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Sample records for 1h-1h cosy hmqc

  1. Proton-detected 3D 14N/14N/1H isotropic shift correlation experiment mediated through 1H-1H RFDR mixing on a natural abundant sample under ultrafast MAS

    NASA Astrophysics Data System (ADS)

    Pandey, Manoj Kumar; Nishiyama, Yusuke

    2015-09-01

    In this contribution, we have demonstrated a proton detection-based approach on a natural abundant powdered L-Histidine HCl-H2O sample at ultrafast magic angle spinning (MAS) to accomplish 14N/14N correlation from a 3D 14N/14N/1H isotropic shift correlation experiment mediated through 1H finite-pulse radio frequency-driven recoupling (fp-RFDR). Herein the heteronuclear magnetization transfer between 14N and 1H has been achieved by HMQC experiment, whereas 14N/14N correlation is attained through enhanced 1H-1H spin diffusion process due to 1H-1H dipolar recoupling during the RFDR mixing. While the use of ultrafast MAS (90 kHz) provides sensitivity enhancement through increased 1H transverse relaxation time (T2), the use of micro-coil probe which can withstand strong 14N radio frequency (RF) fields further improves the sensitivity per unit sample volume.

  2. 1H-detected 1H- 1H correlation spectroscopy of a stereo-array isotope labeled amino acid under fast magic-angle spinning

    NASA Astrophysics Data System (ADS)

    Takahashi, Hiroki; Kainosho, Masatsune; Akutsu, Hideo; Fujiwara, Toshimichi

    2010-04-01

    The combined use of selective deuteration, stereo-array isotope labeling (SAIL), and fast magic-angle spinning effectively suppresses the 1H-1H dipolar couplings in organic solids. This method provided the high-field 1H NMR linewidths comparable to those achieved by combined rotation and multiple-pulse spectroscopy. This technique was applied to two-dimensional 1H-detected 1H-1H polarization transfer CHH experiments of valine. The signal sensitivity for the 1H-detected CHH experiments was greater than that for the 13C-detected 1H-1H polarization transfer experiments by a factor of 2-4. We obtained the 1H-1H distances in SAIL valine by CHH experiments with an accuracy of about 0.2 Å by using a theory developed for 1H-1H polarization transfer in 13C-labeled organic compounds.

  3. Three-Dimensional Maximum-Quantum Correlation HMQC NMR Spectroscopy (3D MAXY-HMQC)

    NASA Astrophysics Data System (ADS)

    Liu, Maili; Mao, Xi-An; Ye, Chaohui; Nicholson, Jeremy K.; Lindon, John C.

    1997-11-01

    The extension of two-dimensional maximum-quantum correlation spectroscopy (2D MAXY NMR), which can be used to simplify complex NMR spectra, to three dimensions (3D) is described. A new pulse sequence for 3D MAXY-HMQC is presented and exemplified using the steroid drug dexamethasone. The sensitivity and coherence transfer efficiency of the MAXY NMR approach has also been assessed in relation to other HMQC- and HSQC-based 3D methods.

  4. Crystal structure of 1H,1'H-[2,2'-biimid-azol]-3-ium hydrogen tartrate hemi-hydrate.

    PubMed

    Gao, Xiao-Li; Bian, Li-Fang; Guo, Shao-Wei

    2014-11-01

    In the crystal of the title hydrated salt, C6H7N4 (+)·C4H5O6 (-)·0.5H2O, the bi-imidazole monocation, 1H,1'H-[2,2'-biimidazol]-3-ium, is hydrogen bonded, via N-H⋯O, O-H⋯O and O-H⋯N hydrogen bonds, to the hydrogen tartrate anion and the water mol-ecule, which is located on a twofold rotation axis, forming sheets parallel to (001). The sheets are linked via C-H⋯O hydrogen bonds, forming a three-dimensional structure. There are also C=O⋯π inter-actions present [O⋯π distances are 3.00 (9) and 3.21 (7) Å], involving the carbonyl O atoms and the imidazolium ring, which may help to consolidate the structure. In the cation, the dihedral angle between the rings is 11.6 (2)°.

  5. Proton-detected 3D (15)N/(1)H/(1)H isotropic/anisotropic/isotropic chemical shift correlation solid-state NMR at 70kHz MAS.

    PubMed

    Pandey, Manoj Kumar; Yarava, Jayasubba Reddy; Zhang, Rongchun; Ramamoorthy, Ayyalusamy; Nishiyama, Yusuke

    2016-01-01

    Chemical shift anisotropy (CSA) tensors offer a wealth of information for structural and dynamics studies of a variety of chemical and biological systems. In particular, CSA of amide protons can provide piercing insights into hydrogen-bonding interactions that vary with the backbone conformation of a protein and dynamics. However, the narrow span of amide proton resonances makes it very difficult to measure (1)H CSAs of proteins even by using the recently proposed 2D (1)H/(1)H anisotropic/isotropic chemical shift (CSA/CS) correlation technique. Such difficulties due to overlapping proton resonances can in general be overcome by utilizing the broad span of isotropic chemical shifts of low-gamma nuclei like (15)N. In this context, we demonstrate a proton-detected 3D (15)N/(1)H/(1)H CS/CSA/CS correlation experiment at fast MAS frequency (70kHz) to measure (1)H CSA values of unresolved amide protons of N-acetyl-(15)N-l-valyl-(15)N-l-leucine (NAVL).

  6. Vicinal 1H-1H NMR coupling constants from density functional theory as reliable tools for stereochemical analysis of highly flexible multichiral center molecules.

    PubMed

    López-Vallejo, Fabian; Fragoso-Serrano, Mabel; Suárez-Ortiz, Gloria Alejandra; Hernández-Rojas, Adriana C; Cerda-García-Rojas, Carlos M; Pereda-Miranda, Rogelio

    2011-08-05

    A protocol for stereochemical analysis, based on the systematic comparison between theoretical and experimental vicinal (1)H-(1)H NMR coupling constants, was developed and applied to a series of flexible compounds (1-8) derived from the 6-heptenyl-5,6-dihydro-2H-pyran-2-one framework. The method included a broad conformational search, followed by geometry optimization at the DFT B3LYP/DGDZVP level, calculation of the vibrational frequencies, thermochemical parameters, magnetic shielding tensors, and the total NMR spin-spin coupling constants. Three scaling factors, depending on the carbon atom hybridizations, were found for the (1)H-C-C-(1)H vicinal coupling constants: f((sp3)-(sp3)) = 0.910, f((sp3)-(sp2)) = 0.929, and f((sp2)-(sp2))= 0.977. A remarkable correlation between the theoretical (J(pre)) and experimental (1)H-(1)H NMR (J(exp)) coupling constants for spicigerolide (1), a cytotoxic natural product, and some of its synthetic stereoisomers (2-4) demonstrated the predictive value of this approach for the stereochemical assignment of highly flexible compounds containing multiple chiral centers. The stereochemistry of two natural 6-heptenyl-5,6-dihydro-2H-pyran-2-ones (14 and 15) containing diverse functional groups in the heptenyl side chain was also analyzed by application of this combined theoretical and experimental approach, confirming its reliability. Additionally, a geometrical analysis for the conformations of 1-8 revealed that weak hydrogen bonds substantially guide the conformational behavior of the tetraacyloxy-6-heptenyl-2H-pyran-2-ones.

  7. Selective excitation enables assignment of proton resonances and (1)H-(1)H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy.

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-21

    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 (1)H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as (13)C or (15)N. In this method, after the initial preparation of proton magnetization and cross-polarization to (13)C nuclei, transverse magnetization of desired (13)C 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 (13)C 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 (1)H-(1)H 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.

  8. 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.

  9. Structural, electronic and vibrational properties of N,N'-1H,1H-perfluorobutyl dicyanoperylenecarboxydiimide (PDI-FCN2) crystal.

    PubMed

    Colle, Renato; Grosso, Giuseppe; Cassinese, Antonio; Centore, Roberto

    2013-09-21

    We present a theoretical and experimental investigation of the crystalline structure of N,N'-1H,1H-perfluorobutyl dicyanoperylenecarboxydiimide (PDI-FCN2) that has been deduced combining experimental XRD data, obtained from powders, with global-optimization algorithms which allow to identify Bravais lattice, primitive cell parameters, and space group of the crystal. The XRD spectrum calculated for the proposed crystalline structure very well reproduces the measured XRD data. Our results suggest the triclinic lattice structure of spatial groups P1 and P1, respectively, for the crystalline PDI-FCN2-1,7 and PDI-FCN2-1,6 isomers. In both cases, the primitive cell contains a single molecule. On the proposed crystalline structures, KS-DFT cell energy calculations, including van der Waals interactions, have been performed to assign the minimum energy geometrical structure and orientation of the molecule inside the corresponding primitive cell. These calculations evidence the molecular packing that characterizes the strong anisotropy of the PDI-FCN2 crystal. Electronic band-structures calculated for both isomers within the Kohn-Sham density-functional theory indicate that the crystalline P1 structure is an indirect gap semiconductor, while the P1 structure is a direct gap semiconductor. The electronic band structure calculations on the optimized crystal geometries highlight strong anisotropy in the dispersion curves E(k), which roots at the molecular packing in the crystal. Finally, the vibrational spectrum of both crystalline isomers has been calculated in the harmonic approximation and the dominant vibrational frequencies have been associated to collective motions of selected atoms in the molecules.

  10. Structural, electronic and vibrational properties of N,N'-1H,1H-perfluorobutyl dicyanoperylenecarboxydiimide (PDI-FCN2) crystal

    NASA Astrophysics Data System (ADS)

    Colle, Renato; Grosso, Giuseppe; Cassinese, Antonio; Centore, Roberto

    2013-09-01

    We present a theoretical and experimental investigation of the crystalline structure of N,N'-1H,1H-perfluorobutyl dicyanoperylenecarboxydiimide (PDI-FCN2) that has been deduced combining experimental XRD data, obtained from powders, with global-optimization algorithms which allow to identify Bravais lattice, primitive cell parameters, and space group of the crystal. The XRD spectrum calculated for the proposed crystalline structure very well reproduces the measured XRD data. Our results suggest the triclinic lattice structure of spatial groups Poverline{1} and P1, respectively, for the crystalline PDI-FCN2-1,7 and PDI-FCN2-1,6 isomers. In both cases, the primitive cell contains a single molecule. On the proposed crystalline structures, KS-DFT cell energy calculations, including van der Waals interactions, have been performed to assign the minimum energy geometrical structure and orientation of the molecule inside the corresponding primitive cell. These calculations evidence the molecular packing that characterizes the strong anisotropy of the PDI-FCN2 crystal. Electronic band-structures calculated for both isomers within the Kohn-Sham density-functional theory indicate that the crystalline Poverline{1} structure is an indirect gap semiconductor, while the P1 structure is a direct gap semiconductor. The electronic band structure calculations on the optimized crystal geometries highlight strong anisotropy in the dispersion curves E(k), which roots at the molecular packing in the crystal. Finally, the vibrational spectrum of both crystalline isomers has been calculated in the harmonic approximation and the dominant vibrational frequencies have been associated to collective motions of selected atoms in the molecules.

  11. Population transfer HMQC for half-integer quadrupolar nuclei

    SciTech Connect

    Wang, Qiang; Xu, Jun; Feng, Ningdong; Deng, Feng E-mail: jean-paul.amoureux@univ-lille1.fr; Li, Yixuan; Trébosc, Julien; Lafon, Olivier; Hu, Bingwen; Chen, Qun; Amoureux, Jean-Paul E-mail: jean-paul.amoureux@univ-lille1.fr

    2015-03-07

    This work presents a detailed analysis of a recently proposed nuclear magnetic resonance method [Wang et al., Chem. Commun. 49(59), 6653-6655 (2013)] for accelerating heteronuclear coherence transfers involving half-integer spin quadrupolar nuclei by manipulating their satellite transitions. This method, called Population Transfer Heteronuclear Multiple Quantum Correlation (PT-HMQC), is investigated in details by combining theoretical analyses, numerical simulations, and experimental investigations. We find that compared to instant inversion or instant saturation, continuous saturation is the most practical strategy to accelerate coherence transfers on half-integer quadrupolar nuclei. We further demonstrate that this strategy is efficient to enhance the sensitivity of J-mediated heteronuclear correlation experiments between two half-integer quadrupolar isotopes (e.g., {sup 27}Al-{sup 17}O). In this case, the build-up is strongly affected by relaxation for small T{sub 2}′ and J coupling values, and shortening the mixing time makes a huge signal enhancement. Moreover, this concept of population transfer can also be applied to dipolar-mediated HMQC experiments. Indeed, on the AlPO{sub 4}-14 sample, one still observes experimentally a 2-fold shortening of the optimum mixing time albeit with no significant signal gain in the {sup 31}P-({sup 27}Al) experiments.

  12. Physics at CELSIUS and COSY

    SciTech Connect

    Machner, H.

    2006-02-11

    We review some selected experimental results achieved at the synchrotrons CELSIUS in Sweden and COSY in Germany. They concentrate on meson production with emphasis on the underlying quark structure. The project WASA at COSY is discussed and the search for symmetry breaking in decays of {eta} and {eta}' mesons is highlighted.

  13. Physics at COSY-Juelich

    SciTech Connect

    Stroeher, Hans

    2011-10-21

    COSY, a storage and cooler synchrotron, which is fed by an injector cyclotron, is operated at Forschungszentrum Juelich (Germany). It provides phase space cooled polarized or unpolarized beams of protons and deuterons with momenta between 0.3 and 3.7 GeV/c for internal experiments and to external target stations. The major experimental facilities, used for the ongoing physics program, are ANKE and WASA (internal) and TOF (external). A new internal target station to investigate polarization build-up by spin-filtering (PAX) has recently been commissioned. COSY is the machine for hadron spin physics on a world-wide scale, which is also used for tests in conjunction with plans to build a dedicated storage ring for electric dipole moment (EDM) measurements of proton, deuteron and {sup 3}He. In this contribution recent results as well as future plans are summarized.

  14. N*ews from COSY

    NASA Astrophysics Data System (ADS)

    Ströher, Hans

    2012-04-01

    COSY, a storage and cooler synchrotron, which is fed by an injector cyclotron, is operated at Forschungszentrum Jülich (Germany). It provides phase space cooled polarized or unpolarized beams of protons and deuterons with momenta between 0.3 and 3.7 GeV/c for internal experiments and to external target stations. The major experimental facilities, used for the ongoing physics program, are ANKE and WASA (internal) and TOF (external). A new internal target station to investigate polarization build-up by spin-filtering (PAX) has recently been commissioned. COSY is the machine for hadron spin physics on a world-wide scale, which in recent times is also used for tests in conjunction with plans to build a dedicated storage ring for electric dipole moment (EDM) measurements of proton, deuteron and 3He. In this contribution selected experimental results from the N*-program are presented.

  15. Elucidation of the structures of residual and dissolved pine kraft lignins using an HMQC NMR technique.

    PubMed

    Balakshin, Mikhail Yu; Capanema, Ewellyn A; Chen, Chen-Loung; Gracz, Hanna S

    2003-10-08

    Comparative studies on the structures of residual and dissolved lignins isolated from pine kraft pulp and pulping liquor have been undertaken using the (1)H-(13)C HMQC NMR technique, GPC, and sugar analysis to elucidate the reaction mechanisms in kraft pulping and the lignin reactivity. A modified procedure for the isolation of enzymatic residual lignins has resulted in an appreciable decrease in protein contaminants in the residual lignin preparations (N content < 0.2%). The very high dispersion of HMQC spectra allows identification of different lignin moieties, which signals appear overlapped in 1D (13)C NMR spectra. Elucidation of the role of condensation reactions indicates that an increase in the degree of lignin condensation during pulping results from accumulation of original condensed lignin moieties rather than from the formation of new alkyl-aryl structures. Among aryl-vinyl type moieties, only stilbene structures are accumulated in lignin in appreciable amounts. Benzyl ether lignin-carbohydrate bonds involving primary hydroxyl groups of carbohydrates have been detected in residual and dissolved lignin preparations. Structures of the alpha-hydroxyacid type have been postulated to be among the important lignin degradation products in kraft pulping. The effect of the isolation method on the lignin structure and differences between the residual and dissolved lignins are discussed.

  16. Recent Results from Experiments at COSY

    SciTech Connect

    Goldenbaum, Frank

    2010-08-05

    In hadron physics, experiments using hadronic probes may shed light on open questions on the structure of hadrons, their interactions that are subject to the strong force and on the symmetries of nature. Therefore a major focus of the physics program studied at the COoler SYnchrotron COSY of the Forschungszentrum Juelich is the production of mesons and hyperons in hadron- hadron scattering with the aim to investigate relevant production processes, interactions of the participating particles as well as symmetries and symmetry breaking. The COoler SYnchrotron COSY at Juelich accelerates protons and deuterons with momenta up to 3.7 GeV/c covering hadron physics in the light quark sector. The availability of the beam cooling systems allow precision measurements, using polarized proton and deuteron beams in combination with polarized Hydrogen or Deuterium targets. Due to the excellent experimental conditions at COSY single- and double-polarization measurements can be performed with high reaction rates. With the operation of the recently installed WASA-at-COSY apparatus, high-statistics studies aiming at rare decays of {eta} and {eta}{sup '} are effectively turning COSY into a meson factory. This contribution summarizes the ongoing physics program at the COSY facility, using the detector systems ANKE, WASA and COSY-TOF highlighting a few selective recent results and outlining future developments. The research at COSY also provides a step towards the realization of FAIR with studies on spin manipulation and polarization build-up of protons in polarized targets.

  17. Unequivocal assignments of flavonoids from Tephrosia sp. (Fabaceae).

    PubMed

    Arriaga, A M C; Lima, J Q; Vasconcelos, J N; de Oliveira, M C F; Andrade-Neto, M; Santiago, G M P; Uchoa, D E A; Malcher, G T; Mafezoli, J; Braz-Filho, R

    2009-06-01

    (1)H and (13)C NMR chemical shifts of praecansone B, pongaflavone and dehydrorotenone isolated from Tephrosia egregia Sandw and obovatin from T. toxicaria Pers. were unambiguously assigned by 1D and 2D NMR experiments including (1)H, (1)H COSY, gHMQC and gHMBC, allowing the correction of literature assignments.

  18. Highly oxygenated monoterpenes from Chenopodium ambrosioides.

    PubMed

    Ahmed, A A

    2000-07-01

    Three new monoterpenes (3-5) were isolated from an organic extract of the aerial parts of Chenopodium ambrosioides. Structures were established on the basis of MS and NMR spectroscopic ((1)H, (13)C, (1)H-(1)H COSY, HMQC and HMBC) data.

  19. Acylated pregnane glycosides from Caralluma russeliana.

    PubMed

    Abdel-Sattar, Essam; Ahmed, Ahmed A; Hegazy, Mohamed-Elamir F; Farag, Mohamed A; Al-Yahya, Mohammad Abdul-Aziz

    2007-05-01

    The chloroform extract of the aerial parts of Caralluma russeliana yielded four acylated pregnane glycosides, namely russeliosides E-H, three were found now. The structures of the compounds were elucidated using MS, 1H NMR, 13C NMR, 1H-1H COSY, HMQC, NOESY and HMBC experiments.

  20. Probing hydrogen bonding in cocrystals and amorphous dispersions using (14)N-(1)H HMQC solid-state NMR.

    PubMed

    Tatton, Andrew S; Pham, Tran N; Vogt, Frederick G; Iuga, Dinu; Edwards, Andrew J; Brown, Steven P

    2013-03-04

    Cocrystals and amorphous solid dispersions have generated interest in the pharmaceutical industry as an alternative to more established solid delivery forms. The identification of intermolecular hydrogen bonding interactions in a nicotinamide palmitic acid cocrystal and a 50% w/w acetaminophen-polyvinylpyrrolidone solid dispersion are reported using advanced solid-state magic-angle spinning (MAS) NMR methods. The application of a novel (14)N-(1)H HMQC experiment, where coherence transfer is achieved via through-space couplings, is shown to identify specific hydrogen bonding motifs. Additionally, (1)H isotropic chemical shifts and (14)N electric field gradient (EFG) parameters, both accessible from (14)N-(1)H HMQC experiments, are shown to be sensitive to changes in hydrogen bonding geometry. Numerous indicators of molecular association are accessible from this experiment, including NH cross-peaks occurring from intermolecular hydrogen bonds and changes in proton chemical shifts or electric field gradient parameters. First-principles calculations using the GIPAW approach that yield accurate estimates of isotropic chemical shifts, and EFG parameters were used to assist in assignment. It is envisaged that (14)N-(1)H HMQC solid state NMR experiments could become a valuable screening technique of solid delivery forms in the pharmaceutical industry.

  1. Making Submicron CoSi2 Structures On Silicon Substrates

    NASA Technical Reports Server (NTRS)

    Nieh, Simon K. W.; Lin, True-Lon; Fathauer, Robert W.

    1989-01-01

    Experimetnal fabrication process makes submicron-sized structures of single-crystal metallic CoSi2 on silicon substrates. Amorphous Co:Si(1:2) crystallized by electron beam becoming single-crystal CoSi2. Remaining amorphous Co:Si then preferentially etched away. When fully developed, process used to make fine wires or dots exhibiting quantum confinement of charge carriers.

  2. Electrostatic potential map modelling with COSY Infinity

    NASA Astrophysics Data System (ADS)

    Maloney, J. A.; Baartman, R.; Planche, T.; Saminathan, S.

    2016-06-01

    COSY Infinity (Makino and Berz, 2005) is a differential-algebra based simulation code which allows accurate calculation of transfer maps to arbitrary order. COSY's existing internal procedures were modified to allow electrostatic elements to be specified using an array of field potential data from the midplane. Additionally, a new procedure was created allowing electrostatic elements and their fringe fields to be specified by an analytic function. This allows greater flexibility in accurately modelling electrostatic elements and their fringe fields. Applied examples of these new procedures are presented including the modelling of a shunted electrostatic multipole designed with OPERA, a spherical electrostatic bender, and the effects of different shaped apertures in an electrostatic beam line.

  3. Physics at COSY-Jülich

    NASA Astrophysics Data System (ADS)

    Ströher, Hans

    2011-10-01

    COSY, a storage and cooler synchrotron, which is fed by an injector cyclotron, is operated at Forschungszentrum Jülich (Germany). It provides phase space cooled polarized or unpolarized beams of protons and deuterons with momenta between 0.3 and 3.7 GeV/c for internal experiments and to external target stations. The major experimental facilities, used for the ongoing physics program, are ANKE and WASA (internal) and TOF (external). A new internal target station to investigate polarization build-up by spin-filtering (PAX) has recently been commissioned. COSY is the machine for hadron spin physics on a world-wide scale, which is also used for tests in conjunction with plans to build a dedicated storage ring for electric dipole moment (EDM) measurements of proton, deuteron and 3He. In this contribution recent results as well as future plans are summarized.

  4. Making CoSi(2) Layers By Ion Implantation

    NASA Technical Reports Server (NTRS)

    Namavar, Fereydoon

    1994-01-01

    Monolithic photovoltaic batteries containing vertical cells include buried CoSi(2) contact layers. Vertical-junction photovoltaic cells in series fabricated in monolithic structure. N- and p-doped silicon layers deposited epitaxially. The CoSi(2) layers, formed by ion implantation and annealing, serve as thin, low-resistance ohmic contacts between cells.

  5. Meson-production experiments at COSY-Jülich

    NASA Astrophysics Data System (ADS)

    Büscher, M.

    2010-09-01

    Selected results from experiments at COSY-Jülich are presented: an attempt to measure the mass of the η meson with high precision (ANKE facility), first steps towards the detection of rare η decays (WASA), and several measurements of Kbar K-pair production (ANKE, COSY-11, MOMO).

  6. Spin Filtering Studies at COSY and AD

    SciTech Connect

    Nass, Alexander

    2009-08-04

    The high physics potential of experiments with stored high-energy polarized antiprotons led to the proposal of PAX (Polarized Antiproton eXperiment) for the High Energy Storage Ring (HESR) of the FAIR at GSI (Darmstadt/Germany). It is proposed to polarize a stored antiproton beam by means of spin filtering with a polarized H (D) gas target. The feasibility of spin filtering has been demonstrated in the FILTEX experiment. The current interpretation foresees a self-cancellation of the electron contribution to the filtering process and only the hadronic contribution is effective. Several experimental studies with protons (at COSY/Juelich) as well as antiprotons (at AD/CERN) will be carried out to test the principle and measure p-barp-vector and p-bard-vector cross sections. A polarized internal gas target (PIT) with surrounding Silicon detectors immersed into a low-beta section has to be set up.

  7. Spin Filtering Studies at COSY and AD

    NASA Astrophysics Data System (ADS)

    Nass, Alexander

    2009-08-01

    The high physics potential of experiments with stored high-energy polarized antiprotons led to the proposal of PAX (Polarized Antiproton eXperiment) [1] for the High Energy Storage Ring (HESR) of the FAIR at GSI (Darmstadt/Germany). It is proposed to polarize a stored antiproton beam by means of spin filtering with a polarized H (D) gas target. The feasibility of spin filtering has been demonstrated in the FILTEX experiment. The current interpretation foresees a self-cancellation of the electron contribution to the filtering process and only the hadronic contribution is effective. Several experimental studies with protons (at COSY/Jülich) as well as antiprotons (at AD/CERN) will be carried out to test the principle and measure p¯p⃗ and p¯d⃗ cross sections. A polarized internal gas target (PIT) with surrounding Silicon detectors immersed into a low-β section has to be set up.

  8. Two compounds from Peucedanum dissolutum.

    PubMed

    Wu, Xian-Li; Li, Yi; Kong, Ling-Yi; Min, Zhi-Da

    2004-12-01

    A new compound, 3'(R)-O-beta-D-glucopyranosyl-3',4'-dihydroxanthyletin (1), and a known compound, prim-O-glucosylcimifugin (2), were isolated from the roots of Peucedanum dissolutum. The structure of 1 was elucidated by spectral evidence and chemical reaction. The NMR signals of carbons and protons of 2 were assigned for the first time by analysis of (1)H-(1)H COSY, HMQC and HMBC spectra.

  9. Two new pentacyclic triterpenoids from Lantana camara LINN.

    PubMed

    Begum, Sabira; Zehra, Syeda Qamar; Siddiqui, Bina Shaheen

    2008-09-01

    Two new pentacyclic triterpenoids, namely lantanoic acid (1) and camaranoic acid (2), and six known compounds such as lantic acid, camarinic acid, camangeloyl acid, camarinin, oleanonic acid, and ursonic acid were isolated from the aerial parts of Lantana camara LINN. Structures of the new constituents were elucidated by chemical transformation and spectral studies including 1D ((1)H- and (13)C-NMR) and 2D ((1)H-(1)H correlation spectroscopy (COSY), nuclear Overhauser effect spectroscopy (NOESY), (1)H-(1)H total correlation spectroscopy (TOCSY), J-resolved, (1)H-detected heteronuclear multiple quantum coherence (HMQC), and heteronuclear multiple bond connectivity (HMBC)) NMR spectroscopy.

  10. COSI: The Compton Spectrometer and Imager Science Program

    NASA Astrophysics Data System (ADS)

    Tomsick, John; Jean, Pierre; Chang, Hsiang-Kuang; Boggs, Steven; Zoglauer, A.; Von Ballmoos, Peter; Amman, Mark; Chiu, Jeng-Lun; Chang, Yuan-Hann.; Chou, Yi; Kierans, Carolyn; Lin, Chih-Hsun.; Lowell, Alex; Shang, Jie-Rou.; Tseng, Chao-Hsiung; Yang, Chien-Ying

    The Compton Spectrometer and Imager (COSI), which was formerly known as the Nuclear Compton Telescope (NCT), is a balloon-borne soft gamma-ray telescope (0.2-5 MeV) designed to probe the origins of Galactic positrons, uncover sites of nucleosynthesis in the Galaxy, and perform pioneering studies of gamma-ray polarization in a number of source classes. COSI uses a compact Compton telescope design, resulting from a decade of development under NASA's ROSES program - a modern take on techniques successfully pioneered by COMPTEL on CGRO. We have rebuilt the COSI instrument and flight systems, upgraded for balloon flights and improved polarization sensitivity. We will present the redesign of COSI and the overall goals of the 5-year science program. Three science flights are planned to fulfill the COSI science goals: an LDB in 2014 from Antarctica on a superpressure balloon (SuperCOSI), followed by two 100-day ULDB flights from New Zealand. COSI is a wide-field survey telescope designed to perform imaging, spectroscopy, and polarization measurements. It employs a novel Compton telescope design utilizing a compact array of cross-strip germanium detectors (GeDs) to resolve individual gamma-ray interactions with high spectral and spatial resolution. The COSI array is housed in a common vacuum cryostat cooled by a mechanical cryocooler. An active CsI shield encloses the cryostat on the sides and bottom. The FoV of the instrument covers 25% of the full sky at a given moment. The COSI instrument is mature, building upon considerable heritage from the previous NCT balloon instrument that underwent a successful technology demonstration flight in June 2005 from Fort Sumner, NM, a successful "first light" science flight from Fort Sumner in May 2009, and quickly turned around and delivered on time for a launch campaign from Alice Springs, Australia in June 2010, where it unfortunately suffered a launch mishap. The NCT instrument and Flight System are being rebuilt under the NASA

  11. CLIP-COSY: A Clean In-Phase Experiment for the Rapid Acquisition of COSY-type Correlations.

    PubMed

    Koos, Martin R M; Kummerlöwe, Grit; Kaltschnee, Lukas; Thiele, Christina M; Luy, Burkhard

    2016-06-27

    The COSY experiment is an essential homonuclear 2D NMR experiment for the assignment of resonances. Its multiplet line shape, however, is often overly complicated, potentially leads to signal intensity losses, and is responsible for long minimum overall acquisition times. Herein, we present CLIP-COSY, a COSY-type experiment yielding clean in-phase peaks. It can be recorded within a few minutes and benefits from enhanced signal intensities for most cross-peaks. In combination with non-uniform sampling, the experiment times can be further reduced, and the in-phase multiplets enable the application of modern homonuclear decoupling techniques in both dimensions. As antiphase cancelations are avoided, CLIP-COSY can also be applied to macromolecules and other samples with broadened lines.

  12. The Compton Spectrometer and Imager (COSI) Superpressure Balloon Payload

    NASA Astrophysics Data System (ADS)

    Boggs, Steven E.

    2014-08-01

    The Compton Spectrometer and Image (COSI) is a ULDB-borne soft gamma-ray telescope (0.2-5 MeV) designed to probe the origins of Galactic positrons, uncover sites of nucleosynthesis in the Galaxy, and perform pioneering studies of gamma-ray polarization in a number of source classes. COSI uses a compact Compton telescope design, resulting from a decade of development under NASA’s ROSES program - a modern take on techniques successfully pioneered by COMPTEL on CGRO. COSI performs groundbreaking science by combining improvements in sensitivity, spectral resolution, and sky coverage. The COSI instrument and flight systems have been designed for flight on NASA’s 18 MCF superpressure balloon (SPB). We are now beginning a series science flights to fulfill the COSI science goals: a SPB in 2014 from Antarctica, followed by two 100-day ULDB flights from New Zealand.COSI is a wide-field survey telescope designed to perform imaging, spectroscopy, and polarization measurements. It employs a novel Compton telescope design utilizing a compact array of cross-strip germanium detectors (GeDs) to resolve individual gamma-ray interactions with high spectral and spatial resolution. The COSI array is housed in a common vacuum cryostat cooled by a mechanical cryocooler. An active CsI Shield encloses the cryostat on the sides and bottom. The FoV of the instrument covers 25% of the full sky at a given moment.The COSI instrument builds upon considerable heritage from the previous Nuclear Compton Telescope (NCT) balloon instrument that underwent a successful technology demonstration flight in June 2005 from Fort Sumner, NM, a successful “first light” science flight from Fort Sumner in May 2009, and a launch campaign from Alice Springs, Australia in June 2010, where it unfortunately suffered a launch mishap. COSI has been upgraded from the previous NCT instrument by conversion to a detector configuration optimized for polarization sensitivity and addition of a cryocooler to remove

  13. EPIC Muon Cooling Simulations using COSY INFINITY

    SciTech Connect

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

    2011-03-01

    Next gen­er­a­tion mag­net sys­tems need­ed for cool­ing chan­nels in both neu­tri­no fac­to­ries and muon col­lid­ers will be in­no­va­tive and com­pli­cat­ed. De­sign­ing, sim­u­lat­ing and op­ti­miz­ing these sys­tems is a chal­lenge. Using COSY IN­FIN­I­TY, a dif­fer­en­tial al­ge­bra-based code, to sim­u­late com­pli­cat­ed el­e­ments can allow the com­pu­ta­tion and cor­rec­tion of a va­ri­ety of high­er order ef­fects, such as spher­i­cal and chro­mat­ic aber­ra­tions, that are dif­fi­cult to ad­dress with other sim­u­la­tion tools. As an ex­am­ple, a he­li­cal dipole mag­net has been im­ple­ment­ed and sim­u­lat­ed, and the per­for­mance of an epicyclic para­met­ric ion­iza­tion cool­ing sys­tem for muons is stud­ied and com­pared to sim­u­la­tions made using G4Beam­line, a GEAN­T4 toolk­it.

  14. Studying the magnetic properties of CoSi single crystals

    SciTech Connect

    Narozhnyi, V. N. Krasnorussky, V. N.

    2013-05-15

    The magnetic properties of CoSi single crystals have been measured in a range of temperatures T = 5.5-450 K and magnetic field strengths H {<=} 11 kOe. A comparison of the results for crystals grown in various laboratories allowed the temperature dependence of magnetic susceptibility {chi}(T) = M(T)/H to be determined for a hypothetical 'ideal' (free of magnetic impurities and defects) CoSi crystal. The susceptibility of this ideal crystal in the entire temperature range exhibits a diamagnetic character. The {chi}(T) value significantly increases in absolute value with decreasing temperature and exhibits saturation at the lowest temperatures studied. For real CoSi crystals of four types, paramagnetic contributions to the susceptibility have been evaluated and nonlinear (with respect to the field) contributions to the magnetization have been separated and taken into account in the calculations of {chi}(T).

  15. Polarization of stored beam by spin-filtering at COSY

    NASA Astrophysics Data System (ADS)

    Ciullo, G.

    2014-01-01

    In the challenging aim to achieve polarized antiproton, the PAX collaboration performed dedicated measurements of the spin-dependent polarizing cross section for p- p scattering at COSY. The result, under a very nice control of the process, agrees with the theoretical previsions, and confirms the pursuability of the spin-filtering for polarizing antiprotons.

  16. Physics Program at COSY-Juelich with Polarized Hadronic Probes

    SciTech Connect

    Kacharava, Andro

    2009-08-04

    Hadron physics aims at a fundamental understanding of all particles and their interactions that are subject to the strong force. Experiments using hadronic probes could contribute to shed light on open questions on the structure of hadrons and their interaction as well as the symmetries of nature. The COoler SYnchrotron COSY at the Forschungszentrum Juelich accelerates protons and deuterons with momenta up to 3.7 GeV/c. The availability of both an electron cooler as well as a stochastic beam cooling system allows for precision measurements, using polarized proton and deuteron beams in combination with polarized Hydrogen or Deuterium targets.This contribution summarizes the ongoing physics program at the COSY facility using ANKE, WASA and TOF detector systems with polarized hadronic probes, highlighting recent results and outlining the new developments.

  17. Microstructural characterization of as-cast Co-Si alloys

    SciTech Connect

    Faria, M.I.S.T. . E-mail: ismenia@phase.faenquil.br; Coelho, G.C.; Nunes, C.A.; Avillez, R.R.

    2006-01-15

    This work presents results of microstructural characterization of as-cast Co-Si alloys. The alloys of different compositions were prepared by arc melting Co (min. 99.97%) and Si (min. 99.99%) under argon atmosphere in a water-cooled copper crucible with a nonconsumable tungsten electrode and titanium getter. All samples were characterized by scanning electron microscopy (SEM) using back-scattered electron (BSE) mode and X-ray diffraction (XRD). A good conformity between the currently accepted Co-Si phase diagram and the experimental results from this work was verified. No indication of the {beta}Co{sub 2}Si was observed in the as-cast microstructures. As in previous investigations, the Co{sub 3}Si phase has not been observed in the samples at room temperature; however, microstructural evidence suggests its stability at high temperature.

  18. Recent Results from the WASA-at-COSY Experiment

    SciTech Connect

    Kupsc, Andrzej

    2011-10-24

    Studies of light meson decays are the key experiments for the WASA detector at COSY-Juelich. One of the world largest data samples of the {eta} meson decays have been recently collected in the pd {yields}{sup 3}He{eta} and in the pp {yields} pp{eta} reactions. The status of the analysis of various decay channels and the further plans for the light meson decay program are presented.

  19. First internal and external experiments at COSY Juelich

    NASA Astrophysics Data System (ADS)

    Prasuhn, D.; Maier, R.; Bechstedt, U.; Dietrich, J.; Hacker, U.; Martin, S.; Stockhorst, H.; Tölle, R.; Grzonka, D.; Nake, C.; Mosel, F.

    1995-02-01

    The inauguration of the cooler synchrotron COSY Jülich was celebrated on April 1st, 1993. After the first successful acceleration to proton momenta above 800 GeV/ c, beamtimes for experiments were scheduled in parallel to further machine development. The first experiment was the internal target experiment EDDA, which investigated the energy dependence of the p-p interaction. It makes use of a 3 × 4 μm 2 thin CH 2 fiber as an internal target. The thickness of the fiber is more than adequate to achieve high luminosities, so the intensity of the stored beam has to be reduced to 10 7 p. On the other hand, it is thin enough to achieve beam lifetimes of 3 s at 1.4 GeV/ c. Details of the target fabrication and the first experimental results will be discussed. Both external experimental facilities at COSY, the time-of-flight spectrometer, and the magnetic spectrometer BIG KARL use a liquid hydrogen (deuterium) target. The first experiments were carried out at proton energies between 300 MeV and 500 MeV. Also, these experimental data will be presented. Two further internal experiments are prepared for the installation into the COSY ring. The target for the first experiment is a gas-jet target, the second experiment uses ribbon targets for the interaction. The status of both experimental setups will be shown.

  20. Interaction of Cu with CoSi2 with and without TiNx barrier layers

    NASA Astrophysics Data System (ADS)

    Olowolafe, J. O.; Li, Jian; Blanpain, B.; Mayer, J. W.

    1990-09-01

    Thermally induced interactions of Cu with CoSi2, with and without interposed TiNx layers, have been studied using Rutherford backscattering spectrometry, Auger electron spectroscopy, and x-ray diffraction. Cu diffuses through a preformed CoSi2 layer to form the structure Cu/CoSi2/Cu3Si/Si at temperatures above 300 °C, and no dissociation of CoSi2 occurs. A 50 nm TiNx(x≊1) layer is observed to be an effective diffusion barrier up to about 500 °C between Cu and CoSi2.

  1. Ultrafast acquisition of (1)H-(1)H dipolar correlation experiments in spinning elastomers.

    PubMed

    Rouger, Laetitia; Yon, Maxime; Sarou-Kanian, Vincent; Fayon, Franck; Dumez, Jean-Nicolas; Giraudeau, Patrick

    2017-02-09

    We show that two widely used 2D solid-state NMR (ssNMR) pulse sequences can be implemented in an ultrafast (UF) manner, and yield 2D spectra of elastomers in a single scan, under magic-angle spinning. UF 2D ssNMR provides an acceleration of one to several orders of magnitude for classic experiments.

  2. Fabrication of nanometer single crystal metallic CoSi2 structures on Si

    NASA Technical Reports Server (NTRS)

    Nieh, Kai-Wei (Inventor); Lin, True-Lon (Inventor); Fathauer, Robert W. (Inventor)

    1991-01-01

    Amorphous Co:Si (1:2 ratio) films are electron gun-evaporated on clean Si(111), such as in a molecular beam epitaxy system. These layers are then crystallized selectively with a focused electron beam to form very small crystalline Co/Si2 regions in an amorphous matrix. Finally, the amorphous regions are etched away selectively using plasma or chemical techniques.

  3. Jusbetonin, the first indolo[3,2-b]quinoline alkaloid glycoside, from Justicia betonica.

    PubMed

    Subbaraju, Gottumukkala V; Kavitha, Jakka; Rajasekhar, Dodda; Jimenez, Jorge I

    2004-03-01

    A new indolo[3,2-b]quinoline alkaloid glycoside, jusbetonin (1), and three known alkaloids, namely, 10H-quindoline (2), 6H-quinindoline (3), and 5H,6H-quinindolin-11-one (4), have been isolated from the leaves of Justicia betonica. The structure of 1 was established on the basis of 1D and 2D NMR ((1)H-(1)H COSY, HMQC, and HMBC) and HRFABMS data. Compound 1 is the first example of a glycosylated indolo[3,2-b]quinoline alkaloid, while compound 4 was isolated for the first time from a natural source.

  4. The O-polysaccharide from the lipopolysaccharide of Providencia stuartii O44 contains L-quinovose, a 6-deoxy sugar rarely occurring in bacterial polysaccharides.

    PubMed

    Kocharova, Nina A; Ovchinnikova, Olga G; Toukach, Filip V; Torzewska, Agnieszka; Shashkov, Alexander S; Knirel, Yuriy A; Rozalski, Antoni

    2005-05-23

    The O-polysaccharide (O-antigen) of Providencia stuartii O44:H4 (strain 3768/51) was obtained by mild acid degradation of the lipopolysaccharide and studied by sugar and methylation analyses along with (1)H and (13)C NMR spectroscopy, including 2D (1)H,(1)H COSY, TOCSY, ROESY, and H-detected (1)H,(13)C HSQC, and HMQC-TOCSY experiments. The O-polysaccharide was found to have a branched hexasaccharide repeating unit of the following structure: [Formula: see text].

  5. A fatty acid glycoside from a marine-derived fungus isolated from mangrove plant Scyphiphora hydrophyllacea.

    PubMed

    Zeng, Yan-Bo; Wang, Hui; Zuo, Wen-Jian; Zheng, Bo; Yang, Tao; Dai, Hao-Fu; Mei, Wen-Li

    2012-03-01

    To study the antimicrobial components from the endophytic fungus A1 of mangrove plant Scyphiphora hydrophyllacea Gaertn. F., a new fatty acid glucoside was isolated by column chromatography from the broth of A1, and its structure was identified as R-3-hydroxyundecanoic acid methylester-3-O-α-l-rhamnopyranoside (1) by spectroscopic methods including 1D and 2D NMR (HMQC, (1)H-(1)H COSY and HMBC) and chemical methods. Antimicrobial assay showed compound 1 possessed modest inhibitory effect on Saphylococcus aureus and methicillin-resistant S. aureus (MRSA) using the filter paper disc agar diffusion method.

  6. Eurycomaoside: a new quassinoid-type glycoside from the roots of Eurycoma longifolia.

    PubMed

    Bedir, Erdal; Abou-Gazar, Hassan; Ngwendson, Julius Ngunde; Khan, Ikhlas Ahmad

    2003-11-01

    A new C(19)-quassinoid-type glycoside has been isolated from the roots of Eurycoma longifolia. The structure elucidation of the compound was achieved by a combination of one- and two-dimensional NMR techniques, including (1)H-(1)H-correlation spectroscopy (COSY), (1)H-(13)C-heteronuclear correlation spectroscopy (HMQC), and (1)H-(13)C-heteronuclear multiple-bond correlation spectroscopy (HMBC), as well as high resolution electrospray ionization Fourier transformation mass spectrometry (HR-ESI-FT-MS) data. The C(1)-glycosidation site in the quassinoid framework is encountered for the first time.

  7. Sapinmusaponins F-J, bioactive tirucallane-type saponins from the galls of Sapindus mukorossi.

    PubMed

    Huang, Hui-Chi; Tsai, Wei-Jern; Morris-Natschke, Susan L; Tokuda, Harukuni; Lee, Kuo-Hsiung; Wu, Yang-Chang; Kuo, Yao-Haur

    2006-05-01

    Five new tirucallane-type saponins, sapinmusaponins F-J (1-5), were isolated from the galls of Sapindus mukorossi. The structures of these saponins were elucidated on the basis of spectroscopic analysis including 1D and 2D NMR techniques ((1)H-(1)H COSY, HMQC, HMBC, TOCSY, and NOESY). Compounds 1-5 showed anti-platelet-aggregation effects, but no obvious cytotoxic activity for platelets as assayed by lactate dehydrogenase (LDH) leakage. Compounds 1-5 also showed moderate activity in a 12-O-tetradecanoylphorbol-13-acetate (TPA)-induced Epstein-Barr virus early antigen (EBV-EA) activation assay.

  8. 11α-Ethoxy-β-boswellic acid and nizwanone, a new boswellic acid derivative and a new triterpene, respectively, from Boswellia sacra.

    PubMed

    Al-Harrasi, Ahmed; Ali, Liaqat; Ur Rehman, Najeeb; Hussain, Javid; Hussain, Hidayat; Al-Rawahi, Ahmed; Shamim Rizvi, Tania

    2013-08-01

    A new boswellic acid derivative, 11α-ethoxy-β-boswellic acid (EBA; 1) and a new ursane-type triterpene, named nizwanone (2), were isolated from Omani frankincense Boswellia sacra Flueck. together with two known compounds papyriogenin B and rigidenol. The structures of 1 and 2 were elucidated by detailed spectroscopic analysis using (1) H- and (13) C-NMR, (1) H,(1) H-COSY, HMQC, HMBC, and HR-EI-MS techniques. The relative configurations of 1 and 2 were assigned by comparative analysis of the NMR spectral data with those of known analogs together with NOESY experiments. Structures of known compounds were identified by comparison with the reported data.

  9. Water-soluble constituents from aerial roots of Ficus microcarpa.

    PubMed

    Ouyang, M-A; Kuo, Y-H

    2006-01-01

    Three new water-soluble constituents [ficuscarpanoside B (1), (7E,9Z)-dihydrophaseic acid 3-O-beta-D-glucopyranoside (4) and ficuscarpanic acid (6)] and the natural product 2,2'-dihydroxyl ether (7) have been isolated, together with three known compounds [(7S,8R)-syringoylglycerol (2), (7S,8R)-syringoylglycerol-7-O-beta-D-glucopyranoside (3) and icariside D2 (5)] from the aerial roots of Ficus microcarpa. Identification of their structures was achieved by 1D and 2D NMR experiments, including 1H-1H COSY, NOESY, HMQC and HMBC methods and FAB mass spectral data.

  10. NMR characterisation of inulin-type fructooligosaccharides as the major water-soluble carbohydrates from Matricaria maritima (L.).

    PubMed

    Cérantola, Stéphane; Kervarec, Nelly; Pichon, Roger; Magné, Christian; Bessieres, Marie-Anne; Deslandes, Eric

    2004-10-04

    By use of 1H and 13C NMR spectroscopy including 2D 1H,1H DQF-COSY/TOCSY and 1H,13C HMQC/HMBC experiments, the main water-soluble carbohydrate components extracted from leaves of Matricaria maritima were identified as oligofructans composed of a linear chain of (2-->1)-linked beta-D-fructofuranosyl residues specifying an inulin-type structure. Alpha-D-Glcp-(1-->2)-[beta-D-Fruf-(2-->1)-beta-D-Frucf]n-(2-->1)-beta-D-Fruf.

  11. NMR assignments and X-ray diffraction spectra for two unusual kaurene diterpenes from Erythroxylum barbatum.

    PubMed

    dos Santos, Claudio Costa; Sousa Lima, Mary Anne; Braz-Filho, Raimundo; de Simone, Carlos Alberto; Silveira, Edilberto Rocha

    2005-12-01

    The structural characterization of two new, unusual kaurene diterpenes isolated from roots of Erythroxylum barbatum is described. 1D NMR and several 2D shift-correlated NMR pulse sequences (1H,1H-COSY, HMQC, HMBC and NOESY) were used for structure elucidation and the unambiguous 1H and 13C chemical shifts assignments. Single crystal X-ray diffraction analysis was also used to confirm the final relative configuration of the compounds possessing the C-20 methyl and the CH2-15 methylene groups in cis-orientation.

  12. Subsurface Growth of CoSi2 by Deposition of Co on Si-Capped CoSi2 Seed Regions

    NASA Technical Reports Server (NTRS)

    Fathauer, R. W.; George, T.; Pike, W. T.

    1991-01-01

    At a growth temperature of 800 C, Co deposited on Si(111) diffuses through a Si cap and exhibits oriented growth on buried CoSi2 grains, a process referred to as endotaxy. This occurs preferentially to surface nucleation of CoSi2 provided the thickness of the Si cap is less than a critical value between 100 and 200 nm for a deposition rate of 0.01 nm/s. Steady-state endotaxy is modeled under the assumption that the process is controlled by Co diffusion.

  13. Interfacial stability of CoSi2/Si structures grown by molecular beam epitaxy

    NASA Technical Reports Server (NTRS)

    George, T.; Fathauer, R. W.

    1992-01-01

    The stability of CoSi2/Si interfaces was examined in this study using columnar silicide structures grown on (111) Si substrates. In the first set of experiments, Co and Si were codeposited using MBE at 800 C and the resulting columnar silicide layer was capped by epitaxial Si. Deposition of Co on the surface of the Si capping layer at 800 C results in the growth of the buried silicide columns. The buried columns grow by subsurface diffusion of the deposited Co, suppressing the formation of surface islands of CoSi2. The column sidewalls appear to be less stable than the top and bottom interfaces, resulting in preferential lateral growth and ultimately in the coalescence of the columns to form a continuous buried CoSi2 layer. In the second set of experiments, annealing of a 250 nm-thick buried columnar layer at 1000 C under a 100 nm-thick Si capping layer results in the formation of a surface layer of CoSi2 with a reduction in the sizes of the CoSi2 columns. For a sample having a thicker Si capping layer the annealing leads to Ostwald ripening producing buried equiaxed columns. The high CoSi2/Si interfacial strain could provide the driving force for the observed behavior of the buried columns under high-temperature annealing.

  14. Disorder dependent half-metallicity in Mn{sub 2}CoSi inverse Heusler alloy

    SciTech Connect

    Singh, Mukhtiyar; Saini, Hardev S.; Thakur, Jyoti; Reshak, Ali H.; Kashyap, Manish K.

    2013-12-15

    Heusler alloys based thin-films often exhibit a degree of atomic disorder which leads to the lowering of spin polarization in spintronic devices. We present ab-initio calculations of atomic disorder effects on spin polarization and half-metallicity of Mn{sub 2}CoSi inverse Heusler alloy. The five types of disorder in Mn{sub 2}CoSi have been proposed and investigated in detail. The A2{sub a}-type and B2-type disorders destroy the half-metallicity whereas it sustains for all disorders concentrations in DO{sub 3a}- and A2{sub b}-type disorder and for smallest disorder concentration studied in DO{sub 3b}-type disorder. Lower formation energy/atom for A2{sub b}-type disorder than other four disorders in Mn{sub 2}CoSi advocates the stability of this disorder. The total magnetic moment shows a strong dependence on the disorder and the change in chemical environment. The 100% spin polarization even in the presence of disorders explicitly supports that these disorders shall not hinder the use of Mn{sub 2}CoSi inverse Heusler alloy in device applications. - Graphical abstract: Minority-spin gap (E{sub g↓}) and HM gap (E{sub sf}) as a function of concentrations of various possible disorder in Mn{sub 2}CoSi inverse Heusler alloy. The squares with solid line (black color)/dotted line (blue color)/dashed line (red color) reperesents E{sub g↓} for DO{sub 3a}-/DO{sub 3b}-/A2{sub b}-type disorder in Mn{sub 2}CoSi and the spheres with solid line (black color)/dottedline (blue color)/dashed line (red color) represents E{sub sf} for DO{sub 3a}-/DO{sub 3b}-/A2{sub b}-type disorder in Mn{sub 2}CoSi. - Highlights: • The DO{sub 3}- and A2-type disorders do not affect the half-metallicity in Mn{sub 2}CoSi. • The B2-type disorder solely destroys half-metallicity in Mn{sub 2}CoSi. • The A2-type disorder most probable to occur out of all three types. • The total spin magnetic moment strongly depends on the disorder concentrations.

  15. The TRIC Experiment: A P-even Time-Reversal Invariance Test at COSY

    SciTech Connect

    Eversheim, P.D.

    2005-10-26

    At the cooler synchrotron COSY at Juelich a novel (P-even, T-odd) true null test was proposed, that is supposed to measure the time-reversal invariance sensitive observable, the total cross-section correlation Ay,xz, to an accuracy of 10-6. This observable is measured in a transmission experiment of a circulating vector polarized (Py) proton beam through an internal tensor polarized (Pxz) atomic deuteron target. The experiment uses the COSY facility as an accelerator, an ideal forward spectrometer, and as a detector. At present the experimental focus lies on the development of a precise current measurement via a Beam-Current-Transformer (BCT), its precise read-out and analysis. So far, we succeeded to meet the BCT's accuracy specification. With the help of this accurate current measurement the development of a proper long living proton beam in COSY at the optimum energy, where the experiment has its highest sensitivity, is in progress.

  16. Q.E.COSY: determining sign and size of small deuterium residual quadrupolar couplings using an extended E.COSY principle.

    PubMed

    Tzvetkova, Pavleta; Luy, Burkhard

    2016-05-01

    Residual quadrupolar couplings contain important structural information comparable with residual dipolar couplings. However, the measurement of sign and size of especially small residual quadrupolar couplings is difficult. Here, we present an extension of the E.COSY principle to spin systems consisting of a Spin 1 coupled to a spin ½ nucleus, which allows the determination of the sign of the quadrupolar coupling of the Spin 1 nucleus relative to the heteronuclear coupling between the spins. The so-called Q.E.COSY approach is demonstrated with its sign-sensitivity using variable angle NMR, stretched gels and liquid crystalline phases applied to various CD and CD3 groups. Especially the sign-sensitive measurement of residual quadrupolar couplings that remain unresolved in conventional deuterium 1D spectra is shown.

  17. Exclusive near threshold two-pion production with the MOMO experiment at COSY

    NASA Astrophysics Data System (ADS)

    Bavink, S.; Bellemann, F.; Berg, A.; Bisplinghoff, J.; Bohlscheid, G.; Ernst, J.; Henrich, C.; Hinterberger, F.; Ibald, R.; Jahn, R.; Jarczyk, L.; Joosten, R.; Kozela, A.; Machner, H.; Magiera, A.; Maschuw, R.; Mayer-Kuckuk, T.; Mertler, G.; Munkel, J.; Neumann-Cosel, P. v.; Rosendaal, D.; Rossen, P. v.; Schnitker, H.; Scho, K.; Smyrski, J.; Strzalkowski, A.; Tölle, R.; Wurzinger, R.

    1997-05-01

    Near threshold two pion production via the reaction pd→3Heπ+π- was measured kinematically complete with the MOMO experiment at COSY. A remarkable deviation of the obtained two pion invariant mass spectra from phase space as well as a predominant sidewise and back to back emission of the two mesons was observed.

  18. Exclusive near threshold two-pion production with the MOMO experiment at COSY

    NASA Astrophysics Data System (ADS)

    Bavink, S.; Bellemann, F.; Berg, A.; Bisplinghoff, J.; Bohlscheid, G.; Ernst, J.; Henrich, C.; Hinterberger, F.; Ibald, R.; Jahn, R.; Jarczyk, L.; Joosten, R.; Kozela, A.; Machner, H.; Magiera, A.; Maschuw, R.; Mayer-Kuckuk, T.; Mertler, G.; Munkel, J.; Neumann-Cosel, P. v.; Rosendaal, D.; Rossen, P. v.; Schnitker, H.; Scho, K.; Smyrski, J.; Strzalkowski, A.; Tölle, R.; Wurzinger, R.

    1998-03-01

    Near threshold two pion production via the reaction pd → 3Heπ +π - was measured kinematically complete with the MOMO experiment at COSY. A remarkable deviation of the obtained two pion invariant mass spectra from phase space as well as a predominant back to back and sidewise emission of the two pions was observed.

  19. Development of cluster-jet targets: From COSY-11 to FAIR

    SciTech Connect

    Taeschner, A.; General, S.; Otte, J.; Rausmann, T.; Khoukaz, A.

    2007-11-07

    The development of cluster-jet targets of Muenster type is presented. Starting with the first target installed at the COSY-11 experiment the progress is described which was made at a cluster-jet target facility installed in Muenster leading to a prototype for a cluster-jet target for the upcoming PANDA experiment at FAIR.

  20. The upcoming balloon campaign of the Compton Spectrometer and Imager (COSI)

    NASA Astrophysics Data System (ADS)

    Chiu, J.-L.; Boggs, S. E.; Chang, H.-K.; Tomsick, J. A.; Zoglauer, A.; Amman, M.; Chang, Y.-H.; Chou, Y.; Jean, P.; Kierans, C.; Lin, C.-H.; Lowell, A.; Shang, J.-R.; Tseng, C.-H.; von Ballmoos, P.; Yang, C.-Y.

    2015-06-01

    The Compton Spectrometer and Imager (COSI), formerly known as the Nuclear Compton Telescope (NCT), is a balloon-borne soft gamma-ray telescope (0.2-5 MeV) designed to study astrophysical sources of nuclear-line emission and gamma-ray polarization. The heart of COSI is a compact array of cross-strip germanium detectors (GeDs), providing excellent spectral resolution ( 0.2 - 1 %) and the capability to track individual photon interactions with full 3D position resolution to 1.6 mm3. COSI is built upon considerable heritage from the previous NCT balloon instrument, which has flown successfully on two conventional balloon flights to date. The Crab Nebula was detected at a significance of 6σ in the second flight, which is the first reported detection of an astrophysical source by a compact Compton telescope. COSI has been upgraded from the previous NCT instrument to be an Ultra Long Duration Balloon (ULDB) payload, utilizing a new detector configuration optimized for polarization sensitivity and employing a mechanical cryocooler to remove consumables (LN2) for ULDB flights. The instrument is being integrated for a ULDB flight in December 2014 from Antarctica on a superpressure balloon. Here we will present the redesign of the instrument and our current progress in preparing for the flight.

  1. Determination of long-range scalar 1H-1H coupling constants responsible for polarization transfer in SABRE

    NASA Astrophysics Data System (ADS)

    Eshuis, Nan; Aspers, Ruud L. E. G.; van Weerdenburg, Bram J. A.; Feiters, Martin C.; Rutjes, Floris P. J. T.; Wijmenga, Sybren S.; Tessari, Marco

    2016-04-01

    SABRE (Signal Amplification By Reversible Exchange) nuclear spin hyperpolarization method can provide strongly enhanced NMR signals as a result of the reversible association of small molecules with para-hydrogen (p-H2) at an iridium metal complex. The conversion of p-H2 singlet order to enhanced substrate proton magnetization within such complex is driven by the scalar coupling interactions between the p-H2 derived hydrides and substrate nuclear spins. In the present study these long-range homonuclear couplings are experimentally determined for several SABRE substrates using an NMR pulse sequence for coherent hyperpolarization transfer at high magnetic field. Pyridine and pyrazine derivatives appear to have a similar ∼1.2 Hz 4J coupling to p-H2 derived hydrides for their ortho protons, and a much lower 5J coupling for their meta protons. Interestingly, the 4J hydride-substrate coupling for five-membered N-heterocyclic substrates is well below 1 Hz.

  2. Determination of long-range scalar (1)H-(1)H coupling constants responsible for polarization transfer in SABRE.

    PubMed

    Eshuis, Nan; Aspers, Ruud L E G; van Weerdenburg, Bram J A; Feiters, Martin C; Rutjes, Floris P J T; Wijmenga, Sybren S; Tessari, Marco

    2016-04-01

    SABRE (Signal Amplification By Reversible Exchange) nuclear spin hyperpolarization method can provide strongly enhanced NMR signals as a result of the reversible association of small molecules with para-hydrogen (p-H2) at an iridium metal complex. The conversion of p-H2 singlet order to enhanced substrate proton magnetization within such complex is driven by the scalar coupling interactions between the p-H2 derived hydrides and substrate nuclear spins. In the present study these long-range homonuclear couplings are experimentally determined for several SABRE substrates using an NMR pulse sequence for coherent hyperpolarization transfer at high magnetic field. Pyridine and pyrazine derivatives appear to have a similar ∼1.2 Hz (4)J coupling to p-H2 derived hydrides for their ortho protons, and a much lower (5)J coupling for their meta protons. Interestingly, the (4)J hydride-substrate coupling for five-membered N-heterocyclic substrates is well below 1 Hz.

  3. Precise momentum determination of the external COSY proton beam near 1930 MeV//c

    NASA Astrophysics Data System (ADS)

    Betigeri, M. G.; Bojowald, J.; Budzanowski, A.; Chatterjee, A.; Drochner, M.; Ernst, J.; Förtsch, S.; Freindl, L.; Frekers, D.; Garske, W.; Grewer, K.; Hamacher, A.; Hawash, M.; Igel, S.; Ilieva, I.; Jahn, R.; Jarczyk, L.; Kemmerling, G.; Kilian, K.; Kliczewski, S.; Klimala, W.; Kolev, D.; Kutsarova, T.; Lieb, B. J.; Lippert, G.; Machner, H.; Magiera, A.; Maier, R.; Nann, H.; Plendl, H. S.; Protic, D.; Razen, B.; von Rossen, P.; Roy, B.; Siudak, R.; Smyrski, J.; Strzałkowski, A.; Tsenov, R.; Zolnierczuk, P. A.; Zwoll, K.; GEM Collaboration

    1999-05-01

    We present a method to determine precisely the absolute momentum of the external proton beam from the Jülich Cooler Synchrotron COSY near 1930 MeV /c. In the pp → d π+ reaction at 1930.477 MeV /c incident beam momentum, the forward going pions ( θ c.m.=0° ) and the backward going deuterons ( θ c.m.=180° ) have the same laboratory momentum. Such coincident pion-deuteron events are detected in the focal plane of the magnetic spectrometer BIG KARL located at θ lab=0° . Using the nearly linear dependence of the difference between the measured pion and deuteron momenta as a function of the proton beam momentum, the absolute momentum of the external proton beam from COSY near 1930 MeV /c was determined with a precision of 5.2×10 -5.

  4. The H and D Polarized Target for Spin-Filtering Measurements at COSY

    NASA Astrophysics Data System (ADS)

    Ciullo, Giuseppe; Statera, Marco; Lenisa, Paolo; Nass, Alexander; Tagliente, Giuseppe

    2016-04-01

    In the main frame of the PAX (Polarized Antiproton eXperiments) collaboration, which engaged the challenging purpose of polarizing antiproton beams, the possibility to have H or D polarized targets requires a daily switchable source and its diagnostics: mainly change is a dual cavity tunable for H and D. The commissioning of PAX has been fullfilled, for the transverse case, on the COSY (COoler SYnchrotron) proton ring, achieving milestones on spin-dependent cross-section measurements. Now the longitudinal case could provide sensitive polarization results. An H or D source allows the exploration of the spin-filtering process with a deuterium polarized target, and opens new chances for testing Time Reversal Invariance at COSY (TRIC).

  5. Endotaxial growth of CoSi2 within (111) oriented Si in a molecular beam epitaxy system

    NASA Technical Reports Server (NTRS)

    George, T.; Fathauer, R. W.

    1991-01-01

    A new mode of growth is reported in which buried metallic layers can be fabricated within a single-crystal semiconductor through preferential subsurface growth on previously-grown 'seed' regions. The deposition of Co at 800 C at a rate of 0.01 nm/s on (111) Si substrates containing buried CoSi2 columns 40-100 nm below the Si surface results in the growth and coalescence of these subsurface columns. The formation of a CoSi2 layer on the Si surface is suppressed by this growth mode. It is proposed that the high diffusion rate of Co at 800 C, coupled with the high growth rate of CoSi2 at the subsurface columns, is responsible for this preferred 'endotaxial' growth mode. This growth technique was used to produce a continuous buried single-crystal layer of CoSi2 under a single-crystal Si capping layer.

  6. Negative ion source development at the cooler synchrotron COSY/Jülich

    NASA Astrophysics Data System (ADS)

    Felden, O.; Gebel, R.; Maier, R.; Prasuhn, D.

    2013-02-01

    The Nuclear Physics Institute at the Forschungszentrum Jülich, a member of the Helmholtz Association, conducts experimental and theoretical basic research in the field of hadron, particle, and nuclear physics. It operates the cooler synchrotron COSY, an accelerator and storage ring, which provides unpolarized and polarized proton and deuteron beams with beam momenta of up to 3.7 GeV/c. Main activities of the accelerator division are the design and construction of the high energy storage ring HESR, a synchrotron and part of the international FAIR project, and the operation and development of COSY with injector cyclotron and ion sources. Filament driven volume sources and a charge exchange colliding beams source, based on a nuclear polarized atomic beam source, provide unpolarized and polarized H- or D- routinely for more than 6500 hours/year. Within the Helmholtz Association's initiative Accelerator Research and Development, ARD, the existing sources at COSY, as well as new sources for future programs, are investigated and developed. The paper reports about these plans, improved pulsed beams from the volume sources and the preparation of a source for the ELENA project at CERN.

  7. The Storage Cell for the Tri-Experiment at COSY-JÜLICH

    NASA Astrophysics Data System (ADS)

    Felden, O.; Gebel, R.; Glende, M.; Lehrach, A.; Maier, R.; Prasuhn, D.; von Rossen, P.; Bisplinghoff, J.; Eversheim, P. D.; Hinterberger, F.

    2002-04-01

    At the EDDA experiment in the cooler synchrotron COSY in Jülich an atomic beam target is used which provides the designed polarization and density distribution. To increase the target density significantly a storage cell has been developed and implemented. This will contribute to a higher accuracy for the test of Time Reversal Invariance (TRI) which will be performed at the EDDA target place. To obtain the higher luminosity the target density and the transmission of the COSY beam through the cell were determined in their dependence on the cell aperture. Low storage cell apertures increase the target density in the cell but reduce the transmission of the circulating proton beam. To find the optimal cell design the transmission of the COSY beam was measured with movable scrapers and tested with an aperture at EDDA simulating the storage cell. The target density was calculated by Monte Carlo simulations for several cell geometries. An additional gain in target density is achieved by cooling the cell. A Teflon coating of the cell reduces depolarization of the target gas. First measurements with the EDDA detector have shown that the target density as well as the polarization are within the range of the expected values.

  8. Xenon-ion-induced and thermal mixing of Co/Si bilayers and their interplay

    NASA Astrophysics Data System (ADS)

    Novaković, M.; Zhang, K.; Popović, M.; Bibić, N.; Hofsäss, H.; Lieb, K. P.

    2011-05-01

    Studies on ion-irradiated transition-metal/silicon bilayers demonstrate that interface mixing and silicide phase formation depend sensitively on the ion and film parameters, including the structure of the metal/Si interface. Thin Co layers e-gun evaporated to a thickness of 50 nm on Si(1 0 0) wafers were bombarded at room temperature with 400-keV Xe + ions at fluences of up to 3 × 10 16 cm -2. We used either crystalline or pre-amorphized Si wafers the latter ones prepared by 1.0-keV Ar-ion implantation. The as-deposited or Xe-ion-irradiated samples were then isochronally annealed at temperatures up to 700 °C. Changes of the bilayer structures induced by ion irradiation and/or annealing were investigated with RBS, XRD and HRTEM. The mixing rate for the Co/c-Si couples, Δ σ2/ Φ = 3.0(4) nm 4, is higher than the value expected for ballistic mixing and about half the value typical for spike mixing. Mixing of pre-amorphized Si is much weaker relative to crystalline Si wafers, contrary to previous results obtained for Fe/Si bilayers. Annealing of irradiated samples produces very similar interdiffusion and phase formation patterns above 400 °C as in the non-irradiated Co/Si bilayers: the phase evolution follows the sequence Co 2Si → CoSiCoSi 2.

  9. The Scalar Resonances a0/f0(980) at COSY

    SciTech Connect

    Buescher, M.

    2006-02-11

    Fundamental properties of the scalar resonances a0/f0(980), like their masses, widths and couplings to KK-bar, are poorly known. In particular, precise knowledge of the latter quantity would be of great importance since it can be related to the KK-bar content of these resonances.An experimental program is under way at COSY-Juelich aiming at the extraction of the isospin violating a0/f0 mixing amplitude {lambda} which is in leading order proportional to the product of the coupling constants of the a0 and f0 to kaons. a0/f0 production is studied in pp, pn and dd interactions, both for the KK-bar and the {pi}{eta}/{pi}{pi} decays, using the ANKE and WASA spectrometers. The latter will be available for measurements at COSY in 2007.As a first step, isovector KK-bar production has been measured in the reaction pp {yields} dK+K-bar0. The data reveal dominance of the a{sub 0}{sup +} channel, thus demonstrating the feasibility of scalar meson studies at COSY. Analyses of KK-bar- and K-bard-FSI effects yield the corresponding scattering lengths, a(KK-bar)I=1 = -(0.02 {+-} 0.03) - i(0.61 {+-} 0.05) fm and vertical bar Re a(K-bard) vertical bar {<=}1.3 fm, Im a(K-bard){<=}1.3 fm.

  10. A new COmpact hyperSpectral Imaging system (COSI) for UAS

    NASA Astrophysics Data System (ADS)

    Sima, Aleksandra; Baeck, Pieter-Jan; Delalieux, Stephanie; Livens, Stefan; Blommaert, Joris; Delauré, Bavo; Boonen, Miet

    2016-04-01

    This presentation gives an overview of the new COmpact hyperSpectral Imaging (COSI) system recently developed at the Flemish Institute for Technological Research (VITO, Belgium) and suitable for multirotor Remotely Piloted Aircraft Systems (RPAS) platforms. The camera is compact and lightweight, with a total mass of less than 500g including: an embedded computer, storage and power distribution unit. Such device miniaturization was possible thanks to the application of linear variable filters technology, in which image lines in the across flight direction correspond to different spectral bands as well as a different location on the ground (frame camera). The scanning motion is required to retrieve the complete spectrum for every point on the ground. The COSI camera captures data in 72 narrow (FWHM: 5nm to 10 nm) bands in the spectral range of 600-900 nm. Such spectral information is highly favourable for vegetation studies, since the main chlorophyll absorption feature centred around 680 nm is measured, as well as, the red-edge region (680 nm to 730 nm) which is often linked to plant stress. The NIR region furthermore reflects the internal plant structure, and is often linked to leaf area index and plant biomass. Next to the high spectral resolution, the COSI imager also provides a very high spatial data resolution i.e. images captured with a 9mm lens at 40m altitude cover a swath of ~40m with a ~2cm ground sampling distance. A dedicated data processing chain transforms the raw images into various information and action maps representing the status of the vegetation health and thus allowing for optimization of the management decisions within agricultural fields. In a number of test flights, hyperspectral COSI imager data were acquired covering diverse environments, e.g.: strawberry fields, natural grassland or pear orchards. Next to the COSI system overview, examples of collected data will be presented together with the results of the spectral data analysis. Lessons

  11. First Experiments with the Polarized Internal Gas Target (PIT) at ANKE/COSY

    SciTech Connect

    Engels, R.; Lorentz, B.; Prasuhn, D.; Rathmann, F.; Sarkadi, J.; Schleichert, R.; Seyfarth, H.; Stroeher, H.; Chiladze, D.; Dymov, S.; Grigoryev, K.; Mikirtychyants, M.; Kacharava, A.; Klehr, F.; Mikirtychyants, S.; Vasilyev, A.; Schieck, H. Paetz gen.; Steffens, E.

    2009-08-04

    For future few-nucleon interaction studies with polarized beams and targets at COSY-Juelich, a polarized internal storage-cell gas target was implemented at the magnet spectrometer ANKE. First commissioning of the polarized Atomic Beam Source (ABS) at ANKE was carried out and some improvements of the system have been done. Storage-cell tests to determine the COSY beam dimensions have been performed. Electron cooling combined with stacking and stochastic cooling have been studied. Experiments with N{sub 2} gas in the storage cell to simulate the background produced by beam interaction with the aluminum cell walls were performed to investigate the beam heating by the target gas. The analysis of the d-vectorp-vector->dp and d-vectorp-vector->(dp{sub sp})pi{sup 0} reactions showed that events from different positions of the extended target can be clearly identified in the ANKE detector system. The polarization of the atomic beam of the ABS, positioned close to the strong dipole magnet D2 of ANKE, was tuned with a Lamb-shift polarimeter (LSP) beneath the target chamber. With use of the known analyzing powers of the quasi-free np->dpi{sup 0} reaction, the polarization in the storage cell was measured to be Q{sub y} = 0.79+-0.07 in the vertical stray field of the D2 magnet acting as a holding field. The target thickness achieved was 2x10{sup 13} atoms/cm{sup 2} for one hyperfine state populated in the ABS beam only. With a COSY beam intensity of 6x10{sup 9} stored polarized deuterons in the ring, the luminosity for double polarized experiments was 1x10{sup 29} cm{sup -2} s{sup -1}.

