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Sample records for 1h-1h cosy hmqc

  1. Dynamic stereochemistry of erigeroside by measurement of 1H- 1H and 13C- 1H coupling constants

    NASA Astrophysics Data System (ADS)

    Tafazzoli, Mohsen; Ghiasi, Mina; Moridi, Mahdi

    2008-07-01

    Erigeroside was extracted from Satureja khuzistanica Jamzad (Marzeh Khuzistani in Persian, family of lamiaceae), and 1H, 13C, 13C{ 1H}, 1H- 1H COSY, HMQC and J-HMBC were obtained to identify this compound and determine a complete set of J-coupling constants ( 1JC-H, 2JC-H, 3JC-H and 3JH-H) values within the exocyclic hydroxymethyl group (CH 2OH) and anomeric center. In parallel, density functional theory (DFT) using B3LYP functional and split-valance 6-311++G** basis set has been used to optimized the structures and conformers of erigeroside. In all calculations solvent effects were considered using a polarized continuum (overlapping spheres) model (PCM). The dependencies of 1J, 2J and 3J involving 1H and 13C on the C 5'-C 6' ( ω), C 6'-O 6' ( θ) and C 1'-O 1' ( φ) torsion angles in erigeroside were computed using DFT method. Complete hyper surfaces for 1JC1',H1', 2JC5',H6'R, 2JC5',H6'S, 2JC6',H5', 3JC4',H6'R, 3JC4',H6'S and 2JH6'R-H5'S as well as 3JH5',H6'R were obtained and used to derive Karplus equations to correlate these couplings to ω, θ and φ. These calculated J-couplings are in agreement with experimental values. These results confirm the reliability of DFT calculated coupling constants in aqueous solution.

  2. 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.

  3. Hydrophobization of epoxy nanocomposite surface with 1H,1H,2H,2H-perfluorooctyltrichlorosilane for superhydrophobic properties

    NASA Astrophysics Data System (ADS)

    Psarski, Maciej; Marczak, Jacek; Celichowski, Grzegorz; Sobieraj, Grzegorz B.; Gumowski, Konrad; Zhou, Feng; Liu, Weimin

    2012-10-01

    Nature inspires the design of synthetic materials with superhydrophobic properties, which can be used for applications ranging from self-cleaning surfaces to microfluidic devices. Their water repellent properties are due to hierarchical (micrometer- and nanometre-scale) surface morphological structures, either made of hydrophobic substances or hydrophobized by appropriate surface treatment. In this work, the efficiency of two surface treatment procedures, with a hydrophobic fluoropolymer, synthesized and deposited from 1H,1H,2H,2H-perfluorooctyltrichlorosilane (PFOTS) is investigated. The procedures involved reactions from the gas and liquid phases of the PFOTS/hexane solutions. The hierarchical structure is created in an epoxy nanocomposite surface, by filling the resin with alumina nanoparticles and micron-sized glass beads and subsequent sandblasting with corundum microparticles. The chemical structure of the deposited fluoropolymer was examined using XPS spectroscopy. The topography of the modified surfaces was characterized using scanning electron microscopy (SEM), and atomic force microscopy (AFM). The hydrophobic properties of the modified surfaces were investigated by water contact and sliding angles measurements. The surfaces exhibited water contact angles of above 150° for both modification procedures, however only the gas phase modification provided the non-sticking behaviour of water droplets (sliding angle of 3°). The discrepancy is attributed to extra surface roughness provided by the latter procedure.

  4. 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.

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

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-05-28

    Dynamics plays important roles in determining the physical, chemical, and functional properties of a variety of chemical and biological materials. However, a material (such as a polymer) generally has mobile and rigid regions in order to have high strength and toughness at the same time. Therefore, it is difficult to measure the role of mobile phase without being affected by the rigid components. Herein, we propose a highly sensitive solid-state NMR approach that utilizes a dipolar-coupling based filter (composed of 12 equally spaced 90° RF pulses) to selectively measure the correlation of (1)H chemical shifts from the mobile regions of a material. It is interesting to find that the rotor-synchronized dipolar filter strength decreases with increasing inter-pulse delay between the 90° pulses, whereas the dipolar filter strength increases with increasing inter-pulse delay under static conditions. In this study, we also demonstrate the unique advantages of proton-detection under ultrafast magic-angle-spinning conditions to enhance the spectral resolution and sensitivity for studies on small molecules as well as multi-phase polymers. Our results further demonstrate the use of finite-pulse radio-frequency driven recoupling pulse sequence to efficiently recouple weak proton-proton dipolar couplings in the dynamic regions of a molecule and to facilitate the fast acquisition of (1)H/(1)H correlation spectrum compared to the traditional 2D NOESY (Nuclear Overhauser effect spectroscopy) experiment. We believe that the proposed approach is beneficial to study mobile components in multi-phase systems, such as block copolymers, polymer blends, nanocomposites, heterogeneous amyloid mixture of oligomers and fibers, and other materials. PMID:26026440

  6. Observation of 1H-13C and 1H-1H proximities in a paramagnetic solid by NMR at high magnetic field under ultra-fast MAS.

    PubMed

    Li, Shenhui; Trébosc, Julien; Lafon, Olivier; Zhou, Lei; Shen, Ming; Pourpoint, Frédérique; Amoureux, Jean-Paul; Deng, Feng

    2015-02-01

    The assignment of NMR signals in paramagnetic solids is often challenging since: (i) the large paramagnetic shifts often mask the diamagnetic shifts specific to the local chemical environment, and (ii) the hyperfine interactions with unpaired electrons broaden the NMR spectra and decrease the coherence lifetime, thus reducing the efficiency of usual homo- and hetero-nuclear NMR correlation experiments. Here we show that the assignment of (1)H and (13)C signals in isotopically unmodified paramagnetic compounds with moderate hyperfine interactions can be facilitated by the use of two two-dimensional (2D) experiments: (i) (1)H-(13)C correlations with (1)H detection and (ii) (1)H-(1)H double-quantum↔single-quantum correlations. These methods are experimentally demonstrated on isotopically unmodified copper (II) complex of l-alanine at high magnetic field (18.8 T) and ultra-fast Magic Angle Spinning (MAS) frequency of 62.5 kHz. Compared to (13)C detection, we show that (1)H detection leads to a 3-fold enhancement in sensitivity for (1)H-(13)C 2D correlation experiments. By combining (1)H-(13)C and (1)H-(1)H 2D correlation experiments with the analysis of (13)C longitudinal relaxation times, we have been able to assign the (1)H and (13)C signals of each l-alanine ligand. PMID:25557861

  7. CHHC and 1H-1H Magnetization Exchange: Analysis by Experimental Solid-State NMR and 11-Spin Density-Matrix Simulations

    PubMed Central

    Aluas, Mihaela; Tripon, Carmen; Griffin, John M.; Filip, Xenia; Ladizhansky, Vladimir; Griffin, Robert G.; Brown, Steven P.; Filip, Claudiu

    2009-01-01

    A protocol is presented for correcting the effect of non-specific cross polarization in CHHC solid-state MAS NMR experiments, thus allowing the recovery of the 1H-1H magnetization exchange functions from the mixing-time dependent buildup of experimental CHHC peak intensity. The presented protocol also incorporates a scaling procedure to take into account the effect of multiplicity of a CH2 or CH3 moiety. Experimental CHHC buildup curves are presented for L-Tyrosine.HCl samples where either all or only one in ten molecules are U-13C labeled. Good agreement between experiment and 11-spin SPINEVOLUTION simulation (including only isotropic 1H chemical shifts) is demonstrated for the initial buildup (tmix < 100 μs) of CHHC peak intensity corresponding to an intramolecular close (2.5 Å) H-H proximity. Differences in the initial CHHC buildup are observed between the 1 in 10 dilute and 100 % samples for cases where there is a close intermolecular H-H proximity in addition to a close intramolecular H-H proximity. For the dilute sample, CHHC cross peak intensities tended to significantly lower values for long mixing times (500 μs) as compared to the 100 % sample. This difference is explained as being due to the dependence of the limiting total magnetization on the ratio Nobs/Ntot between the number of protons that are directly attached to a 13C nucleus and hence contribute significantly to the observed 13C CHHC NMR signal, and the total number of 1H spins into the system. 1H-1H magnetization exchange curves extracted from CHHC spectra for the 100 % L-Tyrosine.HCl sample exhibit a clear sensitivity to the root sum squared dipolar coupling, with fast build-up being observed for the shortest intramolecular distances (2.5 Å) and slower, yet observable build-up for the longer intermolecular distances (up to 5 Å). PMID:19467890

  8. 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. PMID:26203019

  9. 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.

  10. 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.

  11. Population transfer HMQC for half-integer quadrupolar nuclei.

    PubMed

    Wang, Qiang; Li, Yixuan; Trébosc, Julien; Lafon, Olivier; Xu, Jun; Hu, Bingwen; Feng, Ningdong; Chen, Qun; Amoureux, Jean-Paul; Deng, Feng

    2015-03-01

    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., (27)Al-(17)O). In this case, the build-up is strongly affected by relaxation for small T2' 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 AlPO4-14 sample, one still observes experimentally a 2-fold shortening of the optimum mixing time albeit with no significant signal gain in the (31)P-{(27)Al} experiments. PMID:25747074

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

    PubMed

    Pandey, Manoj Kumar; Nishiyama, Yusuke

    2015-09-01

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

  13. Constant time INEPT CT-HSQC (CTi-CT-HSQC) - A new NMR method to measure accurate one-bond J and RDCs with strong 1H-1H couplings in natural abundance

    NASA Astrophysics Data System (ADS)

    Yu, Bingwu; van Ingen, Hugo; Freedberg, Darón I.

    2013-03-01

    Strong 1H-1H coupling can significantly reduce the accuracy of 1JCH measured from frequency differences in coupled HSQC spectra. Although accurate 1JCH values can be extracted from spectral simulation, it would be more convenient if the same accurate 1JCH values can be obtained experimentally. Furthermore, simulations reach their limit for residual dipolar coupling (RDC) measurement, as many significant, but immeasurable RDCs are introduced into the spin system when a molecule is weakly aligned, thus it is impossible to have a model spin system that truly represents the real spin system. Here we report a new J modulated method, constant-time INEPT CT-HSQC (CTi-CT-HSQC), to accurately measure one-bond scalar coupling constant and RDCs without strong coupling interference. In this method, changing the spacing between the two 180° pulses during a constant time INEPT period selectively modulates heteronuclear coupling in quantitative J fashion. Since the INEPT delays for measuring one-bond carbon-proton spectra are short compared to 3JHH, evolution due to (strong) 1H-1H coupling is marginal. The resulting curve shape is practically independent of 1H-1H coupling and only correlated to the heteronuclear coupling evolution. Consequently, an accurate 1JCH can be measured even in the presence of strong coupling. We tested this method on N-acetyl-glucosamine and mannose whose apparent isotropic 1JCH values are significantly affected by strong coupling with other methods. Agreement to within 0.5 Hz or better is found between 1JCH measured by this method and previously published simulation data. We further examined the strong coupling effects on RDC measurements and observed an error up to 100% for one bond RDCs using coupled HSQC in carbohydrates. We demonstrate that RDCs can be obtained with higher accuracy by CTi-CT-HSQC, which compensates the limitation of simulation method.

  14. Responsive Copolymer Brushes of Poly[(2-(Methacryloyloxy)Ethyl) Trimethylammonium Chloride] (PMETAC) and Poly((1) H,(1) H,(2) H,(2) H-Perfluorodecyl acrylate) (PPFDA) to Modulate Surface Wetting Properties.

    PubMed

    Politakos, Nikolaos; Azinas, Stavros; Moya, Sergio Enrique

    2016-04-01

    Polymer brushes have a large potential for controlling properties such as surface lubrication or wetting through facile functionalization. Polymer chemistry, chain density, and length impact on the wetting properties of brushes. This study explores the use of diblock copolymer brushes with different block length and spatial arrangement of the blocks to tune surface wettability. Block copolymer brushes of the polyelectrolyte [2-(methacryloyloxy)ethyl] trimethylammonium chloride (PMETAC) with a contact angle of 17° and a hydrophobic block of (1) H, (1) H, (2) H, (2) H-perfluorodecyl Acrylate (PPFDA) with a contact angle of 130° are synthesized by RAFT polymerization. By changing the sequence of polymerization either block is synthesized as top or bottom block. By varying the concentration of initiator the length of the blocks is varied. Contact angle values with intermediate values between 17° and 130° are measured. In addition, by changing solvent pH and in presence of a different salt the contact angle of the copolymer brushes can be fine tuned. Brushes are characterized by atomic force microscopy, Raman confocal microscopy, and X-ray photoelectron spectroscopy. PMID:26872001

  15. 1H,1H,5H-Perfluoropentyl-1,1,2,2-tetrafluoroethylether as a co-solvent for high voltage LiNi1/3Co1/3Mn1/3O2/graphite cells

    NASA Astrophysics Data System (ADS)

    Wang, Chengyun; Zuo, Xiaoxi; Zhao, Minkai; Xiao, Xin; Yu, Le; Nan, Junmin

    2016-03-01

    1H,1H,5H-Perfluoropentyl-1,1,2,2-tetrafluoroethylether (F-EAE) mixed with ethylene carbonate (EC), diethyl carbonate (DEC), and lithium hexafluorophosphate (LiPF6) is evaluated as a co-solvent high-potential electrolyte of LiNi1/3Co1/3Mn1/3O2/graphite batteries. Linear sweep voltammetry (LSV) and cyclic voltammetry (CV) indicate that the EC/DEC-based electrolyte with F-EAE possesses a high oxidation potential (>5.2 V vs. Li/Li+) and excellent film-forming characteristics. With 40 wt% F-EAE in the electrolyte, the capacity retention of the LiNi1/3Co1/3Mn1/3O2/graphite pouch cells that are cycled between 3.0 and 4.5 V is significantly improved from 28.8% to 86.8% after 100 cycles. In addition, electrochemical impedance spectroscopy (EIS) of three-electrode pouch cells, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) are used to characterize the effects of F-EAE on the enhanced capacity retention. It is demonstrated that F-EAE facilitates the formation of a stable surface electrolyte interface (SEI) layer with low impedance on the anode and effectively suppresses an increase in the charge-transfer resistance on the cathode. These results suggest that F-EAE can serve as an alternative electrolyte solvent for 4.5 V high voltage rechargeable lithium-ion batteries.

  16. 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.

  17. Spin-filtering at COSY

    NASA Astrophysics Data System (ADS)

    Weidemann, Christian; PAX Collaboration

    2011-05-01

    The Spin Filtering experiments at COSY and AD at CERN within the framework of the Polarized Antiproton EXperiments (PAX) are proposed to determine the spin-dependent cross sections in bar pp scattering by observation of the buildup of polarization of an initially unpolarized stored antiproton beam after multiple passage through an internal polarized gas target. In order to commission the experimental setup for the AD and to understand the relevant machine parameters spin-filtering will first be done with protons at COSY. A first major step toward this goal has been achieved with the installation of the required mini-β section in summer 2009 and it's commissioning in January 2010. The target chamber together with the atomic beam source and the so-called Breit-Rabi polarimeter have been installed and commissioned in summer 2010. In addition an openable storage cell has been used. It provides a target thickness of 5·1013 atoms/cm2. We report on the status of spin-filtering experiments at COSY and the outcome of a recent beam time including studies on beam lifetime limitations like intra-beam scattering and the electron-cooling performance as well as machine acceptance studies.

  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. PMID:10924182

  19. Signal enhancement of J-HMQC experiments in solid-state NMR involving half-integer quadrupolar nuclei.

    PubMed

    Wang, Qiang; Trébosc, Julien; Li, Yixuan; Xu, Jun; Hu, Bingwen; Feng, Ningdong; Chen, Qun; Lafon, Oliver; Amoureux, Jean-Paul; Deng, Feng

    2013-07-28

    We show that for half-integer quadrupolar nuclei, the manipulation of the satellite transitions can accelerate and enhance coherence transfer to other isotopes. This novel strategy is demonstrated to improve the sensitivity of (31)P-{(27)Al} J-HMQC experiments for a layered aluminophosphate Mu-4. PMID:23770976

  20. 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.

  1. The physics program of PAX at COSY

    NASA Astrophysics Data System (ADS)

    Valdau, Yury; Aksentyev, Alexander; Eversheim, Dieter; Lorentz, Bernd

    2016-02-01

    The construction of the PAX installation was inspired by the idea to make a beam of polarized antiprotons available for the experiments at the HESR FAIR. A spin filtering experiment with transversally polarized protons was realized using the new PAX installation at COSY. The results of this measurement are in perfect agreement with the FILTEX experiment. Hence, filtering is a viable method to produce a stored beam of polarized antiprotons. Another experiment which can be pursued using the PAX installation is the test of Time Reversal Invariance at COSY (TRIC). The goal of the TRIC experiment is to improve the present upper limit on violation of the T-odd P-even interaction by an order of magnitude using a genuine null observable available in a double polarized pd scattering. The status of the PAX spin filtering experiments as well as present understanding of the possible systematic uncertainties in TRIC are presented in this contribution.

  2. COSY - a cooler synchrotron and storage ring

    SciTech Connect

    Martin, S.A.; Berg, G.P.A.; Hacker, U.; Hardt, A.; Kohler, M.; Osterfeld, F.; Prasuhn, D.; Riepe, G.; Rogge, M.; Schult, O.W.B.

    1985-10-01

    The storage ring COSY with phase space cooling and RF acceleration is designed to accept protons and light ions injected from the existing cyclotron JULIC or protons from the LINAC of the proposed neutron spallation source (SNQ). The lay-out of COSY was developed in cooperation with the Universities in Nordrhein-Westfalen and meets the experimental requirements of variable and high quality beams which are necessary for future nuclear research under discussion. The three essential properties of the storage ring will be: high luminosities and very efficient use of the beam in the storage ring by thin internal targets; energy variability in the range of 20 MeV to 1.5 GeV by RF acceleration; and very high beam quality through phase space cooling.

  3. 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.

  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. 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.

  6. 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.

  7. The Proposed 2 MeV Electron Cooler for COSY

    SciTech Connect

    Dietrich, Juergen; Parkhomchuk, Vasily V.; Reva, Vladimir B.; Vedenev, Maxim A.

    2006-03-20

    The design, construction and installation of a 2 MeV electron cooling system for COSY is proposed to further boost the luminosity even with strong heating effects of high-density internal targets. In addition the design of the 2 MeV electron cooler for COSY is intended to test some new features of the high energy electron cooler for HESR at GSI. The design of the 2 MeV electron cooler will be accomplished in cooperation with the Budker Institute of Nuclear Physics in Novosibirsk, Russia. Starting with the boundary conditions of the existing electron cooler at COSY the requirements and a first general scheme of the 2 MeV electron cooler are described.

  8. Spin-Filtering studies at COSY and AD

    SciTech Connect

    Nass, Alexander

    2008-02-06

    An overview on the present understanding of the methods to polarize an antiproton beam is given and the planned measurements on spin filtering at COSY and AD rings with protons and antiprotons are described. The experimental setup which is being prepared for these measurements is described and focus is given on the polarized internal target.

  9. Automatic control system for the COSY-TOF vacuum system

    NASA Astrophysics Data System (ADS)

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

    2005-02-01

    An automatic control system (ACS) for the vacuum installations of the Time-Of-Flight (TOF) spectrometer at the COoler SYnchrotron (COSY) was developed. SIMATIC S7 software and hardware was used to build the control program and Windows Control Center (WinCC) software was taken to make the human-machine interface. The ACS can work automatically or manually. In both cases there are safety interlocks in order to prevent damage of the accelerator or detector components. The testing was firstly done by using external signals and a simulator in WinCC, then secondly we connected it to a real, small vacuum system. The communication between the SIMATIC S7 hardware and the WinCC, which run in a PC computer, is done by Multi Point Interface (MPI). The ACS is now installed in the COSY-TOF experiment and runs routinely.

  10. Nanostructured CoSi Obtained by Spark Plasma Sintering

    NASA Astrophysics Data System (ADS)

    Longhin, Marco; Viennois, Romain; Ravot, Didier; Robin, Jean-Jacques; Villeroy, Benjamin; Vaney, Jean-Baptiste; Candolfi, Christophe; Lenoir, Bertrand; Papet, Philippe

    2015-06-01

    Cobalt monosilicide is a cheap, environmentally friendly thermoelectric material for medium temperatures (200-700°C). While its power factor is similar to the state-of-the-art thermoelectric materials, its thermal conductivity is too large to reach high ZT values. Nanostructuring might be an interesting strategy to reduce the phonon mean free path thereby improving the thermoelectric performance. In this paper, we report on a 35% reduction of the thermal conductivity of n-type CoSi by a nanostructuring approach. CoSi nanostructured powders were synthesized by arc melting, followed by 4° h mechanical milling. By optimizing the spark plasma sintering thermal and pressure cycle, pellets with 5â€"10% porosity were obtained. During sintering, a small amount of Co2Si extra phase appeared and grains coarsened. After sintering, the pellets remained nanostructured, with an averaged grain size of 70 nm. The reduction of thermal conductivity is ascribed to a decrease in both the electronic and lattice contributions. The former is directly related to a decrease in the electrical conductivity, which appears to be the limiting factor preventing nanostructured CoSi from reaching enhanced thermoelectric performances.

