAL measurements in a spectral region where most of atmospheric constituents and pollutants display absorption lines. The spectral width of the OPA system is line-narrowed by using a master oscillator dye laser as seeder, achieving a linewidth of 0.04 cm -1 (FWHM), a spectral purity larger than 99% and a frequency stability better than 1 pm h -1, with an output energy in the IR of 1-10 mJ. The OPA system was used to perform DIAL measurements in the lower troposphere. Preliminary results in terms of water vapor content and aerosol backscattering profiles are presented and discussed.

  13. Distant radio galaxies in the near IR

    NASA Astrophysics Data System (ADS)

    McCarthy, P. J.; Persson, S. E.; Elston, R.; Eisenhardt, P. R. M.

    1993-01-01

    We are carrying out a program of near IR imaging and spectroscopy of radio galaxies with redshifts of 1.5 and greater. One of its principal goals is to constrain the ages and star formation histories of massive galaxies at early epochs. The radio galaxies are drawn from the survey of 1Jy class sources by McCarthy et al (1989) and McCarthy (1990). The sample contains 18 radio galaxies with redshifts greater than 2 and an additional 10 objects with 1.5 less than z less than 2.0. The redshifts were obtained from long slit spectra with the CTIO 4 m. While the galaxies are quite faint (r approximately = 21-24.5) all have Lyman alpha emission with rest frame equivalent widths of 100 - 1000 A. Multicolor photometry in the g,r,i and J,H,K bands has been obtained with the 2.5-m Du Pont Telescope on Las Campanas and with the Hale 5 m telescope at Palomar. We have recently obtained near IR spectra, using the 4 m telescopes at KPNO and CTIO, of a few objects with the goal of determining the Lyman alpha/H-alpha ratio and hence the reddening.

  14. An IR Navigation System for Pleural PDT

    NASA Astrophysics Data System (ADS)

    Zhu, Timothy; Liang, Xing; Kim, Michele; Finlay, Jarod; Dimofte, Andreea; Rodriguez, Carmen; Simone, Charles; Friedberg, Joseph; Cengel, Keith

    2015-03-01

    Pleural photodynamic therapy (PDT) has been used as an adjuvant treatment with lung-sparing surgical treatment for malignant pleural mesothelioma (MPM). In the current pleural PDT protocol, a moving fiber-based point source is used to deliver the light. The light fluences at multiple locations are monitored by several isotropic detectors placed in the pleural cavity. To improve the delivery of light fluence uniformity, an infrared (IR) navigation system is used to track the motion of the light source in real-time at a rate of 20 - 60 Hz. A treatment planning system uses the laser source positions obtained from the IR camera to calculate light fluence distribution to monitor the light dose uniformity on the surface of the pleural cavity. A novel reconstruction algorithm is used to determine the pleural cavity surface contour. A dual-correction method is used to match the calculated fluences at detector locations to the detector readings. Preliminary data from a phantom shows superior light uniformity using this method. Light fluence uniformity from patient treatments is also shown with and without the correction method.

  15. Perception range prediction for IR pilot sight

    NASA Astrophysics Data System (ADS)

    Weiss, A. Robert; Großmann, Peter; Repasi, Endre; Ritt, Gunnar; Wittenstein, Wolfgang

    2008-04-01

    The increasing use of IR pilot sight in helicopters calls for a reliable prediction of perception ranges for a variety of objects, especially those needed for orientation and those posing as a potential hazard, like power poles, masts, isolated trees etc. Since the visibility of objects in the IR depends mainly on the temperature differences between those objects and a given background and only marginally on illumination, range prediction techniques used for the visual range or light-amplified vision are only of very limited use. While range predictions based on the Johnson criterion do offer some insight into expected ranges, the inherently nominal nature of distance estimates thus obtained hampers their use for an actual field-deployable pre-flight consulting procedure. In order to overcome those limitations, long-term simultaneous measurements of relevant objects and background temperatures and weather data were carried out and used for temperature prediction from prevalent weather conditions. Together with a perception model derived from extensive observer experiments based on synthetic images of the UH Tiger Pilot Sight Unit we developed a perception range prediction package which is currently evaluated by the weather service of the Bundeswehr. We will present results from the observer experiments together with the derived perception models. These are then compared to actual perception ranges as obtained from flight experiments.

  16. Al3AuIr: A New Compound in the Al-Au-Ir System.

    PubMed

    Kadok, Joris; de Weerd, Marie-Cécile; Boulet, Pascal; Gaudry, Émilie; Grin, Yuri; Fournée, Vincent; Ledieu, Julian

    2015-08-17

    A new ternary phase with a composition of Al3AuIr has been found in the Al-rich area of the Al-Au-Ir system. Differential thermal analysis indicates a melting point of 990 °C, and single-crystal X-ray diffraction measurements reveal that this ternary phase adopts a Ni2Al3 structure type (space group P3?m1) with a = 4.2584(5) Å and c = 5.1991(7) Å. This compound is isostructural to the Al3Cu1.5Co0.5 phase also found in the Al-rich part of the Al-Cu-Co ternary diagram. Experimental evidence combined with ab initio calculations point toward an Al3AuIr phase stabilized by a Hume-Rothery mechanism. Quantum chemical calculations indicate two-center and multicenter interactions in the Al3AuIr phase. Layered distribution of two-center interactions separated by regions with four- and five-center bonds suggests a preferential cleavage of the material at puckered planes perpendicular to the [001] direction. PMID:26241194