  12. Structural Characterization and Thermoelectric Properties of Hot-Pressed CoSi Nanocomposites

    NASA Astrophysics Data System (ADS)

    Ioannou, Maria; Symeou, Elli; Giapintzakis, John; Kyratsi, Theodora

    2014-10-01

    Fabrication of nanocomposites by introduction of SiO2 metal oxide nanoparticles into a cobalt silicide thermoelectric matrix is studied. The CoSi matrix material was prepared through solid-state synthesis, and the nano-SiO2 metal oxide was introduced by mechanical grinding. The mixed powders were hot pressed to fabricate nanocomposites. The structural and morphological modifications were studied by powder x-ray diffraction analysis and scanning electron microscopy. The thermoelectric properties of the materials were followed through the Hall effect, Seebeck coefficient, and electrical and thermal conductivities in the temperature range from 300 K to 1000 K.

  13. Magnetic ordering in Sc2CoSi2-type R2FeSi2 (R=Gd, Tb) and R2CoSi2 (R=Y, Gd-Er) compounds

    NASA Astrophysics Data System (ADS)

    Morozkin, A. V.; Knotko, A. V.; Yapaskurt, V. O.; Pani, M.; Nirmala, R.; Quezado, S.; Malik, S. K.

    2016-09-01

    Magnetic and magnetocaloric properties of Sc2CoSi2-type R2TSi2 (R=Gd-Er, T=Fe, Co) compounds have been studied using magnetization data. These indicate the presence of mixed ferromagnetic and antiferromagnetic interactions in these compounds. One observes a ferromagnetic transition followed by an antiferromagnetic order and a further possible spin-reorientation transition at low temperatures. Compared to Gd2{Fe, Co}Si2, the Tb2FeSi2 and {Tb-Er}2CoSi2 compounds exhibit remarkable hysteresis (for e.g. Tb2FeSi2 shows residual magnetization Mres/Tb=2.45 μB, coercive field Hcoer=14.9 kOe, and critical field Hcrit 5 kOe at 5 K) possibly due to the magnetocrystalline anisotropy of the rare earth. The R2{Fe, Co}Si2 show relatively small magnetocaloric effect (i.e. isothermal magnetic entropy change, ΔSm) around the magnetic transition temperature: the maximal value of MCE is demonstrated by Ho2CoSi2 (ΔSm=-8.1 J/kg K at 72 K and ΔSm=-9.4 J/kg K at 23 K in field change of 50 kOe) and Er2CoSi2 (ΔSm=-13.6 J/kg K at 32 K and ΔSm=-8.4 J/kg K at 12 K in field change of 50 kOe).

  14. From CELSIUS to COSY: on the observation of a dibaryon resonance

    NASA Astrophysics Data System (ADS)

    Clement, H.; Bashkanov, M.; Skorodko, T.

    2015-11-01

    Using a high-quality beam of storage rings in combination with a pellet target and a hermetic WASA detector covering practically the full solid angle, two-pion production in nucleon-nucleon collisions has been systematically studied by exclusive and kinematically complete measurements—first at CELSIUS and subsequently at COSY. These measurements resulted in a detailed understanding of the two-pion production mechanism by t-channel meson exchange. The investigation of the ABC effect, which denotes an unusual low-mass enhancement in the ππ-invariant mass spectrum, in double-pionic fusion reactions led the trace to the observation of a narrow dibaryon resonance with I({J}P)=0({3}+) about 80 MeV below the nominal mass of the conventional Δ Δ system. New neutron-proton scattering data, taken with a polarized beam at COSY, produced a pole in the coupled {}3{D}3-3{G}3 partial waves at (2380+/- 10\\-\\i\\40+/- 5) MeV, establishing thus the first observation of a genuine s-channel dibaryon resonance.

  15. Signs of deuteron quadrupole coupling constants from COSY-2D spectra of solids

    NASA Astrophysics Data System (ADS)

    Schlemmer, H.; Haeberlen, U.

    It is shown how the signs of the quadrupole coupling constants (QCCs) of deuterons can be determined from the multiplet structures of the cross peaks in COSY-2D spectra of deuterons in molecular crystals or any other ordered sample. Multiplets arise as a result of dipolar couplings between pairs of deuterons. The 21) multiplet of a cross peak of a dipolar-coupled pair of deuterons consists of a 3 × 3 array of component lines. If the mixing pulse of the COSY sequence is a 90° pulse the multiplet is insensitive to the signs of the deuteron QCCs. If, however, the mixing pulse is a 54°44' pulse only four of the nine components are strong. These are located in one of the four corners of the 3 × 3 array. In which comer of the 3 × 3 array the four strong peaks appear depends on the relative signs of the dipolar and quadrupolar splittings D, ΔωQ1 and ΔωQ2. This can be used as a fingerprint for the relative signs of D, D, ΔωQ1 and ΔωQ2. The experimental conditions of the procedure are explored in an experiment on a single crystal of fully deuterated potassium oxalate monohydrate.

  16. CosI: Development of a low threshold detector for the observation of coherent elastic neutrino-nucleus scattering

    NASA Astrophysics Data System (ADS)

    Fields, Nicole Elizabeth

    I present the development of an experimental setup designed to measure CENNS (coherent elastic neutrino-nucleus scattering), a process that has never been experimentally observed. CosI (Coherent Neutrino Scattering with Cesium Iodide) uses a sodium doped cesium iodide detector intended to be able to observe CENNS at the SNS (Spallation Neutron Source) in Oak Ridge, TN. This thesis describes the experimental design and construction of the CosI apparatus, while sited at the University of Chicago. This thesis also presents the screening of materials for radioactivity in conjunction with simulations of the background contributions from various experimental components to CosI. Background measurements were performed at the University of Chicago with a 2 kg prototype CosI crystal, and those results are presented here. I also present neutrino signal calculations for the full size 15 kg CosI crystal which is to be installed at the SNS. Finally, the feasibility of a CENNS detection at the SNS using the CosI apparatus is discussed. This thesis also makes a contribution to the ongoing search for WIMP (weakly interacting massive particle) dark matter. I present a data-driven method for applying a surface event correction to CoGeNT (Coherent Germanium Neutrino Technology) data. After applying this correction, I then calculate new dark matter limits using the 807 day CoGeNT data set. In addition, I also perform a two dimensional maximum likelihood analysis of low energy CDMS (Cryogenic Dark Matter Search) data. The maximum likelihood analysis reveals a strong preference for a population of nuclear recoil events in the CDMS data set.

  17. CoSi: Correlation of signals-A new measure to assess the correlation of history response curves

    NASA Astrophysics Data System (ADS)

    Murmann, Robert; Harzheim, Lothar; Dominico, Stefan; Immel, Rainer

    2016-12-01

    In the context of CAE work it is often required to assess the level of agreement of two curves objectively, e.g. measured against numerically computed results. Therefore a new comprehensive measure is proposed in this paper. The new measure 'CoSi' (Correlation of Signals) allows to account for uncertainties in both curves. This is achieved by constructing a corridor around one curve which considers deviations in direction of both abscissa and ordinate. Here CoSi differs from other common corridor approaches which consider only the deviation on the ordinate. It is explained how CoSi aligns the two curves taking the uncertainties of the second curve by scaling and shifting into account. This leads to the best theoretical achievable agreement between the two curves. Based on the aligned curves, quality factors are calculated to evaluate the results in terms of amplitudes of the curves, their overall match in shape, the phase between the curves, and all these combined into a comprehensive quality factor. The properties and results of CoSi are compared with other metrics from literature using various examples.

  18. Synthesis, characterization and magnetism of novel Cobalt-åkermanite:Ca2CoSi2O7

    NASA Astrophysics Data System (ADS)

    Barbar, Shiv Kumar; Patel, K. R.; Roy, M.; Sharma, R.; Kumar, Sudhish

    2017-04-01

    Polycrystalline sample of novel Cobalt-åkermanite: Ca2CoSi2O7 was synthesized using solid state reaction method. Room temperature powder X-ray diffraction and dc-electrical conductivity studies confirmed good quality of the synthesized sample in single phase tetragonal structure with space group: P 4 ̅21m. Low value of activation energy estimated from the dc-conductivity study indicates insulating behavior of this compound. Magnetic study showed a paramagnetic nature of Ca2CoSi2O7 at room temperature and antiferromagnetic nature below TN=5.6 K. In this compound weak ferromagnetism co-exist with antiferromagnetism below Neel temperature. Ca2CoSi2O7 displays magnetic field induced weak ferromagnetic transition around 7.4 K. Antiferromagnetic interactions occurs between the nearest neighbor Co2+ ions, as indicated by the negative sign of Weiss constant, θP=-22.7 K. Estimated value of the effective magnetic moment, μeff=4.75μB is found to be larger than the spin-only value of magnetic moment of Co2+ ion in the tetrahedral coordination having three unpaired electrons. These results, suggest that the orbital contribution to magnetic moment in this compound cannot be neglected and the electric polarization through spin dependent p-d hybridization can be expected in Ca2CoSi2O7.

  19. Nucleon-nucleon scattering at small angles, measured at ANKE-COSY

    NASA Astrophysics Data System (ADS)

    Bagdasarian, Z.

    2016-03-01

    The most accepted approach to describe nucleon-nucleon (NN) interaction is the partial wave analysis (PWA), which translates various experimental observables to the common language of the partial waves. The reliable analysis relies not only on the quality experimental data, but also on the measurements of scattering observables over preferably the full angular range. Small angle scattering has been measured for six beam energies between 0.8 and 2.4 GeV using polarized proton beam incident on both proton and deuteron unpolarized targets at COSY-ANKE. This proceeding will report on the published and preliminary results for both pp and pn scattering from this and other recent experiments at ANKE. This study aims to provide the valuable observables to the SAID group in order to improve the phenomenological understanding of the nucleon-nucleon interaction.

  20. COSY Simulations to Guide Commissioning of the St. George Recoil Mass Separator

    NASA Astrophysics Data System (ADS)

    Schmitt, Jaclyn; Moran, Michael; Seymour, Christopher; Gilardy, Gwenaelle; Meisel, Zach; Couder, Manoel

    2015-10-01

    The goal of St. George (STrong Gradient Electromagnetic Online Recoil separator for capture Gamma ray Experiments) is to measure (α, γ) cross sections relevant to stellar helium burning. Recoil separators such as St. George are able to more closely approach the low astrophysical energies of interest because they collect reaction recoils rather than γ-rays, and thus are not limited by room background. In order to obtain an accurate cross section measurement, a recoil separator must be able to collect all recoils over their full range of expected energy and angular spread. The energy acceptance of St. George is currently being measured, and the angular acceptance will be measured soon. Here we present the results of COSY ion optics simulations and magnetic field analyses which were performed to help guide the commissioning measurements and diagnostic upgrades required to complete those measurements. National Science Foundation Research Experiences for Undergraduates program.

  1. Induction of quinone reductase (QR) by withanolides isolated from Physalis angulata L. var. villosa Bonati (Solanaceae).

    PubMed

    Ding, Hui; Hu, Zhijuan; Yu, Liyan; Ma, Zhongjun; Ma, Xiaoqiong; Chen, Zhe; Wang, Dan; Zhao, Xiaofeng

    2014-08-01

    In the present study, the EtOAc extract of the persistent calyx of Physalis angulata L. var. villosa Bonati (PA) was tested for its potential quinone reductase (QR) inducing activity with glutathione (GSH) as the substrate using an UPLC-ESI-MS method. The result revealed that the PA had electrophiles that could induce quinone reductase (QR) activity, which might be attributed to the modification of the highly reactive cysteine residues in Keap1. Herein, three new withanolides, compounds 3, 6 and 7, together with four known withanolides, compounds 1, 2, 4 and 5 were isolated from PA extract. Their structures were determined by spectroscopic techniques, including (1)H-, (13)C NMR (DEPT), and 2D-NMR (HMBC, HMQC, (1)H, (1)H-COSY, NOESY) experiments, as well as by HR-MS. All the seven compounds were tested for their QR induction activities towards mouse hepa 1c1c7 cells.

  2. Structure of the acidic O-specific polysaccharide from Proteus vulgaris O39 containing 5,7-diacetamido-3,5,7,9-tetradeoxy-L-glycero-L-manno-non-2-ulosonic acid.

    PubMed

    Kondakova, A N; Perepelov, A V; Bartodziejska, B; Shashkov, A S; Senchenkova, S N; Wykrota, M; Knirel, Y A; Rozalski, A

    2001-07-12

    The O-specific polysaccharide of Proteus vulgaris O39 was found to contain a new acidic component of Proteus lipopolysaccharides, 5,7-diacetamido-3,5,7,9-tetradeoxy-L-glycero-L-manno-non-2-ulosonic acid (di-N-acetylpseudaminic acid, Pse5Ac7Ac). The following structure of the polysaccharide was determined by NMR spectroscopy, including 2D 1H,(1)H COSY, TOCSY, ROESY, and 1H,(13)C HMQC experiments, along with selective cleavage of the polysaccharide by solvolysis with anhydrous trifluoromethanesulfonic (triflic) acid: -->8)-beta-Psep5Ac7Ac-(2-->3)-alpha-L-FucpNAc-(1-->3)-alpha-D-GlcpNAc-(1--> The structure established is unique among the O-specific polysaccharides, which is in accordance with classification of the strain studied into a separate Proteus serogroup.

  3. Steroidal Saponins from the Rhizomes of Aspidistra typica

    PubMed Central

    Zhao, Yang; Zhao, Jian-Yuan; Zhang, Jie; Pang, Xu; Yu, He-Shui; Jia, De-Xian; Liu, Chao; Yu, Li-Yan; Ma, Bai-Ping

    2016-01-01

    Eleven new furostanol saponins, typaspidosides B-L (1–11), one new spirostanol saponin, typaspidoside M (12), and five known spirostanol saponins, 25S-atropuroside (13), neoaspidistrin (14), (25S)-pratioside D1 (15), 25S-aspidistrin (16) and 25S-neosibiricoside (17) were isolated from the rhizomes of Aspidistra typica Baill. The structures of the new compounds were established using 1D and 2D NMR (1H-1H COSY, HMQC, HMBC and ROESY) spectroscopy, high resolution mass spectrometry, and chemical methods. The aglycones of 1–3 (unusual furostanol saponins with opened E ring type), 9 and 10 (the methoxyl substituent at C-23 position) were found, identified from natural products for the first time. Moreover, the anti-HIV activities of the isolated steroidal glycosides were assessed, and compounds 13, 14, 16 and 17 exhibited high active against HIV-1. PMID:26937954

  4. Cytotoxic withanolides from Physalis angulata L.

    PubMed

    He, Qing-Ping; Ma, Lei; Luo, Jie-Ying; He, Fu-Yuan; Lou, Li-Guang; Hu, Li-Hong

    2007-03-01

    Four new withanolides, physagulins L-O (1-4), were isolated from the MeOH extract of the aerial parts of Physalis angulata L. (Solanaceae), together with seven known withanolides, compounds 5-11. Their structures were determined by spectroscopic techniques, including 1H-, 13C-NMR (DEPT), and 2D-NMR (HMBC, HMQC, 1H,1H-COSY, NOESY) experiments, as well as by HR-MS. All eleven compounds were tested for their antiproliferative activities towards human colorectal-carcinoma (HCT-116) and human non-small-cell lung-cancer (NCI-H460) cells. Compound 5 exhibited the highest anticancer activity against the HCT-116 cell line, with an IC50 value of 1.64+/-0.06 microM. Compound 9 exhibited the highest cytotoxicity towards the NCI-H460 cell line, with an IC50 value of 0.43+/-0.02 microM.

  5. Antioxidant activity of a new phenolic glycoside from Lagenaria siceraria Stand. fruits.

    PubMed

    Mohan, Rahul; Birari, Rahul; Karmase, Aniket; Jagtap, Sneha; Bhutani, Kamlesh Kumar

    2012-05-01

    The antioxidant properties of different extracts of Lagenaria siceraria (bottle gourd) fruit were evaluated. In the process, a new phenolic glycoside (E)-4-hydroxymethyl-phenyl-6-O-caffeoyl-β-d-glucopyranoside (1) was isolated and identified together with 1-(2-hydroxy-4-hydroxymethyl)-phenyl-6-O-caffeoyl-β-d-gluco-pyranoside (2), protocatechuic acid (3), gallic acid (4), caffeic acid (5) and 3,4-dimethoxy cinnamic acid (6). Their structures were elucidated by extensive NMR experiments including (1)H-(1)H (COSY) and (1)H-(13)C (HMQC and HMBC) spectroscopy and chemical evidences. The antioxidant potential of the compound 1 and 2 was tested in different in vitro assay systems such as free radical scavenging assay, 3-(4,5-dimethylthiazole-2-yl)-2,5-diphenyltetrazolium bromide (MTT) reduction assay, superoxide scavenging activity, reducing power assay and linoleic acid peroxidation assay.

  6. Diterpenes from the Trunk of Abies holophylla and Their Potential Neuroprotective and Anti-inflammatory Activities.

    PubMed

    Kim, Chung Sub; Subedi, Lalita; Kim, Sun Yeou; Choi, Sang Un; Kim, Ki Hyun; Lee, Kang Ro

    2016-02-26

    Eleven new abietane-type diterpenes, holophyllins D-N (1-11), and 17 known analogues (12-28), were isolated from a MeOH extract of the trunk of Abies holophylla. The chemical structures of 1-11 were determined through spectroscopic data analysis, including NMR ((1)H and (13)C NMR, DEPT, (1)H-(1)H COSY, HMQC, HMBC, and NOESY) and HRFABMS methods. All isolated compounds (1-28) were evaluated for their cytotoxicity against four human tumor cell lines (A549, SK-OV-3, SK-MEL-2, and HCT-116), for their potential neuroprotective effects through induction of nerve growth factor in C6 glioma cells, and for their effects on nitric oxide levels in lipopolysaccharide-stimulated murine microglia BV2 cells.

  7. Constituents from the stem barks of Canarium bengalense with cytoprotective activity against hydrogen peroxide-induced hepatotoxicity.

    PubMed

    Le, Hoang Thi; Ha, Do Thi; Minh, Chau Thi Anh; Kim, Tae Hoon; Van Kiem, Phan; Thuan, Nguyen Duy; Na, Minkyun

    2012-01-01

    Phytochemical investigation of the stem barks of Canarium bengalense (Burseraceace) resulted in the isolation of a new flavone glycoside (5) together with six known compounds (1-4, 6, and 7). The chemical structure of the new compound was elucidated as 3'-hydroxy-7,4'-dimethoxyflavone-5-O-α-L-arabinofuranosyl-(1→6)-β-D-glucopyranoside by means of 1D and 2D NMR ((1)H-(1)H COSY, HMQC, and HMBC) and MS analyses. To evaluate the in vitro cytoprotective effect, the isolates (1-7) were tested against hydrogen peroxide (H(2)O(2))-induced damage in primary cultured hepatocytes. The viability of hepatocytes was increased by treatment with each compound, except compound 1. Compounds 3, 4, and 7 exerted cytoprotective effects comparable to curcumin, the positive control. Our results suggest that the cytoprotective constituents of C. bengalense may contribute to its traditional use in the treatment of tumor and liver damage.

  8. Molecular-level insights into the oxidative degradation of grafted amines.

    PubMed

    Ahmadalinezhad, Asieh; Tailor, Ritesh; Sayari, Abdelhamid

    2013-08-05

    The oxidative degradation of CO2 adsorbents consisting of amine-grafted pore-expanded mesoporous MCM-41 silica was investigated. The adsorbents were treated under flowing air at various temperatures, and the degree of deactivation was evaluated through the measurement of their CO2 adsorption capacity prior and subsequent to exposure to air. To decipher the chemical structure of surface species upon air-deactivation of grafted amines, a solvent extraction procedure was developed using a deuterated basic solution. The obtained solutions were analyzed by a variety of 1D and 2D NMR spectroscopy techniques, such as (29)Si, (13)C, (1)H, [(1)H,(15)N] HMBC, [(1)H,(13)C] HMQC, COSY and DOSY. The surface species generated by oxidative degradation of amine-grafted silica were found to contain functional groups such as imine, amide and carboxylic groups. Several structural units were conclusively demonstrated.

  9. Structure elucidation of organic compounds from natural sources using 1D and 2D NMR techniques

    NASA Astrophysics Data System (ADS)

    Topcu, Gulacti; Ulubelen, Ayhan

    2007-05-01

    In our continuing studies on Lamiaceae family plants including Salvia, Teucrium, Ajuga, Sideritis, Nepeta and Lavandula growing in Anatolia, many terpenoids, consisting of over 50 distinct triterpenoids and steroids, and over 200 diterpenoids, several sesterterpenoids and sesquiterpenoids along with many flavonoids and other phenolic compounds have been isolated. For Salvia species abietanes, for Teucrium and Ajuga species neo-clerodanes for Sideritis species ent-kaurane diterpenes are characteristic while nepetalactones are specific for Nepeta species. In this review article, only some interesting and different type of skeleton having constituents, namely rearranged, nor- or rare diterpenes, isolated from these species will be presented. For structure elucidation of these natural diterpenoids intensive one- and two-dimensional NMR techniques ( 1H, 13C, APT, DEPT, NOE/NOESY, 1H- 1H COSY, HETCOR, COLOC, HMQC/HSQC, HMBC, SINEPT) were used besides mass and some other spectroscopic methods.

  10. Salvianolic acid Y: a new protector of PC12 cells against hydrogen peroxide-induced injury from Salvia officinalis.

    PubMed

    Gong, Jun; Ju, Aichun; Zhou, Dazheng; Li, Dekun; Zhou, Wei; Geng, Wanli; Li, Bing; Li, Li; Liu, Yanjie; He, Ying; Song, Meizhen; Wang, Yunhua; Ye, Zhengliang; Lin, Ruichao

    2015-01-06

    Salvianolic acid Y (TSL 1), a new phenolic acid with the same planar structure as salvianolic acid B, was isolated from Salvia officinalis. The structural elucidation and stereochemistry determination were achieved by spectroscopic and chemical methods, including 1D, 2D-NMR (1H-1H COSY, HMQC and HMBC) and circular dichroism (CD) experiments. The biosynthesis pathway of salvianolic acid B and salvianolic acid Y (TSL 1) was proposed based on structural analysis. The protection of PC12 cells from injury induced by H2O2 was assessed in vitro using a cell viability assay. Salvianolic acid Y (TSL 1) protected cells from injury by 54.2%, which was significantly higher than salvianolic acid B (35.2%).

  11. Isolation and characterization of water-soluble intermediates of blue pigments transformed from geniposide of Gardenia jasminoides.

    PubMed

    Park, Jee-Eun; Lee, Jae-Youn; Kim, Hong-Gyu; Hahn, Tae-Ryong; Paik, Young-Sook

    2002-10-23

    Gardenia blue dye was obtained through the reaction of methylamine with genipin, the aglycone of geniposide isolated from the fruits of Gardenia jasminoides. The resulting blue pigments were passed through Bio-Gel P-2 resin yielding five fractions, GM1-GM5. Four fractions (GM1-GM4) were all blue pigments, and the first eluted higher molecular weight fraction GM1 had a higher tinctorial strength than the later eluted lower molecular weight fractions, GM2-GM4. The last eluted GM5 fraction with lambda(max) of 292 nm was colorless and was confirmed as the true intermediate of the blue pigments on the basis of UV-vis spectrophotometric evidence. The GM5 fraction was composed of two epimeric isomers, and their structures were characterized by (1)H NMR, (1)H-(1)H COSY, (13)C NMR, and HMQC and HMBC spectral measurements.

  12. Isolation of an alpha-methylene-gamma-butyrolactone derivative, a toxin from the plant pathogen Lasiodiplodia theobromae.

    PubMed

    He, Guochun; Matsuura, Hideyuki; Yoshihara, Teruhiko

    2004-10-01

    Lasiodiplodia theobromae is known as a multi-infectious microorganism that causes considerable crop damage, particularly to tropical fruits. When the fruits are infected by L. theobromae, the typical symptom is the appearance of black spots on the surface of the infected fruit. When injected in to the peel of banana, the culture filtrate of L. theobromae induced formation of black spots. The structure of the isolated compound responsible for this effect was determined to be (3S,4R)-3-carboxy-2-methylene-heptan-4-olide on the basis of analysis of MS, IR, and 1H and 13C NMR spectroscopic data, including HMQC, HMBC, and 1H-1H COSY experiments. The active compound was not only isolated from the culture filtrate derived from potato dextrose medium, but also from the extract of infected peels of bananas.

  13. New Antifungal Pyranoisoflavone from Ficus tikoua Bur.

    PubMed Central

    Wei, Shaopeng; Wu, Wenjun; Ji, Zhiqin

    2012-01-01

    Considering the undesirable attributes of synthetic fungicides and the availability of Ficus species in China, the stem of Ficus tikoua Bur. was investigated. One new antifungal pyranoisoflavone, 5,3′,4′-trihydroxy-2″,2″-dimethylpyrano (5″,6″:7,8) isoflavone (1), together with two known isoflavones, wighteone (2) and lupiwighteone (3) (with previously reported antifungal activities), were isolated from ethyl acetate extract by bioassay-guided fractionation. Their structures were determined by spectroscopic analysis, such as NMR (1H-1H COSY, HMQC, HMBC and NOESY), IR, UV and HRMS, as well as ESI-MSn analyses. The antifungal activities of 1–3 against Phytophthora infestans were evaluated by direct spore germination assay, and the IC50 values were 262.442, 198.153 and 90.365 μg·mL−1, respectively. PMID:22837700

  14. Metal-mediated coupling of a coordinated isocyanide and indazoles.

    PubMed

    Kinzhalov, Mikhail A; Boyarskiy, Vadim P; Luzyanin, Konstantin V; Dolgushin, Fedor M; Kukushkin, Vadim Yu

    2013-08-07

    A reaction between equimolar amounts of cis-[PdCl2(CNCy)2] (1) and indazole (HInd, 2) or 5-methylindazole (HInd(Me), 3) proceeded in refluxing CHCl3 for ca. 6 h affording the aminocarbene species cis-[PdCl2{C(Ind)=N(H)Cy}(CNCy)] (4) or cis-[PdCl2{C(Ind(Me))=N(H)Cy}(CNCy)] (5) in good (72-83%) isolated yields. Complexes 4 and 5 were characterized by elemental analyses (C, H, N), HR ESI(+)-MS, IR, and 1D ((1)H, (13)C{(1)H}) and 2D ((1)H,(1)H-COSY, (1)H,(13)C-HMQC/(1)H,(13)C-HSQC, (1)H,(13)C-HMBC) NMR spectroscopies, and complex 4 as well by X-ray diffraction. The observed coupling represents the first example of metal-mediated integration between any isocyanide and any aromatic heterocyclic system having an HN center.

  15. The Composite Strain Index (COSI) and Cumulative Strain Index (CUSI): methodologies for quantifying biomechanical stressors for complex tasks and job rotation using the Revised Strain Index.

    PubMed

    Garg, Arun; Moore, J Steven; Kapellusch, Jay M

    2016-11-04

    The Composite Strain Index (COSI) quantifies biomechanical stressors for complex tasks consisting of exertions at different force levels and/or with different exertion times. The Cumulative Strain Index (CUSI) further integrates biomechanical stressors from different tasks to quantify exposure for the entire work shift. The paper provides methodologies to compute COSI and CUSI along with examples. Complex task simulation produced 169,214 distinct tasks. Use of average, time-weighted average (TWA) and peak force and COSI classified 66.9, 28.2, 100 and 38.9% of tasks as hazardous, respectively. For job rotation the simulation produced 10,920 distinct jobs. TWA COSI, peak task COSI and CUSI classified 36.5, 78.1 and 66.6% jobs as hazardous, respectively. The results suggest that the TWA approach systematically underestimates the biomechanical stressors and peak approach overestimates biomechanical stressors, both at the task and job level. It is believed that the COSI and CUSI partially address these underestimations and overestimations of biomechanical stressors. Practitioner Summary: COSI quantifies exposure when applied hand force and/or duration of that force changes during a task cycle. CUSI integrates physical exposures from job rotation. These should be valuable tools for designing and analysing tasks and job rotation to determine risk of musculoskeletal injuries.

  16. Using COSI-CORR to Quantify Earthflow Movement Rates Over Decadal Time Scales

    NASA Astrophysics Data System (ADS)

    Cerovski-Darriau, C.; Roering, J. J.

    2011-12-01

    Large, complex earthflow systems can evolve over diverse (seasonal to millennial) timescales and thus require a range of tools to document their kinematics. In many areas, extensive archives of historical aerial photographs offer potential for quantifying decadal fluctuations, but tracking individual features has been impractical over significant temporal and spatial scales. Here, we explore recent software that automates landslide mapping and improves feasibility of tracking deformation at these scales. The Co-registration of Optically Sensed Images and Correlation (COSI-Corr) software allows for correlation between air photographs and LiDAR imagery, and tracks surface deformation over a sequence of aerial surveys. To analyze the efficacy for landslides, we focused on a 1km2 area riddled with active earthflows, shallow landslides, and gullying in the Waipaoa River catchment on the North Island of New Zealand. This area is dominated by Late Cretaceous-Early Tertiary clay-rich mudstones and calcite-rich sandstones with highly sheared and more massive units that fail in diverse fashion. Starting in the 1900s, the area was burned and converted to pastureland, and is now heavily grazed by sheep and cattle. Slope deformation in the study area has accelerated due to this history of land use changes. We used aerial photographs from 1956, 1960, 1979, and 1982 to track slide movement. The photos were scanned at 1200 dpi (21 micron), giving a ground resolution between approximately 0.2-1m/pixel (scale of 1:16000 to 1:47000). We rectified the photos with 2010 orthophotos and a corresponding 1m LiDAR DEM and hillshade map using the COSI-Corr interface in ENVI 4.5. They were then sequentially correlated, which automatically identifies surface changes with sub-pixel resolution. Next we generated a vector field displacement map for each time step with 8m grid nodes. The resulting vector maps show velocities ranging from about 1-5m/yr. This corresponds well with previously

  17. Fabrication and electrical transport properties of binary Co-Si nanostructures prepared by focused electron beam-induced deposition

    NASA Astrophysics Data System (ADS)

    Porrati, F.; Kämpken, B.; Terfort, A.; Huth, M.

    2013-02-01

    CoSi-C binary alloys have been fabricated by focused electron beam-induced deposition by the simultaneous use of dicobaltoctacarbonyl, Co2(CO)8, and neopentasilane, Si5H12, as precursor gases. By varying the relative flux of the precursors, alloys with variable chemical composition are obtained, as shown by energy dispersive x-ray analysis. Room temperature electrical resistivity measurements strongly indicate the formation of cobalt silicide and cobalt disilicide nanoclusters embedded in a carbonaceous matrix. Temperature-dependent electrical conductivity measurements show that the transport properties are governed by electron tunneling between neighboring CoSi or CoSi2 nanoclusters. In particular, by varying the metal content of the alloy, the electrical conductivity can be finely tuned from the insulating regime into the quasi-metallic tunneling coupling regime.

  18. Negative differential resistance of metal (CoSi2)/insulator (CaF2) triple-barrier resonant tunneling diode

    NASA Astrophysics Data System (ADS)

    Watanabe, Masahiro; Suemasu, Takashi; Muratake, Shigeki; Asada, Masahiro

    1993-01-01

    The electron transport and negative differential resistance in metal-insulator nanometer-thick heterostructures are reported for the first time. The structure of the samples is a resonant tunneling diode with three-barriers of 0.9-nm-thick CaF2 layers and two wells of 1.9- and 2.8-nm-thick CoSi2 layers. These layers were grown by means of partially ionized beam epitaxy for CaF2 and a two step growth technique for CoSi2. In the current-voltage characteristics at 77 K, negative differential resistance was observed in the significant number of samples and the typical peak-to-valley ratio was as high as 2. The negative differential resistance observed here can be attributed to the electron transport through the resonant levels in metal/insulator multilayered heterostructures.

  19. A latent reactive handle for functionalising heparin-like and LMWH deca- and dodecasaccharides† †Electronic supplementary information (ESI) available: Details of experimental procedures not contained in the main text and also 1H, 13C, COSY, HMQC/HSQC NMR and MS data for compounds 2–27. CCDC 998097–998099. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5ob01706h

    PubMed Central

    Miller, Gavin J.; Broberg, Karl. R.; Rudd, Claire; Helliwell, Madeleine R.; Jayson, Gordon C.

    2015-01-01

    d-Glucosamine derivatives bearing latent O4 functionality provide modified H/HS-type disaccharide donors for a final stage capping approach enabling introduction of conjugation-suitable, non-reducing terminal functionality to biologically important glycosaminoglycan oligosaccharides. Application to the synthesis of the first O4-terminus modified synthetic LMWH decasaccharide and an HS-like dodecasaccharide is reported. PMID:26381107

  20. Columnar growth of CoSi2 on Si(111), Si(100) and Si(110) by molecular beam epitaxy

    NASA Technical Reports Server (NTRS)

    Fathauer, R. W.; Nieh, C. W.; Xiao, Q. F.; Hashimoto, Shin

    1990-01-01

    Codeposition of silicon and cobalt on heated silicon substrates in ratios several times the silicide stoichiometry is found to result in epitaxial columns of CoSi2 surrounded by a matrix of epitaxial silicon. For (111)-oriented wafers, nearly cylindrical columns are formed, where both columns and surrounding silicon are defect free, as deduced from transmission electron microscopy. Independent control of the column diameter and separation is possible, and diameters of 27-135 nm have been demonstrated.

  1. The control system of the polarized internal target of ANKE at COSY

    NASA Astrophysics Data System (ADS)

    Kleines, H.; Sarkadi, J.; Zwoll, K.; Engels, R.; Grigoryev, K.; Mikirtychyants, M.; Nekipelov, M.; Rathmann, F.; Seyfarth, H.; Kravtsov, P.; Vasilyev, A.

    2006-05-01

    The polarized internal target for the ANKE experiment at the Cooler Synchrotron COSY of the Forschungszentrum Jülich utilizes a polarized atomic beam source to feed a storage cell with polarized hydrogen or deuterium atoms. The nuclear polarization is measured with a Lamb-shift polarimeter. For common control of the two systems, industrial equipment was selected providing reliable, long-term support and remote control of the target as well as measurement and optimization of its operating parameters. The interlock system has been implemented on the basis of SIEMENS SIMATIC S7-300 family of programmable logic controllers. In order to unify the interfacing to the control computer, all front-end equipment is connected via the PROFIBUS DP fieldbus. The process control software was implemented using the Windows-based WinCC toolkit from SIEMENS. The variety of components, to be controlled, and the logical structure of the control and interlock system are described. Finally, a number of applications derived from the present development to other, new installations are briefly mentioned.

  2. A very light and thin liquid hydrogen/deuterium heat pipe target for COSY experiments

    NASA Astrophysics Data System (ADS)

    Abdel-Bary, M.; Abdel-Samad, S.; Kilian, K.

    2005-07-01

    A liquid hydrogen/deuterium heat pipe (HP) target is used at the COSY external experiments TOF, GEM and MOMO. The target liquid is produced at a cooled condenser and guided through a central tube assisted by gravitation into the target cell. An aluminum condenser is used instead of copper, which requires less material, improves conductivities and provides shorter cooling down time. Residual condenser temperature fluctuations in the order of ≈0.4 K are reduced by using thermal resistances between the cooling machine and the condenser of the heat pipe combined with a controlled heating power. A new design with only a 7-mm-diameter HP has been developed. The diameter of the condenser part remains at 16 mm to provide enough condensation area. The small amount of material ensures short cooling down times. A cold gas deuterium HP target has been designed and developed which allows protons with energy ⩽1 MeV to be measured. A 7-mm-diameter HP is used to fill a cooling jacket around the D 2 gas cell with LH 2. The D 2 gas is stabilized at 200 mbar to allow for thin windows. Its density is increased by factor 15 compared to room temperature.

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

    SciTech Connect

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

    2012-07-01

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

  4. Electromagnetic Transition Form Factor of the η meson with WASA-at-COSY

    NASA Astrophysics Data System (ADS)

    Goswami, A.

    2016-11-01

    In this work we present a study of the Dalitz decay η → γe+e-. The aim of this work is to measure the transition form factor of the η meson. The transition form factor of the η meson describes the electromagnetic structure of the meson. The study of the Dalitz decay helps to calculate the transition form factor of the η meson. When a particle is point-like it's decay rate can be calculated within QED. However, the complex structure of the meson modifies its decay rate. The transition form factor is determined by comparing the lepton-antilepton invariant mass distribution with QED. For this study data on proton-proton reaction at a beam energy of 1.4 GeV has been collected with WASA-at-COSY detector at Forschungszentrum Juelich, Germany. In the higher invariant mass region recent theoretical calculations slightly deviate from the fit to the data. We expect better results in the higher invariant mass region than previous measurements. The preliminary results of the analysis will be presented.

  5. Compact Hyperspectral Imaging System (cosi) for Small Remotely Piloted Aircraft Systems (rpas) - System Overview and First Performance Evaluation Results

    NASA Astrophysics Data System (ADS)

    Sima, A. A.; Baeck, P.; Nuyts, D.; Delalieux, S.; Livens, S.; Blommaert, J.; Delauré, B.; Boonen, M.

    2016-06-01

    This paper gives an overview of the new COmpact hyperSpectral Imaging (COSI) system recently developed at the Flemish Institute for Technological Research (VITO, Belgium) and suitable for remotely piloted aircraft systems. A hyperspectral dataset captured from a multirotor platform over a strawberry field is presented and explored in order to assess spectral bands co-registration quality. Thanks to application of line based interference filters deposited directly on the detector wafer the COSI camera is compact and lightweight (total mass of 500g), and captures 72 narrow (FWHM: 5nm to 10 nm) bands in the spectral range of 600-900 nm. Covering the region of red edge (680 nm to 730 nm) allows for deriving plant chlorophyll content, biomass and hydric status indicators, making the camera suitable for agriculture purposes. Additionally to the orthorectified hypercube digital terrain model can be derived enabling various analyses requiring object height, e.g. plant height in vegetation growth monitoring. Geometric data quality assessment proves that the COSI camera and the dedicated data processing chain are capable to deliver very high resolution data (centimetre level) where spectral information can be correctly derived. Obtained results are comparable or better than results reported in similar studies for an alternative system based on the Fabry-Pérot interferometer.

  6. Search for the C-violating meson decay η → π0e+e- with WASA-at-COSY

    NASA Astrophysics Data System (ADS)

    Demmich, Kay; Bergmann, Florian; Hüsken, Nils; Khoukaz, Alfons

    2016-11-01

    TheWASA-at-COSY experiment is, besides meson production processes, dedicated to studies on rare and forbidden decays of light mesons. In extensive η-production beam times, a high-statistics data set have been collected by means of proton-proton scattering which opens the door to studies on forbidden decays like the C-parity violating process η → π0e+e-. In this article, an optimized detector calibration leading to a significantly improved missing mass resolution and a preliminary decay analysis are presented.

  7. Interactions of Cu with CoSi2, CrSi2 and TiSi2 with and without TiNx barrier layers

    NASA Astrophysics Data System (ADS)

    Olowolafe, J. O.; Li, Jian; Mayer, J. W.

    1990-12-01

    Interactions of Cu with CoSi2, CrSi2, and TiSi2 with and without interposed TiNx layers have been studied using Rutherford backscattering spectrometry, Auger electron spectrometry, x-ray diffraction, and in situ sheet resistivity measurements. Cu diffuses through a preformed CoSi2 layer to form the structure CoSi2/Cu3Si/Si(100). No dissociation of CoSi2 has been observed. For the Cu/CrSi2/Si system, the outdiffusion of Si leads to the formation of Cu3Si/CrSi2/Si at temperatures above 300 °C. At about the same temperature, Cu diffuses into a TiSi2 layer and to the TiSi2/Si interface to react with both Ti and Si forming Cu3Ti, Cu3Si, and Cu4Si phases. A 50-nm TiNx layer prepared by reactive sputtering was observed to be an effective diffusion barrier between Cu and CoSi2 or CrSi2. A 30-nm layer of TiNx simultaneously grown with TiSi2 by rapid thermal annealing proved effective between Cu and TiSi2 up to 500 °C.

  8. Antiinflammatory and Antioxidant Flavonoids and Phenols from Cardiospermum halicacabum (倒地鈴 Dào Dì Líng)

    PubMed Central

    Cheng, Hui-Ling; Zhang, Li-Jie; Liang, Yu-Han; Hsu, Ya-Wen; Lee, I-Jung; Liaw, Chia-Ching; Hwang, Syh-Yuan; Kuo, Yao-Haur

    2013-01-01

    Seventeen compounds, quercetin-3-O-α-l-rhamnoside (1), kaempferol-3-O-α-L-rhamnoside (2), apigenin-7-O-β-D-glucuronide (3), apigenin 7-O-β-D-glucuronide methyl ester (4), apigenin 7-O-β-D-glucuronide ethyl ester (5), chrysoeriol (6), apigenin (7), kaempferol (8), luteolin (9), quercetin (10), methyl 3,4-dihydroxybenzoate (11), p-coumaric acid (12), 4-hydroxybenzoic acid (13), hydroquinone (14), protocathehuic acid (15), gallic acid (16), and indole-3-carboxylic acid (17), were isolated from the ethanol extract of Taiwanese Cardiospermum halicabum. All chemical structures were determined by physical and extensive spectroscopic analyses such as 1 H Nuclear Magnetic Resonance spectroscopy (NMR), 13C NMR, 1H-1H Correlation spectroscopy (1H-1H COSY), Heteronuclear Multiple Quantum Coherence spectroscopy (HMQC), Heteronuclear Multiple-bond Correlation spectroscopy (HMBC), and Nuclear Overhauser Effect spectroscopy (NOESY), as well as comparison with literature values. Furthermore, the High-Performance Liquid Chromatography- Photodiode Array Detector (HPLC-DAD) fingerprint profile was established for the determination of major constituents in the EtOAc extract and retention times of the isolated compounds. All isolated compounds were also evaluated for antiinflammatory and antioxidant activities. PMID:24716153

  9. DFT studies of the conformational/structural dependencies of geminal 1H,1H scalar coupling 2J(H,H') in substituted methanes.

    PubMed

    Barfield, Michael

    2007-08-01

    A study is presented of the structural dependencies for scalar, interproton J-coupling across two bonds in a series of substituted methanes. The coupled perturbed, density functional theory method with a B3PW91 functional and aug-cc-pVTZ-J basis sets is used to examine coupling between geminal protons (2)J(H,H') in methane and a series of substituted compounds CH(3)X (X = CH3, CH(2)CH(3), CH=CH2, CH=O, and NH2) as functions of the dihedral angle phi measured about the C1-X2 bonds. All four contributions are obtained but all conformational effects are dominated by the Fermi contact term. Simple linear combination of atomic orbitals (LCAO)-molecular orbital (MO) sum-over-states methods are used to examine the relationships of the coupling constants with dihedral angles as well as internal H-C-H and H-C1-X2 angles. This study explores some novel aspects of geminal H-H coupling including an analysis of the asymmetry in the conformational dependencies arising from non-next-nearest neighbor interactions. For each of the substituted methanes, explicit trigonometric/exponential expressions are given and these accurately reproduce the (2)J(H,H') structural dependencies with standard deviations usually less than 0.03 Hz. The molecular structures for representative bicyclic molecules were fully optimized, and DFT results for (2)J(H,H') reproduce all the trends in the experimental data. A discussion is given on the applicability of the equations for H--H coupling in the substituted methanes to coupling in the bicyclic molecules.

  10. In situ transmission electron microscopy study on the epitaxial growth of CoSi2 on Si(111) at temperatures below 150 C

    NASA Technical Reports Server (NTRS)

    Nieh, C. W.; Lin, T. L.

    1989-01-01

    This paper reports an in situ transmission electron microscopy study on the epitaxial growth of CoSi2 on Si(111) from a 10-nm-thick amorphous mixture of Co and Si in the ratio 1:2, which was formed by codeposition of Co and Si near room temperature. Nuclei of CoSi2 are observed in the as-deposited film. These nuclei are epitaxial and extend through the whole film thickness. Upon annealing, these columnar epitaxial CoSi2 grains grow laterally at temperatures as low as 50 C. The kinetics of this lateral epitaxial growth was studied at temperatures between 50 and 150 C. The activation energy of the growth process is 0.8 + or - 0.1 eV.

  11. Versatile 1H-31P-31P COSY 2D NMR Techniques for the Characterization of Polyphosphorylated Small Molecules

    PubMed Central

    Majumdar, Ananya; Sun, Yan; Shah, Meha; Freel Meyers, Caren L.

    2010-01-01

    Di- and triphosphorylated small molecules represent key intermediates in a wide range of biological and chemical processes. The importance of polyphosphorylated species in biology and medicine underscores the need to develop methods for the detection and characterization of this compound class. We have reported two-dimensional HPP-COSY spectroscopy techniques to identify diphosphate-containing metabolic intermediates at sub-millimolar concentrations in the methylerythritol phosphate (MEP) isoprenoid biosynthetic pathway.1 In this work, we explore the scope of HPP-COSY based techniques to characterize a diverse group of small organic molecules bearing di- and tri-phosphorylated moieties. These include molecules containing P–O–P and P–C–P connectivities, multivalent P(III)–O–P(V) phosphorus nuclei with widely separated chemical shifts, as well as virtually overlapping 31P resonances exhibiting strong coupling effects. We also demonstrate the utility of these experiments to rapidly distinguish between mono- and diphosphates. A detailed protocol for optimizing these experiments to achieve best performance is presented. PMID:20408590

  12. Efficiency of homonuclear Hartmann-Hahn and COSY-type mixing sequences in the presence of scalar and residual dipolar couplings.

    PubMed

    Kramer, Frank; Glaser, Steffen J

    2002-03-01

    In the presence of scalar (J) and residual dipolar (D) couplings, the transfer efficiency of homonuclear Hartmann-Hahn and COSY-type mixing depends on the ratio D/J and on the mixing sequence. This dependence is analyzed theoretically and the results are confirmed experimentally. At least two different mixing sequences are required to yield good transfer efficiencies for all ratios D/J. In contrast to COSY-type experiments, homonuclear Hartmann-Hahn sequences can provide efficient transfer even if the sum of D and J is zero, i.e., if the coupling vanishes in the weak coupling limit.

  13. Application of 13C-labeling and 13C-13C COSY NMR experiments in the structure determination of a microbial natural product.

    PubMed

    Kwon, Yun; Park, Sunghyouk; Shin, Jongheon; Oh, Dong-Chan

    2014-08-01

    The elucidation of the structures of complex natural products bearing many quaternary carbons remains challenging, even in this advanced spectroscopic era. (13)C-(13)C COSY NMR spectroscopy shows direct couplings between (13)C and (13)C, which comprise the backbone of a natural product. Thus, this type of experiment is particularly useful for natural products bearing consecutive quaternary carbons. However, the low sensitivity of (13)C-based NMR experiments, due to the low natural abundance of the (13)C nucleus, is problematic when applying these techniques. Our efforts in the (13)C labeling of a microbial natural product, cyclopiazonic acid (1), by feeding (13)C-labeled glucose to the fungal culture, enabled us to acquire (13)C-(13)C COSY NMR spectra on a milligram scale that clearly show the carbon backbone of the compound. This is the first application of (13)C-(13)C COSY NMR experiments for a natural product. The results suggest that (13)C-(13)C COSY NMR spectroscopy can be routinely used for the structure determination of microbial natural products by (13)C-enrichment of a compound with (13)C-glucose.

  14. Fabrication and electrical transport properties of binary Co-Si nanostructures prepared by focused electron beam-induced deposition

    SciTech Connect

    Porrati, F.; Huth, M.; Kaempken, B.; Terfort, A.

    2013-02-07

    CoSi-C binary alloys have been fabricated by focused electron beam-induced deposition by the simultaneous use of dicobaltoctacarbonyl, Co{sub 2}(CO){sub 8}, and neopentasilane, Si{sub 5}H{sub 12}, as precursor gases. By varying the relative flux of the precursors, alloys with variable chemical composition are obtained, as shown by energy dispersive x-ray analysis. Room temperature electrical resistivity measurements strongly indicate the formation of cobalt silicide and cobalt disilicide nanoclusters embedded in a carbonaceous matrix. Temperature-dependent electrical conductivity measurements show that the transport properties are governed by electron tunneling between neighboring CoSi or CoSi{sub 2} nanoclusters. In particular, by varying the metal content of the alloy, the electrical conductivity can be finely tuned from the insulating regime into the quasi-metallic tunneling coupling regime.

  15. CoSi2 growth on Si(001) by reactive deposition epitaxy: Effects of high-flux, low-energy ion irradiation

    NASA Astrophysics Data System (ADS)

    Lim, C. W.; Greene, J. E.; Petrov, I.

    2006-07-01

    CoSi2 layers, <40nm thick, were grown on Si(001) by reactive deposition epitaxy (RDE) in which Co was deposited at 700°C by magnetically unbalanced ultrahigh vacuum magnetron sputtering. X-ray diffraction pole figures and transmission electron microscopy (TEM) reveal that the layers, which exhibit a cube-on-cube epitaxial relationship with the substrate, (001)CoSi2‖(001)Si and [100]CoSi2‖[100]Si, contain fourfold symmetric {111} twinned domains oriented such that {221}CoSi2‖(001)Si and ⟨110⟩CoSi2‖[110]Si. We demonstrate that high-flux low-energy (EAr+=9.6eV) Ar+ ion irradiation during deposition dramatically increases the area fraction fu of untwinned regions from 0.17 in films grown under standard magnetically balanced conditions in which the ratio JAr+/JCo of the incident Ar+ to Co fluxes is 1.4 to 0.72 with JAr+/JCo=13.3. TEM analyses show that the early stages of RDE CoSi2(001) film growth proceed via the Volmer-Weber mode with independent nucleation of both untwinned and twinned islands. Increasing JAr+/JCo results in larger values of both the number density and area of untwinned with respect to twinned islands. The intense Ar+ ion bombardment creates additional low-energy adsorption sites that favor the nucleation of untwinned islands while collisionally enhancing Co surface mobilities which, in turn, increases the probability of itinerant Co adatoms reaching these sites.

  16. Resveratrol tetramer of hopeaphenol isolated from Shorea johorensis (Dipterocarpaceae)

    NASA Astrophysics Data System (ADS)

    Aisha, Farra; Din, Laily B.; Yaacob, W. A.

    2014-09-01

    Hopeaphenol (1) as a resveratrol tetramer was isolated from the bark of Shorea johorensis collected from Imbak Canyon, Sabah, Malaysia. The structure of this compound was determined by the spectroscopic evidences using 1H- and 13C-NMR assigned with HSQC, HMBC, 1H-1H COSY and 1H-1H NOESY spectra, mass spectrum, and by comparison with reported data.

  17. Increased effective barrier heights in Schottky diodes by molecular-beam epitaxy of CoSi2 and Ga-doped Si on Si(111)

    NASA Technical Reports Server (NTRS)

    Fathauer, R. W.; Lin, T. L.; Grunthaner, P. J.; Andersson, P. O.; Iannelli, J. M.

    1988-01-01

    Increasing the effective Schottky-barrier height of epitaxial CoSi2/Si(111) diodes by the use of thin, highly doped Si layers in close proximity to the metal-semiconductor interface has been studied. Intrinsic Si, Si doped by coevaporation of Ga, and epitaxial CoSi2 layers have all been grown in the same molecular-beam epitaxy system. Current-voltage and photoresponse characterization yield barrier heights ranging from 0.61 eV for a sample with no p(+) layer to 0.89 eV for a sample with a 20-nm-thick p(+) layer. These results are compared to theoretical values based on a one-dimensional solution of Poisson's equation under the depletion approximation.

  18. Formation of Bamboo-Like Carbon Nanotubes and Nanofibers Using Co-Si-O and Co-Si Catalysts

    NASA Astrophysics Data System (ADS)

    Chang, Hui Lin; Tzu Kuo, Cheng

    2010-04-01

    Bamboo-like carbon nanotubes were synthesized by microwave plasma chemical vapor deposition (MPCVD) using CH4 and N2 as source gases in various ratios. Two types of catalytic films, namely, a condition 1, Co film/SiO2/Si substrate, and, a Co film/Si substrate layer with rapid thermal annealing (RTA; condition 2), were used as catalysts to grow carbon nanotubes. The interaction between the catalytic film and the Si substrate or between the catalytic film and the SiO2 interlayer occurred during the H2 reduction step before nanotube growth. The chemical compositions of catalytic particles capping the carbon nanotubes were identified by energy-dispersive X-ray spectroscopy (EDS) as Co-Si-O and Co-Si for conditions 1 and 2, respectively. The growth of the base and tip growths was investigated and is suggested to be governed by the capillary effect and the strength of adhesion between the catalytic particles and the underlayer. Transmission electron microscopy (TEM) analysis reveals that the carbon nanotubes and nanofibers have bamboo-like structures with hollow internal compartments. The formation mechanisms of these bamboo-like structures are discussed.

  19. BIG KARL and COSY: Examples for high performance magnet design taught by {open_quotes}Papa Klaus{close_quotes}

    SciTech Connect

    Bechtstedt, U.; Hacker, U.; Maier, R.; Martin, S.; Berg, G.P.A.; Hardt, A.; Huerlimann, W.; Meissburger, J.; Roemer, J.G.M.

    1995-02-01

    The past decades have seen a tremendous development in nuclear, middle, and high energy physics. This advance was in a great part promoted by the availability of newer and more powerful instruments. Over time, these instruments grew in size as well as in sophistication and precision. Nearly all these devices had one fundamental thing in common - magnetic fields produced with currents and iron. The precision demanded by the new experiments and machines did bring the magnet technology to new frontiers requiring the utmost in the accuracy of magnetic fields. The complex properties of the iron challenged innumerable physicists in the attempt to force the magnetic fields into the desired shape. Experience and analytical insight were the pillars for coping with those problems and only few mastered the skills and were in addition able to communicate their intricate knowledge. It was a fortuitous situation that the authors got to know Klaus Halbach who belonged to those few and who shared his knowledge contributing thus largely to the successful completion of two large instruments that were built at the Forschungszentrum Juelich, KFA, for nuclear and middle energy physics. In one case the efforts went to the large spectrometer named BIG KARL whose design phase started in the early 70`s. In the second case the work started in the early 80`s with the task to build a high precision 2.5 GeV proton accelerator for cooled stored and extracted beams known as COSY-Juelich.

  20. Isovalent substitutes play in different ways: Effects of isovalent substitution on the thermoelectric properties of CoSi0.98B0.02

    NASA Astrophysics Data System (ADS)

    Sun, Hui; Lu, Xu; Morelli, Donald T.

    2016-07-01

    Boron-added CoSi, CoSi0.98B0.02, possesses a very high thermoelectric power factor of 60 μW cm-1 K-2 at room temperature, which is among the highest power factors that have ever been reported for near-room-temperature thermoelectric applications. Since the electrical properties of this material have been tuned properly, isovalent substitution for its host atoms is intentionally employed to reduce the lattice thermal conductivity while maintaining the electronic properties unchanged. In our previous work, the effect of Rh substitution for Co atoms on the thermoelectric properties of CoSi0.98B0.02 has been studied. Here, we present a study of the substitution of Ge for Si atoms in this compound. Even though Ge and Rh are isovalent with their corresponding host atoms, they play different roles in determining the electrical and thermal transport properties. Through the evaluation of the lattice thermal conductivity by the Debye approximation and the comparison between the high-temperature Seebeck coefficients, we propose that Rh substitution leads to a further overlapping of the conduction and the valence bands, while Ge substitution only shifts the Fermi level upward into the conduction band. Our results show that the influence of isovalent substitution on the electronic structure cannot be ignored when the alloying method is used to improve thermoelectric properties.

  1. Isovalent substitutes play in different ways: Effects of isovalent substitution on the thermoelectric properties of CoSi0.98B0.02

    DOE PAGES

    Sun, Hui; Lu, Xu; Morelli, Donald T.

    2016-07-21

    Boron-added CoSi, CoSi0.98B0.02, possesses a very high thermoelectric power factor of 60 μW cm-1 K-2 at room temperature, which is among the highest power factors that have ever been reported for near-room-temperature thermoelectric applications. Since the electrical properties of this material have been tuned properly, isovalent substitution for its host atoms are intentionally employed to reduce the lattice thermal conductivity while maintaining the electronic properties unchanged. In our previous work, the effect of Rh substitution for Co atoms on the thermoelectric properties of CoSi0.98B0.02 has been studied. Here we present a study of the substitution of Ge for Si atomsmore » in this compound. Even though Ge and Rh are isovalent with their corresponding host atoms, they play different roles in determining the electrical and thermal transport properties. Through the evaluation of the lattice thermal conductivity by the Debye approximation and the comparison between the high-temperature Seebeck coefficients, we propose that Rh substitution leads to a further overlapping of the conduction and the valence bands while Ge substitution only shifts the Fermi level upward into the conduction band. Lastly, our results show that the influence of isovalent substitution on the electronic structure cannot be ignored when the alloying method is used to improve thermoelectric properties.« less

  2. Growth of single-crystal columns of CoSi2 embedded in epitaxial Si on Si(111) by molecular beam epitaxy

    NASA Technical Reports Server (NTRS)

    Fathauer, R. W.; Nieh, C. W.; Xiao, Q. F.; Hashimoto, Shin

    1989-01-01

    The codeposition of Si and Co on a heated Si(111) substrate is found to result in epitaxial columns of CoSi2 if the Si:Co ratio is greater than approximately 3:1. These columns are surrounded by an Si matrix which shows bulk-like crystalline quality based on transmission electron microscopy and ion channeling. This phenomenon has been studied as functions of substrate temperature and Si:Co ratio. Samples with columns ranging in average diameter from approximately 25 to 130 nm have been produced.

  3. Self-aligned silicides for Ohmic contacts in complementary metal-oxide-semiconductor technology: TiSi2, CoSi2, and NiSi

    NASA Astrophysics Data System (ADS)

    Zhang, S.-L.; Smith, U.

    2004-07-01

    Metal silicides continue to play an indispensable role during the remarkable development of microelectronics. Along with several other technological innovations, the implementation of the self-aligned silicide technology paved the way for a rapid and successful miniaturization of device dimensions for metal-oxide-semiconductor field-effect transistors (MOSFETs) in pace with the Moore's law. The use of silicides has also evolved from creating reliable contacts for diodes, to generating high-conductivity current paths for local wiring, and lately to forming low-resistivity electrical contacts for MOSFETs. With respect to the choice of silicides for complementary metal-oxide-semiconductor (CMOS) technology, a convergence has become clear with the self-alignment technology using only a limited number of silicides, namely TiSi2, CoSi2, and NiSi. The present work discusses the advantages and limitations of TiSi2, CoSi2, and NiSi using the development trend of CMOS technology as a measure. Specifically, the reactive diffusion and phase formation of these silicides in the three terminals of a MOSFET, i.e., gate, source, and drain, are analyzed. This work ends with a brief discussion about future trends of metal silicides in micro/nanoelectronics with reference to potential material aspects and device structures outlined in the International Technology Roadmap for Semiconductors. .

  4. 1H, 13C NMR spectral and single crystal structural studies of toxaphene congeners. Quantum chemical calculations for preferred conformers of 2,5- endo,6- exo,8,9,9,10,10-octachloro-2-bornene and their DFT/GIAO 13C chemical shifts

    NASA Astrophysics Data System (ADS)

    Laihia, K.; Valkonen, A.; Kolehmainen, E.; Suontamo, R.; Nissinen, M.; Nikiforov, V.; Selivanov, S.

    2005-11-01

    The 1H and 13C NMR chemical shifts for six toxaphene congeners: 2- exo,3- endo,6- exo,8,9,10-hexachloro- ( 1), 2- exo,3- endo,5- exo,9,9,10,10-heptachloro- ( 2), 2- exo,3- endo,6- exo,8,9,10,10-heptachloro- ( 3), 2- exo,3- endo,5- exo,6- endo,8,9,10-heptachloro- ( 4), 2- exo,3- endo,5- exo,6- endo,8,9,9,10-octachlorobornane ( 5) and 2,5- endo,6- exo,8,9,9,10,10-octachloro-2-bornene ( 6) are reported. Their chemical shift assignments have been obtained by means of Pulsed Field Gradient (PFG) Double Quantum Filtered (DQF) 1H, 1H correlation spectroscopy (COSY), PFG 1H, 13C Heteronuclear Multiple Quantum Coherence (HMQC) and PFG 1H, 13C Heteronuclear Multiple Bond Correlation (HMBC) experiments. A single crystal X-ray structural analysis was made for compounds 1, 3, 4 and 6. The prevalences of two octachlorobornene rotamers ( 6 a, 6 b) were elucidated by ab initio MO method and single point DFT/GIAO calculations for 13C chemical shifts. Theoretical calculations proved that the single crystal structure of 6 corresponds its most stable conformer in solution.

  5. New chromone and triglyceride from Cucumis melo seeds.

    PubMed

    Ibrahim, Sabrin R M

    2014-02-01

    Re-investigation of the MeOH extract of the seeds of Cucumis melo L. var. reticulatus (Cucurbitaceae) led to the isolation of a new chromone derivative (5,7- dihydroxy-2-[2-(3-methoxy-4-hydroxyphenyl)ethyl]chromone (5) and a triglyceride (1,3-di-(6Z,9Z)-docosa-6,9-dienoyl-2-(6Z) hexacos-6-enoylglycerol (1), together with three known compounds; alpha-spinasterol (2), stigmasta-7,22,25-trien-3-ol (3), and D:B-friedoolean-5-ene-3-beta-ol (4), are reported from this species for the first time. Their structures were determined by extensive 1D (1H, 13C, and DEPT) and 2D (1H-1H COSY, HMQC, and HMBC) NMR and mass spectral measurements. Compound 5 displayed significant cytotoxic activity against L5178Y cells, with an ED50 of 5 microM. The MeOH extract and 5 showed antioxidant activity using the DPPH assay.

  6. Structure of the O-polysaccharide leads to classification of Proteus penneri 31 in Proteus serogroup O19.

    PubMed

    Kondakova, Anna N; Zych, Krystyna; Senchenkova, Sof'ya N; Zabłotni, Agnieszka; Shashkov, Alexander S; Knirel, Yuriy A; Sidorczyk, Zygmunt

    2003-10-24

    O-polysaccharide was obtained by mild acid degradation of the lipopolysaccharide (LPS) of Proteus penneri strain 31. Sugar and methylation analyses along with NMR spectroscopic studies, including 2D 1H,1H COSY, TOCSY, ROESY, 1H,13C and 1H,31P HMQC experiments, demonstrated the following structure of the polysaccharide: [carbohydrate structure: see text] where FucNAc is 2-acetamido-2,6-dideoxygalactose and EtnP is 2-aminoethyl phosphate. The polysaccharide studied has the same carbohydrate backbone as the O-polysaccharide of Proteus vulgaris O19. Based on this finding and close serological relatedness of the LPS of the two strains, it is proposed to classify P. penneri 31 in Proteus serogroup O19 as an additional subgroup. In contrast, D-GlcNAc6PEtn and alpha-L-FucNAc-(1-->3)-D-GlcNAc shared with a number of other Proteus O-polysaccharides could not provide any significant cross-reactivity of the corresponding LPS with rabbit polyclonal O-antiserum against P. penneri 31.

  7. Sesquiterpenes inhibiting the microglial activation from Laurus nobilis.

    PubMed

    Chen, Hongqiang; Xie, Chunfeng; Wang, Hao; Jin, Da-Qing; Li, Shen; Wang, Meicheng; Ren, Quanhui; Xu, Jing; Ohizumi, Yasushi; Guo, Yuanqiang

    2014-05-21

    The inhibitory reagents to inhibit the activation of microglial cells may be potentially useful for the treatment of neurodegenerative diseases. The leaves of the plant Laurus nobilis belonging to the family Lauraceae, namely, bay leaves, have been used as a popular spice, and their extract showed moderate inhibition on microglial activation. A further phytochemical investigation of the leaves led to the isolation of two new (1, 2) and eight known (3-10) sesquiterpenes. Their structures were elucidated on the basis of extensive 1D and 2D NMR (HMQC, HMBC, (1)H-(1)H COSY, and NOESY) spectroscopic data analyses and Chem3D modeling. The following biological studies disclosed that these isolated compounds showed inhibitory activities on LPS-induced microglial activation. The results of our phytochemical investigation, including two new sesquiterpenes (1 and 2) and the first report of two compounds (3 and 4) from this species, further revealed the chemical composition of bay leaves as a popular spice, and the biological studies implied that bay leaves, containing bioactive substances with the inhibition of microglial activation, were potentially beneficial to human health.

  8. Isolation and structure determination of one new metabolite isolated from the red fermented rice of Monascus purpureus.

    PubMed

    Cheng, Ming-Jen; Chen, Jih-Jung; Wu, Ming-Der; Yang, Ping-Shin; Yuan, Gwo-Fang

    2010-06-01

    The n-BuOH-soluble portion of the 95% EtOH extract of red fermented rice fermented with the yellow mutant of the fungus Monascus purpureus BCRC 38113 (Monascaceae) led to the isolation of one new pyran-2-one derivative, namely peroxymonascuspyrone (1), along with nine known compounds, monasfluore A (2), monasfluore B (3), 3-epi-betulinic acid (4), 3-epi-betulinic acid acetate (5), alpha-tocospiro A (6), friedelan-3-one (7), alpha-cadinol (8), anticopalol (9), and spathulenol (10). Interestingly, this is the first report of a naturally occurring pyran-2-one skeleton isolated from Monascus sp. Their structures and relative configurations were elucidated by spectroscopic methods, including 1D- and 2D-NMR ((1)H,(1)H-COSY, HMQC, HMBC and NOESY), as well as low- and high-resolution mass spectrometric analyses. In addition, cytotoxicities against MCF-7, NCI-H460 and SF-268 cancer cell lines were measured in vitro; the results revealed that these metabolites have no cytotoxicity against the selected tumour cells.

  9. Amaryllidaceae alkaloids from the bulbs of Lycoris radiata with cytotoxic and anti-inflammatory activities.

    PubMed

    Liu, Zhi-Ming; Huang, Xiao-Yun; Cui, Mao-Rong; Zhang, Xiao-De; Chen, Zhao; Yang, Ben-Shou; Zhao, Xiao-Kun

    2015-03-01

    Four new Amaryllidaceae alkaloids, (+)-1-hydroxy-ungeremine (1), (+)-6β-acetyl-8-hydroxy-9-methoxy-crinamine (2), (+)-2-hydroxy-8-demethyl-homolycorine-α-N-oxide (3), (+)-N-methoxylcarbonyl-2-demethyl-isocorydione (4), together with two known compounds, (+)-6β-acetyl-crinamine (5) and 8-demethyl-homolycorine-α-N-oxide (6) were isolated from the ethanol extract of the bulbs of Lycoris radiata. Structural elucidation of all the compounds were performed by spectral methods such as 1D and 2D ((1)H-(1)H COSY, HMQC, and HMBC) NMR spectroscopy, in addition to high resolution mass spectrometry. All the isolated alkaloids were in vitro evaluated for their cytotoxic activities against eight tumor cell lines (BEN-MEN-1, CCF-STTG1, CHG-5, SHG-44, U251, BGC-823, HepG2 and SK-OV-3) and anti-inflammatory activities against Cox-1 and Cox-2. As a result, alkaloids 1 and 4 exhibited significant cytotoxic activities against all tested tumor cell lines except against BEN-MEN-1. Additionally, alkaloids 1 and 4 possessed selective inhibition of Cox-2 comparable with the standard drug NS-398 (>90%).

  10. Cytotoxic and antimalarial amaryllidaceae alkaloids from the bulbs of Lycoris radiata.

    PubMed

    Hao, Bin; Shen, Shu-Fang; Zhao, Qing-Jie

    2013-02-25

    Phytochemical investigation of the 80% ethanol extract of the bulbs of Lycoris radiata resulted in the isolation of five new Amaryllidaceae alkaloids: (+)-5,6-dehydrolycorine (1), (+)-3α,6β-diacetyl-bulbispermine (2), (+)-3α-hydroxy-6β-acetyl- bulbispermine (3), (+)-8,9-methylenedioxylhomolycorine-N-oxide (5), and 5,6-dihydro-5- methyl-2-hydroxyphenanthridine (7), together with two known compounds, (+)-3α-methoxy- 6β-acetylbulbispermine (4) and (+)-homolycorine- N-oxide (6). Structural elucidation of all the compounds were performed by spectral methods such as 1D and 2D (1H-1H COSY, HMQC, and HMBC) NMR spectroscopy, in addition to high resolution mass spectrometry. Alkaloid 1 showed potent cytotoxicity against astrocytoma and glioma cell lines (CCF-STTG1, CHG-5, SHG-44, and U251), as well as HL-60, SMMC-7721, and W480 cell lines with IC(50) values of 9.4-11.6 μM. Additonally, compound 1 exhibited antimalarial activity with IC(50) values of 2.3 μM for D-6 strain and 1.9 μM for W-2 strain of Plasmodium falciparum.

  11. Image cross-correlation using COSI-Corr: A versatile technique to monitor and quantity surface deformation in space and time

    NASA Astrophysics Data System (ADS)

    Leprince, S.; Ayoub, F.; Avouac, J.

    2011-12-01

    We have developed a suite of algorithms for precise Co-registration of Optically Sensed Images and Correlation (COSI-Corr) which were implemented in a software package first released to the academic community in 2007. Its capability for accurate surface deformation measurement has proved useful for a wide variety of applications. We present the fundamental principles of COSI-Corr, which are the key ingredients to achieve sub-pixel registration and sub-pixel measurement accuracy, and we show how they can be applied to various types of images to extract 2D, 3D, or even 4D deformation fields of a given surface. Examples are drawn from recent collaborative studies and include: (1) The study of the Icelandic Krafla rifting crisis that occurred from 1975 to 1984 where we used a combination of archived airborne photographs, declassified spy satellite imagery, and modern satellite acquisitions to propose a detailed 2D displacement field of the ground; (2) The estimation of glacial velocities from fast New Zealand glaciers using successive ASTER acquisitions; (3) The derivation of sand dunes migration rates; (4) The estimation of ocean swell velocity taking advantage of the short time delay between the acquisition of different spectral bands on the SPOT 5 satellite; (5) The derivation of the full 3D ground displacement field induced by the 2010 Mw 7.2 El Mayor-Cucapah Earthquake, as recorded from pre- and post-event lidar acquisitions; (6) And, the estimation of 2D in plane deformation of mechanical samples under stress in the lab. Finally, we conclude by highlighting the potential future and implication of applying such correlation techniques on a large scale to provide global monitoring of our environment.

  12. Isovalent substitutes play in different ways: Effects of isovalent substitution on the thermoelectric properties of CoSi0.98B0.02

    SciTech Connect

    Sun, Hui; Lu, Xu; Morelli, Donald T.

    2016-07-21

    Boron-added CoSi, CoSi0.98B0.02, possesses a very high thermoelectric power factor of 60 μW cm-1 K-2 at room temperature, which is among the highest power factors that have ever been reported for near-room-temperature thermoelectric applications. Since the electrical properties of this material have been tuned properly, isovalent substitution for its host atoms are intentionally employed to reduce the lattice thermal conductivity while maintaining the electronic properties unchanged. In our previous work, the effect of Rh substitution for Co atoms on the thermoelectric properties of CoSi0.98B0.02 has been studied. Here we present a study of the substitution of Ge for Si atoms in this compound. Even though Ge and Rh are isovalent with their corresponding host atoms, they play different roles in determining the electrical and thermal transport properties. Through the evaluation of the lattice thermal conductivity by the Debye approximation and the comparison between the high-temperature Seebeck coefficients, we propose that Rh substitution leads to a further overlapping of the conduction and the valence bands while Ge substitution only shifts the Fermi level upward into the conduction band. Lastly, our results show that the influence of isovalent substitution on the electronic structure cannot be ignored when the alloying method is used to improve thermoelectric properties.

  13. Development of a Standardized Methodology for the Use of COSI-Corr Sub-Pixel Image Correlation to Determine Surface Deformation Patterns in Large Magnitude Earthquakes.

    NASA Astrophysics Data System (ADS)

    Milliner, C. W. D.; Dolan, J. F.; Hollingsworth, J.; Leprince, S.; Ayoub, F.