  11. Earth Surface Monitoring with COSI-Corr, Techniques and Applications

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

    Co-registration of Optically Sensed Images and Correlation (COSI-Corr) is a software package developed at the California Institute of Technology (USA) for accurate geometrical processing of optical satellite and aerial imagery. Initially developed for the measurement of co-seismic ground deformation using optical imagery, COSI-Corr is now used for a wide range of applications in Earth Sciences, which take advantage of the software capability to co-register, with very high accuracy, images taken from different sensors and acquired at different times. As long as a sensor is supported in COSI-Corr, all images between the supported sensors can be accurately orthorectified and co-registered. For example, it is possible to co-register a series of SPOT images, a series of aerial photographs, as well as to register a series of aerial photographs with a series of SPOT images, etc... Currently supported sensors include the SPOT 1-5, Quickbird, Worldview 1 and Formosat 2 satellites, the ASTER instrument, and frame camera acquisitions from e.g., aerial survey or declassified satellite imagery. Potential applications include accurate change detection between multi-temporal and multi-spectral images, and the calibration of pushbroom cameras. In particular, COSI-Corr provides a powerful correlation tool, which allows for accurate estimation of surface displacement. The accuracy depends on many factors (e.g., cloud, snow, and vegetation cover, shadows, temporal changes in general, steadiness of the imaging platform, defects of the imaging system, etc...) but in practice, the standard deviation of the measurements obtained from the correlation of mutli-temporal images is typically around 1/20 to 1/10 of the pixel size. The software package also includes post-processing tools such as denoising, destriping, and stacking tools to facilitate data interpretation. Examples drawn from current research in, e.g., seismotectonics, glaciology, and geomorphology will be presented. COSI-Corr is

  12. Dendrocyin: an isocucurbitacin with novel cyclic side chain from Dendrosicyos socotrana.

    PubMed

    Hussein, Hosny A; Abdel-Halim, Osama B; Marwan, El-Sayed M; El-Gamal, Ali A; Mosana, Ramazy

    2004-09-01

    Dendrosicyos socotrana Balf.f. is a unique species (Cucurbitaceae) native to Socotra island in the horn of Africa. From the chloroform extract of the stems, A new isocucurbitacin (Dendrocyin) with unusual cyclization in the side chain; 24beta-ethoxy-20-25-epoxy-3alpha,16alpha-dihydroxy-9-methyl-19-norlanost-5(6) ene-2,11,22-trione has been isolated alongside isocucurbitacin R. Their structural configuration were established by usual spectroscopic (1H NMR, 13C NMR and DEPT) and two-dimensional NMR techniques (1H-1H Cosy, HMBC and HMQC). PMID:15451315

  13. NMR assignments of unusual flavonoids from the kino of Eucalyptus citriodora.

    PubMed

    Freitas, Marinalva Oliveira; Lima, Mary Anne S; Silveira, Edilberto R

    2007-03-01

    Two unusual flavonoids, 3,5,4',5''-tetrahydroxy-7-methoxy-6-[1-(p-hydroxy-phenyl)ethyl]flavanone (1) and 3,5,7,4',5''-pentahydroxy-6-[1-(p-hydroxy-phenyl)ethyl] flavanone (2), were isolated from the kino of Eucalyptus citriodora. Structural elucidation of the new compounds were established on the basis of spectral data, particularly by the use of 1D NMR and several 2D shift-correlated NMR pulse sequences ((1)H, (1)H-COSY, HMQC, HMBC). PMID:17221924

  14. Oxygenated Cembranoids from the Soft Coral Sinularia flexibilis.

    PubMed

    Su, Ching-Chyuan; Wong, Bing-Sang; Chin, Chuen; Wu, Yu-Jen; Su, Jui-Hsin

    2013-01-01

    Chemical examination of the Taiwanese soft coral Sinularia flexibilis led to the isolation of five cembrane-based diterpenoids 1-5, including two new metabolites, 11-acetylsinuflexolide (1) and 11-acetyldihydrosinuflexolide (2). The structures of the new metabolites were determined based on extensive spectroscopic analysis, particularly mass spectrometry and 2D NMR (1H-1H COSY, HMQC, HMBC, and NOESY) spectroscopy. Metabolites 1, 3 and 4 exhibited moderate to weak cytotoxicity to human tumor cell lines, HeLa, HEp-2, MCF-7 and MDA-MB-231. PMID:23429272

  15. NMR study on cis-N-[4-[4-(1,2-benzisozole-3-yl)-1-piperazinyl] butyl]cyclohexane-1,2-dicarboximide monohydrochloride dihydrate.

    PubMed

    Feng, Yongbin; Lin, Jimao; Lin, Zhenguang; Li, Hongmei

    2006-02-01

    Cis-N-[4-[4-(1,2-benzisozole-3-yl)-1-piperazinyl]butyl]cyclohexane-1,2-dicarboximide monohydrochloride dihydrate was studied spectroscopically. Complete NMR assignments were made using DEPT, H-H COSY, as well as HMQC and HMBC heteronuclear correlation techniques. The hydrochloride salt was found at delta > 10. The dihydrate was present in the region delta 3-4 in DMSO-d6 solvent. Asymmetry carbon C3 brought chemical-shift-nonequivalent of cis-cyclohexanyl group, splitting four systems H1, H1', H2 and H2'. Diamagnetic anisotropy of benzisozolyl group results in three troops peaks of piperazinyl group. PMID:16406787

  16. Two new sesquiterpenoids from endophytic fungus J3 isolated from Mangrove Plant Ceriops tagal.

    PubMed

    Zeng, Yan-Bo; Gu, Hai-Gang; Zuo, Wen-Jian; Zhang, Li-Li; Bai, Hong-Jin; Guo, Zhi-Kai; Proksch, Peter; Mei, Wen-Li; Dai, Hao-Fu

    2015-01-01

    Two new sesquiterpenoids, named 2α-hydroxyxylaranol B (1) and 4β-hydroxyxylaranol B (2), together with a known diterpenoid 3,4-seco-sonderianol (3) were isolated from the fermentation of endophytic fungus J3 of Ceriops tagal. Their structures were elucidated based on spectroscopic methods including 1D and 2D NMR (HMQC, (1)H-(1)H COSY and HMBC). All compounds were evaluated for their cytotoxic activities by MTT method, and compound 3 exhibited cytotoxic activities against K562, SGC-7901, and BEL-7402 cell lines. PMID:25060947

  17. 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.

  18. Threshold hyperon production in proton proton collisions at COSY-11

    NASA Astrophysics Data System (ADS)

    Rożek, T.; Grzonka, D.; Adam, H.-H.; Budzanowski, A.; Czyżykiewicz, R.; Janusz, M.; Jarczyk, L.; Kamys, B.; Khoukaz, A.; Kilian, K.; Klaja, P.; Kowina, P.; Moskal, P.; Oelert, W.; Piskor-Ignatowicz, C.; Przerwa, J.; Ritman, J.; Sefzick, T.; Siemaszko, M.; Smyrski, J.; Täschner, A.; Winter, P.; Wolke, M.; Wüstner, P.; Zhang, Z.; Zipper, W.

    2006-12-01

    The Σ+ hyperon production was measured at the COSY-11 spectrometer via the pp → nK+Σ+ reaction at excess energies of Q = 13 MeV and Q = 60 MeV. These measurements continue systematic hyperon production studies via the pp → pK+ Λ /Σ0 reactions where a strong decrease of the cross section ratio close-to-threshold was observed. In order to verify models developed for the description of the Λ and Σ0 production we have performed the measurement on the Σ+ hyperon and found unexpectedly that the total cross section is by more than one order of magnitude larger than predicted by all anticipated models. After the reconstruction of the kaon and neutron four momenta, the Σ+ is identified via the missing mass technique. Details of the method and the measurement will be given and discussed in view of theoretical models.

  19. 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.

  20. 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.

  1. Budker INP Proposals for HESR and COSY Electron Cooler Systems

    SciTech Connect

    Bocharov, V.; Bryzgunov, M.; Bubley, A.; Gosteev, V.; Kazarezov, I.; Kryuchkov, A.; Panasyuk, V.; Parkhomchuk, V.; Pavlov, V.; Pestrikov, D.; Reva, V.; Shamovskij, V.; Skrinsky, A.; Sukhina, B.; Vedenev, M.; Vostrikov, V.

    2006-03-20

    The subject of the report is the problem of the technical feasibility of fast electron cooling in the energy range between 0.8 and 14.5 GeV. It is very useful for one of the major objectives of the GSI and COSY future plans. For the realization of the cooler device BINP team proposes the design that is like the conventional and elaborated for the low energy cooling (up to 300 keV). The main features of this design are the accelerating tube immersed in the magnetic field along the whole length and the strong magnetic field in the cooling section. The physics of electron cooling is based on the idea of the fast magnetized cooling. The cooling force at strong magnet field was measured at many experiments and can be surely estimated. The magnetized cooling rate enables to obtain the required beam parameters, eliminate the beam heating due to intrabeam scattering, fluctuations of ionization energy losses and multiple scattering in the internal target.

  2. Cosis: cost of service information system. Model-simulation

    SciTech Connect

    Not Available

    1982-05-10

    The Cost of Service Information System of models (COSIS) is an integrated, electric utility strategic planning system. This system of five models, written in FORTRAN, provides a framework for the examination of a wide range of utility strategics or environmental conditions. The five models are: (1) LAm which derives projected load duration curves for up to 30 years on a system level to serve as input to capacity expansion and production simulating models. (2) PCS (Production Cost Simulation) which projects energy production by generating unit as a function of the unit's equivalent availability, capacity, loading position, and the energy supply demands on the system. (3) FRED which calculates the monthly average profile at the system level from the historical or reference year. (4) RAm (Regulatory Analysis Model) which performs up to 30 years of financial statements for an electric utility. (5) ACE which performs cost allocations based on financial projections from ths RAm model. The models are written in Fortran for implementation on UNIVAC 1100/84 computers operating under OS.

  3. 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.

  4. Preparation and electrochemical properties of Co-Si 3N 4 nanocomposites

    NASA Astrophysics Data System (ADS)

    Yao, S. M.; Xi, K.; Li, G. R.; Gao, X. P.

    Cobalt nanoparticles on an amorphous Si 3N 4 matrix were synthesized by direct ball-milling of Co and Si 3N 4 powders for an improvement of their electrochemical performance. The microstructure, morphology and chemical state of the ball-milled Co-Si 3N 4 composites are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The electrochemical performance of Co-Si 3N 4 composites was investigated by galvanostatic charge-discharge process and cyclic voltammetry (CV) technique. It is found that metallic Co nanoparticles of 10-20 nm in size are highly dispersed on the amorphous inactive Si 3N 4 matrix after the ball-milling. The composite with a Co/Si molar ratio of 2/1 shows the optimized electrochemical performance, including discharge capacity and cycle stability. The formation of Co nanoparticles with a good reaction activity is responsible for the discharge capacity of the composites. The reversible faradic reaction between Co and β-Co(OH) 2 is dominant for ball-milled Co-Si 3N 4 composite. The surface modification of the hydrogen storage PrMg 12-Ni composites using Co-Si 3N 4 composites can enhance the initial discharge capacity based on the hydrogen electrochemical oxidation and Co redox reaction.

  5. New developments and prospects on COSI, the simulation software for fuel cycle analysis

    SciTech Connect

    Eschbach, R.; Meyer, M.; Coquelet-Pascal, C.; Tiphine, M.; Krivtchik, G.; Cany, C.

    2013-07-01

    COSI, software developed by the Nuclear Energy Direction of the CEA, is a code simulating a pool of nuclear power plants with its associated fuel cycle facilities. This code has been designed to study various short, medium and long term options for the introduction of various types of nuclear reactors and for the use of associated nuclear materials. In the frame of the French Act for waste management, scenario studies are carried out with COSI, to compare different options of evolution of the French reactor fleet and options of partitioning and transmutation of plutonium and minor actinides. Those studies aim in particular at evaluating the sustainability of Sodium cooled Fast Reactors (SFR) deployment and the possibility to transmute minor actinides. The COSI6 version is a completely renewed software released in 2006. COSI6 is now coupled with the last version of CESAR (CESAR5.3 based on JEFF3.1.1 nuclear data) allowing the calculations on irradiated fuel with 200 fission products and 100 heavy nuclides. A new release is planned in 2013, including in particular the coupling with a recommended database of reactors. An exercise of validation of COSI6, carried out on the French PWR historic nuclear fleet, has been performed. During this exercise quantities like cumulative natural uranium consumption, or cumulative depleted uranium, or UOX/MOX spent fuel storage, or stocks of reprocessed uranium, or plutonium content in fresh MOX fuel, or the annual production of high level waste, have been computed by COSI6 and compared to industrial data. The results have allowed us to validate the essential phases of the fuel cycle computation, and reinforces the credibility of the results provided by the code.

  6. Scanning tunneling microscopy observation of ultrathin epitaxial CoSi2(111) films grown at a high temperature

    NASA Astrophysics Data System (ADS)

    Alekseev, A. A.; Olyanich, D. A.; Utas, T. V.; Kotlyar, V. G.; Zotov, A. V.; Saranin, A. A.

    2015-10-01

    Scanning tunneling microscopy (STM) is used to study the basic laws of growth of ultrathin epitaxial CoSi2(111) films with Co coverages up to 4 ML formed upon sequential deposition of Co and Si atoms taken in a stoichiometric ratio onto the Co-Si(111) surface at room temperature and subsequent annealing at 600-700°C. When the coverage of Co atoms is lower than ~2.7 ML, flat CoSi2 islands up to ~3 nm high with surface structure 2 × 2 or 1 × 1 grow. It is shown that continuous epitaxial CoSi2 films containing 3-4 triple Si-Co-Si layers grow provided precise control of deposition. CoSi2 films can contain inclusions of the local regions with (2 × 1)Si reconstruction. At a temperature above 700°C, a multilevel CoSi2 film with pinholes grows because of vertical growth caused by the difference between the free energies of the CoSi2(111) and Si(111) surfaces. According to theoretical calculations, structures of A or B type with a coordination number of 8 of Co atoms are most favorable for the CoSi2(111)2 × 2 interface.

  7. Nanostructuration of CoSi by mechanical milling and mechanical alloying

    NASA Astrophysics Data System (ADS)

    Longhin, Marco; Viennois, Romain; Ravot, Didier; Robin, Jean-Jacques; Papet, Philippe

    2014-12-01

    CoSi is an inexpensive thermoelectric material for medium temperature (200-500 °C). Its power factor is as large as the state of the art materials; however, its thermal conductivity is too large. Then, improving its thermoelectric performances implies increasing the scattering of phonons, which can be performed by nanostructuring the material. In this paper we investigate the effect of nanostructuration on the structure, microstructure, lattice dynamics and stability of CoSi. We obtained powders of about 13 nm by mechanical milling bulk CoSi for only four hours or by mechanical alloying pure elements for twelve hours. Nanostructuration induces a 0.1% expansion of the lattice parameter. Raman spectroscopy, associated to ab initio calculations, highlights the effectiveness of nanostructuration on phonon scattering, showing a reduction of the phonon relaxation time by as much as 80%. Powders are stable up to 450 °C; then grains coarsen and a partial degradation of the material occurs, probably due to silicon sublimation. Our results indicate that nanostructuration should be considered when interested to reduce CoSi thermal conductivity.

  8. Validation of the controlled ovarian stimulation impact measure (COSI): assessing the patient perspective

    PubMed Central

    2013-01-01

    Background Controlled Ovarian Stimulation (COS) is the first step for in vitro fertilization (IVF) treatment, a treatment often described and experienced as stressful to patients and their partners. COS also requires concerted efforts by the patients in administering medication and general compliance to treatment protocols. Little is known about the impacts on patients that may be specific to this important first step in treatment. The absence of a conceptually sound and well-validated measure assessing patient experience and functioning during ovarian stimulation has been an obstacle to understanding the impacts of ovarian stimulation on women pursuing IVF. To address this gap, the Controlled Ovarian Stimulation Impact Measure (COSI) was developed based upon accepted methods for designing patient reported outcome (PRO) measures. The purpose of this study was to psychometrically validate the COSI. Methods 267 patients from three countries (Ireland, United Kingdom, United States) were administered the COSI. Psychometric validation was conducted according to an a priori statistical analysis plan. Results The final 28-item COSI was found to have robust scale structure with four domains: Interference in Daily Life (Work and Home), Injection Burden, Psychological Health and Compliance Worry. Internal consistency of all domains was adequate (between 0.80 to 0.87) as was test-retest reliability (between 0.72-0.87). All a-priori hypotheses for convergent and known-groups validity tests were met. Conclusions There is a measurable impact of COS on patient functioning and well-being. The COSI is a well-developed and validated PRO measure of this impact. Future work should include examination of responsiveness and confirmation of concepts in non-western countries. PMID:23902854

  9. 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 ∼1.2Hz (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 1Hz. PMID:26859865

  10. 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.

  11. 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).

  12. Magnetic structure of the ferromagnetic new ternary silicide Nd5CoSi2.

    PubMed

    Mayer, C; Gaudin, E; Gorsse, S; Porcher, F; André, G; Chevalier, B

    2012-04-01

    Nd(5)CoSi(2) was obtained from the elements by arc-melting followed by annealing at 883 K. Its investigation by single-crystal x-ray and neutron powder diffraction shows that this ternary silicide crystallizes as Nd(5)Si(3) in a tetragonal structure deriving from the Cr(5)B(3)-type (I4/mcm space group; a = 7.7472(2) and c = 13.5981(5) Å as unit cell parameters). The structural refinements confirm the mixed occupancy on the 8h site between Si and Co atoms, as already observed for Gd(5)CoSi(2). Magnetization and specific heat measurements reveal a ferromagnetic behavior below T(C) = 55 K for Nd(5)CoSi(2). This magnetic ordering is further evidenced by neutron powder diffraction investigation revealing between 1.8 K and T(C) a canted ferromagnetic structure in the direction of the c-axis described by a propagation vector k = (0 0 0). At 1.8 K, the two Nd(3+) ions carry ordered magnetic moments equal respectively to 1.67(7) and 2.37(7) μ(B) for Nd1 and Nd2; these two moments exhibit a canting angle of θ = 4.3(6)°. This magnetic structure presents some similarities with that reported for Nd(5)Si(3). PMID:22392874

  13. 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

  14. An unusual lanostane-type triterpenoid, spiroinonotsuoxodiol, and other triterpenoids from Inonotus obliquus.

    PubMed

    Handa, Noriko; Yamada, Takeshi; Tanaka, Reiko

    2010-10-01

    An unusual lanostane-type triterpenoid, spiroinonotsuoxodiol (1), and two lanostane-type triterpenoids, inonotsudiol A (2) and inonotsuoxodiol A (3), were isolated from the sclerotia of Inonotus obliquus. Their structures were determined to be (3S,7S,9R)-3,7-dihydroxy-7(8-->9)abeo-lanost-24-en-8-one (1), lanosta-8,24-dien-3beta,11beta-diol (2), and (22R)-3beta,22-dihydroxylanosta-8,24-dien-11-one (3) on the basis of NMR spectroscopy, including 1D and 2D ((1)H-(1)H COSY, NOESY, HMQC, HMBC) NMR, and FABMS. Compounds 1-3 showed moderate activity against cultured P388, L1210, HL-60 and KB cells. PMID:20691456

  15. 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.

  16. Steroidal Saponins from the Rhizomes of Aspidistra typica.

    PubMed

    Cui, Jiang-Ming; Kang, Li-Ping; 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

  17. Structure of the O-specific polysaccharide from a marine bacterium Echinicola pacifica КММ 6172(Т) containing 2,3-diacetamido-2,3-dideoxy-D-glucuronic acid.

    PubMed

    Tomshich, Svetlana V; Kokoulin, Maxim S; Kalinovsky, Anatoliy I; Nedashkovskaya, Ol'ga I; Komandrova, Nadezhda A

    2016-04-29

    The O-polysaccharide was isolated from the lipopolysaccharide of Echinicola pacifica KMM 6172(T) and studied by chemical analyses along with (1)H and (13)C NMR spectroscopy, including (1)H, (1)H COSY, 1D and 2D TOCSY, ROESY, (1)H, (13)С HMQC, HMBC and H2BC experiments. It was found that the polysaccharide is built up of branched pentasaccharide repeating units, containing D-galactose (Gal), L-rhamnose (Rha), 2-acetamido-2-deoxy-D-glucose (GlcNAc), two residues of 2,3-diacetamido-2,3-dideoxy-D-glucuronic acid (GlcNAc3NAcA) and O-acetyl group in nonstoichiometric amount and has the following structure. PMID:27015142

  18. Triterpenoid saponins from Fagonia indica.

    PubMed

    Shaker, K H; Bernhardt, M; Elgamal, M H; Seifert, K

    1999-08-01

    Two new triterpenoid saponins, 3-O-{[beta-D-glucopyranosyl-(1-->2)]-[alpha-L-arabinopyranosyl-(1- ->3)]- alpha-L-arabinopyranosyl}-ursolic acid-28-O-[beta-D-glucopyranosyl] ester (indicasaponin A), 3-O-{[beta-D-glucopyranosyl-(1-->2)]-[alpha-L-arabinopyranosyl-(1- ->3)]- alpha-L-arabinopyranosyl}-oleanolic acid-28-O-[beta-D-glucopyranosyl] ester (indicasaponin B) and two known triterpenoid saponins, 3-O-[beta-D-glucopyranosyl-(1-->3)-alpha-L-arabinopyranosyl]-ur solic acid-28-O-[beta-D-glucopyranosyl] ester, 3-O-[beta-D-glucopyranosyl-(1-->3)-alpha-L-arabinopyranosyl]-olean olic acid-28-O-[beta-D-glucopyranosyl] ester have been isolated from Fagonia indica. The structures were determined primarily by NMR spectroscopy. The assignment of NMR signals was performed by means of 1H-1H COSY, NOESY, ROESY, TOCSY, HMQC and HMBC experiments. PMID:10444859

  19. Further saponins from Fagonia cretica.

    PubMed

    Abdel-Khalik, S M; Miyase, T; Melek, F R; el-Ashaal, H A

    2001-03-01

    Three triterpenoid saponins including two new ones were isolated and identified from the aerial parts of Fagonia cretica. The new saponins were characterized as 3-O-[beta-D-xylopyranosyl(1-->2)alpha-L-arabinopyranosyl]27-hydroxyoleanolic acid 28-O-[beta-D-glucopyranosyl(1-->6)beta-D-glucopyranosyl]ester and 3 beta-O-[beta-D-xylopyranosyl(1-->2)alpha-L-arabinopyranosyl] olean-12-en-27-al-28-oic acid 28-O-[beta-D-glucopyranosyl(1-->6)beta-D-glycopyranosyl] ester. The structures were determined by spectral analyses. The NMR assignments were made by means of HOHAHA, 1H-1H COSY, HMQC, HMBC spectra and NOE studies. PMID:11265595

  20. Neuroprotective and antioxidant lanostanoid triterpenes from the fruiting bodies of Ganoderma atrum.

    PubMed

    Qiu, Junming; Wang, Xiang; Song, Chengguang

    2016-03-01

    Five new lanostanoid triterpenes were isolated from the ethanol extract of the fruiting bodies of Ganoderma atrum. The structures of the isolated compounds were established based on 1D and 2D ((1)H-(1)H COSY, HMQC, and HMBC) NMR spectroscopy, in addition to high resolution mass spectrometry. The isolated compounds were tested in vitro for neuroprotective activities against 6-OHDA-induced cell death in SH-SY5Y cells and radical scavenging activities. As a result, compounds 2 and 5 exhibited potent neuroprotective activity against 6-OHDA-induced cell death in SH-SY5Y cells with the lowest IC50 value (0.5 μM) while compounds 1, 3 and 4 possessed significant neuroprotective activity with IC50 value less than 10 μM. Additionally, all tested compounds 1-6 showed the comparable free radical scavenging activities with the standard drug trolox in both ABTS (+) and DPPH experiment. PMID:26709153

  1. 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

  2. Microsphaerones A and B, two novel gamma-pyrone derivatives from the sponge-derived fungus Microsphaeropsis sp.

    PubMed

    Wang, Chang-Yun; Wang, Bin-Gui; Brauers, Gernot; Guan, Hua-Shi; Proksch, Peter; Ebel, Rainer

    2002-05-01

    Two new metabolites, microsphaerones A (1) and B (2), were identified from the EtOAc extract of the culture of an undescribed fungus of the genus Microsphaeropsis, isolated from the Mediterranean sponge Aplysina aerophoba. Compounds 1 and 2 represent the first examples of gamma-pyrone derivatives of the fungal genus Microsphaeropsis. The structures of the compounds were elucidated on the basis of comprehensive spectral analysis ((1)H, (13)C, (1)H-(1)H COSY, HMQC, and HMBC NMR, as well as low- and high-resolution ESI and EIMS experiments). The (S)-2-methylsuccinic acid moiety present in 1 was established by GC-MS analysis of a hydrolysis product. PMID:12027766

  3. 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. PMID:26812172

  4. Structure elucidation of a bioactive polysaccharide from fruiting bodies of Hericium erinaceus in different maturation stages.