  17. Intercalation of IR absorber into layered double hydroxides: Preparation, thermal stability and selective IR absorption

    SciTech Connect

    Zhu, Haifeng; Tang, Pinggui; Feng, Yongjun; Wang, Lijing; Li, Dianqing

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer PMIDA anions were intercalated into Mg{sub 2}Al-NO{sub 3} LDH by anion-exchange method. Black-Right-Pointing-Pointer The prepared material has highly selective IR absorption property in 9-11 {mu}m. Black-Right-Pointing-Pointer The obtained material has practical applications as heat-retaining additive. -- Abstract: N-phosphonomethyl aminodiacetic acid (PMIDA) was intercalated into the interlayer spacing of layered double hydroxides (LDH) by an anion-exchange method. The intercalated LDHs were characterized by various techniques such as powder X-ray diffraction (XRD), FT-IR spectroscopy, elemental analysis and simultaneous thermogravimetric and mass spectrometry (TG-MS) in details. The results show the formation of Mg{sub 2}Al-PMIDA LDH based on the expansion of d-spacing from 0.89 nm to 1.22 nm and the disappearance of the characteristic IR absorption band at 1384 cm{sup -1} for NO{sub 3}{sup -} anions. The incorporation of Mg{sub 2}Al-PMIDA LDH into the low density polyethylene (LDPE) as an additive enhances the selectivity of IR absorption in the main wavelength region 9-11 {mu}m for radiant heat loss at night. Mg{sub 2}Al-PMIDA LDH as a heat-retaining additive has practical application in agricultural plastic films.

  18. Improving O2 production of WO3 photoanodes with IrO2 in acidic aqueous electrolyte.

    PubMed

    Spurgeon, Joshua M; Velazquez, Jesus M; McDowell, Matthew T

    2014-02-28

    WO3 is a promising candidate for a photoanode material in an acidic electrolyte, in which it is more stable than most metal oxides, but kinetic limitations combined with the large driving force available in the WO3 valence band for water oxidation make competing reactions such as the oxidation of the acid counterion a more favorable reaction. The incorporation of an oxygen evolving catalyst (OEC) on the WO3 surface can improve the kinetics for water oxidation and increase the branching ratio for O2 production. Ir-based OECs were attached to WO3 photoanodes by a variety of methods including sintering from metal salts, sputtering, drop-casting of particles, and electrodeposition to analyze how attachment strategies can affect photoelectrochemical oxygen production at WO3 photoanodes in 1 M H2SO4. High surface coverage of catalyst on the semiconductor was necessary to ensure that most minority-carrier holes contributed to water oxidation through an active catalyst site rather than a side-reaction through the WO3/electrolyte interface. Sputtering of IrO2 layers on WO3 did not detrimentally affect the energy-conversion behavior of the photoanode and improved the O2 yield at 1.2 V vs. RHE from ~0% for bare WO3 to 50-70% for a thin, optically transparent catalyst layer to nearly 100% for thick, opaque catalyst layers. Measurements with a fast one-electron redox couple indicated ohmic behavior at the IrO2/WO3 junction, which provided a shunt pathway for electrocatalytic IrO2 behavior with the WO3 photoanode under reverse bias. Although other OECs were tested, only IrO2 displayed extended stability under the anodic operating conditions in acid as determined by XPS. PMID:24435160

  19. 40 CFR 721.1750 - 1H-Benzotriazole, 5-(pen-tyl-oxy)- and 1H-ben-zo-tri-a-zole, 5-(pen-tyl-oxy)-, sodium and...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false 1H-Benzotriazole, 5-(pen-tyl-oxy)- and 1H-ben-zo-tri-a-zole, 5-(pen-tyl-oxy)-, sodium and potassium salts. 721.1750 Section 721.1750 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES...

  20. Antimicrobial activity, structural evaluation and vibrational (FT-IR and FT-Raman) study of pyrrole containing vinyl derivatives.

    PubMed

    Singh, R N; Rawat, Poonam; Sahu, Sangeeta; Kumar, Yashvinder

    2016-02-01

    In this paper we present structural and vibrational study of three vinylpyrrole derivatives: 2-Cyano-3-(1H-pyrrol-2-yl)-acrylamide (CPA), 1-(1H-Pyrrol-2-yl)-Pent-1-en-3-one (PP) and 1-(1H-Pyrrol-2-yl)-but-1-en-3-one (PB), using ab initio, DFT and experimental approaches. The quantum chemical calculation have been performed on B3LYP method and 6-311+G(d,p) basis set. The experimental FT-IR and Raman wavenumbers were compared with the respective theoretical values obtained from DFT calculations and found to agree well. The experimental FT-IR and Raman study clearly indicate that the compound exist as dimer in solid state. The binding energies of (CPA), (PP) and (PB) dimers are found to be 20.95, 18.75 and 19.18kcal/mol, respectively. The vibrational analysis shows red shifts in vN-H and vCO stretching as result of dimer formation. Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using NBO analysis. Topological and energetic parameters reveal the nature of interactions in dimer. The local electronic descriptors analyses were used to predict the reactive sites in the molecule. Calculated first static hyperpolarizability of CPA, PP and PB is found to be 10.41×10(-30), 18.93×10(-30), 18.29×10(-30)esu, respectively, shows that investigated molecules will have non-linear optical response and might be used as non-linear optical (NLO) material. These vinylpyrrole compounds (CPA), (PP) and (PB) showed antifungal and antibacterial activity against Aspergillus niger and gram-positive bacteria Bacillus subtili. PMID:26513227