    2014-12-01

    Coseismic surface deformation is typically measured in the field by geologists and with a range of geophysical methods such as InSAR, LiDAR and GPS. Current methods, however, either fail to capture the near-field coseismic surface deformation pattern where vital information is needed, or lack pre-event data. We develop a standardized and reproducible methodology to fully constrain the surface, near-field, coseismic deformation pattern in high resolution using aerial photography. We apply our methodology using the program COSI-corr to successfully cross-correlate pairs of aerial, optical imagery before and after the 1992, Mw 7.3 Landers and 1999, Mw 7.1 Hector Mine earthquakes. This technique allows measurement of the coseismic slip distribution and magnitude and width of off-fault deformation with sub-pixel precision. This technique can be applied in a cost effective manner for recent and historic earthquakes using archive aerial imagery. We also use synthetic tests to constrain and correct for the bias imposed on the result due to use of a sliding window during correlation. Correcting for artificial smearing of the tectonic signal allows us to robustly measure the fault zone width along a surface rupture. Furthermore, the synthetic tests have constrained for the first time the measurement precision and accuracy of estimated fault displacements and fault-zone width. Our methodology provides the unique ability to robustly understand the kinematics of surface faulting while at the same time accounting for both off-fault deformation and measurement biases that typically complicates such data. For both earthquakes we find that our displacement measurements derived from cross-correlation are systematically larger than the field displacement measurements, indicating the presence of off-fault deformation. We show that the Landers and Hector Mine earthquake accommodated 46% and 38% of displacement away from the main primary rupture as off-fault deformation, over a mean

  14. Stereoselective synthesis, spectral and antimicrobial studies of some cyanoacetyl hydrazones of 3-alkyl-2,6-diarylpiperidin-4-ones

    NASA Astrophysics Data System (ADS)

    Velayutham Pillai, M.; Rajeswari, K.; Vidhyasagar, T.

    2014-11-01

    A series of novel cyanoacetyl hydrazones of 3-alkyl-2,6-diarylpiperidin-4-ones were synthesized stereoselectively and characterized by IR, Mass, 1H NMR, 13C NMR, 1H-1H COSY and 1H-13C COSY spectra. The stereochemistry of the synthesized compounds was established using NMR spectra. Antimicrobial screening of the synthesized compounds revealed their antibacterial and antifungal potencies. Growth inhibition of Enterobacter Aerogenes by compound 15 was found to be superior to the standard drug.

  15. Characterization of a cinnamoyl derivative from broccoli (Brassica oleracea L. var. italica) florets.

    PubMed

    Survay, Nazneen Shaik; Kumar, Brajesh; Upadhyaya, Chandrama Prakash; Ko, Eunyoung; Lee, Choonghwan; Choi, Jung Nam; Yoon, Do-Young; Jung, Yi-Sook; Park, Se Won

    2010-12-01

    A new intact glucosinolate Cinnamoyl derivative [6'-O-trans-(4″- hydroxy cinnamoyl)-4-(methylsulphinyl) butyl glucosinolate] (A) has been isolated from Broccoli (Brassica oleracea L. var. italica) florets. The compound was isolated and characterized by LC, MS-ESI, FTIR, (1)H and (13)C NMR as well as (1)H-(1)H COSY, DEPT 135° spectrometric experiments.

  16. Characterization and thermal isomerization of (all-E)-lycopene.

    PubMed

    Takehara, Munenori; Nishimura, Masatoshi; Kuwa, Takahiro; Inoue, Yoshinori; Kitamura, Chitoshi; Kumagai, Tsutomu; Honda, Masaki

    2014-01-08

    A large amount of (all-E)-lycopene was successfully purified from tomato paste using an improved method that included a procedure to wash crystalline powder with acetone. The total yield of the pure (all-E) form was at least 30%. The melting point of (all-E)-lycopene was determined to be 176.35 °C by differential scanning calorimetry (DSC) measurements. Bathochromic shifts were observed in the absorption maxima of all solvents tested (at most a 36 nm shift for λ2 in carbon disulfide, as was observed in hexane) and were accompanied by absorbance decreases, namely, a hypochromic effect, showing a higher correlation between the position and the intensity of the main absorption bands. This bathochromic shift was dependent upon the polarizability of the solvent rather than its polarity. The structure of (all-E)-lycopene in CDCl3 and C6D6 was identified on the basis of one- and two-dimensional nuclear magnetic resonance (NMR) spectra, including (1)H and (13)C NMR, homonuclear correlation spectroscopy ((1)H-(1)H COSY), heteronuclear multiple-quantum coherence (HMQC), and heteronuclear multiple-bond connectivity (HMBC). The rate constants of the decrease in (all-E)-lycopene with hexane and benzene were calculated to be 3.19 × 10(-5) and 3.55 × 10(-5) s(-1), respectively. The equilibrium constants between (all-E) and (13Z) isomers were estimated to be 0.29 in hexane and 0.31 in benzene, respectively, from the point at which the amount of (13Z)-lycopene reached its maximum.

  17. Chemical Components from Aloe and their Inhibition of Indoleamine 2, 3-dioxygenase

    PubMed Central

    Sun, Ya Nan; Li, Lin Ying; Li, Wei; Kang, Jong Seong; Hwang, Inkyu; Kim, Young Ho

    2017-01-01

    Background: In Korea, Aloe is routinely ingested as a traditional medicine or as a component of health beverages. Objective: To research the inhibition of indoleamine 2, 3-dioxygenase (IDO) activities of components from Aloe. Materials and Methods: the compounds were isolated by a combination of silica gel and YMC Rp-18 column chromatography, and their structures were identified by analysis of spectroscopic data (1D, 2D-NMR, and MS). All of the isolated compounds were examined for their ability to inhibit IDO, which actively suppresses immune functions by catalyzing the rate limiting reaction in the conversion of tryptophan to kynurenine. Results: In this phytochemical study, 18 known compounds were isolated from aqueous dissolved Aloe exudates. All of the isolated compounds were examined for their ability to inhibit IDO activities for a series of anthraquinone derivatives (1-7) isolated from the Aloe extract; the IC50 values of these compounds ranged from 39.41 to 53.93 µM. Enzyme kinetic studies of their modes of inhibition indicated that all of the compounds were uncompetitive inhibitors. Conclusion: The aqueous dissolved Aloe exudate can be used as a source of novel natural IDO inhibitors and merit testing as therapeutic agents in the treatments of cancer and immunopathologic diseases, such as autoimmune, inflammatory, and allergic disorders. SUMMARY In this study, 18 known compounds were isolated from aqueous dissolved Aloe exudates. All of the isolated compounds were examined for their ability to inhibit indoleamine 2, 3-dioxygenase (IDO) activities for a series of anthraquinone derivatives (1−7) isolated from the Aloe extract. Abbreviation used: IDO: inhibit indoleamine 2, 3-dioxygenase, TMS: tetramethylsilane, HMQC: heteronuclear multiple quantum correlation, HMBC: heteronuclear multiple bond correlation, COSY: 1H-1H correlation spectroscopy, ESI-MS: Electrospray ionization mass spectrometry, DMSO: dimethyl sulfoxide PMID:28216884

  18. Search for η-mesic 4He in the dd →3He nπ0 and dd →3He pπ- reactions with the WASA-at-COSY facility

    NASA Astrophysics Data System (ADS)

    Adlarson, P.; Augustyniak, W.; Bardan, W.; Bashkanov, M.; Bergmann, F. S.; Berłowski, M.; Bhatt, H.; Bondar, A.; Büscher, M.; Calén, H.; Ciepał, I.; Clement, H.; Czerwiński, E.; Demmich, K.; Engels, R.; Erven, A.; Erven, W.; Eyrich, W.; Fedorets, P.; Föhl, K.; Fransson, K.; Goldenbaum, F.; Goswami, A.; Grigoryev, K.; Gullström, C.-O.; Heijkenskjöld, L.; Hejny, V.; Hüsken, N.; Jarczyk, L.; Johansson, T.; Kamys, B.; Kelkar, N. G.; Kemmerling, G.; Khatri, G.; Khoukaz, A.; Khreptak, O.; Kirillov, D. A.; Kistryn, S.; Kleines, H.; Kłos, B.; Krzemień, W.; Kulessa, P.; Kupść, A.; Kuzmin, A.; Lalwani, K.; Lersch, D.; Lorentz, B.; Magiera, A.; Maier, R.; Marciniewski, P.; Mariański, B.; Morsch, H.-P.; Moskal, P.; Ohm, H.; Perez del Rio, E.; Piskunov, N. M.; Prasuhn, D.; Pszczel, D.; Pysz, K.; Pyszniak, A.; Ritman, J.; Roy, A.; Rudy, Z.; Rundel, O.; Sawant, S.; Schadmand, S.; Schätti-Ozerianska, I.; Sefzick, T.; Serdyuk, V.; Shwartz, B.; Sitterberg, K.; Skorodko, T.; Skurzok, M.; Smyrski, J.; Sopov, V.; Stassen, R.; Stepaniak, J.; Stephan, E.; Sterzenbach, G.; Stockhorst, H.; Ströher, H.; Szczurek, A.; Trzciński, A.; Varma, R.; Wolke, M.; Wrońska, A.; Wüstner, P.; Yamamoto, A.; Zabierowski, J.; Zieliński, M. J.; Złomańczuk, J.; Żuprański, P.; Żurek, M.

    2017-03-01

    The search for 4He- η bound states was performed with the WASA-at-COSY facility via the measurement of the excitation function for the dd →3He nπ0 and dd →3He pπ- processes. The deuteron beam momentum was varied continuously between 2.127 GeV/c and 2.422 GeV/c, corresponding to the excess energy for the dd →4He η reaction ranging from Q = - 70 MeV to Q = 30 MeV. The luminosity was determined based on the dd →3He n reaction and the quasi-free proton-proton scattering via dd → ppnspectatornspectator reactions. The excitation functions, determined independently for the measured reactions, do not reveal a structure which could be interpreted as a narrow mesic nucleus. Therefore, the upper limits of the total cross sections for the bound state production and decay in dd →(4He- η) bound →3He nπ0 and dd →(4He- η) bound →3He pπ- processes were determined taking into account the isospin relation between the both of the considered channels. The results of the analysis depend on the assumptions of the N*(1535) momentum distribution in the anticipated mesic-4He. Assuming, as in the previous works, that this is identical with the distribution of nucleons bound with 20 MeV in 4He, we determined that (for the mesic bound state width in the range from 5 MeV to 50 MeV) the upper limits at 90% confidence level are about 3 nb and about 6 nb for nπ0 and pπ- channels, respectively. However, based on the recent theoretical findings of the N*(1535) momentum distribution in the N*-3He nucleus bound by 3.6 MeV, we find that the WASA-at-COSY detector acceptance decreases and hence the corresponding upper limits are 5 nb and 10 nb for nπ0 and pπ- channels respectively.

  19. Structural and spectroscopic investigation on a new potentially bioactive di-hydrazone containing thiophene heterocyclic rings

    NASA Astrophysics Data System (ADS)

    Nogueira, Vanessa de S.; Ramalho Freitas, Maria Clara; Cruz, Wellington S.; Ribeiro, Tatiana S.; Resende, Jackson A. L. C.; Rey, Nicolás A.

    2016-02-01

    Hydrazones and several substituted hydrazones are associated with a broad spectrum of biological activities, as well as compounds containing the thiophene ring. In this context, a novel di-hydrazone derived from 2-thiophenecarboxylic acid hydrazide was synthesized and completely characterized by elemental analysis, XRD, FT-IR, Raman and UV-Vis spectroscopies, thermogravimetry, 1H NMR, 1H-1H COSY and 1H-1H ROESY. A preliminary in silico pharmacological evaluation was also performed in order to assess the performance of the new compound regarding some molecular properties relevant for a drug's pharmacokinetics in the human body.

  20. Alkaloids from Hippeastrum morelianum Lem. (Amaryllidaceae).

    PubMed

    Giordani, Raquel B; de Andrade, Jean P; Verli, Hugo; Dutilh, Julie H; Henriques, Amélia T; Berkov, Strahil; Bastida, Jaume; Zuanazzi, José Angelo S

    2011-10-01

    The Amaryllidaceae family has proven to be a rich source of active molecules. As part of an ongoing project, we report a phytochemical study of Hippeastrum morelianum (Amaryllidaceae), from which we have isolated two homolycorine-type alkaloids, the new 2α,7-dimethoxyhomolycorine (1) and the poorly described candimine (2), as well as six known alkaloids: tazettine, pretazettine, 3-epimacronine, haemanthamine, hamayne and trisphaeridine. For reference purposes, the NMR of the isolated compounds was unequivocally described, based on 2D NMR measurements including (1)H-(1)H COSY, (1)H-(1)H NOESY, HSQC and HMBC.

  1. Isolation and structural elucidation of chemical constituents from the fruits of Morinda citrifolia Linn.

    PubMed

    Siddiqui, Bina S; Sattar, Fouzia A; Ahmad, Fayaz; Begum, Sabira

    2007-08-01

    The fruits of Morinda citrifolia, Linn. afforded a new constituent, morinaphthalenone (1), and three known constituents, scopoletin (2), 1, 3-dimethoxy-anthraquinone (3) and 1, 2-dihydroxy-anthraquinone (4). The structures of these isolated compounds were determined by spectroscopic methods, including 1D- and 2D-NMR (COSY-45, HMQC, HMBC) techniques, as well as by comparison with published values.

  2. Chemical constituents of Tephrosia purpurea.

    PubMed

    Khalafalah, Ali K; Yousef, Afifi H; Esmail, Abeer M; Abdelrazik, Mohamed H; Hegazy, Mohamed E F; Mohamed, Abou-El-Hamd H

    2010-03-01

    In continuation of our chemical investigation on some medicinal plants of the genus Tephrosia, reinvestigation of the methylenechloride/methanol (1:1) extract of the aerial parts of Tephrosia purpurea yielded an aromatic ester 1, a sesquiterpene 2 and prenylated flavonoid 3. The structures of the compounds were established by comprehensive NMR studies, including DEPT, COSY, NOE, HMQC, HMBC, EIMS and CIMS.

  3. Biotransformation of glabratephrin, a rare type of isoprenylated flavonoids, by Aspergillus niger.

    PubMed

    Mohamed, Abou-El-Hamd H; Khalafallah, Ali K; Yousof, Afifi H

    2008-01-01

    Microbial transformation of glabratephrin, the major isolated compound from Tephrosia purpurea, afforded pseudosemiglabrin. The formation of the transformed compound seems to be performed via ring opening-closure of a five-membered ring causing transformation from a spiro into a fused system. The structure of the transformed compound was determined by comprehensive NMR studies, including DEPT, COSY, HMQC, NOE and MS.

  4. A new sweet dihydrochalcone-glucoside from leaves of Lithocarpus pachyphyllus (Kurz) Rehd. (Fagaceae).

    PubMed

    Qin, Xiang-Dong; Liu, Ji-Kai

    2003-01-01

    A new sweet dihydrochalcone-glucoside, trilobatin 2"-acetate (1), was isolated from the leaves of Lithocarpus pachyphyllus, together with phlorizin and trilobatin. The structures were established by spectroscopic methods, including one- and two-dimensional NMR (COSY, HMQC and HMBC).

  5. New indole alkaloid from Peschiera affinis (Apocynaceae).

    PubMed

    Santos, Allana Kellen L; Machado, Luciana L; Bizerra, Ayla Marcia C; Monte, Francisco José Q; Santiago, Gilvandete M P; Braz-Filho, Raimundo; Lemos, Telma L G

    2012-06-01

    A new indole alkaloid of the pyridocarbazole type, named 6N-hydroxy-olivacine, and two known compounds, 2N-oxide-olivacine and olivacine, were isolated from roots of Peschiera affinis. The structures of the compounds were determined by spectroscopic {IR and extensive NMR (COSY, HMQC, HMBCand NOESY)} and EIMS analysis.

  6. The structure of the O-polysaccharide from the lipopolysaccharide of Providencia stuartii O47.

    PubMed

    Ovchinnikova, Olga G; Kocharova, Nina A; Bakinovskiy, Leon V; Torzewska, Agnieszka; Shashkov, Alexander S; Knirel, Yuriy A; Rozalski, Antoni

    2004-10-20

    The O-polysaccharide was obtained by mild acid degradation of the lipopolysaccharide of Providencia stuartii O47:H4, strain 3646/51. Studies by sugar and methylation analyses along with Smith degradation and 1H and 13C NMR spectroscopy, including two-dimensional 1H,1H COSY, TOCSY, ROESY and H-detected 1H,13C HSQC and HMBC experiments, showed that the polysaccharide has a branched hexasaccharide repeating unit with the following structure: [carbohydrate structure: see text

  7. Structural determination of two new steroidal saponins from Smilax china.

    PubMed

    Huang, Hui-Lian; Liu, Rong-Hua; Shao, Feng

    2009-09-01

    Two new steroidal saponins (1 and 2) were isolated from the BuOH fraction of the 70% EtOH extract of the tubes of Smilax china, together with four known analogues, 3-6. The structures of the new compounds were elucidated by means of chemical evidence and spectroscopic analyses, including HR-MS, IR, (1)H- and (13)C-NMR, and 2D experiments ((1)H-(1)H COSY, HSQC and HMBC).

  8. A new lyoniresinol derivative from Smilax microphylla.

    PubMed

    Liu, Li-Sha; Huang, Hui-Lian; Liu, Rong-Hua; Ren, Gang; Shao, Feng; Ye, Yao-Hui; Lin, Tao

    2013-01-01

    A new lignan, lyoniresinol-9-O-8"-syringylglycerol ether (1), together with five known compounds, piceatannol (2), resveratrol (3), oxyresveratrol (4), quercetin-3'-glucoside (5) and diosgenin (6) were isolated from the rhizomes of Smilax microphylla. The structure of the new compound was determined by means of chemical evidence and 1D-and 2D-NMR (1H, 13C, HSQC, HMBC, 1H-1H COSY and NOESY) spectroscopic analysis and HR-ESI-MS.

  9. Sesquiterpene constituents from the soft coral Sinularia nanolobata.

    PubMed

    Ngoc, Ninh Thi; Huong, Pham Thi Mai; Thanh, Nguyen Van; Cuong, Nguyen Xuan; Nam, Nguyen Hoai; Thung, Do Cong; Kiem, Phan Van; Minh, Chau Van

    2017-02-28

    Using various chromatographic separations, four sesquiterpenes (1-4), including two new compounds, nanolobatols A and B (1 and 2), were isolated from the Vietnamese soft coral Sinularia nanolobata. Their structures were determined on the basis of spectroscopic data ((1)H and (13)C NMR, HSQC, HMBC, (1)H-(1)H COSY, NOESY and FT-ICR-MS) and by comparison with the literature values. The cytotoxic activity of isolated compounds against a panel of eight human cancer cell lines was also evaluated.

  10. Structure elucidation and complete NMR spectral assignments of four new diterpenoids from Smallantus sonchifolius.

    PubMed

    Dou, De-Qiang; Tian, Fang; Qiu, Ying-Kun; Kang, Ting-Guo; Dong, Feng

    2008-08-01

    Four new diterpenoids, named smaditerpenic acid A-D, together with five known compounds, were isolated from the H(2)O extract of the leaves of Smallantus sonchifolius (yacon) cultivated in Liaoning, China and their structures were elucidated on the basis of one- and two-dimensional NMR (including (1)H, (13)C-NMR, (1)H-(1)H COSY, HSQC, TOCSY, HMBC, and ROESY), electrospray ionization mass spectrometry (ESI-MS), and chemical methods.

  11. Quantitative time- and frequency-domain analysis of the two-pulse COSY revamped by asymmetric Z-gradient echo detection NMR experiment: Theoretical and experimental aspects, time-zero data truncation artifacts, and radiation damping.

    PubMed

    Kirsch, Stefan; Hull, William E

    2008-07-28

    The two-pulse COSY revamped by asymmetric Z-gradient echo detection (CRAZED) NMR experiment has the basic form 90 degrees -Gdelta-t(rec)-beta-nGdelta-t(rec)-FID, with a phase-encoding gradient pulse G of length delta applied during the evolution time tau for transverse magnetization, readout pulse beta, rephasing gradient nGdelta, and recovery time t(rec) prior to acquisition of the free-induction decay. Based on the classical treatment of the spatially modulated dipolar demagnetizing field and without invoking intermolecular multiple-quantum coherence, a new formulation of the first-order approximation for the theoretical solution of the nonlinear Bloch equations has been developed. The nth-order CRAZED signal can be expressed as a simple product of a scaling function C(n)(beta,tau) and a signal amplitude function A(n)(t), where the domain t begins immediately after the beta pulse. Using a single-quantum coherence model, a generalized rf phase shift function has also been developed, which explains all known phase behavior, including nth-order echo selection by phase cycling. Details of the derivations are provided in two appendices as supplementary material. For n>1, A(n)(t) increases from zero to a maximum value at t=t(max) before decaying and can be expressed as a series of n exponential decays with antisymmetric binomial coefficients. Fourier transform gives an antisymmetric binomial series of Lorentzians, where the composite lineshape exhibits negative wings, zero integral, and a linewidth that decreases with n. Analytical functions are presented for t(max) and A(n)(t(max)) and for estimating the maximal percent error incurred for A(n)(t(max)) when using the first-order model. The preacquisition delay Delta=delta+t(rec) results in the loss of the data points for t=0 to Delta. Conventional Fourier transformation produces time-zero truncation artifacts (reduced negative wing amplitude, nonzero integral, and reduced effective T(2) ( *)), which can be avoided by

  12. Spasmolytic effects of Scrophularia nodosa extract on isolated rabbit intestine.

    PubMed

    Ahmad, Mansoor; Muhammad, Noor; Mehjabeen; Jahan, Noor; Ahmad, Manzoor; Obaidullah; Qureshi, Mahmood; Jan, Syed Umar

    2012-01-01

    Scrophularia nodosa (figwort), an indigenous medicinal plant grows in moist and cultivated waste ground. It contains saponins, cardioactive glycosides, flavonoids, resin, sugar and organic acids. It is traditionally used for anti-inflammatory purpose and in skin disorders. It has diuretic and cardiac stimulant properties. The present studies were carried out on crude extract of Scrophularia nodosa and its n-hexane, chloroform, ethyl acetate, n-butanol and aqueous fractions. During phytochemical studies seven known compounds of flavonoid nature were isolated from the chloroform fraction of crude extract of S. nodosa. The structures of these compounds were elucidated by spectroscopic (UV, IR, Mass (EIMS, HREIMS) and NMR ((1)H-NMR, (13)C-NMR, DEPT, and (1)H-(1)H, COSY, HMQC, HMBC and NOESY) techniques. Compound 1 was identified as 5, 4`-hydroxy-3, 6, 7-trimethoxyflavone, compound 2 as 5-hydroxy-3,6,7,4'-tetramethoxyflavone, compound 3 as Centaurein, compound 4 as 5-hydroxy-7,8,2',3',4'-pentamethoxyflavone (Serpyllin), compound 5 as Kaempferol 7-O-α-L-rhamnopyranoside, compound 6 as sakuranetin 4'-O (6''-O-α-L-rhamnopyranosyl)-β-D-glucopyranoside (Vitexoside) and compound 7 as Spinoside. Crude extract and its fractions were tested on isolated rabbit intestine (in vitro) for their effects. The results of crude extract and its fractions in different doses showed the decrease in normal movement of the smooth muscles of rabbit intestine (jejunum). The chloroform fraction showed maximum relaxant effect (77.37%) at 15mg/ml dose and aqueous fraction showed 38.56% spasmogenic response which was not present in the crude extract. Further study was carried out on different fractions to investigate the possible mechanism of action of S. nodosa extract. For this purpose spasmolytic effect of different fractions were compared with agonist and antagonist activities of standard drugs including adrenaline, atropine andacetylcholine (1x10(-2), 1x10(-4) and 10(-6) M conc.). It is

  13. One new triterpene ester from Nepeta suavis.

    PubMed

    Hussain, Javid; Khan, Farman Ullah; Ur Rehman, Najeeb; Ullah, Riaz; Mohmmad, Zia; Tasleem, S; Naeem, A; Shah, M Raza

    2009-12-01

    One new tetracyclic triterpene ester (1) has been isolated from the chloroform-soluble portion of the whole plant of Nepeta suavis along with two known compounds, namely artemetin (2) and jaceidin (3). The structures of the isolated compounds were assigned on the basis of their (1)H and (13)C NMR spectra including two-dimensional NMR techniques such as COSY, HMQC, and HMBC experiments and comparison with the literature data.

  14. Chemical analysis of an immunostimulating (1→4)-, (1→6)-branched glucan from an edible mushroom, Calocybe indica.

    PubMed

    Mandal, Eshita Kar; Maity, Kousik; Maity, Saikat; Gantait, Sanjoy K; Behera, Birendra; Maiti, Tapas K; Sikdar, Samir R; Islam, Syed S

    2012-01-10

    An immunostimulating water-soluble glucan was isolated from hot aqueous extract of fruit bodies of an edible mushroom Calocybe indica. Structural investigation of the glucan was carried out using acid hydrolysis, methylation analysis, and NMR studies ((1)H, (13)C, DEPT-135, TOCSY, DQF-COSY, NOESY, ROESY, HMQC, and HMBC). On the basis of above-mentioned experiments, the structure of the repeating unit of the polysaccharide was established as [see figure in text]. This glucan stimulated the splenocytes and thymocytes.

  15. Cichorin A: a new benzo-isochromene from Cichorium intybus.

    PubMed

    Hussain, Hidayat; Hussain, Javid; Saleem, Muhammad; Miana, Ghulam Abbas; Riaz, Muhammad; Krohn, Karsten; Anwar, Saeed

    2011-06-01

    One new benzo-isochromene, named cichorin A (1), together with three known compounds oleanolic acid, β-sitosterol, and β-sitosterol glucopyranoside, was isolated from Cichorium intybus. The structure of the new compound was elucidated by detailed spectroscopic analysis such as (1)H, (13)C NMR, COSY, HMQC, HMBC, and HR-EI-MS. Relative configuration of asymmetric centers of cichorin A (1) was determined by the analysis of the (1)H NMR coupling constants together with the NOESY experiment.

  16. A new dihydrofuranocoumarin from Opopanax hispidus (Friv.) Griseb.

    PubMed

    Ghasemi, Sabrieh; Habibi, Zohreh

    2014-01-01

    Phytochemical investigation of chloroform extract of the aerial parts of Opopanax hispidus afforded a new dihydrofuranocoumarin, 3'-isobutyryl-3'-hydroxymarmesin (1a), together with six known coumarins, oreoselon, peucedanin, officinalin, smirniorin, 4'-acetyl-3'-isobutyryl-3'-hydroxymarmesin and 3'-hydroxyprantschimgin. The structures of the compounds were determined by their comprehensive spectroscopic analysis (IR, EI-MS, (1)H NMR, (13)C NMR, HMBC, COSY, HMBC and HMQC), elemental analysis and comparison with literature data.

  17. Alkaloids from Fissistigma latifolium (Dunal) Merr.

    PubMed

    Alias, Asmah; Hazni, Hazrina; Jaafar, Faridahanim Mohd; Awang, Khalijah; Ismail, Nor Hadiani

    2010-06-24

    A phytochemical study of the bark of Fissistigma latifolium (Annonaceae) yielded a new aporphine alkaloid, (-)-N-methylguattescidine (1), and eight known alkaloids: liriodenine (2), oxoxylopine (3), (-)-asimilobine (4), dimethyltryptamine (5), (-)-remerine (6), (-)-anonaine (7), columbamine (8) and lysicamine (9). The compounds were isolated using various chromatographic methods and structural elucidation was accomplished by means of spectroscopic methods, notably 1D-NMR ((1)H, (13)C, DEPT), 2D-NMR (COSY, HMQC, HMBC), UV, IR and MS.

  18. General occurrence of the glucosinolate glucocochlearin within the Cochlearia genus.

    PubMed

    Dauvergne, Xavier; Cérantola, Stéphane; Salaün, Stéphanie; Magné, Christian; Kervarec, Nelly; Bessières, Marie-Anne; Deslandes, Eric

    2006-09-04

    A natural compound, glucocochlearin, was isolated from the aerial parts of 10 different Cochlearia species. The purification of this compound was achieved through HPLC. The identity of the product was established mainly on the basis of spectroscopic NMR (1H, 13C, COSY, TOCSY, HMQC, HMBC, J-MOD) and high resolution mass spectroscopy data. This compound can be considered as a chemomarker of the genus Cochlearia.

  19. New flavonoid C-O-C dimers and other chemical constituents from Garcinia brevipedicellata stem heartwood.

    PubMed

    Abderamane, Bintou; Tih, Anastasie E; Ghogomu, Raphael T; Blond, Alain; Bodo, Bernard

    The methanol extract of the stem heartwood of Garcinia brevipedicellata has furnished three new flavonoid C-O-C dimers, brevipedicilones A (6), B (8) and C (10), along with five previously reported flavonoid dimers, viz. amentoflavone (1), 4″'-O-methylamentoflavone (2), robustaflavone (3), 4'-O-methyl robustaflavone (4) and tetrahinokiflavone (5). The new structures, which are composed of flavanone-flavanonol or flavanonol-flavanonol sub-units, were established based on spectroscopic analysis including 1D and 2D NMR (1H-1H COSY, HSQC, HMBC, and NOESY) spectroscopy, and by comparing their spectral data with those reported for related compounds.

  20. Anti-inflammatory dimeric furanocoumarins from the roots of Angelica dahurica.

    PubMed

    Yang, Wan-Qing; Song, Yue-Lin; Zhu, Zhi-Xiang; Su, Cong; Zhang, Xu; Wang, Juan; Shi, She-Po; Tu, Peng-Fei

    2015-09-01

    Seven new dimeric furanocoumarins, dahuribiethrins A-G (1-7), were isolated from the roots of Angelica dahurica. Their structures were determined by chemical derivatization and extensive spectroscopic techniques, including (1)H NMR, (13)C NMR, HSQC, (1)H-(1)H COSY, HMBC, and NOESY experiments. Compounds 2, 3, 4, and 5 exhibited significant inhibition of nitric oxide production in the lipopolysaccharide (LPS)-stimulated RAW264.7 macrophage cells with IC50 values in the range of 8.8-9.8 μM.

  1. Sannastatin, a novel toxic macrolactam polyketide glycoside produced by actinomycete Streptomyces sannanensis.

    PubMed

    Yang, Sheng-Xiang; Gao, Jin-Ming; Zhang, An-Ling; Laatsch, Hartmut

    2011-07-01

    A new rare 20-membered macrocyclic lactam incorporating a diene conjugated olefin, designated sannastatin (1), together with the known structurally related vicenistatin (2), has been isolated from the cultures of Streptomyces sannanensis, a bacteria found in the feces of Ailuropoda melanoleuca. The structure of the new compound was established on the basis of extensive spectroscopic analyses including 1D- and 2D-NMR ((1)H-(1)H COSY, TOCSY, HSQC, HMBC, and NOESY) experiments. Compounds 1 and 2 displayed significant growth inhibitory activity against the brine shrimp (Artemia salina) larvae.

  2. Tzumin A and B, two new lignan derivatives from the barks of Sassafras tzumu.

    PubMed

    Lu, Haixiao; Wu, Feiyan; Jiang, Meixiao; Liang, Weijiang

    2017-04-01

    Two new lignan compounds, 5'-allyl-2,2'-dihydroxy-[1,1'-biphenyl]-5-carboxylic acid (1) and 4,4'-diallyl-[1,1'-biphenyl]-2,2'-diol (2), together with four known compounds (3-6), were isolated from the barks of Sassafras tzumu. The new compounds were determined by NMR ((1)H and (13)C NMR, HSQC, HMBC, (1)H-(1)H COSY, NOESY/ROESY), and MS analysis. Compounds 1-3 showed potent AChE inhibitory activities, with IC50 values of 2.00, 1.81 and 1.91 μM, respectively.

  3. Structure and cross-reactivity of the O-antigen of Providencia stuartii O18 containing 3-acetamido-3,6-dideoxy-D-glucose.

    PubMed

    Kocharova, Nina A; Błaszczyk, Aleksandra; Zatonsky, George V; Torzewska, Agnieszka; Bystrova, Olga V; Shashkov, Alexander S; Knirel, Yuriy A; Rozalski, Antoni

    2004-01-22

    The O-polysaccharide (O-antigen) of Providencia stuartii O18 was obtained by mild acid degradation of the lipopolysaccharide and studied by chemical methods and NMR spectroscopy, including 2D 1H,1H COSY, TOCSY, NOESY and 1H,13C HSQC experiments. The following structure of the tetrasaccharide repeating unit of the polysaccharide was established: [structure: see text] where Qui3NAc is 3-acetamido-3,6-dideoxyglucose. Anti-P. stuartii O18 serum cross-reacted with the O-antigen of Proteus genomospecies 4, which could be accounted for the marked structural similarities of the main chain.

  4. The structure of the O-polysaccharide from the lipopolysaccharide of Providencia stuartii O57 containing an amide of D-galacturonic acid with L-alanine.

    PubMed

    Kocharova, Nina A; Ovchinnikova, Olga G; Bushmarinov, Ivan S; Toukach, Filip V; Torzewska, Agnieszka; Shashkov, Alexander S; Knirel, Yuriy A; Rozalski, Antoni

    2005-03-21

    The O-polysaccharide (O-antigen) was obtained by mild acid degradation of the lipopolysaccharide of Providencia stuartii O57:H29. Studies by sugar and methylation analyses along with (1)H and (13)C NMR spectroscopy, including two-dimensional (1)H,(1)H COSY, TOCSY, ROESY, H-detected (1)H,(13)C HSQC, and HMBC experiments, showed that the polysaccharide contains an amide of D-galacturonic acid with L-alanine and has the following pentasaccharide repeating unit: [formula: see text

  5. Flavonoid glycosides and their p-coumaroyl esters from Campylospermum calanthum leaves.

    PubMed

    Elo Manga, Savio S; Tih, Anastasie E; Abderamane, Bintou; Ghogomu, Raphael T; Blond, Alain; Bodo, Bernard

    2012-01-01

    Six new compounds, comprising three flavonoid glycosides and their respective coumaroyl esters, have been isolated and characterized from the methanol extract of the leaves of Campylospermum calanthum, along with three known flavonoid aglycones, 7-O-methyl apigenin (1), 7-O-methyl luteolin (2), and 7-O-methyl quercetin (3). Their structures were elucidated based on chemical evidence as well as spectroscopic analysis including 1D and 2D NMR (1H-1H COSY, HSQC, HMBC, and NOESY) spectroscopy and by comparing their spectral data with those reported for related compounds.

  6. A new sesquiterpenoid quinone with cytotoxicity from Abelmoschus sagittifolius.

    PubMed

    Chen, De-Li; Zhang, Xiao-Po; Ma, Guo-Xu; Wu, Hai-Feng; Yang, Jun-Shan; Xu, Xu-Dong

    2016-01-01

    A new sesquiterpenoid quinone, Acyl hibiscone B (1), together with five known compounds, (R)-lasiodiplodin (2), (R)-de-O-methyllasiodiplodin, (3) dibutyl phthalate (4), (R)-9-phenylnonan-2-ol (5) and hibiscone B (6), was obtained from the stem tuber of Abelmoschus sagittifolius. The structure of compound 1 was elucidated by analysing its (1)H and (13)C NMR, (1)H-(1)H COSY, HSQC, HMBC, NOESY and HR-ESI-MS values. Compound 1 showed significant cytotoxicity against Hela and HepG-2 human cancer cell lines.

  7. A new coumestan from Tephrosia calophylla.

    PubMed

    Hari Kishore, Pennaka; Vijaya Bhaskar Reddy, Mopuru; Gunasekar, Duvvuru; Marthanda Murthy, Madugula; Caux, Cristelle; Bodo, Bernard

    2003-02-01

    A new coumestan, tephcalostan (1) has been isolated from the whole plant of Tephrosia calophylla BEDD. together with two known flavonoids, 7-O-methylglabranin (2) and kaempferol 3-O-beta-D-glucopyranoside (3). The structure of tephcalostan was elucidated as 5'-(R)-8, 9-methylenedioxy-5'-isopropenyl-4', 5'-dihydrofurano[2', 3':2, 3]coumestan by extensive one-and two-dimensional (1D- and 2D-)-NMR techniques including (1)H-(1)H correlation spectroscopy (COSY), heteronuclear single quantum coherence (HSQC), heteronuclear multiple bond connectivity (HMBC) and nuclear Overhauser enhancement spectroscopy (NOESY) experiments.

  8. Structural study of (±) alkyl 3-hydroxy-1-azabicyclo[2.2.2]octane-3-carboxylates

    NASA Astrophysics Data System (ADS)

    Arias-Pérez, M. S.; Cosme, A.; Gálvez, E.; Sanz-Aparicio, J.; Fonseca, I.; Bellanato, J.

    2003-01-01

    A series of α-hydroxyesters derived from (±) 3-hydroxy-1-azabicyclo[2.2.2]octane-3-carboxylic acid was synthesised and studied by IR and NMR spectroscopy. The combined use of 1H- 1H COSY and 1H- 13C correlation spectra of these compounds helped in the unambiguous assignments of the bicyclic carbon and proton resonances. The crystal structure of ethyl (±) 3-hydroxy-1-azabicyclo[2.2.2]octane-3-carboxylate was determined by X-ray diffraction.

  9. Identification, isolation and characterization of a new degradation product in sultamicillin drug substance.

    PubMed

    Kumar, Vundavilli Jagadeesh; Gupta, P Badarinadh; Kumar, K S R Pavan; Ray, Uttam Kumar; Sreenivasulu, B; Kumar, G S Siva; Rao, K Ranga; Sharma, Hemant Kumar; Mukkanti, K

    2011-02-20

    A new degradant of sultamicillin drug substance was found during the gradient reverse phase HPLC analysis of stability storage samples. The level of this degradant impurity was observed up to 1.0%. The impurity (formaldehyde adduct with 5-oxo-4-phenylimidazolidin-1-yl moiety) was identified by LC/MS and was characterized by ((1)H NMR, (13)C NMR, 2D-NMR ((1)H-(1)H COSY, NOESY, HSQC and HMBC), LC/MS/MS, MS/TOF, elemental analysis and IR. This impurity was prepared by isolation and co-injected into HPLC system to confirm the retention time.

  10. New Prenylxanthones from the Deep-Sea Derived Fungus Emericella sp. SCSIO 05240

    PubMed Central

    Fredimoses, Mangaladoss; Zhou, Xuefeng; Lin, Xiuping; Tian, Xinpeng; Ai, Wen; Wang, Junfeng; Liao, Shengrong; Liu, Juan; Yang, Bin; Yang, Xianwen; Liu, Yonghong

    2014-01-01

    Four new prenylxanthones, emerixanthones A–D (1–4), together with six known analogues (5–10), were isolated from the culture of the deep-sea sediment derived fungus Emericella sp. SCSIO 05240, which was identified on the basis of morphology and ITS sequence analysis. The newstructures were determined by NMR (1H, 13C NMR, HSQC, HMBC, and 1H-1H COSY), MS, CD, and optical rotation analysis. The absolute configuration of prenylxanthone skeleton was also confirmed by the X-ray crystallographic analysis. Compounds 1 and 3 showed weak antibacterial activities, and 4 displayed mild antifungal activities against agricultural pathogens. PMID:24879543

  11. α-Glucosidase inhibitor from Buthus martensi Karsch.

    PubMed

    Kim, Shin-Duk

    2013-01-15

    A bioassay-guided fractionation of an ethanol extract of Buthus martensi Karsch led to the isolation of a potent α-glucosidase inhibitor (compound S). The structure was elucidated as a novel β-carboline glucoalkaloid, harmanyl β-d-glucopyranoside, on the basis of spectral data, including (1)H NMR, (13)C NMR, (1)H-(1)H COSY, NOESY, and HMBC. Compound S showed potent inhibitory activity against α-glucosidase, with an IC(50) value of 24 μM. A Lineweaver-Burk plot indicated that its inhibition of α-glucosidase was uncompetitive, with a Ki value of 16.1 μM.

  12. New clerodane diterpenoids from Croton crassifolius.

    PubMed

    Qiu, Maosong; Cao, Di; Gao, Youheng; Li, Shuhua; Zhu, Jinping; Yang, Bao; Zhou, Lian; Zhou, Yuan; Jin, Jing; Zhao, Zhongxiang

    2016-01-01

    Two new clerodane diterpenoids (1-2), one new clerodane diterpenoid alkaloid (3), as well as thirteen known compounds were isolated from Croton crassifolius. The structures of new compounds were established by a combination of spectroscopic methods, including HRMS, (1)H NMR, (13)C NMR, (1)H (1)H COSY, HSQC, HMBC, NOESY and X-ray crystallographic analysis. Compound 3 is firstly reported as the clerodane-type diterpenoid alkaloid in natural products. All of the compounds were evaluated for in vitro cytotoxic activities against CT26.WT cell using the MTT method.

  13. Identification of two novel Prodelphinidin A-type dimers from roasted hazelnut skins ( Corylus avellana L.).

    PubMed

    Esatbeyoglu, Tuba; Wray, Victor; Winterhalter, Peter

    2013-12-26

    Two new A-type dimeric prodelphinidins, EGC-(2β→O7, 4β→8)-C and EGC-(2β→O5, 4β→6)-C, were isolated from the skins of roasted hazelnut ( Corylus avellana L.) by low-speed rotary countercurrent chromatography (LSRCCC) and final purification by preparative HPLC. Their structures were determined by a combination of mass spectrometry (HPLC-ESI-MS(n) and HR-ESI-MS) and NMR spectroscopy that included the application of 2D methods ((1)H-(1)H COSY, HSQC, HMBC, and NOESY). Furthermore, circular dichroism (CD) and acid-catalyzed degradation (phloroglucinolysis) confirmed the proposed structures.

  14. Epitaxial CoSi2 on MOS devices

    DOEpatents

    Lim, Chong Wee; Shin, Chan Soo; Petrov, Ivan Georgiev; Greene, Joseph E.

    2005-01-25

    An Si.sub.x N.sub.y or SiO.sub.x N.sub.y liner is formed on a MOS device. Cobalt is then deposited and reacts to form an epitaxial CoSi.sub.2 layer underneath the liner. The CoSi.sub.2 layer may be formed through a solid phase epitaxy or reactive deposition epitaxy salicide process. In addition to high quality epitaxial CoSi.sub.2 layers, the liner formed during the invention can protect device portions during etching processes used to form device contacts. The liner can act as an etch stop layer to prevent excessive removal of the shallow trench isolation, and protect against excessive loss of the CoSi.sub.2 layer.

  15. CosI: Coherent Neutrino Scattering with Cesium Iodide

    NASA Astrophysics Data System (ADS)

    Fields, Nicole; Collar, Juan; Hossbach, Todd; Orrell, John; Perumpilly, Gopakumar

    2014-03-01

    Coherent neutrino scattering is a process predicted by the standard model of particle physics that has not yet been observed. For low enough energy neutrinos, O (10 MeV , their scattering cross section is predicted to increase with the square of the number of neutrons in a nucleus. Several difficulties must be overcome in order to observe coherent neutrino scattering, including finding a high-intensity source of these medium-energy neutrinos, a detector with a low enough threshold, and a low enough background. The Spallation Neutron Source (SNS) at Oak Ridge National Laboratory is a convenient source of medium-energy neutrinos and has the added benefit of a neutrino source with known time structure. CsI(Na) is an inorganic scintillator with a relatively high light yield of 39,000 photons/MeV and its emission spectrum is well matched with commonly used biakali photomultiplier tubes (PMTs). Background measurements of a 2 kg CsI(Na) crystal show that these crystals can be grown and encapsulated in a radioclean way.

  16. Spectral assignments and structural studies of a warfarin derivative stereoselectively formed by tandem cyclization

    NASA Astrophysics Data System (ADS)

    Velayutham Pillai, M.; Rajeswari, K.; Vidhyasagar, T.

    2015-11-01

    The structural elucidation of a Mannich condensation product of rac-Warfarin with benzaldehyde and methyl amine was carried out using IR, Mass, 1H NMR, 13C NMR, 1H-1H COSY, 1H-13C COSY, DEPT-135, HMBC, NOESY spectra and single crystal X-ray diffraction. Formation of a new pyran ring via a tandem cyclization in the presence of methyl amine was observed. The optimized geometry and HOMO-LUMO energy gap along with other important physical parameters were found by Gaussian 09 program using HF 6-31G (d, p) and B3YLP/DFT 6-31G (d, p) level of theory. The preferred conformation of the piperidine ring in solution state was found to be chair from the NMR spectra. Single crystal X-ray diffraction and optimized geometry (by theoretical study) also confirms the chair conformation in the solid state.

  17. Structure of the O-polysaccharide of Providencia stuartii O4 containing 4-(N-acetyl-L-aspart-4-yl)amino-4,6-dideoxy-D-glucose.

    PubMed

    Kocharova, Nina A; Torzewska, Agnieszka; Zatonsky, George V; Błaszczyk, Aleksandra; Bystrova, Olga V; Shashkov, Alexander S; Knirel, Yuriy A; Rozalski, Antoni

    2004-01-22

    The O-polysaccharide of Providencia stuartii O4 was obtained by mild acid degradation of the lipopolysaccharide, and the following structure of the pentasaccharide repeating unit was established: [structure: see text] where D-Qui4N(L-AspAc) is 4-(N-acetyl-L-aspart-4-yl)amino-4,6-dideoxy-D-glucose, which has not been hitherto found in bacterial polysaccharides. Structural studies were performed using sugar and methylation analyses, Smith degradation and NMR spectroscopy, including conventional 2D 1H,1H COSY, TOCSY, NOESY and 1H,13C HSQC experiments as well as COSY and NOESY experiments run in an H(2)O-D(2)O mixture to reveal correlations for NH protons.

  18. Cytotoxic benzil and coumestan derivatives from Tephrosia calophylla.

    PubMed

    Ganapaty, Seru; Srilakshmi, Guttula Veera Kantha; Pannakal, Steve Thomas; Rahman, Hafizur; Laatsch, Hartmut; Brun, Reto

    2009-01-01

    A benzil, calophione A, 1-(6'-Hydroxy-1',3'-benzodioxol-5'-yl)-2-(6''-hydroxy-2''-isopropenyl-2'',3''-dihydro-benzofuran-5''-yl)-ethane-1,2-dione and three coumestan derivatives, tephcalostan B, C and D were isolated from the roots of Tephrosia calophylla. Their structures were deduced from spectroscopic data, including 2D NMR (1)H-(1)H COSY and (13)C-(1)H COSY experiments. Compounds were evaluated for cytotoxicity against RAW (mouse macrophage cells) and HT-29 (colon cancer cells) cancer cell lines and antiprotozoal activity against various parasitic protozoa. Calophione A exhibited significant cytotoxicity with IC(50) of 5.00 (RAW) and 2.90microM (HT-29), respectively.

  19. Vibrational spectroscopic study, structural analysis, photophysical properties and theoretical calculations of cis-(±)-2,4,5-tris(pyridin-2-yl)imidazoline

    NASA Astrophysics Data System (ADS)

    Baldenebro-López, Jesús; Báez-Castro, Alberto; Glossman-Mitnik, Daniel; Höpfl, Herbert; Cruz-Enríquez, Adriana; Miranda-Soto, Valentín; Parra-Hake, Miguel; Campos-Gaxiola, José J.

    2017-02-01

    cis-(±)-2,4,5-tris(pyridin-2-yl)imidazoline has been fully characterized by FT-IR, FT-Raman, UV-Vis and fluorescence spectroscopy, one- and two-dimensional NMR spectroscopy (1H, 1H-1H gCOSY, 1H-1H gNOESY,13C{1H} ATP, 1H-13C and 1H-15N gHSQC and 1H-13C gHMBC), high-resolution mass spectrometry (HR-FAB+), TG-DSC analysis and low-temperature single-crystal X-ray diffraction analysis. Additionally, the molecular geometry and the vibrational infrared and Raman frequencies were calculated by density functional theory using the M06/6-31G(d) level of theory, showing good agreement with the experimental results. The title compound showed interesting photophysical properties, which were studied experimentally in solution and in the solid state by UV-Vis and fluorescence spectroscopy and compared to the theoretically obtained parameters using TD-DFT calculations. Natural and Mulliken atomic charges and the molecular electrostatic potential (MEP) have been mapped.

  20. Structure of the O-polysaccharide of Proteus vulgaris O44: a new O-antigen that contains an amide of D-glucuronic acid with L-alanine.

    PubMed

    Toukach, Filip V; Perepelov, Andrei V; Bartodziejska, Beata; Shashkov, Alexander S; Blaszczyk, Aleksandra; Arbatsky, Nikolay P; Rozalski, Antoni; Knirel, Yuriy A

    2003-06-23

    The O-polysaccharide of Proteus vulgaris O44, strain PrK 67/57 was studied by 1H and 13C NMR spectroscopy, including 2D COSY, TOCSY, ROESY, H-detected 1H, 13C HMQC, HMQC-TOCSY and HMBC experiments. The polysaccharide was found to contain an amide of D-glucuronic acid with L-alanine [D-GlcA6(L-Ala)], and the following structure of the linear pentasaccharide repeating unit was established: [structure: see text]. The structural data of the O-polysaccharide and the results of serological studies with P. vulgaris O44 O-antiserum showed that the strain studied is unique among Proteus bacteria, which is in agreement with its classification in a separate Proteus serogroup, O44.

  1. Glycosylamines of 4,6-O-butylidene-alpha-D-glucopyranose: synthesis and characterization of glycosylamines, and the crystal structure of 4,6-O-butylidene-N-(o-chlorophenyl)-beta-D-glucopyranosylamine.

    PubMed

    Rajsekhar, Gudneppanavar; Rao, Chebrolu P; Saarenketo, Pauli K; Kolehmainen, Erkki; Rissanen, Kari

    2002-02-11

    A total of nine glycosylamines of 4,6-O-butylidene-alpha-D-glucopyranose were synthesized using primary amines having various groups in their ortho- or para-positions. Among these, six are monoglycosylamines, including one primary glycosylamine, and three are bis-glycosylamines. All these compounds were characterized by 1H, 1H-1H COSY, 1H-13C COSY and 13C NMR spectroscopy and FTIR spectra. The FAB mass spectra provided the molecular weights of the products by exhibiting the corresponding molecular ion peaks. The crystal structure of 4,6-O-butylidene-N-(o-chlorophenyl)-beta-D-glucopyranosylamine revealed the C-1 glycosylation, the beta-anomeric nature, and the 4C1 chair conformation of the saccharide unit in the product. In the lattice two types of dimers exist. While one type of dimer is formed through O-H...O type of interactions, the other type is formed via C-H...O type of interactions. In the direction of these C-H...O type of interactions, the dimeric units are connected to form a chain.

  2. A New Sucrase Enzyme Inhibitor from Azadirachta indica

    PubMed Central

    Abdelhady, Mohamed I. S.; Shaheen, Usama; Bader, Ammar; Youns, Mahmoud A.

    2016-01-01

    Background: Sucrase enzyme inhibitor considered as an oral anti-diabetic therapy that delays the absorption of eaten carbohydrates, reducing the postprandial glucose and insulin peaks to reach normoglycemia. Materials and Methods: Chromatographic fractionation of the hydroalcoholic extract of leaves of Azadirachta indica growing in KSA, followed by in-vitro assay of sucrase enzyme inhibition activity. Results: This investigation led to the isolation of a new remarkable sucrase enzyme inhibitor; 4’-methyl Quercetin-7-O-β-D-glucuronopyranoside (1) alongside with four known compounds; 2,3-hexahydroxydiphenoyl-(α/β)-D-4C1-glucopyranose (2), Avicularin (3), Castalagin (4) and Quercetin-3-O-glucoside (5). The structure of the new compound (1) was elucidated on the basis of its spectral data, including ESI-MS, UV, 1H NMR, 13C NMR, 1H-1H COSY, HSQC, NOESY and HMBC. Conclusion: Under the assay conditions, hydroalcoholic extract of A. indica and compounds 1-5 exhibited significant sucrase enzyme inhibitory activity. SUMMARY Chromatographic fractionation of the hydroalcoholic extract of leaves of Azadirachta indica, led to the Isolation of a new flavonoid glycoside named 4’-methyl Quercetin-7-O-β-D-glucuronopyranoside, alongside to other 4 known polyphenols. The hydroalcoholic extract as well as the isolated compounds exhibited significant sucrase enzyme inhibitory activity. Abbreviations used: ESI-MS; electrospray ionization-mass spectrometry, UV; ultraviolet, NMR; nuclear magnetic resonance, 1H-1H COSY; 1H-1H correlation spectroscopy, NOESY; nuclear overhauser effect spectroscopy, and HSQC; heteronuclear multiple bond correlation. A. indica; Azadirachta indica. PMID:27563214

  3. Simultaneously cycled NMR spectroscopy.

    PubMed

    Parish, David M; Szyperski, Thomas

    2008-04-09

    Simultaneously cycled (SC) NMR was introduced and exemplified by implementing a set of 2-D [1H,1H] SC exclusive COSY (E.COSY) NMR experiments, that is, rf pulse flip-angle cycled (SFC), rf pulse phase cycled (SPC), and pulsed field gradient (PFG) strength cycled (SGC) E.COSY. Spatially selective 1H rf pulses were applied as composite pulses such that all steps of the respective cycles were affected simultaneously in different slices of the sample. This increased the data acquisition speed for an n-step cycle n-fold. A high intrinsic sensitivity was achieved by defining the cycles in a manner that the receiver phase remains constant for all steps of the cycle. Then, the signal resulting from applying the cycle corresponded to the sum of the signals from all steps of the cycle. Hence, the detected free induction decay did not have to be separated into the contributions arising from different slices, and read-out PFGs, which not only greatly reduce sensitivity but also negatively impact lineshapes in the direct dimension, were avoided. The current implementation of SFC E.COSY reached approximately 65% of the intrinsic sensitivity of the conventional phase cycled congener, making this experiment highly attractive whenever conventional data acquisition is sampling limited. Highly resolved SC E.COSY yielding accurate 3J-coupling values was recorded for the 416 Da plant alkaloid tomatidine within 80 min, that is, 12 times faster than with conventional phase cycled E.COSY. SC NMR is applicable for a large variety of NMR experiments and thus promises to be a valuable addition to the arsenal of approaches for tackling the NMR sampling problem to avoid sampling limited data acquisition.

  4. A new triterpenoid saponin from Gymnema sylvestre.

    PubMed

    Zhang, Man-Qi; Liu, Yue; Xie, Sheng-Xu; Xu, Tun-Hai; Liu, Tong-Hua; Xu, Ya-Juan; Xu, Dong-Ming

    2012-01-01

    Besides four known compounds, a new triterpenoid saponin was isolated from the stems of Gymnema sylvestre. The structure of the new triterpenoid saponin was established as 3β,16β,22α-trihydroxy-olean-12-ene 3-O-β-D-xylopyranosyl-(1 → 6)-β-D-glucopyranosyl-(1 → 6)-β-D-glucopyranoside (1) on the basis of 1D and 2D NMR techniques, including COSY, HMBC, HMQC, and NOESY correlations. Four known compounds 2, 3, 4, and 5 were identified on the basis of spectroscopic data.

  5. Bioactive metabolites produced by Chaetomium globosum, an endophytic fungus isolated from Ginkgo biloba.

    PubMed

    Qin, Jian-Chun; Zhang, Ya-Mei; Gao, Jin-Ming; Bai, Ming-Sheng; Yang, Sheng-Xiang; Laatsch, Hartmut; Zhang, An-Ling

    2009-03-15

    A novel cytotoxic chlorinated azaphilone derivative named chaetomugilin D (1), together with three known metabolites, chaetomugilin A (2), chaetoglobosins A (3) and C (4), has been isolated by a bioassay-guided fractionation from the EtOAc extract of the cultures of Chaetomium globosum, an endophytic fungus found in the leaves of Ginkgo biloba. Structure of 1 was established by analyses of spectroscopic methods, including 2D-NMR experiments (COSY, NOESY, HMQC, and HMBC). Compounds 1-4 displayed significant growth inhibitory activity against the brine shrimp (Artemia salina) and Mucor miehei.

  6. Total NMR assignments of new [C7-O-C7'']-biflavones from leaves of the limonene-carvone chemotype of Lippia alba (Mill) N. E. Brown.

    PubMed

    Barbosa, Francisco Geraldo; Lima, Mary Anne Sousa; Silveira, Edilberto Rocha

    2005-04-01

    Phytochemical analysis of leaves of the limonene-carvone chemotype of Lippia alba led to the isolation of two biflavonoids with a new structural pattern with an ether linkage: 5,5''-dihydroxy-6,4',6'',3''',4'''-pentamethoxy-[C(7)--O--C(7'')]-biflavone (1) and 4',4,5,5''-tetrahydroxy-6,6'',3'''-trimethoxy-[C(7)--O--C(7'')]-biflavone (2). Structural elucidation of the new compounds was established on the basis of spectral data, through the use of 1D NMR and several 2D shift correlated NMR pulse sequences (COSY, HMQC, HMBC and NOESY).

  7. Two new phthalate derivatives from Nepeta clarkei (Labiatae).

    PubMed

    Hussain, Javid; Rehman, Najeeb Ur; Hussain, Hidayat; Ali, Liaqat; Al-Harrasi, Ahmed

    2012-01-01

    Two new phthalates bis(2-ethylundecyl)phthalate and bis(2-ethyltridecyl)phthalate have been isolated from the chloroform-soluble portion of the whole plant of Nepeta clarkei along with one known compound β-amyrin. The structures of the two new compounds and β-amyrin were assigned on the basis of their ¹H and ¹³C NMR spectra including 2D NMR techniques such as COSY, HMQC, and HMBC experiments and compared with the literature data.

  8. Structural identification and cytotoxic activity of a polysaccharide from the fruits of Lagenaria siceraria (Lau).

    PubMed

    Ghosh, Kaushik; Chandra, Krishnendu; Ojha, Arnab K; Sarkar, Siddik; Islam, Syed S

    2009-03-31

    A water-soluble polysaccharide, isolated from fruiting bodies of Lagenaria siceraria, is composed of methyl-alpha-d-galacturonate, 3-O-acetyl methyl-alpha-d-galacturonate, and beta-d-galactose in a ratio of nearly 1:1:1. Compositional analysis, methylation analysis, periodate oxidation, and NMR studies ((1)H, (13)C, 2D-COSY, TOCSY, NOESY, HMQC, and HMBC) revealed the presence of the following repeating unit in the polysaccharide: [carbohydrate structure: see text] This polysaccharide showed cytotoxic activity in vitro against human breast adenocarcinoma cell line (MCF-7).

  9. Cucurbitane-type triterpenoids from the fruit pulp of Momordica charantia.

    PubMed

    Liao, Yun-Wen; Chen, Chiy-Rong; Kuo, Yueh-Hsiung; Hsu, Jue-Liang; Shih, Wen-Ling; Cheng, Hsueh-Ling; Huang, Tzou-Chi; Chang, Chi-I

    2012-12-01

    Three new cucurbitane-type triterpenoids, 5beta,19-epoxy-23(R)-methoxycucurbita-6,24-dien-3beta-ol (1), 5beta,19-epoxy-23(S)-methoxycucurbita-6,24-dien-3beta-ol (2), and 3beta-hydroxy-23(R)-methoxycucurbita-6,24-dien-5beta,19-olide (3), were isolated from the fruit pulp of Momordica charantia. Their structures were established on the basis of extensive NMR (1H, 13C, COSY, HMQC, HMBC, and NOESY) and EI-MS studies. Compound 1 exhibited cytotoxic activity against the SK-Hep 1 cell line.

  10. Chemical analysis and study of immunoenhancing and antioxidant property of a glucan isolated from an alkaline extract of a somatic hybrid mushroom of Pleurotus florida and Calocybe indica variety APK2.

    PubMed

    Maity, Kousik; Kar Mandal, Eshita; Maity, Saikat; Gantait, Sanjoy K; Das, Debsankar; Maiti, Swatilekha; Maiti, Tapas K; Sikdar, Samir R; Islam, Syed S

    2011-11-01

    A water-soluble glucan isolated from an alkaline extract of fruit bodies of a somatic hybrid mushroom PCH9FB of Pleurotus florida and Calocybe indica var. APK2 strains showed antioxidant properties with immune activation of macrophage, splenocyte, and thymocyte. On the basis of acid hydrolysis, methylation, periodate oxidation and NMR studies ((1)H, (13)C, DEPT-135, DQF-COSY, TOCSY, NOESY, ROESY, HMQC, and HMBC) the structure of the repeating unit of the glucan was established as: [structure: see text].

  11. Structural characterization of an immunoenhancing cytotoxic heteroglycan isolated from an edible mushroom Calocybe indica var. APK2.

    PubMed

    Mandal, Eshita Kar; Maity, Kousik; Maity, Saikat; Gantait, Sanjoy K; Maiti, Swatilekha; Maiti, Tapas K; Sikdar, Samir R; Islam, Syed S

    2011-10-18

    A water-soluble polysaccharide of an edible mushroom Calocybe indica var. APK2 showed immunoenhancing (macrophage, splenocyte, thymocyte, and bone marrow activation) and cytotoxic activity toward HeLa cell lines and found to consist of D-glucose, D-galactose, and L-fucose in a molar ratio of nearly 3:1:1. On the basis of acid hydrolysis, methylation analysis, and NMR studies ((1)H, (13)C, DEPT-135, TOCSY, DQF-COSY, NOESY, ROESY, HMQC, and HMBC), the structure of the repeating unit of the fuco-galacto-glucan was established as: [see formula in text].

  12. Structure and immunology of a heteroglycan from somatic hybrid mushroom of Pleurotus florida and Calocybe indica var. APK2.

    PubMed

    Dey, Biswajit; Bhunia, Sanjoy K; Maity, Kankan K; Patra, Sukesh; Mandal, Soumitra; Behera, Birendra; Maiti, Tapas K; Sikdar, Samir R; Islam, Syed S

    2013-01-01

    A water soluble polysaccharide was isolated from the aqueous extract of the fruit bodies of somatic hybrid mushroom PCH3FB, obtained through protoplast fusion between the strains Pleurotus florida and Calocybe indica var. APK2. On the basis of sugar analysis, methylation analysis, periodate oxidation, and NMR studies ((1)H, (13)C, DEPT-135, DQF-COSY, TOCSY, NOESY, ROESY, HMQC and HMBC), the structure of the repeating unit of the polysaccharide was established as: [formula, see text] This molecule showed macrophage, splenocyte and thymocyte activations.

  13. Structural characterization and study of immunoenhancing and antioxidant property of a novel polysaccharide isolated from the aqueous extract of a somatic hybrid mushroom of Pleurotus florida and Calocybe indica variety APK2.

    PubMed

    Maity, Kousik; Kar Mandal, Eshita; Maity, Saikat; Gantait, Sanjoy K; Das, Debsankar; Maiti, Swatilekha; Maiti, Tapas K; Sikdar, Samir R; Islam, Syed S

    2011-03-01

    A water-soluble polysaccharide was isolated from the aqueous extract of the fruit bodies of somatic hybrid PCH9FB, obtained through intergeneric protoplast fusion between the strains Pleurotus florida and Calocybe indica var. On the basis of total acid hydrolysis, the polysaccharide was found to contain galactose, fucose, and glucose in a molar ratio of nearly 2:1:2. Methylation analysis and NMR experiments ((1)H, (13)C, DEPT-135, DQF-COSY, TOCSY, NOESY, ROESY, HMQC, and HMBC) showed that the structure of the repeating unit present in the polysaccharide was This molecule showed macrophage, splenocyte, thymocyte activation as well as antioxidant property.

  14. Phenolic compounds from the stem bark Erythrina Orientalis and detection of antimalaria activity by ELISA

    NASA Astrophysics Data System (ADS)

    Tjahjadarie, Tjitjik Srie; Saputri, Ratih Dewi; Tanjung, Mulyadi

    2016-03-01

    Erythrina orientalis has local name "Dadap". This plant has known producing alkaloids, flavonoids, pterocarpans, stilbenes, and arylbenzofurans which are active compounds.Three prenylated flavonoids, 8-prenyl-daidzein (1), alpinumisoflavone (2) and 4'-O-methyl licoflavanone (3) had been isolated from the stem bark of Erythrina Orientalis. The structures were elucidated on the basis of spectroscopic data,which are IR, UV, MS, and NMR 1D (1H-NMR and 13C-NMR) and 2D (COSY, HMQC, and HMBC).

  15. Forazoline A: Marine-derived polyketide with antifungal in vivo efficacy

    DOE PAGES

    Wyche, Thomas P.; Piotrowski, Jeff S.; Hou, Yanpeng; ...

    2014-09-04

    Forazoline A, a novel antifungal polyketide with in vivo efficacy against Candida albicans, was discovered using LCMS-based metabolomics to investigate marine-invertebrate-associated bacteria. Forazoline A had a highly unusual and unprecedented skeleton. Acquisition of 13C–13C gCOSY and 13C–15N HMQC NMR data provided the direct carbon–carbon and carbon–nitrogen connectivity, respectively. This approach represents the first example of determining direct 13C–15N connectivity for a natural product. In this paper, using yeast chemical genomics, we propose that forazoline A operated through a new mechanism of action with a phenotypic outcome of disrupting membrane integrity.

  16. Isosakuranetin-5-O-rutinoside: a new flavanone with antidepressant activity isolated from Salvia elegans Vahl.

    PubMed

    González-Cortazar, Manáses; Maldonado-Abarca, Ana María; Jiménez-Ferrer, Enrique; Marquina, Silvia; Ventura-Zapata, Elsa; Zamilpa, Alejandro; Tortoriello, Jaime; Herrera-Ruiz, Maribel

    2013-10-25

    Ursolic acid (1) and a new flavanone, 5-O-(6-rhamnosylglucoside)-7-hydroxy-4'-methoxyflavanone (2), were isolated from the leaves of Salvia elegans Vahl. These natural products displayed antidepressant activity in mice as determined by means of a forced swimming test (FST) evaluation. Structural elucidation was carried out by chemical derivatization (acetylation) and spectroscopic analyses, such as 1H- and 13C-NMR and two-dimensional (2-D) COSY, heteronuclear multiple quantum coherence (HMQC), and heteronuclear multiple-bond correlation (HMBC) spectroscopy experiments.

  17. Cichorins B and C: two new benzo-isochromenes from Cichorium intybus.

    PubMed

    Hussain, Hidayat; Hussain, Javid; Ali, Samina; Al-Harrasi, Ahmed; Saleem, Muhammad; Miana, Ghulam Abbas; Riaz, Muhammad; Anwar, Saeed; Hussain, Sajjad; Ali, Liaqat

    2012-01-01

    Two new benzo-isochromenes, named cichorins B (1) and C (2), were isolated from Cichorium intybus. The structures of the new compounds were elucidated by detailed spectroscopic analysis such as ¹H, ¹³C NMR, COSY, HMQC, HMBC, and HR-EI-MS. Relative configurations of asymmetric centers of cichorins B and C were determined by the analysis of the ¹H NMR coupling constants together with the 2D NOESY and 1D NOE experiments as well as from [α]²⁵(D) value.

  18. Chemical analysis of a polysaccharide of unripe (green) tomato (Lycopersicon esculentum).

    PubMed

    Chandra, Krishnendu; Ghosh, Kaushik; Ojha, Arnab K; Islam, Syed S

    2009-11-02

    A polysaccharide (PS-I) isolated from the aqueous extract of the unripe (green) tomatoes (Lycopersicon esculentum) consists of D-galactose, D-methyl galacturonate, D-arabinose, L-arabinose, and L-rhamnose. Structural investigation of the polysaccharide was carried out using total acid hydrolysis, methylation analysis, periodate oxidation study, and NMR studies ((1)H, (13)C, DQF-COSY, TOCSY, NOESY, ROESY, HMQC, and HMBC). On the basis of above-mentioned experiments the structure of the repeating unit of the polysaccharide (PS-I) was established as: [structure: see text].

  19. Structure of a new acidic O-antigen of Proteus vulgaris O22 containing O-acetylated 3-acetamido-3,6-dideoxy-D-glucose.

    PubMed

    Toukach, F V; Bartodziejska, B; Senchenkova, S N; Wykrota, M; Shashkov, A S; Rozalski, A; Knirel, Y A

    1999-05-31

    The acidic O-specific polysaccharide of Proteus vulgaris O22 was studied using 1H and 13C NMR spectroscopy, including 2D COSY, TOCSY, NOESY, and H-detected 1H, 13C heteronuclear multiple-quantum coherence (HMQC) experiments, and the following structure for the branched pentasaccharide repeating unit was established: [sequence: see text] where Qui3NAc is 3-acetamido-3,6-dideoxyglucose, O-acetylation of QuiNAc at position 4 is stoichiometric and at position 2 nonstoichiometric. Serological relationships of P. vulgaris O22 with some other Proteus strains were substantiated on the level of the O-antigen structures.

  20. Structure and cross-reactivity of the O-antigen of Proteus vulgaris O8.

    PubMed

    Perepelov, A V; Babicka, D; Shashkov, A S; Arbatsky, N P; Senchenkova, S N; Rozalski, A; Knirel, Y A

    1999-05-31

    A high-molecular-mass O-specific polysaccharide was obtained by mild acid degradation of Proteus vulgaris O8 lipopolysaccharide followed by gel permeation chromatography. Studies of the polysaccharide by sugar and methylation analyses and 1H and 13C NMR spectroscopy, including 2D COSY, TOCSY, NOESY, and H-detected 1H, 13C heteronuclear multiple-quantum coherence (HMQC) experiments, demonstrated the presence of a tetrasaccharide repeating unit having the following structure: [sequence: see text] The role of an epitope associated with the alpha-L-FucpNAc-(1-->3)-D-GlcpNAc disaccharide in serological cross-reactivity of P. vulgaris O8 is discussed.

  1. A new bioactive steroidal saponin from Sansevieria cylindrica.

    PubMed

    Da Silva Antunes, Alexandra; Da Silva, Bernadete Pereira; Parente, José Paz; Valente, Ana Paula

    2003-02-01

    A new steroidal saponin was isolated from the leaves of Sansevieria cylindrica. Its structure was established as (3beta,12beta,15alpha,25S)-26-(beta-D-glucopyranosyloxy)-22-hydroxyfurost-5-en-3-yl 12-O- (6-deoxy-alpha-L-mannopyranosyl)-15-O-(6-deoxy-alpha-L-mannopyranosyl)-beta-D-glucopyranoside. The structural identification was performed using detailed analyses of (1)H and (13)C NMR spectra including 2D NMR spectroscopic techniques (COSY, HETCOR, HMBC and HMQC) and chemical conversions. The steroidal saponin showed no haemolytic effects in the in vitro assays and demonstrated inhibition of the capillary permeability activity.

  2. A new steroidal saponin from Agave shrevei.

    PubMed

    Pereira Da Silva, Bernadete; Valente, Ana Paula; Paz Parente, José

    2006-04-01

    A new steroidal saponin was isolated from the leaves of Agave shrevei. Its structure was established as 3-[O-beta-D-glucopyranosyl-(1-->2)-O-[O-beta-D-glucopyranosyl-(1-->4)-O-[O-beta-D-glucopyranosyl-(1-->6)]-O-beta-D-glucopyranosyl-(1-->4)-beta-D-galactopyranosyl)-oxy]-(3beta,5alpha,25R)-spirostane. The structural identification was performed using detailed analyses of 1H- and 13C-NMR spectra including 2D NMR spectroscopic techniques (COSY, HETCOR, HMBC, and HMQC) and chemical conversions. The haemolytic activity of the steroidal saponin was evaluated using an in vitro assay.

  3. Structural studies of a heteropolysaccharide (PS-I) isolated from hot water extract of fruits of Psidium guajava (Guava).

    PubMed

    Mandal, Soumitra; Sarkar, Ramsankar; Patra, Pradip; Nandan, Chanchal K; Das, Debsankar; Bhanja, Sunil K; Islam, Syed S

    2009-07-27

    A water-soluble polysaccharide was isolated from hot aqueous extracts of fruits of Psidium guajava. The polysaccharide was found to contain 2-O-methyl-l-arabinose, 2-O-acetyl-D-galactose, and D-methyl galacturonate in a molar ratio of approximately 1:1:1. On the basis of acid hydrolysis, methylation analysis, periodate oxidation, and NMR studies ((1)H, (13)C, TOCSY, DQF-COSY, NOESY, ROESY, HMQC, and HMBC), the structure of the repeating unit of the polysaccharide was established as [carbohydrate structure: see text].

  4. Isolation and anti-hepatitis B virus activity of dibenzocyclooctadiene lignans from the fruits of Schisandra chinensis.

    PubMed

    Xue, Yongbo; Li, Xifeng; Du, Xue; Li, Xiaonian; Wang, Weiguang; Yang, Jianhong; Chen, Jijun; Pu, Jianxin; Sun, Handong

    2015-08-01

    Seven lignans with a dibenzocyclooctadiene skeleton, termed schinlignans A-G, and a 6,7-seco-homolignan, schischinone, together with seven known lignans, were isolated from the fruits of Schisandra chinensis (Turcz.) Baill. Their structures were elucidated by extensive spectroscopic methods, including HRESIMS, IR, UV, and 2D NMR (COSY, HMQC, COSY, and HMBC experiments). The stereochemistry at the chiral centers and the biphenyl moiety, were determined using ROESY, as well as via interpretation of their ECD spectra. Schinlignan G and methylgomisin O exhibited potent anti-hepatitis B virus activity against HBV DNA replication with IC50 values of 5.13 and 5.49μgmL(-1), respectively.

  5. Fluorine detected 2D NMR experiments for the practical determination of size and sign of homonuclear F-F and heteronuclear C-F multiple bond J-coupling constants in multiple fluorinated compounds.