    PubMed

    Li, Qiao-Zhen; Wu, Di; Zhou, Shuai; Liu, Yan-Fang; Li, Zheng-Peng; Feng, Jie; Yang, Yan

    2016-06-25

    HPB-3, a heteropolysaccharide, with a mean molecular weight of 1.5×10(4)Da, was obtained from the maturating-stage IV, V and VI fruiting body of Hericium erinaceus, exhibited higher macrophages stimulation activities, was able to upregulate the functional events mediated by activated macrophages, such as production of nitric oxide (NO). Monosaccharide composition analysis showed that HPB-3 comprised l-fucose, d-galactose and d-glucose in the ratio of 5.2:23.9:1. Its chemical structure was characterized by sugar and methylation analysis, along with (1)H and (13)C NMR spectroscopy, including (1)H-(1)H COSY, TOCSY, NOESY, HMQC and HMBC experiments. The results indicated that HPB-3 contained a-(1/6)-linked galactopyranosyl backbone, partially with a side chain composed of α-l-fucopyranose at the O-2 position. The predicted primary structure of the polysaccharide was established as below. PMID:27083809

  5. 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. PMID:15474567

  6. Anti-Mycobacterial Nucleoside Antibiotics from a Marine-Derived Streptomyces sp. TPU1236A

    PubMed Central

    Bu, Ying-Yue; Yamazaki, Hiroyuki; Ukai, Kazuyo; Namikoshi, Michio

    2014-01-01

    Five new nucleoside antibiotics, named streptcytosines A–E (1–5), and six known compounds, de-amosaminyl-cytosamine (6), plicacetin (7), bamicetin (8), amicetin (9), collismycin B (10), and SF2738 C (11), were isolated from a culture broth of Streptomyces sp. TPU1236A collected in Okinawa, Japan. The structures of new compounds were elucidated on the basis of their spectroscopic data (HRFABMS, IR, UV, and 2D NMR experiments including 1H-1H COSY, HMQC, HMBC, and NOESY spectra). Streptcytosine A (1) belonged to the amicetin group antibiotics, and streptcytosines B–E (2–5) were derivatives of de-amosaminyl-cytosamine (6), 2,3,6-trideoxyglucopyranosyl cytosine. Compound 1 inhibited the growth of Mycobacterium smegmatis (MIC = 32 µg/mL), while compounds 2–5 were not active at 50 µg/disc. Bamicetin (8) and amicetin (9) showed the MICs of 16 and 8 µg/mL, respectively. PMID:25522318

  7. 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

  8. Echo Planar Correlated Spectroscopic Imaging (EP-COSI): Implementation and Pilot Evaluation in Human Calf in Vivo#

    PubMed Central

    Lipnick, Scott; Verma, Gaurav; Ramadan, Saadallah; Furuyama, Jon; Thomas, M. Albert

    2010-01-01

    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 MR Spectroscopic Imaging (MRSI). A novel four dimensional (4D) echo-planar correlated spectroscopic imaging (EP-COSI) was implemented on a whole body 3T 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 radio-frequency (RF) pulses (90°-180°-90°). After the initial optimization using phantom solutions, the EP-COSI data were recorded in 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 (IMCL) and extramyocellular lipids (EMCL) 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. PMID:20574964

  9. Search for the η-mesic Helium bound state with the WASA-at-COSY facility

    NASA Astrophysics Data System (ADS)

    Skurzok, Magdalena; Krzemień, Wojciech; Rundel, Oleksandr; Moskal, Pawel

    2016-05-01

    We performed a search for 4He-η bound state with high statistics and high acceptance with the WASA-at-COSY facility using a ramped beam technique. The signature of η-mesic nuclei is searched for in dd → 3Henπ0 and dd → 3Hepπ- reactions by the measurement of the excitation functions in the vicinity of the η production threshold. This paper presents the experimental method and the preliminary results of the data analysis for dd → 3Henπ0 process.

  10. 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).

  11. Structure determination of the CoSi2(111) surface using medium-energy ion scattering

    NASA Astrophysics Data System (ADS)

    Vrijmoeth, J.; Schins, A. G.; van der Veen, J. F.

    1989-08-01

    The surface structure of epitaxially grown CoSi2 crystals on Si(111) has been investigated with use of medium-energy ion scattering. A Co- or a Si-rich surface composition is obtained, depending on the preparation conditions. The structure of the Co-rich surface is shown to be bulklike, i.e., the crystal is terminated by a Si-Co-Si triple layer. The Si-rich surface is found to have, on top of the last Si-Co-Si triple layer, a Si double layer of the same orientation as the CoSi2 bulk lattice. This accounts for the difficulty to grow a 180°-rotated Si film on top of CoSi2(111) by normal molecular-beam-epitaxy techniques. The topmost Co atoms of the Si-rich surface are eightfold coordinated.

  12. 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.

  13. Extraction of D- beams from the cyclotron JULIC for injection into the cooler synchrotron COSY

    NASA Astrophysics Data System (ADS)

    Bräutigam, W.; Brings, R.; Gad, N.; Gebel, R.; Jungwirth, H.; Maier, R.; Rindfleisch, U.

    2001-12-01

    The cooler synchrotron COSY was intended from its inception to provide also deuteron beams which, in addition to protons, could considerably expand the range of experiments accessible at this accelerator facility. A major obstacle to deliver the required D- beams with the injector cyclotron JULIC has been its electrostatic septum deflector at extraction. After the conversion of JULIC into a negative ion machine, operation of the original deflector at the voltage levels necessary for D- extraction proved to be impossible with reversed polarity due to severe electrical strength problems like sparking and dark currents. The design and development of a suitable septum deflector turned out to be a challenging and tedious process lasting several years. The new device is in operation since January 2000 and the cyclotron was successfully tested in October for delivering D- beams at 75 MeV with an extracted current in the order of 10 μA. Development, test procedures and characteristics of the new electrostatic septum deflector are reported together with its operational performance to date. Results achieved during the first test run with D- ions are presented, including injection and acceleration of the deuteron beam in COSY.

  14. Initial Research of np Scattering with Polarized Deuterium Target at ANKE/COSY

    NASA Astrophysics Data System (ADS)

    Gou, B.

    2016-02-01

    The quasi-free np charge-exchange reaction pd→ →{pp}sn has to be employed to extend the investigations of np scattering at ANKE to the highest energy available at COSY. As the proof-of-principle experiment, the initial research has been conducted at proton energy Tp = 600 MeV using a polarized Deuterium target. The vector and tensor analyzing powers Ay and Ayy were measured for momentum transfers q ⩾ 160 MeV/c. These data connect smoothly with the previous measurements at q ⩽ 140 MeV/c performed using a polarized deuteron beam. The reported data are well reproduced by the impulse approximation using the SAID np amplitudes. The results therefore proves that it is possible to continue the np programme at higher energies at ANKE.

  15. 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.

  16. Study of charge symmetry breaking in dd collisions with WASA-at-COSY

    SciTech Connect

    Wronska, Aleksandra

    2011-10-24

    Charge symmetry is an approximate symmetry of the strong interaction. Studies of its breaking can yield information on the u and d quark mass difference. A theoretical collaboration is currently working on the description of charge symmetry breaking mechanisms for dd{yields}{alpha}{pi}{sup 0} and np{yields}d{pi}{sup 0} within Chiral Perturbation Theory, using the data from TRI-UMF and IUCF. One of the items in the program of the WASA-at-COSY collaboration is to extend the data base for the dd{yields}{alpha}{pi}{sup 0} reaction to higher energies, which would allow the extraction of the information on the p-wave. Status of the analysis of experimental data along with the preliminary results from the pilot run will be presented here.

  17. 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.

  18. Extending long-range heteronuclear NMR connectivities by HSQMBC-COSY and HSQMBC-TOCSY experiments

    NASA Astrophysics Data System (ADS)

    Saurí, Josep; Marcó, Núria; Williamson, R. Thomas; Martin, Gary E.; Parella, Teodor

    2015-09-01

    The detection of long-range heteronuclear correlations presenting J(CH) coupling values smaller than 1-2 Hz is a challenge in the structural analysis of small molecules and natural products. HSQMBC-COSY and HSQMBC-TOCSY pulse schemes are evaluated as complementary NMR methods to standard HMBC/HSQMBC experiments. Incorporation of an additional J(HH) transfer step in the basic HSQMBC pulse scheme can favor the sensitive observation of traditionally missing or very weak correlations and, in addition, facilitates the detection of a significant number of still longer-range connectivities to both protonated and non-protonated carbons under optimum sensitivity conditions. A comparative 1H-13C study is performed using strychnine as a model compound and several examples are also provided including 1H-15N applications.

  19. Estimation of Systematic Errors for Deuteron Electric Dipole Moment Search at COSY

    NASA Astrophysics Data System (ADS)

    Chekmenev, Stanislav

    2016-02-01

    An experimental method which is aimed to find a permanent EDM of a charged particle was proposed by the JEDI (Jülich Electric Dipole moment Investigations) collaboration. EDMs can be observed by their influence on spin motion. The only possible way to perform a direct measurement is to use a storage ring. For this purpose, it was decided to carry out the first precursor experiment at the Cooler Synchrotron (COSY). Since the EDM of a particle violates CP invariance it is expected to be tiny, treatment of all various sources of systematic errors should be done with a great level of precision. One should clearly understand how misalignments of the magnets affects the beam and the spin motion. It is planned to use a RF Wien filter for the precusor experiment. In this paper the simulations of the systematic effects for the RF Wien filter device method will be discussed.

  20. Toward polarized antiprotons: machine development for spin-filtering experiments at COSY

    NASA Astrophysics Data System (ADS)

    Weidemann, Christian; the PAX Collaboration

    2015-11-01

    In 2011 the Polarized Antiproton eXperiments Collaboration has performed a successful spin-filtering test using protons at {T}p=49.3 MeV at the COSY ring in Jülich, which allowed the determination of the spin-dependent polarizing cross section, that compares well with the theoretical prediction from the nucleon-nucleon potential and it confirms that spin filtering can be adopted as a method to polarize a stored beam. The document concentrates on the commissioning of the experimental equipment and the machine studies conducted to achieve the required beam lifetimes of τ =8000 s in the presence of a dense polarized hydrogen storage cell target of areal density {d}{{t}}=(5.5+/- 0.2)× {10}13 {atoms} {{cm}}-2. The developed techniques can be directly applied to antiproton machines and allow for the determination of the spin-dependent \\bar{p}p cross sections via spin filtering.

  1. 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

  2. Sensitivity of CoSi2 precipitation in silicon to extra-low dopant concentrations. II. First-principles calculations

    NASA Astrophysics Data System (ADS)

    Borodin, V. A.; Ganchenkova, M. G.; Ruault, M.-O.; Fortuna, F.

    2015-01-01

    The paper is the second part of the study on the influence of very low dopant content in silicon on CoSi2 precipitation during high-temperature cobalt ion implantation into transmission electron microscope samples. It deals with the computational justification of various assumptions used in Paper I when rationalizing the kinetics of cobalt clustering in ion-implanted intrinsic silicon (both undoped and containing low concentrations of phosphorus atoms). In particular, it is proven that divacancies are efficient nucleation centers for the new Co-Si phase. It is shown that the capture of vacancies and divacancies on phosphorus atoms increases their lifetime in silicon matrix, but practically does not affect the mechanism of their interaction with interstitial cobalt atoms. Finally, it is demonstrated that the mobility of phosphorus interstitials at temperatures of our experiment is orders of magnitude higher than might be expected from the published literature data.

  3. 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.

  4. Early stages of epitaxial CoSi 2 formation on Si(111) surface as investigated by ARUPS, XPS, LEED and work function variation

    NASA Astrophysics Data System (ADS)

    Pirri, C.; Peruchetti, J. C.; Gewinner, G.; Derrien, J.

    1985-04-01

    We performed the CoSi 2 formation on a clean (7 × 7) Si(111) surface under UHV conditions. The used techniques were angle resolved UV photoemission, X-ray photoemission, work function change and low energy electron diffraction in order to study the electronic and structural properties of the interface during its formation. At room temperature, a small amount of Co reacts strongly with Si to form an interfacial and very thin cobalt suicide. The ultraviolet photoelectron spectrum displays already two features corresponding respectively to the Co 3d and Si 3p electron bonding states and the Co 3d non-bonding states. With increasing coverage ( θ ≳ 4 ML) it seems that the interfacial suicide prevents further Co-Si interdiffusion to achieve the suicide reaction and a metal rich film is found. At high temperature (˜ 600°C) and in the first monolayer range, several superstructures are found (√7 × √7, and 2 × 2). They are induced by a Co-Si bidimensional compound where the Co atoms are not yet completely surrounded by Si atoms as in their bulk CoSi 2 structure. With increasing coverage, a CoSi 2-like photoemission spectrum is observed reflecting the formation of the disilicide. The LEED pattern testifies an epitaxial growth displaying a (1 × 1) CoSi 2 diagram. The work function change technique also reflects faithfully this growth.

  5. In situ study of the endotaxial growth of hexagonal CoSi2 nanoplatelets in Si(001)

    NASA Astrophysics Data System (ADS)

    da Silva Costa, Daniel; Huck-Iriart, Cristián; Kellermann, Guinther; Giovanetti, Lisandro J.; Craievich, Aldo F.; Requejo, Félix G.

    2015-11-01

    This investigation aims at studying-by in situ grazing-incidence small-angle x-ray scattering-the process of growth of hexagonal CoSi2 nanoplatelets endotaxially buried in a Si(001) wafer. The early formation of spherical Co nanoparticles with bimodal size distribution in the deposited silica thin film during a pretreatment at 500 °C and their subsequent growth at 700 °C were also characterized. Isothermal annealing at 700 °C promotes a drastic reduction in the number of the smallest Co nanoparticles and a continuous decrease in their volume fraction in the silica thin film. At the same time, Co atoms diffuse across the SiO2/Si(001) interface into the silicon wafer, react with Si, and build up thin hexagonal CoSi2 nanoplatelets, all of them with their main surfaces parallel to Si{111} crystallographic planes. The observed progressive growths in thickness and lateral size of the hexagonal CoSi2 nanoplatelets occur at the expense of the dissolution of the small Co nanoparticles that are formed during the pretreatment at 500 °C and become unstable at the annealing temperature (700 °C). The kinetics of growth of the volume fraction of hexagonal platelets is well described by the classical Avrami equation.

  6. 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.

  7. The low-temperature crystal structure of the multiferroic melilite Ca2CoSi2O7.

    PubMed

    Sazonov, Andrew; Hutanu, Vladimir; Meven, Martin; Roth, Georg; Kézsmárki, István; Murakawa, Hiroshi; Tokura, Yoshinori; Náfrádi, Bálint

    2016-02-01

    In the antiferromagnetic ground state, below TN ≃ 5.7 K, Ca2CoSi2O7 exhibits strong magnetoelectric coupling. For a symmetry-consistent theoretical description of this multiferroic phase, precise knowledge of its crystal structure is a prerequisite. Here we report the results of single-crystal neutron diffraction on Ca2CoSi2O7 at temperatures between 10 and 250 K. The low-temperature structure at 10 K was refined assuming twinning in the orthorhombic space group P2(1)2(1)2 with a 3 × 3 × 1 supercell [a = 23.52 (1), b = 23.52 (1), c = 5.030 (3) Å] compared with the high-temperature normal state [tetragonal space group P42(1)m, a = b ≃ 7.86, c ≃ 5.03 Å]. The precise structural parameters of Ca2CoSi2O7 at 10 K are presented and compared with the literature X-ray diffraction results at 130 and 170 K (low-temperature commensurate phase), as well as at ∼ 500 K (high-temperature normal phase). PMID:26830804

  8. Electronic and atomic structure of thin CoSi2 films on Si(111) and Si(100)

    NASA Astrophysics Data System (ADS)

    Chambliss, D. D.; Rhodin, T. N.; Rowe, J. E.

    1992-01-01

    The electronic and atomic structure of very thin epitaxial cobalt silicide films was studied to provide insight into the initial stages of interface formation. Thin CoSi2 films (3-30 Å) on Si(111) and Si(100) were studied experimentally using angle-resolved photoemission spectroscopy, low-energy electron diffraction (LEED), and Auger electron spectroscopy, and computationally using the pseudofunction method of Kasowski for determining the electronic band structure. The experimental and computational results support the models of Hellman and Tung for Co-rich and Si-rich CoSi2(111) surfaces. The surface-state dispersion that we measure for the Co-rich variant agrees with the behavior that we calculate for the Hellman-Tung model. For the Si-rich variant, the essentially bulklike bonding environment of the outermost Co atoms in the Hellman-Tung model agrees with the photoemission results. Preliminary results for thin films of CoSi2 on Si(100) grown by a template technique show clearly a strong dependence of film quality on the annealing temperature and initial Co thickness. A model for surface structure is suggested that accounts for LEED and photoemission results.

  9. 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.

  10. Spin coherence time studies of a horizontally polarized deuteron beam at COSY

    NASA Astrophysics Data System (ADS)

    G Guidoboni JEDI Collaboration

    2015-11-01

    The measurement of a non-zero electric dipole moment (EDM) aligned along the spin of sub-atomic particles would probe new physics beyond the standard model. It has been proposed to search for the EDM of charged particles using a storage ring and a longitudinally polarized beam. The EDM signal would be a rotation of the polarization from the horizontal plane toward the vertical direction as a consequence of the radial electric field always present in the particle frame. This experiment requires ring conditions that can ensure a lifetime of the in-plane polarization (spin coherence time, SCT) up to 1000 s. A study has begun at the COoler SYnchrotron (COSY) located at the Forschungszentrum Jülich to examine the effects of emittance and momentum spread on the SCT of a polarized deuteron beam at 0.97 GeV c-1. A special Data AcQuisition has been developed in order to provide a direct measurement of a rapidly rotating horizontal polarization as a function of time. The set of data presented here shows how second-order effects from emittance and momentum spread of the beam affect the lifetime of the horizontal polarization of a bunched beam. It has been demonstrated that sextupole fields can be used to correct for these depolarizing sources and increase the SCT up to hundreds of seconds.

  11. Directional dichroism of THz radiation in Sr2CoSi2O7

    NASA Astrophysics Data System (ADS)

    Rõõm, Toomas; Nagel, U.; Kocsis, V.; Szaller, D.; Kézsmárki, I.; Tokunaga, Y.; Taguchi, Y.; Tokura, Y.

    2014-03-01

    The microscopic mechanism of magnetoelectric coupling in akermanite-like Co-oxide multiferroics is unique because the local electric polarization mainly arises from the hybridization of Co ion and its ligands orbitals and is less affected by the details of the actual magnetic order of Co spins. As a consequence of this magnetoelectric effect, the spin waves located in the THz range exhibit giant directional dichroism in Ba2CoGe2O7 [S. Bordacs et al., Nature Physics 8, 734 (2012)]. Here we studied spin excitations in a sister compound Sr2CoSi2O7 in magnetic fields up to 17 T. We found that the giant directional dichroism at THz frequencies is present below the Neel temperature (TN) where the spins are ordered antiferromagnetically and persists as well above TN due to the large uniform magnetization and electric polarization induced by the external magnetic field. The relation of the observed ac magnetoelectric effect to the dc magnetoelectric effect studied by Akaki et al. [Phys. Rev. B 86, 060413(R) (2012)] is also discussed. The support by the Estonian Ministry of Education and Research (SF0690029s09) and Estonian Science Foundation (ETF8703, ETF8170) is acknowledged.

  12. 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

  13. 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. PMID:17559165

  14. Ion-beam mixed ultra-thin cobalt suicide (CoSi2) films by cobalt sputtering and rapid thermal annealing

    NASA Astrophysics Data System (ADS)

    Kal, S.; Kasko, I.; Ryssel, H.