    PubMed

    Aspers, Ruud L E G; Ampt, Kirsten A M; Dvortsak, Peter; Jaeger, Martin; Wijmenga, Sybren S

    2013-06-01

    The use of fluorine in molecules obtained from chemical synthesis has become increasingly important within the pharmaceutical and agricultural industry. NMR characterization of these compounds is of great value with respect to their structure elucidation, their screening in metabolomics investigations and binding studies. The favorable NMR properties of the fluorine nucleus make NMR with fluorine detection of great value in this respect. A suite of NMR 2D F-F- and F-C-correlation experiments with fluorine detection was applied to the assignment of resonances, (n)J(CF)- and (n)J(FF)-couplings as well as the determination of their size and sign. The utilization of this experiment suite was exemplarily demonstrated for a highly fluorinated vinyl alkyl ether. Especially F-C HSQC and J-scaled F-C HMBC experiments allowed determining the size of the J-couplings of this compound. The relative sign of its homo- and heteronuclear couplings was achieved by different combinations of 2D NMR experiments, including non-selective and F2-selective F-C XLOC, F2-selective F-C HMQC, and F-F COSY. The F2-one/two-site selective F-C XLOC versions were found highly useful, as they led to simplifications of the common E.COSY patterns and resulted in a higher confidence level of the assignment by using selective excitation. The combination of F2-one/two-site selective F-C XLOC experiments with a F2-one-site selective F-C HMQC experiment provided the signs of all (n)J(CF)- and (n)J(FF)-couplings in the vinyl moiety of the test compound. Other combinations of experiments were found useful as well for special purposes when focusing for example on homonuclear couplings a combination of F-F COSY-10 with a F2-one-site selective F-C HMQC could be used. The E.COSY patterns in the spectra demonstrated were analyzed by use of the spin-selective displacement vectors, and in case of the XLOC also by use of the DQ- and ZQ-displacement vectors. The variety of experiments presented shall contribute to

  6. Triblock Terpolymers by Simultaneous Tandem Block Polymerization (STBP).

    PubMed

    Freudensprung, Ines; Klapper, Markus; Müllen, Klaus

    2016-02-01

    A route of synthesizing triblock terpolymers in a one-pot, "one-step" polymerization approach is presented. The combination of two distinct polymerization techniques through orthogonal catalyst/initiator functionalities attached to a polymeric linker furnishes novel pathways to ABC-terpolymers. Both polymerizations have to be compatible regarding mechanisms, chosen monomers, and solvents. Here, an α,ω-heterobifunctional poly(ethylene glycol) serves as poly-meric catalyst/initiator to obtain triblock terpolymers of poly(norbornene)-b-poly(ethylene glycol)-b-poly(L-lactic acid) PNB-PEG-PLLA via simultaneous ring opening metathesis poly-merization and ring opening polymerization in a fast one-pot polymerization. Structural characterization of the polymers is provided via (1)H-, DOSY-, and (1)H,(1)H-COSY-NMR, while solution and thin film self-assembly are investigated by dynamic light scattering and atomic force microscopy.

  7. Complex mixture analysis of organic compounds in green coffee bean extract by two-dimensional NMR spectroscopy.

    PubMed

    Wei, Feifei; Furihata, Kazuo; Hu, Fangyu; Miyakawa, Takuya; Tanokura, Masaru

    2010-11-01

    A complex mixture analysis by one- and two-dimensional nuclear magnetic resonance (NMR) spectroscopy was carried out for the first time for the identification and quantification of organic compounds in green coffee bean extract (GCBE). A combination of (1)H-(1)H DQF-COSY, (1)H-(13)C HSQC, and (1)H-(13)C CT-HMBC two-dimensional sequences was used, and 16 compounds were identified. In particular, three isomers of caffeoylquinic acid were identified in the complex mixture without any separation. In addition, GCBE components were quantified by the integration of carbon signals by use of a relaxation reagent and an inverse-gated decoupling method without a nuclear Overhauser effect. This NMR methodology provides detailed information about the kinds and amounts of GCBE components, and in our study, the chemical makeup of GCBE was clarified by the NMR results.

  8. Nardosinanols A-I and lemnafricanol, sesquiterpenes from several soft corals, Lemnalia sp., Paralemnalia clavata, Lemnalia africana, and Rhytisma fulvum fulvum.

    PubMed

    Bishara, Ashgan; Yeffet, Dina; Sisso, Mor; Shmul, Guy; Schleyer, Michael; Benayahu, Yehuda; Rudi, Amira; Kashman, Yoel

    2008-03-01

    Ten new sesquiterpenes, nardosinanols A-I ( 1- 9) and lemnafricanol ( 10), have been isolated from several Kenyan soft corals, i.e., from Lemnalia sp., Paralemnalia clavata, Lemnalia africana, and Rhytisma fulvum fulvum. The structures and relative stereochemistry of these compounds were elucidated by interpretation of MS, COSY ( (1)H- (1)H correlations), HSQC, HMBC, and NOESY NMR spectroscopic experiments and in the case of 5 also by chemical transformation to compounds 11 and 12. Nine compounds ( 1- 9) are based on the nardosinane skeleton ( 1- 6 are nardosinanes and 7- 9 nornardosinanes). Lemnafricanol ( 10) possesses a novel tricyclic skeleton. Compounds 3, 7, and 10 were found to be toxic to brine shrimp with LC 50 values of 4.0, 0.35, and 0.32 microM, respectively.

  9. New structure for the O-polysaccharide of Providencia alcalifaciens O27 and revised structure for the O-polysaccharide of Providencia stuartii O43.

    PubMed

    Ovchinnikova, Olga G; Bushmarinov, Ivan S; Kocharova, Nina A; Toukach, Filip V; Wykrota, Marianna; Shashkov, Alexander S; Knirel, Yuriy A; Rozalski, Antoni

    2007-06-11

    The O-polysaccharide was obtained by mild acid degradation of the lipopolysaccharide from Providencia alcalifaciens O27 and studied by sugar and methylation analyses along with (1)H and (13)C NMR spectroscopy, including 2D (1)H,(1)H COSY, TOCSY, ROESY, H-detected (1)H,(13)C HSQC, and HMBC experiments. It was found that the polysaccharide is built up of linear partially O-acetylated tetrasaccharide repeating units and has the following structure: [structure: see text] where Qui4NFo stands for 4-formamido-4,6-dideoxyglucose (4-formamido-4-deoxyquinovose). The O-polysaccharide structure of Providencia stuartii O43 established earlier was revised with respect to the configuration of the constituent 4-amino-4,6-dideoxyhexose (from Rha4N to Qui4N).

  10. Phenolic compounds with IL-6 inhibitory activity from Aster yomena.

    PubMed

    Kim, A Ryun; Jin, Qinglong; Jin, Hong-Guang; Ko, Hae Ju; Woo, Eun-Rhan

    2014-07-01

    A new biflavonoid, named asteryomenin (1), as well as six known phenolic compounds, esculetin (2), 4-O-β-D-glucopyranoside-3-hydroxy methyl benzoate (3), caffeic acid (4), isoquercitrin (5), isorhamnetin-3-O-glucoside (6), and apigenin (7) were isolated from the aerial parts of Aster yomena. The structures of compounds (1-7) were identified based on 1D and 2D NMR, including (1)H-(1)H COSY, HSQC, HMBC and NOESY spectroscopic analyses. Compounds 2-7 were isolated from this plant for the first time. For these isolates, the inhibitory activity of IL-6 production in the TNF-α stimulated MG-63 cell was examined. Among these isolates, compounds 4 and 7 appeared to have potent inhibitory activity of IL-6 production in the TNF-α stimulated MG-63 cell, while compounds 1-3 and 5-6 showed moderate activity.

  11. Design, synthesis, characterization and in vitro and in vivo anti-inflammatory evaluation of novel pyrazole-based chalcones.

    PubMed

    Chavan, Hemant V; Adsul, Laxman K; Kotmale, Amol S; Dhakane, Valmik D; Thakare, Vishnu N; Bandgar, Babasaheb P

    2015-02-01

    Abstract A series of novel pyrazole-based chalcones have been designed, synthesized from 1-methyl-5-(2,4,6-trimethoxyphenyl)-1H-pyrazole (6). The structures of regioisomers 6 and 7 were determined by 2D (1)H-(1)H COSY, (1)H-(13)C HSQC and (1)H-(13)C HMBC experiments. The newly synthesized compounds were tested for their inhibitory activity against COX-1 and COX-2 using an in vitro cyclooxygenase (COX) inhibition assay. Moreover, they were investigated in vivo for their anti-inflammatory activities using carrageenan-induced rat paw edema model for acute inflammation and cotton pellet-induced granuloma model for chronic inflammation. All the synthesized compounds showed potential to demonstrate anti-inflammatory activities, of particular interest compounds 10i, 10e, 10f, and 10h were found to be potent anti-inflammatory agents.

  12. A new ent-clerodane diterpenoid from Crassocephalum bauchiense Huch. (Asteraceae).

    PubMed

    Tchinda, Alembert T; Mouokeu, Simplice R; Ngono, Rosalie A N; Ebelle, Madeleine R E; Mokale, Aristide L K; Nono, Diane K; Frédérich, Michel

    2015-01-01

    A phytochemical investigation of the whole plant of Crassocephalum bauchiense Huch. resulted in the isolation of a new clerodane diterpenoid, ent-2β,18,19-trihydroxycleroda-3,13-dien-16,15-olide (1), together with two known flavonoids 3',5-dihydroxy-4',5',6,7,8-pentamethoxyflavone (2) and 4',5-dihydroxy-3',5',6,7,8-pentamethoxyflavone (3). The compounds were tested against the chloroquine-sensitive 3D7 strain of Plasmodium falciparum. Compound 2 showed weak activity (IC50 = 10.1 g/mL) whilst compounds 1 and 3 were inactive. The structures of the compounds were elucidated by using detailed spectral analyses, especially (1)H and (13)C NMR, (1)H-(1)H COSY, NOESY, HMBC and HR-ESI-MS.

  13. Antimycobacterial physalins from Physalis angulata L. (Solanaceae).

    PubMed

    Januário, A H; Filho, E Rodrigues; Pietro, R C L R; Kashima, S; Sato, D N; França, S C

    2002-08-01

    Crude extracts and fractions from aerial parts of Physalis angulata have been bioassayed for antimycobacterial activity. Fraction A1-29-12 containing physalins B, F and D exhibited a minimum inhibitory concentration value (MIC) against Mycobacterium tuberculosis H(37)Rv strain of 32 microg/mL. Purified physalin B and physalin D were also tested showing MIC values against Mycobacterium tuberculosis H(37)Rv strain of > 128 microg/mL and 32 microg/mL respectively, suggesting that physalin D plays a relevant role in the antimycobacterial activity displayed. Structural elucidation of both physalins D and B was based on detailed (13)C and (1)H NMR spectral analysis with the aid of 2D-correlation spectroscopy ((1)H-(1)H, COSY, HSQC and HMBC). The assignment of the (13)C chemical shift for physalin D is reported here for the first time.

  14. Design, synthesis, characterization and anti-inflammatory evaluation of novel pyrazole amalgamated flavones.

    PubMed

    Chavan, Hemant V; Bandgar, Babasaheb P; Adsul, Laxman K; Dhakane, Valmik D; Bhale, Pravin S; Thakare, Vishnu N; Masand, Vijay

    2013-03-01

    A series of novel pyrazole amalgamated flavones has been designed and synthesized from 1-methyl-5-(2,4,6-trimethoxy-phenyl)-1H-pyrazole 6. The structures of regioisomers 6 and 7 were resolved by 2D (1)H-(1)H COSY, (1)H-(13)C HSQC and (1)H-(13)C HMBC experiments. The newly synthesized compounds were tested for their in vitro COX inhibition and in vivo carrageenan induced hind paw edema in rats and acetic acid induced vascular permeability in mice. Although the compounds have inhibitory profile against both COX-1 and COX-2, some of the compounds are found to be selective against COX-2, supported by inhibition of paw edema and vascular permeability. Docking studies were also carried out to determine the structural features which sway the anti-inflammatory activity of the tested compounds. The keto and phenolic -OH are major factors that are prominently involved in interaction with COX-2 active site.

  15. Evaluation of antinociceptive and anti-inflammatory activities of a new triterpene saponin from Bauhinia variegata leaves.

    PubMed

    Mohamed, Mona A; Mammoud, Madeha R; Hayen, Heiko

    2009-01-01

    A new triterpene saponin, named as 23-hydroxy-3alpha-[O-alpha-L-1C4-rhamnopyranosyl-(1"-->4')-O-alpha-L-4C1-arabinopyranosyl-oxy]olean-12-en-28-oic acid O-alpha-L-1C4-rhamnopyranosyl-(1"'-->4")-O-beta-D-4C1-glucopyranosyl-(1"-->6"')-O-beta-D-4C1-glucopyranosyl ester (9), was isolated from the leaves of Bauhinia variegata Linn. In addition, six flavonoid compounds along with two cinnamic acid derivatives were isolated and identified based on their chromatographic properties, and chemical and spectral data (ESI-high resolution-MSn, 1H NMR, 13C NMR, 1H-1H COSY, HSQC, and HMBC). Compound 9 was found to be nontoxic (LD50) and to have significant anti-inflammatory and antinociceptive activities. It also showed a slight antischistosomal activity.

  16. Spectroscopic, crystal structural and electrochemical studies of zinc(II)-Schiff base complex obtained from 2,3-diaminobenzene and 2-hydroxy naphthaldehyde.

    PubMed

    Ouari, Kamel; Bendia, Sabrina; Weiss, Jean; Bailly, Corinne

    2015-01-25

    Mononuclear zinc(II) complex, [Zn(II)L], where L is a dianionic ligand, has been synthesized and characterized by elemental analysis, electronic, IR and NMR [(1)H, (13)C, DEPT, (1)H-(1)H COSY, ROESY, HSQC and HMBC] spectroscopic techniques. Structural analysis of the complex by single crystal X-ray crystallography shows the presence of a distorted square planar coordination geometry (NNOO) of the metal center. The crystal of the title complex C28H18N2O2Zn belongs to the orthorhombic system with space group Pmn21. Electrochemical behavior of the Zn(II)L complex has been investigated by cyclic voltammetry on glassy carbon and platinum electrodes in DMF at 100 mV/s scan rate.

  17. Synthesis, NMR spectroscopic characterization and structure of a divinyldisilazane-(triphenylphosphine)platinum(0) complex: observation of isotope-induced chemical shifts (1)Δ(12/13)C((195)Pt).

    PubMed

    Wrackmeyer, Bernd; Klimkina, Elena V; Schmalz, Thomas; Milius, Wolfgang

    2013-05-01

    Tetramethyldivinyldisilazane-(triphenylphosphine)platinum(0) was prepared, characterized in solid state by X-ray crystallography and in solution by multinuclear magnetic resonance spectroscopy ((1)H, (13)C, (15)N, (29)Si, (31)P and (195)Pt NMR). Numerous signs of spin-spin coupling constants were determined by two-dimensional heteronuclear shift correlations (HETCOR) and two-dimensional (1)H/(1)H COSY experiments. Isotope-induced chemical shifts (1)Δ(12/13)C((195)Pt) were measured from (195)Pt NMR spectra of the title compound as well as of other Pt(0), Pt(II) and Pt(IV) compounds for comparison. In contrast to other heavy nuclei such as (199)Hg or (207)Pb, the "normal" shifts of the heavy isotopomers to low frequencies are found, covering a range of >500 ppb.

  18. [Studies on chemical structures of two iso-acetogenins from Annona reticulata].

    PubMed

    Yu, J G; Liu, D; Xu, L Z; Yang, S L

    1997-12-01

    Two annonaceous acetogenins: squamone (1) and isoannonareticin (2) have been isolated from the seeds of Annona reticulata L. (Annonaceae). 1 and 2 were shown to be mixtures of 2-epimers by the successful separation of their acetates with preparative TLC, giving: 2,4-cis-squamone diacetate (1a-1), 2,4-trans-squamone diacetate (1a-2), 2,4-cis-isoannonareticin diacetate (2a-1) and 2,4-trans-isoannonareticin diacetate (2a-2). The 2,4-cis-squamone (1-1) and 2,4-trans-isoannonareticin (2-1) are new annonaceous acetogenins. Their structures and relative stereochemistry were elucidated on the basis of spectral analysis (1H-1H COSY and NOE).

  19. Novel synthesis, structural analysis, photophysical properties and theoretical study of 2,4,5-tris(2-pyridyl)imidazole

    NASA Astrophysics Data System (ADS)

    Báez-Castro, Alberto; Baldenebro-López, Jesús; Glossman-Mitnik, Daniel; Höpfl, Herbert; Cruz-Enríquez, Adriana; Miranda-Soto, Valentín; Parra-Hake, Miguel; Campos-Gaxiola, José J.

    2015-11-01

    2,4,5-Tris(2-pyridyl)imidazole has been successfully synthetized by a novel synthetic route and fully characterized by FT-IR,UV-Vis and fluorescence spectroscopy, one- and two-dimensional NMR spectroscopy (1H, 13C{1H} ATP, 1H-1H COSY, NOESY 1H-13C HSQC and HMBC) high-resolution, mass spectrometry (HR-FAB+), and single-crystal X-ray diffraction analysis. Additionally, the molecular geometry, vibrational frequencies and infrared intensities were calculated by density functional theory using the M06/6-31G(d) level of theory, showing good agreement with the experimental results. The title compound showed interesting photophysical properties, which were studied experimentally in solution and in the solid state by UV-Vis and fluorescence spectroscopy, and theoretically using TD-DFT calculations. Natural and Mulliken atomic charges and the molecular electrostatic potential (MEP) have been mapped.

  20. X-ray structure, NMR and stability-in-solution study of 6-(furfurylamino)-9-(tetrahydropyran-2-yl)purine - A new active compound for cosmetology

    NASA Astrophysics Data System (ADS)

    Walla, Jan; Szüčová, Lucie; Císařová, Ivana; Gucký, Tomáš; Zatloukal, Marek; Doležal, Karel; Greplová, Jarmila; Massino, Frank J.; Strnad, Miroslav

    2010-06-01

    The crystal and molecular structure of 6-(furfurylamino)-9-(tetrahydropyran-2-yl)purine ( 1) was determined at 150(2) K. The compound crystallizes in monoclinic P2 1/ c space group with a = 10.5642(2), b = 13.6174(3), c = 10.3742(2) Å, V = 1460.78(5) Å 3, Z = 4, R( F) = for 3344 unique reflections. The purine moiety and furfuryl ring are planar and the tetrahydropyran-2-yl is disordered in the ratio 1:3, probably due to the chiral carbon atom C(17). The individual 1H and 13C NMR signals were assigned by 2D correlation experiments such as 1H- 1H COSY and ge-2D HSQC. Stability-in-solution was determined in methanol/water in acidic pH (3-7).

  1. Diterpenoid alkaloids and flavonoids from Delphinium trichophorum.

    PubMed

    Lin, Chao-Zhan; Zhao, Zhong-Xiang; Xie, Si-Min; Mao, Ju-Hua; Zhu, Chen-Chen; Li, Xiao-Hui; Zeren-dawa, Bairi; Suolang-qimei, Kangsa; Zhu, Dun; Xiong, Tian-Qin; Wu, Ai-Zhi

    2014-01-01

    Five hetisane-type C20-diterpenoid alkaloids, trichodelphinines A-E, one delnudine-type C20-diterpenoid alkaloid, trichodelphinine F and three known flavonoids, quercetin, quercetin 3-O-β-D-glucopyranoside, and quercetin 3-O-β-D-glucopyranoside-7-O-α-L-arabinopyranoside, were isolated from whole plants of Delphinium trichophorum Franch. Their structures were elucidated on the basis of extensive spectroscopic analysis, including HSQC, HMBC, (1)H-(1)H COSY, NOESY and X-ray crystallographic analysis, and from chemical evidence. The cytotoxic activities of the diterpenoid alkaloids were evaluated using the MTT method, and the IC50 values of their cytotoxicity against A549 cancer cells ranged from 12.03 to 52.79 μM.

  2. Thiotagetin A, a new cytotoxic thiophene from Tagetes minuta.

    PubMed

    Ibrahim, Sabrin R M; Mohamed, Gamal A

    2017-03-01

    Phytochemical investigation of the n-hexane fraction of the methanolic extract of Tagetes minuta L. (Asteraceae) aerial parts afforded a new thiophene derivative: thiotagetin A (3), together with β-sitosterol (1) and stigmasterol (2). The structure of the new thiophene was identified by UV, IR, 1D ((1)H and (13)C), 2D ((1)H-(1)H COSY, HSQC and HMBC) NMR and HRESIMS spectral data. Compound 3 displayed cytotoxic activity against KB and MCF7 cancer cell lines with ED50 values of 2.03 and 3.88 μg/mL, respectively, compared to adriamycin (0.26 and 0.07 μg/mL, respectively).

  3. Determination of Three-Bond1H3‧-31P Couplings in Nucleic Acids and Protein-Nucleic Acid Complexes by QuantitativeJCorrelation Spectroscopy

    NASA Astrophysics Data System (ADS)

    Clore, G. Marius; Murphy, Elizabeth C.; Gronenborn, Angela M.; Bax, Ad

    1998-09-01

    A new sensitive two-dimensional quantitativeJcorrelation experiment is described for measuring3JH3‧-Pcouplings in nucleic acids and protein-nucleic acid complexes. The method is based on measuring the change in intensity of the1H-1H cross peaks in a constant-time1H-1H COSY experiment which occurs in the presence and absence of3JH3‧-Pdephasing during the constant-time evolution period. For protein-nucleic acid complexes where the protein is13C-labeled but the nucleic acid is not,12C-filtering is readily achieved by the application of a series of13C purge pulses during the constant time evolution period without any loss of signal-to-noise of the nucleic acid cross peaks. The method is demonstrated for the Dickerson DNA dodecamer and a 19 kDa complex of the transcription factor SRY with a 14mer DNA duplex. The same approach should be equally applicable to numerous other problems, including the measurement ofJH-Cdcouplings in cadmium-ligated proteins, or3JCHcouplings in other selectively enriched compounds.

  4. Photochemical route to actinide-transition metal bonds: synthesis, characterization and reactivity of a series of thorium and uranium heterobimetallic complexes

    SciTech Connect

    Ward, Ashleigh; Lukens, Wayne; Lu, Connie; Arnold, John

    2014-04-01

    A series of actinide-transition metal heterobimetallics has been prepared, featuring thorium, uranium and cobalt. Complexes incorporating the binucleating ligand N[-(NHCH2PiPr2)C6H4]3 and Th(IV) (4) or U(IV) (5) with a carbonyl bridged [Co(CO)4]- unit were synthesized from the corresponding actinide chlorides (Th: 2; U: 3) and Na[Co(CO)4]. Irradiation of the isocarbonyls with ultraviolet light resulted in the formation of new species containing actinide-metal bonds in good yields (Th: 6; U: 7); this photolysis method provides a new approach to a relatively rare class of complexes. Characterization by single-crystal X-ray diffraction revealed that elimination of the bridging carbonyl is accompanied by coordination of a phosphine arm from the N4P3 ligand to the cobalt center. Additionally, actinide-cobalt bonds of 3.0771(5) and 3.0319(7) for the thorium and uranium complexes, respectively, were observed. The solution state behavior of the thorium complexes was evaluated using 1H, 1H-1H COSY, 31P and variable-temperature NMR spectroscopy. IR, UV-Vis/NIR, and variable-temperature magnetic susceptibility measurements are also reported.

  5. The Legionella pneumophila replication vacuole: making a cosy niche inside host cells.

    PubMed

    Isberg, Ralph R; O'Connor, Tamara J; Heidtman, Matthew

    2009-01-01

    The pathogenesis of Legionella pneumophila is derived from its growth within lung macrophages after aerosols are inhaled from contaminated water sources. Interest in this bacterium stems from its ability to manipulate host cell vesicular-trafficking pathways and establish a membrane-bound replication vacuole, making it a model for intravacuolar pathogens. Establishment of the replication compartment requires a specialized translocation system that transports a large cadre of protein substrates across the vacuolar membrane. These substrates regulate vesicle traffic and survival pathways in the host cell. This Review focuses on the strategies that L. pneumophila uses to establish intracellular growth and evaluates why this microorganism has accumulated an unprecedented number of translocated substrates that are targeted at host cells.

  6. Materials Data on Er3CoSi3 (SG:12) by Materials Project

    SciTech Connect

    Kristin Persson

    2016-07-25

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  7. Low Gilbert damping in Co2FeSi and Fe2CoSi films

    NASA Astrophysics Data System (ADS)

    Sterwerf, Christian; Paul, Soumalya; Khodadadi, Behrouz; Meinert, Markus; Schmalhorst, Jan-Michael; Buchmeier, Mathias; Mewes, Claudia K. A.; Mewes, Tim; Reiss, Günter

    2016-08-01

    Thin highly textured Fe1+xCo2-xSi (0 ≤ x ≤ 1) films were prepared on MgO (001) substrates by magnetron co-sputtering. Magneto-optic Kerr effect (MOKE) and ferromagnetic resonance (FMR) measurements were used to investigate the composition dependence of the magnetization, the magnetic anisotropy, the gyromagnetic ratio, and the relaxation of the films. Both MOKE and FMR measurements reveal a pronounced fourfold anisotropy for all films. In addition, we found a strong influence of the stoichiometry on the anisotropy as the cubic anisotropy strongly increases with increasing Fe concentration. The gyromagnetic ratio is only weakly dependent on the composition. We find low Gilbert damping parameters for all films with values down to 0.0012 ±0.00010.0007 for Fe1.75Co1.25Si. The effective damping parameter for Co2FeSi is found to be 0.0018 ±0.00040.0034 . We also find a pronounced anisotropic relaxation, which indicates significant contributions of two-magnon scattering processes that is strongest along the easy axes of the films. This makes thin Fe1+xCo2-xSi films ideal materials for the application in spin transfer-torque magnetic RAM (STT-MRAM) devices.

  8. Spin Filtering of Stored (Anti)Protons: from FILTEX to COSY to AD to FAIR

    SciTech Connect

    Nikolaev, Nikolai; Pavlov, Fyodor

    2007-06-13

    We review the theory of spin filtering of stored (anti)protons by multiple passage through the polarized internal target (PIT). Implications for the antiproton polarization buildup in the proposed PAX experiment at FAIR GSI are discussed.

  9. RT/OS — realtime programming and application environment for the COSY control system

    NASA Astrophysics Data System (ADS)

    Weinert, A.; Hacker, U.; Haberbosch, Ch.; Henn, K.; Simon, M.

    1994-12-01

    This paper presents the highlights and constraints of RT/OS and how it can be used at other places. The support of approximately 1000 VME and VXI CPUs in network-based multiprocessor systems needs a special set of programming tools and application environment which are bundled as the RT/OS Real-Time-Operating-System. Supporting the Motorola 680χ0 processors and micro-controller with a development system on UNIX and MS-DOS platforms, the tool set gives the opportunity of bringing small embedded controllers as well as VME multiprocessor systems into operation. The tool set includes a cross compiler and a special version of a remote debugger, as well as application support such as downloading and configuration management. The main feature is a modular kernel with message-based task switching, using the rendezvous principle to allow easy extension. Special features of this kernel for a distributed system are networking with the Berkeley socket library supporting TCP/IP, XNS and Novell Netware, a multiprocessor system on VMEbus with the interprocessor Communication Module (IPC), a device driver library for almost every G64 I/O card using a FieldBus Interface called PDV and a X11R4 port.

  10. Materials Data on CoSi (SG:198) by Materials Project

    SciTech Connect

    Kristin Persson

    2016-02-10

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  11. Materials Data on Nb4CoSi (SG:124) by Materials Project

    SciTech Connect

    Kristin Persson

    2015-02-09

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  12. Structure of the O-polysaccharide and serological cross-reactivity of the Providencia stuartii O33 lipopolysaccharide containing 4-(N-acetyl-D-aspart-4-yl)amino-4,6-dideoxy-D-glucose.

    PubMed

    Torzewska, Agnieszka; Kocharova, Nina A; Zatonsky, George V; Blaszczyk, Aleksandra; Bystrova, Olga V; Shashkov, Alexander S; Knirel, Yuriy A; Rozalski, Antoni

    2004-06-01

    The O-polysaccharide of Providencia stuartii O33 was obtained by mild acid degradation of the lipopolysaccharide and the following structure of the tetrasaccharide repeating unit was established: -->6)-alpha-D-GlcpNAc-(1-->4)-alpha-D-GalpA-(1-->3)-alpha-D-GlcpNAc-(1-->3)-beta-D-Quip4N(Ac-D-Asp)-(1-->, where d-Qui4N(Ac-D-Asp) is 4-(N-acetyl-D-aspart-4-yl)amino-4,6-dideoxy-D-glucose. Structural studies were performed using sugar and methylation analyses and NMR spectroscopy, including conventional 2D 1H, 1H COSY, TOCSY, NOESY and 1H, 13C HSQC experiments as well as COSY and NOESY experiments in an H2O-D2O mixture to reveal correlations for NH protons. The O-polysaccharide of P. stuartii O33 shares an alpha-D-GlcpNAc-(1-->3)-beta-D-Quip4N(Ac-D-Asp) epitope with that of Proteus mirabilis O38, which seems to be responsible for a marked serological cross-reactivity of anti-P. stuartii O33 serum with the lipopolysaccharide of the latter bacterium. P. stuartii O33 is serologically related also to P. stuartii O4, whose O-polysaccharide contains a lateral beta-D-Qui4N(Ac-L-Asp) residue.

  13. Novel syntheses of hexahydro-1H-pyrrolo[1,2-a]ĭmidazoles and Octahydroimidazo[1,2-a]pyridines.

    PubMed

    Katritzky, A R; Qiu, G; He, H Y; Yang, B

    2000-06-16

    1-Phenyl-5-(benzotriazol-1-yl)hexahydro-1H-pyrrolo[1,2-a]ĭmidazole (18) and 1-phenyl-5-benzotriazolyloctahydroimidazo[1,2-a]pyridine (27) were readily prepared from succindialdehyde or glutaraldehyde, benzotriazole, and N-phenylethylenediamine. Synthons 18 and 27 reacted with Grignard reagents, allylsilanes, silyl ethers, and triethyl phosphite to produce 1-phenyl-5-substituted-hexahydro-1H-pyrrolo[1,2-a]ĭmidazoles 20a-f, 22, 24a,b, and 25 and 1-phenyl-5-substituted-octahydroimidazo[1, 2-a]pyridines 28a-e, 32, 33a,b, and 34 in good to excellent yields. The configurations of 20, 22, 24, and 25 were determined to be cis isomers by NOE experiment, while the configurations and conformations of 28a-e, 32, 33a,b, and 34 were elucidated by (1)H-(1)H COSY and (1)H-(13)C COSY.

  14. Constant-time 2D and 3D through-bond correlation NMR spectroscopy of solids under 60 kHz MAS

    PubMed Central

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2016-01-01

    Establishing connectivity and proximity of nuclei is an important step in elucidating the structure and dynamics of molecules in solids using magic angle spinning (MAS) NMR spectroscopy. Although recent studies have successfully demonstrated the feasibility of proton-detected multidimensional solid-state NMR experiments under ultrafast-MAS frequencies and obtaining high-resolution spectral lines of protons, assignment of proton resonances is a major challenge. In this study, we first re-visit and demonstrate the feasibility of 2D constant-time uniform-sign cross-peak correlation (CTUC-COSY) NMR experiment on rigid solids under ultrafast-MAS conditions, where the sensitivity of the experiment is enhanced by the reduced spin-spin relaxation rate and the use of low radio-frequency power for heteronuclear decoupling during the evolution intervals of the pulse sequence. In addition, we experimentally demonstrate the performance of a proton-detected pulse sequence to obtain a 3D 1H/13C/1H chemical shift correlation spectrum by incorporating an additional cross-polarization period in the CTUC-COSY pulse sequence to enable proton chemical shift evolution and proton detection in the incrementable t1 and t3 periods, respectively. In addition to through-space and through-bond 13C/1H and 13C/13C chemical shift correlations, the 3D 1H/13C/1H experiment also provides a COSY-type 1H/1H chemical shift correlation spectrum, where only the chemical shifts of those protons, which are bonded to two neighboring carbons, are correlated. By extracting 2D F1/F3 slices (1H/1H chemical shift correlation spectrum) at different 13C chemical shift frequencies from the 3D 1H/13C/1H spectrum, resonances of proton atoms located close to a specific carbon atom can be identified. Overall, the through-bond and through-space homonuclear/heteronuclear proximities determined from the 3D 1H/13C/1H experiment would be useful to study the structure and dynamics of a variety of chemical and biological

  15. New cytotoxic 1-azaanthraquinones and 3-aminonaphthoquinone from the stem bark of Goniothalamus marcanii.

    PubMed

    Soonthornchareonnon, N; Suwanborirux, K; Bavovada, R; Patarapanich, C; Cassady, J M

    1999-10-01

    Guided by brine shrimp toxicity and human tumor cell toxicity, fractionation of the alcoholic extract from the stem bark of Goniothalamus marcanii led to the isolation of four new 1-azaanthraquinones: marcanines B (3), C (4), D (5), and E (6), along with two known derivatives: marcanine A and dielsiquinone. A new 5-hydroxy-3-amino-2-aceto-1,4-naphthoquinone (7), a possible 1-azaanthraquinone biosynthetic precursor, was also isolated. The structures of the compounds were elucidated by spectroscopic analyses, mainly 1D and 2D NMR techniques ((1)H, (13)C, NOEDS, COSY, HMQC, and HMBC), as well as comparison with literature data. All the compounds except 6 were evaluated for cytotoxic activity. They exhibited significant cytotoxicity against several human tumor cell lines, A-549, HT-29, MCF7, RPMI, and U251 with the ED(50) in the range of 0.04-3.03 microM.

  16. Antisweet saponins from Gymnema sylvestre.

    PubMed

    Ye, W; Liu, X; Zhang, Q; Che, C T; Zhao, S

    2001-02-01

    Three new oleanane-type triterpene glycosides (1-3), along with the sodium salt of alternoside II (4), were isolated from an ethanol extract of the leaves of Gymnema sylvestre. The structures of these new saponins were identified as 21 beta-O-benzoylsitakisogenin 3-O-beta-D-glucopyranosyl(1-->3)-beta-D-glucuronopyranoside (1), the potassium salt of longispinogenin 3-O-beta-D-glucopyranosyl(1-->3)-beta-D-glucuronopyranoside (2), and the potassium salt of 29-hydroxylongispinogenin 3-O-beta-D-glucopyranosyl(1-->3)-beta-D-glucuronopyranoside (3). The aglycon of 3, gymnemagenol (3a), was characterized as 3 beta,16 beta,28, 29-tetrahydroxyolean-12-ene. Structure elucidation was accomplished by interpretation of NMR (DQF-COSY, HMQC, and HMBC) results, FABMS, and hydrolysis. Saponin 1 and the sodium salt of alternoside II (4) exhibited antisweet activity.

  17. Flavonoid glycosides from Prunus armeniaca and the antibacterial activity of a crude extract.

    PubMed

    Rashid, Fahima; Ahmed, Rehana; Mahmood, Azhar; Ahmad, Zaheer; Bibi, Nazia; Kazmi, Shahana Urooj

    2007-08-01

    Investigations on the chemical constituents of the fruits of Prunus armeniaca have led to the isolation of two new flavonoid glycosides, 4',5,7-trihydroxy flavone-7-O-[beta-D-mannopyranosyl (1'''-->2")]-beta-D-allopyranoside (1) and 3,4',5,7-tetrahydroxy-3',5'-di-methoxy flavone 3-O-[alpha-L-rhamnopyranosyl (1'''-->6")]-beta-D-galactopyranoside (2), from the butanolic fraction of the fruits. The butanolic extract exhibited antibacterial activity against both Gram positive and Gram negative bacteria. The structures of these compounds were elucidated through spectral studies, including 2D-NMR (COSY, NOESY, J-resolved), HMQC and HMBC experiments.

  18. Analgesic, anti-inflammatory, and CNS depressant activities of new constituents of Nepeta clarkei.

    PubMed

    Hussain, Javid; Ur Rehman, Najeeb; Hussain, Hidayat; Al-Harrasi, Ahmed; Ali, Liaqat; Rizvi, Tania Shamim; Ahmad, Mansoor; Mehjabeen

    2012-04-01

    Two new pentacyclic triterpenes named kirmanoic acid (1) and kurramanoic acid (2) have been isolated from the chloroform-soluble portion of the whole plant of Nepeta clarkei Hook. The structures of the two new compounds were assigned on the basis of their ¹H and ¹³C NMR spectra including two-dimensional NMR techniques such as COSY, HMQC, and HMBC experiments. Kirmanoic acid (1) was investigated for analgesic, anti-inflammatory, and CNS depressant activities. Interestingly kirmanoic acid (1) showed strong analgesic activity than standard drug in acetic induced writhing and formalin tests. Similarly kirmanoic acid (1) also showed strong anti-inflammatory activity than its standard drug. The gross behavioral study of kirmanoic acid (1) revealed that it exhibited mild CNS stimulant and muscle relaxant in the mice. Compound 1 showed a slight increase in Locomotor activity and possesses the antidepressant effect.

  19. (6R,9S)-6′-(4″-Hydroxybenzoil)-Roseoside, a new megastigmane derivative, isolated from Ouratea polyantha Engl. (Ocnhaceae) and its effect over hepatic glucose-6-phosphatase

    PubMed Central

    Bermúdez, Jairo; Rodríguez, María; Hasegawa, Masahisa; González-Mujica, Freddy; Duque, Sandra; Ito, Yoichiro

    2012-01-01

    A new megastigmane derivative, (6R,9S)-6′-(4″-hydroxybenzoil)-roseoside 1 and two known compounds, the biflavone agathisflavone 2 and the carboxylic acid derivative 4-hydroxibenzoic acid 3 were isolated and purified from leaves and stems of Ouratea polyantha Engl. Agathisflavone was isolated in a single high-speed counter-current chromatography run, meanwhile the megastigmane and the carboxylic acid derivatives were purified in two steps, a combination of high-speed countercurrent chromatography and analytical column chromatography. All structures were elucidated on the basis of spectral evidences and comparisons with literatures. Compound 1 was characterized by [α]D20, UV-Vis, IR, MS, 1H-NMR, 13C-NMR, HMQC, HMBC, COSY and NOESY. Compounds 1 and 2 were tested as hepatic glucose-6-phosphatase inhibitors. PMID:22978207

  20. Phenolics and Polyphenolics from Melastomataceae Species.

    PubMed

    Serna, Diana Marcela Ocampo; Martínez, José Hipólito Isaza

    2015-09-25

    The Melastomataceae family, the seventh largest flowering plants, has been studied in several fronts of natural product chemistry, including terpenoids, simple phenolics, flavonoids, quinones, lignans and their glycosides, as well as a vast range of tannins or polyphenols. This review concerns the phenolic and polyphenolic metabolites described in the literature for several genera of this family, the mode of isolation and purification, and the structure elucidation of these new natural products that has been achieved by extensive spectral analyses, including ESI-MS, ¹H-, (13)C-NMR spectra and two-dimensional experiments, COSY, TOCSY, J-resolved, NOESY, HMQC, DEPT, and HMBC, as well as chemical and enzymatic degradations and the chemotaxonomic meaning. Finally, a general biogenetic pathway map for ellagitannins is proposed on the bases of the most plausible free radical C-O oxidative coupling.

  1. Structural elucidation of polysaccharide containing 3-O-methyl galactose from fruiting bodies of Pleurotus citrinopileatus.

    PubMed

    He, Pengfei; Zhang, Anqiang; Zhou, Saijing; Zhang, Fuming; Linhardt, Robert J; Sun, Peilong

    2016-11-03

    A water-soluble polysaccharide containing 3-O-methyl galactose (PCP60W) was isolated from fruiting bodies of Pleurotus citrinopileatus and purified by anion-exchange and gel column chromatography. This polysaccharide has an average molecular weight of 2.74 × 10(4) Da and its structure was elucidated using monosaccharide composition and methylation analysis combined with one- and two-dimensional (COSY, TOCSY, NOESY, HMQC and HMBC) NMR spectroscopy. PCP60W was shown to be a linear partially 3-O-methylated α-galactopyranan comprised of 6-linked galactose, 6-linked 3-O-methyl galactose and 4-linked glucose in a ratio of 3.0:1.0:0.6. This work provides additional evidence for the view that 3-O-methyl galactose is common to the genus Pleurotus.

  2. Peltomexicanin, a Peltogynoid Quinone Methide from Peltogyne Mexicana Martínez Purple Heartwood.

    PubMed

    Gutiérrez-Macías, Paulina; Peralta-Cruz, Javier; Borja-de-la-Rosa, Amparo; Barragán-Huerta, Blanca E

    2016-02-04

    Peltomexicanin (7,10-dihydroxy-6,12-dioxa-5H-tetraphen-3-one) is a new peltogynoid quinone methide isolated from Palo Morado (Peltogyne mexicana Martínez) heartwood by column chromatography. Its chemical structure was elucidated by IR, NMR (¹H, (13)C), 2D NMR experiments (COSY, NOESY, HMQC, and HSQC), ESI-MS, and UV-Vis spectroscopic analysis. According to HPLC quantification, this compound is the main pigment and accounts for 1.21% of Palo Morado heartwood material. The antioxidant activity of peltomexicanin and dried methanolic extract (DEx) of purple heartwood was evaluated using the radical of 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) assay, and the corresponding values expressed as Trolox equivalents (µmol TE/mg sample) were 4.25 and 4.57, respectively.

  3. Chemical analysis of new water-soluble (1→6)-, (1→4)-α, β-glucan and water-insoluble (1→3)-, (1→4)-β-glucan (Calocyban) from alkaline extract of an edible mushroom, Calocybe indica (Dudh Chattu).

    PubMed

    Mandal, Soumitra; Maity, Kankan K; Bhunia, Sanjoy K; Dey, Biswajit; Patra, Sukesh; Sikdar, Samir R; Islam, Syed S

    2010-12-10

    Two different glucans (PS-I, water-soluble; and PS-II, water-insoluble) were isolated from the alkaline extract of fruit bodies of an edible mushroom Calocybe indica. On the basis of acid hydrolysis, methylation analysis, periodate oxidation, and NMR analysis ((1)H, (13)C, DEPT-135, TOCSY, DQF-COSY, NOESY, ROESY, HMQC, and HMBC), the structure of the repeating unit of these polysaccharides were established as: PS-I: →6)-β-D-Glcp-(1→6)-β-D-glcp-(1→6)-)-β-D-Glcp-(1→ α-D=Glcp (Water-soluble glucan). PS-II: →3)-β-D-Glcp-(1→3)-β-D-glcp-(1→3)-)-β-D-Glcp-(1→3)-β-D-Glcp-(1→ β-D-Glcp (Water-insoluble glucan, Calocyban).

  4. Forazoline A: Marine-derived polyketide with antifungal in vivo efficacy

    SciTech Connect

    Wyche, Thomas P.; Piotrowski, Jeff S.; Hou, Yanpeng; Braun, Doug; Deshpande, Raamesh; McIlwain, Sean; Ong, Irene M.; Myers, Chad L.; Guzei, Ilia A.; Westler, William M.; Andes, David R.; Bugni, Tim S.

    2014-09-04

    Forazoline A, a novel antifungal polyketide with in vivo efficacy against Candida albicans, was discovered using LCMS-based metabolomics to investigate marine-invertebrate-associated bacteria. Forazoline A had a highly unusual and unprecedented skeleton. Acquisition of 13C–13C gCOSY and 13C–15N HMQC NMR data provided the direct carbon–carbon and carbon–nitrogen connectivity, respectively. This approach represents the first example of determining direct 13C–15N connectivity for a natural product. In this paper, using yeast chemical genomics, we propose that forazoline A operated through a new mechanism of action with a phenotypic outcome of disrupting membrane integrity.

  5. Cytotoxic activity of C-geranyl compounds from Paulownia tomentosa fruits.

    PubMed

    Smejkal, Karel; Babula, Petr; Slapetová, Tereza; Brognara, Eleonora; Dall'acqua, Stefano; Zemlicka, Milan; Innocenti, Gabbriella; Cvacka, Josef

    2008-10-01

    The newly discovered 5,7-dihydroxy-6-geranylchromone ( 1) was isolated from PAULOWNIA TOMENTOSA fruit and subsequently characterized. The structure of the isolated compound was elucidated on the basis of extensive NMR experiments including HMQC, HMBC, COSY, and NOESY, as well as HR-MS, IR, and UV. The cytotoxicity of 1 was evaluated using a plant cell model represented by tobacco BY-2 cells. The other phytoconstituents ( 2 - 8) previously isolated from P. TOMENTOSA were similarly evaluated together with the known flavanones 10 and 11. The cytotoxicity (human erythro-leukaemia cell line K562) and activity on erythroid differentiation of compounds 2 - 9 and 12 and 13 have also been evaluated. Acteoside ( 2) was determined to be the most toxic of the compounds tested on BY-2 cells, diplacone ( 6) on the K562 cell line. Some aspects of the relationship between the flavanone skeleton substitution and the metabolic activation necessary for a toxic effect are discussed.

  6. Isolation, NMR Spectral Analysis and Hydrolysis Studies of a Hepta Pyranosyl Diterpene Glycoside from Stevia rebaudiana Bertoni.

    PubMed

    Chaturvedula, Venkata Sai Prakash; Chen, Steven; Yu, Oliver; Mao, Guohong

    2013-09-30

    From the commercial extract of the leaves of Stevia rebaudiana Bertoni, a minor steviol glycoside, 13-[(2-O-β-D-glucopyranosyl-3-O-β-D-glucopyranosyl-β-D-glucopyranosyl)oxy] ent-kaur-16-en-19-oic acid-[(2-O-(3-O-β-D-glucopyranosyl-α-L-rhamnopyranosyl)-3-O-β-D-glucopyranosyl-β-D-glucopyranosyl) ester] (1); also known as rebaudioside O having seven sugar units has been isolated. Its structural characterization has been achieved by the extensive 1D (1H and 13C), and 2D NMR (COSY, HMQC, HMBC) as well as mass spectral data. Further, hydrolysis studies were performed on rebaudioside O using acid and enzymatic methods to identify aglycone and sugar residues in its structure as well as their configurations.

  7. Isolation, NMR Spectral Analysis and Hydrolysis Studies of a Hepta Pyranosyl Diterpene Glycoside from Stevia rebaudiana Bertoni

    PubMed Central

    Chaturvedula, Venkata Sai Prakash; Chen, Steven; Yu, Oliver; Mao, Guohong

    2013-01-01

    From the commercial extract of the leaves of Stevia rebaudiana Bertoni, a minor steviol glycoside, 13-[(2-O-β-d-glucopyranosyl-3-O-β-d-glucopyranosyl-β-d-glucopyranosyl)oxy] ent-kaur-16-en-19-oic acid-[(2-O-(3-O-β-d-glucopyranosyl-α-l-rhamnopyranosyl)-3-O-β-d-glucopyranosyl-β-d-glucopyranosyl) ester] (1); also known as rebaudioside O having seven sugar units has been isolated. Its structural characterization has been achieved by the extensive 1D (1H and 13C), and 2D NMR (COSY, HMQC, HMBC) as well as mass spectral data. Further, hydrolysis studies were performed on rebaudioside O using acid and enzymatic methods to identify aglycone and sugar residues in its structure as well as their configurations. PMID:24970189

  8. Anti-ulcer xanthones from the roots of Hypericum oblongifolium Wall.

    PubMed

    Ali, Mumtaz; Latif, Abdul; Zaman, Khair; Arfan, Mohammad; Maitland, Derek; Ahmad, Habib; Ahmad, Manzoor

    2014-06-01

    Three new xanthones, hypericorin C (1), hypericorin D (2) and 3,4-dihydroxy-5-methoxyxanthone (3), along with eight known compounds; 2,3-dimethoxyxanthone (4), 3,4-dihydroxy-2-methoxyxanthone (5), 3,5-dihydroxy-1-methoxyxanthone (6), 3-acetylbetulinic acid (7), 10H-1,3-dioxolo[4,5-b]xanthen-10-one (8), 3-hydroxy-2-methoxyxanthone (9), 3,4,5-trihydroxyxanthone (10) and betulinic acid (11) were isolated from the roots of Hypericum oblongifolium. The structures of the new compounds 1, 2 and 3 were deduced by spectroscopic techniques [ESI MS, (1)H NMR, (13)C NMR, and 2D NMR (HMQC, HMBC, COSY and NOESY)]. The entire series of compounds were evaluated for anti-ulcer activity.

  9. In vitro and in vivo study of cucurbitacins-type triterpene glucoside from Citrullus colocynthis growing in Saudi Arabia against hepatocellular carcinoma.

    PubMed

    Ayyad, Seif-Eldin N; Abdel-Lateff, Ahmed; Alarif, Walied M; Patacchioli, Francesca R; Badria, Farid A; Ezmirly, Saleh T

    2012-03-01

    Chromatographic investigation of fruits obtained from Citrullus colocynthis, growing in Saudi Arabia, led to isolation of two compounds; Cucurbitacin E glucoside (Cu E, 1), and Cucurbitacin I glucoside (Cu I, 2). The chemical structures of 1 and 2, were elucidated by spectroscopic analyses include; 1D ((1)H and (13)C) and 2D (COSY, HMQC and HMBC) NMR and ESI-MS spectroscopy. The in vitro cytotoxic activity against hepatoma cell line (HepG2) and mice-bearing tumor of Ehrlich's ascites carcinoma (EAC) of the compounds were estimated. Both compounds had potent inhibitory activity on HepG2 with IC(50) 3.5 and 2.8 nmol/mL, respectively. In addition to these activities, the in vivo study employing EAC, showed the capability of both compounds to prolong the survival time, life span and normalize the biochemical parameters of the infected mice with EAC.

  10. Two novel clerodane diterpenenes with NGF-potentiating activities from the twigs of Croton yanhuii.

    PubMed

    Sun, Yihang; Wang, Meicheng; Ren, Quanhui; Li, Shen; Xu, Jing; Ohizumi, Yasushi; Xie, Chunfeng; Jin, Da-Qing; Guo, Yuanqiang

    2014-06-01

    Nerve growth factor (NGF) and analog reagents to promote the neurite outgrowth of nerve cells against the neuron degeneration are expected to be potentially useful for the medical treatment of Alzheimer's disease. In our focus on the discovery of bioactive diterpenes, we investigated the chemical constituents of the plant Croton yanhuii. This investigation led to the isolation and identification of two novel clerodane diterpenes (1 and 2). Their structures were elucidated on the basis of extensive 1D and 2D NMR (COSY, HMQC, HMBC, and NOESY) and mass (ESIMS and HR-ESIMS) spectroscopic data analyses. Further biological screenings showed that both of the compounds enhanced NGF-mediated neurite outgrowth from PC12 cells.

  11. A new phthalide derivative from Peperomia nivalis.

    PubMed

    Vásquez-Ocmín, Pedro; Haddad, Mohamed; Gadea, Alice; Jullian, Valérie; Castillo, Denis; Paloque, Lucie; Cerapio, Juan Pablo; Bourdy, Geneviève; Sauvain, Michel

    2017-01-01

    One new phthalide (1) was isolated from aerial parts of Peperomia nivalis, along with known compounds (2 and 3), reported in this species for the first time. The structure of the new compound was characterised on the basis of 1D ((1)H and (13)C NMR), 2D (COSY, HMQC, HMBC and NOESY) NMR and high-resolution mass spectral (HRMS) data. Compound 2 was isolated from a natural source for the first time but previously synthesised. Compounds 1-3 were evaluated for their anti-Helicobacter pylori and anti-Plasmodium falciparum activities. Compound 1 showed moderate activities against H. pylori (MIC 47.5 μM) and the F32-Tanzania strain of P. falciparum (IC50 8.5 μM). Compounds 2 and 3 exhibited weak anti-H. pylori activity (MIC 241.3 and 237.6 μM, respectively) and were inactive against P. falciparum.

  12. Structure of the O-specific polysaccharide of the bacterium Proteus vulgaris O23.

    PubMed

    Perepelov, A V; Shashkov, A S; Babichka, D; Senchenkova, S N; Bartodziejska, B; Rozalski, A; Knirel, Y A

    2000-09-01

    An acidic O-specific polysaccharide was obtained by mild acid degradation of the lipopolysaccharide of the bacterium Proteus vulgaris O23 (strain PrK 44/57) and found to contain 2-acetamido-2-deoxy-D-galactose, 2-acetamido-2-deoxy-D-glucose, and D-galacturonic acid. Based on 1H- and 13C-NMR spectroscopic studies, including two-dimensional correlation spectroscopy (COSY), total correlation spectroscopy (TOCSY), nuclear Overhauser effect spectroscopy (NOESY), and 1H,13C heteronuclear multiple-quantum coherence (HMQC) experiments, the following structure of the branched tetrasaccharide repeating unit of the polysaccharide was established: [figure], where the degree of O-acetylation of the terminal GalA residue at position 4 is about 80%. A structural similarity of the O-specific polysaccharides of P. vulgaris O23 and P. mirabilis O23 is discussed.

  13. Acylated and non-acylated flavonol monoglycosides from the Indian minor spice Nagkesar (Mammea longifolia).

    PubMed

    Jagan Mohan Rao, Lingamallu; Yada, Hiroshi; Ono, Hiroshi; Yoshida, Mitsuru

    2002-05-22

    A methanol extract of nagkesar (buds of Mammea longifolia), which showed strong radical scavenging activity, yielded 13 compounds by separations using column chromatography and HPLC. Structure elucidation of these compounds was achieved by (1)H and (13)C NMR, including DQF-COSY, TOCSY, DEPT, HMQC, HSQC, and HMBC. They include two new compounds, quercetin 3-O-(2' ',4' 'di-E-p-coumaroyl)-alpha-L-rhamno-pyranoside and quercetin 3-O-(3' ',4' '-di-E-p-coumaroyl)-alpha-L-rhamnopyranoside, along with known compounds kaempferol, quercetin, the isopropylidenedioxy derivative of shikimic acid, kaempferol 3-O-(2' ',4' '-di-E-p-coumaroyl)-alpha-L-rhamnopyranoside, kaempferol 3-O-(3' ',4' '-di-E-p-coumaroyl)-alpha-L-rhamnopyranoside, kaempferol 3-O-alpha-L-rhamnopyranoside, quercetin 3-O-alpha-L-rhamnopyranoside, shikimic acid, kaempferol 3-O-beta-D-glucopyranoside, quercetin 3-O-beta-D-glucopyranoside, and beta-sitosterol 3-O-beta-D-glucopyranoside.

  14. Antimicrobial compounds from Pimpinella species growing in Turkey.

    PubMed

    Tabanca, Nurhayat; Bedir, Erdal; Kirimer, Nese; Baser, K Husnu Can; Khan, Shabana I; Jacob, Melissa R; Khan, Ikhlas A

    2003-10-01

    A new, 4-(2-propenyl)-phenyl angelate ( 1) and four known phenylpropanoids ( 2 - 5), were isolated from Pimpinella isaurica, a species endemic in Turkey. One new sesquiterpene, 1-methyl-4-(5-methyl-1-methylenehex-4-enyl)-7-oxabicyclo[4.1.0]heptane ( 6) was obtained from P. aurea and two known phenylpropanoids were isolated ( 7, 8), from P. corymbosa. The structure elucidation of the new compounds 1 and 6 was achieved by a combination of one- ( (1)H, and (13)C) and two-dimensional NMR techniques (G-DQF-COSY, G-HMQC, and G-HMBC) and LC-ESI-FTMS. Compounds 1, 2, 4, 6, 7, 8 have been evaluated for their antimalarial and antimicrobial activities. Compound 1, 2, 4, 6, 8 had antimicrobial activity against Mycobacterium intracellulare with IC (50) values of 7.0, 15.0, 2.5, 10.0 and 1.5 microg/mL, respectively.

  15. Quinic acid derivatives from Pimpinella brachycarpa exert anti-neuroinflammatory activity in lipopolysaccharide-induced microglia.

    PubMed

    Lee, Seung Young; Moon, Eunjung; Kim, Sun Yeou; Lee, Kang Ro

    2013-04-01

    Five new quinic acid derivatives (1-5), together with 10 known quinic acid derivatives (6-15), were isolated from the MeOH extract of Pimpinella brachycarpa (Umbelliferae). Their structures were established on the basis of spectroscopic analyses including extensive 2D NMR studies (COSY, HMQC and HMBC). Isolated compounds 1-15 were evaluated for their inhibitory activities on nitric oxide (NO) production in an activated murine microglial cell line. Compounds 2, 3, 8 and 11 significantly inhibited NO production without high cell toxicity in lipopolysaccharide (LPS)-activated BV-2 cells, a microglia cell line (IC50=4.66, 12.52, 9.04 and 12.11 μM, respectively).

  16. Complete structure of the cell surface polysaccharide of Streptococcus oralis ATCC 10557: A receptor for lectin-mediated interbacterial adherence

    SciTech Connect

    Abeygunawardana, C.; Bush, C.A. ); Cisar, J.O. )

    1991-07-02

    Lectin-carbohydrate binding is known to play an important role in a number of different cell-cell interactions including those between certain species of oral streptococci and actinomyces that colonize teeth. The cell wall polysaccharides of Streptococcus oralis ATCC 10557, S. oralis 34, and Streptococcus mitis J22, although not identical antigenically, each function as a receptor molecule for the galactose and N-acetylgalactosamine reactive fimbrial lectins of Actinomyces viscosus and Actinomyces naeslundii. Carbohydrate analysis of the receptor polysaccharide isolated from S. oralis ATCC 10557 shows galactose (3 mol), glucose (1 mol), GalNAc (1 mol), and rhamnose (1 mol). {sup 1}H NMR spectra of the polysaccharide show that is partially O-acetylated. Analysis of the {sup 1}H NMR spectrum of the de-O-acetylated polysaccharide shows that it is composed of repeating subunits containing six monosaccharides and that the subunits are joined by a phosphodiester linkage. The {sup 1}H and {sup 13}C NMR spectra were completely assigned by two-dimensional homonuclear correlation methods and by {sup 1}H-detected heteronuclear multiple-quantum correlation ({sup 1}H({sup 13}C)HMQC). The complete {sup 1}H and {sup 13}C assignment of the native polysaccharide was carried out by the same techniques augmented by a {sup 13}C-coupled hybrid HMQC-COSY method, which is shown to be especially useful for carbohydrates in which strong coupling and overlapping peaks in the {sup 1}H spectrum pose difficulties.

  17. The use of a selective saturation pulse to suppress t1 noise in two-dimensional 1H fast magic angle spinning solid-state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Robertson, Aiden J.; Pandey, Manoj Kumar; Marsh, Andrew; Nishiyama, Yusuke; Brown, Steven P.

    2015-11-01

    A selective saturation pulse at fast magic angle spinning (MAS) frequencies (60+ kHz) suppresses t1 noise in the indirect dimension of two-dimensional 1H MAS NMR spectra. The method is applied to a synthetic nucleoside with an intense methyl 1H signal due to triisopropylsilyl (TIPS) protecting groups. Enhanced performance in terms of suppressing the methyl signal while minimising the loss of signal intensity of nearby resonances of interest relies on reducing spin diffusion - this is quantified by comparing two-dimensional 1H NOESY-like spin diffusion spectra recorded at 30-70 kHz MAS. For a saturation pulse centred at the methyl resonance, the effect of changing the nutation frequency at different MAS frequencies as well as the effect of changing the pulse duration is investigated. By applying a pulse of duration 30 ms and nutation frequency 725 Hz at 70 kHz MAS, a good compromise of significant suppression of the methyl resonance combined with the signal intensity of resonances greater than 5 ppm away from the methyl resonance being largely unaffected is achieved. The effectiveness of using a selective saturation pulse is demonstrated for both homonuclear 1H-1H double quantum (DQ)/single quantum (SQ) MAS and 14N-1H heteronuclear multiple quantum coherence (HMQC) two-dimensional solid-state NMR experiments.

  18. The use of a selective saturation pulse to suppress t1 noise in two-dimensional (1)H fast magic angle spinning solid-state NMR spectroscopy.

    PubMed

    Robertson, Aiden J; Pandey, Manoj Kumar; Marsh, Andrew; Nishiyama, Yusuke; Brown, Steven P

    2015-11-01

    A selective saturation pulse at fast magic angle spinning (MAS) frequencies (60+kHz) suppresses t1 noise in the indirect dimension of two-dimensional (1)H MAS NMR spectra. The method is applied to a synthetic nucleoside with an intense methyl (1)H signal due to triisopropylsilyl (TIPS) protecting groups. Enhanced performance in terms of suppressing the methyl signal while minimising the loss of signal intensity of nearby resonances of interest relies on reducing spin diffusion--this is quantified by comparing two-dimensional (1)H NOESY-like spin diffusion spectra recorded at 30-70 kHz MAS. For a saturation pulse centred at the methyl resonance, the effect of changing the nutation frequency at different MAS frequencies as well as the effect of changing the pulse duration is investigated. By applying a pulse of duration 30 ms and nutation frequency 725 Hz at 70 kHz MAS, a good compromise of significant suppression of the methyl resonance combined with the signal intensity of resonances greater than 5 ppm away from the methyl resonance being largely unaffected is achieved. The effectiveness of using a selective saturation pulse is demonstrated for both homonuclear (1)H-(1)H double quantum (DQ)/single quantum (SQ) MAS and (14)N-(1)H heteronuclear multiple quantum coherence (HMQC) two-dimensional solid-state NMR experiments.

  19. Determination of size and sign of hetero-nuclear coupling constants from 2D 19F-13C correlation spectra

    NASA Astrophysics Data System (ADS)

    Ampt, Kirsten A. M.; Aspers, Ruud L. E. G.; Dvortsak, Peter; van der Werf, Ramon M.; Wijmenga, Sybren S.; Jaeger, Martin

    2012-02-01

    Fluorinated organic compounds have become increasingly important within the polymer and the pharmaceutical industry as well as for clinical applications. For the structural elucidation of such compounds, NMR experiments with fluorine detection are of great value due to the favorable NMR properties of the fluorine nucleus. For the investigation of three fluorinated compounds, triple resonance 2D HSQC and HMBC experiments were adopted to fluorine detection with carbon and/or proton decoupling to yield F-C, F-C{H}, F-C{Cacq} and F-C{H,Cacq} variants. Analysis of E.COSY type cross-peak patterns in the F-C correlation spectra led, apart from the chemical shift assignments, to determination of size and signs of the JCH, JCF, and JHF coupling constants. In addition, the fully coupled F-C HMQC spectrum of steroid 1 was interpreted in terms of E.COSY type patterns. This example shows how coupling constants due to different nuclei can be determined together with their relative signs from a single spectrum. The analysis of cross-peak patterns, as presented here, not only provides relatively straightforward routes to the determination of size and sign of hetero-nuclear J-couplings in fluorinated compounds, it also provides new and easy ways for the determination of residual dipolar couplings and thus for structure elucidation. The examples and results presented in this study may contribute to a better interpretation and understanding of various F-C correlation experiments and thereby stimulate their utilization.

  20. Materials Data on Na2Co(Si2O5)2 (SG:2) by Materials Project

    DOE Data Explorer

    Kristin Persson

    2014-11-02

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  1. Bioactive phenylpropanoid analogues from Piper betle L. var. haldia leaves.

    PubMed

    Atiya, Akhtar; Sinha, Barij Nayan; Lal, Uma Ranjan

    2017-02-15

    Phytochemical analyses of the chloroform extract of Piper betle L. var. birkoli, Piperaceae, leaves led to the isolation of two new phenylpropanoid analogues: bis-chavicol dodecanoyl ester (2) and bis-hydroxychavicol dodecanoyl ester (3), along with one known compound: allyl-3-methoxy-4-hydroxybenzene (1) on the basis of spectroscopic data 1D ((1)H and (13)C) and 2D ((1)H-(1)H COSY and HMBC) NMR, as well as ESI-MS, FT-IR, HR-ESI-MS and LC-ESI-MS. Compound 2 and 3 exhibited excellent antioxidant DPPH radical scavenging activity with IC50 values of 12.67 μg/mL and 1.08 μg/mL compared to ascorbic acid as a standard antioxidant drug with IC50 value of 6.60 μg/mL. Evaluation of cytotoxic activity against two human oral cancer cell lines (AW13516 and AW8507) showed significant effect with GI50 values of 19.61 and 23.01 μg/mL for compound 2 and 10.25 and 13.12 μg/mL for compound 3, compared to Doxorubicin(®) as a standard cytotoxic drug with GI50 value of < 10 μg/mL.

  2. The NMR studies on two new furostanol saponins from Agave sisalana leaves.

    PubMed

    Zou, Peng; Fu, Jing; Yu, He-shui; Zhang, Jie; Kang, Li-ping; Ma, Bai-ping; Yan, Xian-zhong

    2006-12-01

    The detailed NMR studies and full assignments of the 1H and 13C spectral data for two new furostanol saponins isolated from Agave sisalana leaves are described. Their structures were established using a combination of 1D and 2D NMR techniques including 1H, 13C, 1H-1H COSY, TOCSY, HSQC, HMBC and HSQC-TOCSY, and also FAB-MS spectrometry and chemical methods. The structures were established as (25S)-26-(beta-D-glucopyranosyl)-22 xi-hydroxyfurost-12-one-3beta-yl-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->3)-O-[O-beta-D-glucopyranosyl-(1-->2)]-O-beta-D-glucopyranosyl-(1-->4)-beta-D-galacto- pyranoside (1) and (25S)-26-(beta-D-glucopyranosyl)-22xi-hydroxyfurost-5-en-12-one-3beta-yl-O-alpha-L-rhamno- pyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->3)-O-[O-beta-D-glucopyranosyl-(1-->2)]-O-beta-D-glucopyranosyl- (1-->4)-beta-D-galactopyranoside (2).

  3. One pot synthesis of Curcumin-NSAIDs prodrug, spectroscopic characterization, conformational analysis, chemical reactivity, intramolecular interactions and first order hyperpolarizability by DFT method

    NASA Astrophysics Data System (ADS)

    Srivastava, Sangeeta; Gupta, Preeti; Sethi, Arun; Singh, Ranvijay Pratap

    2016-08-01

    A novel Curcumin-NSAIDs prodrug 4-((1E, 3Z, 6E)-3-hydroxy-(4-hydroxy-3-methoxyphenyl)-5-oxohepta-1,3,3-trienyl)-2-methoxyphenyl-2-(4-isobutylphenyl) propanoate (2) derivative was synthesized by Steglich esterification in high yield and characterized with the help of 1H, 13C NMR, 1H-1H COSY, UV, FT-IR spectroscopy and mass spectrometry. The molecular geometry of synthesized compound was calculated in ground state by Density functional theory (DFT/B3LYP) using two different basis set 6-31G (d, p) and 6-311G (d, p). Conformational analysis of 2 was carried out to determine the most stable conformation. Stability of the molecule as a result of hyperconjugative interactions and electron delocalization were analysed using Natural bond orbital (NBO) analysis. Intramolecular interactions were analysed by AIM (Atom in molecule) approach. Global and local reactivity descriptors were calculated to study the reactive site within molecule. The electronic properties such as HOMO and LUMO energies were calculated using time dependent Density Functional Theory (TD-DFT). The vibrational wavenumbers were calculated using DFT method and assigned with the help of potential energy distribution (PED). First hyperpolarizability value has been calculated to describe the nonlinear optical (NLO) property of the synthesized compound. Molecular electrostatic potential (MEP) for synthesized compounds have also been determined to check their electrophilic or nucleophilic reactivity.

  4. Steroidal saponins from the fruits of Solanum torvum.

    PubMed

    Colmenares, Alida Pérez; Rojas, Luis B; Mitaine-Offer, Anne-Claire; Pouységu, Laurent; Quideau, Stéphane; Miyamoto, Tomofumi; Tanaka, Chiaki; Paululat, Thomas; Usubillaga, Alfredo; Lacaille-Dubois, Marie-Aleth

    2013-02-01

    Seven steroidal glycosides have been isolated from the fruits of Solanum torvum Swartz. Their structures were established by 2D NMR spectroscopic techniques ((1)H,(1)H-COSY, TOCSY, NOESY, HSQC, and HMBC) and mass spectrometry as (25S)-26-(β-D-glucopyranosyloxy)-3-oxo-5α-furost-20(22)-en-6α-yl-O-β-D-xylopyranoside (1), (25S)-26-(β-D-glucopyranosyloxy)-3-oxo-22α-methoxy-5α-furostan-6α-yl-O-β-D-xylopyranoside (2), (25S)-26-(β-D-glucopyranosyloxy)-3β-hydroxy-22α-methoxy-5α-furostan-6α-yl-O-α-L-rhamnopyranosyl-(1→3)-β-D-glucopyranoside (3), (25S)-3β-hydroxy-5α-spirostan-6α-yl-O-β-D-xylopyranoside (4), (25S)-3-oxo-5α-spirostan-6α-yl-O-β-D-xylopyranoside (5), (25S)-3β-hydroxy-5α-spirostan-6α-yl-O-β-D-glucopyranoside (6), (25S)-3β,27-dihydroxy-5α-spirostan-6α-yl-O-β-D-glucopyranoside (7).

  5. Identification of diterpene alkaloids from Aconitum napellus subsp. firmum and GIRK channel activities of some Aconitum alkaloids.

    PubMed

    Kiss, Tivadar; Orvos, Péter; Bánsághi, Száva; Forgo, Peter; Jedlinszki, Nikoletta; Tálosi, László; Hohmann, Judit; Csupor, Dezső

    2013-10-01

    Diterpene alkaloids neoline (1), napelline (2), isotalatizidine (3), karakoline (4), senbusine A (5), senbusine C (6), aconitine (7) and taurenine (8) were identified from Aconitum napellus L. subsp. firmum, four (2-4, 6) of which are reported for the first time from this plant. The structures were determined by means of LC-MS, 1D and 2D NMR spectroscopy, including (1)H-(1)H COSY, NOESY, HSQC and HMBC experiments. Electrophysiological effects of the isolated compounds, together with nine diterpene alkaloids previously obtained from Aconitum toxicum and Consolida orientalis were investigated on stable transfected HEK-hERG (Kv11.1) and HEK-GIRK1/4 (Kir3.1 and Kir3.4) cell lines using automated patch clamp equipment. Significant blocking activity on GIRK channel was exerted by aconitine (7) (45% at 10 μM), but no blocking activities of the other investigated compounds were detected. The tested compounds were inactive on hERG channel in the tested concentration. The comparison of the previously reported metabolites of A. napellus subsp. firmum and compounds identified in our experiment reveals substantial variability of the alkaloid profile of this taxon.

  6. Antioxidant C-glycosylflavones of Drymaria cordata (Linn.) Willd.

    PubMed

    Nono, Raymond N; Nguelefack-Mbuyo, Elvine P; Nzowa, Laurence K; Ponou, Beaudelaire K; Teponno, Rémy B; Nguelefack, Télesphore B; Barboni, Luciano; Tapondjou, Léon A; Park, Hee-Juhn

    2016-01-01

    A new C-glycosylflavone, drymaritin E (6-C-(3-keto-β-digitoxopyranosyl)-4'-O-(β-D-glucopyranosyl)-7-methoxyl-5,4'-dihydroxylflavone) 1 was isolated from the oily upper phase (SU) of the MeOH extract from aerial parts of Drymaria cordata together with two known compounds (cassiaoccidentalin A 2 and anemonin 3) and an inseparable mixture of two known C-glycosylflavones 5,4'-dihydroxy-7-methoxyflavone-6-C-(2''-O-α-L-rhamnopyranosyl)-β-D-glucopyranoside 4a and 5,7,3',4'-tetrahydroxyflavone-6-C-(2''-O-α-L-rhamnopyranosyl)-β-D-glucopyranoside 4b. The alkaline hydrolysis of 3 led to a new hemisynthetic derivative, sodium anemonate (sodium 2-((1'E) 2'-sodium-carboxylate-vinyl)-5-oxo-cyclohex-1-ene carboxylate) 3a. The chemical structures were determined by spectroscopic methods ((1)H NMR, (13)C NMR, (1)H-(1)H COSY, HMBC, HSQC, and NOESY) and mass spectrometry (ESI-MS). C-glycosylflavones had significant free radical-scavenging activities on the radical 2,2-diphenyl-1-picrylhydrazyl (DPPH). However, SU and compounds 3 and 3a exhibited no activity. In particular, compound 1 exhibited a concentration-dependent radical scavenging activity on DPPH with EC50 of 31.43 µg/mL.

  7. Antimicrobial activity of Calotropis procera Ait. (Asclepiadaceae) and isolation of four flavonoid glycosides as the active constituents.

    PubMed

    Nenaah, Gomah

    2013-07-01

    Antimicrobial activity of solvent extracts and flavonoids of Calotropis procera growing wild in Saudi Arabia was evaluated using the agar well-diffusion method. A bioassay-guided fractionation of the crude flavonoid fraction (Cf3) of MeOH extract which showed the highest antimicrobial activity led to the isolation of four flavonoid glycosides as the bioactive constituents. Structure of compounds have been elucidated using physical and spectroscopic methods including (UV, IR, (1)H, (13)C-NMR, DEPT, 2D (1)H-(1)H COSY, HSQC, HMBC and NOESY). Compounds were found to be the 3-O-rutinosides of quercetin, kaempferol and isorhamnetin, besides the flavonoid 5-hydroxy-3,7-dimethoxyflavone-4'-O-β-glucopyranoside. Most of the isolated extracts showed antimicrobial activity against the test microorganisms, where the crude flavonoid fraction was the most active, diameter of inhibition zones ranged between 15.5 and 28.5 mm against the tested bacterial strains, while reached 30 mm against the fungal Candida albicans. The minimal inhibitory concentrations varied from 0.04 to 0.32 mg/ml against all of the tested microorganisms in case of the crude flavonoid fraction. Quercetin-3-O-rutinoside showed superior activity over the remainder flavonoids. The Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis) were more susceptible than the Gram-negative (Pseudomonas aeruginosa and Salmonella enteritidis) and the yeast species were more susceptible than the filamentous fungi. The study recommend the use of such natural products as antimicrobial biorationals.

  8. Synthesis of 21,23-selenium- and tellurium-substituted 5-porphomethenes, 5,10-porphodimethenes, 5,15-porphodimethenes, and porphotrimethenes and their interactions with mercury.

    PubMed

    Ahmad, Sohail; Yadav, Kumar Karitkey; Bhattacharya, Soumee; Chauhan, Prashant; Chauhan, S M S

    2015-04-17

    The 3+1 condensation of symmetrical 16-Selena/telluratripyrranes with symmetrical selenophene-2,5-diols/tellurophene-2,5-diols in the presence of BF3-etheratre or BF3-methanol followed by oxidation with DDQ gave 5,10-porphodimethenes, whereas the process with unsymmetrical selenophene-2,5-diols/tellurophene-2,5-diols gave 5-porphomethenes. In addition, the reaction of unsymmetrical 16-Selena/telluratripyrranes with symmetrical selenophene-2,5-diols/tellurophene-2,5-diols gave the corresponding porphotrimethenes, whereas the process with unsymmetrical selenophene-2,5-diols/tellurophene-2,5-diols gave the 5,15-porphodimethenes. The structures of different products were characterized by IR, (1)H and (13)C NMR, (1)H-(1)H COSY, CHN analysis, and mass spectrometry. The binding of mercury with the calix[4]phyrins mentioned above had been observed in the decreasing order of porphodimethenes > porphomethenes > porphotrimethenes by UV-vis and (1)H NMR spectroscopy.

  9. Five new alkaloids from Coptidis Rhizoma-Euodiae Fructus couple and their cytotoxic activities against gastrointestinal cancer cells.

    PubMed

    Qian, Ping; Yang, Xiu-Wei

    2014-03-01

    A new indoloquinazoline alkaloid, 10-methoxywuchuyuamide I (1), three new benzylisoquinoline alkaloids, named as coptichic aldehyde (2), coptichine (3) and 13-carboxaldehyde-8-oxocoptisine (4), and a new isoindoline alkaloid, named as coptichinamide (5), together with two known alkaloids, wuchuyuamide I (6) and 8-oxocoptisine (7) were isolated from the Coptidis Rhizoma-Euodiae Fructus couple. Their chemical structures were determined by extensive spectroscopic analyses, including IR, UV, EI-MS, HRESI-MS, 1D and 2D NMR data ((1)H NMR, (13)C NMR, (1)H-(1)H COSY, HSQC and HMBC). Cytotoxicities of the isolated alkaloids against NCI-N87 and Caco-2 cell lines were evaluated. Four benzylisoquinoline alkaloids 2-4 and 7 showed inhibitory activities against NCI-N87 cell with IC50 values range from 8.92 to 35.98 μM. The alkaloid 3 was a new antiproliferation compound against NCI-N87 cells. The results provided valuable information for further investigation of alkaloid 3 as a chemopreventive agent.

  10. Identification of endogenous metabolites in human sperm cells using proton nuclear magnetic resonance ((1) H-NMR) spectroscopy and gas chromatography-mass spectrometry (GC-MS).

    PubMed

    Paiva, C; Amaral, A; Rodriguez, M; Canyellas, N; Correig, X; Ballescà, J L; Ramalho-Santos, J; Oliva, R

    2015-05-01

    The objective of this study was to contribute to the first comprehensive metabolomic characterization of the human sperm cell through the application of two untargeted platforms based on proton nuclear magnetic resonance ((1) H-NMR) spectroscopy and gas chromatography coupled to mass spectrometry (GC-MS). Using these two complementary strategies, we were able to identify a total of 69 metabolites, of which 42 were identified using NMR, 27 using GC-MS and 4 by both techniques. The identity of some of these metabolites was further confirmed by two-dimensional (1) H-(1) H homonuclear correlation spectroscopy (COSY) and (1) H-(13) C heteronuclear single-quantum correlation (HSQC) spectroscopy. Most of the metabolites identified are reported here for the first time in mature human spermatozoa. The relationship between the metabolites identified and the previously reported sperm proteome was also explored. Interestingly, overrepresented pathways included not only the metabolism of carbohydrates, but also of lipids and lipoproteins. Of note, a large number of the metabolites identified belonged to the amino acids, peptides and analogues super class. The identification of this initial set of metabolites represents an important first step to further study their function in male gamete physiology and to explore potential reasons for dysfunction in future studies. We also demonstrate that the application of NMR and MS provides complementary results, thus constituting a promising strategy towards the completion of the human sperm cell metabolome.

  11. Hyphenating Centrifugal Partition Chromatography with Nuclear Magnetic Resonance through Automated Solid Phase Extraction.

    PubMed

    Bisson, Jonathan; Brunel, Marion; Badoc, Alain; Da Costa, Grégory; Richard, Tristan; Mérillon, Jean-Michel; Waffo-Téguo, Pierre

    2016-10-18

    Centrifugal partition chromatography (CPC) and all countercurrent separation apparatus provide chemists with efficient ways to work with complex matrixes, especially in the domain of natural products. However, despite the great advances provided by these techniques, more efficient ways of analyzing the output flow would bring further enhancement. This study describe a hyphenated approach made by coupling NMR with CPC through a hybrid-indirect coupling made possible by using a solid phase extraction (SPE) apparatus intended for high-pressure liquid chromatography (HPLC)-NMR hyphenation. Some hardware changes were needed to adapt the incompatible flow-rates and a reverse-engineering approach that led to the specific software required to control the apparatus. 1D (1)HNMR and (1)H-(1)H correlation spectroscopy (COSY) spectra were acquired in reasonable time without the need for any solvent-suppression method thanks to the SPE nitrogen drying step. The reduced usage of expensive deuterated solvents from several hundreds of milliliters to the milliliter order is the major improvement of this approach compared to the previously published ones.

  12. Hyphenation of capillary HPLC to microcoil (1)H NMR spectroscopy for the determination of tocopherol homologues.

    PubMed

    Krucker, Manfred; Lienau, Annette; Putzbach, Karsten; Grynbaum, Marc David; Schuler, Paul; Albert, Klaus

    2004-05-01

    Highly selective reversed phases (C(30) phases) are self-packed in 250 microm inner diameter fused-silica capillaries and employed for capillary HPLC separation of shape-constrained natural compounds (tocopherol homologues, vitamin E). Miniaturized hyphenated systems such as capillary HPLC-ESI-MS (positive ionization mode) and, with special emphasis, continuous-flow capillary HPLC- NMR are used for structural determination of the separated compounds. Despite the small amount of sample available (1.33 microg of each tocopherol), the authors have been able to monitor the capillary HPLC separation under continuous-flow (1)H NMR conditions, thus allowing an immediate peak identification. Further structural assignment was carried out in the stopped-flow NMR mode as shown, for example, by a 2D (1)H,(1)H COSY NMR spectrum of alpha-tocopherol. We demonstrate in this paper the considerable potential of hyphenated capillary separations coupled to MS and NMR for the investigation of restricted amounts of sample.

  13. Use of NMR-Based Metabolomics To Chemically Characterize the Roasting Process of Chicory Root.

    PubMed

    Wei, Feifei; Furihata, Kazuo; Zhang, Mimin; Miyakawa, Takuya; Tanokura, Masaru

    2016-08-16

    Roasted chicory root (Cichorium intybus) has been widely accepted as the most important coffee substitute. In this study, a nuclear magnetic resonance (NMR)-based comprehensive analysis was performed to monitor the substantial changes in the composition of chicory root during the roasting process. A detailed signal assignment of dried raw and roasted chicory roots was carried out using (1)H, (13)C, (1)H-(1)H DQF-COSY, (1)H-(13)C edited-HSQC, (1)H-(13)C CT-HMBC, and (1)H-(13)C HSQC-TOCSY NMR spectra. On the basis of the signal assignments, 36 NMR-visible components were monitored simultaneously during roasting. Inulins, sucrose, and most of the amino acids were largely degraded during the roasting process, whereas monosaccharides decreased at the beginning and then increased until the dark roasting stage. Acetamide, 5-hydroxymethylfurfural, di-d-fructose dianhydride, and norfuraneol were newly formed during roasting. Furthermore, a principal component analysis score plot indicated that similar chemical composition profiles could be achieved by roasting the chicory root either at a higher firepower for a shorter time or at a lower firepower for a longer time.

  14. A new anthraquinone and eight constituents from Hedyotis caudatifolia Merr. et Metcalf: isolation, purification and structural identification.

    PubMed

    Luo, Peng; Su, Jiale; Zhu, Yilin; Wei, Jianhua; Wei, Wanxing; Pan, Weigao

    2016-10-01

    Hedyotis caudatifolia Merr. et Metcalf. (HC), a folk medicine in Yao nationalities areas in China, was used to investigate the chemical constituents. Through silica gel and Sephadex LH-20 column chromatography, nine compounds were isolated and purified. By physical and chemical properties, IR, MS (EI-MS, high resolution EI-MS), 1D NMR ((1)H NMR, (13)C NMR) and 2D NMR (HSQC, (1)H-(1)H COSY, HMBC), their structures were identified as β-sitosterol (1), stigmasterol (2), scopolin (3), 2-hydroxy-1,7,8-trimethoxyanthracene-9,10-dione (4), oleanolic acid (5), ursolic acid (6), methyl barbinervate (7), β-daucosterol (8) and p-Hydroxybenzoic acid (9). These compounds were isolated from HC for the first time, and 4 a new anthraquinone whose biological activities are worth to be investigated in future. These compounds may contribute to the HC's pharmacological effects on treating diseases, and may be used as candidates for control index in establishing the quality control standard of HC.

  15. Synthesis, characterization, computational calculation and biological studies of some 2,6-diaryl-1-(prop-2-yn-1-yl)piperidin-4-one oxime derivatives

    NASA Astrophysics Data System (ADS)

    Sundararajan, G.; Rajaraman, D.; Srinivasan, T.; Velmurugan, D.; Krishnasamy, K.

    2015-03-01

    A new series of 2,6-diaryl-1-(prop-2-yn-1-yl)piperidin-4-one oximes (17-24) were designed and synthesized from 2,6-diarylpiperidin-4-one oximes (9-16) with propargyl bromide. Unambiguous structural elucidation has been carried out by investigating IR, NMR (1H, 13C, 1H-1H COSY and HSQC), mass spectral techniques and theoretical (DFT) calculations. Further, crystal structure of compound 17 was evaluated by single crystal X-ray diffraction analysis. Single crystal X-ray structural analysis of compound 17 evidenced that the configuration about Cdbnd N double bond is syn to C-5 carbon (E-form). The existence of chair conformation was further confirmed by theoretical DFT calculation. All the synthesized compounds were screened for in vitro antimicrobial activity against a panel of selected bacterial and fungal strains using Ciprofloxacin and Ketoconazole as standards. The minimum inhibition concentration (MIC) results revealed that most of the 2,6-diaryl-1-(prop-2-yn-1-yl)piperidin-4-one oximes (17, 19, 20 and 23) exhibited better activity against the selected bacterial and fungal strains.

  16. Two novel bioactive glucosinolates from Broccoli (Brassica oleracea L. var. italica) florets.

    PubMed

    Survay, Nazneen Shaik; Kumar, Brajesh; Jang, Mi; Yoon, Do-Young; Jung, Yi-Sook; Yang, Deok-Chun; Park, Se Won

    2012-09-01

    Two novel glucosinolates along with one known glucosinolate were isolated from Broccoli (Brassica oleracea L. var. italica) florets. Their structures were established mainly by 1D ((1)H and (13)C NMR), 2D NMR ((1)H-(1)H COSY, DEPT 135°, HSQC and HMBC), and Tandem MS-MS spectrometric data as 2-mercaptomethyl sulfinyl glucosinolate [(Z)-4-(methylsulfinyl)-N-(sulfooxy)-2-((2'S,3'R,4'S,5'S,6'R)-3',4',5'-trihydroxy-6'(hydroxylmethyl)-2'-mercapto tetrahydro-2H-pyran-2-yl) butane amide] 1, (Z)-1-((2S,5S)-5-hydroxytetra-hydro-2H-pyran-2-ylthio)-2-(1H-indol-3-yl) ethylidene amino sulfate 2 and a known cinnamoyl [6'-O-trans-(4″-hydroxy cinnamoyl)4-(methylsulphinyl)butyl glucosinolate] 3. Compound 1 exhibited scavenging activity against DPPH with an inhibitory concentration IC(50) of 20 mM, whereas compound 3 was a weak antioxidant when compared to the standard quercetin (5 mM) as a positive control. Both the compounds showed a significant and similar antimicrobial activity against Staphylococcus aureus with an IC(50) of <625 μg/mL when compared to antibiotic duricef. Against Salmonella typhimurium the IC(50) of 1 and 3 was determined as <625 μg/mL and <1250 μg/mL, respectively, when compared to ampicillin (IC(50) ≤ 39 μg/mL) as a positive control.

  17. Hepatoprotective triterpene saponins from the roots of Glycyrrhiza inflata.

    PubMed

    Zheng, Yun-Feng; Wei, Juan-Hua; Fang, Shi-Qi; Tang, Yu-Ping; Cheng, Hai-Bo; Wang, Tian-Lin; Li, Cun-Yu; Peng, Guo-Ping

    2015-04-09

    Two novel oleanane-type triterpene saponins, licorice-saponin P2 (1) and licorice-saponin Q2 (3), together with nine known compounds 2, 4-11, have been isolated from the water extract of the roots of Glycyrrhiza inflata. The structures of these compounds were elucidated on the basis of spectroscopic analysis, including 2D-NMR experiments (1H-1H COSY, HSQC, HMBC and ROESY). In in vitro assays, compounds 2-4, 6 and 11 showed significant hepatoprotective activities by lowering the ALT and AST levels in primary rat hepatocytes injured by D-galactosamine (D-GalN). In addition, compounds 2-4, 6, 7 and 11 were found to inhibit the activity of PLA2 with IC50 values of 6.9 μM, 3.6 μM, 16.9 μM, 27.1 μM, 32.2 μM and 9.3 μM, respectively, which might be involved in the regulation of the hepatoprotective activities observed.

  18. A new flavonol glycoside from the medicinal halophyte Suaeda fruticosa.

    PubMed

    Oueslati, Samia; Ksouri, Riadh; Pichette, André; Lavoie, Serge; Girard-Lalancette, Karl; Mshvildadze, Vakhtang; Abdelly, Chedly; Legault, Jean

    2014-01-01

    A new flavonol glycoside, namely 3-(α-rhamnopyranosyl-(1 → 2)-[β-xylopyranosyl-(1 → 6)]-β-glucopyranosyloxy) isorhamnetin was reported from methanol extracts of aerial parts of Suaeda fruticosa for the first time. In this work, liquid chromatography coupled to atmospheric pressure chemical ionisation mass spectrometry, high-resolution mass spectrometry and nuclear magnetic resonance spectroscopy were used to identify this new compound. Structure was elucidated on the basis of extensive spectroscopic analysis, including HSQC, HMBC and (1)H-(1)H COSY. Antioxidant potentialities of a pure compound were evaluated. The estimation of antioxidant capacities using oxygen radical absorbance capacity (ORAC method) and a cell based-assay (WS1) indicated that this new flavonol exhibited the highest antioxidant activities with an ORAC value of 5.0 ± 0.3 μmol Trolox/μmol and inhibited the tBH-induced oxidation of 2',7'-dichlorofluorescin with an IC50 value of 4.9 ± 0.6 μM.

  19. A definitive analytical spectroscopic study of Indian yellow, an ancient pigment used for dating purposes.

    PubMed

    de Faria, Dalva L A; Edwards, Howell G M; Careaga, Valeria; Walt, Nicholas; Maier, Marta S

    2017-02-01

    The Raman spectrum of tartrazine has been mistakenly reported as being that of Indian yellow in the literature, which has serious consequences for the identification of this pigment in art works regarding their authentication. Unlike tartrazine, Indian yellow (a natural mixture of the magnesium and calcium salts of euxanthic acid) exhibits in its Raman spectrum a strong fluorescent background when visible excitation is used, however, excitation in the near infrared (1064nm) permitted the observation of the Raman bands from the raw pigment with the main features placed at 1346, 1368, 1425, 1441 and 1626cm(-1). Indian yellow identification was assured by (1)H and (13)C Nuclear Magnetic Resonance characterization and the complete assignment of the proton and carbon resonances was accomplished using heteronuclear single quantum correlation (HSQC), heteronuclear multiple bond correlation (HMBC), nuclear overhauser effect spectroscopy (NOESY) and (1)H-(1)H correlation spectroscopy (COSY). Scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and X-ray fluorescence (XRF) analyzes were also conducted on a genuine sample of this historical pigment.

  20. Isoorientin, a Selective Inhibitor of Cyclooxygenase-2 (COX-2) from the Tubers of Pueraria tuberosa.

    PubMed

    Sumalatha, Manne; Munikishore, Rachakunta; Rammohan, Aluru; Gunasekar, Duvvuru; Kumar, Kotha Anil; Reddy, Kakularam Kumar; Azad, Rajaram; Reddanna, Pallu; Bodo, Bernard

    2015-10-01

    Bioassay-guided fraction of the methanol extract of the roots of Pueraria tuberose DC yielded puerarin, an isoflavone C-glycoside (PT-1), isoorientin, a flavone C-glycoside (PT-2) and mangiferin, a xanthone C-glycoside (PT-3). The extracts and the isolated compounds were screened for potent anti-inflammatory components inhibiting the cyclooxygenases (COX-1 and COX-2) and 5-lipoxygenase (5-LOX), the target enzymes of inflammation, by employing spectroscopic/polorographic methods. Among these, isoorientin was found to be a potent inhibitor of COX-2with an IC50 value of 39 μM. Docking studies were carried out to understand the interactions of isorientin (PT-2) with COX-2.The structures of the isolates were determined by mass spectrometry and 2D-NMR techniques including HSQC, HMBC, NOESY and 1H-1H COSY experiments. Although isoorientin and mangiferin have been reported from several plant sources, this is the first report of their isolation from a Pueraria species.

  1. Isolation and structure elucidation of cytotoxic polyacetylenes and polyenes from Echinacea pallida.

    PubMed

    Pellati, Federica; Calò, Samuele; Benvenuti, Stefania; Adinolfi, Barbara; Nieri, Paola; Melegari, Michele

    2006-07-01

    Bioassay-guided fractionation of n-hexane extracts of Echinacea pallida (Asteraceae) roots led to the isolation and structure elucidation of two polyacetylenes (1, 3) and three polyenes (2, 4, 5). Two are known hydroxylated compounds, namely 8-hydroxy-pentadeca-(9E)-ene-11,13-diyn-2-one (1) and 8-hydroxy-pentadeca-(9E,13Z)-dien-11-yn-2-one (2). Two dicarbonylic constituents, namely pentadeca-(9E)-ene-11,13-diyne-2,8-dione (3) and pentadeca-(9E,13Z)-dien-11-yne-2,8-dione (4), were isolated and characterized for the first time. Furthermore, the structure elucidation of pentadeca-(8Z,13Z)-dien-11-yn-2-one (5) is described. The structure of the compounds isolated was determined on the basis of UV, IR, NMR (including 1D and 2D NMR experiments, such as 1H-1H gCOSY, gHSQC-DEPT, gHMBC, gNOESY) and MS spectroscopic data. The cytotoxic activity of the isolated constituents against MIA PaCa-2 human pancreatic adenocarcinoma cells was evaluated in the concentration range 1-100 microg/ml. Results show that the hydroxylated compounds (1, 2) have low cytotoxicity, while the more hydrophobic polyacetylenes (3) and polyenes (4, 5) displayed moderate activity.

  2. Synthesis and characterization of chitosan alkyl urea.

    PubMed

    Wang, Jing; Jiang, Ji-Zhou; Chen, Wei; Bai, Zheng-Wu

    2016-07-10

    Chitosan is a versatile material employed for various purposes in many fields including the development of chiral stationary phases for enantioseparation. Chitosan alkyl urea is a kind of intermediate used to prepare enantioseparation materials. In order to synthesize the intermediates, in the present work, a new way to prepare chitosan alkyl urea has been established: chitosan was first reacted with methyl chloroformate yielding N-methoxyformylated chitosan, which was then converted to chitosan alkyl urea through amine-ester exchange reaction. With a large excess of methyl chloroformate and primary amine of low stereohindrance, the amino group in chitosan could be almost completely converted to ureido group. The as-prepared chitosan alkyl urea derivatives were characterized by IR, (1)H NMR, (13)C NMR,(1)H-(1)H COSY and (1)H-(13)C HSQC NMR spectra. The chemical shifts of hydrogen and carbon atoms of glucose unit were assigned. It was found that the degree of substitution was obviously lower if cyclopropyl amine, aniline, tert-butyl amine and diethyl amine were used as reactants for the amine-ester exchange reaction. The reason was explained with the aid of theoretical calculations.

  3. Odisolane, a Novel Oxolane Derivative, and Antiangiogenic Constituents from the Fruits of Mulberry (Morus alba L.).

    PubMed

    Lee, Seoung Rak; Park, Jun Yeon; Yu, Jae Sik; Lee, Sung Ok; Ryu, Ja-Young; Choi, Sang-Zin; Kang, Ki Sung; Yamabe, Noriko; Kim, Ki Hyun

    2016-05-18

    Mulberry, the fruit of Morus alba L., is known as an edible fruit and commonly used in Chinese medicines as a warming agent and as a sedative, tonic, laxative, odontalgic, expectorant, anthelmintic, and emetic. Systemic investigation of the chemical constituents of M. alba fruits led to the identification of a novel oxolane derivative, (R*)-2-((2S*,3R*)-tetrahydro-2-hydroxy-2-methylfuran-3-yl)propanoic acid (1), namely, odisolane, along with five known heterocyclic compounds (2-6). The structure of the new compound was elucidated on the basis of HR-MS, 1D and 2D NMR ((1)H-(1)H COSY, HSQC, HMBC, and NOESY) data analysis. Compound 1 has a novel skeleton that consists of 8 carbon units with an oxolane ring, which until now has never been identified in natural products. The isolated compounds were subjected to several activity tests to verify their biological function. Among them, compounds 1, 3, and 5 significantly inhibited cord formation in HUVECs. The action mechanism of compound 3, which had the strongest antiangiogenic activity, was mediated by decreasing VEGF, p-Akt, and p-ERK protein expression. These results suggest that compounds isolated from M. alba fruits might be beneficial in antiangiogenesis therapy for cancer treatment.

  4. Salicin derivatives from Salix glandulosa and their biological activities.

    PubMed

    Kim, Chung Sub; Subedi, Lalita; Park, Kyoung Jin; Kim, Sun Yeou; Choi, Sang Un; Kim, Ki Hyun; Lee, Kang Ro

    2015-10-01

    Two new salicin derivatives, saliglandin (1) and 6'-O-(Z)-p-coumaroylsalicin (2), along with fourteen known analogues (3-16) were isolated from the twigs of Salix glandulosa Seemen. The structures of 1-16 were characterized by the use of NMR methods ((1)H and (13)C NMR, (1)H-(1)H COSY, HSQC and HMBC), chemical hydrolysis, and GC/MS. The full NMR data assignment of the known compounds 6, 13, and 14 are reported for the first time. Isolated compounds were evaluated for their nitric oxide (NO) inhibitory efficacy in lipopolysaccharide (LPS)-activated microglial cell (BV-2). Compounds 2, 5, 8-16 significantly inhibited NO production, compound 11 being the most efficacious (IC50 13.57 μM) respectively. Moreover, compound 16 dramatically increased the nerve growth factor (NGF) production (165.24 ± 11.1%) in C6 glioma cells. Taken together, these results revealed that salicin derivatives from Salix glandulosa might have potent effect as anti-neuroinflammatory agents.

  5. Biotransformation of the antiviral drugs acyclovir and penciclovir in activated sludge treatment.

    PubMed

    Prasse, Carsten; Wagner, Manfred; Schulz, Ralf; Ternes, Thomas A

    2011-04-01

    The biotransformation of the two antiviral drugs, acyclovir (ACV) and penciclovir (PCV), was investigated in contact with activated sludge. Biodegradation kinetics were determined, and transformation products (TPs) were identified using Hybrid Linear Ion Trap- FT Mass Spectrometry (LTQ Orbitrap Velos) and 1D (1H NMR, 13C NMR) and 2D (1H,1H-COSY, 1H-(13)C-HSQC) NMR Spectroscopy. ACV and PCV rapidly dissipated in the activated sludge batch systems with half-lives of 5.3 and 3.4 h and first-order rate constants in relation to the amount of suspended solids (SS) of 4.9±0.1 L gss(-1) d(-1) and 7.6±0.3 L gss(-1) d(-1), respectively. For ACV only a single TP was found, whereas eight TPs were identified for PCV. Structural elucidation of TPs exhibited that transformation only took place at the side chain leaving the guanine moiety unaltered. The oxidation of the primary hydroxyl group in ACV resulted in the formation of carboxy-acyclovir (Carboxy-ACV). For PCV, transformation was more diverse with several enzymatic reactions taking place such as the oxidation of terminal hydroxyl groups and β-oxidation followed by acetate cleavage. Analysis of different environmental samples revealed the presence of Carboxy-ACV in surface and drinking water with concentrations up to 3200 ng L(-1) and 40 ng L(-1), respectively.

  6. The structure and immunoreactivity of exopolysaccharide isolated from Lactobacillus johnsonii strain 151.

    PubMed

    Górska-Frączek, Sabina; Sandström, Corine; Kenne, Lennart; Paściak, Mariola; Brzozowska, Ewa; Strus, Magdalena; Heczko, Piotr; Gamian, Andrzej

    2013-08-30

    The exopolysaccharide (EPS) structure from Lactobacillus johnsonii strain 151 isolated from the intestinal tract of mice was investigated. Sugar and methylation analyses together with (1)H and (13)C NMR spectroscopy, including two-dimensional (1)H,(1)H COSY, TOCSY, NOESY, and (1)H,(13)C HSQC, HMBC experiments, revealed that the repeating unit of the EPS is the linear pentasaccharide: →6)-α-d-Galp-(1→6)-α-d-Glcp-(1→3)-β-d-Galf-(1→3)-α-d-Glcp-(1→2)-β-d-Galf-(1→ The immunoreactivity of two structurally different exopolysaccharides isolated from L. johnsonii, 151 and 142 (Carbohydr. Res. 2010, 345, 108-114), was compared. Both EPSs differed in their reactivity with antisera. EPS from L. johnsonii 151 reacted with anti-Lactobacillus polyclonal sera against cells of five different strains, while EPS from L. johnsonii 142 was found to react only with its own antiserum. The broader specificity and higher reactivity of EPS from 151 strain than EPS from 142 strain were also observed with human sera. The physiological antibodies recognizing polysaccharide antigens were present in both adults and umbilical cord blood sera. A highly specific EPS 142 bearing strain was isolated from experimentally induced inflammatory bowel disease (IBD) mice, while a strain with EPS 151 isolated from the intestinal tract of healthy mice is characterized by a broad immune reactivity common structure.

  7. A new indole glycoside from the seeds of Raphanus sativus.

    PubMed

    Jin, Hong-Guang; Ko, Hae Ju; Chowdhury, Md Anisuzzaman; Lee, Dong-Sung; Woo, Eun-Rhan

    2016-06-01

    A new indole glycoside, β-D-glucopyranosyl 2-(methylthio)-1H-indole-3-carboxylate, named raphanuside A (1), as well as eight known compounds, β-D-fructofuranosyl-(2 → 1)-(6-O-sinapoyl)-α-D-glucopyranoside (2), (3-O-sinapoyl)-β-D-fructofuranosyl-(2 → 1)-α-D-glucopyranoside (3), (3-O-sinapoyl)-β-D-fructofuranosyl-(2 → 1)-(6-O-sinapoyl)-α-D-glucopyranoside (4), (3,4-O-disinapoyl)-β-D-fructofuranosyl-(2 → 1)-(6-O-sinapoyl)-α-D-glucopyranoside (5), isorhamnetin 3,4'-di-O-β-D-glucoside (6), isorhamnetin 3-O-β-D-glucoside-7-O-α-L-rhamnoside (7), isorhamnetin 3-O-β-D-glucoside (8) and 3'-O-methyl-(-)-epicatechin 7-O-β-D-glucoside (9) were isolated from the seeds of Raphanus sativus. Furthermore, compounds 1-3 and 6-9, were isolated from this plant for the first time. The structures of compounds 1-9 were identified using 1D and 2D NMR, including (1)H-(1)H COSY, HSQC, HMBC and NOESY spectroscopic analyses. The inhibitory activity of these isolated compounds against interleukin-6 (IL-6) production in TNF-α stimulated MG-63 cells was also examined.

  8. Isolation of brassicasterol, its synthetic prodrug-crystal structure, stereochemistry and theoretical studies

    NASA Astrophysics Data System (ADS)

    Sethi, Arun; Prakash, Rohit; Srivastava, Sangeeta; Amandeep; Bishnoi, Abha; Singh, Ranvijay Pratap

    2014-07-01

    In the present study brassicasterol (1), was isolated from the chloroform extract of the flowers of Allamanda violacea and identified with the help of different spectroscopic techniques like 1H, 13C, 2D NMR (1H-1H COSY), IR, UV and mass spectrometry. A novel prodrug was synthesized by carrying out esterification of brassicasterol (1) with the well known drug naproxen using Steglich esterification to give 3β-(2-(6-methoxynaphthalene-2yl) propionoxy) 24 methyl cholest-5, 22-dien (2). Compounds 2 was subjected to single crystal X-ray diffraction technique and crystallized out in monoclinic form having P21 space group and stabilized by CH-π interactions. Structure and stereochemistry of compound 2 was established with the help of modern spectroscopic techniques like 1H NMR, IR, UV, mass spectrometry as well as with single crystal X-ray diffraction. Molecular geometry and vibrational frequencies of compounds 1 and 2 were calculated by density functional method (DFT/B3LYP) using 6-31G (d, p) basis set, bond parameters and IR frequencies were correlated with the experimental data. 1H and 13C chemical shifts of compound 1 and 1H chemical shifts of compound 2 were calculated with GIAO method and correlated with experimental data. Hyperconjugative interactions were studied with the help of natural bond order analysis (NBO). Electronic properties of both the compounds such as HOMO-LUMO energies were measured with the help of time dependent DFT method.

  9. Fischer indolisation of N-(α-ketoacyl)anthranilic acids into 2-(indol-2-carboxamido)benzoic acids and 2-indolyl-3,1-benzoxazin-4-ones and their NMR study.

    PubMed

    Proisl, Karel; Kafka, Stanislav; Urankar, Damijana; Gazvoda, Martin; Kimmel, Roman; Košmrlj, Janez

    2014-12-21

    N-(α-ketoacyl)anthranilic acids reacted with phenylhydrazinium chloride in boiling acetic acid to afford 2-(indol-2-carboxamido)benzoic acids in good to excellent yields and 2-indolyl-3,1-benzoxazin-4-ones as by-products. The formation of the latter products could easily be suppressed by a hydrolytic workup. Alternatively, by increasing the reaction temperature and/or time, 2-indolyl-3,1-benzoxazin-4-ones can be obtained exclusively. Optimisations of the reaction conditions as well as the scope and the course of the transformations were investigated. The products were characterized by (1)H, (13)C and (15)N NMR spectroscopy. The corresponding resonances were assigned on the basis of the standard 1D and gradient selected 2D NMR experiments ((1)H-(1)H gs-COSY, (1)H-(13)C gs-HSQC, (1)H-(13)C gs-HMBC) with (1)H-(15)N gs-HMBC as a practical tool to determine (15)N NMR chemical shifts at the natural abundance level of (15)N isotope.

  10. The Effect of Substituent, Degree of Acetylation and Positioning of the Cationic Charge on the Antibacterial Activity of Quaternary Chitosan Derivatives

    PubMed Central

    Sahariah, Priyanka; Gaware, Vivek S.; Lieder, Ramona; Jónsdóttir, Sigríður; Hjálmarsdóttir, Martha Á.; Sigurjonsson, Olafur E.; Másson, Már

    2014-01-01

    A series of water-soluble cationic chitosan derivatives were prepared by chemoselective functionalization at the amino group of five different parent chitosans having varying degrees of acetylation and molecular weight. The quaternary moieties were introduced at different alkyl spacer lengths from the polymer backbone (C-0, C-2 and C-6) with the aid of 3,6-di-O-tert-butyldimethylsilyl protection of the chitosan backbone, thus allowing full (100%) substitution of the free amino groups. All of the derivatives were characterized using 1H-NMR, 1H-1H COSY and FT-IR spectroscopy, while molecular weight was determined by GPC. Antibacterial activity was investigated against Gram positive S. aureus and Gram negative E. coli. The relationship between structure and activity/toxicity was defined, considering the effect of the cationic group’s structure and its distance from the polymer backbone, as well as the degree of acetylation within a molecular weight range of 7–23 kDa for the final compounds. The N,N,N-trimethyl chitosan with 100% quaternization showed the highest antibacterial activity with moderate cytotoxicity, while increasing the spacer length reduced the activity. Trimethylammoniumyl quaternary ammonium moieties contributed more to activity than 1-pyridiniumyl moieties. In general, no trend in the antibacterial activity of the compounds with increasing molecular weight or degree of acetylation up to 34% was observed. PMID:25196937

  11. Glycosylation of aromatic amines I: Characterization of reaction products and kinetic scheme.

    PubMed

    Gokhale, Madhushree Y; Kearney, William R; Kirsch, Lee E

    2009-01-01

    The reactions of aliphatic and aromatic amines with reducing sugars are important in both drug stability and synthesis. The formation of glycosylamines in solution, the first step in the Maillard reaction, does not typically cause browning but results in decreased potency and is hence significant from the aspect of drug instability. The purpose of this research was to present (1) unreported ionic equilibria of model reactant (kynurenine), (2) the analytical methods used to characterize and measure reaction products, (3) the kinetic scheme used to measure reaction rates and (4) relevant properties of various reducing sugars that impact the reaction rate in solution. The methods used to identify the reversible formation of two products from the reaction of kynurenine and monosaccharides included LC mass spectrometry, UV spectroscopy, and 1-D and 2-D (1)H-(1)H COSY NMR spectroscopy. Kinetics was studied using a stability-indicating HPLC method. The results indicated the formation of alpha and beta glycosylamines by a pseudo first-order reversible reaction scheme in the pH range of 1-6. The forward reaction was a function of initial glucose concentration but not the reverse reaction. It was concluded that the reaction kinetics and equilibrium concentrations of the glycosylamines were pH-dependent and also a function of the acyclic content of the reacting glucose isomer.

  12. Purification and identification of two antifungal cyclic dipeptides from Bacillus cereus subsp. thuringiensis associated with a rhabditid entomopathogenic nematode especially against Fusarium oxysporum.

    PubMed

    Kumar, S Nishanth; Nambisan, Bala; Mohandas, C

    2014-04-01

    The cell-free culture filtrate of Bacillus cereus subsp. thuringiensis associated with an entomopathogenic nematode (EPN), Rhabditis (Oscheius) sp., exhibited strong antimicrobial activity. The ethyl acetate extract of the bacterial culture filtrate was purified by silica gel column chromatography to obtain two cyclic dipeptides (CDPs). The structure and absolute stereochemistry of this compound were determined based on extensive spectroscopic analyses (FABMS, (1)H NMR, (13)C NMR, (1)H-(1)H COSY, (1)H-(13)C HMBC) and Marfey's method. The compounds were identified as cyclo(D-Pro-L-Met) and cyclo(D-Pro-D-Tyr). CDPs showed significantly higher activity than the standard fungicide bavistin against agriculturally important fungi, viz., Fusarium oxysporum, Rhizoctonia solani and Penicillium expansum. The highest activity of 2 µg/ml by cyclo(D-Pro-D-Tyr) was recorded against F. oxysporum, a plant pathogen responsible for causing fusarium wilt followed by R. solani, a pathogen that causes root rot and P. expansum. To our knowledge, this is the first report on the isolation of these compounds from Rhabditis EPN bacterial strain Bacillus cereus subsp. thuringiensis.

  13. Preparative isolation and purification of cuminaldehyde and p-menta-1,4-dien-7-al from the essential oil of Cuminum cyminum L. by high-speed counter-current chromatography.

    PubMed

    Chen, Qinqin; Hu, Xuefang; Li, Jingming; Liu, Ping; Yang, Yang; Ni, Yuanying

    2011-03-09

    High-speed counter-current chromatography (HSCCC) technique in semi-preparative scale was successfully used in isolation and purification of cuminaldehyde and p-menta-1,4-dien-7-al from the essential oil of Cuminum cyminum L. by using a two-phase solvent system composed of n-hexane-methanol-water (5:4:1, v/v/v). The targeted compounds were isolated, collected, purified by HSCCC in the head-tail mode, and then analyzed by gas chromatography (GC). A total of 12.72 ± 0.22 mg of cuminaldehyde and 10.61 ± 0.27 mg of p-menta-1,4-dien-7-al were obtained from 50 mg of the essential oil of C. cyminum L. in less than 6 h, with purities of 95.42% and 97.21%, respectively. In addition to GC-EI/MS, the identity of the cuminaldehyde was further confirmed with the retention time using the method of standard addition, while, the structural identification of p-menta-1,4-dien-7-al was performed with GC-EI/MS, (1)H NMR and (1)H-(1)H COSY.

  14. Amaryllidaceae alkaloids with new framework types from Zephyranthes candida as potent acetylcholinesterase inhibitors.

    PubMed

    Zhan, Guanqun; Liu, Junjun; Zhou, Junfei; Sun, Bin; Aisa, Haji Akber; Yao, Guangmin

    2017-02-15

    Three new Amaryllidaceae alkaloids, named zephycandidines I-III (1-3), were isolated from Zephyranthes candida. The structures of 1-3 were elucidated by spectroscopic analyses including HRESIMS, (1)H NMR, (13)C NMR, DEPT, HSQC, (1)H-(1)H COSY, HMBC, ROESY, and electronic circular dichroism (ECD), as well as ECD calculation. The absolute configuration of 1 was finally established by single crystal X-ray diffraction using Cu Kα radiation. Zephycandidines I (1) and III (3) with new framework types represent the first example of 7-phenyl-hexahydroindole and 5,2'-dimethyl-biphenyl-2-ylamine alkaloids, respectively, and their plausible biosynthetic pathway are proposed. Zephycandidine II (2) is the first C3a-phenyl-hexahydroindole type alkaloid isolated from the genus of Zephyranthes. These new alkaloids 1-3 were evaluated for their acetylcholinesterase (AChE) inhibitory activities, and 3 showed potent AChE inhibitory activity with an IC50 value of 8.82 μM, suggesting that the framework of 5,2'-dimethyl-biphenyl-2-ylamine in 3 may be a potential group for the AChE inhibitory activity. The docking studies of 1-3 and galanthamine with AChE revealed that interactions with W286 and Y337 are necessary for the AChE inhibitory activity.

  15. The effect of substituent, degree of acetylation and positioning of the cationic charge on the antibacterial activity of quaternary chitosan derivatives.

    PubMed

    Sahariah, Priyanka; Gaware, Vivek S; Lieder, Ramona; Jónsdóttir, Sigríður; Hjálmarsdóttir, Martha Á; Sigurjonsson, Olafur E; Másson, Már

    2014-08-21

    A series of water-soluble cationic chitosan derivatives were prepared by chemoselective functionalization at the amino group of five different parent chitosans having varying degrees of acetylation and molecular weight. The quaternary moieties were introduced at different alkyl spacer lengths from the polymer backbone (C-0, C-2 and C-6) with the aid of 3,6-di-O-tert-butyldimethylsilyl protection of the chitosan backbone, thus allowing full (100%) substitution of the free amino groups. All of the derivatives were characterized using 1H-NMR, 1H-1H COSY and FT-IR spectroscopy, while molecular weight was determined by GPC. Antibacterial activity was investigated against Gram positive S. aureus and Gram negative E. coli. The relationship between structure and activity/toxicity was defined, considering the effect of the cationic group's structure and its distance from the polymer backbone, as well as the degree of acetylation within a molecular weight range of 7-23 kDa for the final compounds. The N,N,N-trimethyl chitosan with 100% quaternization showed the highest antibacterial activity with moderate cytotoxicity, while increasing the spacer length reduced the activity. Trimethylammoniumyl quaternary ammonium moieties contributed more to activity than 1-pyridiniumyl moieties. In general, no trend in the antibacterial activity of the compounds with increasing molecular weight or degree of acetylation up to 34% was observed.

  16. Ruthenium(II) bipyridine complexes bearing new keto-enol azoimine ligands: Synthesis, structure, electrochemistry and DFT calculations

    NASA Astrophysics Data System (ADS)

    Al-Noaimi, Mousa; Awwadi, Firas F.; Mansi, Ahmad; Abdel-Rahman, Obadah S.; Hammoudeh, Ayman; Warad, Ismail

    2015-01-01

    The novel azoimine ligand, Phsbnd NHsbnd Ndbnd C(COCH3)sbnd NHPh(Ctbnd CH) (H2L), was synthesized and its molecular structure was determined by X-ray crystallography. Catalytic hydration of the terminal acetylene of H2L in the presence of RuCl3·3H2O in ethanol at reflux temperature yielded a ketone (L1 = Phsbnd Ndbnd Nsbnd C(COCH3)dbnd Nsbnd Ph(COCH3) and an enol (L2 = Phsbnd Ndbnd Nsbnd C(COCH3)dbnd Nsbnd PhC(OH)dbnd CH2) by Markovnikov addition of water. Two mixed-ligand ruthenium complexes having general formula, trans-[Ru(bpy)(Y)Cl2] (1-2) (where Y = L1 (1) and Y = L2 (2), bpy is 2.2‧-bipyrdine) were achieved by the stepwise addition of equimolar amounts of (H2L) and bpy ligands to RuCl3·3H2O in absolute ethanol. Theses complexes were characterized by elemental analyses and spectroscopic (IR, UV-Vis, and NMR (1D 1H NMR, 13C NMR, (DEPT-135), (DEPT-90), 2D 1H-1H and 13C-1H correlation (HMQC) spectroscopy)). The two complexes exhibit a quasi-reversible one electron Ru(II)/Ru(III) oxidation couple at 604 mV vs. ferrocene/ferrocenium (Cp2Fe0/+) couple along with one electron ligand reduction at -1010 mV. The crystal structure of complex 1 showed that the bidentate ligand L1 coordinates to Ru(II) by the azo- and imine-nitrogen donor atoms. The complex adopts a distorted trans octahedral coordination geometry of chloride ligands. The electronic spectra of 1 and 1+ in dichloromethane have been modeled by time-dependent density functional theory (TD-DFT).

  17. Synthesis, spectroscopic characterization, photochemical and photophysical properties and biological activities of ruthenium complexes with mono- and bi-dentate histamine ligand.

    PubMed

    Cardoso, Carolina R; de Aguiar, Inara; Camilo, Mariana R; Lima, Márcia V S; Ito, Amando S; Baptista, Maurício S; Pavani, Christiane; Venâncio, Tiago; Carlos, Rose M

    2012-06-14

    The monodentate cis-[Ru(phen)(2)(hist)(2)](2+)1R and the bidentate cis-[Ru(phen)(2)(hist)](2+)2A complexes were prepared and characterized using spectroscopic ((1)H, ((1)H-(1)H)COSY and ((1)H-(13)C)HSQC NMR, UV-vis, luminescence) techniques. The complexes presented absorption and emission in the visible region, as well as a tri-exponential emission decay. The complexes are soluble in aqueous and non-aqueous solution with solubility in a buffer solution of pH 7.4 of 1.14 × 10(-3) mol L(-1) for (1R + 2A) and 6.43 × 10(-4) mol L(-1) for 2A and lipophilicity measured in an aqueous-octanol solution of -1.14 and -0.96, respectively. Photolysis in the visible region in CH(3)CN converted the starting complexes into cis-[Ru(phen)(2)(CH(3)CN)(2)](2+). Histamine photorelease was also observed in pure water and in the presence of BSA (1.0 × 10(-6) mol L(-1)). The bidentate coordination of the histamine to the ruthenium center in relation to the monodentate coordination increased the photosubstitution quantum yield by a factor of 3. Pharmacological studies showed that the complexes present a moderate inhibition of AChE with an IC(50) of 21 μmol L(-1) (referred to risvagtini, IC(50) 181 μmol L(-1) and galantamine IC(50) 0.006 μmol L(-1)) with no appreciable cytotoxicity toward to the HeLa cells (50% cell viability at 925 μmol L(-1)). Cell uptake of the complexes into HeLa cells was detected by fluorescence confocal microscopy. Overall, the observation of a luminescent complex that penetrates the cell wall and has low cytotoxicity, but is reactive photochemically, releasing histamine when irradiated with visible light, are interesting features for application of these complexes as phototherapeutic agents.

  18. Molecular, spectroscopic and thermal studies on catechol, 4,5-dibromocatechol, resorcinol, hydroquinone and 4-4‧-dihydroxybiphenyl derivatives armed with benzothiazole moieties

    NASA Astrophysics Data System (ADS)

    Alshargabi, Arwa; Yeap, Guan-Yeow; Mahmood, Wan Ahmad Kamil; Samikannu, Rakesh

    2013-05-01

    A new series of catechol, 4,5-dibromocatechol, resorcinol, hydroquinone and 4-4'-dihydroxybiphenyl derivatives possessing two benzothiazole moieties at respective positions of 1,2, 1,3, 1,4 and/or 4,4' has successfully been synthesized. The molecular structures were fully elucidated by spectroscopic techniques (1H NMR, 13C NMR and two dimensional COSY, HMBC, HMQC, DEPT-135 and DEPT-90). The connectivity study between the cause of using different core systems in the target compounds and the anisotropic behavior as inferred from phase transition temperature and relevant morphology studies has led to some unique features arising from this series. Compounds with ortho substituent exhibit enantiotropic N and SmA phases. The analogues containing resorcinol and 4,4'-disubstituentbiphenyl show enanotiotropic nematic behavior while the hydroquinone derivative induces the formation of monotropic nematogen. An extensive study to further substantiate the relationship between the stability of the nematic phase and associated transition temperatures due to different core systems is also reported.

  19. Physicochemical characterization and toxicological evaluation of plant-based anionic polymers and their nanoparticulated system for ocular delivery.

    PubMed

    Pathak, Deepa; Kumar, Prashant; Kuppusamy, Gowthamarajan; Gupta, Ankur; Kamble, Bhagyashree; Wadhwani, Ashish

    2014-12-01

    The water-soluble fractions of mucilages and gum from the seeds of fenugreek, isphagula and mango bark exudate were isolated, purified and characterized using X-ray diffraction (XRD) spectrometry, Fourier transform infrared spectroscopy (FT-IR), maldi/GC-MS, elemental analysis, 1D ((1)H and (13)C) and 2D (HMQC, COSY) nuclear magnetic resonance spectroscopy (NMR). The fenugreek mucilage was identified to be a galactomannan chain consisting of 4 units of galactose attached to the backbone of 6 mannose units in 1:1.5 ratio. The isphagula mucilage was identified to be an arabinoxylan polysaccharide chain consisting of 4 units of arabinofuranose attached to the backbone of 9 xylopyrannose units in 1:3 ratio. The mango gum showed the presence of amylose, α-arabinofuranosyl and β-galactopyranosyl, respectively. The characterized mucilages and gum were individually formulated into nanoparticulate system using their complementarily charged polymer chitosan. The particles were observed to be spherical in shape in the range of 61.5-90 nm having zetapotential between 31 and 34 mV and PDI of 0.097-0.241. The prepared nanoparticles were observed to be nonirritant and nontoxic in vitro and in vivo upto 2000 μg/ml. Therefore, these mucilages and gum can be the alternatives of anionic polymers for the ocular drug delivery system.

  20. Structure of the O-specific polysaccharide of Proteus vulgaris O4 containing a new component of bacterial polysaccharides, 4,6-dideoxy-4.

    PubMed

    Perepelov, A V; Babicka, D; Senchenkova, S N; Shashkov, A S; Moll, H; Rozalski, A; Zähringer, U; Knirel, Y A

    2001-03-22

    A high-molecular-mass O-specific polysaccharide was obtained by mild acid degradation of Proteus vulgaris O4 lipopolysaccharide followed by GPC. The polysaccharide was studied by chemical methods along with 1H and 13C NMR spectroscopy, including two-dimensional COSY, TOCSY, NOESY, H-detected 1H,13C HMQC, and 1H,13C HMBC experiments. Solvolysis of the polysaccharide with trifluoromethanesulfonic (triflic) acid resulted in a GlcpA-(1 --> 3)-GlcNAc disaccharide and a novel amino sugar derivative, 4,6-dideoxy-4-[N-[(R)-3-hydroxybutyryl]-L-alanyl]amino-D-glucose [Qui4N(HbAla)]. On the basis of the data obtained, the following structure of the tetrasaccharide repeating unit of the O-specific polysaccharide was established: --> 4)-beta-D-GlcpA-(1 --> 3)-beta-D-GlcpNAc-(1 --> 2)-beta-D-Quip4N(HbAla)-(1 --> 3)-alpha-D-Galp-(1 -->. This structure is unique among the O-specific polysaccharides, which is in accordance with classification of the strain studied in a separate Proteus serogroup.

  1. Cu(I) complexes bearing the new sterically demanding and coordination flexible tris(3-phenyl-1-pyrazolyl)methanesulfonate ligand and the water-soluble phosphine 1,3,5-triaza-7-phosphaadamantane or related ligands.

    PubMed

    Wanke, Riccardo; Smoleński, Piotr; da Silva, M Fátima C Guedes; Martins, Luísa M D R S; Pombeiro, Armando J L

    2008-11-03

    The new sterically hindered scorpionate tris(3-phenylpyrazolyl)methanesulfonate (Tpms(Ph))(-) has been synthesized and its coordination behavior toward a Cu(I) center, in the presence of 1,3,5-triaza-7-phosphaadamantane (PTA), N-methyl-1,3,5-triaza-7-phosphaadamantane tetraphenylborate ((mPTA)[BPh4]) or hexamethylenetetramine (HMT) has been studied. The reaction between Li(Tpms(Ph)) (1) and [Cu(MeCN)4][PF6] yields [Cu(Tpms(Ph))(MeCN)] (2) which, upon further acetonitrile displacement on reaction with PTA, HMT, or (mPTA)[BPh4], gives the corresponding complexes [Cu(Tpms(Ph))(PTA)] (3), [Cu(Tpms(Ph))(HMT)] (4), and [Cu(Tpms(Ph))(mPTA)][PF6] (5). All the compounds have been characterized by (1)H, (31)P, (13)C, COSY or HMQC-NMR, IR, elemental analysis, and single crystal X-ray diffraction. In the complexes (3) and (5), which bear a phosphine ligand (i.e., PTA and mPTA, respectively), the new scorpionate ligand shows the typical N, N, N-coordination mode, whereas in (2) and (4), bearing a N-donor ligand (i.e., MeCN and HMT, respectively), it binds the metal via the N,N,O chelating mode, involving the sulfonate moiety.

  2. Synthesis and characterization of N,N'-bis[4-[1-(2-hidroxyethoxy)]salicylidine]-phenyldiamine-nickel(II)] complex

    NASA Astrophysics Data System (ADS)

    Shamsuddin, Roshatiara binti; Karim, Nurul Huda Abd

    2016-11-01

    N,N'-bis[4-[1-(2-hidroxyethoxy)]salicylidine]-phenyldiamine-nickel(II) complex has been synthesized by treating N,N'-bis-4-(hydroxysalicylidene)-phenylenediamine-nickel(II) complex with 2-chloroethanol and nickel(II) acetate tetrahydrate in ethanol solvent. The resulting complex formed was characterized using standard spectroscopic and structural techniques which includes 1H, 13C, COSY and HMQC NMR spectroscopy, FTIR spectroscopy and ESI-MS spectrometry. The 1H NMR spectrum displayed all the expected signals with right integration and multiplicity. The formation of Schiff base can be seen at 8.54 ppm for the formation of diimine and the disappearance of aldehyde peak at 9.88 ppm corresponding to the starting material confirms the full conversion. The presence of resonance peak at 3.76 ppm and 4.00 ppm corresponding to the ethyl group of the hydroxyl side chain also confirm the formation of the complex. The FTIR spectrum of the complex confirmed the expected C=N band at 1577 cm-1 and C-H for sp3 stretching band at 2878 cm-1. The formation of the new complex was also confirmed by ESI(+)-MS spectrometry, which showed the molecular peak with adduct ions at [M+K]+=531 a.m.u and [M+Na]+=515 a.m.u.

  3. Nine phenylethanoid glycosides from Magnolia officinalis var. biloba fruits and their protective effects against free radical-induced oxidative damage

    PubMed Central

    Ge, Lanlan; Zhang, Wenhui; Zhou, Gao; Ma, Bingxin; Mo, Qigui; Chen, Yuxin; Wang, Youwei

    2017-01-01

    To systematically study the chemical constituents in Magnolia officinalis var. biloba fruits, nine phenylethanoid glycosides were isolated by solvent extraction, silica gel, and preparative high-performance liquid chromatography (HPLC). Their structures were elucidated by 1D and 2D NMR analyses, including COSY, HMQC and HMBC correlations, and HPLC analysis of sugar residue. Nine phenylethanoid glycosides, namely, magnoloside Ia (1), magnoloside Ic (2), crassifolioside (3), magnoloside Ib (4), magnoloside IIIa (5), magnoloside IVa (6), magnoloside IIa (7), magnoloside IIb (8) and magnoloside Va (9), were first isolated from the n-butanol fraction of Magnolia officinalis var. biloba fruits alcohol extract. Free radical scavenging activities of the nine phenylethanoid glycosides were assessed using the DPPH, ABTS, and superoxide anion radical scavenging assays. Simultaneously, protective effects of all compounds against free radical-induced oxidative damage were evaluated by two different kinds of mitochondrial damage model. The protective effects were assessed by mitochondrial swelling, the formations of malondialdehyde (MDA) and lipid hydroperoxide (LOOH), the activities of catalase (CAT), glutathione reductase (GR) and superoxide dismutase (SOD). All phenylethanoid glycosides showed significant protective effects. PMID:28349971

  4. Preparation and structural characterization of poly-mannose synthesized by phosphoric acid catalyzation under microwave irradiation.

    PubMed

    Wang, Haisong; Cheng, Xiangrong; Shi, Yonghui; Le, Guowei

    2015-05-05

    Poly-mannose with molecular weight of 2.457 kDa was synthesized using d-mannose as substrate and phosphoric acid as catalyst under the condition of microwave irradiation for the first time. The optimum reaction conditions were microwave output power of 900 W, temperature 115°C, proton concentration 2.5 mol/L, and microwave irradiation time 5 min. The actual maximum yield was 91.46%. After purified by Sepherdex G-25 column chromatography, the structural features of poly-mannose were investigated by high-performance anion-exchange chromatography (HPAEC), high-performance gel-permeation chromatography (HPGPC), infrared (IR) spectroscopy, methylation analysis and NMR spectroscopy analysis ((1)H, (13)C, COSY, TOCSY, HMQC, and HMBC). HPAEC analysis showed that the composition of synthetic polysaccharides was d-mannose, its purity was demonstrated by HPGPC as a single symmetrical sharp peak, and additionally IR spectra demonstrated the polymerization of d-mannose. Methylation analysis and NMR spectroscopy revealed that the backbone of poly-mannose consisting of (1→3)-linked β-d-Manp, (1→3)-linked α-d-Manp, and (1→6)-linked α-d-Manp residues, and the main chain were branched at the O-2, O-3, O-4, O-6 position.

  5. Lignans and neolignans from Stelleropsis antoninae

    PubMed Central

    Gohari, A.R.; Saeidnia, S; Bayati-Moghadam, M; Amin, Gh

    2011-01-01

    Background and the purpose of the study Stelleropsis antoninae Pobed. (Family: Thymelaeaceae) grows wildly as an herbaceous plant in Iran. Most of the Thymelaeaceous plants contain lignans and neolignans, which have important pharmacologically properties. In the present study, the isolation and identification of the main lignans and neolignans of S. antoninae, which has not been previously reported is described and compared to other species. Methods Column (CC) and High Performance Liquid Chromatographic (HPLC) methods were used for the isolation and purification, and 1H-NMR, 13C-NMR, HMBC, HMQC, H-H COSY and MS were employed for the identification of the compounds isolated from the methanol extract. Results From the methanol extract of the aerial parts of S. antoninae four lignans, syringaresinol (1), syringaresinol 4-O-β-D-glucopyranoside (4), syringaresinol 4-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranoside (5), liriodendrin (6), and two neolignans, 5-methoxylariciresinol 4’-O- β-D-glucopyranoside (3) and dehydrodiconiferyl alcohol 4-O-β -D-glucopyranoside (2) were isolated and identified. Major conclusion The results of this study show that siringaresinol, a well-known bioavtive compound, and its glucosides are the main lignans, and lariciresinol and coniferyl alcohol derivatives are the main neolignans of S. antoninae. PMID:22615643

  6. Chemical constituents and biological activities of Senecio aegyptius var. discoideus Boiss.

    PubMed

    Hassan, Wafaa; Al-Gendy, Amal; Al-Youssef, Hanan; El-Shazely, Assem

    2012-01-01

    A new eremophilane sesquiterpene, 1-beta-hydroxy-8-oxoeremophila-7,9-dien-12-oic acid (1), in addition to two known flavonol glycosides, rutin (2) and quercetin-3-O-glucoside-7-O-rutinoside (3), was isolated from the ethyl acetate fraction obtained from the aqueous alcoholic extract of the aerial parts of Senecio aegyptius var. discoideus Boiss. (family Asteraceae). The chemical structures of the isolated compounds were established by 1D and 2D NMR analysis (1H, 13C, COSY, HMQC, HMBC), MS and UV data, and through comparison with the literature. The ethyl acetate fraction and the isolated rutin showed significant cytotoxic activity against colorectal carcinoma (HCT 116) and to less extent against brain (U 251) and breast carcinoma (MCF 7). The ethyl acetate fraction showed a significant level of activity against Klebsiella pneumoniae, while the total extract showed the best antifungal activity against Candida albicans and Saccharomyces cerevisiae. DPPH radical scavenging activity of the ethyl acetate fraction was significant (96.7%) when compared to ascorbic acid. It also showed anti-inflammatory activity but no diuretic effect.

  7. Synthesis, Characterization and Antitumor Activity of cis-bis(acylthioureato) platinum(II) Complexes, cis-[PtL2] [HL1=N,N-Diphenyl-N'-Benzoylthiourea or HL2=N,N-diphenyl-N'-(p-nitrobenzoyl)thiourea

    PubMed Central

    Hernández, Wilfredo; Muñoz, Juan Carlos; Beyer, Lothar; Schröder, Uwe; Ferreira, Jorge; Pavani, Mario

    2003-01-01

    A low-molecular weight chromium-containing fraction of the material resulting from dichromate reduction by bovine liver homogenate was investigated by NMR and ES-MS. The ES-MS spectrum showed a readily detectable peak at m/z 786.1. The same molecular weight reasonably agreed with the relatively low diffusion coefficient measured by NMR-DOSY experiments on the main species observed in the 1H NMR spectrum. At least two downfield shifted and broad paramagnetic signals were apparent in the 1H NMR spectrum. Temperature dependence of chemical shift was exploited in order to estimate the diamagnetic shift of the signals in the diamagnetic region of the spectrum. 2D TOCSY, NOESY, COSY and 1H-13C HMQC spectra revealed the presence of aromatic protons (which were assigned as His residues), Gly and some other short chain amino-acids. Combinations of the molecular masses of such components together with acetate (which is present in the solution) and chromium atoms allowed a tentative proposal of a model for the compound. PMID:18365059

  8. Lanostane triterpenoids and sterols from Antrodia camphorata.

    PubMed

    Huang, Hui-Chi; Liaw, Chih-Chuang; Yang, Hsin-Ling; Hseu, You-Cheng; Kuo, Hsiou-Ting; Tsai, Yao-Ching; Chien, Shih-Chang; Amagaya, Sakae; Chen, Yu-Chang; Kuo, Yueh-Hsiung

    2012-12-01

    Four lanostane triterpenes, 3,7,11-trioxo-5α-lanosta-8,24(E)-dien-26-oic acid, methyl 11α-3,7-dioxo-5α-lanosta-8,24(E)-dien-26-oate, methyl 3,7,11,12,15,23-hexaoxo-5α-lanost-8-en-26-oate, and ethyl 3,7,11,12,15,23-hexaoxo-5α-lanost-8-en-26-oate, two sterols, (14α,22E)-14-hydroxyergosta-7,22-diene-3,6-dione and a steroid named as camphosterol A were isolated from a mixture of fruiting bodies and mycelia of solid cultures of Antrodia camphorata. The ¹H and ¹³C NMR spectra of all compounds were fully assigned using a combination of 2D NMR experiments, including COSY, HMQC, HMBC and NOESY sequences. Six compounds were evaluated for cytotoxicity against several human tumor cell lines, all of which has moderate activity.

  9. Glucosamine and Glucosamine-6-phosphate Derivatives: Catalytic Cofactor Analogs for the glmS Ribozyme

    PubMed Central

    Posakony, Jeffrey J.; Ferré-D'Amaré, Adrian R.

    2013-01-01

    Two analogues of glucosamine-6-phosphate (GlcN6P, 1) and five of glucosamine (GlcN, 2) were prepared for evaluation as catalytic cofactor of the glmS ribozyme, a bacterial gene-regulatory RNA that controls cell wall biosynthesis. Glucosamine and allosamine with 3-azido substitutions were prepared by SN2 reactions of the respective 1,2,4,6-protected sugars; final acidic hydrolysis afforded the fully deprotected compounds as their TFA salts. A 6-phospho-2-aminoglucolactam (31) was prepared from glucosamine in a 13-step synthesis, which included a late-stage POCl3-phosphorylation. A simple and widely applicable 2-step procedure with the triethylsilyl (TES) protecting group was developed to selectively expose the 6-OH group in N-protected glucosamine analogs, which provided another route to chemical phosphorylation. Mitsunobu chemistry afforded 6-cyano (35) and 6-azido (36) analogues of GlcN-(Cbz) and the selectivity for the 6-position was confirmed by NMR (COSY, HMBC, HMQC) experiments. Compound 36 was converted to the fully deprotected 6-azido-GlcN (37) and 2,6-diaminoglucose (38) analogs. A 2-hydroxylamino glucose (42) analogue was prepared via an oxaziridine (41). Enzymatic phosphorylation of 42 and chemical phosphorylation of its 6-OH precursor (43) were possible, but 42 and the 6-phospho product (44) were unstable under neutral or basic conditions. Chemical phosphorylation of the previously described 2-guanidinyl-glucose (46) afforded its 6-phospho analogue (49) after final deprotection. PMID:23578404

  10. Biosynthesis of xyrrolin, a new cytotoxic hybrid polyketide/non-ribosomal peptide pyrroline with anticancer potential, in Xylaria sp. BCC 1067.

    PubMed

    Phonghanpot, Suranat; Punya, Juntira; Tachaleat, Anuwat; Laoteng, Kobkul; Bhavakul, Vanida; Tanticharoen, Morakot; Cheevadhanarak, Supapon

    2012-04-16

    A gene from Xylaria sp. BCC 1067, pks3, that encodes a putative 3660-residue hybrid polyketide synthase (PKS)/non-ribosomal peptide synthetase (NRPS) was characterised by targeted gene disruption in combination with comprehensive product identification. Studies of the features of a corresponding mutant, YA3, allowed us to demonstrate that pks3 is responsible for the synthesis of a new pyrroline compound, named xyrrolin, in the wild-type Xylaria sp. BCC 1067. The structure of xyrrolin was established by extensive spectroscopic and spectrometric analyses, including low- and high-resolution MS, IR, (1)H NMR, (13)C NMR, (13)C NMR with Dept135, HMQC 2D NMR, HMBC 2D NMR and COSY 2D NMR. On the basis of the Pks3 domain organisation and the chemical structure of xyrrolin, we proposed that biosynthesis of this compound requires the condensation of a tetraketide and an L-serine unit, followed by Dieckmann or reductive cyclisation and enzymatic removal of ketone residue(s). Bioassays of the pure xyrrolin further displayed cytotoxicity against an oral cavity (KB) cancer cell line.

  11. Antioxidant and Anti-Osteoporotic Activities of Aromatic Compounds and Sterols from Hericium erinaceum.

    PubMed

    Li, Wei; Lee, Sang Hyun; Jang, Hae Dong; Ma, Jin Yeul; Kim, Young Ho

    2017-01-11

    Hericium erinaceum, commonly called lion's mane mushroom, is a traditional edible mushroom widely used in culinary applications and herbal medicines in East Asian countries. In this study, a new sterol, cerevisterol 6-cinnamate (6), was isolated from the fruiting bodies of H. erinaceum together with five aromatic compounds 1-5 and five sterols 7-11. The chemical structures of these compounds were elucidated using chemical and physical methods and comparison of HRESIMS, ¹D-NMR (¹H, (13)C, and DEPT) and 2D-NMR (COSY, HMQC, HMBC, and NOESY) spectra with previously reported data. The antioxidant and anti-osteoporotic activities of extracts and the isolated compounds 1-11 were investigated. All compounds exhibited peroxyl radical-scavenging capacity but only compounds 1, 3, and 4 showed potent reducing capacity. Moreover, compounds 1, 2, 4, and 5 showed moderate effects on cellular antioxidant activity and inhibited the receptor activator of nuclear factor κB ligand (RANKL)-induced osteoclastic differentiation. These results suggested that H. erinaceum could be utilized in the development of natural antioxidant and anti-osteoporotic nutraceuticals and functional foods.

  12. New constituents from noni (Morinda citrifolia) fruit juice.

    PubMed

    Samoylenko, Volodymyr; Zhao, Jianping; Dunbar, D Chuck; Khan, Ikhlas A; Rushing, James W; Muhammad, Ilias

    2006-08-23

    Morinda citrifolia L. (Rubiaceae), known as noni, has a long history of traditional use in the Hawaiian and Tahitian islands. More recently, an array of commercial noni fruit juice products are gaining popularity as dietary supplements, with claims of anticancer and immunostimulant activities. The biologically active principles of noni are not fully known. In continuation of work on the isolation of markers from dietary supplements, this paper reports the isolation of three new markers, namely, 1-O-(3'-methylbut-3'-enyl)-beta-D-glucopyranose (1), 1-n-butyl-4-(5'-formyl-2'-furanyl)methyl succinate (2), and 4-epi-borreriagenin (3), together with the known iridoid glycosides asperulosidic acid (4) and deacetylasperulosidic acid (5) and a mixture of 1-n-butyl-4-methyl-2-hydroxysuccinate (6a) and 1-n-butyl-4-methyl-3-hydroxysuccinate (6b), as well as a mixture of alpha- and beta-glucopyranose from noni fruit juice obtained from Puerto Rico. The structures of compounds were based on 1H and 13C NMR, mainly 2D NMR COSY, HMQC, HMBC, and NOESY experiments, and HRMS. Furthermore, samples from fresh-squeezed noni fruit juice from Japan revealed the presence of scopoletin (7), in addition to compounds 1-6, indicating no significant differences in the marker constituents of noni collected from Atlantic and Pacific regions.

  13. Inferences on the Nature of a Cr(V) or Cr(IV) Species Formed by Reduction of Dichromate by a Bovine Liver Homogenate: NMR and Mass-Spectrometric Studies

    PubMed Central

    Gaggelli, Elena; D'Amelio, Nicola; Gaggelli, Nicola; Bovalini, Lucia; Paffetti, Alessandro; Trabalzini, Lorenza

    2003-01-01

    A low-molecular weight chromium-containing fraction of the material resulting from dichromate reduction by bovine liver homogenate was investigated by NMR and ES-MS. The ES-MS spectrum showed a readily detectable peak at m/z = 786.1. The same molecular weight reasonably agreed with the relatively low diffusion coefficient measured by NMR-DOSY experiments on the main species observed in the 1H NMR spectrum. At least two downfield shifted and broad paramagnetic signals were apparent in the 1H NMR spectrum. Temperature dependence of chemical shift was exploited in order to estimate the diamagnetic shift of the signals in the diamagnetic region of the spectrum. 2D TOCSY, NOESY, COSY and 1H-3C HMQC spectra revealed the presence of aromatic protons (which were assigned as His residues), Gly and some other short chain amino-acids. Combinations of the molecular masses of such components together with acetate (which is present in the solution) and chromium atoms allowed a tentative proposal of a model for the compound. PMID:18365060

  14. Structure of the O-specific polysaccharide of Proteus vulgaris O15 containing a novel regioisomer of N-acetylmuramic acid, 2-acetamido-4-O-[(R)-1-carboxyethyl]-2-deoxy-D-glucose.

    PubMed

    Perepelov, Andrei V; Torzewska, Agnieszka; Shashkov, Alexander S; Ziolkowski, Andrzej; Senchenkova, Sof'ya N; Rozalski, Antoni; Knirel, Yuriy A

    2002-11-29

    An acidic O-specific polysaccharide was obtained by mild acid degradation of the lipopolysaccharide of Proteus vulgaris O15 and studied by sugar and methylation analyses along with 1H and 13C NMR spectroscopy, including 2D COSY, TOCSY, ROESY, and H-detected 1H,(13)C HMQC experiments. The polysaccharide was found to contain an ether of GlcNAc with lactic acid, and the following structure of the repeating unit was established:-->3)-alpha-D-GlcpNAc4(R-Lac)6Ac-(1-->2)-beta-D-GlcpA-(1-->3)-alpha-L-6dTalp2Ac-(1-->3)-beta-D-GlcpNAc-(1-->where L-6dTal and D-GlcNAc4(R-Lac) are 6-deoxy-L-talose and 2-acetamido-4-O-[(R)-1-carboxyethyl]-2-deoxy-D-glucose, respectively. The latter sugar, which to our knowledge has not been hitherto found in nature, was isolated from the polysaccharide by solvolysis with anhydrous triflic acid and identified by comparison with the authentic synthetic compound. Serological studies with the Smith-degraded polysaccharide showed an importance of 2-substituted GlcA for manifesting of the immunospecificity of P. vulgaris O15.

  15. Structural and serological studies of the related O-specific polysaccharides of Proteus vulgaris O21 and Proteus mirabilis O48 having oligosaccharide-phosphate repeating units.

    PubMed

    Bartodziejska, B; Toukach, F V; Vinogradov, E V; Senchenkova, S N; Shashkov, A S; Ziolkowski, A; Czaja, J; Perry, M B; Knirel, Y A; Rozalski, A

    2000-12-01

    The O-specific polysaccharide chains (O-antigens) of the lipopolysaccharides (LPSs) of Proteus mirabilis O48 and Proteus vulgaris O21 were found to have tetrasaccharide and pentasaccharide repeating units, respectively, interlinked by a glycosidic phosphate. Polysaccharides and an oligosaccharide were derived from the LPSs by various degradation procedures and studied by 1H and 13C NMR spectroscopy, including 2D COSY, TOCSY, NOESY, H-detected 1H,13C and 1H,31P HMQC experiments. The following related structures of the repeating units of the O-antigens were established (top: Proteus mirabilis O48; bottom: Proteus vulgaris O21) The O-specific polysaccharide of P. vulgaris O21 has the same structure as that of Hafnia allvei 744 and PCM 1194 [Petersson C., Jachymek, W., Klonowska, A., Lugowski, C., Niedziela, T. & Kenne, L. (1997) Eur. J. Biochem., 245, 668-675], except that the GlcN residue carries the N-acetyl rather than the N-[(R)-3-hydroxybutyryl] group. Serological investigations confirmed the close relatedness of the Proteus and Hafnia O-antigens studied.