    1995-10-01

    The influence of ion-beam mixing on ultra-thin cobalt silicide (CoSi2) formation was investigated by characterizing the ion-beam mixed and unmixed CoSi2 films. A Ge+ ion-implantation through the Co film prior to silicidation causes an interface mixing of the cobalt film with the silicon substrate and results in improved silicide-to-silicon interface roughness. Rapid thermal annealing was used to form Ge+ ion mixed and unmixed thin CoSi2 layer from 10 nm sputter deposited Co film. The silicide films were characterized by secondary neutral mass spectroscopy, x-ray diffraction, tunneling electron microscopy (TEM), Rutherford backscattering, and sheet resistance measurements. The experi-mental results indicate that the final rapid thermal annealing temperature should not exceed 800°C for thin (<50 nm) CoSi2 preparation. A comparison of the plan-view and cross-section TEM micrographs of the ion-beam mixed and unmixed CoSi2 films reveals that Ge+ ion mixing (45 keV, 1 × 1015 cm-2) produces homogeneous silicide with smooth silicide-to-silicon interface.

  15. Recent results from the NN-interaction studies with polarized beams and targets at ANKE-COSY

    NASA Astrophysics Data System (ADS)

    Dymov, Sergey

    2016-02-01

    Adding to the nucleon-nucleon scattering database is one of the major priorities of the ANKE collaboration. Such data are necessary ingredients, not only for the understanding of nuclear forces, but also for the description of meson production and other nuclear reactions at intermediate energies. By measuring the cross section, deuteron analysing powers, and spin-correlation parameters in the dp → {pp}sn reaction, where {pp}s represents the 1S0 state, information has been obtained on small-angle neutron-proton spin-flip charge-exchange amplitudes. The measurements of pp elastic scattering by the COSY-EDDA have had a major impact on the partial wave analysis of this reaction above 1 GeV. However, these experiments only extended over the central region of c.m. angles, 300 < θcm < 1500, that has left major ambiguities in the phase shift analysis by the SAID group. In contrast, the small angle region is accessible at ANKE-COSY, that allowed measurement of the differential cross section and the analysing power at 50 < θcm < 300 in the 0.8 — 2.8 GeV energy range. The data on the pn elastic scattering are much more scarce than those of pp, especially in the region above 1.15 GeV. The study of the dp → {pp}s n reaction provides the information about the pn elastic scattering at large angles. The small angle scattering was studied with the polarized proton COSY beam and an unpolarised deuterium gas target. The detection the spectator proton in the ANKE vertex silicon detector allowed to use the deuterium target as an effective neutron one. The analysing powers of the process were obtained at six beam energies from 0.8 to 2.4 GeV.

  16. Dependence of Sheet Resistance of CoSi2 with Gate Length of 30 nm on Thickness of Titanium Nitride Capping Layer in Co-Salicide Process

    NASA Astrophysics Data System (ADS)

    Kawamura, Kazuo; Inagaki, Satoshi; Saiki, Takashi; Nakamura, Ryo; Kataoka, Yuji; Kase, Masataka

    2007-11-01

    Since the distribution of gate resistance using cobalt silicide (CoSi2) increases markedly for gate lengths of 30 nm or less, CoSi2 is now being replaced by NiSi. However, CoSi2 still has the advantages of a high thermal stability and a low degree of roughness at the interface between the silicide and silicon layers owing to the low degree of mismatch (1.2%) of between their lattice constants. We have achieved excellent sheet resistance (Rs) with a gate length Lg=30 nm by optimizing the thickness of a cobalt capping layer of titanium nitride. The results shows an abnormal Rs behavior, in which one σ of Rs increases with capping layer thickness in the range of 10-50 nm, while it decreases with increasing capping layer thickness in the range of 0-10 nm. Unlike the results of a previous report [K. Goto et al.: IEDM Tech. Dig., 1995, p. 449], the variation in the Rs with a gate length Lg=30 nm is small, even without a TiN capping layer thickness down to 5-10 nm. We suggest that the uniformity of Rs is determined by the thickness of the CoSi layer after selective etching and the titanium concentration in the CoSi layer for capping TiN thicknesses of 10-50 nm, while the uniformity is determined by the titanium concentration and the damage sustained during selective etching for TiN thickness of 0-10 nm. For this optimization, CoSi2 is applicable to the 65 nm node technology node or beyond.

  17. Study on the electronic structure and Fermi surface of 3d-transition-metal disilisides CoSi2

    NASA Astrophysics Data System (ADS)

    Hamid, A. S.

    2012-09-01

    We have investigated the electronic structure, the momentum density distribution ρ( p), and the Fermi surface FS of single crystals of the Pyrite-type 3d-transition-metal disilisides CoSi2. The band structure calculations, the density of states DOS, and the FS, in vicinity of Fermi level, have been carried out using the full-potential linearized augmented plane wave FP-LAPW method within generalized gradient approximation GGA for exchange and correlation potential. The measurements have been performed via the 2D angular correlation of annihilation radiation ACAR experiments. ρ( p) has been reconstructed by using the Fourier transformation technique. The FS has been reconstructed within the first Brillion zone BZ through the Locks, Crisp, and West LCW folding procedures. The analysis confirmed that Si 3 sp states hybrid with both Co 3 d- t 2 g and Co 3 d- e g states around Γ and X points, respectively. The dimensions of the FS of CoSi2 have been compared to the present calculations as well as to the earlier results.

  18. Electrical and structural properties of buried CoSi2 layers in Si(100) grown by molecular beam allotaxy

    NASA Astrophysics Data System (ADS)

    Dolle, M.; Gassig, U.; Bay, H. L.; Schueppen, A.; Mantl, S.

    1994-12-01

    Buried, single-crystal CoSi2 layers in Si(100) were fabricated by molecular beam allotaxy, a new two-step method to fabricate buried epitaxial layers. At first CoSi2 precipitates embedded in Si(100) were grown in a molecular beam system. In a second step a continuous, buried silicide layer was formed by rapid thermal annealing. Buried layers with thicknesses ranging from 27 to 224 nm were fabricated and investigated by transmission electron microscopy, Rutherford backscattering, He ion channelling and various electrical methods. Electrical resistivity measurements between 4.2 and 300 K revealed a specific resistivity of 14 micro-Ohm cm at room temperature and 1 micro-Ohm cm at 4.2 K. The temperature dependence follows the Bloch-Grueneisen relation. The resistivity increases with decreasing layer thickness. Schottky diodes were fabricated and characterized using I-V and I-T methods. Excellent diodes were produced with barrier heights of 0.64+/-0.03 eV and idealities of 1.08.

  19. 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.

  20. 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.

  1. Sensitivity of CoSi2 precipitation in silicon to extra-low dopant concentrations. I. Experiment

    NASA Astrophysics Data System (ADS)

    Fortuna, F.; Ruault, M.-O.; Borodin, V. A.; Ganchenkova, M. G.; Kaïtasov, O.

    2015-01-01

    We demonstrate that the precipitation of cobalt disilicide phase in silicon during high-temperature (500 °C and 650 °C) implantation is noticeably affected by impurities of phosphorus and boron. Measurements of B-type CoSi2 cluster sizes and number densities as a function of implantation dose indicate that the number density of clusters progressively increases as the phosphorus concentration increases from 7 × 1011 to 8 × 1013 cm-3. A tentative explanation of these observations is proposed based on the previously suggested mechanism of precipitate nucleation, and on the results of first principles calculations summarized in Paper II, published as a follow-up paper. The results imply that utmost care is to be taken when dealing with transition metal precipitation during ion implantation into silicon because variations in the dopant content can affect the reproducibility of results even at extremely low dopant concentrations.

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

    DOE PAGESBeta

    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

  3. 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.

  4. Endotaxial growth of CoSi2 nanowires on Si(001) surface: The influence of surface reconstruction

    NASA Astrophysics Data System (ADS)

    Ong, Bin Leong; Ong, Sheau Wei; Tok, Eng Soon

    2016-05-01

    Evidence for the influence of Si(001)-(2 × 1) surface reconstruction on the elongation direction of CoSi2 flat islands is discussed in this paper. Step height analysis of these flat islands shows that flat island heights, HA, follow discrete values of NA such that HA = mNA + c, where NA = 1, 2, 3, …, m is equivalent to the number of monoatomic step height (1.4 Å) of the Si(001) surface, and c is the initial island height when NA = 0. The NA values were found to be correlated to the flat island elongation direction with respect to the (2 × 1) dimer rows. For a given terrace, the preferred elongation direction of these flat islands is parallel to the Si dimer rows. As a result, orthogonally elongated islands are clearly resolved on adjacent terraces, which are separated by monoatomic steps. The endotaxial growth of these flat islands is thus also influenced by the anisotropic adatom diffusion due to (2 × 1) surface reconstruction.

  5. 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.

  6. 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.

  7. Saponins from Fagonia glutinosa.

    PubMed

    Melek, F R; Miyase, T; el-Gindy, M R; Abdel-Khalik, S M; Ghaly, N S; el-Kady, M

    2000-10-01

    Twelve triterpenoid saponins, including six new, were isolated and identified from the aerial parts of Fagonia glutinosa. The new saponins were characterised as 3-O-[beta-D-glucopyranosyl(1-->2)][beta-D-glucopyranosyl(1-->3)]-alpha-L - arabinopyranosyl-27-hydroxy oleanolic acid 28-O-beta-D-glucopyranosyl ester, 3-O-[beta-D-glucopyranosyl(1-->3)]-alpha-L-arabinopyranosyl ursolic acid, 3-O-alpha-L-arabinopyranosyl ursolic acid 28-O-beta-D-glucopyranosyl ester, 3-O-[beta-D-xylopyranosyl(1-->2)][beta- D-glucopyranosyl(1-->3)]-alpha-L-arabinopyranosyl ursolic acid, 3-O-[beta-D-glucopyranosyl(1-->2)][beta-D- glucopyranosyl(1-->3)]-alpha-L-arabinopyranosyl ursolic acid 28-O-beta-D-glucopyranosyl ester and 3-O-[beta-D-glucopyranosyl(1-->2)][beta-D-glucopyranosyl(1-->3)]-alpha-L - arabinopyranosyl-27-hydroxy ursolic acid 28-O-beta-D-glucopyranosyl ester. The structures of the saponins were established by spectral and chemical evidences. The assignments of the NMR signals were performed by means of HOHAHA, 1H-1H COSY, ROE, HMQC and HMBC experiments. PMID:11082842

  8. Triterpenoid saponins from Fagonia cretica.

    PubMed

    Abdel Khalik, S M; Miyase, T; El-Ashaal, H A; Melek, F R

    2000-08-01

    Four new triterpenoid saponins were isolated and identified from the aerial parts of Fagonia cretica. They were characterized as 3-O-[beta-D-glucopyranosyl (1-->2)-alpha-L-arabinopyranosyl] hederagenin 28-O-beta-D-glucopyranosyl ester, 3-O-[beta-D-glucopyranosyl (1-->2)-alpha-L-arabinopyranosyl] oleanolic acid 28-O-[beta-D-glucopyranosyl (1-->6)-beta-D-glucopyranosyl] ester, 3-O-[beta-D-glucopyranosyl (1-->2)-alpha-L-arabinopyranosyl] 27-hydroxy oleanolic acid 28-O-[beta-D-glucopyranosyl (1-->6)-beta-D-glucopyranosyl] ester and 3beta-O-[beta-D-glucopyranosyl (1-->2)-alpha-L-arabinopyranosyl] olean-12-en-27-al-28-oic acid 28-O-[beta-D-glucopyranosyl (1-->6)-beta-D-glucopyranosyl] ester. The structures of the saponins were assigned by spectral analyses (FABMS, 1H, 13C NMR, 1H-1H COSY, TOCSY, HMQC and HMBC spectra) and NOE experiments. To the best of our knowledge the genin 3beta hydroxy olean-12-en-27-al-28-oic acid is new. PMID:11014278

  9. X-ray and DFT Study of Glaucocalyxin A Compound with Cytotoxic Activity

    NASA Astrophysics Data System (ADS)

    Wang, Fu-dong; Wang, Tao; Wu, An-an; Ding, Lan; Wang, Han-qing

    2009-06-01

    The title compound glaucocalyxin A (1) (7α, 14β-dihydroxy-ent-kaur-16-en-3,15-dione) isolated from the leaves of isodon excisoides was characterized by IR, 1H NMR, 13C NMR, 1H-1H COSY, HMQC, HMBC, and EIMS, and its crystal structure was determined by single-crystal X-ray diffraction. The X-ray crystal structure revealed that the molecular backbone of the chosen crystal is a tetracyclic system, including three six-membered rings and a five-membered ring, and the three six-membered rings are in a chair-like conformation. The five-membered ring adopts a twisted envelope-like conformation, and its geometrical parameters were compared with theoretical calculations at the B3LYP and HF level of theory. The molecules form extensive networks through the intra- and intermolecular hydrogen bonds. The experimental NMR data were interpreted with the aid of magnetic shielding constant calculations, by means of the GIAO (gauge-lncluding atomic orbitals) method. Calculated and experimental results were compared with a satisfactory level of agreement. Molecular electrostatic potential map was used in an attempt to identify key features of the diterpenoid glaucocalyxin A that is necessary for its activity. Calculations of molecular electrostatic potential and stabilization energies suggest that the protonation of glaucocalyxin A will be able to occur on carbonyl oxygen atoms.

  10. 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. PMID:24801989

  11. Dynamic stereochemistry of Topiramate (anticonvulsant drug) in solution: theoretical approaches and experimental validation.

    PubMed

    Ghiasi, Mina; Oskouie, Afsaneh Arefi; Saeidian, Hamdollah

    2012-02-01

    Topiramate, an antiepileptic drug, was synthesized with an improved protocol and identified by (1)H NMR, (13)C NMR, (1)H-(1)H COSY, HMQC and HMBC spectrum. In parallel, density functional theory (DFT) using B3LYP functional and split-valance 6-311++G** basis set has been used to optimize the structures and conformers of Topiramate. Also experimental and theoretical methods have been used to correlate the dependencies of (1)J and (2)J involving (1)H and (13)C on the C1-C2 (ω) and C1-O1 (θ) torsion angles in the glycosidic part of Topiramate. New Karplus equations are proposed to assist in the structural interpretation of these couplings. Importantly, due to the sensitivity of some couplings, most notably (2)J(H1R,H1S), (2)J(C2,H1R) and (2)J(C2,H1S) values depend on both C-C (ω) and C-O (θ) torsion angles. Analyses of experimental coupling constants for protons on the pyranose ring of Topiramate indicate a twist boat structure for Topiramate in solution. In all calculations solvent effects were considered using a polarized continuum model (PCM). PMID:22188614

  12. NMR assignments of the major cannabinoids and cannabiflavonoids isolated from flowers of Cannabis sativa.

    PubMed

    Choi, Young Hae; Hazekamp, Arno; Peltenburg-Looman, Anja M G; Frédérich, Michel; Erkelens, Cornelis; Lefeber, Alfons W M; Verpoorte, Robert

    2004-01-01

    The complete 1H- and 13C-NMR assignments of the major Cannabis constituents, delta9-tetrahydrocannabinol, tetrahydrocannabinolic acid, delta8-tetrahydrocannabinol, cannabigerol, cannabinol, cannabidiol, cannabidiolic acid, cannflavin A and cannflavin B have been determined on the basis of one- and two-dimensional NMR spectra including 1H- and 13C-NMR, 1H-1H-COSY, HMQC and HMBC. The substitution of carboxylic acid on the cannabinoid nucleus (as in tetrahydrocannabinolic acid and cannabidiolic acid) has a large effect on the chemical shift of H-1" of the C5 side chain and 2'-OH. It was also observed that carboxylic acid substitution reduces intermolecular hydrogen bonding resulting in a sharpening of the H-5' signal in cannabinolic acid in deuterated chloroform. The additional aromaticity of cannabinol causes the two angular methyl groups (H-8 and H-9) to show identical 1H-NMR shifts, which indicates that the two aromatic rings are in one plane in contrast to the other cannabinoids. For the cannabiflavonoids, the unambiguous assignments of C-3' and C-4' of cannflavin A and B were determined by HMBC spectra. PMID:15595449

  13. 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.

  14. Structure of the O-specific polysaccharide from the marine bacterium Rheinheimera japonica KMM 9513(T), containing N-glycosidic bond between monosaccharides.

    PubMed

    Kokoulin, Maxim S; Kalinovsky, Anatoly I; Tomshich, Svetlana V; Romanenko, Lyudmila A; Mikhailov, Valery V; Komandrova, Nadezhda A

    2016-06-01

    The O-specific polysaccharide was isolated from the lipopolysaccharide of type strain Rheinheimera japonica KMM 9513(T) and studied by sugar analysis, Smith degradation, and two-dimensional (1)H and (13)C NMR spectroscopy including (1)H,(1)H-TOCSY, (1)H,(1)H-COSY, (1)H,(1)H-ROESY, (1)H,(13)C-HSQC, (1)H,(13)C-HMBC, (1)H,(13)C-H2BC and (1)H,(13)C-HSQC-TOCSY experiments. The new structure of the O-specific polysaccharide of R. japonica KMM 9513(T) containing N-glycosidic bond was established. PMID:27077821

  15. A novel PH-cT-COSY methodology for measuring JPH coupling constants in unlabeled nucleic acids. application to HIV-2 TAR RNA.

    PubMed

    Carlomagno, Teresa; Hennig, Mirko; Williamson, James R

    2002-01-01

    A quantitative analysis of JPH scalar couplings in nucleic acids is difficult due to small couplings to phosphorus, the extreme overlap of the sugar protons and the fast relaxation of the spins involved in the magnetization transfer. Here we present a new methodology that relies on heteronuclear Constant Time Correlation Spectroscopy (CT-COSY). The three vicinal 3JPH3', 3JPHS' and 3JPHS" scalar couplings can be obtained by monitoring the intensity decay of the P1-H3'(i-1) peak as a function of the constant time T in a 2D correlation map. The advantage of the new method resides in the possibility of measuring the two 3JPH5' and 3JPH5" scalar couplings even in the presence of overlapped H5'/H5" resonances, since the quantitative information is extracted from the intensity decay of the P-H3' peak. Moreover, the relaxation of the H3' proton is considerably slower than that of the H5'/H5" geminal protons and the commonly populated conformations of the phosphate backbone are associated with large 3JPH3' couplings and relatively small 3JPH5'/H5". These two facts lead to optimal signal-to-noise ratio for the P-H3' correlation compared to the P-H5'/H5" correlation. The heteronuclear CT-COSY experiment is suitable for oligonucleotides in the 10-15 kDa molecular mass range and has been applied to the 30mer HIV-2 TAR RNA. The methodology presented here can be used to measure P-H dipolar couplings (DPH) as well. We will present qualitative results for the measurement of P-Hbase and P-H2' dipolar couplings in the HIV-2 TAR RNA and will discuss the reasons that so far precluded the quantification of the DPHS for the 30mer RNA. PMID:11885982

  16. 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.

  17. Two-dimensional incommensurately modulated structure of (Sr0.13Ca0. 87)2CoSi2O7 crystals.

    PubMed

    Bagautdinov, B; Hagiya, K; Kusaka, K; Ohmasa, M; Iishi, K

    2000-10-01

    The incommensurate structure of (Sr(0.13)Ca(0.87))(2)CoSi(2)O(7) at room temperature has been determined from single-crystal X-ray diffraction data. The compound has a non-centrosymmetric tetragonal basic cell of a = 7.8743 (4) and c = 5.0417 (2) A with the space group P4;2(1)m. The refinements of the basic structure converged to R = 0.038 for 757 main reflections. The two-dimensional incommensurate structure is characterized by the wavevectors q(1) = 0.286 (3)(a* + b*) and q(2) = 0.286 (3)(-a* + b*), where a*, b* are the reciprocal lattice vectors of the basic structure. With the (3 + 2)-dimensional superspace group P(p4mg)(P4;2(1)(m)), the refinements converged to R = 0.071 for 1697 observed reflections (757 main and 940 satellite reflections). The structure is described in terms of displacement of the atoms, rotation, distortion of CoO(4) and SiO(4) tetrahedra, and the partial ordering of the Sr and Ca atoms accompanied with the modulation. Correlated evolution of these features throughout the crystal gives rise to various oxygen coordination around Ca/Sr. Comparison of the derived modulated structure to that of Ca(2)CoSi(2)O(7) clarified that the partial substitution of Ca by large alkaline-earth atoms such as Sr should decrease the distortion of the polyhedra around the cations. PMID:11006557

  18. (1S)-1-Phenylethanaminium 4-{[(1S,2S)-1-hydroxy-2,3-dihydro-1H,1'H-[2,2'-biinden]-2-yl]methyl}benzoate.

    PubMed

    Frampton, Christopher S; Zhang, Tao; Scalabrino, Gaia A; Frankish, Neil; Sheridan, Helen

    2012-08-01

    The title molecular salt, C(8)H(12)N(+)·C(26)H(21)O(3)(-), contains a dimeric indane pharmacophore that demonstrates potent anti-inflammatory activity. The indane group of the anion exhibits some disorder about the α-C atom, which appears common to many structures containing this group. A model to account for the slight disorder was attempted, but this was deemed unsuccessful because applying bond-length constraints to all the bonds about the α-C atom led to instability in the refinement. The absolute configuration was determined crystallographically as S,S,S by anomalous dispersion methods with reference to both the Flack parameter and Bayesian statistics on Bijvoet differences. The configuration was also determined by an a priori knowledge of the absolute configuration of the (1S)-1-phenylethanaminium counter-ion. The molecules pack in the crystal structure to form an infinite two-dimensional hydrogen-bond network in the (100) plane of the unit cell. PMID:22850861

  19. High-Resolution Pyrimidine- and Ribose-Specific 4D HCCH-COSY Spectra of RNA Using the Filter Diagonalization Method

    PubMed Central

    Douglas, Justin T.; Latham, Michael P.; Armstrong, Geoffrey S.; Bendiak, Brad; Pardi, Arthur

    2010-01-01

    NMR spectra of nucleic acids suffer from severe peak overlap, which complicates resonance assignments. 4D NMR experiments can overcome much of the degeneracy in 2D and 3D spectra; however, the linear increase in acquisition time with each new dimension makes it impractical to acquire high-resolution 4D spectra using standard Fourier Transform (FT) techniques. The Filter Diagonalization Method (FDM) is a numerically efficient algorithm that fits the entire multi-dimensional time-domain data to a set of multi-dimensional oscillators. Selective 4D constant-time HCCH-COSY experiments that correlate the H5-C5-C6-H6 base spin systems of pyrimidines or the H1′-C1′-C2′-H2′ spin systems of ribose sugars were acquired on the 13C-labeled Iron Responsive Element RNA. FDM-processing of these 4D experiments recorded with only 8 complex points in the indirect dimensions showed superior spectral resolution than FT-processed spectra. Practical aspects of obtaining optimal FDM-processed spectra are discussed. The results here demonstrate that FDM-processing can be used to obtain high-resolution 4D spectra on a medium sized RNA in a fraction of the acquisition time normally required for high-resolution, high-dimensional spectra. PMID:18626775

  20. Metabolic flux and metabolic network analysis of Penicillium chrysogenum using 2D [13C, 1H] COSY NMR measurements and cumulative bondomer simulation.