  16. Constituents of Asparagus officinalis evaluated for inhibitory activity against cyclooxygenase-2.

    PubMed

    Jang, Dae Sik; Cuendet, Muriel; Fong, Harry H S; Pezzuto, John M; Kinghorn, A Douglas

    2004-04-21

    As part of a project directed toward the discovery of new cancer chemopreventive agents from plants, two new natural products, asparagusic acid anti-S-oxide methyl ester (1) and asparagusic acid syn-S-oxide methyl ester (2), a new acetylenic compound, 2-hydroxyasparenyn [3',4'-trans-2-hydroxy-1-methoxy-4-[5-(4-methoxyphenoxy)-3-penten-1-ynyl]-benzene] (3), as well as eleven known compounds, asparenyn (4), asparenyol (5), (+/-)-1-monopalmitin (6), ferulic acid (7), 1,3-O-di-p-coumaroylglycerol (8), 1-O-feruloyl-3-O-p-coumaroylglycerol (9), blumenol C, (+/-)-epipinoresinol, linoleic acid, 1,3-O-diferuloylglycerol, and 1,2-O-diferuloylglycerol, were isolated from an ethyl acetate-soluble fraction of the methanol extract of the aerial parts of Asparagus officinalis (Asparagus), using a bioassay based on the inhibition of cyclooxygenase-2 to monitor chromatographic fractionation. The structures of compounds 1-3 were elucidated by 1D- and 2D-NMR experiments ((1)H NMR, (13)C NMR, DEPT, COSY, HMQC, HMBC and NOESY). All the isolates were evaluated for their inhibitory effects against both cyclooxygenase-1 and -2, with the most active compound being linoleic acid.

  17. Constituents of Musa x paradisiaca cultivar with the potential to induce the phase II enzyme, quinone reductase.

    PubMed

    Jang, Dae Sik; Park, Eun Jung; Hawthorne, Michael E; Vigo, Jose Schunke; Graham, James G; Cabieses, Fernando; Santarsiero, Bernard D; Mesecar, Andrew D; Fong, Harry H S; Mehta, Rajendra G; Pezzuto, John M; Kinghorn, A Douglas

    2002-10-23

    A new bicyclic diarylheptanoid, rel-(3S,4aR,10bR)-8-hydroxy-3-(4-hydroxyphenyl)-9-methoxy-4a,5,6,10b-tetrahydro-3H-naphtho[2,1-b]pyran (1), as well as four known compounds, 1,2-dihydro-1,2,3-trihydroxy-9-(4-methoxyphenyl)phenalene (2), hydroxyanigorufone (3), 2-(4-hydroxyphenyl)naphthalic anhydride (4), and 1,7-bis(4-hydroxyphenyl)hepta-4(E),6(E)-dien-3-one (5), were isolated from an ethyl acetate-soluble fraction of the methanol extract of the fruits of Musa x paradisiaca cultivar, using a bioassay based on the induction of quinone reductase (QR) in cultured Hepa1c1c7 mouse hepatoma cells to monitor chromatographic fractionation. The structure and relative stereochemistry of compound 1 were elucidated unambiguously by one- and two-dimensional NMR experiments ((1)H NMR, (13)C NMR, DEPT, COSY, HMQC, HMBC, and NOESY) and single-crystal X-ray diffraction analysis. Isolates 1-5 were evaluated for their potential cancer chemopreventive properties utilizing an in vitro assay to determine quinone reductase induction and a mouse mammary organ culture assay.

  18. Identification of MMP-1 and MMP-9 inhibitors from the roots of Eleutherococcus divaricatus, and the PAMPA test.

    PubMed

    Załuski, Daniel; Mendyk, Ewaryst; Smolarz, Helena D

    2016-01-01

    The purpose of this study was the isolation of metalloproteinases MMP-1 and MMP-9 inhibitors from the chloroform extract of the Eleutherococcus divaricatus roots. Using GC-MS, (1)H and (13)C NMR, HMQC, HMBC, COSY and DEPT, (+)-sesamin has been identified as a new anti-MMP inhibitor. We report for the first time that (+)-sesamin inhibited MMP-1 and MMP-9 activity in 40% and 17%, respectively. The high inhibitory potential has been shown by ursolic acid (90.9% and 89.8% for MMP-1 and MMP-9). In the PAMPA test, the Pe value for sesamin was established as 17.4 × 10(-6) cm/s, that for ursolic acid as 30.0 × 10(- 6) cm/s. Verapamil and theophylline were used as a positive and negative control (Pe 42.1 and 2.9 × 10(-6) cm/s). To our best knowledge, no information was available on this activity of sesamin and other compounds. These studies provide a biochemical basis for the regulation of MMP-1 and MMP-9 by E. divaricatus compounds.

  19. Lipoxygenase inhibitory sphingolipids from Launaea nudicaulis.

    PubMed

    Riaz, Naheed; Parveen, Shehla; Saleem, Muhammad; Ali, Muhammad Shaiq; Malik, Abdul; Ashraf, Muhammad; Afzal, Iftikhar; Jabbar, Abdul

    2012-01-01

    Four new sphingolipids: nudicaulin A [(2S,3S,4R,14E)-2-{[octadecanoyl]amino}tetraeicos-14-ene-1,3,4-triol; 1], nudicaulin B [(2S,3S,4R,14E)-2-{[(2R)-2-hydroxyoctadecanoyl]amino}tetraeicos-14-ene-1,3,4-triol; 2], nudicaulin C [(2S,3S,4R,14E)-2-{[(2R)-2-hydroxyoctadecanoyl]amino}tetraeicos-14-ene-1,3,4-triol-1-O-β-D-glucopyranoside; 3], and nudicaulin D [(2S,3S,4R)-2-{[(2R,3S,12E)-2,3-dihydroxyeicos-12-enoyl]amino}octadecane-1,3,4-triol; 4] together with 1-hexatriacontanol, β-sitosterol, octadecyl 4-hydroxycinnamate, elaidic acid, cholesta-5,22-diene-3,7-diol, oleanolic acid, apigenin, and β-sitosterol 3-O-β-D-glucopyranoside were isolated from the methanolic extract of the whole plant of Launaea nudicaulis. Their structures were elucidated using ¹H and ¹³C NMR spectra and 2D NMR analyses (HMQC, HMBC, and COSY) in combination with mass spectrometry (EI-MS, HR-EI-MS, FAB-MS, and HR-FAB-MS) experiments and comparison with literature data of related compounds. Compounds 1-4 displayed moderate inhibitory potential against enzyme lipoxygenase in concentration-dependent manner with IC₅₀ value ranges 103-193 μM.

  20. Synthesis, structural, conformational and DFT studies of N-3 and O-4 alkylated regioisomers of 5-(hydroxypropyl)pyrimidine

    NASA Astrophysics Data System (ADS)

    Salihović, Mirsada; Osmanović, Amar; Špirtović-Halilović, Selma; Roca, Sunčica; Meščić, Andrijana; Vujisić, Ljubodrag; Trifunović, Snežana; Završnik, Davorka; Sofić, Emin

    2015-07-01

    Because of the great pharmacological potential of the pyrimidine motif, novel C-5 substituted N-3 acyclic and O-4 acyclic pyrimidine derivatives were prepared as an interesting class of compounds for biological evaluation. Introduction of the 2,3-dihydroxypropyl (DHP) and penciclovir (PCV)-like side chains to 2-methoxypyrimidin-4-one (2) afforded a mixture of N- and O-acyclic pyrimidine nucleosides in the ratio of 54: 29 (3:4) and 57:21 (5:6) with N-3 isomer being dominant. Distinction between N- and O-alkylated pyrimidine moiety was deduced from extensive experimental FT-IR, HPLC-MS and 1D (1H, 13C) and 2D (COSY, HMQC and HMBC) NMR analyses. The N-, O-regioisomers were also examined by computational method at density functional theory (DFT) RB3LYP/6-31G(d), 6-31G∗∗ and 6-31+G∗ levels. DFT global chemical reactivity descriptors (total energy, chemical hardness, electronic chemical potential and electrophilicity) were calculated for the isomers and used to predict and describe their relative stability and reactivity. The chemical reactivity indices were related to the C2sbnd N3sbnd C4 bond angle. Theoretical predictions can be used to compare chemical reactivity and stability with future biological evaluation and behaviour of these compounds.

  1. Monoterpene Unknowns Identified Using IR, [to the first power]H-NMR, [to the thirteenth power]C-NMR, DEPT, COSY, and HETCOR

    ERIC Educational Resources Information Center

    Alty, Lisa T.

    2005-01-01

    A study identifies a compound from a set of monoterpenes using infrared (IR) and one-dimensional (1D) nuclear magnetic resonance (NMR) techniques. After identifying the unknown, each carbon and proton signal can be interpreted and assigned to the structure using the information in the two-dimensional (2D) NMR spectra, correlation spectroscopy…

  2. Heteronuclear three-dimensional NMR spectroscopy. Natural abundance sup 13 C chemical shift editing of sup 1 H- sup 1 H COSY spectra

    SciTech Connect

    Fesik, S.W.; Gampe, R.T. Jr.; Zuiderweg, E.R.P. )

    1989-01-18

    It has been demonstrated that heteronuclear 3D NMR spectroscopy can be effectively applied to small molecules with {sup 13}C at natural abundance. A 78mM solution of the aminoglycoside, kanamycin A was used for this experiment. The heteronuclear 3D NMR spectroscopy is shown to be a useful method for resolving spectral overlap in all frequency domains. 10 refs., 2 figs.

  3. Growth of YBa sub 2 Cu sub 3 O sub 7 minus x thin films on Si with a CoSi sub 2 buffer layer

    SciTech Connect

    Luo, L.; Muenchausen, R.E.; Maggiore, C.J. ); Jimenez, J.R.; Schowalter, L.J. )

    1991-01-28

    By using the pulsed laser deposition technique, high-temperature superconducting YBa{sub 2}Cu{sub 3}O{sub 7{minus}{ital x}} (YBCO) films were grown on Si(001) with a 36 nm single-crystal {l angle}001{r angle} oriented CoSi{sub 2} buffer layer. The films, grown at a substrate temperature of {similar to}700 {degree}C, have a metallic resistive temperature dependence with zero resistance at 85 K. X-ray diffraction, scanning electron microscopy, and ion channeling studies show that the YBCO films are polycrystalline but are strongly {ital c}-axis oriented normal to the Si substrate. Diffusion at the interface between the YBCO film and silicide buffer layer was minimized. This is essential to the growth of high-temperature superconducting films on Si substrates.

  4. The new Schiff base 4-[(4-Hydroxy-3-fluoro-5-methoxy-benzylidene)amino]-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazol-3-one: Experimental, DFT calculational studies and in vitro antimicrobial activity

    NASA Astrophysics Data System (ADS)

    İskeleli, Nazan Ocak; Alpaslan, Yelda Bingöl; Direkel, Şahin; Ertürk, Aliye Gediz; Süleymanoğlu, Nevin; Ustabaş, Reşat

    2015-03-01

    The synthesized Schiff base, 4-[(4-Hydroxy-3-fluoro-5-methoxy-benzylidene)amino]-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazol-3-one (I), has been characterized by 13C NMR, 1H NMR, 2D NMR (1H-1H COSY and 13C APT), FT-IR, UV-vis and X-ray single-crystal techniques. Molecular geometry of the compound I in the ground state, vibrational frequencies and chemical shift values have been calculated by using the density functional method (DFT) with 6-311++G(d,p) basis set. The obtained results indicate that optimized geometry can well reflect the crystal structural parameters. The differences between experimental and calculated results of FT-IR and NMR have supported the existence of intermolecular (O-H⋯O type) and intramolecular (C-H⋯O type) hydrogen bonds in the crystal structure. Molecular electrostatic potential (MEP), frontier molecular orbital analysis (HOMO-LUMO) and electronic absorption spectra were carried out at B3LYP/6-311G++(d,p). HOMO-LUMO electronic transition of 3.92 eV is due to contribution of the bands the n → π∗. The antimicrobial activity of the compound I was determined against the selected 11 bacteria and 8 fungi by microdilution broth assay with Alamar Blue. In vitro studies showed that the compound I has no antifungal effect for selected fungal isolates. However, the compound I shows remarkable antibacterial effect for the bacteria; Streptococcus pneumoniae, Haemophilus influenzae and Enterococcus faecalis.

  5. NMR Metabolic profiling of green tea (Camellia sinensis L.) leaves grown at Kemuning, Indonesia

    NASA Astrophysics Data System (ADS)

    Wahyuni, D. S. C.; Kristanti, M. W.; Putri, R. K.; Rinanto, Y.

    2017-01-01

    Green tea (Camellia sinensis L.) has been famous as a beverage and natural medicine. It contains a broad range of primary and secondary metabolites i.e. polyphenols. Nuclear Magnetic Resonance (NMR) has been widely used for metabolic profiling in medicinal plants. It provides a very fast and detailed analysis of the biomolecular composition of crude extracts. Moreover, an NMR spectrum is a physical characteristic of a compound and thus highly reproducible. Therefore, this study aims to profile metabolites of three different varieties of green tea C. Sinensis grown in Kemuning, Middle Java. Three varieties of green tea collected on Kemuning (TR1 2025, Gambung 4/5, and Chiaruan 143) were used in this study. 1H-NMR spectra were recorded at 230C on a 400 MHz Agilent WB (Widebore). The analysis was performed on dried green tea leaves and analyzed by 1H-NMR, 2D-J-resolved and 1H-1H correlated spectroscopy (COSY). MestRenova version 11.0.0 applied to identify metabolites in samples. A 1H-NMR spectrum of tea showed amino acids and organic acids signal at the area δ 0.8–4.0. These were theanine, alanine, threonine, succinic acid, aspartic acid, lactic acid. Anomeric protons of carbohydrate were shown by the region of β-glucose, α-glucose, fructose and sucrose. The phenolic region was depicted at area δ 5.5-8.5. Epigallocatechin derivates and caffeine were detected in the tea leaves. The detail compound identification was observed and discussed in the text.

  6. The new Schiff base 4-[(4-Hydroxy-3-fluoro-5-methoxy-benzylidene)amino]-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazol-3-one: experimental, DFT calculational studies and in vitro antimicrobial activity.

    PubMed

    İskeleli, Nazan Ocak; Alpaslan, Yelda Bingöl; Direkel, Şahin; Ertürk, Aliye Gediz; Süleymanoğlu, Nevin; Ustabaş, Reşat

    2015-03-15

    The synthesized Schiff base, 4-[(4-Hydroxy-3-fluoro-5-methoxy-benzylidene)amino]-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazol-3-one (I), has been characterized by (13)C NMR, (1)H NMR, 2D NMR ((1)H-(1)H COSY and (13)C APT), FT-IR, UV-vis and X-ray single-crystal techniques. Molecular geometry of the compound I in the ground state, vibrational frequencies and chemical shift values have been calculated by using the density functional method (DFT) with 6-311++G(d,p) basis set. The obtained results indicate that optimized geometry can well reflect the crystal structural parameters. The differences between experimental and calculated results of FT-IR and NMR have supported the existence of intermolecular (O-H⋯O type) and intramolecular (C-H⋯O type) hydrogen bonds in the crystal structure. Molecular electrostatic potential (MEP), frontier molecular orbital analysis (HOMO-LUMO) and electronic absorption spectra were carried out at B3LYP/6-311G++(d,p). HOMO-LUMO electronic transition of 3.92eV is due to contribution of the bands the n→π∗. The antimicrobial activity of the compound I was determined against the selected 11 bacteria and 8 fungi by microdilution broth assay with Alamar Blue. In vitro studies showed that the compound I has no antifungal effect for selected fungal isolates. However, the compound I shows remarkable antibacterial effect for the bacteria; Streptococcus pneumoniae, Haemophilus influenzae and Enterococcus faecalis.

  7. Resolution-optimized NMR measurement of (1)D(CH), (1)D(CC) and (2)D(CH) residual dipolar couplings in nucleic acid bases.

    PubMed

    Boisbouvier, Jérôme; Bryce, David L; O'neil-Cabello, Erin; Nikonowicz, Edward P; Bax, Ad

    2004-11-01

    New methods are described for accurate measurement of multiple residual dipolar couplings in nucleic acid bases. The methods use TROSY-type pulse sequences for optimizing resolution and sensitivity, and rely on the E.COSY principle to measure the relatively small two-bond (2)D(CH) couplings at high precision. Measurements are demonstrated for a 24-nt stem-loop RNA sequence, uniformly enriched in (13)C, and aligned in Pf1. The recently described pseudo-3D method is used to provide homonuclear (1)H-(1)H decoupling, which minimizes cross-correlation effects and optimizes resolution. Up to seven (1)H-(13)C and (13)C-(13)C couplings are measured for pyrimidines (U and C), including (1)D(C5H5), (1)D(C6H6), (2)D(C5H6), (2)D(C6H5), (1)D(C5C4), (1)D(C5C6), and (2)D(C4H5). For adenine, four base couplings ((1)D(C2H2), (1)D(C8H8), (1)D(C4C5), and (1)D(C5C6)) are readily measured whereas for guanine only three couplings are accessible at high relative accuracy ((1)D(C8H8), (1)D(C4C5), and (1)D(C5C6)). Only three dipolar couplings are linearly independent in planar structures such as nucleic acid bases, permitting cross validation of the data and evaluation of their accuracies. For the vast majority of dipolar couplings, the error is found to be less than +/-3% of their possible range, indicating that the measurement accuracy is not limiting when using these couplings as restraints in structure calculations. Reported isotropic values of the one- and two-bond J couplings cluster very tightly for each type of nucleotide.

  8. Direct Analysis of Free and Sulfite-Bound Carbonyl Compounds in Wine by Two-Dimensional Quantitative Proton and Carbon Nuclear Magnetic Resonance Spectroscopy.

    PubMed

    Nikolantonaki, Maria; Magiatis, Prokopios; Waterhouse, Andrew L

    2015-11-03

    Recent developments that have accelerated 2D NMR methods and improved quantitation have made these methods accessible analytical procedures, and the large signal dispersion allows for the analysis of complex samples. Few natural samples are as complex as wine, so the application to challenges in wine analysis look promising. The analysis of carbonyl compounds in wine, key oxidation products, is complicated by a multitude of kinetically reversible adducts, such as acetals and sulfonates, so that sample preparation steps can generate complex interferences. These challenges could be overcome if the compounds could be quantified in situ. Here, two-dimensional ((1)H-(1)H) homonuclear and heteronuclear ((13)C-(1)H) single quantum correlations (correlation spectroscopy, COSY, and heteronuclear single quantum coherence, HSQC) nuclear magnetic resonance spectra of undiluted wine samples were observed at natural abundance. These techniques achieve simultaneous direct identification and quantitation of acetaldehyde, pyruvic acid, acetoin, methylglyoxal, and α-ketoglutaric acid in wine with only a small addition of D2O. It was also possible to observe and sometimes quantify the sulfite, hydrate, and acetal forms of the carbonyl compounds. The accuracy of the method was tested in wine samples by spiking with a mixture of all analytes at different concentrations. The method was applied to 15 wine samples of various vintages and grape varieties. The application of this method could provide a powerful tool to better understand the development, evolution, and perception of wine oxidation and insight into the impact of these sulfite bound carbonyls on antimicrobial and antioxidant action by SO2.

  9. Structural characterization of highly glucosylated crocins and regulation of their biosynthesis during flower development in Crocus

    PubMed Central

    Ahrazem, Oussama; Rubio-Moraga, Angela; Jimeno, Maria L.; Gómez-Gómez, Lourdes

    2015-01-01

    Crocin biosynthesis in Crocus has been proposed to proceed through a zeaxanthin cleavage pathway catalyzed by carotenoid cleavage dioxygenase 2 (CCD2), and followed by glucosylation reactions catalyzed by CsGT2 (UGT74AD1). In Crocus ancyrensis flowers, crocins with eight (crocin-1), seven (crocin-2), and six glucose (crocin-3) moieties accumulated both in stigma and tepals. We have characterized the structure of these highly glucosylated crocins and follow up their accumulation by high-resolution liquid chromatography coupled with diode array detector along the development of both tissues, and coupled to the isolation and analysis of the expression of eighteen genes (PSY-I, PSY-II, PDS-(I-V), ISO-ZDS, ZDS, CtrISO, LYC-I and II, BCH, CaCCD2, UGT74AD2-5) related with the apocarotenoid metabolism in C. ancyrensis tepals and stigmas. Structure elucidation of crocin-1 and crocin-2 was done by the combined use of 1D and 2D [1H, 1H] (gCOSY and TOCSY and ROESY) and [1H-13C] NMR experiments, revealing that for crocin-1 was all-trans-crocetin O-[β-D- Glucopyranosyl)-(1→4)-(β-D-glucopyranosyl)-(1→2)]-O-[β-D-glucopyranosyl-(1→6)]-β-D-glucopyranosyl diester, while crocin-2 showed an identical structure except for the absence of one glucose residue in one end of the molecule. Crocins accumulation was not synchronically regulated in stigma and tepals, although in both cases crocins accumulation parallels tissue development, decreasing at anthesis. The expression of the carotenogenic genes PSY, ZDS-V, BCH, and LCY-II was correlated with crocins accumulation. In addition, CaCCD2 and only one of the four glucosyltransferase encoding genes, UGT74AD2, were highly expressed, and the expression was correlated with high levels of crocins accumulation in stigma and tepals. PMID:26582258

  10. Antiplatelet aggregation triterpene saponins from the barks of Ilex rotunda.

    PubMed

    Fan, Zhen; Zhou, Lian; Xiong, Tianqin; Zhou, Jinsong; Li, Qingguo; Tan, Qinglong; Zhao, Zhongxiang; Jin, Jing

    2015-03-01

    Four new triterpene saponins, rotundinosides A-D (1-4) and seven known triterpene saponins (5-11) were isolated from a methanol extract of the barks of Ilex rotunda Thunb. The new saponins were characterized as 3-O-β-d-glucopyranosy1-(1→2)-β-d-xylopyranosyl siaresinolic acid 28-O-β-d-glucopyranoside (1), 3-O-[β-d-glucopyranosy1-(1→2)-β-d-xylopyranosyl]-3β,19α-dihydroxyurs-12-en-28-oic-O-β-d-glucopranosy1ester (2), 3-O-[α-l-rhamnopyranosyl-(1→2)-β-d-glucopyranosy1-(1→2)-α-l-arabinopyranosyl]-3β,19α-dihydroxyurs-12-en-28-oic-O-β-d-glucopyranosy1 ester (3), and 3-O-α-l-rhamanopyranosyl-(1→2)-β-d-glucopyranosy1-(1→2)-α-l-arabinopyranosyl ilexgenin B 28-O-β-d-glucopyranosy1 ester (4), respectively. Their structures were established by extensive spectroscopic analysis, including HSQC, HMBC, (1)H-(1)H COSY, NOESY and acid hydrolysis, and also by the comparison of their spectroscopic data with those of related compounds. The known compounds 5-11 were all obtained from this species for the first time. The biological activity of compounds 1-11 against ADP induced platelet aggregation in rabbit plasma was determined. Among the tested compounds 1, 3, 5 and 10 exhibited strong inhibition of platelet aggregation in vitro, with IC50 values of 11.4±2.2, 10.4±1.3, 13.2±2.4, and 15.1±3.4μM, respectively.

  11. Solid state and solution properties of lanthanide(III) complexes of a tetraiminodiphenolate macrocyclic ligand. X-ray structure, 1H NMR and luminescence spectral studies

    NASA Astrophysics Data System (ADS)

    Bag, Pradip; Dutta, Supriya; Flörke, Ulrich; Nag, Kamalaksha

    2008-11-01

    The lanthanide(III) complexes of composition [Ln(LH 2)(H 2O) 3Cl]Cl 2 (Ln = La-Lu and Y, 1- 15) derived from the tetraiminodiphenolate macrocyclic ligand L 2- have been prepared and characterized. In these compounds, the two uncoordinated imine nitrogens of the macrocycle are protonated and hydrogen-bonded with the metal-bound phenolate oxygens and thereby provide a zwitterionic structure to the ligand. The X-ray crystal structure of the compounds of La and Nd have been determined and they are found to be isostructural. The coordination polyhedra for the eight-coordinated metal centre in the complex cation [Ln(N 2O 2)(O 3Cl)] 2+ can be described as distorted square antiprism. Intermolecular hydrogen-bondings involving the three coordinated water molecules and the two uncoordinated chloride ions give rise to the 2-D network in which the chlorides are triply hydrogen-bridged and the water molecules are doubly hydrogen-bridged. Moreover, the aromatic rings in this network are involved in π-π interaction in two different ways. 1H NMR spectra of the complexes in (CD 3) 2SO have been studied. The spectral assignments for the paramagnetic complexes of Ce-Eu have been made from { 1H- 1H} COSY spectra and longitudinal relaxation time ( T1) measurements. It is inferred that the complex species [Ln(LH 2){(CD 3) 2SO} 4] 3+ that exist in solution are isostructural for the compounds of La-Eu. The contact and pseudo-contact contribution to the isotropic paramagnetic shifts in the complexes of Ce-Eu have been estimated. The luminescence spectra of the complexes of La, Sm, Eu and Tb have been studied in methanol-ethanol (1:4) glassy matrix and in the solid state at 77 K, and the quantum yields have been estimated.

  12. The Effect of Terminal Substitution on the Helical Carbon Structure of Fluoro-Alkane Chains: a Pure Rotational Study of CH2OH-Cn-1F2n-1 (n = 4, 5,& 6)

    NASA Astrophysics Data System (ADS)

    Schwartz, Aaron Z. A.; Maturo, Mark P.; Obenchain, Daniel A.; Cooke, S. A.

    2016-06-01

    Continuing a series of studies to investigate the change in structure of hydrocarbons as the amount of fluorination is increased to varying degrees of substitution, we present a survey on the change in the helical nature of the fluorinated carbon backbone when a -CH2OH group is substituted for a terminal - CF3 group. Spectra for 1H,1H-heptafluorobutan-1-ol, 1H,1H-nonafluoropentan-1-ol, and 1H,1H-undecafluorohexan-1-ol were collected separately using a chirped-pulse FTMW spectrometer in the range of 7-13 GHz. Only one conformation was observed for each molecule. Additional measurements of the 1H,1H-heptafluorobutan-1-ol were completed using a Balle-Flygare cavity instrument. Assignments of the singly-substituted 13C isotopologues of the 1H,1H-heptafluorobutan-1-ol were also measured. A comparison of both ab initio and experimental structures will be presented.

  13. NMR structure analysis of uniformly 13C-labeled carbohydrates.

    PubMed

    Fontana, Carolina; Kovacs, Helena; Widmalm, Göran

    2014-06-01

    In this study, a set of nuclear magnetic resonance experiments, some of them commonly used in the study of (13)C-labeled proteins and/or nucleic acids, is applied for the structure determination of uniformly (13)C-enriched carbohydrates. Two model substances were employed: one compound of low molecular weight [(UL-(13)C)-sucrose, 342 Da] and one compound of medium molecular weight ((13)C-enriched O-antigenic polysaccharide isolated from Escherichia coli O142, ~10 kDa). The first step in this approach involves the assignment of the carbon resonances in each monosaccharide spin system using the anomeric carbon signal as the starting point. The (13)C resonances are traced using (13)C-(13)C correlations from homonuclear experiments, such as (H)CC-CT-COSY, (H)CC-NOESY, CC-CT-TOCSY and/or virtually decoupled (H)CC-TOCSY. Based on the assignment of the (13)C resonances, the (1)H chemical shifts are derived in a straightforward manner using one-bond (1)H-(13)C correlations from heteronuclear experiments (HC-CT-HSQC). In order to avoid the (1) J CC splitting of the (13)C resonances and to improve the resolution, either constant-time (CT) in the indirect dimension or virtual decoupling in the direct dimension were used. The monosaccharide sequence and linkage positions in oligosaccharides were determined using either (13)C or (1)H detected experiments, namely CC-CT-COSY, band-selective (H)CC-TOCSY, HC-CT-HSQC-NOESY or long-range HC-CT-HSQC. However, due to the short T2 relaxation time associated with larger polysaccharides, the sequential information in the O-antigen polysaccharide from E. coli O142 could only be elucidated using the (1)H-detected experiments. Exchanging protons of hydroxyl groups and N-acetyl amides in the (13)C-enriched polysaccharide were assigned by using HC-H2BC spectra. The assignment of the N-acetyl groups with (15)N at natural abundance was completed by using HN-SOFAST-HMQC, HNCA, HNCO and (13)C-detected (H)CACO spectra.

  14. C-Glucoside xanthone from the stem bark extract of Bersama engleriana

    PubMed Central

    Djemgou, Pierre C.; Hussien, Taha A.; Hegazy, Mohamed-Elamir F.; Ngandeu, François; Neguim, Gilles; Tane, Pierre; Mohamed, Abou-El-Hamd H.

    2010-01-01

    Background: The genus Bersama belongs to the Melianthaceae family and comprises of four species (B. swinnyi, B. yangambiensis, B. abyssinica, and B. engleriana) all of which are very high trees; the latter two detected species are found in Cameroon. Previous phytochemical investigation on B. yangambiensis, B. swinnyi, and B. abyssinica led to the isolation of triterpenes, saponins, flavonoids, and xanthones. Method: The stem bark of B. engleriana were collected in the village, Baham near Bafoussam city, Cameroon in August 2003 and identifi ed by Dr. Onana National Herbaruim, Yaoundι, Cameroon. The air dried and powdered stem bark of B. engleriana (1 kg) was extracted at room temperature with CH2Cl2-MeOH (1:1) 5 L for 48 hours. The mixture of the solvent was removed by evaporation to yield 200 g of crude extract. The latter was then dissolved in CH2Cl2 to give the CH2Cl2 soluble fraction of 5 g and a remaining gum of 195 g. Part of the remaining gum (22 g) was dissolved in water and extracted four times with butanol to give 12 g of red oil; which was then separated by paper chromatography, with butanol-acetic acid-water (4:1:5), to give 3 g of orange gum; purification was carried out on HPLC with MeOH (100%) to yield 2 g of mangiferin (1) as red oil. The CH2Cl2 soluble extract was eluted on silica gel n-hexane-CH2Cl2 gradient ratio and Sephadex LH-20 (n-hexane -CH2Cl2 -MeOH, (7:4:0.5) to afford compounds swinniol (2), Δ4-stigmaster-3β-ol (3), 4-methylstigmaster-5,23-dien-3β-ol(4). Results: Herein, we carried out a phytochemical study of the stem bark of B. engleriana, and we report herein the isolation and structural elucidation of mangiferin, in addition to three triterpenes, previously reported from other species of the genus.[35] The assignment of the signals of mangiferin was determined using 1H, 13C-NMR, and 2D-NMR spectral data (HMQC, COSY, HMBC). The terpenoids were identifi ed by comparison of their 1H and 13C-NMR spectra with the literature data

  15. Anti-spasmodic action of crude methanolic extract and a new compound isolated from the aerial parts of Myrsine africana

    PubMed Central

    2011-01-01

    Background Myrsine africana is an herbaceous plant that is traditionally used as appetizer and carminative. Locally, it is used for the treatment of pulmonary tuberculosis, rheumatism and diarrhea by healers. The aims of the current study were to screen the crude methanol extract obtained from the aerial parts (leaves and stem) of M. africana, for antispasmodic actions on isolated tissues and further to subject the ethyl acetate (EtOAc) fraction of plant to column chromatography for isolation of pure compounds. Methods The antispasmodic action of the crude methanol extract was measured on the spontaneous rabbit's jejunum preparations at concentration 0.01, 0.03, 0.1, 0.3, 1.0, 5.0 and 10.0 mg/ml. The crude extract was also applied, in similar concentrations, on KCl (80 mM) induced contractions to explain its possible mode of action. Results A new compound Myrsigenin was isolated from the EtOAc fraction of M. africana. The structure of the compound was identified with the help of 13C-NMR, 1H-NMR, HMBC, HMQC, NOESY and COSY. The plant crude methanol extract showed a significant antispasmodic action on rabbit jejunum and abolished the tissue contraction completely at concentration of 5.0 mg/ml. Conclusion The study concludes that the methanol crude extract of aerial parts of M. africana has antispasmodic action possibly through the calcium channel blocking mechanisms. A new compound Myrsigenin was isolated from the EtOAc fraction of the plant. PMID:21733176

  16. A novel diterpene skeleton: identification of a highly aromatic, cytotoxic and antioxidant 5-methyl-10-demethyl-abietane-type diterpene from Premna serratifolia.

    PubMed

    Habtemariam, Solomon; Varghese, George K

    2015-01-01

    Premna serratifolia Linn. (syn: . P. corymbosa (Burm. f.) Merr., P. integrifolia L. and P. obtusifolia R. Br.) is a member of the Verbenaceae family that is extensively used in the Ayurvedic system of medicine in India. As part of our continuous pharmacological and phytochemical studies on medicinal plants, we have screened the methanolic extracts of leaves, root bark (RB) and root wood of P. serratifolia for cytotoxic activity against two cancer cell lines: SHSY-5Y neuroblastoma and B16 melanoma cells. The RB extract that showed promising activity was fractionated using solvents of increasing polarity followed by a combination of Sephadex LH-20 column and Combiflash chromatography as well as HPLC to afford the active principle. Comprehensive spectroscopic analysis including 1D and 2D NMR (COSY, HMQC, HMBC, NOESY) and MS analysis revealed the identity of the isolated compound as 11,12,16-trihydroxy-2-oxo-5-methyl-10-demethyl-abieta-1[10],6,8,11,13-pentene that appears to be a novel compound based on a new diterpene skeleton. The cytotoxic activity of the isolated compound was 21 and 23 times higher than the crude extract against the SHSY-5Y and B16 cells, respectively. The novel compound also possesses in vitro antioxidant effects as evidenced by the DPPH (2,2-diphenyl-1-picrylhydrazyl) radical scavenging effect where an IC50 value of 20.4 ± 1.3 μM was obtained. In comparison, the positive control, caffeic acid, showed an IC50 value of 14.4 ± 1.6 μM.

  17. Simultaneous determination of three diarylheptanoids and an alpha-tetralone derivative in the green walnut husks (Juglans regia L.) by high-performance liquid chromatography with photodiode array detector.

    PubMed

    Liu, Junxi; Meng, Min; Li, Chen; Huang, Xinyi; Di, Duolong

    2008-05-09

    By optimizing extraction, separation and analytical conditions, a reliable and accurate high-performance liquid chromatographic (HPLC) method coupled with photodiode array detector (DAD) at room temperature is developed for simultaneous determination of three diarylheptanoids (juglanin A, juglanin B, rhoiptelol) and an alpha-tetralone derivative (regiolone) in methanol extracts from the green walnut husks (Juglans regia L.) The sample pretreatment process involved the reflux extraction using methanol as the extract with a ratio of liquor to sample of 15 mL/g. The separation was achieved on a SinoChrom ODS-AP C(18) column with gradient elution using acetonitrile and 2% (v/v) acetic acid in water. The intra-day and inter-day precision (RSD%) for the analytes ranged from 1.08 to 1.51 and 0.60 to 1.13, respectively. The average recoveries obtained were from 88.4% to 96.2% for the analytes with RSDs below 3.13%. The correlation coefficients of the calibration curve exceeded 0.999. The detection limits were 0.51, 0.25, 0.32 and 0.35 ng at a signal-to-noise ratio of 3, respectively. Quantitative analyses of the samples from different grown sites and in obtained different months showed that the contents of the analytes varied significantly. The method was then successfully applied for the detection and isolation of a new diarylheptanoid derivative in the green walnut husks (J. regia L.). The structure of the new compound was elucidated by various spectroscopic methods including 2D NMR techniques (COSY, HMQC, HMBC), HR-ESI-MS and X-ray single-crystal diffraction analysis.

  18. Towards Elucidating Carnosic Acid Biosynthesis in Lamiaceae: Functional Characterization of the Three First Steps of the Pathway in Salvia fruticosa and Rosmarinus officinalis.

    PubMed

    Božić, Dragana; Papaefthimiou, Dimitra; Brückner, Kathleen; de Vos, Ric C H; Tsoleridis, Constantinos A; Katsarou, Dimitra; Papanikolaou, Antigoni; Pateraki, Irini; Chatzopoulou, Fani M; Dimitriadou, Eleni; Kostas, Stefanos; Manzano, David; Scheler, Ulschan; Ferrer, Albert; Tissier, Alain; Makris, Antonios M; Kampranis, Sotirios C; Kanellis, Angelos K

    2015-01-01

    Carnosic acid (CA) is a phenolic diterpene with anti-tumour, anti-diabetic, antibacterial and neuroprotective properties that is produced by a number of species from several genera of the Lamiaceae family, including Salvia fruticosa (Cretan sage) and Rosmarinus officinalis (Rosemary). To elucidate CA biosynthesis, glandular trichome transcriptome data of S. fruticosa were mined for terpene synthase genes. Two putative diterpene synthase genes, namely SfCPS and SfKSL, showing similarities to copalyl diphosphate synthase and kaurene synthase-like genes, respectively, were isolated and functionally characterized. Recombinant expression in Escherichia coli followed by in vitro enzyme activity assays confirmed that SfCPS is a copalyl diphosphate synthase. Coupling of SfCPS with SfKSL, both in vitro and in yeast, resulted in the synthesis miltiradiene, as confirmed by 1D and 2D NMR analyses (1H, 13C, DEPT, COSY H-H, HMQC and HMBC). Coupled transient in vivo assays of SfCPS and SfKSL in Nicotiana benthamiana further confirmed production of miltiradiene in planta. To elucidate the subsequent biosynthetic step, RNA-Seq data of S. fruticosa and R. officinalis were searched for cytochrome P450 (CYP) encoding genes potentially involved in the synthesis of the first phenolic compound in the CA pathway, ferruginol. Three candidate genes were selected, SfFS, RoFS1 and RoFS2. Using yeast and N. benthamiana expression systems, all three where confirmed to be coding for ferruginol synthases, thus revealing the enzymatic activities responsible for the first three steps leading to CA in two Lamiaceae genera.

  19. Synthesis and study of the spectroscopic and redox properties of Ru(II),Pt(II) mixed-metal complexes bridged by 2,3,5,6-tetrakis(2-pyridyl)pyrazine.

    PubMed

    Zhao, Shengliang; Arachchige, Shamindri M; Slebodnick, Carla; Brewer, Karen J

    2008-07-21

    The mixed-metal supramolecular complexes [(tpy)Ru(tppz)PtCl](PF6)3 and [ClPt(tppz)Ru(tppz)PtCl](PF6)4 (tpy = 2,2':6',2''-terpyridine and tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine) were synthesized and characterized. These complexes contain ruthenium bridged by tppz to platinum centers to form stereochemically defined linear assemblies. X-ray crystallographic determinations of the two complexes confirm the identity of the metal complexes and reveal intermolecular interactions of the Pt sites in the solid state for [(tpy)Ru(tppz)PtCl](PF6)3 with a Pt...Pt distance of 3.3218(5) A. The (1)H NMR spectra show the expected splitting patterns characteristic of stereochemically defined mixed-metal systems and are assigned with the use of (1)H-(1)H COSY and NOESY. Electronic absorption spectroscopy displays intense ligand-based pi --> pi* transitions in the UV and MLCT transitions in the visible. Electrochemically [(tpy)Ru(tppz)PtCl](PF6)3 and [ClPt(tppz)Ru(tppz)PtCl](PF6)4 display reversible Ru (II/III) couples at 1.63 and 1.83 V versus Ag/AgCl, respectively. The complexes display very low potential tppz (0/-) and tppz(-/2-) couples, relative to their monometallic synthons, [(tpy)Ru(tppz)](PF6)2 and [Ru(tppz)2](PF6)2, consistent with the bridging coordination of the tppz ligand. The Ru(dpi) --> tppz(pi*) MLCT transitions are also red-shifted relative to the monometallic synthons occurring in the visible centered at 530 and 538 nm in CH3CN for [(tpy)Ru(tppz)PtCl](PF6)3 and [ClPt(tppz)Ru(tppz)PtCl](PF6)4, respectively. The complex [(tpy)Ru(tppz)PtCl](PF6)3 displays a barely detectable emission from the Ru(dpi) --> tppz(pi*) (3)MLCT in CH 3CN solution at RT. In contrast, [ClPt(tppz)Ru(tppz)PtCl](PF6)4 displays an intense emission from the Ru(dpi) --> tppz(pi*) (3)MLCT state at RT with lambda max(em) = 754 nm and tau = 80 ns.

  20. New ursane triterpenoids from Ficus pandurata and their binding affinity for human cannabinoid and opioid receptors.

    PubMed

    Khedr, Amgad I M; Ibrahim, Sabrin R M; Mohamed, Gamal A; Ahmed, Hany E A; Ahmad, Amany S; Ramadan, Mahmoud A; El-Baky, Atef E Abd; Yamada, Koji; Ross, Samir A

    2016-07-01

    Phytochemical investigation of Ficus pandurata Hance (Moraceae) fruits has led to the isolation of two new triterpenoids, ficupanduratin A [1β-hydroxy-3β-acetoxy-11α-methoxy-urs-12-ene] (11) and ficupanduratin B [21α-hydroxy-3β-acetoxy-11α-methoxy-urs-12-ene] (17), along with 20 known compounds: α-amyrin acetate (1), α-amyrin (2), 3β-acetoxy-20-taraxasten-22-one (3), 3β-acetoxy-11α-methoxy-olean-12-ene (4), 3β-acetoxy-11α-methoxy-12-ursene (5), 11-oxo-α-amyrin acetate (6), 11-oxo-β-amyrin acetate (7), palmitic acid (8), stigmast-4,22-diene-3,6-dione (9), stigmast-4-ene-3,6-dione (10), stigmasterol (12), β-sitosterol (13), stigmast-22-ene-3,6-dione (14), stigmastane-3,6-dione (15), 3β,21β-dihydroxy-11α-methoxy-olean-12-ene (16), 3β-hydroxy-11α-methoxyurs-12-ene (18), 6-hydroxystigmast-4,22-diene-3-one (19), 6-hydroxystigmast-4-ene-3-one (20), 11α,21α-dihydroxy-3β-acetoxy-urs-12-ene (21), and β-sitosterol-3-O-β-D-glucopyranoside (22). Compound 21 is reported for the first time from a natural source. The structures of the 20 compounds were elucidated on the basis of IR, 1D ((1)H and (13)C), 2D ((1)H-(1)H COSY, HSQC, HMBC and NOESY) NMR and MS spectroscopic data, in addition to comparison with literature data. The isolated compounds were evaluated for their anti-microbial, anti-malarial, anti-leishmanial, and cytotoxic activities. In addition, their radioligand displacement affinity on opioid and cannabinoid receptors was assessed. Compounds 4, 11, and 15 exhibited good affinity towards the CB2 receptor, with displacement values of 69.7, 62.5 and 86.5 %, respectively. Furthermore, the binding mode of the active compounds in the active site of the CB2 cannabinoid receptors was investigated through molecular modelling.

  1. Oxidation of Pt-bound bis-hydroxylamine as a novel route to unexplored dinitrosoalkane ligated species.

    PubMed

    Luzyanin, Konstantin V; Gushchin, Pavel V; Pombeiro, Armando J L; Haukka, Matti; Ovcharenko, Victor I; Kukushkin, Vadim Yu

    2008-08-04

    The reaction of K 2[PtCl 4] and HO(H)NCMe 2CMe 2N(H)OH.H 2SO 4 ( BHA.H 2SO 4; 2) in a molar ratio 1:2 at 20-25 degrees C in water affords a mixture of [Pt(BHA) 2][PtCl 4] ( 5) and [Pt(BHA-H) 2] ( 6) ( BHA- H = anionic monodeprotonated form of BHA) which, upon heating at 80-85 degrees C for 12 h or on prolonged keeping at 20-25 degrees C for 2 weeks, is subject to a slow transformation giving [PtCl 2(BHA)] ( 7). The latter compound is also obtained from the reaction between K[PtCl 3(Me 2 SO)] and 2. The chlorination of [PtCl 2(BHA)] ( 7) in freshly distilled dry chloroform leads to the selective oxidation of one N(H)OH group yielding [PtCl 2{HO(H) NCMe 2CMe 2 N=O}] ( 13), while the chlorination in water produces the complex [PtCl 2(O= NCMe 2CMe 2 N=O)] ( 14) bearing the unexplored dinitrosoalkane species. Treatment of 14 with 2 equiv of 1,2-bis-(diphenylphosphino)ethane (dppe) in CH 2Cl 2 results in the liberation of the dinitrosoalkane ligand followed by its fast cyclization giving the alpha-dinitrone (3,3,4,4-tetramethyl-1,2-diazete-1,2-dioxide) in solution and the solid [Pt(dppe) 2](Cl) 2. The Pt (II) complexes with hydroxylamino ( intersection)oximes [PtCl 2{HO(H) NC(Me) 2C(R)= NOH}] (R = Me 8; R = Ph 9) upon their oxidation with Cl 2 in CHCl 3 afford the nitrosoalkane derivatives [PtCl 2{O= NCMe 2C(R)= NOH}] (R = Me 16; Ph 17), respectively, while the corresponding chlorination of the bis-chelates [Pt{HO(H) NCMe 2C(R)= NOH} 2] (R = Me 10; Ph 11) gives [Pt{O= NCMe 2C(R)= NO} 2] (R = Me 18; Ph 19). The formulation of 5- 19 is based on C, H, and N microanalyses, IR, 1D ( (1)H, (13)C{ (1)H}, (195)Pt) and 2D ( (1)H, (1)H-COSY, (1)H, (13)C-HSQC) NMR spectroscopies, and X-ray diffraction for five complexes ( 5, 7, and 12- 14).

  2. Cyclic dipeptides from rhabditid entomopathogenic nematode-associated Bacillus cereus have antimicrobial activities.

    PubMed

    Nishanth Kumar, S; Nath, Vishnu Sukumari; Pratap Chandran, R; Nambisan, Bala

    2014-02-01

    The cell free culture filtrate of Bacillus cereus associated with an entomopathogenic nematode, Rhabditis (Oscheius) sp. exhibited strong antimicrobial activity. The ethyl acetate extract of the bacterial culture filtrate was purified by silica gel column chromatography to obtain four bioactive compounds. The structure and absolute stereochemistry of these compounds were determined based on extensive spectroscopic analyses (FABMS, (1)H NMR, (13)C NMR, (1)H-(1)H COSY, (1)H-(13)C HMBC) and Marfey's method. The compounds were identified as cyclic dipeptides (CDPs): cyclo(L-Pro-L-Trp), cyclo(L-Leu-L-Val), cyclo(D-Pro-D-Met), and cyclo(D-Pro-D-Phe), respectively. Compounds recorded significant antibacterial activity against all the test bacteria (Staphylococcus epidermidis, Staphylococcus aureus, Klebsiella pneumoniae, Escherichia coli, Pseudomonas aeruginosa and methicillin-resistant S. aureus) except cyclo(L-Leu-L-Val). Cyclo(L-Leu-L-Val) recorded activity only against Gram positive bacteria. Best antibacterial activity was recorded by cyclo(L-Pro-L-Trp) against S. aureus (4 μg/ml). The four compounds were active against all the five fungi tested (Trichophyton rubrum, Aspergillus flavus, Candida albicans, Candida tropicalis and Cryptococcus neoformans) and the activity was compared with amphotericin B, the standard fungicide. The highest activity of 1 μg/ml by cyclo(L-Pro-L-Trp) was recorded against T. rubrum, a human pathogen responsible for causing athlete's foot, jock itch, and ringworm. The activity of cyclo(L-Pro-L-Trp) against T. rubrum, C. neoformans and C. albicans were better than amphotericin B, the standard antifungal agent. To our knowledge, this is the first report of antifungal activity of CDPs against the human pathogenic fungi T. rubrum and C. neoformans. The four CDPs are nontoxic to healthy human cell line up to 200 μg/ml. We conclude that the bacterium associated with entomopathogenic nematode is promising sources of natural antimicrobial

  3. Solution behavior and complete sup 1 H and sup 13 C NMR assignments of the coenzyme B sub 12 derivative (5 prime -deoxyadenosyl)cobinamide using modern 2D NMR experiments, including 600-MHz sup 1 H NMR data

    SciTech Connect

    Pagano, T.G.; Yohannes, P.G.; Marzilli, L.G. ); Hay, B.P.; Scott, J.R.; Finke, R.G. )

    1989-02-15

    Two-dimensional (2D) NMR methods have been used to assign completely the {sup 1}H and {sup 13}C NMR spectra of the (5{prime}-deoxyadenosyl)cobinamide cation (AdoCbi{sup +}) in D{sub 2}O. Most of the {sup 1}H spectral assignments were made by using 2D homonuclear shift correlation spectroscopy (COSY), homonuclear Hartmann-Hahn spectroscopy (HOHAHA), absorption-mode (phase sensitive) 2D nuclear Overhauser effect (NOE) spectroscopy, and spin-locked NOE spectroscopy (also called ROESY, for rotating-frame Overhauser enhancement spectroscopy). Most of the protonated carbon resonances were assigned by using {sup 1}H-detected heteronuclear multiple-quantum coherence (HMQC) spectroscopy. The nonprotonated carbon resonances, as well as the remaining unassigned {sup 1}H and {sup 13}C NMR signals, were assigned from long-range {sup 1}H-{sup 13}C connectivities determined from {sup 1}H-detected multiple-bond heteronuclear multiple-quantum coherence spectroscopy (HMBC). Comparison of the {sup 13}C chemical shifts and {sup 1}H NOEs of AdoCbi{sup +} with those of coenzyme B{sup 12} ((5{prime}-deoxyadenosyl)cobalamin) and its benzimidazole-protonated, base-off form indicates that the electronic properties and structure of AdoCbi{sup +} are similar to that of coenzyme B{sup 12} in the protonated, base-off form. The {sup 13}C chemical shifts of most of the carbons of AdoCbi{sup +} do not vary significantly from those of base-off, benzimidazole-protonated coenzyme B{sup 12}, indicating that the electronic environment of the corrin ring is also similar in both compounds. However, significant differences in the chemical shifts of some of the corresponding carbons of the b, d, e, and f corrin side chains in AdoCbi{sup +} and in base-off, benzimidazole-protonated coenzyme B{sub 12} indicate that the positions of these side chains may be different in AdoCbi{sup +} compared to base-off coenzyme B{sup 12}.

  4. Neuroprotective Properties of Compounds Extracted from Dianthus superbus L. against Glutamate-induced Cell Death in HT22 Cells

    PubMed Central

    Yun, Bo-Ra; Yang, Hye Jin; Weon, Jin Bae; Lee, Jiwoo; Eom, Min Rye; Ma, Choong Je

    2016-01-01

    -methoxy-4-hydroxyphenylethanol (8), hydroferulic acid (9), and methyl hydroferulate (10) were isolated from D. superbus extract4-hydroxy-benzeneacetic acid and 4-methoxybenzeneacetic acid showed significant protective activity against glutamate-induced toxicity in HT22 cells. Abbreviations used: CNS: Central nervous system, ROS: Reactive oxygen species, CHCl3: Chloroform, EtOAc: Ethyl acetate, BuOH: Butanol, HPLC: High performance liquid chromatography, TLC: Thin layer chromatography, MPLC: Middle performance liquid chromatography, MeOH: Methanol, OD: Optical density, COSY: Correlation spectroscopy, HMQC: Heteronuclear multiple-quantum correlation, HMBC: Heteronuclear multiple-bond correlation, HR-MS: High-resolution molecular spectroscopy, MTT: 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide. PMID:27076746

  5. Lanthanide complexes of chiral 3 + 3 macrocycles derived from (1R,2R)-1,2-diaminocyclohexane and 2,6-diformyl-4-methylphenol.

    PubMed

    Paluch, Marta; Lisowski, Jerzy; Lis, Tadeusz

    2006-01-14

    The enantiopure amine macrocycle H(3)L, as well as the parent macrocyclic Schiff base H(3)L1, the 3 + 3 condensation product of (1R,2R)-1,2-diaminocyclohexane and 2,6-diformyl-4-methylphenol, are able to form mononuclear complexes with lanthanide(III) ions. The lanthanide(III) complexes of H(3)L have been studied in solution using NMR spectroscopy and electrospray mass spectrometry. The NMR spectra indicate the presence of complexes of low C(1) and C(2) symmetry. The (1)H and (13)C NMR signals of the Lu(III) complex obtained from H(3)L have been assigned on the basis of COSY, TOCSY, NOESY, ROESY and HMQC spectra. The NMR data reveal unsymmetrical binding of lanthanide(III) ion and the presence of a dynamic process corresponding to rotation of Lu(III) within the macrocycle. The [Ln(H(4)L)(NO(3))(2)](NO(3))(2)(Ln = Sm(III), Eu(III), Dy(III), Yb(III) and Lu(III)) complexes of the cationic ligand H(4)L(+) have been isolated in pure form. The X-ray analysis of the [Eu(H(4)L)(NO(3))(2)](NO(3))(2) complex confirms the coordination mode of the macrocycle determined on the basis of NMR results. In this complex the europium(III) ion is bound to three phenolate oxygen atoms and two amine nitrogen atoms of the monoprotonated macrocycle H(4)L(+), as well as to two axial bidendate nitrate anions. In the presence of a base, mononuclear La(III), Ce(III) and Pr(III) complexes of the deprotonated form of the ligand L(3-) can be obtained. When 2 equivalents of Pr(III) are used in this synthesis Na(3)[Pr(2)L(NO(3))(2)(OH)(2)](2)NO(3).5H(2)O is obtained. The NMR, ES MS and an X-ray crystal model of this complex show coordination of two Pr(III) ions by the macrocycle L. The X-ray crystal structure of the free macrocycle H(3)L1 has also been determined. In contrast to macrocyclic amine H(3)L, the Schiff base H(3)L1 adopts a cone-type conformation resembling calixarenes.

  6. Enantiomeric self-recognition in homo- and heterodinuclear macrocyclic lanthanide(III) complexes.

    PubMed

    Lisowski, Jerzy

    2011-06-20

    The controlled formation of lanthanide(III) dinuclear μ-hydroxo-bridged [Ln(2)L(2)(μ-OH)(2)X(2)](n+) complexes (where X = H(2)O, NO(3)(-), or Cl(-)) of the enantiopure chiral macrocycle L is reported. The (1)H and (13)C NMR resonances of these complexes have been assigned on the basis of COSY, NOESY, TOCSY, and HMQC spectra. The observed NOE connectivities confirm that the dimeric solid-state structure is retained in solution. The enantiomeric nature of the obtained chiral complexes and binding of hydroxide anions are reflected in their CD spectra. The formation of the dimeric complexes is accompanied by a complete enantiomeric self-recognition of the chiral macrocyclic units. The reaction of NaOH with a mixture of two different mononuclear lanthanide(III) complexes, [Ln(1)L](3+) and [Ln(2)L](3+), results in formation of the heterodinuclear [Ln(1)Ln(2)L(2)(μ-OH)(2)X(2)](n+) complexes as well as the corresponding homodinuclear complexes. The formation of the heterodinuclear complex is directly confirmed by the NOESY spectra of [EuLuL(2)(μ-OH)(2)(H(2)O)(2)](4+), which reveal close contacts between the macrocyclic unit containing the Eu(III) ion and the macrocyclic unit containing the Lu(III) ion. While the relative amounts of homo- and heterodinuclear complexes are statistical for the two lanthanide(III) ions of similar radii, a clear preference for the formation of heterodinuclear species is observed when the two mononuclear complexes contain lanthanide(III) ions of markedly different sizes, e.g., La(III) and Yb(III). The formation of heterodinuclear complexes is accompanied by the self-sorting of the chiral macrocyclic units based on their chirality. The reactions of NaOH with a pair of homochiral or racemic mononuclear complexes, [Ln(1)L(RRRR)](3+)/[Ln(2)L(RRRR)](3+), [Ln(1)L(SSSS)](3+)/[Ln(2)L(SSSS)](3+), or [Ln(1)L(rac)](3+)/[Ln(2)L(rac)](3+), results in mixtures of homochiral, homodinuclear and homochiral, heterodinuclear complexes. On the contrary, no

  7. The quantitation of nuclear Overhauser effect methods for total conformational analysis of peptides in solution. Application to gramicidin S.

    PubMed Central

    Jones, C R; Sikakana, C T; Hehir, S; Kuo, M C; Gibbons, W A

    1978-01-01

    The [1H:1H] nuclear Overhauser effects (NOE's) and spin-lattice relaxation times (T1's) are reported for the backbone protons of the decapeptide gramicidin S. Several methods for calculating interproton distances from these measurements are presented. Ratios of interproton distances were obtained from [1H:1H] NOE's and from the combination of [1H:1H]NOE'S and T1 values. Actual proton-proton distances were calculated from these ratios either by using the known distance between two geminal protons or distances derived from scalar coupling constants. The interproton distances calculated for gramicidin S are consistent with a II' beta-turn/antiparallel beta-sheet conformation. PMID:83886

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

    PubMed

    Zhang, Rongchun; Nishiyama, Yusuke; Ramamoorthy, Ayyalusamy

    2015-10-28

    A proton-detected 3D (1)H/(13)C/(1)H chemical shift correlation experiment is proposed for the assignment of chemical shift resonances, identification of (13)C-(1)H connectivities, and proximities of (13)C-(1)H and (1)H-(1)H nuclei under ultrafast magic-angle-spinning (ultrafast-MAS) conditions. Ultrafast-MAS is used to suppress all anisotropic interactions including (1)H-(1)H 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) (1)H/(1)H and 2D (13)C/(1)H (F2/F3) chemical shift correlation spectra extracted from the 3D spectrum enable the identification of (1)H-(1)H proximity and (13)C-(1)H connectivity. In addition, the 2D (F1/F2) (1)H/(13)C chemical shift correlation spectrum, incorporated with proton magnetization exchange via the fp-RFDR recoupling of (1)H-(1)H dipolar couplings, enables the measurement of proximities between (13)C and even the remote non-carbon-bonded protons. The 3D experiment also gives three-spin proximities of (1)H-(1)H-(13)C chains. Experimental results obtained from powder samples of L-alanine and L-histidine ⋅ H2O ⋅ HCl demonstrate the efficiency of the 3D experiment.

  9. 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 ṡ H2O ṡ HCl demonstrate the efficiency of the 3D experiment.

  10. 1H Photo-CIDNP Enhancements in Heteronuclear Correlation NMR Spectroscopy

    PubMed Central

    Sekhar, Ashok; Cavagnero, Silvia

    2009-01-01

    Photochemically induced dynamic nuclear polarization (photo-CIDNP) is usually employed as a probe of solvent exposure, in biomolecular NMR. The potential of the photo-CIDNP effect for sensitivity enhancement, however, remains poorly explored. Here, we introduce 1H-photo-CIDNP in heteronuclear correlation spectroscopy at low laser irradiation power (1 W), and compare the sensitivity of various 1H-Photo-CIDNP-enhanced- (HPE) 1H◻15N heteronuclear correlation pulse sequences, including HSQC, HMQC, and SOFAST-HMQC, in terms of their ability to detect the Trp indole Hε1 resonance. Both Trp and the Trp-containing protein apoHmpH were analyzed using flavin mononucleotide as photosensitizer in aqueous solutions either containing or lacking urea. We find that 1H◻15N photo-CIDNP-SOFAST-HMQC, denoted here as HPE-SOFAST-HMQC, yields a two-fold higher signal-to-noise per unit time than the parent SOFAST-HMQC for the solvent-exposed Trp of urea-unfolded apoHmpH. Thus, HPE-SOFAST-HMQC is the most sensitive heteronuclear correlation pulse sequence for the detection of solvent-exposed Trp. PMID:19462951

  11. Revised NMR data for incartine: an alkaloid from Galanthus elwesii.

    PubMed

    Berkov, Strahil; Reyes-Chilpa, Ricardo; Codina, Carles; Viladomat, Francesc; Bastida, Jaume

    2007-07-12

    Phytochemical studies on Galanthus elwesii resulted in the isolation of five alkaloids: incartine, hordenine, hippeastrine, 8-O-demethylhomolycorine and lycorine. The NMR data given previously for incartine were revised and completed by two-dimensional 1H-1H and 1H-13C chemical shift correlation experiments. In vitro studies on the bioactivity of incartine were carried out.

  12. Stacking structure of confined 1-butanol in SBA-15 investigated by solid-state NMR spectroscopy.

    PubMed

    Lin, Yun-Chih; Chou, Hung-Lung; Sarma, Loka Subramanyam; Hwang, Bing-Joe

    2009-10-12

    Understanding the complex thermodynamic behavior of confined amphiphilic molecules in biological or mesoporous hosts requires detailed knowledge of the stacking structures. Here, we present detailed solid-state NMR spectroscopic investigations on 1-butanol molecules confined in the hydrophilic mesoporous SBA-15 host. A range of NMR spectroscopic measurements comprising of (1)H spin-lattice (T(1)), spin-spin (T(2)) relaxation, (13)C cross-polarization (CP), and (1)H,(1)H two-dimensional nuclear Overhauser enhancement spectroscopy ((1)H,(1)H 2D NOESY) with the magic angle spinning (MAS) technique as well as static wide-line (2)H NMR spectra have been used to investigate the dynamics and to observe the stacking structure of confined 1-butanol in SBA-15. The results suggest that not only the molecular reorientation but also the exchange motions of confined molecules of 1-butanol are extremely restricted in the confined space of the SBA-15 pores. The dynamics of the confined molecules of 1-butanol imply that the (1)H,(1)H 2D NOESY should be an appropriate technique to observe the stacking structure of confined amphiphilc molecules. This study is the first to observe that a significant part of confined 1-butanol molecules are orientated as tilted bilayered structures on the surface of the host SBA-15 pores in a time-average state by solid-state NMR spectroscopy with the (1)H,(1)H 2D NOESY technique.

  13. Aircraft Performance Optimization with Thrust Vector Control.

    DTIC Science & Technology

    1985-12-01

    cosY cosX (i) *’ii Y f V cosY sinx (2) h V sinY (3) mV T cosE cosv - D -mg sinY (4) 1 X cosP cosy - Ysil = mV {T cose sinv - Q + mg sinp cosy) (5) X sl...V f g { cos(N + T + a) cosv - - sinyl (23) T x"= Vos {_[cos(6N + T + a) sin v cos i + sin(N + T + a) sinu] L + L sin p) (24)w y Rf 1w[sin(6N + T + a

  14. Washable and antibacterial superhydrophbic fabric

    NASA Astrophysics Data System (ADS)

    Ou, Junfei; Wang, Zhile; Wang, Fajun; Xue, Mingshan; Li, Wen; Amirfazli, Alidad

    2016-02-01

    Inspired by the high adherence of mussel and the excellent water repellency of lotus leaf, superhydrophobic fabric is fabricated via the sequential deposition of polydopamine, Ag2O, and 1H,1H,2H,2H-perfluorodecanethiol, which shows excellent washability and high anti-bacterial activity due to the strong interfacial interaction and the surface silver species as well as the non-wettability, respectively.

  15. Guiding the self-assembly of a second-generation polyphenylene dendrimer into well-defined patterns.

    PubMed

    Heyen, An J J Ver; Buron, Cédric C; Tianshi, Qin; Bauer, Roland; Jonas, Alain M; Müllen, Klaus; De Schryver, Frans C; De Feyter, Steven

    2008-08-01

    A second-generation polyphenylene dendrimer 1 is shown to self-assemble into nanofibers. To guide the formation of the dendrimer fibers into well-defined patterns, 1H,1H,2H,2H-perfluorodecyltrichlorosilane is grafted in the gas phase onto a silicon substrate. De-wetting of the solution on the nanopatterned surface results in the formation of a nanostructured template, into which fiber growth subsequently occurs under the constraints set by the de-wetted morphology.

  16. The calyxolanes: new 1,3-diphenylbutanoid metabolites isolated from the Caribbean marine sponge Calyx podatypa.

    PubMed

    Rodríguez, A D; Cóbar, O M; Padilla, O L

    1997-09-01

    Calyxolanes A (1) and B (2) are rare 1,3-diphenylbutanoid compounds isolated from the marine sponge Calyx podatypa collected in Puerto Rico. Their structures, including relative stereochemistry, have been determined by spectroscopic methods. The unique 2,4-diphenyloxolane function in 1 and 2 was established by 2D 1H-1H and 1H-13C NMR correlation experiments and confirmed by mass spectral analysis. A suggestion is made as to their biogenetic origin.

  17. High-resolution NMR characterization of low abundance oligomers of amyloid-β without purification.

    PubMed

    Kotler, Samuel A; Brender, Jeffrey R; Vivekanandan, Subramanian; Suzuki, Yuta; Yamamoto, Kazutoshi; Monette, Martine; Krishnamoorthy, Janarthanan; Walsh, Patrick; Cauble, Meagan; Holl, Mark M Banaszak; Marsh, E Neil G; Ramamoorthy, Ayyalusamy

    2015-07-03

    Alzheimer's disease is characterized by the misfolding and self-assembly of the amyloidogenic protein amyloid-β (Aβ). The aggregation of Aβ leads to diverse oligomeric states, each of which may be potential targets for intervention. Obtaining insight into Aβ oligomers at the atomic level has been a major challenge to most techniques. Here, we use magic angle spinning recoupling (1)H-(1)H NMR experiments to overcome many of these limitations. Using (1)H-(1)H dipolar couplings as a NMR spectral filter to remove both high and low molecular weight species, we provide atomic-level characterization of a non-fibrillar aggregation product of the Aβ1-40 peptide using non-frozen samples without isotopic labeling. Importantly, this spectral filter allows the detection of the specific oligomer signal without a separate purification procedure. In comparison to other solid-state NMR techniques, the experiment is extraordinarily selective and sensitive. A resolved 2D spectra could be acquired of a small population of oligomers (6 micrograms, 7% of the total) amongst a much larger population of monomers and fibers (93% of the total). By coupling real-time (1)H-(1)H NMR experiments with other biophysical measurements, we show that a stable, primarily disordered Aβ1-40 oligomer 5-15 nm in diameter can form and coexist in parallel with the well-known cross-β-sheet fibrils.

  18. High-resolution NMR characterization of low abundance oligomers of amyloid-β without purification

    NASA Astrophysics Data System (ADS)

    Kotler, Samuel A.; Brender, Jeffrey R.; Vivekanandan, Subramanian; Suzuki, Yuta; Yamamoto, Kazutoshi; Monette, Martine; Krishnamoorthy, Janarthanan; Walsh, Patrick; Cauble, Meagan; Holl, Mark M. Banaszak; Marsh, E. Neil. G.; Ramamoorthy, Ayyalusamy

    2015-07-01

    Alzheimer’s disease is characterized by the misfolding and self-assembly of the amyloidogenic protein amyloid-β (Aβ). The aggregation of Aβ leads to diverse oligomeric states, each of which may be potential targets for intervention. Obtaining insight into Aβ oligomers at the atomic level has been a major challenge to most techniques. Here, we use magic angle spinning recoupling 1H-1H NMR experiments to overcome many of these limitations. Using 1H-1H dipolar couplings as a NMR spectral filter to remove both high and low molecular weight species, we provide atomic-level characterization of a non-fibrillar aggregation product of the Aβ1-40 peptide using non-frozen samples without isotopic labeling. Importantly, this spectral filter allows the detection of the specific oligomer signal without a separate purification procedure. In comparison to other solid-state NMR techniques, the experiment is extraordinarily selective and sensitive. A resolved 2D spectra could be acquired of a small population of oligomers (6 micrograms, 7% of the total) amongst a much larger population of monomers and fibers (93% of the total). By coupling real-time 1H-1H NMR experiments with other biophysical measurements, we show that a stable, primarily disordered Aβ1-40 oligomer 5-15 nm in diameter can form and coexist in parallel with the well-known cross-β-sheet fibrils.

  19. Phase transformations in ion-irradiated silicides

    NASA Technical Reports Server (NTRS)

    Hewett, C. A.; Lau, S. S.; Suni, I.; Hung, L. S.

    1985-01-01

    The present investigation has three objectives. The first is concerned with the phase transformation of CoSi2 under ion implantation and the subsequent crystallization characteristics during annealing, taking into account epitaxial and nonepitaxial recrystallization behavior. The second objective is related to a study of the general trend of implantation-induced damage and crystallization behavior for a number of commonly used silicides. The last objective involves a comparison of the recrystallization behavior of cosputtered refractory silicides with that of the ion-implanted silicides. It was found that epitaxial regrowth of ion-irradiated CoSi2 occurred for samples with an epitaxial seed left at the Si/CoSi2 interface. A structural investigation of CoSi2 involving transmission electron microscopy (TEM) showed that after high-dose implantation CoSi2 is amorphous.

  20. Fabrication of photovoltaic laser energy converterby MBE

    NASA Technical Reports Server (NTRS)

    Lu, Hamilton; Wang, Scott; Chan, W. S.

    1993-01-01

    A laser-energy converter, fabricated by molecular beam epitaxy (MBE), was developed. This converter is a stack of vertical p-n junctions connected in series by low-resistivity, lattice matched CoSi2 layers to achieve a high conversion efficiency. Special high-temperature electron-beam (e-beam) sources were developed especially for the MBE growth of the junctions and CoSi2 layers. Making use of the small (greater than 1.2 percent) lattice mismatch between CoSi2 and Si layers, high-quality and pinhole-free epilayers were achieved, providing a capability of fabricating all the junctions and connecting layers as a single growth process with one pumpdown. Well-defined multiple p-n junctions connected by CoSi2 layers were accomplished by employing a low growth temperature (greater than 700 C) and a low growth rate (less than 0.5 microns/hour). Producing negligible interdiffusion, the low growth temperature and rate also produced negligible pinholes in the CoSi2 layers. For the first time, a stack of three p-n junctions connected by two 10(exp -5) Ohm-cm CoSi2 layers was achieved, meeting the high conversion efficiency requirement. This process can now be optimized for high growth rate to form a practical converter with 10 p-n junctions in the stack.

  1. Assessing the quality of conformal treatment planning: a new tool for quantitative comparison.

    PubMed

    Menhel, J; Levin, D; Alezra, D; Symon, Z; Pfeffer, R

    2006-10-21

    We develop a novel radiotherapy plan comparison index, critical organ scoring index (COSI), which is a measure of both target coverage and critical organ overdose. COSI is defined as COSI=1-(V(OAR)>tol/TC), where V(OAR)>tol is the fraction of volume of organ at risk receiving more than tolerance dose, and TC is the target coverage, VT,PI/VT, where VT,PI is the target volume receiving at a least prescription dose and VT is the total target volume. COSI approaches unity when the critical structure is completely spared and the target coverage is unity. We propose a two-dimensional, graphical representation of COSI versus conformity index (CI), where CI is a measure of a normal tissue overdose. We show that this 2D representation is a reliable, visual quantitative tool for evaluating competing plans. We generate COSI-CI plots for three sites: head and neck, cavernous sinus, and pancreas, and evaluate competing non-coplanar 3D and IMRT treatment plans. For all three sites this novel 2D representation assisted the physician in choosing the optimal plan, both in terms of target coverage and in terms of critical organ sparing. We verified each choice by analysing individual DVHs and isodose lines. Comparing our results to the widely used conformation number, we found that in all cases where there were discrepancies in the choice of the best treatment plan, the COSI-CI choice was considered the correct one, in several cases indicating that a non-coplanar 3D plan was superior to the IMRT plans. The choice of plan was quick, simple and accurate using the new graphical representation.

  2. Synthesis, potentiometric, kinetic, and NMR Studies of 1,4,7,10-tetraazacyclododecane-1,7-bis(acetic acid)-4,10-bis(methylenephosphonic acid) (DO2A2P) and its complexes with Ca(II), Cu(II), Zn(II) and lanthanide(III) ions.

    PubMed

    Kálmán, Ferenc K; Baranyai, Zsolt; Tóth, Imre; Bányai, István; Király, Róbert; Brücher, Ernö; Aime, Silvio; Sun, Xiankai; Sherry, A Dean; Kovács, Zoltán

    2008-05-05

    an OH (-) assisted process but, unlike formation of Ln(DOTA) complexes, rearrangement of Ln(H 2DO2A2P)* also takes place spontaneously likely as a result of transfer of one of the protons from a ring nitrogen to a phosphonate group. The order of the OH (-) assisted formation rates of complexes is DOTA > DO2A2P > DOTP while the order of the proton assisted dissociation rates of the Gd (3+) complexes is reversed, DOTP > DO2A2P > DOTA. (1)H and (13)C NMR spectra of Eu(DO2A2P) and Lu(DO2A2P) were assigned using two-dimensional correlation spectroscopy (2D COSY), heteronuclear multiple quantum coherence (HMQC), heteronuclear chemical shift correlation (HETCOR), and exchange spectroscopy (EXSY) NMR methods. Two sets of (1)H NMR signals were observed for Eu(DO2A2P) characteristic of the presence of two coordination isomers in solution, a twisted square antiprism (TSAP) and a square antiprism (SAP), in the ratio of ~93% and ~7%, respectively. Line shape analysis of the (1)H NMR spectra of Lu(DO2A2P) gave lower activation parameters compared to La(DOTP) for interconversion between coordination isomers. This indicates that the Ln(DO2A2P) complexes are less rigid probably due to the different size and spatial requirements of the carboxylate and phosphonate groups.

  3. Determination of fluorotelomer alcohols in selected consumer products and preliminary investigation of their fate in the indoor environment.