    PubMed

    van Winden, Wouter A; van Gulik, Walter M; Schipper, Dick; Verheijen, Peter J T; Krabben, Preben; Vinke, Jacobus L; Heijnen, Joseph J

    2003-07-01

    At present two alternative methods are available for analyzing the fluxes in a metabolic network: (1) combining measurements of net conversion rates with a set of metabolite balances including the cofactor balances, or (2) leaving out the cofactor balances and fitting the resulting free fluxes to measured (13)C-labeling data. In this study these two approaches are applied to the fluxes in the glycolysis and pentose phosphate pathway of Penicillium chrysogenum growing on either ammonia or nitrate as the nitrogen source, which is expected to give different pentose phosphate pathway fluxes. The presented flux analyses are based on extensive sets of 2D [(13)C, (1)H] COSY data. A new concept is applied for simulation of this type of (13)C-labeling data: cumulative bondomer modeling. The outcomes of the (13)C-labeling based flux analysis substantially differ from those of the pure metabolite balancing approach. The fluxes that are determined using (13)C-labeling data are shown to be highly dependent on the chosen metabolic network. Extending the traditional nonoxidative pentose phosphate pathway with additional transketolase and transaldolase reactions, extending the glycolysis with a fructose 6-phosphate aldolase/dihydroxyacetone kinase reaction sequence or adding a phosphoenolpyruvate carboxykinase reaction to the model considerably improves the fit of the measured and the simulated NMR data. The results obtained using the extended version of the nonoxidative pentose phosphate pathway model show that the transketolase and transaldolase reactions need not be assumed reversible to get a good fit of the (13)C-labeling data. Strict statistical testing of the outcomes of (13)C-labeling based flux analysis using realistic measurement errors is demonstrated to be of prime importance for verifying the assumed metabolic model. PMID:12740935

  1. Novel triterpenoid acyl esters and alkaloids from Anoectochilus roxburghii.

    PubMed

    Han, Mei-Hua; Yang, Xiu-Wei; Jin, Yan-Ping

    2008-01-01

    Two novel sorghumol acyl esters, sorghumol 3-O-Z-p-coumarate and sorghumol 3-O-E-p-coumarate, and a novel alkaloid, anoectochine, were isolated from the whole plants of Anoectochilus roxburghii along with one known triterpenoid, sorghumol. Their structures were established by their detailed spectral studies, including two-dimensional NMR ((1)H-(1)H COSY, HSQC and HMBC). PMID:18435530

  2. Asterosaponins isolated from the starfish Asterias amurensis.

    PubMed

    Hwang, In Hyun; Kim, Dong Woo; Kim, Su Jeong; Min, Byung Sun; Lee, Seung Ho; Son, Jong Keun; Kim, Cheorl-Ho; Chang, Hyeun Wook; Na, Minkyun

    2011-01-01

    Three new asterosaponins 1-3 and four known saponins 4-7 have been isolated from the starfish Asterias amurensis LÜTKEN. By means of high magnetic field 1D- and 2D-NMR ((1)H-(1)H correlation spectroscopy (COSY), total correlation spectroscopy (TOCSY), heteronuclear multiple quantum coherence (HMQC), heteronuclear single quantum coherence (HSQC), heteronuclear multiple bond correlation (HMBC), and nuclear Overhauser effect spectroscopy (NOESY)) and MS analyses, the chemical structures of new compounds were determined to be 6α-O-[β-D-fucopyranosyl-(1→2)-β-D-galactopyranosyl-(1→4)-[β-D-quinovopyranosyl-(1→2)]-β-D-quinovopyranosyl-(1→3)-β-D-galactopyranosyl]-5α-chol-9(11)-en-23-one-3β-yl sodium sulfate (1), 6α-O-[β-D-fucopyranosyl-(1→2)-β-D-galactopyranosyl-(1→4)-[β-D-quinovopyranosyl-(1→2)]-β-D-quinovopyranosyl-(1→3)-β-D-galactopyranosyl]-5α-cholesta-9(11),24-dien-23-one-3β-yl sodium sulfate (2), and 6α-O-[β-D-fucopyranosyl-(1→2)-β-D-galactopyranosyl-(1→4)-[β-D-quinovopyranosyl-(1→2)]-β-D-quinovopyranosyl-(1→3)-β-D-galactopyranosyl]-5α-cholest-9(11)-en-23-one-3β-yl sodium sulfate (3). In addition, the NMR data for known saponins 4-7 were completely assigned by extensive 2D-NMR analysis without chemical degradation. PMID:21212551

  3. Improving the resolution in proton-detected through-space heteronuclear multiple quantum correlation NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Shen, Ming; Trébosc, J.; Lafon, O.; Pourpoint, F.; Hu, Bingwen; Chen, Qun; Amoureux, J.-P.

    2014-08-01

    Connectivities and proximities between protons and low-gamma nuclei can be probed in solid-state NMR spectroscopy using two-dimensional (2D) proton-detected heteronuclear correlation, through Heteronuclear Multiple Quantum Correlation (HMQC) pulse sequence. The indirect detection via protons dramatically enhances the sensitivity. However, the spectra are often broadened along the indirect F1 dimension by the decay of heteronuclear multiple-quantum coherences under the strong 1H-1H dipolar couplings. This work presents a systematic comparison of the performances of various decoupling schemes during the indirect t1 evolution period of dipolar-mediated HMQC (D-HMQC) experiment. We demonstrate that 1H-1H dipolar decoupling sequences during t1, such as symmetry-based schemes, phase-modulated Lee-Goldburg (PMLG) and Decoupling Using Mind-Boggling Optimization (DUMBO), provide better resolution than continuous wave 1H irradiation. We also report that high resolution requires the preservation of 1H isotropic chemical shifts during the decoupling sequences. When observing indirectly broad spectra presenting numerous spinning sidebands, the D-HMQC sequence must be fully rotor-synchronized owing to the rotor-synchronized indirect sampling and dipolar recoupling sequence employed. In this case, we propose a solution to reduce artefact sidebands caused by the modulation of window delays before and after the decoupling application during the t1 period. Moreover, we show that 1H-1H dipolar decoupling sequence using Smooth Amplitude Modulation (SAM) minimizes the t1-noise. The performances of the various decoupling schemes are assessed via numerical simulations and compared to 2D 1H-{13C} D-HMQC experiments on [U-13C]-L-histidineṡHClṡH2O at various magnetic fields and Magic Angle spinning (MAS) frequencies. Great resolution and sensitivity enhancements resulting from decoupling during t1 period enable the detection of heteronuclear correlation between aliphatic protons and

  4. Spectroscopic characterization of the 1-substituted 3,3-diphenyl-4-(2'-hydroxyphenyl)azetidin-2-ones: Application of 13C NMR, 1H- 13C COSY NMR and mass spectroscopy

    NASA Astrophysics Data System (ADS)

    Singh, Girija S.; Pheko, Tshepo

    2008-08-01

    The article deals with spectroscopic characterization of azetidin-2-ones. The presence of substituents like hydroxyl, fluoro, methoxy and benzhydryl, etc., on the azetidin-2-one ring significantly affects the IR absorption and 13C NMR frequencies of the carbonyl group present in these compounds. The presence of an ester carbonyl group or too many methine protons in the molecule has been observed to limit the scope of IR and 1H NMR spectroscopy in unambiguous assignment of the structure. The application of 13C NMR, 2D NMR ( 1H- 13C COSY) and mass spectroscopy in characterization of complex azetidin-2-ones is discussed. An application of the latter two techniques is described in deciding unequivocally between an azetidin-2-one ring and chroman-2-one ring structure for the product obtained by treatment of the 1-substituted 3,3-diphenyl-4-[2'-( O-diphenylacyl)hydroxyphenyl]-2-azetidinones with ethanolic sodium hydroxide at room temperature.

  5. 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.

  6. Melicilamide A: a new ceramide from Milicia excelsa.

    PubMed

    Hussain, Hidayat; Nyongha, Awazi Tengu; Dongo, Etienne; Ahmed, Ishtiaq; Zhang, Wen

    2013-01-01

    This article deals with a phytochemical investigation of Melicia excelsa from which melicilamide A (1), a new ceramide has been isolated. Its structure was determined by comprehensive analyses of its (1)H- and (13)C-NMR, COSY, HMQC and HMBC spectroscopic, EI-MS and ESI-MS data. The remaining one known compound was identified as β-sitosterol glucopyranoside. PMID:22963402

  7. 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. PMID:18470882

  8. Terpene hydrocarbons in Pimpinella anisum L.

    PubMed

    Burkhardt, G; Reichling, J; Martin, R; Becker, H

    1986-06-20

    The essential oil of anise (fruits and shoots) was investigated focusing on the composition of the hydrocarbon fraction. Several sesquiterpenes were identified by GC-MS and the relative composition of the fractions was established by GC analysis. gamma-Himachalene and the diterpene neophytadiene were isolated by TLC and column chromatography at low temperatures. Their structures were determined by MS and NMR including 1H-1H correlated COSY and NOE experiments. PMID:3737372

  9. Jaspiferin G, a new isomalabaricane-type triterpenoid from the sponge Jaspis stellifera.

    PubMed

    Xu, Wei-Guo; Wang, Jia; Xing, Guo-Sheng; Xu, Jiao-Jiao; Qiao, Wei; Zhao, Chuan; Tang, Sheng-An

    2016-01-01

    A new isomalabaricane-type triterpenoid, jaspiferin G (1), together with four known isomalabaricane-type triterpenoids, isogeoditin A (2), 13-(E)-isogeoditin A (3), jaspolide E (4), and 22,23-dihydrostellettin D (5), was isolated from the marine sponge Jaspis stellifera. The structures were elucidated on the basis of spectroscopic data ((1)H and (13)C NMR, (1)H(-1)H COSY, HSQC, HMBC, and ROESY) and mass spectrometry. PMID:27101546

  10. A xanthanolide diol and a dimeric xanthanolide from Xanthium species.

    PubMed

    Ahmed, A A; Mahmoud, A A; El-Gamal, A A

    1999-06-01

    Extracts of the aerial parts of Xanthium strumarium and fruit of X. pungens afforded a new Xanthanolide diol derivative, 11alpha,13-dihydroxyxanthatin and a new dimeric xanthanolide sesquiterpene lactone, pungiolide C, in addition to some known compounds. The structures of the new compounds were determined by spectroscopic methods particularly high resolution (1)H-, (13)C-NMR and 2D (1)H- (1)H and (1)H- (13)C COSY NMR analysis. PMID:17260271

  11. 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

  12. Dihydrofolate reductase: Sequential resonance assignments using 2D and 3D NMR and secondary structure determination in solution

    SciTech Connect

    Carr, M.D.; Birdsall, B.; Jimenez-Barbero, J.; Polshakov, V.I.; McCormick, J.E.; Feeney, J.; Frenkiel, T.A.; Bauer, C.J. ); Roberts, G.C.K. )

    1991-06-25

    Three-dimensional (3D) heteronuclear NMR techniques have been used to make sequential {sup 1}H and {sup 15}H resonance assignments for most of the residues of Lactobacillus casei dihydrofolate reductase (DHFR), a monomeric protein of molecular mass 18,300 Da. A uniformly {sup 15}N-labeled sample of the protein was prepared and its complex with methotrexate (MTX) studied by 3D {sup 15}N/{sup 1}H nuclear Overhauserheteronuclear multiple quantum coherence (NOESY-HMQC), Harmann-Hahn-heteronuclear multiple quantum coherence (HOHAHA-HMQC), and HMQC-NOESY-HMQC experiments. These experiments overcame most of the spectral overlap problems caused by chemical shift degeneracies in 2D spectra and allowed the {sup 1}H-{sup 1}H through-space and through-bond connectivities to be identified unambiguously, leading to the resonance assignments. The novel HMQC-NOESY-HMQC experiment allows NOE cross peaks to be detected between NH protons even when their {sup 1}H chemical shifts are degenerate as long as the amide {sup 15}N chemical shifts are nondegenerate. The 3D experiments, in combination with conventional 2D NOESY, COSY, and HOHAHA experiments on unlabelled and selectively deuterated DHFR, provide backbone assignments for 146 of the 162 residues and side-chain assignments for 104 residues of the protein. Data from the NOE-based experiments and identification of the slowly exchanging amide protons provide detailed information about the secondary structure of the binary complex of the protein with methotrexate.

  13. Precise Determination of Enantiomeric Excess by a Sensitivity Enhanced Two-Dimensional Band-Selective Pure-Shift NMR.

    PubMed

    Rachineni, Kavitha; Kakita, Veera Mohana Rao; Dayaka, Satyanarayana; Vemulapalli, Sahithya Phani Babu; Bharatam, Jagadeesh

    2015-07-21

    Unambiguous identification and precise quantification of enantiomers in chiral mixtures is crucial for enantiomer specific synthesis as well as chemical analysis. The task is often challenging for mixtures with high enantiomeric excess and for complex molecules with strong (1)H-(1)H scalar (J) coupling network. The recent advancements in (1)H-(1)H decoupling strategies to suppress the J-interactions offered new possibilities for NMR based unambiguous discrimination and quantification enantiomers. Herein, we discuss a high resolution two-dimensional pure-shift zCOSY NMR method with homonuclear band-selective decoupling in both the F1 and F2 dimensions (F1F2-HOBS-zCOSY). This advanced method shows a sharp improvement in resolution over the other COSY methods and also eliminates the problems associated with the overlapping decoupling sidebands. The efficacy of this method has been exploited for precise quantification of enantiomeric excess (ee) ratio (R/S) up to 99:1 in the presence of very low concentrations of chiral lanthanide shift reagents (CLSR) or chiral solvating agents (CSA). The F1F2-HOBS-zCOSY is simple and can be easily implemented on any modern NMR spectrometers, as a routine analytical tool. PMID:26091767

  14. Isolation by high-pressure liquid chromatography of cis-trans isomers of β-apo-12'-carotenal and determination of their configurations by 1H NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Hu, Ying; Mizoguchi, Tadashi; Kurimoto, Yoshitaka; Koyama, Yasushi

    1995-10-01

    High-pressure liquid chromatography of an isomeric mixture of β-apo-12'-carotenal, which was obtained by iodine-sensitized photo-isomerization, resolved eleven peaks of cis-trans isomers. The configurations of eight isomers, i.e., all-trans, 9-, 13-, 15-, 13'-mono-cis, and 9,13-, 9,13'- and 13,13'-di-cis, were determined by 1H NMR spectroscopy. 1H, 1H COSY and long-range 1H, 1H COSY spectra was used for the assignments of all the 1H signals. The isomerization shifts of the olefinic 1H signals and the NOE correlations, which were identified in the 1H, 1H NOESY spectra, were used for the configurational determinations. In relation to the difference in isomeric composition between retinoids and carotenoids, the cis configurations found in the present compound (C 25 aldehyde) are compared with those found in retinal (C 20 aldehyde) and β-apo-8'-carotenal (C 30 aldehyde) having a shorter and a longer conjugated chain, respectively.

  15. Triterpenes from Euphorbia rigida

    PubMed Central

    Gherraf, Noureddine; Zellagui, Amar; Mohamed, Naglaa S.; Hussien, Taha A.; Mohamed, Tarik A.; Hegazy, Mohamed-Elamir F.; Rhouati, Salah; Moustafa, Mahmoud F. M.; El-Sayed, Magdi A.; Mohamed, Abou El-Hamd H.

    2010-01-01

    Phytochemical studies of the aerial parts of Euphorbia rigida afforded three triterpenes: betulin (1), cycloart-23Z-ene-3, 25-diol (2) and cycloartan-3, 24, 25-triol (3), firstly isolated from this plant. The structures and relative stereochemistry were determined on the basis of extensive spectroscopic analyses, including 1D and 2D NMR experiments (1H NMR, 13C NMR, COSY, NOESY, HMQC and HMBC). PMID:21808559

  16. Detailed 1H and 13C NMR structural assignment and relative stereochemistry determination for three new and one known semi-synthetic sesquiterpene lactones

    NASA Astrophysics Data System (ADS)

    Sass, Daiane Cristina; Heleno, Vladimir Constantino Gomes; Soares, Ana Carolina Ferreira; Lopes, João Luis Callegari; Constantino, Mauricio Gomes

    2012-01-01

    In this work is described a complete 1H and 13C NMR analysis for a group of four sesquiterpene lactones, three previously unknown. The unequivocal assignments were achieved by 1H NMR, 13C{ 1H} NMR, J-resolved, gCOSY, gHMQC, gHMBC and NOESY experiments and no ambiguities were left behind. All hydrogen coupling constants were measured, clarifying all hydrogen signals multiplicities.

  17. A New Cucurbitane Glycoside from Siraitia grosvenorii.

    PubMed

    Chaturvedula, Venkata Sai Prakash; Meneni, Srinivasa Rao

    2015-09-01

    A systematic phytochemical study of the commercial extract of Luo Han Guo (Siraitia grosvenorii) resulted in the isolation of an additional minor new cucurbitane glycoside, mogroside V Al (1). The structure of the new compound was characterized on the basis of 1D (1H and 13C NMR) and 2D (COSY, HMQC, HMBC and NOESY) NMR and high resolution mass spectral (HRMS) data, as well as hydrolysis studies. PMID:26594748

  18. Cordioxime: a new dioxime gamma-lactam from Cordia platythyrsa.

    PubMed

    Christelle, Tsague Dongmo; Hussainb, Hidayat; Dongo, Etienne; Julius, Oben Enyong; Hussain, Javid

    2011-08-01

    Cordia platythyrsa Baker is known for its medicinal value. This paper deals with a phytochemical investigation of this species, from which cordioxime (1), a new dioxime y-lactam has been isolated. Its structure was determined by comprehensive analyses of its 1H and 13C NMR, COSY, HMQC, and HMBC spectroscopic, and HREIMS data. The remaining two known compounds were identified as beta-sitosterol, and beta-sitosterol glucopyranoside. PMID:21922919

  19. Flavanones from Miconia prasina

    PubMed Central

    Tarawneh, Amer H.; León, Francisco; Ibrahim, Mohammed A.; Pettaway, Sara; McCurdy, Christopher R.; Cutler, Stephen J.

    2014-01-01

    A glycosidic flavanone miconioside C (1) has been isolated from the methanolic extract of the stems of Miconia prasina, together with 7-O-β-D-apiofuranosyl-(1→6)-β-D-glucopyranosylmatteucinol (2), miconioside B (3), matteucinol (4), farrerol (5) and desmethoxymatteucinol (6). Their structures were mainly established by extensive NMR studies (1H NMR, 13C NMR, DEPT, 1H-1H COSY, HSQC, HMBC) and mass spectrometry. The compounds 1- 3 were evaluated for in vitro binding assays using cannabinoid receptors (CB1 and CB2). PMID:24976876

  20. Spectroscopic and structural elucidation of merocyanine dye 2,5-[1-metyl-4-[2-(4-hydroxyphenyl)ethenyl)]piridinium]-hexane tetraphenylborate aggregation processes.

    PubMed

    Koleva, Bojidarka B; Stoyanov, Stanimir; Kolev, Tsonko; Petkov, Ivan; Spiteller, Michael

    2008-12-01

    Structural and spectroscopic elucidation of merocyanine dye, 2,5-[1-metyl-4-[2-(4-hydroxyphenyl)ethenyl)]piridinium]-hexane tetraphenylborate, is performed in gas and condense phase by means of solution and solid-state conventional and linear-polarized IR-spectroscopy of oriented colloids in nematic liquid crystal suspension, UV-vis and fluorescence methods, HPLC MS/MS tandem and ESI mass spectrometry, (1)H, (13)C and (1)H-(1)H COSY NMR, TGV and DSC methods. Quantum chemical DFT calculations are performed for structural optimization and spectroscopic properties prediction. PMID:18400554

  1. Structural elucidation, optical, magnetic and nonlinear optical properties of oxystyryl dyes.

    PubMed

    Koleva, Bojidarka B; Stoyanov, Stanimir; Kolev, Tsonko; Petkov, Ivan; Spiteller, Michael

    2009-01-01

    Structure, magnetic and optical properties of tetraphenylborate salts of 2,5-[1-methyl-4-[2-(4-hydroxyphenyl)ethenyl]piridinium]-propane and butane are performed in gas and condense phase by means of solution and solid-state conventional and linear-polarized IR-spectroscopy of oriented colloids in nematic liquid crystal suspension, UV-vis and fluorescence methods, HPLC tandem ESI mess spectrometry (MS/MS), (1)H, (13)C and (1)H-(1)H COSY NMR, TGV and DSC methods. Quantum chemical DFT calculations are used for performing of the structures, optical and nonlinear optical properties of the studied compounds. PMID:18722806

  2. Terpenoids from Euphorbia pekinensis.

    PubMed

    Fang, Fu-Hu; Li, Wen-Hai; Han, Zheng-Zhi; Huang, Wen-Jun; Li, Dong-Xu; Zhao, Sha; Tang, Min-Hao; Yuan, Cheng-Shan

    2015-01-01

    Euphorpekone A (1) and euphorpekone B (2), two new diterpenoids, 3β-hydroxy-25-methyloxylanosta-8,23-diene, a new triterpenoid (3), together with a known triterpenoid, 3β,25-dihydroxylanosta-8,23-diene (4), were isolated from Euphorbia pekinensis Rupr. Their structures were elucidated on the basis of UV, IR, 1D ((1)H, (13)C, NOE) and 2D ((1)H-(1)H COSY, HSQC, HMBC) NMR, HR-ESI-MS, X-ray diffraction analysis, and CD method. PMID:26654567

  3. 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. PMID:26230217

  4. 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. PMID:21640585

  5. Stevisalioside A, a novel bitter-tasting ent-atisene glycoside from the roots of Stevia salicifolia.

    PubMed

    Mata, R; Rodríguez, V; Pereda-Miranda, R; Kaneda, N; Kinghorn, A D

    1992-05-01

    A new acetylated ent-atisene glycoside, stevisalioside A [1], has been isolated as a bitter-tasting principle from Stevia salicifolia roots. The structure was established by the interpretation of spectral data, with the nmr assignments of this compound being based on 1H-1H COSY, 1H-13C HETCOR, and selective INEPT experiments. A rearrangement product 4 of the aglycone moiety obtained by alkaline hydrolysis supported the structure of 1. This is the first report of the occurrence of an atisane-type diterpene from the genus Stevia. PMID:1517738

  6. 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. PMID:26611371

  7. Owariensisone: a new iridolactone from the whole plant of Brillantaisia owariensis P. Beauv.

    PubMed

    Foning Tebou, Perrin Lanversin; Mabou, Florence Déclaire; Ngnokam, David; Harakat, Dominique; Voutquenne-Nazabadioko, Laurence

    2016-07-01

    From the whole plant of Brillantaisia owariensis P. Beauv, a new iridolactone, owariensisone (1) together with six known compounds (nepetin-7-O-glucoside, choline, sucrose, mannitol, xylitol, 1-O-palmitoyl-2-eicosanoyl-3-O-(6-amino-6-deoxy)-β-d-glucopyranosyl-glycerol) were isolated. Structures of these compounds were established by direct interpretation of their spectral data, mainly HR-TOFESIMS, 1-D NMR ((1)H and (13)C) and 2-D NMR ((1)H-(1)H COSY, HSQC, HMBC, NOESY, TOCSY and DOCSY) and by comparison with the literature. PMID:26732013

  8. Spectroscopic and structural elucidation of merocyanine dye 2,5-[1-metyl-4-[2-(4-hydroxyphenyl)ethenyl)]piridinium]-hexane tetraphenylborate. Aggregation processes

    NASA Astrophysics Data System (ADS)

    Koleva, Bojidarka B.; Stoyanov, Stanimir; Kolev, Tsonko; Petkov, Ivan; Spiteller, Michael

    2008-12-01

    Structural and spectroscopic elucidation of merocyanine dye, 2,5-[1-metyl-4-[2-(4-hydroxyphenyl)ethenyl)]piridinium]-hexane tetraphenylborate, is performed in gas and condense phase by means of solution and solid-state conventional and linear-polarized IR-spectroscopy of oriented colloids in nematic liquid crystal suspension, UV-vis and fluorescence methods, HPLC MS/MS tandem and ESI mass spectrometry, 1H, 13C and 1H- 1H COSY NMR, TGV and DSC methods. Quantum chemical DFT calculations are performed for structural optimization and spectroscopic properties prediction.