    PubMed

    Liu, Xiaoyu; Guo, Zhishi; Folk, Edgar E; Roache, Nancy F

    2015-06-01

    The U.S. Environmental Protection Agency (EPA) has established an ongoing effort to identify the major perfluorocarboxylic acid (PFCA) sources in nonoccupational indoor environments and characterize their transport and fate. This study determined the concentrations of fluorotelomer alcohols (FTOHs), which are the precursors to PFCAs, in fifty-four consumer products collected from the U.S. open market in the years of 2011 and 2013. The products included carpet, commercial carpet-care liquids, household carpet/fabric-care liquids, treated apparel, treated home textiles, treated non-woven medical garments, floor waxes, food-contact paper, membranes for apparel, and thread-sealant tapes. The FTOHs quantified were 1H,1H,2H,2H-perfluoro-1-octanol (6:2 FTOH), 1H,1H,2H,2H-perfluoro-1-decanol (8:2 FTOH), and 1H,1H,2H,2H-perfluoro-1-dodecanol (10:2 FTOH). The content of 6:2 FTOH ranged from non-delectable to 331μgg(-1), 8:2 FTOH from non-delectable to 92μgg(-1), and 10:2 FTOH from non-detectable to 24μgg(-1). In addition, two consumer products from the home textile category were tested in the washing-drying process. One product from the treated apparel category and one from the home textile category were tested in the micro-scale chamber under elevated temperatures. The experimental data show that the washing-drying process with one cycle did not significantly reduce the FTOH concentrations in the tested consumer products. FTOH off-gassing was observed under accelerated aging conditions. Future tests should include air sampling to allow determination of the absolute emission rates at different temperatures. The results of this study should be informative to exposure assessment and risk management.

  4. Insights into atomic-level interaction between mefenamic acid and eudragit EPO in a supersaturated solution by high-resolution magic-angle spinning NMR spectroscopy.

    PubMed

    Higashi, Kenjirou; Yamamoto, Kazutoshi; Pandey, Manoj Kumar; Mroue, Kamal H; Moribe, Kunikazu; Yamamoto, Keiji; Ramamoorthy, Ayyalusamy

    2014-01-06

    The intermolecular interaction between mefenamic acid (MFA), a poorly water-soluble nonsteroidal anti-inflammatory drug, and Eudragit EPO (EPO), a water-soluble polymer, is investigated in their supersaturated solution using high-resolution magic-angle spinning (HRMAS) nuclear magnetic resonance (NMR) spectroscopy. The stable supersaturated solution with a high MFA concentration of 3.0 mg/mL is prepared by dispersing the amorphous solid dispersion into a d-acetate buffer at pH 5.5 and 37 °C. By virtue of MAS at 2.7 kHz, the extremely broad and unresolved (1)H resonances of MFA in one-dimensional (1)H NMR spectrum of the supersaturated solution are well-resolved, thus enabling the complete assignment of MFA (1)H resonances in the aqueous solution. Two-dimensional (2D) (1)H/(1)H nuclear Overhauser effect spectroscopy (NOESY) and radio frequency-driven recoupling (RFDR) under MAS conditions reveal the interaction of MFA with EPO in the supersaturated solution at an atomic level. The strong cross-correlations observed in the 2D (1)H/(1)H NMR spectra indicate a hydrophobic interaction between the aromatic group of MFA and the backbone of EPO. Furthermore, the aminoalkyl group in the side chain of EPO forms a hydrophilic interaction, which can be either electrostatic or hydrogen bonding, with the carboxyl group of MFA. We believe these hydrophobic and hydrophilic interactions between MFA and EPO molecules play a key role in the formation of this extremely stable supersaturated solution. In addition, 2D (1)H/(1)H RFDR demonstrates that the molecular MFA-EPO interaction is quite flexible and dynamic.

  5. New pregnane glycosides from Gymnema sylvestre.

    PubMed

    Xu, Rui; Yang, Yu; Zhang, Yang; Ren, Fengxia; Xu, Jinlong; Yu, Nengjiang; Zhao, Yimin

    2015-02-12

    Four new pregnane glycosides 1-4 were isolated from the ethanol extract of the stem of Gymnema sylvestre and named gymsylvestrosides A-D. Hydrolysis of compound 1 under the catalysis of Aspergilus niger β-glucosidase afforded compound 5 (gymsylvestroside E). Their structures were determined by spectroscopic methods such as HRESIMS, 1D and 2D NMR, as well as HMQC-TOCSY experiment. Compounds 1-4 were screened for Saccharomyces cerevisiae α-glucosidase inhibitory activity.

  6. Four new lactones from Botrytis cinerea.

    PubMed

    Colmenares, Ana J; Durán-Patrón, Rosa M; Hernández-Galán, Rosario; Collado, Isidro G

    2002-11-01

    Four new lactones (1-4) have been isolated from Botrytis cinerea. Their structures were elucidated by interpretation of spectral data, mainly (1)H and (13)C NMR, including two-dimensional analysis (HOMOCOSY, HMQC, and HMBC). The phytotoxic activities of these new natural products have been evaluated. Compounds 1-3 were inactive, while 4 showed a phytotoxic effect when tested up to 250 ppm.

  7. Structural determination of prunusins A and B, new C-alkylated flavonoids from Prunus domestica, by 1D and 2D NMR spectroscopy.

    PubMed

    Mahmood, Azhar; Fatima, Itrat; Kosar, Shaheen; Ahmed, Rehana; Malik, Abdul

    2010-02-01

    Prunusins A (1) and B (2), the new C-alkylated flavonoids, have been isolated from the seed kernels of Prunus domestica. Their structures were assigned from (1)H and (13)C nuclear magnetic resonating spectra, DEPT and by correlation spectroscopy, HMQC and HMBC experiments. 3, 5, 7, 4'-Tetrahydroxyflavone (3) and 3, 5, 7-trihydroxy-8, 4'-dimethoxyflavone (4) have also been reported from this species. Both compounds (1) and (2) showed significant antifungal activity against pathogenic fungus Trichophyton simmi.

  8. Salvinicins A and B, new neoclerodane diterpenes from Salvia divinorum.

    PubMed

    Harding, Wayne W; Tidgewell, Kevin; Schmidt, Matthew; Shah, Kushal; Dersch, Christina M; Snyder, John; Parrish, Damon; Deschamps, Jeffrey R; Rothman, Richard B; Prisinzano, Thomas E

    2005-07-07

    [reaction: see text] Two new neoclerodane diterpenes, salvinicins A (4) and B (5), were isolated from the dried leaves of Salvia divinorum. The structures of these compounds were elucidated by spectroscopic techniques, including (1)H and (13)C NMR, NOESY, HMQC, and HMBC. The absolute stereochemistry of these compounds was assigned on the basis of single-crystal X-ray crystallographic analysis of salvinicin A (4) and a 3,4-dichlorobenzoate derivative of salvinorin B.

  9. Salvinicins A and B, New Neoclerodane Diterpenes from Salvia divinorum

    PubMed Central

    Harding, Wayne W.; Tidgewell, Kevin; Schmidt, Matthew; Shah, Kushal; Dersch, Christina M.; Snyder, John; Parrish, Damon; Deschamps, Jeffrey R.; Rothman, Richard B.

    2008-01-01

    Two new neoclerodane diterpenes, salvinicins A (4) and B (5), were isolated from the dried leaves of Salvia divinorum. The structures of these compounds were elucidated by spectroscopic techniques, including 1H and 13C NMR, NOESY, HMQC, and HMBC. The absolute stereochemistry of these compounds was assigned on the basis of single crystal X-ray crystallographic analysis of salvinicin A (4) and a 3,4-dichlorobenzoate derivative of salvinorin B. PMID:15987194

  10. A new C-Glycosylflavone from Encyclia michuacana

    NASA Astrophysics Data System (ADS)

    Tovar-Gijón, Claudia E.; Hernández-Carlos, Beatriz; Burgueño-Tapia, Eleuterio; Cedillo-Portugal, Ernestina; Joseph-Nathan, Pedro

    2006-02-01

    The methanol extracts from Encyclia michuacana tubercles yielded the new 8- C-(6-deoxy-β- D-glucopyranosyl)apigenin ( 1) together with known 1-(3'-hydroxy-5'-methoxyphenyl)-2-(4″-hydroxy-5″-methoxyphenyl)ethane ( 2) and 2-(4-hydroxybenzyl)malic acid ( 3). The new structure was elucidated using spectroscopic methods, mainly 1D and 2D NMR. The β-anomer for 1 was supported by comparison of the experimental 1H- 1H coupling constant values with those generated employing a generalized Karplus-type relationship using dihedral angles extracted from DFT calculations.

  11. A smart surface with switchable wettability by an ionic liquid.

    PubMed

    Chang, Li; Liu, Hongliang; Ding, Yi; Zhang, Jiajing; Li, Li; Zhang, Xiqi; Liu, Mingzhu; Jiang, Lei

    2017-02-28

    Smart control of surface wettability by ionic liquids (ILs) is significant for designing IL-related intelligent materials and devices. Herein, we present mixed molecular brushes comprised of poly(phenylethyl methacrylate) and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (PPhEtMA-co-PFDMS) grafted surfaces that are capable of dynamically regulating 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm][NTf2]) wettability. (1)H NMR and quartz crystal microbalance characterization demonstrate that the wettability changes result from a temperature-dominated cation-π interaction between [EMIm][NTf2] and PPhEtMA-co-PFDMS brushes.

  12. Complete assignment of NMR data of 22 phenyl-1H-pyrazoles' derivatives.

    PubMed

    de Oliveira, Aline Lima; Alves de Oliveira, Carlos Henrique; Mairink, Laura Maia; Pazini, Francine; Menegatti, Ricardo; Lião, Luciano Morais

    2011-08-01

    Complete assignment of (1)H and (13)C NMR chemical shifts and J((1)H/(1)H and (1)H/(19)F) coupling constants for 22 1-phenyl-1H-pyrazoles' derivates were performed using the concerted application of (1)H 1D and (1)H, (13)C 2D gs-HSQC and gs-HMBC experiments. All 1-phenyl-1H-pyrazoles' derivatives were synthesized as described by Finar and co-workers. The formylated 1-phenyl-1H-pyrazoles' derivatives were performed under Duff's conditions.

  13. Thermoresponsive PNIPAAm-modified cotton fabric surfaces that switch between superhydrophilicity and superhydrophobicity

    NASA Astrophysics Data System (ADS)

    Jiang, Cheng; Wang, Qihua; Wang, Tingmei

    2012-03-01

    Thermoresponsive poly(N-isopropylacrylamide) (PNIPAAm) was grafted onto the cotton fabric by atom transfer radical polymerization (ATRP). Introducing 1H,1H,2H,2H-perfluorodecyltriethoxysilane (PFDTS) onto the surface, the density of PNIPAAm chains can be adjusted because of the competitive reactions of (3-aminopropyl) triethoxysilane (APS) and PFDTS. With the appropriate ratio of APS and PFDTS, the cotton fabric can be switched from superhydrophilic to superhydrophobic by controlling temperature. The prepared cotton fabric may find application in functional textiles, soft and folding superhydrophobic materials.

  14. Controlled modulation of electronic properties of graphene by self-assembled monolayers on SiO2 substrates.

    PubMed

    Yan, Zheng; Sun, Zhengzong; Lu, Wei; Yao, Jun; Zhu, Yu; Tour, James M

    2011-02-22

    In this study, with self-assembled monolayers (SAMs) of aminopropyl-, ammoniumpropyl-, butyl-, and 1H,1H,2H,2H-perfluorooctyltriethoxysilanes deposited in-between graphene and the SiO(2) substrate, a controlled doping of graphene was realized with a threshold voltage ranging from -18 to 30 V. In addition, the SAMs are covalently bonded to the SiO(2) surface rather than the graphene surface, thereby producing minimal effects on the mobility of the graphene. Finally, it is more stable than conventional noncovalent dopants.

  15. Extending the Lifetime of Perovskite Solar Cells using a Perfluorinated Dopant.

    PubMed

    Salado, Manuel; Ramos, F Javier; Manzanares, Valentin M; Gao, Peng; Nazeeruddin, Mohammad Khaja; Dyson, Paul J; Ahmad, Shahzada

    2016-09-22

    The principle limitation of perovskite solar cells is related to their instability and, hence, their limited lifetime. Herein, we employ an imidazolium iodide dopant, 1-methyl-3-(1H,1H,2H,2H-nonafluorohexyl)-imidazolium iodide, containing a perfluorous appendage, which leads to prolonged (unencapsulated, under Ar atmosphere) device activities exceeding 100 days without compromising the power conversion efficiency and other photovoltaic parameters. The extended lifetime of the device can be attributed, at least in part, to the hydrophobic nature of the imidazolium iodide salt. The functionalization of the perovskite material was found to have negligible influence on the perovskite crystal structure.

  16. Structure and gene cluster of the O-antigen of Escherichia coli O133.

    PubMed

    Shashkov, Alexander S; Zhang, Yuanyuan; Sun, Qiangzheng; Guo, Xi; Senchenkova, Sof'ya N; Perepelov, Andrei V; Knirel, Yuriy A

    2016-07-22

    The O-specific polysaccharide (O-antigen) of Escherichia coli O133 was obtained by mild acid hydrolysis of the lipopolysaccharide of E. coli O133. The structure of the hexasaccharide repeating unit of the polysaccharide was elucidated by (1)H and (13)C NMR spectroscopy, including a two-dimensional (1)H-(1)H ROESY experiment: Functions of genes in the O-antigen gene cluster were putatively identified by comparison with sequences in the available databases and, particularly, an encoded predicted multifunctional glycosyltransferase was assigned to three α-l-rhamnosidic linkages.

  17. Derivatives of pyrazinecarboxylic acid: 1H, 13C and 15N NMR spectroscopic investigations.

    PubMed

    Holzer, Wolfgang; Eller, Gernot A; Datterl, Barbara; Habicht, Daniela

    2009-07-01

    NMR spectroscopic studies are undertaken with derivatives of 2-pyrazinecarboxylic acid. Complete and unambiguous assignment of chemical shifts ((1)H, (13)C, (15)N) and coupling constants ((1)H,(1)H; (13)C,(1)H; (15)N,(1)H) is achieved by combined application of various 1D and 2D NMR spectroscopic techniques. Unequivocal mapping of (13)C,(1)H spin coupling constants is accomplished by 2D (delta,J) long-range INEPT spectra with selective excitation. Phenomena such as the tautomerism of 3-hydroxy-2-pyrazinecarboxylic acid are discussed.

  18. DFT molecular modeling and NMR conformational analysis of a new longipinenetriolone diester

    NASA Astrophysics Data System (ADS)

    Cerda-García-Rojas, Carlos M.; Guerra-Ramírez, Diana; Román-Marín, Luisa U.; Hernández-Hernández, Juan D.; Joseph-Nathan, Pedro

    2006-05-01

    The structure and conformational behavior of the new natural compound (4 R,5 S,7 S,8 R,9 S,10 R,11 R)-longipin-2-en-7,8,9-triol-1-one 7-angelate-9-isovalerate (1) isolated from Stevia eupatoria, were studied by molecular modeling and NMR spectroscopy. A Monte Carlo search followed by DFT calculations at the B3LYP/6-31G* level provided the theoretical conformations of the sesquiterpene framework, which were in full agreement with results derived from the 1H- 1H coupling constant analysis.

  19. A proof for negative vicinal proton-proton and proton-carbon spin-spin couplings in aliphatic aldehydes by using temperature and solvent dependence. Conformational studies on glycolaldehyde and di- tert-butyl ethanal

    NASA Astrophysics Data System (ADS)

    Laatikainen, Reino; Král, Vladimir; Äyräs, Pertti

    A negative 1H, 1H three-bond coupling 3J( CHO), H) was found for glycolaldehyde by varying solvent composition. A negative 3J( CHO), C) is demonstrated for di- tert-butyl ethanal by following the temperature dependence of the coupling. 3JgB( CHO), H) of -0.73 and 3Jg( CHO), C) of -0.26 Hz (g = gauche) for the compounds were estimated by fitting the temperature dependence of the couplings by using the two-site approach. The conformational behavior of the vicinal couplings in aliphatic aldehydes and the conformations of the title compounds are briefly discussed.

  20. 1H and 13C NMR Chemical Shift Assignments and Conformational Analysis for the Two Diastereomers of the Vitamin K Epoxide Reductase Inhibitor Brodifacoum

    SciTech Connect

    Cort, John R.; Cho, Herman M.

    2009-10-01

    Proton and 13C NMR chemical shift assignments and 1H-1H scalar couplings for the two diastereomers of the vitamin K epoxide reductase (VKOR) inhibitor brodifacoum have been determined from acetone solutions containing both diastereomers. Data were obtained from homo- and heteronuclear correlation spectra acquired at 1H frequencies of 750 and 900 MHz over a 268-303 K temperature range. Conformations inferred from scalar coupling and 1-D NOE measurements exhibit large differences between the diastereomers. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  1. Revised NMR data for 9-O-demethylgalanthine: an alkaloid from Zephyranthes robusta (Amaryllidaceae) and its biological activity.

    PubMed

    Safratová, Marcela; Novák, Zdenek; Kulhánková, Andrea; Kunes, Jirí; Hrabinová, Martina; Jun, Daniel; Macáková, Katerina; Opletal, Lubomír; Cahlíková, Lucie

    2014-06-01

    Ongoing studies of Zephyranthes robusta resulted in the isolation of the lycorine-type alkaloid previously called carinatine and 10-O-demethylgalanthine. The NMR data given previously for this compound were revised and completed by two-dimensional 1H-1H and 1H-13C chemical shift correlation experiments. The name of the isolated compound was corrected to 9-O-demethylgalanthine in accordance with the currently used system of numbering of lycorine-type alkaloids. 9-O-Demethylgalanthine and galanthine, a previously isolated alkaloid from Z robusta, were inactive in acetylcholinesterase/butyrylcholinesterase assays (IC50 > 500 microM), but showed important prolyl oligopeptidase inhibition activity.

  2. Conformational evaluation and detailed 1H and 13C NMR assignments of eremophilanolides.

    PubMed

    Burgueño-Tapia, Eleuterio; Hernández, Luis R; Reséndiz-Villalobos, Adriana Y; Joseph-Nathan, Pedro

    2004-10-01

    Extensive application of 1D and 2D NMR methodology, combined with molecular modeling, allowed the complete 1H and 13C NMR assignments of eremophilanolides from Senecio toluccanus. Comparison of the experimental 1H, 1H coupling constant values with those generated employing a generalized Karplus-type relationship, using dihedral angles extracted from MMX and DFT calculations, revealed that the epoxidized eremophilanolides 1 and 2 show conformational rigidity at room temperature, whereas molecules 3-6, containing an isolated double bond, are conformationally mobile.

  3. A study of dipolar interactions and dynamic processes of water molecules in tendon by 1H and 2H homonuclear and heteronuclear multiple-quantum-filtered NMR spectroscopy.

    PubMed

    Eliav, U; Navon, G

    1999-04-01

    The effect of proton exchange on the measurement of 1H-1H, 1H-2H, and 2H-2H residual dipolar interactions in water molecules in bovine Achilles tendons was investigated using double-quantum-filtered (DQF) NMR and new pulse sequences based on heteronuclear and homonuclear multiple-quantum filtering (MQF). Derivation of theoretical expressions for these techniques allowed evaluation of the 1H-1H and 1H-2H residual dipolar interactions and the proton exchange rate at a temperature of 24 degrees C and above, where no dipolar splitting is evident. The values obtained for these parameters at 24 degrees C were 300 and 50 Hz and 3000 s-1, respectively. The results for the residual dipolar interactions were verified by repeating the above measurements at a temperature of 1.5 degrees C, where the spectra of the H2O molecules were well resolved, so that the 1H-1H dipolar interaction could be determined directly from the observed splitting. Analysis of the MQF experiments at 1.5 degrees C, where the proton exchange was in the intermediate regime for the 1H-2H dipolar interaction, confirmed the result obtained at 24 degrees C for this interaction. A strong dependence of the intensities of the MQF signals on the proton exchange rate, in the intermediate and the fast exchange regimes, was observed and theoretically interpreted. This leads to the conclusion that the MQF techniques are mostly useful for tissues where the residual dipolar interaction is not significantly smaller than the proton exchange rate. Dependence of the relaxation times and signal intensities of the MQF experiments on the orientation of the tendon with respect to the magnetic field was observed and analyzed. One of the results of the theoretical analysis is that, in the fast exchange regime, the signal decay rates in the MQF experiments as well as in the spin echo or CPMG pulse sequences (T2) depend on the orientation as the square of the second-rank Legendre polynomial.

  4. Synthesis and spectroscopy studies of the inclusion complex of 3-amino-5-methyl pyrazole with beta-cyclodextrin.

    PubMed

    Louiz, S; Labiadh, H; Abderrahim, R

    2015-01-05

    Amino pyrazole belongs to anti-inflammatory class, and is characterized by a low solubility in water. (In order to increase its solubility in water, inclusion complex of amino pyrazole with β-CD was obtained.) The inclusion complex obtained between AMP and β-cyclodextrin, was characterized by FT-IR, (1)H NMR, (1)H-(1)H NOESY, (13)C NMR, DEPT, XHCOR, spectra, through TG analysis, DTA, DSC and Scanning Electron Microscopy (SEM). The stoichiometry of inclusion complex is 1:1 (guest-host) and K stability is 1.1 × 10(4)M(-1).

  5. Synthesis and spectroscopy studies of the inclusion complex of 3-amino-5-methyl pyrazole with beta-cyclodextrin

    NASA Astrophysics Data System (ADS)

    Louiz, S.; Labiadh, H.; Abderrahim, R.

    2015-01-01

    Amino pyrazole belongs to anti-inflammatory class, and is characterized by a low solubility in water. (In order to increase its solubility in water, inclusion complex of amino pyrazole with β-CD was obtained.) The inclusion complex obtained between AMP and β-cyclodextrin, was characterized by FT-IR, 1H NMR, 1H-1H NOESY, 13C NMR, DEPT, XHCOR, spectra, through TG analysis, DTA, DSC and Scanning Electron Microscopy (SEM). The stoichiometry of inclusion complex is 1:1 (guest-host) and K stability is 1.1 × 104 M-1.

  6. Electronic properties of Co and Ni silicides: a theoretical approach using extended Huckel method

    NASA Astrophysics Data System (ADS)

    Galvan, D. H.; Posada Amarillas, A.; Samaniego Reyna, J. C.; García-Méndez, M.; Farías, M. H.

    2004-11-01

    Calculations of electronic structure, total and projected density of states (DOS), crystal orbital overlap population (COOP), and average net charge, and also Mulliken population analysis, were performed to study electronic properties of Co and Ni silicides. Analysis of the energy bands depicts metallic behavior for both silicides.The projected DOS yields an indication that hybridization occurs for Co and Ni silicides. The hybridized band in CoSi2 is composed of Co d and p orbitals and Si p and s orbitals, while in NiSi2 the hybridized band is formed by Ni d and p orbitals with Si p orbitals. The fact that the Fermi energy crosses a small part of the DOS, as is the case of CoSi2, yields an indication of the different electronic properties of CoSi2 when compared to NiSi2. The hybridization is stronger in CoSi2 than in NiSi2. Mulliken population analysis provides an indication that a smaller charge distribution exists in NiSi2 when compared to CoSi2. This difference in charge distribution accounts for the different electronic behavior, in agreement with the DOS analysis. Moreover, COOP analysis provides an indication of the existence of covalent bonding between M and Si (M = Ni, Co), this being stronger in Co than in Ni silicides. Furthermore, the average net charge in both compounds yields an indication that there is a charge transfer from M towards Si.

  7. Echo planar correlated spectroscopic imaging: implementation and pilot evaluation in human calf in vivo.

    PubMed

    Lipnick, Scott; Verma, Gaurav; Ramadan, Saadallah; Furuyama, Jon; Thomas, M Albert

    2010-10-01

    Exploiting the speed benefits of echo-planar imaging (EPI), the echo-planar spectroscopic imaging (EPSI) sequence facilitates recording of one spectral and two to three spatial dimensions faster than the conventional magnetic resonance spectroscopic imaging (MRSI). A novel four dimensional (4D) echo-planar correlated spectroscopic imaging (EP-COSI) was implemented on a whole body 3 T MRI scanner combining two spectral with two spatial encodings. Similar to EPSI, the EP-COSI sequence used a bipolar spatial read-out train facilitating simultaneous spatial and spectral encoding, and the conventional phase and spectral encodings for the other spatial and indirect spectral dimensions, respectively. Multiple 2D correlated spectroscopy (COSY) spectra were recorded over the spatially resolved volume of interest (VOI) localized by a train of three slice-selective radiofrequency (RF) pulses (90°-180°-90°). After the initial optimization using phantom solutions, the EP-COSI data were recorded from the lower leg of eight healthy volunteers including one endurance trained volunteer. Pilot results showed acceptable spatial and spectral quality achievable using the EP-COSI sequence. There was a detectable separation of cross peaks arising from the skeletal muscle intramyocellular lipids (IMCLs) and extramyocellular lipids (EMCLs) saturated and unsaturated pools. Residual dipolar interaction between the N-methylene and N-methyl protons of creatine/phosphocreatine (Cr/PCr) was also observed in the tibialis anterior region.

  8. Comparison of various NMR methods for the indirect detection of nitrogen-14 nuclei via protons in solids

    NASA Astrophysics Data System (ADS)

    Shen, Ming; Trébosc, Julien; O'Dell, Luke A.; Lafon, Olivier; Pourpoint, Frédérique; Hu, Bingwen; Chen, Qun; Amoureux, Jean-Paul

    2015-09-01

    We present an experimental comparison of several through-space Hetero-nuclear Multiple-Quantum Correlation experiments, which allow the indirect observation of homo-nuclear single- (SQ) or double-quantum (DQ) 14N coherences via spy 1H nuclei. These 1H-{14N} D-HMQC sequences differ not only by the order of 14N coherences evolving during the indirect evolution, t1, but also by the radio-frequency (rf) scheme used to excite and reconvert these coherences under Magic-Angle Spinning (MAS). Here, the SQ coherences are created by the application of center-band frequency-selective pulses, i.e. long and low-power rectangular pulses at the 14N Larmor frequency, ν0(14N), whereas the DQ coherences are excited and reconverted using rf irradiation either at ν0(14N) or at the 14N overtone frequency, 2ν0(14N). The overtone excitation is achieved either by constant frequency rectangular pulses or by frequency-swept pulses, specifically Wide-band, Uniform-Rate, and Smooth-Truncation (WURST) pulse shapes. The present article compares the performances of four different 1H-{14N} D-HMQC sequences, including those with 14N rectangular pulses at ν0(14N) for the indirect detection of homo-nuclear (i) 14N SQ or (ii) DQ coherences, as well as their overtone variants using (iii) rectangular or (iv) WURST pulses. The compared properties include: (i) the sensitivity, (ii) the spectral resolution in the 14N dimension, (iii) the rf requirements (power and pulse length), as well as the robustness to (iv) rf offset and (v) MAS frequency instabilities. Such experimental comparisons are carried out for γ-glycine and L-histidine.HCl monohydrate, which contain 14N sites subject to moderate quadrupole interactions. We demonstrate that the optimum choice of the 1H-{14N} D-HMQC method depends on the experimental goal. When the sensitivity and/or the robustness to offset are the major concerns, the D-HMQC sequence allowing the indirect detection of 14N SQ coherences should be employed. Conversely

  9. Reaction path and crystallograpy of cobalt silicide formation on silicon(001) by reaction deposition epitaxy

    NASA Astrophysics Data System (ADS)

    Lim, Chong Wee

    CaF2-structure CoSi2 layers were formed on Si(001) by reactive deposition epitaxy (RDE) and compared with CoSi2 layers obtained by conventional solid phase growth (SPG). In the case of RDE, CoSi 2 formation occurred during Co deposition at elevated temperature while for SPG, Co was deposited at 25°C and silicidation took place during subsequent annealing. My results demonstrate that RDE CoSi2 layers are epitaxial with a cube-on-cube relationship, 001CoSi2 ‖001Si and 100CoSi2 ‖100 Si . In contrast, SPG films are polycrystalline with a mixed 111/002/022/112 orientation. I attribute the striking difference to rapid Co diffusion during RDE for which the high Co/Si reactivity gives rise to a flux-limited reaction resulting in the direct formation of the disilicide phase. Initial formation of CoSi2(001) follows the Volmer-Weber mode with two families of island shapes: inverse pyramids and platelets. The rectangular-based pyramidal islands extend along orthogonal <110> directions, bounded by four {111} CoSi2/Si interfaces, and grow with a cube-on-cube orientation with respect to Si(001). Platelet-shaped islands are bounded across their long <110> directions by {111} twin planes and their narrow <110> directions by 511CoSi2 ‖111Si interfaces. The top and bottom surfaces are {22¯1}, with 22¯1 CoSi2‖001 Si , and {1¯1¯1}, with 1¯1¯ 1CoSi2‖ 11¯1Si , respectively. The early stages of film growth (tCo ≤ 13 A) are dominated by the twinned platelets due to a combination of higher nucleation rates and rapid elongation along preferred <110> directions. However, at tCo ≥ 13 A, island coalescence becomes significant as orthogonal platelets intersect and block elongation along fast growth directions. Further island growth becomes dominated by the untwinned islands. I show that high-flux low-energy Ar+ ion irradiation during RDE growth dramatically increases the area fraction of untwinned regions from 0.17 in films grown under standard magnetically balanced

  10. Selective Detection of 1H NMR Resonances of 13CH n Groups Using Two-Dimensional Maximum-Quantum Correlation Spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, M.; Farrant, R. D.; Nicholson, J. K.; Lindon, J. C.

    Methods for editing spectra based upon maximum-quantum filtering in two-dimensional 1H NMR are presented (MAXY NMR). Separation of 1H resonances from 13CH, 13CH 2, and 13CH 3 groups is demonstrated, using the coherence of the attached natural-abundance 13C spin. Two-dimensional correlation pulse sequences based on J connectivity (MAXY-COSY), total J connectivity (MAXY-TOCSY), and NOE and exchange processes (MAXY-NOESY) are given and exemplified using dexamethasone as a model compound. In addition, an improved form of a 13CH 2 only COSY spectrum (gem-COSY) is shown, and the application of z magnetic-field gradients is demonstrated as an alternative to phase cycling. The approach should have utility in the assignment of complex 1H NMR spectra which arise from peptides or complex mixtures such as biofluids.

  11. Studies of Beam Dynamics in Cooler Rings

    SciTech Connect

    Dietrich, J.; Stein, J.; Meshkov, I.; Sidorin, A.; Smirnov, A.

    2006-03-20

    This report describes the numerical simulation of the crystalline proton beam formation in COSY using BETACOOL code. The study includes the description of experimental results at NAP-M storage ring where the large reduction of the momentum spread was observed for first time. The present simulation shows that this behavior of proton beam can not be explained as ordered state of protons. The numerical simulation of crystalline proton beams was done for COSY parameters. The number of protons when the ordering state can be observed is limited by value 106 particles and momentum spread less then 10-6. Experimental results for the attempt to achieve of ordered state of proton beam for COSY is presented. This work is supported by RFBR grant no. 05-02-16320 and INTAS grant no. 03-54-5584.

  12. Structural Modulation from 1D Chain to 3D Framework: Improved Thermostability, Insensitivity, and Energies of Two Nitrogen-Rich Energetic Coordination Polymers.

    PubMed

    Guo, Zhaoqi; Wu, Yunlong; Deng, Chongqing; Yang, Guoping; Zhang, Jiangong; Sun, Zhihua; Ma, Haixia; Gao, Chao; An, Zhongwei

    2016-11-07

    Two new energetic coordination polymers (CPs) [Pb(BT)(H2O)3]n (1) and [Pb3(DOBT)3(H2O)2]n·(4H2O)n (2) with 1D and 3D structures were synthesized by employing two rational designed ligands, 1H,1'H-5,5'-bitetrazole (H2BT) and 1H,1'H-[5,5'-bitetrazole]-1,1'-diol ligands (DHBT), respectively. Thermal analyses and sensitivity tests show that the 3D architecture reinforces the network of 2 which has higher thermal stability and lower sensitivity than that of 1. Through oxygen-bomb combustion calorimetry the molar enthalpy of formation of 2 is derived to be much higher than that of 1 as well as the reported CPs. Herein, more importantly, the heats of detonation (ΔHdet) were calculated according to the decomposition products of TG-DSC-MS-FTIR simultaneous analyses for the first time. The calculated results show that ΔHdet of 2 is 23% higher than that of 1. This research demonstrates that 3D energetic CP with outstanding energetic properties can be obtained through efficient and reasonable design.

  13. Tuning Oleophobicity of Silicon Oxide Surfaces with Mixed Monolayers of Aliphatic and Fluorinated Alcohols.

    PubMed

    Lee, Austin W H; Gates, Byron D

    2016-12-13

    We demonstrate the formation of mixed monolayers derived from a microwave-assisted reaction of alcohols with silicon oxide surfaces in order to tune their surface oleophobicity. This simple, rapid method provides an opportunity to precisely tune the constituents of the monolayers. As a demonstration, we sought fluorinated alcohols and aliphatic alcohols as reagents to form monolayers from two distinct constituents for tuning the surface oleophobicity. The first aspect of this study sought to identify a fluorinated alcohol that formed monolayers with a relatively high surface coverage. It was determined that 1H,1H,2H,2H-perfluoro-1-octanol yielded high quality monolayers with a water contact angle (WCA) value of ∼110° and contact angle values of ∼80° with toluene and hexadecane exhibiting both an excellent hydrophobicity and oleophobicity. Tuning of the oleophobicity of the modified silicon oxide surfaces was achieved by controlling the molar ratio of 1H,1H,2H,2H-perfluoro-1-octanol within the reaction mixtures. Surface oleophobicity progressively decreased with a decrease in the fluorinated alcohol content while the monolayers maintained their hydrophobicity with WCA values of ∼110°. The simple and reliable approach to preparing monolayers of a tuned composition that is described in this article can be utilized to control the fluorocarbon content of the hydrophobic monolayers on silicon oxide surfaces.

  14. Effect of transition metal salts on the initiated chemical vapor deposition of polymer thin films

    SciTech Connect

    Kwong, Philip; Seidel, Scott; Gupta, Malancha

    2015-05-15

    In this work, the effect of transition metal salts on the initiated chemical vapor deposition of polymer thin films was studied using x-ray photoelectron spectroscopy. The polymerizations of 4-vinyl pyridine and 1H,1H,2H,2H-perfluorodecyl acrylate were studied using copper(II) chloride (CuCl{sub 2}) and iron(III) chloride (FeCl{sub 3}) as the transition metal salts. It was found that the surface coverages of both poly(4-vinyl pyridine) (P4VP) and poly(1H,1H,2H,2H-perfluorodecyl acrylate) were decreased on CuCl{sub 2}, while the surface coverage of only P4VP was decreased on FeCl{sub 3}. The decreased polymer surface coverage was found to be due to quenching of the propagating radicals by the salt, which led to a reduction of the oxidation state of the metal. The identification of this reaction mechanism allowed for tuning of the effectiveness of the salts to decrease the polymer surface coverage through the adjustment of processing parameters such as the filament temperature. Additionally, it was demonstrated that the ability of transition metal salts to decrease the polymer surface coverage could be extended to the fabrication of patterned cross-linked coatings, which is important for many practical applications such as sensors and microelectronics.

  15. Proton-Detected Solid-State NMR Spectroscopy of Bone with Ultrafast Magic Angle Spinning

    NASA Astrophysics Data System (ADS)

    Mroue, Kamal H.; Nishiyama, Yusuke; Kumar Pandey, Manoj; Gong, Bo; McNerny, Erin; Kohn, David H.; Morris, Michael D.; Ramamoorthy, Ayyalusamy

    2015-07-01

    While obtaining high-resolution structural details from bone is highly important to better understand its mechanical strength and the effects of aging and disease on bone ultrastructure, it has been a major challenge to do so with existing biophysical techniques. Though solid-state NMR spectroscopy has the potential to reveal the structural details of bone, it suffers from poor spectral resolution and sensitivity. Nonetheless, recent developments in magic angle spinning (MAS) NMR technology have made it possible to spin solid samples up to 110 kHz frequency. With such remarkable capabilities, 1H-detected NMR experiments that have traditionally been challenging on rigid solids can now be implemented. Here, we report the first application of multidimensional 1H-detected NMR measurements on bone under ultrafast MAS conditions to provide atomistic-level elucidation of the complex heterogeneous structure of bone. Our investigations demonstrate that two-dimensional 1H/1H chemical shift correlation spectra for bone are obtainable using fp-RFDR (finite-pulse radio-frequency-driven dipolar recoupling) pulse sequence under ultrafast MAS. Our results infer that water exhibits distinct 1H-1H dipolar coupling networks with the backbone and side-chain regions in collagen. These results show the promising potential of proton-detected ultrafast MAS NMR for monitoring structural and dynamic changes caused by mechanical loading and disease in bone.

  16. Smart, Sustainable, and Ecofriendly Chemical Design of Fully Bio-Based Thermally Stable Thermosets Based on Benzoxazine Chemistry.

    PubMed

    Froimowicz, Pablo; R Arza, Carlos; Han, Lu; Ishida, Hatsuo

    2016-08-09

    A smart synthetic chemical design incorporating furfurylamine, a natural renewable amine, into a partially bio-based coumarin-containing benzoxazine is presented. The versatility of the synthetic approach is shown to be flexible and robust enough to be successful under more ecofriendly reaction conditions by replacing toluene with ethanol as the reaction solvent and even under solventless conditions. The chemical structure of this coumarin-furfurylamine-containing benzoxazine is characterized by FTIR, (1) H NMR spectroscopy and two-dimensional (1) H-(1) H nuclear Overhauser effect spectroscopy (2D (1) H-(1) H NOESY). The thermal properties of the resin toward polymerization are characterized by differential scanning calorimetry (DSC) and the thermal stability of the resulting polymers by thermogravimetric analysis (TGA). The results reveal that the furanic moiety induces a co-operative activating effect, thus lowering the polymerization temperature and also contributes to a better thermal stability of the resulting polymers. These results, in addition to those of natural renewable benzoxazine resins reviewed herein, highlight the positive and beneficial implication of designing novel bio-based polybenzoxazine and possibly other thermosets with desirable and competitive properties.

  17. Differential protonation and dynamic structure of doxylamine succinate in solution using 1H and 13C NMR.

    PubMed

    Somashekar, B S; Nagana Gowda, G A; Ramesha, A R; Khetrapal, C L

    2004-07-01

    A protonation and dynamic structural study of doxylamine succinate, a 1:1 salt of succinic acid with dimethyl-[2-(1-phenyl-1-pyridin-2-yl-ethoxy)ethyl]amine, in solution using one- and two-dimensional 1H and 13C NMR experiments at variable temperature and concentration is presented. The two acidic protons of the salt doxylamine succinate are in 'intermediate' exchange at room temperature, as evidenced by the appearance of a broad signal. This signal evolves into two distinct signals below about -30 degrees C. A two-dimensional 1H-1H double quantum filtered correlation experiment carried out at -55 degrees C shows protonation of one of the acidic protons to the dimethylamine nitrogen. A two-dimensional rotating frame 1H-1H NOE experiment at the same temperature reveals that the other proton remains with the succinate moiety. Comparison of the 1H and 13C chemical shifts and the 13C T1 relaxation times of the salt with those of the free base further substantiate the findings.

  18. Characterization of Si/CoSi2/Si(111) heterostructures using Auger plasmon losses

    NASA Technical Reports Server (NTRS)

    Schowengerdt, F. D.; Lin, T. L.; Fathauer, R. W.; Grunthaner, P. J.

    1989-01-01

    The Si/CoSi2/Si heterostructures prepared by codeposition and solid-phase epitaxy on Si(111) substrates were characterized using Auger plasmon data as a measure of Si overlayer thickness. The method of calibration is described, and the results of two studies, including a study of islanding in Si/CoSi2/Si and a study of diffusion in CoSi2/Si are presented, illustrating the utility of the Auger plasmon loss technique. It is shown that, most likely, the diffusion proceeds through residual defects in the CoSi2.

  19. Electron Cooling of Intense Ion Beam

    SciTech Connect

    Dietrich, J.; Kamerdjiev, V.; Maier, R.; Prasuhn, D.; Stein, J.; Stockhorst, H.; Korotaev, Yu.; Meshkov, I.; Sidorin, A.; Smirnov, A.

    2006-03-20

    Results of experimental studies of the electron cooling of a proton beam at COSY (Juelich, Germany) are presented. Intensity of the proton beam is limited by two general effects: particle loss directly after the injection and development of instability in a deep cooled ion beam. Results of the instability investigations performed at COSY during last years are presented in this report in comparison with previous results from HIMAC (Chiba, Japan) CELSIUS (Uppsala, Sweden) and LEAR (CERN). Methods of the instability suppression, which allow increasing the cooled beam intensity, are described. This work is supported by RFBR grant no. 05-02-16320 and INTAS grant no. 03-54-5584.

  20. Simultaneous measurement of J(HH) and two different (n)J(CH) coupling constants from a single multiply edited 2D cross-peak.

    PubMed

    Saurí, Josep; Parella, Teodor

    2013-07-01

    Three different J-editing methods (IPAP, E.COSY and J-resolved) are implemented in a single NMR experiment to provide spin-state-edited 2D cross-peaks from which a simultaneous measurement of different homonuclear and heteronuclear coupling constants can be performed. A new J-selHSQMBC-IPAP experiment is proposed for the independent measurement of two different (n)J(CH) coupling constants along the F2 and F1 dimensions of the same 2D cross-peak. In addition, the E.COSY pattern provides additional information about the magnitude and relative sign between J(HH) and (n)J(CH) coupling constants.

  1. Partial-wave analysis of nucleon-nucleon elastic scattering data

    NASA Astrophysics Data System (ADS)

    Workman, Ron L.; Briscoe, William J.; Strakovsky, Igor I.

    2016-12-01

    Energy-dependent and single-energy fits to the existing nucleon-nucleon database have been updated to incorporate recent measurements. The fits cover a region from threshold to 3 GeV, in the laboratory kinetic energy, for proton-proton scattering, with an upper limit of 1.3 GeV for neutron-proton scattering. Experiments carried out at the COSY-WASA and COSY-ANKE facilities have had a significant impact on the partial-wave solutions. Results are discussed in terms of both partial-wave and direct reconstruction amplitudes.

  2. A solid-state spectrometer for cooled beams with high acceptance and resolution in space and energy

    NASA Astrophysics Data System (ADS)

    Igel, S.; Budzanowski, A.; Drochner, M.; Frekers, D.; Garske, W.; Grewer, K.; Hamacher, A.; Kemmerling, G.; Kilian, K.; Kliczewski, S.; Machner, H.; Plendl, H.; Protić, D.; Razen, B.; Srikantiah, R. V.; Zwoll, K.

    1997-02-01

    The GEM detector, a hybrid system consisting of the Germanium Wall and the magnetic spectrometer BIG KARL, was developed to investigate meson production and meson-nucleus interaction with cooled external proton beams from the COSY accelerator at Jülich. The Germanium Wall is a stack of up to four annular position-sensitive semiconductor detectors made from high-purity germanium. Its special structure allows experiments with high counting rates. Design features and results from first test runs with the uncooled COSY beam are presented.

  3. Preventing Early Leaving in VET: Distributed Pedagogical Leadership in Characterising Five Types of Successful Organisations

    ERIC Educational Resources Information Center

    Jappinen, Aini-Kristiina

    2010-01-01

    This paper presents 14 organisers of upper secondary education in Finland with exceptionally low dropout rates. As a case study in which common strengths were defined, five types of organisations with typical characteristics were found: "Working life-oriented," "Networked and team-based," "Cosy and traditional,"…

  4. Positional calibrations of the germanium double sided strip detectors for the Compton spectrometer and imager

    NASA Astrophysics Data System (ADS)

    Lowell, A.; Boggs, S.; Chiu, J. L.; Kierans, C.; McBride, S.; Tseng, C. H.; Zoglauer, A.; Amman, M.; Chang, H. K.; Jean, P.; Lin, C. H.; Sleator, C.; Tomsick, J.; von Ballmoos, P.; Yang, C. Y.

    2016-08-01

    The Compton Spectrometer and Imager (COSI) is a medium energy gamma ray (0.2 - 10 MeV) imager designed to observe high-energy processes in the universe from a high altitude balloon platform. At its core, COSI is comprised of twelve high purity germanium double sided strip detectors which measure particle interaction energies and locations with high precision. This manuscript focuses on the positional calibrations of the COSI detectors. The interaction depth in a detector is inferred from the charge collection time difference between the two sides of the detector. We outline our previous approach to this depth calibration and also describe a new approach we have recently developed. Two dimensional localization of interactions along the faces of the detector (x and y) is straightforward, as the location of the triggering strips is simply used. However, we describe a possible technique to improve the x/y position resolution beyond the detector strip pitch of 2 mm. With the current positional calibrations, COSI achieves an angular resolution of 5.6 +/- 0.1 degrees at 662 keV, close to our expectations from simulations.

  5. Columnar and subsurface silicide growth with novel molecular beam epitaxy techniques

    NASA Technical Reports Server (NTRS)

    Fathauer, R. W.; George, T.; Pike, W. T.

    1992-01-01

    We have found novel growth modes for epitaxial CoSi2 at high temperatures coupled with Si-rich flux ratios or low deposition rates. In the first of these modes, codeposition of metal and Si at 600-800 C with excess Si leads to the formation of epitaxial silicide columns surrounded by single-crystal Si. During the initial stages of the deposition, the excess Si grows homoepitaxially in between the silicide, which forms islands, so that the lateral growth of the islands is confined. Once a template layer is established by this process, columns of silicide form as a result of selective epitaxy of silicide on silicide and Si on Si. This growth process allows nanometer control over silicide particles in three dimensions. In the second of these modes, a columnar silicide seed layer is used as a template to nucleate subsurface growth of CoSi2. With a 100 nm Si layer covering CoSi2 seeds, Co deposited at 800C and 0.01 nm/s diffuses down to grow on the buried seeds rather than nucleating surface silicide islands. For thicker Si caps or higher deposition rates, the surface concentration of Co exceeds the critical concentration for nucleation of islands, preventing this subsurface growth mode from occurring. Using this technique, single-crystal layers of CoSi2 buried under single-crystal Si caps have been grown.

  6. The Effect of Humor on Learning in a Planetarium.

    ERIC Educational Resources Information Center

    Fisher, Martin S.

    1997-01-01

    The effect of humor on retention of information was examined at the planetarium at Ohio's Center of Science and Industry (COSI) in Columbus, OH. Results showed that the visitors who saw a humorous show retained less of the instructional material and scored lower on the test than the visitors who saw a nonhumorous show. (Author/DKM)

  7. Complete 1H and 13C NMR assignments and Z/E-stereoconfiguration determination of isomers of 1,4-diketone derivatives.

    PubMed

    Xu, Guohua; Yin, Guodong; Guo, Wenbo; Wu, Anxin; Cui, Yanfang

    2008-01-01

    Complete 1H and 13C NMR assignments and Z/E-stereoconfiguration determination for a series of new isomers of 1,4-diketone derivatives obtained via self-sorting tandem reaction were accomplished by means of one- and two-dimentional NMR experiments including 1H, 13C, gCOSY, gHSQC, gHMBC, and NOESY.

  8. Three new phenolic compounds from Dalbergia odorifera.

    PubMed

    Wang, Hao; Dong, Wen-Hua; Zuo, Wen-Jian; Wang, Hui; Zhong, Hui-Min; Mei, Wen-Li; Dai, Hao-Fu

    2014-12-01

    Three new phenolic compounds (1-3) were isolated from the heartwood of Dalbergia odorifera T. Chen. (Leguminosae). Their structures were established based on spectroscopic methods including 1D and 2D NMR (HSQC, COSY, HMBC and ROESY). Compound 2 exhibited cytotoxicity against BEL-7402 tumor cell lines.

  9. Complete assignment of the (1)H and (13)C NMR spectra of cis and trans isonucleoside derivatives of purine with a tetrahydropyran ring.

    PubMed

    Besada, Pedro; Costas, Tamara; Terán, Carmen

    2010-06-01

    (1)H and (13)C NMR chemical shifts of cis and trans isonucleoside analogues of purine in which the furanose moiety is substituted by a tetrahydropyran ring were completely assigned using one- and two-dimensional NMR experiments that include NOE, DEPT, COSY and HSQC. The significant (1)H and (13)C NMR signals differentiating between the cis and trans stereoisomers were compared.

  10. 3+2-Dipolar cycloaddition of dianhydrohexitol azidoderivatives with N-arylmaleimides

    NASA Astrophysics Data System (ADS)

    Gella, I. M.; Babak, N. L.; Drushlyak, T. G.; Shishkina, S. V.; Musatov, V. I.; Lipson, V. V.

    2015-11-01

    Dianhydrohexitol azides dipolar 3+2 cycloaddition with N-arylmaleimides has been studied with NMR (1H and 13C, COSY, NOESY and HSQC) and X-ray analysis. In spite of low asymmetrical induction in this reaction, diastereomerically pure products have been obtained. These products are interesting over their structural similarity to griseolic acid derivatives and dihydropyrrolotriazoles, significant for pharmaceutics.

  11. A Profiling System for the Assessment of Individual Needs for Rehabilitation With Hearing Aids

    PubMed Central

    de Ronde-Brons, I.

    2016-01-01

    This study focuses on the development of a profiling system to specify the needs of hearing-aid candidates. As a basis for the profile of compensation needs, we used a slightly modified version of the Amsterdam Inventory of Disability and Handicap, combined with the well-known Client-Oriented Scale of Improvement (COSI). The first questionnaire results in scores for six audiological dimensions: detection, speech in quiet, speech in noise, localization, focus or discrimination, and noise tolerance. The goal of this study was to determine whether the six dimensions derived from the disability questionnaire are appropriate to also categorize individual COSI targets. The results show a good agreement between eight audiologists in the categorization of COSI goals along the six dimensions. The results per dimension show that the dimension focus or discrimination can be regarded as superfluous. Possible additional dimensions were tinnitus and listening effort. The results indicate that it is possible to translate individual user needs (administered using COSI) into more general dimensions derived from a disability questionnaire. This allows to summarize the compensation needs for individual patients in a profile of general dimensions, based on the degree of disability and the individual user needs. This profile can be used as a starting point in hearing aid selection. This approach also offers a well-structured method for the evaluation of the postfitting results. PMID:27815547

  12. Calibration of the Compton Spectrometer and Imager in preparation for the 2014 balloon campaign

    NASA Astrophysics Data System (ADS)

    Kierans, C. A.; Boggs, S. E.; Lowell, A.; Tomsick, J.; Zoglauer, A.; Amman, M.; Chiu, J.-L.; Chang, H.-K.; Lin, C.-H.; Jean, P.; von Ballmoos, P.; Yang, C.-Y.; Shang, J.-R.; Tseng, C.-H.; Chou, Y.; Chang, Y.-H.

    2014-07-01

    The Compton Spectrometer and Imager (COSI) is a balloon-borne soft gamma-ray (0.2-5 MeV) telescope designed to perform wide-field imaging, high-resolution spectroscopy, and novel polarization measurements of astrophysical sources. COSI employs a compact Compton telescope design, utilizing 12 cross-strip germanium detectors to track the path of incident photons, where position and energy deposits from Compton interactions allow for a reconstruction of the source position in the sky, an inherent measure of the linear polarization, and significant background reduction. The instrument has recently been rebuilt with an updated and optimized design; the polarization sensitivity and effective area have increased due to a change in detector configuration, and the new lightweight gondola is suited to fly on ultra-long duration flights with the addition of a mechanical cryocooler system. COSI is planning to launch from the Long Duration Balloon site at McMurdo Station, Antarctica, in December 2014, where our primary science goal will be to measure gamma-ray burst (GRB) polarization. In preparation for the 2014 campaign, we have performed preliminary calibrations of the energy and 3-D position of interactions within the detector, and simulations of the angular resolution and detector efficiency of the integrated instrument. In this paper we will present the science goals for the 2014 COSI campaign and the techniques and results of the preliminary calibrations.

  13. Antiproliferative oleanane saponins from Dizygotheca elegantissima.

    PubMed

    Vassallo, Antonio; Pesca, Mariasabina; Ambrosio, Letizia; Malafronte, Nicola; Melle, Nadia Dekdouk; Dal Piaz, Fabrizio; Severino, Lorella

    2012-11-01

    Four new oleanane saponins (1-4), together with three known saponins, were isolated from the aerial parts of Dizygotheca elegantissima R. Vig. & Guillaumin. Their structures were elucidated by 1D and 2D NMR experiments including 1D TOCSY, DQF-COSY, HSQC, and HMBC spectroscopy, as well as ESIMS analysis. The antiproliferative activity of all isolated compounds was evaluated.

  14. Complete Assignment of (1)H-NMR Resonances of the King Cobra Neurotoxin CM-11.

    PubMed

    Pang, Yu-Xi; Liu, Wei-Dong; Liu, Ai-Zhuo; Pei, Feng-Kui

    1997-01-01

    The king cobra (Ophiophagus Hannah) neurotoxin CM-Il is long-chain peptide with 72 amino acid residues. Its complete assignment of (1)H-NMR resonances was obtained using various 2D-NMR technologies, including DQF-COSY, clean-TOCSY and NOESY.

  15. A Novel Multi-voxel Based Quantitation of Metabolites and Lipids Non-invasively Combined with Diffusion Weighted Imaging in Breast Cancer

    DTIC Science & Technology

    2011-09-01

    Thomas, Ph.D. CONTRACTING ORGANIZATION : University of California...5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION REPORT NUMBER University of California...COSY data recorded in breast cancer, iii) To record DWI and to calculate ADC maps in breast cancer patients and healthy controls, and iv) To correlate

  16. Beam Energy Calibration with Meson Production

    NASA Astrophysics Data System (ADS)

    Razen, B.; Betigeri, M. G.; Bojowald, J.; Budzanowski, A.; Chatterjee, A.; Drochner, M.; Ernst, J.; Foertsch, S.; Freindl, L.; Frekers, D.; Garske, W.; Grewer, K.; Hamacher, A.; Hawash, M.; Igel, S.; Ilieva, I.; Jahn, R.; Jarczyk, L.; Kemmerling, G.; Kilian, K.; Kliczewski, S.; Klimala, W.; Kolev, D.; Kutsarova, T.; Lieb, B. J.; Lippert, G.; Machner, H.; Magiera, A.; Maier, R.; Nann, H.; Plendl, H. S.; Protic, D.; Razen, B.; von Rossen, P.; Roy, B.; Siudak, R.; Smyrski, J.; Strzalkowski, A.; Tsenov, R.; Zolnierczuk, P. A.

    1998-11-01

    The magnetic spectrometer BIG KARL is used to get energy calibration fix-points for the external beam of COSY-Juelich. These fixpoints were obtained by measuring the meson-production reaction pp → dπ+ close to threshold and at the beam momentum, where the forward pions and the backward deuterons have the same momentum.

  17. Structure elucidation and NMR assignments of two unusual monoterpene indole alkaloids from Psychotria stachyoides.

    PubMed

    Pimenta, Antonia Torres Avila; Braz-Filho, Raimundo; Delprete, Piero Giuseppe; de Souza, Elnatan Bezerra; Silveira, Edilberto Rocha; Lima, Mary Anne Sousa

    2010-09-01

    Two unusual monoterpene indole alkaloids, stachyoside (1) and nor-methyl-23-oxo-correantoside (2), have been isolated from the aerial parts of Psychotria stachyoides. The structural elucidation of both compounds was performed by the aid of HRESIMS, FT-IR, and 1D- and 2D-NMR techniques including COSY, HSQC, HMBC, and NOESY.

  18. Line-narrowing in proton-detected nitrogen-14 NMR.

    PubMed

    Cavadini, Simone; Vitzthum, Veronika; Ulzega, Simone; Abraham, Anuji; Bodenhausen, Geoffrey

    2010-01-01

    In solids spinning at the magic angle, the indirect detection of single-quantum (SQ) and double-quantum (DQ) (14)N spectra (I=1) via spy nuclei S=1/2 such as protons can be achieved in the manner of heteronuclear single- or multiple-quantum correlation (HSQC or HMQC) spectroscopy. The HMQC method relies on the excitation of two-spin coherences of the type T(11)(I)T(11)(S) and T(21)(I)T(11)(S) at the beginning of the evolution interval t(1). The spectra obtained by Fourier transformation from t(1) to omega(1) may be broadened by the homogenous decay of the transverse terms of the spy nuclei S. This broadening is mostly due to homonuclear dipolar S-S' interactions between the proton spy nuclei. In this work we have investigated the possibility of inserting rotor-synchronized symmetry-based C or R sequences and decoupling schemes such as Phase-Modulated Lee-Goldburg (PMLG) sequences in the evolution period. These schemes reduce the homonuclear proton-proton interactions and lead to an enhancement of the resolution of both SQ and DQ proton-detected (14)N HMQC spectra. In addition, we have investigated the combination of HSQC with symmetry-based sequences and PMLG and shown that the highest resolution in the (14)N dimension is achieved by using HSQC in combination with symmetry-based sequences of the R-type. We show improvements in resolution in samples of l-alanine and the tripeptide ala-ala-gly (AAG). In particular, for l-alanine the width of the (14)N SQ peak is reduced from 2 to 1.2 kHz, in agreement with simulations. We report accurate measurements of quadrupolar coupling constants and asymmetry parameters for amide (14)N in AAG peptide bonds.

  19. Fluxionality in a paramagnetic seven-coordinate iron(II) complex: a variable-temperature, two-dimensional NMR and DFT study.

    PubMed

    Lonnon, David G; Ball, Graham E; Taylor, Ivan; Craig, Donald C; Colbran, Stephen B

    2009-06-01

    The preparation and detailed characterizations of the high-spin seven-coordinate complexes [M(kappa(7)N-L)](ClO(4))(2) (M = Mn(II), Fe(II); L = N,N,N',N'-tetrakis(2-pyridylmethyl)-2,6-bis(aminomethyl)pyridine) are described. The X-ray crystal structures reveal seven-coordinate metal complex ions. Consideration of continuous shape measures reveals that the coordination environments about the metal ions are better described as having (C(s)) face-capped trigonal prismatic symmetry than (C(2)) pentagonal bipyramidal symmetry. The (S = (5)/(2)) Mn(II) species shows complicated X-band electron paramagnetic resonance (EPR) spectra and broad, unrevealing (1)H NMR spectra. In contrast, the (S = 2) Fe(II) complex is EPR-silent and shows completely interpretable (1)H NMR spectra containing the requisite number of paramagnetically shifted peaks in the range delta +150 to -60. The (13)C NMR spectra are likewise informative. Variable-temperature (1)H NMR spectra show coalescences and decoalescences indicative of an intramolecular process that pairwise-exchanges the nonequivalent pyridylmethyl "arms" of the two bis(pyridylmethyl)amine (bpa) domains. A suite of NMR techniques, including T(1) relaxation measurements and variable-temperature (1)H-(1)H correlation spectroscopy, (1)H-(1)H total correlation spectroscopy, (1)H-(1)H nuclear Overhauser effect spectroscopy/exchange spectroscopy, and (1)H-(13)C heteronuclear multiple-quantum coherence experiments, has been used to assign the NMR spectra and characterize the exchange process. Analysis of the data from these experiments yields the following thermodynamic parameters for the exchange: DeltaH++ = 53.6 +/- 2.8 kJ mol(-1), DeltaS++ = -10.0 +/- 9.8 J K(-1) mol(-1), and DeltaG++ (298 K) = 50.6 kJ mol(-1). Density functional theory (B3LYP) calculations have been used to explore the energetics of possible mechanistic pathways for the underlying fluxional process. The most plausible mechanism found involves dissociation of a

  20. Dibenzocyclooctadiene lignans from Schisandra chinensis and their inhibitory activity on NO production in lipopolysaccharide-activated microglia cells.

    PubMed

    Hu, Di; Yang, Zhiyou; Yao, Xuechun; Wang, Hua; Han, Na; Liu, Zhihui; Wang, Yu; Yang, Jingyu; Yin, Jun

    2014-08-01

    Four dibenzocyclooctadiene lignans, schisanchinins A-D, and 10 known compounds were isolated from the EtOAc extract of fruits of Schisandra chinensis (Turcz.) Baill. Structures of compounds 1-4 were elucidated using a combination of spectroscopic techniques, including MS, UV and IR, NMR ((1)H NMR, (13)C NMR, HMQC, HMBC). The stereochemistry of the chiral centers and the biphenyl configuration were determined using NOESY, as well as analysis of CD spectra. In vitro activity assays showed that 11 of the 14 compounds exhibited inhibitory activity on lipopolysaccharide (LPS)-induced NO release in primary murine BV2 microglia cells.

  1. Isolation of alpha-glusosidase inhibitors from hyssop (Hyssopus officinalis).

    PubMed

    Matsuura, Hideyuki; Miyazaki, Hiroyuki; Asakawa, Chikako; Amano, Midori; Yoshihara, Teruhiko; Mizutani, Junya

    2004-01-01

    alpha-Glucosidase inhibitory activity was found in aqueous methanol extracts of dried hyssop (Hyssopus officinalis) leaves. Active principles against alpha-glucosidase, prepared from rat small intestine acetone powders, were isolated and characterized. The structures of these isolated compounds were determined to be (7S, 8S)-syringoylglycerol-9-O-(6'-O-cinnamoyl)-beta-D-glucopyranoside and (7S, 8S)-syringoylglycerol 9-O-beta-D-glucopyranoside by analysis of physical and spectroscopic data (FDMS, 1H NMR, 13C NMR, HMQC, and HMBC experiments) together with chemical syntheses.

  2. Plantazolicin A and B: structure elucidation of ribosomally synthesized thiazole/oxazole peptides from Bacillus amyloliquefaciens FZB42.

    PubMed

    Kalyon, Bahar; Helaly, Soleiman E; Scholz, Romy; Nachtigall, Jonny; Vater, Joachim; Borriss, Rainer; Süssmuth, Roderich D

    2011-06-17

    The structures of the ribosomally synthesized peptide antibiotics from Bacillus amyloliquefaciens FZB42, plantazolicin A and B, have been elucidated by high resolving ESI-MSMS, 2D (1)H-(13)C-correlated NMR spectroscopy as well as (1)H-(15)N-HMQC/(1)H-(15)N-HMBC NMR experiments. (15)N-labeling prior to the experiments facilitated the structure determination, unveiling a hitherto unusual number of thiazoles and oxazoles formed from a linear 14mer precursor peptide. This finding further extends the number of known secondary metabolites from B. amyloliquefaciens and represents a new type of secondary metabolites from the genus Bacillus.

  3. 2D NMR analysis of highly restricted internal rotation in 2-methylthio-3H-4- p-bromophenyl)-7-[( ortho- and para-substituted)-phenylthio]-1,5-benzodiazepines

    NASA Astrophysics Data System (ADS)

    Cortes C., E.; Becerra L., M. I.; Osornio P., Y. M.; Díaz T., E.; Jankowski, K.

    2000-08-01

    The complete assignments of twelve 4-ary1-7-thioary1-1,5-benzodiazepines 1H and 13C spectra, performed with the use of high resolution variable solvent and temperature 1D and 2D techniques (e.g. HOMOCOSY, NOESY, HMQC and HMBC), lead to the determination of conformational equilibria between two rotamers having the aromatic ring of the thioaryl oriented in a perpendicular or helical orientation toward the benzodiazepine ring. The restricted rotation was evaluated from the population of these conformers.

  4. Structure and serological specificity of a new acidic O-specific polysaccharide of Proteus vulgaris O45.

    PubMed

    Bartodziejska, B; Shashkov, A S; Torzewska, A; Grachev, A A; Ziolkowski, A; Paramonov, N A; Rozalski, A; Knirel, Y A

    1999-01-01

    The following structure of the O-specific polysaccharide (OPS) of Proteus vulgaris O45 lipopolysaccharide (LPS) was established using 1H- and 13C-NMR spectroscopy, including two-dimensional NOESY and H-detected 1H, 13C heteronuclear multiple-quantum coherence ( HMQC) experiments: [structure: see text text] Immunochemical studies, using rabbit polyclonal anti-P. vulgaris O45 serum and LPS, OPS and Smith-degraded OPS of P. vulgaris O45, showed the importance of beta-D-GlcA in manifesting the serological specificity of the O-antigen studied.

  5. Enaminones in heterocyclic synthesis: a novel route to tetrahydropyrimidines, dihydropyridines, triacylbenzenes and naphthofurans under microwave irradiation.

    PubMed

    Al-Mousawi, Saleh Mohammed; El-Apasery, Morsy Ahmed; Elnagdi, Mohamed H

    2009-12-25

    Condensation of phthalimidoacetone (1) with DMFDMA (N,N-Dimethylformamide dimethyl acetal) has afforded enaminone 2. Refluxing 2 with equimolecular amounts of benzaldehyde and urea in acetic acid afforded a mixture of tetrahydropyrimidine 5 and the dihydropyridine 6. Compound 2 undergoes self-condensation on heating in acetic acid or under microwave irradiation in presence of acidic zeolite to give 1,3,5-triacylbenzene 9. Reacting enaminone 11a with naphthoquinone 15 afforded the naphthofuran 18. The possible formation of the aldehyde 19 was excluded based on an HMQC experiment, which revealed that the carbonyl carbon is not linked to any hydrogen.

  6. Exploring the functional mealtime associations of older adults through consumer segmentation and a means-end chain approach.

    PubMed

    den Uijl, Louise C; Jager, Gerry; de Graaf, Cees; Kremer, Stefanie

    2016-12-01

    Senior consumers are a rapidly growing and highly heterogeneous part of the world's population. This group does not always meet its recommended protein intake, which can negatively impact on their physical functioning and quality of life. To date, little is known about their motivations to consume protein-rich meals. In the current study, we therefore aim to identify consumer segments within the group of vital community-dwelling older adults on the basis of mealtime functionality (for example 'I eat because I'm hungry', or 'I eat because it is cosy'). To this end, we first conducted an online survey to identify these functional mealtime expectations of older consumers (study I, n = 398, 158 males, mean age 65.8 (y) ± 5.9 (SD)). To obtain further insights regarding mealtime functionality and proteins/protein enrichment, laddering interviews were conducted with a subgroup of the segmentation study participants (study II, n = 40, 20 males, mean age 66.9 (y) ± 4.8 (SD)). The results of the online survey showed three consumer clusters: cosy socialisers, physical nutritioners, and thoughtless rewarders. Thoughtless rewarders tend to eat without having explicit thoughts about it, they eat for the reward, and score highest on environmental awareness. Both the segmentation and the in-depth interviews showed that, for the cosy socialisers, the cosiness and social function of a meal are important motivators, whereas for the physical nutritioners the focus is more on the health and nutrient aspects of a meal. For cosy socialisers, protein enrichment can best be achieved through addition of protein-rich ingredients, whereas, for physical nutritioners, addition of protein powder is preferred. These results provide practical guidelines for the development of protein-rich meals and communication strategies tailored to the needs of specific vital community-dwelling older subgroups.

  7. Helimagnetic order in bulk MnSi and CoSi/MnSi superlattices

    NASA Astrophysics Data System (ADS)

    Loh, G. C.; Khoo, K. H.; Gan, C. K.

    2017-01-01

    Skyrmions are nanoscopic whirls of spins that reside in chiral magnets. It is only fairly recent that a plethora of applications for these quasiparticles emerges, especially in data storage. On the other hand, spin spirals are the periodic analogs of skyrmions, and are equally imperative in the course of exploration to enhance our understanding of helimagnetism. In this study, a new infrastructure based on the B20 compound, MnSi is propounded as a hosting material for spin spirals; alternating thin layers of CoSi and MnSi in the superlattice form provides a facile way of varying the properties of the spin spirals across a continuum. Using first-principles calculations based on full-potential linearized augmented plane-wave (FLAPW)-based density functional theory (DFT), the spin order of bulk MnSi, MnSi film, and the CoSi/MnSi superlattice is investigated. Spin dispersion plots as a function of propagation vectors show that the spiral size changes in the presence of CoSi - we find that the size of the spiral is reduced in the superlattice with thin CoSi layers (CoSi:MnSi=1:1 thickness ratio), whilst at a larger CoSi:MnSi=2:1 thickness ratio, the material behaves as a ferromagnet. In a similar fashion, the spin moment and orbital occupancy depend significantly on the thickness of the CoSi layers. However, the exchange interaction between Mn atoms appears to be generally impervious to the presence of CoSi. Succinctly, the CoSi/MnSi superlattice could be an excellent functional material in data storage applications.

  8. Fabrication of superhydrophobic and highly oleophobic silicon-based surfaces via electroless etching method

    NASA Astrophysics Data System (ADS)

    Nguyen, Thi Phuong Nhung; Dufour, Renaud; Thomy, Vincent; Senez, Vincent; Boukherroub, Rabah; Coffinier, Yannick

    2014-03-01

    This study reports on a simple method for the preparation of superhydrophobic and highly oleophobic nanostructured silicon surfaces. The technique relies on metal-assisted electroless etching of silicon in sodium tetrafluoroborate (NaBF4) aqueous solution. Then, silver particles were deposited on the obtained surfaces, changing their overall physical morphology. Finally, the surfaces were coated by either C4F8, a fluoropolymer deposited by plasma, or by SiOx overlayers chemically modified with 1H,1H,2H,2H-perfluorodecyltrichlorosilane (PFTS) through silanization reaction. All these surfaces exhibit a superhydrophobic character (large apparent contact angle and low hysteresis with respect to water). In addition, they present high oleophobic properties, i.e. a high repellency to low surface energy liquids with various contact angle hysteresis, both depending on the morphology and type of coating.

  9. Poly(isobutylene) nanoparticles via cationic polymerization in nonaqueous emulsions.

    PubMed

    Schuster, Thomas; Golling, Florian E; Krumpfer, Joseph W; Wagner, Manfred; Graf, Robert; Alsaygh, Abdulhamid A; Klapper, Markus; Müllen, Klaus

    2015-01-01

    The preparation of poly(isobutylene) (PIB) nanoparticles via cationic emulsion polymerization is presented. As a requirement, an oil-in-perfluoroalkane nonaqueous emulsion is developed, which is inert under the carbocationic polymerization conditions. To stabilize the dichloromethane/hexane droplets in the fluorinated, continuous phase, an amphiphilic block copolymer emulsifier is prepared containing PIB and 1H,1H-perfluoroalkylated poly(pentafluorostyrene) blocks. This system allows for the polymerization of isobutylene with number-average molecular weights (Mn) up to 27,000 g mol(-1). The particle morphologies are characterized via dynamic light scattering and electron microscopy. For Mn > 20,000 g mol(-1), the particles exhibit shape-persistence at room temperature and are ≈100 nm in diameter.

  10. Investigation of slow molecular dynamics using R-CODEX

    NASA Astrophysics Data System (ADS)

    Li, Wenbo; McDermott, Ann

    2012-09-01

    A solid state NMR experiment is introduced for probing motions on the millisecond time scale, based on dephasing and refocusing 1H-13C or 1H-15N dipolar couplings. The method is related to the previously described Centerband-Only Detection of Exchange or CODEX experiment. The use of an R-type dipolar recoupling sequence takes advantage of the strong 1H-13C or 1H-15N dipolar coupling, while suppressing the effect of 1H-1H homonuclear coupling. This approach paves the way to detect both the correlation time and reorientational angle of the dynamics in fully protonated samples. The performance of this pulse sequence is demonstrated using imidazole methyl sulfonate.

  11. Investigation of slow molecular dynamics using R-CODEX.

    PubMed

    Li, Wenbo; McDermott, Ann

    2012-09-01

    A solid state NMR experiment is introduced for probing motions on the millisecond time scale, based on dephasing and refocusing (1)H-(13)C or (1)H-(15)N dipolar couplings. The method is related to the previously described Centerband-Only Detection of Exchange or CODEX experiment. The use of an R-type dipolar recoupling sequence takes advantage of the strong (1)H-(13)C or (1)H-(15)N dipolar coupling, while suppressing the effect of (1)H-(1)H homonuclear coupling. This approach paves the way to detect both the correlation time and reorientational angle of the dynamics in fully protonated samples. The performance of this pulse sequence is demonstrated using imidazole methyl sulfonate.

  12. Modulating the Anticancer Activity of Ruthenium(II)-Arene Complexes.

    PubMed

    Clavel, Catherine M; Păunescu, Emilia; Nowak-Sliwinska, Patrycja; Griffioen, Arjan W; Scopelliti, Rosario; Dyson, Paul J

    2015-04-23

    Following the identification of [Ru(η(6)-p-cymene)Cl2(1H,1H,2H,2H-perfluorodecyl-3-(pyridin-3-yl)propanoate)], a ruthenium(II)-arene complex with a perfluoroalkyl-modified ligand that displays remarkable in vitro cancer cell selectivity, a series of structurally related compounds were designed. In the new derivatives, the p-cymene ring and/or the chloride ligands are substituted by other ligands to modulate the steric bulk or aquation kinetics. The new compounds were evaluated in both in vitro (cytotoxicity and migration assays) and in vivo (chicken chorioallantoic membrane) models and were found to exhibit potent antivascular effects.