  9. Structural elucidation, optical, magnetic and nonlinear optical properties of oxystyryl dyes

    NASA Astrophysics Data System (ADS)

    Koleva, Bojidarka B.; Stoyanov, Stanimir; Kolev, Tsonko; Petkov, Ivan; Spiteller, Michael

    2009-01-01

    Structure, magnetic and optical properties of tetraphenylborate salts of 2,5-[1-methyl-4-[2-(4-hydroxyphenyl)ethenyl]piridinium]-propane and butane are performed in gas and condense phase by means of solution and solid-state conventional and linear-polarized IR-spectroscopy of oriented colloids in nematic liquid crystal suspension, UV-vis and fluorescence methods, HPLC tandem ESI mess spectrometry (MS/MS), 1H, 13C and 1H- 1H COSY NMR, TGV and DSC methods. Quantum chemical DFT calculations are used for performing of the structures, optical and nonlinear optical properties of the studied compounds.

  10. Absolute configuration of fusarone, a new azaphilone from the endophytic fungus Fusarium sp. isolated from Melia azedarach, and of related azaphilones.

    PubMed

    Yang, Sheng-Xiang; Gao, Jin-Ming; Laatsch, Hartmut; Tian, Jun-Mian; Pescitelli, Gennaro

    2012-08-01

    A new azaphilone derivative, named fusarone (1), has been isolated from the ethyl acetate soluble extract of the fermentation broth of an endophytic fungus, Fusarium sp. LN-12, isolated from the leaves of Melia azedarach Linn. The structure of the new compound was established on the basis of extensive spectroscopic analysis, including 1D-NMR and 2D-NMR ((1) H-(1)H COSY, TOCSY, HSQC, HMBC, and NOESY) experiments. The absolute configurations of fusarone (1) and of a second related azaphilone were determined by means of electronic circular dichroism spectroscopy and optical rotation calculations. PMID:22678988

  11. Isolation of bioactive biphenyl compounds from the twigs of Chaenomeles sinensis.

    PubMed

    Kim, Chung Sub; Subedi, Lalita; Kwon, Oh Kil; Kim, Sun Yeou; Yeo, Eui-Ju; Choi, Sang Un; Lee, Kang Ro

    2016-01-15

    Investigation of the MeOH extract of Chaenomeles sinensis twigs resulted in the isolation of seven biphenyl compounds (1-7) including a new compound, chaenomin (1). The chemical structures of the isolated compounds were elucidated by extensive NMR data ((1)H and (13)C NMR, (1)H-(1)H COSY, HSQC and HMBC), specific optical rotation, and chemical reaction. Compounds 2 and 6 showed potent cytotoxic activities against four cancer cell lines (A549, SK-OV-3, SK-MEL-2, and HCT15), and compound 7 exhibited potent anti-neuroinflammatory and NGF-potentiating activity. PMID:26706168

  12. 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.

  13. 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

  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. A Novel RF E × B Spin Manipulator at COSY

    NASA Astrophysics Data System (ADS)

    Mey, Sebstian; Gebel, Ralf

    2016-02-01

    The Jülich Electric Dipole Moment Investigations (JEDI) Collaboration is developing tools for the measurement of permanent Electric Dipole Moments (EDMs) of charged, light hadrons in storage rings. While the Standard Model prediction for the EDM gives unobservably small magnitudes, a non-vanishing EDM from 𝒞𝒫 violating sources beyond the standard model can lead to a tiny build-up of vertical polarization in a beforehand horizontally polarized beam. This requires a spin tune modulation by an RF dipole without any excitation of coherent beam oscillations. In the course of 2014, a prototype RF E × B dipole has been successfully commissioned and tested. We verified that the device can be used to continuously flip the vertical polarization of a 970MeV/c deuteron beam without exciting any coherent beam oscillations.

  16. Simulation of 2D NMR Spectra of Carbohydrates Using GODESS Software.

    PubMed

    Kapaev, Roman R; Toukach, Philip V

    2016-06-27

    Glycan Optimized Dual Empirical Spectrum Simulation (GODESS) is a web service, which has been recently shown to be one of the most accurate tools for simulation of (1)H and (13)C 1D NMR spectra of natural carbohydrates and their derivatives. The new version of GODESS supports visualization of the simulated (1)H and (13)C chemical shifts in the form of most 2D spin correlation spectra commonly used in carbohydrate research, such as (1)H-(1)H TOCSY, COSY/COSY-DQF/COSY-RCT, and (1)H-(13)C edHSQC, HSQC-COSY, HSQC-TOCSY, and HMBC. Peaks in the simulated 2D spectra are color-coded and labeled according to the signal assignment and can be exported in JCAMP-DX format. Peak widths are estimated empirically from the structural features. GODESS is available free of charge via the Internet at the platform of the Carbohydrate Structure Database project ( http://csdb.glycoscience.ru ). PMID:27227420

  17. A new xanthone from Garcinia nitida.

    PubMed

    Ee, G C L; Foo, C H; Jong, V Y M; Ismail, N H; Sukari, M A; Taufiq Yap, Y H; Awang, K

    2012-01-01

    A detailed chemical study on the stem bark of Garcinia nitida has led to the isolation of five xanthones. They are 1,6-dihydroxy-5-methoxy-6,6-dimethylpyrano[2',3':2,3]-xanthone (1), inophyllin B (2), osajaxanthone (3), 3-isomangostin (4) and rubraxanthone (5). The structures of these compounds were established using mainly 1-D and 2-D NMR spectroscopy ((1)H, (13)C, DEPT, COSY, HMBC and HMQC) while molecular masses were determined via MS techniques; 1 is a new compound. PMID:22044165

  18. Two new antimicrobial metabolites from the endophytic fungus, Seimatosporium sp.

    PubMed

    Hussain, Hidayat; Krohn, Karsten; Schulz, Barbara; Draeger, Siegfried; Nazir, Mamona; Saleem, Muhammad

    2012-03-01

    Two new acaranoic acids, named seimatoporic acid A and B (1, and 2), together with six known compounds, R-(-)-mellein (3), cis-4-hydroxymellein (4), trans-4-hydroxymellein (5), 4R-hydroxy-5-methylmellein (6), (-)-5-hydroxymethylmellein (7), and ergosterol (8) were isolated from an endophytic fungus, Seimatosporium sp, by a bioassay-guided procedure. The structures of the new compounds have been assigned from analysis of the 1H and 13C NMR spectra, DEPT, and by 2D COSY, HMQC, HMBC and NOESY experiments. A mixture of compounds 1 and 2 showed strong antifungal activity against Botrytis cinerea, Septoria tritici, and Pyricularia oryzae. PMID:22545398

  19. 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. PMID:23088362

  20. 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).

  1. Isolation and characterization of a heteropolysaccharide from the corm of Amorphophallus campanulatus.

    PubMed

    Das, Debsankar; Mondal, Subhas; Roy, Sadhan K; Maiti, Debabrata; Bhunia, Bibhas; Maiti, Tapas K; Islam, Syed S

    2009-12-14

    A water-soluble polysaccharide isolated from the aqueous extract of the corm of Amorphophallus campanulatus was found to contain D-galactose, D-glucose, 4-O-acyl-D-methyl galacturonate, and l-arabinose in a molar ratio 2:1:1:1. Structural investigation of the polysaccharide was carried out using 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 the above-mentioned experiments the structure of the repeating unit of the polysaccharide was established as: This molecule showed splenocyte activation. PMID:19889399

  2. Xanthones with antimalarial activity from Garcinia dulcis.

    PubMed

    Likhitwitayawuid, K; Chanmahasathien, W; Ruangrungsi, N; Krungkrai, J

    1998-04-01

    Chromatographic separation of the EtOH extract of the bark of Garcinia dulcis (Guttiferae) furnished five xanthones, viz 1,7-dihydroxyxanthone (1), 12b-hydroxy-des-D-garcigerrin A (2), 1-O-methylsymphoxanthone (3), symphoxanthone (4), and garciniaxanthone (5). These xanthones 1-5 showed inhibitory effects on the growth of Plasmodium falciparum with IC50 values of 0.96-3.88 micrograms/ml. In addition, revised 13C-NMR assignments of 3 and complete 13C-NMR assignments of 4 were obtained through analysis of their COSY, NOESY, HMQC, and HMBC spectra. PMID:9581528

  3. Oxygenated Cembranoids from the Soft Coral Sinularia flexibilis

    PubMed Central

    Su, Ching-Chyuan; Wong, Bing-Sang; Chin, Chuen; Wu, Yu-Jen; Su, Jui-Hsin

    2013-01-01

    Chemical examination of the Taiwanese soft coral Sinularia flexibilis led to the isolation of five cembrane-based diterpenoids 1–5, including two new metabolites, 11-acetylsinuflexolide (1) and 11-acetyldihydrosinuflexolide (2). The structures of the new metabolites were determined based on extensive spectroscopic analysis, particularly mass spectrometry and 2D NMR (1H–1H COSY, HMQC, HMBC, and NOESY) spectroscopy. Metabolites 1, 3 and 4 exhibited moderate to weak cytotoxicity to human tumor cell lines, HeLa, HEp-2, MCF-7 and MDA-MB-231. PMID:23429272

  4. Unusual isolation of a hemiaminal product from 4-cyclohexyl-3-thiosemicarbazide and di-2-pyridyl ketone: Structural and spectral investigations

    NASA Astrophysics Data System (ADS)

    Suni, V.; Kurup, M. R. Prathapachandra; Nethaji, Munirathinam

    2005-07-01

    Stable hemiaminal product was isolated as single crystals from the condensation reaction of di-2-pyridyl ketone with 4-cyclohexyl-3-thiosemicarbazide and structurally and spectrochemically characterized. The compound is the first report of a stable hemiaminal product of the condensation reaction of a substituted thiosemicarbazone. Spectral characterization was carried out using IR, UV-vis., 1H NMR, 13C NMR, COSY and HMQC. The compound crystallizes into a triclinic lattice with space group P-1. The molecule reveals a highly strained ZE conformation and a one-dimensional packing is effected by a network of intermolecular hydrogen bonding interactions in the unit cell.

  5. Euphane triterpenoids of Cassipourea lanceolata from the Madagascar rainforest*

    PubMed Central

    Hou, Yanpeng; Cao, Shugeng; Brodie, Peggy J.; Miller, James S.; Birkinshaw, Chris; Andrianjafy, Mamisoa N.; Andriantsiferana, Rabodo; Rasamison, Vincent E.; TenDyke, Karen; Shen, Yongchun; Suh, Edward M.; Kingston, David G.I.

    2010-01-01

    Fractionation of an ethanol extract of a Madagascar collection of the leaves and fruit of Cassipourea lanceolata Tul. led to the isolation of three euphane triterpenoids 1–3. The 1H and 13C NMR spectra of all compounds were fully assigned using a combination of 2D NMR experiments, including COSY, TOCSY, HSQC (HMQC), HMBC and ROESY sequences. The three compounds showed weak antiproliferative activities against the A2780 human ovarian cancer cell line, with IC50 values of 25, 25 and 32 μM, respectively. PMID:20074760

  6. Chemical and antibacterial constituents of Skimmia anquetelia.

    PubMed

    Sharma, Rajni Kant; Negi, Devendra Singh; Gibbons, Simon; Otsuka, Hideaki

    2008-02-01

    Investigation of the leaves of Skimmia anquetelia (Rutaceae) led to the isolation of a new coumarin glucoside 7,8-dihdroxy-6-[3'-beta- D-glucopyranosyloxy-2'(xi)-hydroxy-3'-methylbutyl]-coumarin ( 1) together with five known coumarins: 6-(2,3-dihydroxy-3-methylbutyl)-7-methoxycoumarin ( 2), skimmin ( 3), osthol ( 4), esculetin ( 5) and scopuletin ( 6). The antibacterial activity of compounds 1 and 3 was also investigated against the plant bacterial pathogens Agrobacterium tumifaciens, Pseudomonas syringae and Pactobacterium carotovorum. Structures were determined on the basis of analyses of spectral evidence including 1D, 2 D NMR (COSY, HMQC, HMBC and NOESY) and mass spectroscopy. PMID:18240101

  7. Unequivocal NMR assignments: O-methoxy-methyl esters derivatives of acid chromanones from Calophyllum brasiliense CAMB. (Guanandi).

    PubMed

    Caneppele, D; Vieira, P C; Dall'Oglio, E L; da Silva, L E; Sousa, P T

    2008-01-01

    The present work describes the fractionation of the crude hexane extract (EBHEX) from Calophyllum brasiliense (Clusiaceae) stem bark. Derivatization of DCM(2-9) fraction with diazomethane afforded the chromanones inophylloidic acid, isobrasiliensic acid, as well as, a mixture containing isobrasiliensic and brasiliensic acids, in the form of their more stable O-methoxy-methyl esters derivatives 1, 2, and 3, respectively. The isolation of 1 from C. brasiliense is described for the first time herein. The use of two-dimensional NMR methods ((1)H-COSY, HMQC, and HMBC) allowed the precise determination of (13)C and (1)H chemical shifts of compounds 1, 2, and 3. PMID:18626818

  8. 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. PMID:22263590

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

    PubMed

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

    2009-11-01

    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]. PMID:19765690

  10. Synthesis and crystal structure of 2-debenzoyl and 4-deacetyl 1-deoxybaccatin VI derivatives

    NASA Astrophysics Data System (ADS)

    Lin, Hai-Xia; Jiang, Yi-; Chen, Jian-Min; Chen, Jian-Kuan; Chen, Min-Qin

    2005-03-01

    Two novel 4-deacetyl and 2,4-deacyl 1-deoxybaccatin VI derivatives were prepared from 1-deoxybaccatin VI. Their structures were elucidated using extensive spectroscopic techniques (IR, 1HNMR, DEPT, COSY, HMQC and MS). In addition, the conformations for these compounds were obtained by X-ray diffraction methods. Comparisons to 1-deoxybaccatin VI and paclitaxel identify relative differences principally in the cyclohexenyl ring (A ring). Conformational analysis showed that removal of 4-acetyl or 2,4-diacyl moiety has a decisive influence on the conformation of the A ring.

  11. Antitubercular natural products: berberine from the roots of commercial Hydrastis canadensis powder. Isolation of inactive 8-oxotetrahydrothalifendine, canadine, beta-hydrastine, and two new quinic acid esters, hycandinic acid esters-1 and -2.

    PubMed

    Gentry, E J; Jampani, H B; Keshavarz-Shokri, A; Morton, M D; Velde, D V; Telikepalli, H; Mitscher, L A; Shawar, R; Humble, D; Baker, W

    1998-10-01

    Berberine (4) is responsible for the activity of an extract of a commercial root sample of Hydrastis canadensis against multiply drug resistant Mycobacterium tuberculosis. Two new quinic acid feruloyl esters, compounds 2 and 3, have been isolated from the same source along with canadine (1c), 8-oxotetrahydrothalifendine (1), and beta-hydrastine (5). These were found to be inactive. The structures of the new compounds were elucidated from spectral (1H, 13C, HMQC, HMBC, and H-H COSY) and chemical evidences. PMID:9784149

  12. Sensitivity enhanced (14)N/(14)N correlations to probe inter-beta-sheet interactions using fast magic angle spinning solid-state NMR in biological solids.

    PubMed

    Pandey, Manoj Kumar; Amoureux, Jean-Paul; Asakura, Tetsuo; Nishiyama, Yusuke

    2016-08-10

    (14)N/(14)N correlations are vital for structural studies of solid samples, especially those in which (15)N isotopic enrichment is challenging, time-consuming and expensive. Although (14)N nuclei have high isotopic abundance (99.6%), there are inherent difficulties in observing (14)N/(14)N correlations due to limited resolution and sensitivity related to: (i) low (14)N gyromagnetic ratio (γ), (ii) large (14)N quadrupolar couplings, (iii) integer (14)N spin quantum number (I = 1), and (iv) very weak (14)N-(14)N dipolar couplings. Previously, we demonstrated a proton-detected 3D (14)N/(14)N/(1)H correlation experiment at fast magic angle spinning (MAS) on l-histidine·HCl·H2O utilizing a through-bond (J) and residual dipolar-splitting (RDS) based heteronuclear multiple quantum correlation (J-HMQC) sequence mediated through (1)H/(1)H radio-frequency driven recoupling (RFDR). As an extension of our previous work, in this study we show the utility of dipolar-based HMQC (D-HMQC) in combination with (1)H/(1)H RFDR mixing to obtain sensitivity enhanced (14)N/(14)N correlations in more complex biological solids such as a glycyl-l-alanine (Gly-l-Ala) dipeptide, and parallel (P) and antiparallel (AP) β-strand alanine tripeptides (P-(Ala)3 and AP-(Ala)3, respectively). These systems highlight the mandatory necessity of 3D (14)N/(14)N/(1)H measurements to get (14)N/(14)N correlations when the amide proton resonances are overlapped. Moreover, the application of long selective (14)N pulses, instead of short hard ones, is shown to improve the sensitivity. Globally, we demonstrate that replacing J-scalar with dipolar interaction and hard- with selective-(14)N pulses allows gaining a factor of ca. 360 in experimental time. On the basis of intermolecular NH/NH distances and (14)N quadrupolar tensor orientations, (14)N/(14)N correlations are effectively utilized to make a clear distinction between the parallel and antiparallel arrangements of the β-strands in (Ala)3 through the

  13. 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

    NASA Astrophysics Data System (ADS)

    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, nJCF- and nJFF-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 nJCF- and nJFF-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 facilitate the

  14. 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.

  15. 1H and 13C NMR spectral study of some 3,5-bis[(E)-thienylmethylene]piperidin-4-ones

    NASA Astrophysics Data System (ADS)

    Rajeswari, K.; Pandiarajan, K.

    2011-03-01

    1H and 13C NMR spectra have been recorded for 3,5-bis[(E)-thienylmethylene]piperidin-4-one ( 1a), 3',3″-dimethyl-3,5-bis[(E)-thienylmethylene]piperidin-4-one ( 1b), 5',5″-dibromo-3,5-bis[(E)-thienylmethylene]piperidin-4-one ( 1c), their 1-methyl derivatives 2a- c and 3,5-bis[(E)-thienylmethylene]-2r,6c-diphenylpiperidin-4-one ( 3a). For selected compounds 2D spectra have been recorded. The spectral data are used to study the configuration and conformation of these molecules. The chemical shifts are discussed in light of steric, electronic and magnetic anisotropic effects. The magnetic anisotropic effects of thiophene ring and phenyl group are noteworthy. 1H- 1H COSY spectrum of 2b suggests that long-range 1H- 1H coupling, up to seven bonds, is possible in it. HMBC spectrum of 2b displays the magnetic nonequivalence of C-2 and C-6 and protons at these carbons.

  16. 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. PMID:20818806

  17. Chemical constituents from Inonotus obliquus and their biological activities.

    PubMed

    Liu, Chao; Zhao, Cui; Pan, Hong-Hui; Kang, Jie; Yu, Xiong-Tao; Wang, Hong-Qing; Li, Bao-Ming; Xie, Yi-Zhen; Chen, Ruo-Yun

    2014-01-24

    Seven new triterpenes, inonotusol A-G (1-7), one new diterpene, inonotusic acid (8), and 22 known compounds were isolated from Inonotus obliquus. Their structures were elucidated on the basis of spectroscopic analysis, including homonuclear and heteronuclear correlation NMR ((1)H-(1)H COSY, ROESY, HSQC, and HMBC) experiments. In in vitro assays, compounds 6 and 8-16 showed hepatoprotective effects against d-galactosamine-induced WB-F344 cell damage, with inhibitory effects from 34.4% to 81.2%. Compounds 7, 17, and 18 exhibited selective cytotoxicities against KB, Bel-7402, or A-549 cell lines. Compounds 16 and 17 showed inhibitory effects against protein tyrosine kinases, with IC50 values of 24.6 and 7.7 μM, respectively. PMID:24359303

  18. Antiproliferative Cardenolide Glycosides of Elaeodendron alluaudianum from the Madagascar Rainforest1

    PubMed Central

    Hou, Yanpeng; Cao, Shugeng; Brodie, Peggy; Callmander, Martin; Ratovoson, Fidisoa; Randrianaivo, Richard; Rakotobe, Etienne; Rasamison, Vincent E.; Rakotonandrasana, Stephan; TenDyke, Karen; Suh, Edward M.; Kingston, David G. I.