  13. Singlet order conversion and parahydrogen-induced hyperpolarization of 13C nuclei in near-equivalent spin systems

    NASA Astrophysics Data System (ADS)

    Eills, James; Stevanato, Gabriele; Bengs, Christian; Glöggler, Stefan; Elliott, Stuart J.; Alonso-Valdesueiro, Javier; Pileio, Giuseppe; Levitt, Malcolm H.

    2017-01-01

    We have demonstrated two radiofrequency pulse methods which convert the nuclear singlet order of proton spin pairs into the magnetisation of nearby 13C nuclei. These irradiation schemes work well in the near-equivalence regime of the three-spin system, which applies when the difference in the two 1H-13C couplings is much smaller than the 1H-1H coupling. We use pulse sequences to generate thermally polarized singlet states in a reproducible manner, and study the singlet-to-magnetisation transfer step. Preliminary results demonstrate a parahydrogen-enhanced 13C polarization level of at least 9%, providing a signal enhancement factor of more than 9000, using 50% enriched parahydrogen.

  14. Biosynthetic studies on the botcinolide skeleton: new hydroxylated lactones from Botrytis cinerea.

    PubMed

    Reino, José L; Durán-Patrón, Rosa M; Daoubi, Mourad; Collado, Isidro G; Hernández-Galán, Rosario

    2006-01-20

    [reaction: see text] The biosynthetic origin of the botcinolide skeleton was investigated by means of feeding 13C- and 2H-labeled precursors to Botrytis cinerea. Three new compounds, two homobotcinolide derivatives, 3-O-acetylhomobotcinolide (5) and 8-methylhomobotcinolide (6), and a new 11-membered lactone (7), were isolated. Their structures were elucidated on the basis of spectroscopic data, including one-bond and long-range 1H-13C correlations. The relative stereochemistries were determined by combined analyses of NOE data and 1H-1H coupling constants. According to the results of feeding experiments with 13C- and 2H-labeled acetate and l-S-methylmethionine, 5 is an acetate-derived polyketide whose methyl groups originate from l-S-methylmethionine. This is a rare example of the incorporation of a methyl from methionine into a supposed C3 starter unit of the polyketide synthesis.

  15. Preparation of stable ultrahydrophobic and superoleophobic silica-based coating.

    PubMed

    Nimittrakoolchai, On-Uma; Supothina, Sitthisuntorn

    2012-06-01

    Silica-Based coatings having excellent water- and oil-repellent properties and good weathering stability have been deposited onto glass surface by a simple one-step dip coating technique. To achieve ultra water repellency and super oil repellency, the chemical composition of SiO2 nanoparticle employed as surface roughness enhancer and trichloro(1H,1H,2H,2H-perfluorooctyl)silane employed as surface-energy reducing substance was varied. At the optimum synthesis condition, the coating exhibited very high contact angles of 173.2, 146.7 and 147.6 degrees for water, ethylene glycol and seed oil, respectively. The achievement of excellent water- and oil-repellency is also described based on the presence of air trapped in micropore of the coating in addition to its high surface roughness and low surface free energy. The coatings have good weathering stability based on natural and accelerated weathering tests indicating feasibility for practical use.

  16. Significance of symmetry in the nuclear spin Hamiltonian for efficient heteronuclear dipolar decoupling in solid-state NMR: A Floquet description of supercycled rCW schemes

    NASA Astrophysics Data System (ADS)

    Equbal, Asif; Shankar, Ravi; Leskes, Michal; Vega, Shimon; Nielsen, Niels Chr.; Madhu, P. K.

    2017-03-01

    Symmetry plays an important role in the retention or annihilation of a desired interaction Hamiltonian in NMR experiments. Here, we explore the role of symmetry in the radio-frequency interaction frame Hamiltonian of the refocused-continuous-wave (rCW) pulse scheme that leads to efficient 1H heteronuclear decoupling in solid-state NMR. It is demonstrated that anti-periodic symmetry of single-spin operators (Ix, Iy, Iz) in the interaction frame can lead to complete annihilation of the 1H-1H homonuclear dipolar coupling effects that induce line broadening in solid-state NMR experiments. This symmetry also plays a critical role in cancelling or minimizing the effect of 1H chemical-shift anisotropy in the effective Hamiltonian. An analytical description based on Floquet theory is presented here along with experimental evidences to understand the decoupling efficiency of supercycled (concatenated) rCW scheme.

  17. Relationship between Wetting Hysteresis and Contact Time of a Bouncing Droplet on Hydrophobic Surfaces.

    PubMed

    Shen, Yizhou; Tao, Jie; Tao, Haijun; Chen, Shanlong; Pan, Lei; Wang, Tao

    2015-09-23

    The contact time of impacting water droplets on superhydrophobic surfaces directly reflects the extent of thermal and energy conversions between the water droplet and the surface, which is also considered to be crucial to the practical applications. The purpose of this study was to reveal the relationship between the contact time and the wetting hysteresis. We designed and fabricated six classes of surfaces with different extent of hydrophobicity through modifying the microscale/nanoscale hierarchical textured titanium surfaces with 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, and we filmed the contact process of the water droplet impacting on these surfaces using a high-speed camera. It can be concluded that wetting hysteresis played a significant role in determining how long the impacting water droplet can bounce off the surface, based on the interfacial wetting mechanism and the work done against the resistance force generated by contact angle hysteresis during the dynamic process.

  18. Probing intermolecular interactions in a diethylcarbamazine citrate salt by fast MAS (1)H solid-state NMR spectroscopy and GIPAW calculations.

    PubMed

    Venâncio, Tiago; Oliveira, Lyege Magalhaes; Ellena, Javier; Boechat, Nubia; Brown, Steven P

    2017-03-02

    Fast magic-angle spinning (MAS) NMR is used to probe intermolecular interactions in a diethylcarbamazine salt, that is widely used as a treatment against adult worms of Wuchereria bancrofti which cause a common disease in tropical countries named filariasis. Specifically, a dihydrogen citrate salt that has improved thermal stability and solubility as compared to the free form is studied. One-dimensional (1)H, (13)C and (15)N and two-dimensional (1)H-(13)C and (14)N-(1)H heteronuclear correlation NMR experiments under moderate and fast MAS together with GIPAW (CASTEP) calculations enable the assignment of the (1)H, (13)C and (14)N/(15)N resonances. A two-dimensional (1)H-(1)H double-quantum (DQ) -single-quantum (SQ) MAS spectrum recorded with BaBa recoupling at 60kHz MAS identifies specific proton-proton proximities associated with citrate-citrate and citrate-diethylcarbamazine intermolecular interactions.

  19. Electrostatically-driven fast association and perdeuteration allow detection of transferred cross-relaxation for G protein-coupled receptor ligands with equilibrium dissociation constants in the high-to-low nanomolar range.

    PubMed

    Catoire, Laurent J; Damian, Marjorie; Baaden, Marc; Guittet, Eric; Banères, Jean-Louis

    2011-07-01

    The mechanism of signal transduction mediated by G protein-coupled receptors is a subject of intense research in pharmacological and structural biology. Ligand association to the receptor constitutes a critical event in the activation process. Solution-state NMR can be amenable to high-resolution structure determination of agonist molecules in their receptor-bound state by detecting dipolar interactions in a transferred mode, even with equilibrium dissociation constants below the micromolar range. This is possible in the case of an inherent ultra-fast diffusive association of charged ligands onto a highly charged extracellular surface, and by slowing down the (1)H-(1)H cross-relaxation by perdeuterating the receptor. Here, we demonstrate this for two fatty acid molecules in interaction with the leukotriene BLT2 receptor, for which both ligands display a submicromolar affinity.

  20. Spatial structure of fibrinopeptide B in water solution with DPC micelles by NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Blokhin, Dmitriy S.; Fayzullina, Adeliya R.; Filippov, Andrei V.; Karataeva, Farida Kh.; Klochkov, Vladimir V.

    2015-12-01

    Fibrinopeptide B (GluFib) is one of the factors of thrombosis. Normal blood protein soluble, fibrinogen (fibrinopeptide A and fibrinopeptide B), is transformed into the insoluble, fibrin, which in the form of filaments adheres to the vessel wall at the site of injury, forming a grid. However, the spatial structure of this peptide has not been established till now. In this article, GluFib peptide is investigated together with dodecylphosphocholine (DPC) micelles which were used for mimicking the environment of peptide in blood vessels. The spatial structure was obtained by applying 1D and 2D 1H-1H NMR spectroscopy (TOCSY, NOESY). It was shown that the fibrinopeptide B does not have a secondary structure but we can distinguish the fragment Gly 9 - Arg 14 with a good convergence (the backbone RMSD for the Gly9 - Arg14 is 0.18 ± 0.08 Å).

  1. Electrowetting properties of atomic layer deposited Al{sub 2}O{sub 3} decorated silicon nanowires

    SciTech Connect

    Rajkumar, K.; Rajavel, K.; Cameron, D. C.; Mangalaraj, D.; Rajendrakumar, R. T.

    2015-06-24

    This paper reports the electrowetting properties of liquid droplet on superhydrophobic silicon nanowires with Atomic layer deposited (ALD) Al{sub 2}O{sub 3} as dielectric layer. Silicon wafer were etched by metal assisted wet chemical etching with silver as catalyst. ALD Al{sub 2}O{sub 3} films of 10nm thickness were conformally deposited over silicon nanowires. Al{sub 2}O{sub 3} dielectric film coated silicon nanowires was chemically modified with Trichloro (1H, 1H, 2H, 2H-perfluorooctyl) silane to make it superhydrophobic(SHP). The contact angle was measured and all the samples exhibited superhydrophobic nature with maximum contact angles of 163° and a minimum contact angle hysteresis of 6°. Electrowetting induced a maximum reversible decrease of the contact angle of 20°at 150V in air.

  2. High mobility n-type organic thin-film transistors deposited at room temperature by supersonic molecular beam deposition

    SciTech Connect

    Chiarella, F. Barra, M.; Ciccullo, F.; Cassinese, A.; Toccoli, T.; Aversa, L.; Tatti, R.; Verucchi, R.

    2014-04-07

    In this paper, we report on the fabrication of N,N′-1H,1H-perfluorobutil dicyanoperylenediimide (PDIF-CN{sub 2}) organic thin-film transistors by Supersonic Molecular Beam Deposition. The devices exhibit mobility up to 0.2 cm{sup 2}/V s even if the substrate is kept at room temperature during the organic film growth, exceeding by three orders of magnitude the electrical performance of those grown at the same temperature by conventional Organic Molecular Beam Deposition. The possibility to get high-mobility n-type transistors avoiding thermal treatments during or after the deposition could significantly extend the number of substrates suitable to the fabrication of flexible high-performance complementary circuits by using this compound.

  3. Natural-abundance 15N NMR studies of Turkey ovomucoid third domain. Assignment of peptide 15N resonances to the residues at the reactive site region via proton-detected multiple-quantum coherence

    NASA Astrophysics Data System (ADS)

    Ortiz-Polo, Gilberto; Krishnamoorthi, R.; Markley, John L.; Live, David H.; Davis, Donald G.; Cowburn, David

    Heteronuclear two-dimensional 1H{ 15N} multiple-quantum (MQ) spectroscopy has been applied to a protein sample at natural abundance: ovomucoid third domain from turkey ( Meleagris gallopavo), a serine proteinase inhibitor of 56 amino acid residues. Peptide amide 1H NMR assignments obtained by two-dimensional 1H{ 1H} NMR methods (R. Krishnamoorthi and J. L. Markley, unpublished data) led to identification of the corresponding 1H{ 15N} MQ coherence cross peaks. From these, 15N NMR chemical shifts were determined for several specific backbone amide groups of amino acid residues located around the reactive site region of the inhibitor. The results suggest that amide 15N chemical shifts, which are readily obtained in this way, may serve as sensitive probes for conformational studies of proteins.

  4. Impact of surface wettability on S-layer recrystallization: a real-time characterization by QCM-D.

    PubMed

    Iturri, Jagoba; Vianna, Ana C; Moreno-Cencerrado, Alberto; Pum, Dietmar; Sleytr, Uwe B; Toca-Herrera, José Luis

    2017-01-01

    Quartz crystal microbalance with dissipation monitoring (QCM-D) has been employed to study the assembly and recrystallization kinetics of isolated SbpA bacterial surface proteins onto silicon dioxide substrates of different surface wettability. Surface modification by UV/ozone oxidation or by vapor deposition of 1H,1H,2H,2H-perfluorododecyltrichlorosilane yielded hydrophilic or hydrophobic samples, respectively. Time evolution of frequency and dissipation factors, either individually or combined as the so-called Df plots, showed a much faster formation of crystalline coatings for hydrophobic samples, characterized by a phase-transition peak at around the 70% of the total mass adsorbed. This behavior has been proven to mimic, both in terms of kinetics and film assembly steps, the recrystallization taking place on an underlying secondary cell-wall polymer (SCWP) as found in bacteria. Complementary atomic force microscopy (AFM) experiments corroborate these findings and reveal the impact on the final structure achieved.

  5. Investigation of Uña De Gato I. 7-Deoxyloganic acid and 15N NMR spectroscopic studies on pentacyclic oxindole alkaloids from Uncaria tomentosa.

    PubMed

    Muhammad, I; Dunbar, D C; Khan, R A; Ganzera, M; Khan, I A

    2001-07-01

    The C-8-(S) isomer of deoxyloganic acid (7-deoxyloganic acid), together with beta-sitosteryl glucoside, five known stereoisomeric pentacyclic oxindole alkaloids and the tetracyclic oxindole isorhyncophylline, were isolated from the inner bark of Uncaria tomentosa. Structures of the isolated compounds were based on 1H and 13C NMR data, mainly 2D NMR experiments, including 1H-13C HMBC and 1H-1H NOESY correlation. Furthermore, the hitherto unreported 15N chemical shifts of the isomeric oxindole alkaloids, using 1H-15N HMBC experiments, were utilized to facilitate their characterization. Uncarine D showed weak cytotoxic activity against SK-MEL, KB, BT-549 and SK-OV-3 cell lines with IC(50) values between 30 and 40 microg/ml, while uncarine C exhibited weak cytotoxicity only against ovarian carcinoma (IC(50) at 37 microg/ml).

  6. Significance of symmetry in the nuclear spin Hamiltonian for efficient heteronuclear dipolar decoupling in solid-state NMR: A Floquet description of supercycled rCW schemes.

    PubMed

    Equbal, Asif; Shankar, Ravi; Leskes, Michal; Vega, Shimon; Nielsen, Niels Chr; Madhu, P K

    2017-03-14

    Symmetry plays an important role in the retention or annihilation of a desired interaction Hamiltonian in NMR experiments. Here, we explore the role of symmetry in the radio-frequency interaction frame Hamiltonian of the refocused-continuous-wave (rCW) pulse scheme that leads to efficient (1)H heteronuclear decoupling in solid-state NMR. It is demonstrated that anti-periodic symmetry of single-spin operators (Ix, Iy, Iz) in the interaction frame can lead to complete annihilation of the (1)H-(1)H homonuclear dipolar coupling effects that induce line broadening in solid-state NMR experiments. This symmetry also plays a critical role in cancelling or minimizing the effect of (1)H chemical-shift anisotropy in the effective Hamiltonian. An analytical description based on Floquet theory is presented here along with experimental evidences to understand the decoupling efficiency of supercycled (concatenated) rCW scheme.

  7. Non-uniform Sampling and J-UNIO Automation for Efficient Protein NMR Structure Determination

    PubMed Central

    Didenko, Tatiana; Proudfoot, Andrew; Dutta, Samit Kumar; Serrano, Pedro; Wüthrich, Kurt

    2015-01-01

    High-resolution structure determination of small proteins in solution is one of the big assets of NMR spectroscopy in structural biology. Improvements in efficiency of NMR structure determination by advances in NMR experiments and automation of data handling therefore attracts continued interest. Here, non-uniform sampling (NUS) of 3D heteronuclear-resolved [1H,1H]-NOESY data yielded two- to three-fold savings of instrument time for structure determinations of soluble proteins. With the 152-residue protein NP_372339.1 from Staphylococcus aureus and the 71-residue protein NP_346341.1 from Streptococcus pneumonia we show that high-quality structures can be obtained with NUS NMR data, which are equally well amenable to robust automated analysis as the corresponding uniformly sampled data. PMID:26227870

  8. [NMR study of complex formation of aromatic ligands with heptadeoxynucleotide 5'-d(GCGAAGC) forming stable hairpin structure in aqueous solution].

    PubMed

    Veselkov, A N; Eaton, R J; Semanin, A V; Pakhomov, V I; Dymant, L N; Karavaev, L; Davies, D V

    2002-01-01

    Complex formation of hairpin-producing heptadeoxynucleotide 5'-d(GCGAAGC) with aromatic molecules: acridine dye proflavine and anthracycline antibiotic daunomycin was studied by one-dimensional 1H NMR and two-dimensional correlation 1H-1H (2M-TOCSY, 2M-NOESY), 1H-31P (2M-HMBC) NMR spectroscopy (500 and 600 MHz) in aqueous solution. Concentration and temperature dependences for the chemical shifts of ligand protons were measured, molecular models of equilibrium in solution were developed, and equilibrium thermodynamic parameters for the formation of intercalation complexes were calculated. Spatial structures of dye and antibiotic complexes with the heptamer hairpin were constructed on the basis of 2M-NOE data and the calculated values of limiting chemical shifts of ligand protons.

  9. Deciphering the Conformational Choreography of Zinc Coordination Complexes with Standard and Novel Proton NMR Techniques Combined with DFT Methods.

    PubMed

    Pucheta, Jose Enrique Herbert; Prim, Damien; Gillet, Jean Michel; Farjon, Jonathan

    2016-04-04

    The presence of water has been shown to deeply impact the stability and geometry of Zn complexes in solution. Evidence for tetra- and penta-coordinated species in a pyridylmethylamine-Zn(II) model complex is presented. Novel (1) H NMR tools such as T1 -filtered selective exchange spectroscopy and pure shifted gradient-encoded selective refocusing as well as classical 2D ((1) H-(1) H) exchange spectroscopy, diffusion-ordered spectroscopy and T1 ((1) H) measurements, in combination with density functional theory methods allow the full conformational dynamics of a pyridylmethylamine-Zn(II) complex to be revealed. Four conformers and two families of complexes depending on the hydration states are elucidated.

  10. Electrowetting properties of atomic layer deposited Al2O3 decorated silicon nanowires

    NASA Astrophysics Data System (ADS)

    Rajkumar, K.; Rajavel, K.; Cameron, D. C.; Mangalaraj, D.; Rajendrakumar, R. T.

    2015-06-01

    This paper reports the electrowetting properties of liquid droplet on superhydrophobic silicon nanowires with Atomic layer deposited (ALD) Al2O3 as dielectric layer. Silicon wafer were etched by metal assisted wet chemical etching with silver as catalyst. ALD Al2O3 films of 10nm thickness were conformally deposited over silicon nanowires. Al2O3 dielectric film coated silicon nanowires was chemically modified with Trichloro (1H, 1H, 2H, 2H-perfluorooctyl) silane to make it superhydrophobic(SHP). The contact angle was measured and all the samples exhibited superhydrophobic nature with maximum contact angles of 163° and a minimum contact angle hysteresis of 6°. Electrowetting induced a maximum reversible decrease of the contact angle of 20°at 150V in air.

  11. Rapid fabrication and characterization of superhydrophobic tri-dimensional Ni/Al coatings

    NASA Astrophysics Data System (ADS)

    Guo, Xiaogang; Li, Xueming; Wei, Zhibo; Li, Xiaolin; Niu, Lidan

    2016-11-01

    Superhydrophobic tri-dimensional Ni/Al coatings (3DNACs) with great application value have been successfully fabricated via a simple two-step method combined with hydrogen bubble dynamic template and electrophoretic deposition technique after 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane treatment. The surface morphologies and chemical compositions were analyzed by FE-SEM, EDS, XRD, AFM and FT-IR in detail. The water contact angle of superhydrophobic 3DNACs surface was as high as 156 ± 2° (>150) much larger than that of unmodified samples. Moreover, the obtained samples exhibited great thermal properties and combustion performance. Thus, the superhydrophobic 3DNACs with prominent exothermic capability turn out to be a promising novel energy in field of mirco/nano energy materials for longer-term storage or transportation, especially in high humid environment.

  12. Amphiphilic Fluorinated Polymer Nanoparticle Film Formation and Dissolved Oxygen Sensing Application

    NASA Astrophysics Data System (ADS)

    Gao, Yu; Zhu, Huie; Yamamoto, Shunsuke; Miyashita, Tokuji; Mitsuishi, Masaya

    2016-04-01

    Fluorinated polymer nanoparticle films were prepared by dissolving amphiphilic fluorinated polymer, poly (N-1H, 1H-pentadecafluorooctylmethacrylamide) (pC7F15MAA) in two miscible solvents (AK-225 and acetic acid). A superhydrophobic and porous film was obtained by dropcasting the solution on substrates. With higher ratios of AK-225 to acetic acid, pC7F15MAA was densified around acetic acid droplets, leading to the formation of pC7F15MAA nanoparticles. The condition of the nanoparticle film preparation was investigated by varying the mixing ratio or total concentration. A highly sensitive dissolved oxygen sensor system was successfully prepared utilizing a smart surface of superhydrophobic and porous pC7F15MAA nanoparticle film. The sensitivity showed I0/I40 = 126 in the range of dissolved oxygen concentration of 0 ~ 40 mg L-1. The oxygen sensitivity was compared with that of previous reports.

  13. Impact of surface wettability on S-layer recrystallization: a real-time characterization by QCM-D

    PubMed Central

    Vianna, Ana C; Moreno-Cencerrado, Alberto; Pum, Dietmar; Sleytr, Uwe B

    2017-01-01

    Quartz crystal microbalance with dissipation monitoring (QCM-D) has been employed to study the assembly and recrystallization kinetics of isolated SbpA bacterial surface proteins onto silicon dioxide substrates of different surface wettability. Surface modification by UV/ozone oxidation or by vapor deposition of 1H,1H,2H,2H-perfluorododecyltrichlorosilane yielded hydrophilic or hydrophobic samples, respectively. Time evolution of frequency and dissipation factors, either individually or combined as the so-called Df plots, showed a much faster formation of crystalline coatings for hydrophobic samples, characterized by a phase-transition peak at around the 70% of the total mass adsorbed. This behavior has been proven to mimic, both in terms of kinetics and film assembly steps, the recrystallization taking place on an underlying secondary cell-wall polymer (SCWP) as found in bacteria. Complementary atomic force microscopy (AFM) experiments corroborate these findings and reveal the impact on the final structure achieved. PMID:28144568

  14. Charge Retention by Gold Clusters on Surfaces Prepared Using Soft Landing of Mass Selected Ions

    SciTech Connect

    Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia

    2012-01-24

    Monodisperse gold clusters have been prepared on surfaces in different charge states through soft landing of mass-selected ions. Ligand-stabilized gold clusters were prepared in methanol solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine complex in the presence of 1,3-bis(diphenylphosphino)propane. Electrospray ionization was used to introduce the clusters into the gas-phase and mass-selection was employed to isolate a single ionic cluster species (Au11L53+, L = 1,3-bis(diphenylphosphino)propane) which was delivered to surfaces at well controlled kinetic energies. Using in-situ time of flight secondary ion mass spectrometry (TOF-SIMS) it is demonstrated that the Au11L53+ cluster retains its 3+ charge state when soft landed onto the surface of a 1H,1H,2H,2H-

  15. Open-chain unsaturated selanyl sulfides: stereochemical structure and stereochemical behavior of their 77Se-1H spin-spin coupling constants.

    PubMed

    Rusakov, Yury Yu; Krivdin, Leonid B; Penzik, Maxim V; Potapov, Vladimir A; Amosova, Svetlana V

    2012-10-01

    Stereochemical structure of nine Z-2-(vinylsulfanyl)ethenylselanyl organyl sulfides has been investigated by means of experimental measurements and second-order polarization propagator approach calculations of their (1)H-(1)H, (13)C-(1)H, and (77)Se-(1)H spin-spin coupling constants together with a theoretical conformational analysis performed at the MP2/6-311G** level. All nine compounds were shown to adopt the preferable skewed s-cis conformation of their terminal vinylsulfanyl group, whereas the favorable rotational conformations with respect to the internal rotations around the C-S and C-Se bonds of the internal ethenyl group are both skewed s-trans. Stereochemical trends of (77)Se-(1)H spin-spin coupling constants originating in the geometry of their coupling pathways and the selenium lone pair effect were rationalized in terms of the natural J-coupling analysis within the framework of the natural bond orbital approach.

  16. Hydrophobicity and freezing of a water droplet on fluoroalkylsilane coatings with different roughnesses.

    PubMed

    Suzuki, Shunsuke; Nakajima, Akira; Yoshida, Naoya; Sakai, Munetoshi; Hashimoto, Ayako; Kameshima, Yoshikazu; Okada, Kiyoshi

    2007-08-14

    Smooth (Ra approximately 0.1 nm) and rough (Ra approximately 20 nm) coatings of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (FAS-17) were prepared by controlling process conditions. The water contact angles for the smooth and rough coatings were similar (107 degrees and 110 degrees, respectively), but their sliding angles differed considerably (10 degrees and 27 degrees, respectively). The surface potential on the smooth coating, assessed using Kelvin force microscopy, showed a sharp distribution, but that on the rough coating ranged widely, implying large chemical heterogeneity including residual SiOH groups. The freezing temperature of a supercooled water droplet on the rough coating was higher than that on the smooth coating.

  17. Formation of grafted surface layers on silicon dioxide particles and their investigation by means of thermoprogrammed oxidation

    NASA Astrophysics Data System (ADS)

    Aleksandrova, E. O.; Novichkov, R. V.; Olenin, A. Yu.; Zuev, B. K.

    2017-03-01

    Silica nanoparticles are obtained according to the Stober-Fink-Bohn method, and their surfaces are chemically modified with 1H,1H,2H,2H-perfluorodecyltriethoxysilane. It is estimated that sols of porous silica nanoparticles (average sizes, 50-200 nm) form during primary chemical process; the average size of the particles can be increased to 400-500 nm by consecutive growth. Oxythermography (thermoprogrammed oxidation) measurements reveal a stepped dependence between the content of organic substance of nanoparticles and the duration of chemical modification reaction exists. It is concluded that this could be due to the formation of dense shell (or shells) as a result of sols aging between the cycles of growth; such shells impose diffusive restrictions when molecules penetrate into the pores of the internal volume of the particles.

  18. Hydrazine 5,5'-bitetrazole-1,1'-diolate: a promising high density energetic salt with good properties.

    PubMed

    Zhang, Zhi-Bin; Xu, Cai-Xia; Yin, Xin; Zhang, Jian-Guo

    2016-12-21

    The development of new environmentally friendly energetic compounds with reasonable detonation performance and safety is a long-term target in energetic materials research. A new energetic eco-friendly salt of hydrazine 5,5'-bitetrazole-1,1'-diolate (HA·BTO) is developed based on the reaction of 1H,1'H-5,5'-bitetrazole-1,1'-diolate (BTO) with hydrazine hydrochloride (HA·HCl), and fully characterized. The monocrystal of the title salt is obtained and the structure is determined by powder X-ray diffraction and single crystal X-ray diffraction. Results show that the salt belongs to the triclinic space group P1[combining macron] with a relatively high density of 1.912 g cm(-3) under 298 K. The properties of the salt are discussed in detail. The thermal decomposition behaviors of the salt are tested, indicating that the salt has good thermal stability with a decomposition temperature above 200 °C. The enthalpy of formation for the salt is dependent on the combustion heat date measured by oxygen bomb calorimetry with a result of 425.6 kJ mol(-1), which is the same level as TKX-50, and four times higher than that of RDX. The detonation pressure (P) and detonation velocity (D) of the salt are calculated as 8931 m s(-1) and 36.1 GPa, which are higher than those of RDX. In addition, the impact and friction sensitivities are tested through a relevant standard method with a result of 28 J and 120 N, which are better than those of TKX-50. We can draw the conclusion that the salt could provide a promising future in use as a kind of insensitive explosive alternative. The discovery also contributes significantly to the expansion and application of the chemistry of 1H,1'H-5,5'-bitetrazole-1,1'-diolate, as well as N-heterocyclic compounds.

  19. NMR polarization echoes in a nematic liquid crystal

    NASA Astrophysics Data System (ADS)

    Levstein, Patricia R.; Chattah, Ana K.; Pastawski, Horacio M.; Raya, Jésus; Hirschinger, Jérôme

    2004-10-01

    We have modified the polarization echo (PE) sequence through the incorporation of Lee-Goldburg cross polarization steps to quench the 1H-1H dipolar dynamics. In this way, the 13C becomes an ideal local probe to inject and detect polarization in the proton system. This improvement made possible the observation of the local polarization P00(t) and polarization echoes in the interphenyl proton of the liquid crystal N-(4-methoxybenzylidene)-4-butylaniline. The decay of P00(t) was well fitted to an exponential law with a characteristic time τC≈310 μs. The hierarchy of the intramolecular dipolar couplings determines a dynamical bottleneck that justifies the use of the Fermi Golden Rule to obtain a spectral density consistent with the structural parameters. The time evolution of P00(t) was reversed by the PE sequence generating echoes at the time expected by the scaling of the dipolar Hamiltonian. This indicates that the reversible 1H-1H dipolar interaction is the main contribution to the local polarization decrease and that the exponential decay for P00(t) does not imply irreversibility. The attenuation of the echoes follows a Gaussian law with a characteristic time τφ≈527 μs. The shape and magnitude of the characteristic time of the PE decay suggest that it is dominated by the unperturbed homonuclear dipolar Hamiltonian. This means that τφ is an intrinsic property of the dipolar coupled network and not of other degrees of freedom. In this case, one cannot unambiguously identify the mechanism that produces the decoherence of the dipolar order. This is because even weak interactions are able to break the fragile multiple coherences originated on the dipolar evolution, hindering its reversal. Other schemes to investigate these underlying mechanisms are proposed.

  20. Tackling the stacking disorder of melon--structure elucidation in a semicrystalline material.

    PubMed

    Seyfarth, Lena; Seyfarth, Jan; Lotsch, Bettina V; Schnick, Wolfgang; Senker, Jürgen

    2010-03-07

    In this work we tackle the stacking disorder of melon, a layered carbon imide amide polymer with the ideal composition (C(6)N(7)(NH)(NH(2))). Although its existence has been postulated since 1834 the structure of individual melon layers could only recently be solved via electron diffraction and high-resolution (15)N solid-state NMR spectroscopy. With only weak van der Waals interactions between neighboring layers its long range stacking order is poorly defined preventing an efficient use of diffraction techniques. We, therefore, rely on a combination of solid-state NMR experiments and force field calculations. The key information is obtained based on heteronuclear ((1)H-(13)C) and homonuclear ((1)H-(1)H) second moments M(2) acquired from (1)H-(13)C cross polarization experiments. To allow for an interpretation of the polarization transfer rates the resonances in the (13)C MAS spectra have to be assigned and the hydrogen atoms have to be located. The assignment was performed using a two-dimensional (15)N-(13)C iDCP experiment. For the determination of the position of the hydrogen atoms NH and HH distances were measured via(1)H-(15)N Lee-Goldburg CP and (1)H-(1)H double-quantum build-up curves, respectively. Furthermore, the homogeneity of the material under examination was investigated exploiting (15)N spin-diffusion. Based on force field methods 256 structure models with varying lateral arrangements between neighboring layers were created. For each model the M(2) were calculated allowing them to be ranked by comparing calculated and measured M(2) as well as via their force field energies. This allows the creation of markedly structured hypersurfaces with two distinctly favored shift vectors for the displacement of neighboring layers.

  1. High-throughput aided synthesis of the porous metal-organic framework-type aluminum pyromellitate, MIL-121, with extra carboxylic acid functionalization.

    PubMed

    Volkringer, Christophe; Loiseau, Thierry; Guillou, Nathalie; Férey, Gérard; Haouas, Mohamed; Taulelle, Francis; Elkaim, Erik; Stock, Norbert

    2010-11-01

    A new porous metal-organic framework (MOF)-type aluminum pyromellitate (MIL-121 or Al(OH)[H(2)btec]·(guest), (guest = H(2)O, H(4)btec = pyromellitic acid) has been isolated by using a high-throughput synthesis method under hydrothermal conditions. Its structure was determined from powder X-ray diffraction analysis using synchrotron radiation (Soleil, France) and exhibits a network closely related to that of the MIL-53 series. It is a three-dimensional (3D) framework containing one-dimensional (1D) channels delimited by infinite trans-connected aluminum-centered octahedra AlO(4)(OH)(2) linked through the pyromellitate ligand. Here the organic ligand acts as tetradendate linker via two of the carboxylate groups. The two others remain non-bonded in their protonated form, and this constitutes a rare case of the occurrence of both bonding and non-bonding organic functionalities of the MOF family. The non-coordinated -COOH groups points toward the channels to get them an open form configuration. Within the tunnels are located unreacted pyromellitic acid and water species, which are evacuated upon heating, and a porous MIL-121 phase is obtained with a Brunauer-Emmett-Teller (BET) surface area of 162 m(2) g(-1). MIL-121 has been characterized by IR, thermogravimetry (TG) analyses, and solid state NMR spectroscopy employing a couple of two-dimensional (2D) techniques such as (1)H-(1)H SQ-DQ BABA, (1)H-(1)H SQ-SQ RFDR, (27)Al{(1)H} CPHETCOR and (27)Al MQMAS.

  2. Structure of a Conserved Retroviral RNA Packaging Element by NMR Spectroscopy and Cryo-Electron Tomography

    PubMed Central

    Miyazaki, Yasuyuki; Irobalieva, Rossitza N.; Tolbert, Blanton; Smalls-Mantey, Adjoa; Iyalla, Kilali; Loeliger, Kelsey; D’Souza, Victoria; Khant, Htet; Schmid, Michael F.; Garcia, Eric; Telesnitsky, Alice; Chiu, Wah; Summers, Michael F.

    2010-01-01

    The 5′-untranslated regions (5′-UTRs) of all gammaretroviruses contain a conserved “double hairpin motif” (ΨCD) that is required for genome packaging. Both hairpins (SL-C and SL-D) contain GACG tetraloops that, in isolated RNAs, are capable of forming “kissing” interactions stabilized by two intermolecular G-C base pairs. We have determined the three-dimensional structure of the double hairpin from the Moloney Murine Leukemia Virus (MoMuLV) ([ΨCD]2, 132-nucleotides, 42.8 kDaltons) using a 2H-edited NMR spectroscopy-based approach. This approach enabled the detection of 1H-1H dipolar interactions that were not observed in previous studies of isolated SL-C and SL-D hairpin RNAs using traditional 1H-1H correlated and 1H-13C-edited NMR methods. The hairpins participate in intermolecular cross-kissing interactions (SL-C to SL-D’ and SLC’ to SL-D), and stack in an end-to-end manner (SL-C to SL-D and SL-C’ to SL-D’) that gives rise to an elongated overall shape (ca. 95 Å by 45 Å by 25 Å). The global structure was confirmed by cryo-electron tomography (cryo-ET), making [ΨCD]2 simultaneously the smallest RNA to be structurally characterized to date by cryo-ET and among the largest to be determined by NMR. Our findings suggest that, in addition to promoting dimerization, [ΨCD]2 functions as a scaffold that helps initiate virus assembly by exposing a cluster of conserved UCUG elements for binding to the cognate nucleocapsid domains of assembling viral Gag proteins. PMID:20933521

  3. Influence of different light-dark cycles on motility and photosynthesis of Euglena gracilis in closed bioreactors.

    PubMed

    Richter, Peter R; Strauch, Sebastian M; Ntefidou, Maria; Schuster, Martin; Daiker, Viktor; Nasir, Adeel; Haag, Ferdinand W M; Lebert, Michael

    2014-10-01

    Abstract The unicellular photosynthetic freshwater flagellate Euglena gracilis is a promising candidate as an oxygen producer in biological life-support systems. In this study, the capacity of Euglena gracilis to cope with different light regimes was determined. Cultures of Euglena gracilis in closed bioreactors were exposed to different dark-light cycles (40 W/m(2) light intensity on the surface of the 20 L reactor; cool white fluorescent lamps in combination with a 100 W filament bulb): 1 h-1 h, 2 h-2 h, 4 h-4 h, 6 h-6 h, and 8 h-16 h, respectively. Motility and oxygen development in the reactors were measured constantly. It was found that, during exposure to light-dark cycles of 1 h-1 h, 2 h-2 h, 4 h-4 h, and 6 h-6 h, precision of gravitaxis as well as the number of motile cells increased during the dark phase, while velocity increased in the light phase. Oxygen concentration did not yet reach a plateau phase. During dark-light cycles of 8 h-16 h, fast changes of movement behavior in the cells were detected. The cells showed an initial decrease of graviorientation after onset of light and an increase after the start of the dark period. In the course of the light phase, graviorientation increased, while motility and velocity decreased after some hours of illumination. In all light profiles, Euglena gracilis was able to produce sufficient oxygen in the light phase to maintain the oxygen concentration above zero in the subsequent dark phase.

  4. Front End Spectroscopy ASIC for Germanium Detectors

    NASA Astrophysics Data System (ADS)

    Wulf, Eric

    Large-area, tracking, semiconductor detectors with excellent spatial and spectral resolution enable exciting new access to soft (0.2-5 MeV) gamma-ray astrophysics. The improvements from semiconductor tracking detectors come with the burden of high density of strips and/or pixels that require high-density, low-power, spectroscopy quality readout electronics. CMOS ASIC technologies are a natural fit to this requirement and have led to high-quality readout systems for all current semiconducting tracking detectors except for germanium detectors. The Compton Spectrometer and Imager (COSI), formerly NCT, at University of California Berkeley and the Gamma-Ray Imager/Polarimeter for Solar flares (GRIPS) at Goddard Space Flight Center utilize germanium cross-strip detectors and are on the forefront of NASA's Compton telescope research with funded missions of long duration balloon flights. The development of a readout ASIC for germanium detectors would allow COSI to replace their discrete electronics readout and would enable the proposed Gamma-Ray Explorer (GRX) mission utilizing germanium strip-detectors. We propose a 3-year program to develop and test a germanium readout ASIC to TRL 5 and to integrate the ASIC readout onto a COSI detector allowing a TRL 6 demonstration for the following COSI balloon flight. Our group at NRL led a program, sponsored by another government agency, to produce and integrate a cross-strip silicon detector ASIC, designed and fabricated by Dr. De Geronimo at Brookhaven National Laboratory. The ASIC was designed to handle the large (>30 pF) capacitance of three 10 cm^2 detectors daisy-chained together. The front-end preamplifier, selectable inverter, shaping times, and gains make this ASIC compatible with a germanium cross-strip detector as well. We therefore have the opportunity and expertise to leverage the previous investment in the silicon ASIC for a new mission. A germanium strip detector ASIC will also require precise timing of the signals at

  5. Indirect detection of infinite-speed MAS solid-state NMR spectra

    NASA Astrophysics Data System (ADS)

    Perras, Frédéric A.; Venkatesh, Amrit; Hanrahan, Michael P.; Goh, Tian Wei; Huang, Wenyu; Rossini, Aaron J.; Pruski, Marek

    2017-03-01

    Heavy spin-1/2 nuclides are known to possess very large chemical shift anisotropies that can challenge even the most advanced magic-angle-spinning (MAS) techniques. Wide manifolds of overlapping spinning sidebands and insufficient excitation bandwidths often obfuscate meaningful spectral information and force the use of static, low-resolution solid-state (SS)NMR methods for the characterization of materials. To address these issues, we have merged fast-magic-angle-turning (MAT) and dipolar heteronuclear multiple-quantum coherence (D-HMQC) experiments to obtain D-HMQC-MAT pulse sequences which enable the rapid acquisition of 2D SSNMR spectra that correlate isotropic 1H chemical shifts to the indirectly detected isotropic ;infinite-MAS; spectra of heavy spin-1/2 nuclides. For these nuclides, the combination of fast MAS and 1H detection provides a high sensitivity, which rivals the DNP-enhanced ultra-wideline SSNMR. The new pulse sequences were used to determine the Pt coordination environments in a complex mixture of decomposition products of transplatin and in a metal-organic framework with Pt ions coordinated to the linker ligands.

  6. Direct NMR resonance assignments of the active site histidine residue in Escherichia coli thioesterase I/protease I/lysophospholipase L1.

    PubMed

    Wu, Wen-Jin; Tyukhtenko, Sergiy I; Huang, Tai-Huang

    2006-11-01

    Owing to the hydrogen-bond interaction and rapid exchange rate with the bulk water, the transverse relaxation time for the N(delta1)-H proton of the catalytic histidine in Escherichia coli thioesterase I/protease I/lysophospholipase L1 (TEP-I) is rather short. Because of its catalytic importance, it is desirable to detect and assign this proton resonance. In this paper, we report the first direct NMR correlation between the short-lived N(delta1)-H proton and its covalently attached N(delta1)-nitrogen of the catalytic His157 residue in E. coli thioesterase/protease I. We have used gradient-enhanced jump-return spin-echo HMQC (GE-JR SE HMQC) to obtain a direct correlation between the short-lived N(delta1)-H proton and its covalently attached N(delta1)-nitrogen. The sensitivity of detection for the short-lived N(delta1)-H proton was enhanced substantially by improved water suppression, in particular, the suppression of radiation damping via pulsed field gradients.

  7. Application of a microcoil probe head in NMR analysis of chemicals related to the chemical weapons convention.

    PubMed

    Koskela, Harri; Vanninen, Paula

    2008-07-15

    A 1.7-mm microcoil probe head was tested in the analysis of organophosphorus compounds related to the Chemical Weapons Convention. The microcoil probe head demonstrated a high mass sensitivity in the detection of traces of organophosphorus compounds in samples. Methylphosphonic acid, the common secondary degradation product of sarin, soman, and VX, was detected at level 50 ng (0.52 nmol) from a 30-microL water sample using proton-observed experiments. Direct phosphorus observation of methylphosphonic acid with (31)P{(1)H} NMR experiment was feasible at the 400-ng (4.17 nmol) level. Application of the microcoil probe head in the spiked sample analysis was studied with a test water sample containing 2-10 microg/mL of three organophosphorus compounds. High-quality (1)H NMR, (31)P{(1)H} NMR, 2D (1)H-(31)P fast-HMQC, and 2D TOCSY spectra were obtained in 3 h from the concentrated 1.7-mm NMR sample prepared from 1 mL of the water solution. Furthermore, a 2D (1)H-(13)C fast-HMQC spectrum with sufficient quality was possible to measure in 5 h. The microcoil probe head demonstrated a considerable sensitivity improvement and reduction of measurement times for the NMR spectroscopy in identification of chemicals related to the Chemical Weapons Convention.

  8. Preliminary investigation of a highly sulfated galactofucan fraction isolated from the brown alga Sargassum polycystum.

    PubMed

    Bilan, Maria I; Grachev, Alexey A; Shashkov, Alexander S; Thuy, Thanh Thi Thu; Van, Tran Thi Thanh; Ly, Bui Minh; Nifantiev, Nikolay E; Usov, Anatolii I

    2013-08-09

    A fucoidan preparation was isolated from the brown alga Sargassum polycystum (Fucales, Sargassaceae). The preparation was fractionated by anion-exchange chromatography, and two highly sulfated fractions F3 and F4 were obtained. The fractions were quite similar in composition, but different in chemical structure. F4 was analyzed by chemical methods, including desulfation, methylation, Smith degradation, and partial acid hydrolysis with mass-spectrometric monitoring, as well as by NMR spectroscopy. Several 2D NMR procedures, including HMQC-TOCSY and HMQC-NOESY, were used to obtain reliable structural information from the complex spectra. Molecules of F4 were shown to contain a backbone built up mainly of 3-linked α-L-fucopyranose 4-sulfate residues, as in many other fucoidans, but rather short sequences of these residues are interspersed by single 2-linked α-D-galactopyranose residues also sulfated at position 4. This rather unusual structural feature should have a great influence on the conformation of the polymeric molecule and may be important for biological activity of the polysaccharide. Hence, F4 is an example of a new sulfated galactofucan isolated from the brown alga. According to the data obtained, the distribution of galactose residues along the polysaccharide backbone seems to be not strictly regular, but the definitive sequence of monomers in the polymeric molecules awaits additional investigation.

  9. Finite Elements for Fluid Dynamics.

    DTIC Science & Technology

    1980-08-01

    ion; u - ex siny, v cx cosy, A -2e cosy + 2/e 1 as shown in the following table: -9 u v _ L - error h =0.25 0.0.415 0.053 0.184 L 2 -er’ror 10.0163...0.0194 0.097 h =0.225 L - error 2 h 0.0625 numerical rate 1.35 1.45 0.92 of convergenceII (The rates of convergence for all of the problems we solved...shown in the following table: u_ I v L 2- error h = 0.25 0.0628 0.0962 0.333 L2- error h = 0.125 0.0257 0.0382 0.175 L 2- error h = 0.0625 numerical

  10. Upper limit for the cross-section of the overlapping scalar resonances f0(980) and a0(980) produced in proton proton collisions in the range of the reaction threshold

    NASA Astrophysics Data System (ADS)

    Moskal, P.; Adam, H.-H.; Budzanowski, A.; Czyzykiewicz, R.; Grzonka, D.; Janusz, M.; Jarczyk, L.; Kamys, B.; Khoukaz, A.; Kilian, K.; Kolf, C.; Kowina, P.; Lister, T.; Oelert, W.; Piskor-Ignatowicz, C.; Przerwa, J.; Quentmeier, C.; Rozek, T.; Santo, R.; Schepers, G.; Sefzick, T.; Siemaszko, M.; Smyrski, J.; Strzalkowski, A.; Täschner, A.; Winter, P.; Wolke, M.; Wüstner, P.; Zipper, W.

    2003-09-01

    Utilizing a missing mass technique we investigate the pp rightarrow ppX reaction scanning beam energies in the range permitting to create a mass close to that of the f0(980) and a0(980) scalar resonances, but still below the K+K- threshold where they decay dominantly into pipi and pieta mesons, respectively. Prior to the data analysis we introduce a notion of the close to threshold total cross-section for broad resonances. We estimated for the overlapping mesons a0 and f0 the total cross-section to be smaller than 430 nb at excess energy of Q = 5 MeV. The experiment has been performed at the Cooler Synchrotron (COSY) using the COSY-11 facility.

  11. Determination of the total width of the η' meson.

    PubMed

    Czerwiński, E; Moskal, P; Grzonka, D; Czyzykiewicz, R; Gil, D; Kamys, B; Khoukaz, A; Klaja, J; Klaja, P; Krzemień, W; Oelert, W; Ritman, J; Sefzick, T; Siemaszko, M; Silarski, M; Smyrski, J; Täschner, A; Wolke, M; Wüstner, P; Zdebik, J; Zieliński, M; Zipper, W

    2010-09-17

    Taking advantage of both the low-emittance proton beam of the cooler synchrotron COSY and the high momentum precision of the COSY-11 detector system, the mass distribution of the η' meson was measured with a resolution of 0.33  MeV/c2 (FWHM), improving the experimental mass resolution by almost an order of magnitude with respect to previous results. Based on the sample of more than 2300 reconstructed pp → ppη' events, the total width of the η' meson was determined to be Γ(η') = 0.226 ± 0.017(stat) ± 0.014(syst)  MeV/c2.

  12. Dropping In a Microgravity Environment (DIME) Contest

    NASA Technical Reports Server (NTRS)

    2001-01-01

    The first NASA Dropping In a Microgravity Environment (DIME) student competition pilot project came to a conclusion at the Glenn Research Center in April 2001. The competition involved high-school student teams who developed the concept for a microgravity experiment and prepared an experiment proposal. The two student teams - COSI Academy, sponsored by the Columbus Center of Science and Industry, and another team from Cincinnati, Ohio's Sycamore High School, designed a microgravity experiment, fabricated the experimental apparatus, and visited NASA Glenn to operate their experiment in the 2.2 Second Drop Tower. Students from Sycamore High School in Cincinnati, Ohio (girls), and the COSI Academy, Columbus, Ohio (boys), participated. This image is from a digital still camera; higher resolution is not available.

  13. Spectral Domain Analysis of Fin-Line.

    DTIC Science & Technology

    1979-12-01

    For the matrices [ME] and [M5 ], the elements m 11 through m 6 8 are the same. 92 (k lD) 2sinh [ (- 1D ) (hl/D)l ] D) 2 0 mlll j (kclD) 2sin[ (y ,,D...D ) (SD) cosY2 1D -((inD) (8D) cosy 2 "D m24= 0 93 I -j (wLiD) (y 1 ’D)sint (yj1 D) (h 1 /D) IIj (wu~D) (-Y2 D) coshy2 D m 2 6 = _ ww~D) (y2 "D) co s...71 D) (D e 2+(8D) (wilD)(yD) 2a be __* 2 (Ae) * h - ( D) 2 (e -(Ah) +j(kD) 2(a D) 2 A 21 D D D D h h (D) (wu 1D ) (O nD) 2 Ah [sinh2(y1 D) (--)-2

  14. Thermodynamic simulation of the elastic and thermal properties of cobalt monosilicide

    NASA Astrophysics Data System (ADS)

    Povzner, A. A.; Filanovich, A. N.; Nogovitsyna, T. A.

    2016-06-01

    A self-consistent thermodynamic model is used to calculate the temperature dependences of the heat capacity, the thermal expansion coefficient, the bulk compression modulus, the density, Debye temperature, and the Grüneisen parameter of CoSi in the temperature range 0-1400 K. The calculation results agree well with the existing experimental data and can be used to predict the properties of CoSi in the temperature range that has not been experimentally studied. Cobalt monosilicide is shown to have a significant phonon anharmonicity, which can be caused by an electron-phonon interaction, and this anharmonicity should be taken into account in the simulation of its thermoelectric properties.

  15. New sucrose derivatives from the bark of Securidaca longipedunculata.

    PubMed

    De Tommasi, N; Piacente, S; De Simone, F; Pizza, C

    1993-01-01

    Two new bitter principles were isolated from the bark of Securidaca longipedunculata (Polygalaceae) and identified as beta-D-(3,4-disinapoyl)fructofuranosyl-alpha-D-(6-sinapoyl)g lucopyranoside and beta-D-(3-sinapoyl)fructofuranosyl-alpha-D-(6-sinapoyl)gluco pyranoside. The structures were elucidated by a combination of 1H nmr (1D, 2D COSY, 2D HOHAHA), 13C-nmr, and fabms spectra.

  16. Unciflavones A-F, six novel flavonoids from Selaginella uncinata (Desv.) Spring.

    PubMed

    Zou, Hui; Xu, Kang-Ping; Li, Fu-Shuang; Zou, Zhen-Xing; Liu, Rui; Liu, Rui-Huan; Li, Jing; Tan, Lei-Hong; Tan, Gui-Shan

    2014-12-01

    Six new flavonoids, unciflavones A-F (1-6), have been isolated from medicinal plant Selaginella uncinata (Desv.) Spring. Their structures were established on the basis of extensive NMR analysis including 1D NMR ((1)H, (13)C and DEPT) and 2D NMR (COSY, HSQC, HMBC) experiments as well as HRESIMS analysis. All compounds possess exceptional structural features with an aryl substituent at the C-8 position, which are uncommonly encountered in natural resources and firstly reported in genus Selaginella.

  17. DIME Students Discuss Final Drop Tower Experiment Design

    NASA Technical Reports Server (NTRS)

    2002-01-01

    Students discuss fine points of their final design for the Drop Tower experiment during the second Dropping in a Microgravity Environment (DIME) competition held April 23-25, 2002, at NASA's Glenn Research Center. Competitors included two teams from Sycamore High School, Cincinnati, OH, and one each from Bay High School, Bay Village, OH, and COSI Academy, Columbus, OH. DIME is part of NASA's education and outreach activities. Details are on line at http://microgravity.grc.nasa.gov/DIME_2002.html.

  18. Comprehensive Space-Object Characterization using Spectrally Compressive Polarimetric Sensing

    DTIC Science & Technology

    2015-04-08

    identification based upon imag- ing using simultaneous measurements at different wavelengths. AMOS sensors can collect simultaneous images ranging from visible...Synthesis Topical 23 Meeting of the Optical Society of America, Toronto, CA (July 11, 2011). Abstract available at http://www.opticsinfobase.org...polarimetric imaging,” Computational Optical Sens- ing and Imaging (COSI) Topical Meeting of the Optical Society of America, Monterey, CA (24-27 June

  19. Assessment of Efficacy of Activated Charcoal for Treatment of Acute T-2 Toxin Poisoning,

    DTIC Science & Technology

    1986-11-14

    Command 14 November 15Mi IS. "U"SGIEf, OP Rs) 14. i*OXSIT01GMQ AGENCY MAMIE A A0ONZS.S( 1f Etsr *0 CAMORdlim4 OM.0) IL S*Cu~jTY "ALA (of 00* mae ~-s ~ 14L...Procedures of Statistics, McGraw-Hill, New York, 1960. 14. R. C. Hatch, J. D. Clark , A. V. Jain, and R. Weiss, Induced acute aflatox~cosis in goats

  20. A new lignan glycoside from the rhizomes of Imperata cylindrica.

    PubMed

    Lee, Dae-Young; Han, Kyung-Min; Song, Myoung-Chong; Lee, Do-Gyeong; Rho, Yeong-Deok; Baek, Nam-In

    2008-01-01

    A new lignan glycoside, 6-acetyl-1-[1,3-(4,4'-dihydroxy-3,3'-dimethoxy-beta-truxinyl)-beta-d-fructofuranosyl]-alpha-d-glucopyranoside (1), named impecyloside, was isolated from the rhizomes of Imperata cylindrica. The structure of the compound was determined by spectroscopic data including FABMS, UV, IR, 1H NMR and 13C NMR (DEPT) and 2D NMR (COSY, HSQC, HMBC).

  1. Near threshold two meson production with the pd→3Heπ+π- and pd→3HeK+K- reactions

    NASA Astrophysics Data System (ADS)

    Bellemann, F.; Berg, A.; Bisplinghoff, J.; Bohlscheid, G.; Ernst, J.; Henrich, C.; Hinterberger, F.; Ibald, R.; Jahn, R.; Jarczyk, L.; Joosten, R.; Kozela, A.; Machner, H.; Magiera, A.; Maschuw, R.; Mayer-Kuckuk, T.; Mertler, G.; Munkel, J.; von Neumann-Cosel, P.; Rosendaal, D.; von Rossen, P.; Schnitker, H.; Scho, K.; Smyrski, J.; Strzalkowski, A.; Tölle, R.; Wilkin, C.

    2000-06-01

    Near threshold two meson production via the reactions pd→3Heπ+π- and pd→3HeK+K- was measured kinematically complete with the MOMO experiment at COSY. The obtained two pion invariant mass spectra and angular distributions depict a remarkable deviation from phase space. The two kaon data are consistent with phase space topped by a clear signal of the φ meson.

  2. Combat and Operational Stress: Curtailing the Effects Through Leadership and Education

    DTIC Science & Technology

    2010-04-02

    COSI) are defined as "potentially ineversible changes in the brain and mind due to combat or operational stress that exceed in intensity or duration ...their duration . Every Marine, no matter how seasoned or conditioned they are, has a variable breaking point. Leaders must inherently understand this...contribute to COS are arguably unavoidable. The duration or frequency of deployments, horne front stressors, and previous mental health problems

  3. First biosynthetic evidence on the phenyl-containing polyketides of the marine mollusc Scaphander lignarius.

    PubMed

    Cutignano, Adele; Avila, Conxita; Domenech-Coll, Anna; d'Ippolito, Giuliana; Cimino, Guido; Fontana, Angelo

    2008-07-17

    The biosynthesis of lignarenones 1 and 2, the major polyketides of the Mediterranean mollusc Scaphander lignarius is described. The process is primed by benzoic acid and requires acetate and propionate as extender units. The labeling pattern suggests PKS-like synthesis of an unusual E,Z,E-triene chain and origin of the benzoate unit from phenylalanine. 13C-13C NMR COSY has been used to establish the labeling positions due to incorporation of 13C2-acetate.

  4. Shape-Persistent, Truxene-Based, Nano-Sized Bisterpyridine Ruthenium(II) Complexes: Synthesis and Photophysical Properties.

    PubMed

    Wang, Jin-Liang; Chan, Yi-Tsu; Moorefield, Charles N; Pei, Jian; Modarelli, David A; Romano, Natalie C; Newkome, George R

    2010-05-12

    A new series of shape-persistent metallomacromolecules G0 and G1 as well as corresponding ligands, based on thiophene-functionalized bisterpyridine-Ru(II) with truxene moieties, as the nodes, were developed. All new compounds were fully characterized by (1) H, COSY, and (13) C NMR, as well as MALDI-TOF MS. Their photophysical properties revealed that the branched scaffold resulted in high molar absorption coefficients and broad absorption making these materials potential candidates for light-harvesting.

  5. Half-metallicity and magnetism of Ti2Ni1-x CoxAl1-y Siy inverse Heusler alloys

    NASA Astrophysics Data System (ADS)

    Zhou, Ting; Feng, Yu; Chen, Xiaorui; Yuan, Hongkuan; Chen, Hong

    2017-02-01

    Half-metallicity and magnetism of Ti2Ni1-x CoxAl1-y Siy, which are obtained by Co/Si substitutions for Ni/Al of inverse Heusler alloy Ti2NiAl, are investigated by first-principle calculations based on density functional theory (DFT). The optimized lattice constants of the doped systems all conform to the Vegard law as the increase of the impurity concentration, and the magnetic moments obey the Slater-Pauling rule when the half-metallicity is retained. The defect formation energies of the codoped systems are lower than those of the monodoped systems due to the charge compensation effects, thus the Co+Si codoping is more favorable in energy than the Co/Si monodoping. Furthermore, for the Co and Si monodoped systems, the Co monodoping retains the minority-spin bandgap unchanged although the Fermi level moves towards high energy region, and the Si monodoping leads to the minority-spin bandgap narrowing and even the loss of half-metallicity at the high concentration, while for the Co+Si codoped systems, the majority of the codoped compounds obviously show more stable half-metallicity and the minority-spin gap get widened. In particular, the minority-spin band gap of the codoped compounds Ti2Ni0.5Co0.5Al0.5Si0.5 , Ti2Ni0.25Co0.75Al0.5Si0.5 , and Ti2NiCo Al0.25Si0.75 are widened distinctly and their Fermi level are adjusted to the middle of the minority-spin gap, indicating that they possess robust half-metallicity and thus they are promising candidates for spintronics applications.

  6. Alkylamides of Acmella oleracea.

    PubMed

    Cheng, Yuan-Bin; Liu, Rosa Huang; Ho, Meng-Chi; Wu, Tung-Ying; Chen, Ching-Yeu; Lo, I-Wen; Hou, Ming-Feng; Yuan, Shyng-Shiou; Wu, Yang-Chang; Chang, Fang-Rong

    2015-04-16

    Phytochemical investigation of the flowers of Acmella oleracea had resulted in the isolation of one new alkylamide, (2E,5Z)-N-isobutylundeca-2,5-diene-8,10-diynamide (1), together with four known analogues (2-5). The structures of these compounds were determined by the interpretation of spectroscopic methods, especially NMR technologies (COSY, HSQC, HMBC, and NOESY). In addition, a convenient method for concentrating the alkylamide-rich fraction and analyzing fingerprint profile of A. oleracea was established.

  7. Resveratrol tetramer of hopeaphenol isolated from Shorea johorensis (Dipterocarpaceae)

    SciTech Connect

    Aisha, Farra; Din, Laily B.; Yaacob, W. A.

    2014-09-03

    Hopeaphenol (1) as a resveratrol tetramer was isolated from the bark of Shorea johorensis collected from Imbak Canyon, Sabah, Malaysia. The structure of this compound was determined by the spectroscopic evidences using {sup 1}H- and {sup 13}C-NMR assigned with HSQC, HMBC, {sup 1}H−{sup 1}H COSY and {sup 1}H−{sup 1}H NOESY spectra, mass spectrum, and by comparison with reported data.

  8. Rapid microwaves synthesis of CoSi{sub x}/CNTs as novel catalytic materials for hydrogenation of phthalic anhydride

    SciTech Connect

    Zhang, Liangliang; Chen, Xiao; Jin, Shaohua; Guan, Jingchao; Williams, Christopher T.; Peng, Zhijian; Liang, Changhai

    2014-09-15

    CoSi{sub x}/CNTs catalysts with different CoSi{sub x} phases (CoSi, CoSi{sub 2}) have been rapidly synthesized via a microwave-assisted route and applied for the liquid phase hydrogenation of phthalic anhydride. The synthesized catalysts were analyzed and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy-energy dispersive X-ray spectroscopy, thermogravimetric/derivative thermogravimetric analysis. The reaction progress of cobalt silicides and the ratio of Co:Si were monitored at different microwave irradiation times by XRD, giving insight into the formation mechanism. Compared to the Co/CNTs catalyst, all the prepared CoSi{sub x}/CNTs catalysts exhibited excellent activity and good selectivity to phthalide under mild reaction conditions (180–220 °C and 4.0 MPa H{sub 2}). This novel methodology can be applied to the synthesis of other transition metal silicides such as FeSi, Ni{sub 2}Si, and Cu{sub 4}Si. - Graphical abstract: CoSi{sub x}/CNTs catalysts with different CoSi{sub x} phases (CoSi{sub 2}, CoSi) have been rapidly synthesized via microwave-assisted route, which involves the vaporization of CoCl{sub 2} and subsequent reaction of CoCl{sub 2} with Si. - Highlights: • CoSi{sub x}/CNTs catalysts have been rapid synthesized via microwave-assisted route. • The phases of CoSi{sub x} were controlled by varying microwave time and Co:Si ratio. • FeSi, Ni{sub 2}Si and Cu{sub 4}Si were also synthesized via microwave-assisted route. • CoSi{sub x}/CNTs catalysts can be applied in hydrogenation of phthalic anhydride.

  9. Ultrahigh-Resolution Magnetic Resonance in Inhomogeneous Magnetic Fields: Two-Dimensional Long-Lived-Coherence Correlation Spectroscopy

    NASA Astrophysics Data System (ADS)

    Chinthalapalli, Srinivas; Bornet, Aurélien; Segawa, Takuya F.; Sarkar, Riddhiman; Jannin, Sami; Bodenhausen, Geoffrey

    2012-07-01

    A half-century quest for improving resolution in Nuclear Magnetic Resonance (NMR) and Magnetic Resonance Imaging (MRI) has enabled the study of molecular structures, biological interactions, and fine details of anatomy. This progress largely relied on the advent of sophisticated superconducting magnets that can provide stable and homogeneous fields with temporal and spatial variations below ΔB0/B0<0.01ppm. In many cases however, inherent properties of the objects under investigation, pulsating arteries, breathing lungs, tissue-air interfaces, surgical implants, etc., lead to fluctuations and losses of local homogeneity. A new method dubbed “long-lived-coherence correlation spectroscopy” (LLC-COSY) opens the way to overcome both inhomogeneous and homogeneous broadening, which arise from local variations in static fields and fluctuating dipole-dipole interactions, respectively. LLC-COSY makes it possible to obtain ultrahigh resolution two-dimensional spectra, with linewidths on the order of Δν=0.1 to 1 Hz, even in very inhomogeneous fields (ΔB0/B0>10ppm or 5000 Hz at 9.7 T), and can improve resolution by a factor up to 9 when the homogeneous linewidths are determined by dipole-dipole interactions. The resulting LLC-COSY spectra display chemical shift differences and scalar couplings in two orthogonal dimensions, like in “J spectroscopy.” LLC-COSY does not require any sophisticated gradient switching or frequency-modulated pulses. Applications to in-cell NMR and to magnetic resonance spectroscopy (MRS) of selected volume elements in MRI appear promising, particularly when susceptibility variations tend to preclude high resolution.

  10. Natural dibenzoxazepinones from leaves of Carex distachya: Structural elucidation and radical scavenging activity.

    PubMed

    Fiorentino, Antonio; D'Abrosca, Brigida; Pacifico, Severina; Cefarelli, Giuseppe; Uzzo, Piera; Monaco, Pietro

    2007-02-01

    Two new dibenzoxazepinones have been isolated from the leaves of Carex distachya, an herbaceous plant growing in the Mediterranean area. The structures have been elucidated on the basis of their spectroscopic properties. Bidimensional NMR (DQ-COSY, TOCSY, NOESY, ROESY, HSQC, and HMBC) furnished important data useful for the characterization of the molecules. The compounds have been assayed, for the antioxidant activity, by measuring its capacity to scavenge the DPPH, the superoxide anion, and nitric oxide radicals.

  11. Studies of Ionospheric Irregularities: Origins and Effects

    DTIC Science & Technology

    2006-09-30

    data at Hawaii. See http://www.cosis.net/abstracts/EAE03/05826/EAE03-J-05826.pdf. REFERENCES Cerruti, A. P., B. M. Ledvina , and P. M. Kintner...Measurements of equatorial scintillations on the WAAS satellite signal, Radio Sci., in press, 2006. Ledvina , B. M., P. M. Kintner, and J. J. Makela...2000. [published, refereed] Cerruti, A.P., B.M. Ledvina , and P.M. Kintner, Measurements of equatorial scintillations on the WAAS satellite

  12. A new flavonoid and other constituents from Centaurea nicaeensis All. var. walliana M.

    PubMed

    Hammoud, Leila; Seghiri, Ramdane; Benayache, Samir; Mosset, Paul; Lobstein, Annelise; Chaabi, Mehdi; León, Francisco; Brouard, Ignacio; Bermejo, Jaime; Benayache, Fadila

    2012-01-01

    A new flavone glucoside, apigenin 4'-(6″-methylglucuronide) (1), together with six known compounds, cirsilineol, jaceosidin, melitensin, apigenin, apigenin 7-(6″-methylglucuronide) and prunasin, were isolated from the ethanolic extract of the aerial parts of Centaurea nicaeensis All. var. walliana M. (Asteraceae) collected from Souk-Ahras, eastern Algeria. The structures were established by spectral analysis, mainly HRESI-MS, UV and 2D-NMR experiments (COSY, HSQC and HMBC).

  13. Department of Energy Technology Annual Progress Report 1 January - 31 December 1988

    DTIC Science & Technology

    1989-03-01

    Reservoir Simulation . 23 p. Submit- ted for the 10th SPE Symposium on Reservoir Simulation . Hou- ston, February 1989. BECH, N.M.; JENSEN, O.K. and NIELSEN...at the 10th SPE Symposium on Reservoir Simulation . Houston, February 1989. DALL, H. (1988). Development of a computer model for stationary turbulent 3... Reservoir Simulation Program, COSI. Description of a New Input Facility. Rise-M-2729. 227 p. HOJERUP, C.F. (1988). Swedish Boiling Water Reactors

  14. Glucan from hot aqueous extract of an ectomycorrhizal edible mushroom, Russula albonigra (Krombh.) Fr.: structural characterization and study of immunoenhancing properties.

    PubMed

    Nandi, Ashis K; Sen, Ipsita K; Samanta, Surajit; Maity, Kousik; Devi, K Sanjana P; Mukherjee, Shreemoyee; Maiti, Tapas K; Acharya, Krishnendu; Islam, Syed S

    2012-12-01

    A water soluble glucan (PS-I) was isolated from the hot aqueous extract of the fruit bodies of an ectomycorrhizal edible mushroom, Russula albonigra (Krombh.) Fr. The total hydrolysis, methylation analysis, periodate oxidation, and NMR ((1)H, (13)C, DEPT-135, TOCSY, DQF-COSY, NOESY, ROESY, HSQC, and HMBC) studies revealed the presence of the following repeating unit in the polysaccharide: This glucan showed excellent activation of macrophages as well as splenocytes and thymocytes in vitro.

  15. An immunostimulating water insoluble β-glucan of an edible hybrid mushroom: isolation and characterization.

    PubMed

    Maity, Kousik; Samanta, Surajit; Bhanja, Sunil K; Maity, Saikat; Sen, Ipsita K; Maiti, Swatilekha; Behera, Birendra; Maiti, Tapas K; Sikdar, Samir R; Islam, Syed S

    2013-01-01

    An immunostimulating water-insoluble β-glucan isolated from hot alkaline extract of the fruiting bodies of an edible somatic hybrid mushroom of Pleurotus florida and Calocybe indica var. APK2 showed significant macrophage, splenocyte, and thymocyte activations. On the basis of total hydrolysis, methylation analysis, and NMR experiments ((1)H, (13)C, DQF-COSY, TOCSY, NOESY, DEPT-135, and HSQC), the repeating unit of the polysaccharide is established.

  16. Electrical properties and magnetic response of cobalt germanosilicide nanowires.

    PubMed

    Tsai, Chun-I; Wang, Chiu-Yen; Tang, Jianshi; Hung, Min-Hsiu; Wang, Kang L; Chen, Lih-Juann

    2011-12-27

    The effects of partial substitution of Ge for Si in cobalt germanosilicide (CoSi(1-x)Ge(x) and Co(2)Si(1-x)Ge(x)) nanowires (NWs) on the electrical transport, magnetic properties, and magnetoresistance (MR) have been investigated. Cobalt germanosilicide NWs were synthesized by a spontaneous chemical vapor transport growth method. The Ge concentration can be selectively controlled from 0 to 15% and 0-50% for CoSi(1-x)Ge(x) and Co(2)Si(1-x)Ge(x) NWs, respectively, by varying the reaction temperature. Electrical measurements showed that the resistivities of CoSi(1-x)Ge(x) NWs are 90, 60, 30, and 23 μΩ-cm for x = 0, 0.01, 0.05, and 0.15, respectively. Therefore, the electrical resistivity of CoSi(1-x)Ge(x) NWs was found to decrease significantly with an increasing Ge concentration, which is believed to be a result of the band gap narrowing. On the other hand, the Co(2)Si(1-x)Ge(x) (x ≤ 0.5) NWs exhibited ferromagnetism at 300 K, which is attributed to the uncoordinated Co atoms on the NW surface and spin-glass behavior at low temperature. The highest MR response of Co(2)Si(1-x)Ge(x) NWs occurred at x = 0.5, where a MR ratio of 11.7% can be obtained at 10-25 K with a magnetic field of 8 T. The enhanced physical properties of cobalt germanosilicide NWs with Ge substitution shall lead to promising application in the fabrication of nanodevices, including spintronics and serving as the gate and interconnect material.

  17. Inexpert Calibration of Comprehension.

    DTIC Science & Technology

    1986-03-01

    p.TAB Wiscnsi CeterforEduatinJRseiiarchn Schools of Edcatio Universityablit ofW cosi-Mdio Acceso F ,.dr o Dist Sbito cia ~~~~1 j󈧏Atvalabliy C de This...physics experence. These four variables were then entered, as a set, into a hierarchical multiple regression analysis to determine the effect of...The basic strategy of data analysis was to use hierarchical multiple - regression techniques to perform an analysis of variance (Cohen & Cohen, 1977

  18. Student-Designed Fluid Experiment for DIME Competition

    NASA Technical Reports Server (NTRS)

    2002-01-01

    Student-designed and -built apparatus for the second Dropping in a Microgravity Environment (DIME) competition held April 23-25, 2002, at NASA's Glenn Research Center. Competitors included two teams from Sycamore High School, Cincinnati, OH, and one each from Bay High School, Bay Village, OH, and COSI Academy, Columbus, OH. DIME is part of NASA's education and outreach activities. Details are on line at http://microgravity.grc.nasa.gov/DIME_2002.html.

  19. Highly oxygenated sesquiterpenes in Artemisia alba Turra.

    PubMed

    Todorova, Milka; Trendafilova, Antoaneta; Danova, Kalina; Simmons, Luke; Wolfram, Evelyn; Meier, Beat; Riedl, Rainer; Evstatieva, Luba

    2015-02-01

    Ten new sesquiterpene alcohols of which seven germacranes, a eudesmane, a guaiane and an oplopane were isolated from the aerial parts of Artemisia alba Turra. Their structures and relative stereochemistry were elucidated by spectral methods ((1)H and (13)C NMR, COSY, HSQC, HMBC, NOESY, and MS). In addition, the known 7-hydroxycadin-4-en-3-one, centaureidin and axillarin were found for the first time in the studied species.

  20. An EUV Wide-Field Imager and Spectrometer for the ISS

    NASA Technical Reports Server (NTRS)

    Golub, Leon; Savage, Sabrina

    2016-01-01

    The Coronal Spectrographic Imager in the EUV, COSIE, combines a wide-field solar coronal EUV imager (EUVC) and an on-disk EUV imaging spectrometer (EUVS). Located on the International Space Station (ISS), the goal of the mission is to enhance our understanding of the dynamics of the Transition Corona (the region in which the coronal magnetic field transitions from closed to open), and to provide improved detection and tracking of solar eruptive events for space weather research.