    2010-01-01

    Bioassay-guided fractionation of an ethanol extract of a Madagascar collection of Elaeodendron alluaudianum led to the isolation of two new cardenolide glycosides (1 and 2). The 1H and 13C NMR spectra of both compounds were fully assigned using a combination of 2D NMR experiments, including 1H-1H COSY, HSQC, HMBC, and ROESY sequences. Both compounds 1 and 2 were tested against the A2780 human ovarian cancer cell line and the U937 human histiocytic lymphoma cell line assays, and showed significant antiproliferative activity with IC50 values of 0.12 and 0.07 μM against the A2780 human ovarian cancer cell line, and 0.15 and 0.08 μM against the U937 human histiocytic lymphoma cell line, respectively. PMID:19058971

  19. 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).

  20. New antioxidant bibenzyl derivative and isoflavonoid from the Tunisian Salsola tetrandra Folsk.

    PubMed

    Beyaoui, Ahlem; Chaari, Atef; Ghouila, Hatem; Ali Hamza, M'hamed; Ben Jannet, Hichem

    2012-01-01

    Two new phytochemical compounds, Tetranins A and B, 1-(3,5'-dihydroxy-4'-méthoxyphenyl)-2-phenylethanol 1 and 5,2'-dihydroxy-5'-methoxy-6,7-methylenedioxy-isoflavone 2, were isolated from the EtOAc extract of Salsola tetrandra roots. They exhibited a significant antioxidant effect in 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical and 2,2'-azinobis (3-ethylbenzothiazoline-6-sulphonic acid (ABTS) assays. Their structures were elucidated by extensive spectroscopic methods including 1-D-((1)H and (13)C) and 2-D-NMR experiments (CHcorr, HMBC, (1)H-(1)H COSY and NOESY) as well as high-resolution ES-MS and they were found to be quite active as antioxidants in the DPPH and ABTS assays. PMID:21834645

  1. Bis-spirolabdane Diterpenoids from Leonotis nepetaefolia

    PubMed Central

    Li, Jun; Fronczek, Frank R.; Ferreira, Daneel; Burandt, Charles L.; Setola, Vincent; Roth, Bryan L.; Zjawiony, Jordan K.

    2012-01-01

    Ten new bis-spirolabdane diterpenoids, leonepetaefolins A–E (1, 3, 5, 7, 9) and 15-epi-leonepetaefolins A-E (2, 4, 6, 8, 10), together with eight known labdane diterpenoids (11–18) as well as two known flavonoids apigenin and cirsiliol, were isolated from the leaves of Leonotis nepetaefolia. The structures of the new compounds were determined on the basis of 1D-and 2D-NMR experiments including 1H, 13C, DEPT, 1H-1H COSY, HSQC, HMBC, and NOESY. The absolute configuration of an epimeric mixture of 1 and 2 was determined by X-ray crystallographic analysis. The compounds isolated were evaluated for their binding propensity in several CNS G protein-coupled receptor assays in vitro. PMID:22475308

  2. Synthesis, characterization and fluorescence studies of novel bi-phenyl based acrylate and methacrylate

    NASA Astrophysics Data System (ADS)

    Baskar, R.; Subramanian, K.

    2011-09-01

    4-[(1 E)-3-(biphenyl-4-yl)buta-1,3-dien-1-yl]phenyl prop-2-enoate ( ACH) and 4-[(1 E)-3-(biphenyl-4-yl)buta-1,3-dien-1-yl]phenyl 2-methylprop-2-enoate ( MCH) was synthesized from biphenyl in three steps and their structures were confirmed by elemental analysis, IR, NMR ( 1H, 13C, DEPT135, 1H- 1H COSY, 1H- 13C HSQC and 1H- 13C HMBC) spectroscopic techniques. In this present study, various physicochemical characteristics we demonstrate solubility, color, absorbance and fluorescence property of novel biphenyl based acrylate and methacrylate measured in different solvents like benzene, dichloromethane, tetrahydrofuran, acetonitrile, dimethylsulfoxide and ethanol.

  3. Zebiriosides A-L, oleanane saponins from the roots of Dendrobangia boliviana.

    PubMed

    Zebiri, Ilhem; Haddad, Mohamed; Duca, Laurent; Harakat, Dominique; Cabanillas, Billy; Paloque, Lucie; Scandolera, Amandine; Sauvain, Michel; Rengifo, Elsa; Voutquenne-Nazabadioko, Laurence

    2016-10-01

    Twelve oleanane saponins, zebiriosides A-L, were isolated from the roots of Dendrobangia boliviana Rusby, together with two known saponins, talunùmoside I and 3-O-β-d-glucuronopyranosyl serjanic acid. These saponins are glycosides of serjanic or phytolaccinic acid. Their structures were established on two basis: first, their spectral data, mainly HR-TOFESIMS, 1D-NMR ((1)H, (13)C, DEPT) and 2D-NMR ((1)H(1)H COSY, TOCSY, HSQC, HMBC, and ROESY), and second by comparison with literature data. These compounds were evaluated for their cytotoxic, antileishmanial and hemolytic activities. No antileishmanial or hemolytic activities were revealed, however zebirioside C and zebirioside I showed cytotoxicity against fibroblasts with IC50 of 6.4 and 5.6 μM, respectively. PMID:27358036

  4. [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). PMID:11596188

  5. 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. PMID:25128674

  6. 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. PMID:24014305

  7. Dereplication of natural products using minimal NMR data inputs.

    PubMed

    Williams, Russell B; O'Neil-Johnson, Mark; Williams, Antony J; Wheeler, Patrick; Pol, Rostislav; Moser, Arvin

    2015-10-21

    A strategy for the dereplication of a complete or a partial structure using (1)H NMR, (1)H-(13)C HSQC and (1)H-(1)H COSY spectral data, a molecular formula composition range and structural fragments against a massive database of about 22 million compounds is considered. As the increasing availability of public online databases containing natural products continues to grow the potential of utilizing these resources for dereplication purposes increases. This work examines approaches for NMR dereplication of natural products and includes a comparison with approaches for molecular formula and mass-based dereplication. The strategy is an application of computer-assisted structure elucidation using ACD/Structure Elucidator and data obtained from the ChemSpider database hosted by the Royal Society of Chemistry. PMID:26381222

  8. Chemical Constituents of Lecythispisonis (Lecythidaceae)--A New Saponin and Complete 1H and 13C Chemical Shift Assignments.

    PubMed

    Duarte, Rennê C; Matos, Carlos R R; Braz-Filho, Raimundo; Mathias, Leda

    2015-06-01

    A novel triterpenoid saponin 3-O-β-D-glucuronopyranosyl-(1' --> 3)-2α,19α-dihydroxyolean-12-en-28-oic acid [3-O-β-D-glucuronopyranosyl-(1' --> 3)-arjunic acid, 1], ten known compounds [six triterpenoids: α-amyrin (2), β-amyrin (3), germanicol (4), lupeol (5), friedelin (6), friedelanol (7); four steroids--campesterol (8), stigmasterol (9), sitosterol (10), cholesterol (11)], and a long chain alcohol n-eicosan-1-ol (12) were identified in the bark of Lecythis pisonis. The structures were established by 1D and 2D NMR spectroscopy (1H and 13C-NMR, DEPTQ, 1H-1H-COSY, NOESY, HSQC and HMBC), low (CG-MS) and high resolution mass spectrometry (HR-ESI-MS), and infrared (IR) spectral data involving comparison with the literature. PMID:26197504

  9. Trifasciatosides A-J, Steroidal Saponins from Sansevieria trifasciata.

    PubMed

    Teponno, Rémy Bertrand; Tanaka, Chiaki; Jie, Bai; Tapondjou, Léon Azefack; Miyamoto, Tomofumi

    2016-01-01

    Four previously unreported steroidal saponins, trifasciatosides A-D (1-4), three pairs of previously undescribed steroidal saponins, trifasciatosides E-J (5a, b-7a, b) including acetylated ones, together with twelve known compounds were isolated from the n-butanol soluble fraction of the methanol extract of Sansevieria trifasciata. Their structures were elucidated on the basis of detailed spectroscopic analysis, including (1)H-NMR, (13)C-NMR, (1)H-(1)H correlated spectroscopy (COSY), heteronuclear single quantum coherence (HSQC), heteronuclear multiple bond connectivity (HMBC), total correlated spectroscopy (TOCSY), nuclear Overhauser enhancement and exchange spectroscopy (NOESY), electrospray ionization-time of flight (ESI-TOF)-MS and chemical methods. Compounds 2, 4, and 7a, b exhibited moderate antiproliferative activity against HeLa cells. PMID:27581639

  10. Developing SABRE as an analytical tool in NMR

    NASA Astrophysics Data System (ADS)

    Lloyd, Lyrelle Stacey

    Work presented in this thesis centres around the application of the new hyperpolarisation technique, SABRE, within nuclear magnetic resonance spectroscopy, focusing on optimisation of the technique to characterise small organic molecules. While pyridine was employed as a model substrate, studies on a range of molecules are investigated including substituted pyridines, quinolines, thiazoles and indoles are detailed. Initial investigations explored how the properties of the SABRE catalyst effect the extent of polarisation transfer exhibited. The most important of these properties proved to be the rate constants for loss of pyridine and hydrides as these define the contact time of pyridine with the parahydrogen derived hydride ligands in the metal template. The effect of changing the temperature, solvent or concentration of substrate or catalyst are rationalised. For instance, the catalyst ICy(a) exhibits relatively slow ligand exchange rates and increasing the temperature during hyperpolarisation increases the observed signal enhancements. These studies have revealed a second polarisation transfer template can be used with SABRE in which two substrate molecules are bound. This allows the possibility of investigation of larger substrates which might otherwise be too sterically encumbered to bind. Another significant advance relates to the first demonstration that SABRE can be used in conjunction with an automated system designed with Bruker allowing the acquisition of scan averaged, phase cycled and traditional 2D spectra. The system also allowed investigations into the effect of the polarisation transfer field and application of that knowledge to collect single-scan 13C data for characterisation. The successful acquisition of 1H NOESY, 1H-1H COSY, 1H-13C 2D and ultrafast 1H-1H COSY NMR sequences is detailed for a 10 mM concentration sample, with 1H data collected for a 1 mM sample. A range of studies which aim to demonstrate the applicability of SABRE to the

  11. Synthesis and spectroscopic characterization of super-stable rhenium(V)porphyrins

    NASA Astrophysics Data System (ADS)

    Bichan, N. G.; Tyulyaeva, E. Yu.; Khodov, I. A.; Lomova, T. N.

    2014-03-01

    The preparation of rhenium(V) porphyrin complexes {μ-oxo-bis[(oxo)(5,10,15,20-tetraphenyl-21H,23H-porphinato)rhenium(V)] [OReTPP]2O (1), (oxo)(phenoxo)(2,3,7,8,12,13,17,18-octaethyl-5-monophenyl-21H,23H-porphinato)rhenium(V) ORe(PhO)MPOEP (2), (cloro)(oxo)(2,3,7,8,12,13,17,18-octaethyl-5,15-diphenyl-21H,23H-porphinato)rhenium(V) ORe(Cl)5,15DPOEP (4), and (oxo)(phenoxo)(2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphinato)rhenium(V) ORe(PhO)OEP (5)} by the interaction of H2ReCl6 with corresponding porphyrin in boiling phenol is described. (Cloro)(oxo)(2,3,7,8,12,13,17,18-octaethyl-5-monophenyl-21H,23H-porphinato)rhenium(V) ORe(Cl)MPOEP (3) and (oxo)(chloro)(2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphinato)rhenium(V) ORe(Cl)OEP (6) have been prepared by the reaction of axial-ligand substitution from (2) and (5), respectively. Compounds (2-4) were newly synthesized. Characterization of the compounds (1-6) reported herein was made mainly by UV-Visible, IR, 1Н NMR, 1H1H 2D COSY, 1H1H 2D DOSY, 1H1H 2D ROESY, 1H1H 2D TOCSY spectroscopic techniques and elemental analysis. The stability of the complexes in solutions when exposed to strong acids at the presence of atmospheric oxygen has been estimated. Compounds (2-4) and (6) show them super-stable since they do not undergo dissociation along MN bonds in concentrated H2SO4 under heating up to 363 K. Compounds (3) and (4) undergo one-electron oxidation to form stable π-cation radicals ORe(HSO)P under these conditions. The products of the reaction between all studied porphyrins and concentrated H2SO4 were isolated in CHCl3 by reprecipitation onto ice and proved to be rhenium(V) complexes ORe(HSO4)P.

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

    NASA Astrophysics Data System (ADS)

    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

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

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2016-01-21

    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 (1)H/(13)C/(1)H 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 (13)C/(1)H and (13)C/(13)C chemical shift correlations, the 3D (1)H/(13)C/(1)H experiment also provides a COSY-type (1)H/(1)H 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 ((1)H/(1)H chemical shift correlation spectrum) at different (13)C chemical shift frequencies from the 3D (1)H/(13)C/(1)H 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 (1)H/(13)C/(1)H experiment would be useful to study the structure and dynamics of

  14. A new coumarin from the fruits of Coutarea hexandra.

    PubMed

    Olmedo, D; Rodríguez, N; Vásquez, Y; Solís, P N; López-Pérez, J L; Feliciano, A San; Gupta, M P

    2007-06-01

    A new 5-O-beta-D-glucopyranosyl-4-(4-hydroxyphenyl)-7-methoxy-2H-chromen-2-one (1), together with four known compounds, one coumarin, 5-O-beta-D-galactopyranosyl-4-(4-hydroxyphenyl)-7-methoxy-2H-chromen-2-one (2) and three cucurbitacins, 23,24-dihydrocucurbitacin F (3), 23,24-dihydro-25-acetylcucurbitacin F (4) and 2-O-beta-D-glucopyranosyl-23,24-dihydrocucurbitacin F (5) have been isolated and characterised from the ethanol extract of Coutarea hexandra fruits. Their structures have been established by spectroscopic analysis (NMR and MS). Interpretation of the HMQC, HMBC, COSY-45 and NOESY experiments permitted us to establish stereochemistry of the natural products. All compounds were tested in cytotoxicity assays against the breast (MCF-7), lung (H-460), and central nervous system (SF-268) human cancer cell lines. PMID:17613820

  15. New potent P-glycoprotein modulators with the cucurbitane scaffold and their synergistic interaction with doxorubicin on resistant cancer cells.

    PubMed

    Ramalhete, Cátia; Molnár, Joseph; Mulhovo, Silva; Rosário, Virgílio E; Ferreira, Maria-José U

    2009-10-01

    The novel cucurbitacins, balsaminagenin A and B (1-2) and balsaminoside A (3) and the know cucurbitacin karavelagenin C (4), together with five new mono or diacylated derivatives (5-9) of karavelagenin C were evaluated for multidrug resistance reversing activity on human MDR1 gene transfected mouse lymphoma cells. Compounds 2-6 exhibited a strong activity compared with that of the positive control, verapamil. Structure-activity relationships are discussed. Moreover, in the checkerboard model of combination chemotherapy, the interaction between doxorubicin and compounds 2-5 synergistically enhanced the effect of the anticancer drug. Compounds 1-4 were isolated from the aerial parts of Momordica balsamina L. The structures of the compounds were established on the basis of spectroscopic methods including 2D NMR experiments (COSY, HMQC, HMBC and NOESY). PMID:19733087

  16. Heteroglycan from an alkaline extract of a somatic hybrid mushroom (PfloVv1aFB) of Pleurotus florida and Volvariella volvacea: structural characterization and study of immunoenhancing properties.

    PubMed

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

    2012-06-01

    A water soluble heteroglycan, isolated from the alkaline extract of the fruit bodies of the somatic hybrid mushroom (PfloVv1aFB), raised through protoplast fusion between the strains of Pleorutus florida and Volverilla volvacea, was found to consist of (1→3)-, (1→6)-, (1→3,4)-linked, and terminal β-D-Glcp along with (1→2,6)-α-D-Galp and terminal α-D-Manp in a relative proportion of approximately 1:1:1:1:1:1. This polysaccharide exhibited strong immunostimulating activity of macrophages as well as splenocytes and thymocytes. Structural investigation was carried out using sugar analysis, methylation analysis; periodate oxidation study, and NMR experiments ((1)H, (13)C, DEPT-135, DQF-COSY, TOCSY, NOESY, ROESY, HMQC, and HMBC). On the basis of the above mentioned experiments, the structure of the repeating unit of the polysaccharide was established as: [formula see text]. PMID:22572124

  17. Structural characterization and study of immunoenhancing properties of heteroglycan isolated from a somatic hybrid mushroom (PfloVv1aFB) of Pleurotus florida and Volvariella volvacea.

    PubMed

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

    2011-09-27

    A water soluble polysaccharide isolated from the hot aqueous extract of the fruit bodies of the somatic hybrid mushroom (PfloVv1aFB), raised through protoplast fusion between the strains of Pleurotus florida and Volvariella volvacea was found to consist of d-glucose, d-galactose, and d-mannose in a molar ratio of nearly 4:1:1 and showed macrophage, splenocyte, and thymocyte activation. 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: [structure: see text]. PMID:21742315

  18. A (1-->6)-beta-glucan from a somatic hybrid of Pleurotus florida and Volvariella volvacea: isolation, characterization, and study of immunoenhancing properties.

    PubMed

    Das, Debsankar; Mondal, Subhas; Roy, Sadhan K; Maiti, Debabrata; Bhunia, Bibhas; Maiti, Tapas K; Sikdar, Samir R; Islam, Syed S

    2010-05-01

    A water-soluble immunoenhancing polysaccharide was isolated from the aqueous extract of fruit bodies of somatic hybrid (Pflo Vv5 FB), obtained through protoplast fusion between Pleurotus florida and Volvariella volvacea strains. On the basis of acid hydrolysis, the polysaccharide was found to contain glucose only. Methylation analysis, periodate oxidation along with (1)H, DEPT-135, and (13)C NMR spectroscopy, including two-dimensional TOCSY, DQF-COSY, NOESY, ROESY, 1H,13C-HMQC, and HMBC experiments showed that the polysaccharide was a (1-->6)-beta-d-glucan, which was not a constituent of any of the parent mushrooms previously reported. This glucan stimulated the macrophages, splenocytes, and thymocytes. PMID:20347070

  19. Glucans from alkaline extract of a hybrid mushroom (backcross mating between PfloVv12 and Volvariella volvacea): structural characterization and study of immunoenhancing and antioxidant properties.

    PubMed

    Sarkar, Ramsankar; Nandan, Chanchal K; Bhunia, Sanjoy K; Maiti, Swatilekha; Maiti, Tapas K; Sikdar, Samir R; Islam, Syed S

    2012-01-10

    Two different glucans (water-soluble PS-I, water-insoluble PS-II) were isolated from the alkaline extract of the fruit bodies of hybrid mushroom. PS-I was found to consist of only (1→6)-linked β-D-glucopyranose. PS-II was composed of terminal, (1→3,4)-linked, and (1→3)-linked β-D-glucopyranosyl moieties in a molar ratio of nearly 1:1:1. PS-I showed macrophages, splenocytes, and thymocytes activation as well as antioxidant property. On the basis of sugar analysis, 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 these glucans were established as: PMID:22129838

  20. Isolation and characterization of polysaccharides of a hybrid mushroom (backcross mating between PfloVv12 and Volvariella volvacea).

    PubMed

    Nandan, Chanchal K; Sarkar, Ramsankar; Bhanja, Sunil K; Sikdar, Samir R; Islam, Syed S

    2011-11-01

    Three polysaccharide fractions (PS-I, PS-II, and PS-III) were isolated from the aqueous extract of a hybrid mushroom obtained through backcross mating of a somatic hybrid mushroom PfloVv12 (Sterile line) with Volvariella volvacea. PfloVv12 was obtained through protoplast fusion of Pleurotus florida and V. volvacea. PS-I was identified as 1,6-β glucan. PS-II and PS-III were identified as mannoglucogalactan but differing in molecular weights only. On the basis of total acid hydrolysis, methylation analysis, periodate oxidation, and NMR experiment ((1)H, (13)C, DEPT-135, DQF-COSY, TOCSY, NOESY, ROESY, HMQC, and HMBC) the structures of these polysaccharides were established as; PMID:21924407

  1. Apoptosis induction and modulation of P-glycoprotein mediated multidrug resistance by new macrocyclic lathyrane-type diterpenoids.

    PubMed

    Duarte, Noélia; Varga, Andras; Cherepnev, Georg; Radics, Rita; Molnár, Joseph; Ferreira, Maria-José U

    2007-01-01

    The macrocyclic lathyrane diterpenes, latilagascenes D-F (1-3) and jolkinol B (4), were isolated from the methanol extract of Euphorbia lagascae, and evaluated for multidrug resistance reversing activity on mouse lymphoma cells. All compounds displayed very strong activity compared with that of the positive control, verapamil. The structure-activity relationship is discussed. The evaluation of compounds 1 and 4, and of latigascenes A-C (5-7), isolated from the same species, as apoptosis-inducers was also carried out. Compound 1 was the most active. Furthermore, in the model of combination chemotherapy, the interaction between the doxorubicine and latilagascene B (6) was studied in vitro, on human MDR1 gene transfected mouse lymphoma cells, showing that the type of interaction was synergistic. Latilagascenes D-F (1-3) are new compounds whose structures were established on the basis of spectroscopic methods, including 2D NMR experiments (COSY, HMQC, HMBC and NOESY). PMID:17035027

  2. 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. PMID:18729043

  3. Jatrophane and ingenane-type diterpenoids from Euphorbia kansui inhibit the LPS-induced NO production in RAW 264.7 cells.

    PubMed

    Lee, Jin Woo; Jin, Qinghao; Jang, Hari; Lee, Dongho; Han, Sang Bae; Kim, Youngsoo; Hong, Jin Tae; Lee, Mi Kyeong; Hwang, Bang Yeon

    2016-07-15

    Bioactivity-guided fractionation of the MeOH extract from the roots of Euphorbia kansui resulted in the isolation of two new jatrophane-type diterpenoids, kanesulones A (1) and B (2), together with six known jatrophane-type diterpenoids (3-8) and ten known ingenane-type diterpenoids (9-18). Their chemical structures were elucidated on the basis of spectroscopic data interpretation, especially 1D and 2D NMR such as HMQC, HMBC, COSY and NOESY, and HRESIMS data as well as CD analysis. Compounds 1-8 and 11-18 exhibited the inhibitory effects on LPS-induced nitric oxide production with IC50 values ranging from 0.7 to 46.5μM in RAW 264.7 macrophages. PMID:27246615

  4. 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

    2016-01-01

    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. PMID:26861267

  5. Glycosides and xanthine oxidase inhibitors from Conyza bonariensis.

    PubMed

    Kong, L D; Abliz, Z; Zhou, C X; Li, L J; Cheng, C H; Tan, R X

    2001-10-01

    Fractionation of the xanthine oxidase inhibitory methanol extract of Conyza bonariensis afforded three glycosides, in addition to nine known compounds including amyrin, beta-sitostero1 daucosterol, syringic acid 3-hydroxy-5-methoxybenzoic acid, eugenol 4-O-glucopyranoside, and luteolin, apigenin and takakin 8-O-glucuronide. The structures of the glycosides were established by a combination of spectroscopic methods (IR, MS, 1H and 13C NMR, DEPT, COSY, HMQC and HMBC) as 4-hydroxypyridin-3-carboxylic acid 4-O-glucopyranoside, 8-hydroxy-6,7-dihydrolinalool 8-O-glucopyranoside and bonaroside [viz. 1,3,4,12-tetrahydroxy-2-(9-hexadecenoylamino)octadecane 1-O-glucopyranoside]. The in vitro enzyme assay showed that syringic acid and takakin 8-O-glucuronide displayed weak inhibitory activity against xanthine oxidase with IC50 values of 500+/-41 microM and 170+/-12 microM, respectively. PMID:11576616

  6. CT2108A and B: New fatty acid synthase inhibitors as antifungal agents.

    PubMed

    Laakso, Jodi A; Raulli, Robert; McElhaney-Feser, Gail E; Actor, Paul; Underiner, Ted L; Hotovec, Brian J; Mocek, Ursula; Cihlar, Ronald L; Broedel, Sheldon E

    2003-08-01

    A systematic screen for new natural products that displayed antifungal activity by inhibition of fungal fatty acid synthase (FAS) led to the discovery of two new fungal metabolites, designated CT2108A (1) and CT2108B (2). The metabolites were produced by Penicillium solitum (Westling) strain CT2108 and were classified as azaphilones. The structures of these new metabolites were determined using a variety of 1D and 2D NMR experiments, including COSY, HMQC, and HMBC. The chemical conversion of CT2108A to CT2108B was effected using WCl(6). The related metabolite, patulodin (3), was also isolated from the fermentation culture of this P. solitum isolate. Both new compounds inhibited fungal FAS, and neither was found to significantly inhibit human FAS activity. PMID:12932120

  7. Actinotetraose L, a new tetrasaccharide derivative isolated from the mycelia of Amycolatopsis sp. HCa1.

    PubMed

    Guo, Zhi-Kai; Yan, Wei; Tan, Ren-Xiang; Ge, Hui-Ming

    2015-01-01

    A new tetrasaccharide derivative, actinotetraose L (1), was isolated from the methanol extract of the mycelia of the grasshopper-associated rare actinobacterium Amycolatopsis sp. HCa1. The structure of the new compound was elucidated by a combination of 1D, 2D NMR (HMQC, HMBC, COSY, and NOESY), and HR-ESI-MS analyses as O-{3,4-di-O-[(E)-2-ethyl-2-butenoyl]- β-D-glucopyranosyl-(1 → 2)}-O-{3,4-di-O-[(E)-2-methyl-2-butenoyl]-β-D-glucopyranosyl-(1 → 2)}-6,6-di-O-[(E)-2-methyl-2-butenoyl]-α-D-glucopyranosyl-(1 → 1)-α-D-glucopyranoside. The immunosuppressive activity and cytotoxicity of the compound were evaluated by T-cell viability and MTT assays. Nonetheless, no significant activity was observed. PMID:26218137

  8. Phenolics and Polyphenolics from Melastomataceae Species.

    PubMed

    Serna, Diana Marcela Ocampo; Martínez, José Hipólito Isaza

    2015-01-01

    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. PMID:26404220

  9. Structural and spectral perspectives of a novel thiosemicarbazone synthesized from di-2-pyridyl ketone and 4-phenyl-3-thiosemicarbazide

    NASA Astrophysics Data System (ADS)

    Suni, V.; Prathapachandra Kurup, M. R.; Nethaji, Munirathinam

    2006-01-01

    A new thiosemicarbazone, HL is synthesized from di-2-pyridyl ketone and 4-phenyl-3-thiosemicarbazide and structurally and spectrochemically characterized. 1H NMR, 13C NMR, COSY, HMQC and IR spectra of the compound are studied and the proton magnetic resonance spectrum reveals some unprecedented observations. The thione form is predominant in the solid state, as supported by the crystal structure and IR data, while a thiol-thione equilibrium is proposed in the solution state by NMR studies. The compound crystallizes into a monoclinic lattice with space group C2/c and the ZE conformation is exhibited by the thiosemicarbazone. Intra- and intermolecular hydrogen-bonding interactions give rise to a two-dimensional packing in the crystal lattice.

  10. A new highly hydroxylated triterpene from Salvia atropatana Bunge.

    PubMed

    Habibi, Z; Cheraghi, Z; Ghasemi, S; Yousefi, M

    2012-01-01

    One new triterpenoid olean-18-ene-1β, 2α, 3β-triol (1) along with four known compounds were isolated from the chloroform extract of the aerial part of Salvia atropatana Bunge. The known compounds were two flavonoids, 5-hydroxy-7,4'-dimethoxyflavone (2) and 5-hydroxy-6,7,4'-trimethoxyflavone (3), an abietane-type diterpene namely taxodione (4) and a phytosterol namely γ -sitosterol (5). The structure of (1) was elucidated by comprehensive spectroscopic analysis including electron ionization-mass spectra (EI-MS), (1)H NMR, (13)C NMR, distortionless enhancement by polarization transfer (DEPT), H,H correlation spectroscopy (COSY), heteronuclear multiple quantum coherence (HMQC) and heteronuclear multiple bond correlation (HMBC). The structure of known compounds 2-5 were identified by comparison of their spectral data with those reported in the literature. PMID:22017660

  11. Phytochemical and biological studies of Solanum schimperianum Hochst

    PubMed Central

    Al-Oqail, Mai; Hassan, Wafaa H.B.; Ahmad, Mohammad S.; Al-Rehaily, Adnan J.

    2012-01-01

    Chemical reinvestigation of the aerial parts of Solanum schimperianum Hochst led to the isolation of ten compounds, lupeol (1), β-sitosterol (2), β-sitosterol glucoside (3), oleanolic acid (4), teferidin (5), teferin (6), ferutinin (7), 5-hydroxy-3,7,4′-trimethoxyflavone (8), retusin (9) and kaempferol-3-O-β-d-glucopyranoside (10). Compounds 5–7 were isolated for the first time from Solanaceae and compounds 1–4 and 8–9 for the first time from Solanum schimperianum. The structure elucidation of the isolated compounds was based on careful inspection of spectral data including 1D (1H and 13C NMR), 2D (1H–H COSY, HMQC and HMBC, ROESY), UV, MS and IR, in addition to, comparison with literatures. The antimicrobial activity of the extracts as well as the isolated compounds was tested. Only hexane extract showed activity against Bacillus subtilus and Staphylococcus aureus. PMID:23960812

  12. (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

  13. Antibacterial Colorants: Characterization of Prodiginines and Their Applications on Textile Materials

    PubMed Central

    Alihosseini, Farzaneh; Ju, Kou-San; Lango, Jozsef; Hammock, Bruce D.; Sun, Gang

    2010-01-01

    A strain of Vibrio sp. isolated from marine sediments produced large quantities of bright red pigments that could be used to dye many fibers including wool, nylon, acrylics, and silk. Characterization of the pigments by electrospray ionization mass spectrometry (ESI-MS) and nuclear magnetic resonance (NMR) revealed three prodiginine-like structures with nonpolar characteristics and low molecular mass. UV–visible spectra of the major constituent in methanol solution showed absorbance at λmax 530 nm wavelength. The accurate mass result showed that the main isolated product has a molecular mass of m/z 323.1997. Further analysis using mass fragmentation (MS/MS), 1H NMR, COSY, HMQC NMR and DEPT confirmed the detailed structure of the pigment with an elementary composition of C20H25N3O. Fabrics dyed with the microbial prodiginines demonstrated antibacterial activity. PMID:18484779

  14. 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. PMID:22245841

  15. 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

  16. 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

    2013-01-01

    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

  17. 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. PMID:24685507

  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. PMID:22266390

  19. A New Monoterpenoid and a New Flavonoid Glycoside from the Peels of Clausena lansium.

    PubMed

    Deng, Hui-Dong; Cai, Cai-Hong; Liu, Shuai; Zeng, Yan-Bo; Mei, Wen-Li; He, Fan; Hua, Min; Dai, Hao-Fu; Li, Shao-Peng

    2016-05-01

    One new monoterpenoid, nerol oxide-8-carboxylic acid (1), and one new flavonoid glycoside, claulansoside A (2), together with six known compounds, clausenamide (3), quercetin (4), isorhamnetin (5), dihydromyric (6), 2",3"-dihydroxyanisolactone (7) and (E,E)-8-(7-hydroxy-3,7-dimethylocta-2,5-dienyloxy)psoralen (8), have been isolated from the peels of Clausena lansium (Lour.) Skeels. Their structures were determined using a combination of 1D, and 2D NMR (HMQC, HMBC, COSY and NOESY) techniques, and HR-ESI-MS analyses. Compounds 1 and 7 exhibited antibacterial activity against Staphylococcus aureus with the diameter of inhibition zones of 11.5 mm and 14.2 mm. Compounds 3 and 6 showed α-glucosidase inhibitory activity in vitro. PMID:27319119

  20. Investigation of olefinic structures in class I resinites by isolation and characterization of soluble polylabdanoids

    SciTech Connect

    Clifford, D.J.; Botto, R.E.; Anderson, K.B.

    1996-10-01

    Resinites derived from labdatriene structures (Class I) are ubiquitous throughout the geosphere. A soluble polylabdanoid material has been isolated by sequential extraction with organic solvents. Solid- and liquid-state NMR spectroscopy, and Py-GC-MS, indicate that at least for immature resinites, the extractable polymer is representative of the insoluble, polylabdanoid material, which constitutes the bulk of most Class I resinites. With increasing maturity, the dominant chemical transformation that occurs in these materials is the {open_quotes}loss{close_quotes} of exomethylene structures and depletion of olefinic character from {approximately}two to {approximately}one olefin per monomer unit. To investigate the fate of olefinic structures and to determine the nature of the residual olefin distribution in these materials, two-dimensional NMR correlation spectroscopies (COSY and HMQC) and nuclear Overhauser experiments (NOESY) have been undertaken. Results from these analyses and their implications to the maturation of Class-I resinites will be discussed.

  1. Tetranortriterpenes and Limonoids from the Roots of Aphanamixis polystachya.

    PubMed

    Lin, Ching-Jie; Lo, I-Wen; Lin, Yu-Chi; Chen, Shun-Ying; Chien, Ching-Te; Kuo, Yao-Haur; Hwang, Tsong-Long; Liou, Shorong-Shii; Shen, Ya-Ching

    2016-01-01

    Phytochemical investigation of the acetone extract from the roots of Aphanamixis polystachya resulted in isolation of four new tetranortriterpenes (1-4) in addition to one protolimonoid (methyl-1ξ,7R-diacetoxy-23R,25-dihydroxy-20S,24R-21,24-epoxy-3,4-seco-apotirucall-4(28),14(15)-diene-3-oate (5)), five known limonoids (rohituka 3 (6), rohituka 7 (7), nymania 1 (8), rubrin G (9), prieurianin (10)) and a steroid (2,3-dihydroxy-5-pregnan-16-one (11)). Their structures were determined by spectroscopic analyses, including 2D-NMR (COSY, HMQC, HMBC, and NOESY) and high-resolution electrospray ionization mass spectrometry (HRESIMS). Cytotoxic and anti-inflammatory activities of these compounds were evaluated. Compounds 4 and 5 showed significant inhibition against superoxide generation and elastase release by human neutrophils in response to (formyl-l-methionyl-l-leucyl-l-phenylalanine/cytochalasin B) (FMLP/CB). PMID:27598114

  2. 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.

  3. NMR study of thymulin, a lymphocyte differentiating thymic nonapeptide. Conformational states of free peptide in solution.

    PubMed

    Laussac, J P; Cung, M T; Pasdeloup, M; Haran, R; Marraud, M; Lefrancier, P; Dardenne, M; Bach, J F

    1986-06-15

    The nonapeptide less than Glu-Ala-Lys-Ser-Gln-Gly-Gly-Ser-Asn (formerly called serum thymic factor) is a factor produced by the thymic epithelium, which needs a zinc ion to express its immunoregulatory properties. We report here on 1H and 13C NMR investigation of the conformational properties of the free peptide in aqueous medium and in dimethyl sulfoxide-d6 solution by a combination of homo- and heteronuclear one- and two-dimensional experiments. The various resonances have been assigned in a straightforward manner on the basis of 1H,1H COSY spectroscopy for the recognition of the proton spin systems; two-dimensional NOESY spectra with the correlation peaks across amide bonds and for the amino acid sequence assignment; amide bonds and for the amino acid sequence assignment; 13C,1H COSY experiments using selective polarization transfer from 1H- to 13C-nucleus via the 13C,1H long-range couplings for the attribution of the carboxyl and carbonyl groups; and 13C,1H COSY experiments with selective polarization transfer via the 13C,1H direct couplings for the assignment of all the aliphatic carbons. Other experiments such as pH-dependent chemical shifts, combined use of multiple and selective proton-decoupled 1H and 13C NMR spectra, the temperature and the concentration dependence of the proton shifts of the amide resonances, the solvent dependences of peptide carbonyl carbon resonances, and comparison of the spectra with three different analogues were performed. In aqueous solution, the data are compatible with the assumption of a highly mobile dynamic equilibrium among different conformations, whereas in dimethyl sulfoxide-d6, a more rigid structure is found involving three internal hydrogen bonds. These observations provide an insight into the conformational tendencies of this peptidic hormone in two different media. PMID:3711109

  4. Materials Data on Ce2CoSi3 (SG:191) 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

  5. 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.

  6. Texture of CoSi2 Films on Si(111) (110) and (001) Substrates

    SciTech Connect

    K De Keyser; C Detavernier; J Jordan-Sweet; C Lavoie

    2011-12-31

    Synchrotron radiation was used to study the texture of polycrystalline CoSi{sub 2} films that were formed by a solid-state reaction between a 30 nm Co film and Si(111), (110) and (001) substrates. All films were strongly textured, and several texture components were identified. We discuss the simultaneous occurrence of axiotaxy (i.e. alignment of lattice planes across the interface) and several different types of epitaxy in each of the films. Comparison of the different texture components observed on the three substrate orientations suggests a strong preference for the alignment of CoSi{sub 2}{l_brace}110{r_brace} planes in the film with Si{l_brace}110{r_brace} planes in the substrate, and twinning around Si[111] directions.

  7. Microstructural evolution during containerless rapid solidification of Co-Si alloys

    NASA Astrophysics Data System (ADS)

    Yao, Wen-Jing; Wei, Bing-Bo

    2003-11-01

    The Co-12%Si hypoeutectic, Co-12.52%Si eutectic and Co-13%Si hypereutectic alloys are rapidly solidified in a containerless environment in a drop tube. Undercoolings up to 207K (0.14TE) are obtained, which play a dominant role in dendritic and eutectic growth. The coupled zone around Co-12.52%Si eutectic alloy has been calculated, which covers a composition range from 11.6 to 12.7%Si. A microstructural transition from lamellar eutectic to divorced eutectic occurs to Co-12.52%Si eutectic droplets with increasing undercooling. The lamellar eutectic structure of the Co-12.52%Si alloy consists of varepsilonCo and Co3Si phases at small undercooling. The Co3Si phase cannot decompose completely into varepsilonCo and alphaCo2Si phases. As undercooling becomes larger, the Co3Si phase grows very rapidly from the highly undercooled alloy melt to form a divorced eutectic. The structural morphology of the Co-12%Si alloy droplets transforms from varepsilonCo primary phase plus lamellar eutectic to anomalous eutectic, whereas the microstructure of Co-13%Si alloy droplets experiences a `dendritic to equiaxed' structural transition. No matter how large the undercooling is, the varepsilonCo solid solution is the primary nucleation phase. In the highly undercooled alloy melts, the growth of varepsilonCo and Co3Si phases is controlled by solutal diffusion.

  8. 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. PMID:19011659

  9. Localized 2D COSY sequences: Method and experimental evaluation for a whole metabolite quantification approach

    NASA Astrophysics Data System (ADS)

    Martel, Dimitri; Tse Ve Koon, K.; Le Fur, Yann; Ratiney, Hélène

    2015-11-01

    Two-dimensional spectroscopy offers the possibility to unambiguously distinguish metabolites by spreading out the multiplet structure of J-coupled spin systems into a second dimension. Quantification methods that perform parametric fitting of the 2D MRS signal have recently been proposed for resolved PRESS (JPRESS) but not explicitly for Localized Correlation Spectroscopy (LCOSY). Here, through a whole metabolite quantification approach, correlation spectroscopy quantification performances are studied. The ability to quantify metabolite relaxation constant times is studied for three localized 2D MRS sequences (LCOSY, LCTCOSY and the JPRESS) in vitro on preclinical MR systems. The issues encountered during implementation and quantification strategies are discussed with the help of the Fisher matrix formalism. The described parameterized models enable the computation of the lower bound for error variance - generally known as the Cramér Rao bounds (CRBs), a standard of precision - on the parameters estimated from these 2D MRS signal fittings. LCOSY has a theoretical net signal loss of two per unit of acquisition time compared to JPRESS. A rapid analysis could point that the relative CRBs of LCOSY compared to JPRESS (expressed as a percentage of the concentration values) should be doubled but we show that this is not necessarily true. Finally, the LCOSY quantification procedure has been applied on data acquired in vivo on a mouse brain.

  10. Formation of CoSi sub 2 in SIMOX wafers by high dose Co implantation

    SciTech Connect

    Sjoreen, T.P. Kernforschungsanlage Juelich GmbH . Inst. fuer Schicht- und Ionentechnik); Jebasinski, R.; Schmidt, K.; Mantl, S. . Inst. fuer Schicht- und Ionentechnik); Holzbrecher, H.; Speier, W. . Zentralabteilung fuer Chemische Analysen)

    1991-01-01

    SIMOX wafers have been implanted with high doses of Co and annealed at high temperatures in order to study the formation of buried single-crystal CoSi{sub 2} layers in this material. For this study SIMOX wafers of (100) oriented Si were implanted at 100--200 keV with doses of 1.2 {minus} 2.0 {times} 10{sup 17} Co{sup +}/cm{sup 2}, and annealed in rapid thermal processor or tube furnace. As-implanted and annealed samples were analyzed by Rutherford backscattering/channeling spectroscopy (RBS), cross-sectional transmission electron microscopy (XTEM), secondary ion mass spectroscopy, and the Van der Pauw technique. The best buried CoSi{sub 2} layers were obtained at an implantation energy of 100 keV and by subsequent RTA. RBS minimum yields of {approximately}6% were obtained for the buried layer, this is the same as that reported for bulk (100) Si. The measured resistivity of 15 {mu}{Omega}-cm and XTEM confirmed the continuity of the layer. Buried CoSi{sub 2} layers were successfully produced up to an implantation energy of 180 keV. However, as the energy was increased the quality of the CoSi{sub 2} layer degraded, with minimum yields increasing to 24% at 180 keV, and with a corresponding degradation in the minimum yields in the top Si layer. At 200 keV a buried epitaxial layer was not produced. The degradation of crystal quality with ion implantation energy and the failure to produce a buried layer at 200 keV are discussed. 11 refs., 4 figs.

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

    SciTech Connect

    Nikolaev, Nikolai; Pavlov, Fyodor

    2008-04-30

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

  12. 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.

  13. Femtosecond laser heat affected zones profiled in Co/Si multilayer thin films

    SciTech Connect

    Picard, Yoosuf N.; Yalisove, Steven M.

    2008-01-07

    In this letter, we describe an approach for assessing collateral thermal damage resulting from high intensity, femtosecond laser irradiation. Polycrystalline Co thin films deposited on Si (100) substrates and buried under an amorphous Si film were prepared for plan-view transmission electron microscopy (TEM) prior to laser irradiation by femtosecond laser pulses. A heat affected zone (HAZ) resulting from single pulse irradiation at a fluence of 0.9 J/cm{sup 2} was determined by TEM imaging and point-wise selected area diffraction. The spatially Gaussian laser pulse generated a HAZ extending up to 3 {mu}m radially from the femtosecond laser irradiated region.

  14. 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.

  15. New acylated anthocyanins and other flavonoids from the red flowers of Clematis cultivars.

    PubMed

    Hashimoto, Masanori; Suzuki, Toshisada; Iwashina, Tsukasa

    2011-11-01

    Six new acylated cyanidin glycosides, cyanidin 3-O-beta-(2''-E-caffeoylglucopyranosyl)-(1 --> 2)-O-beta-galactopyranoside (1), cyanidin 3-O-beta-(2''-E-caffeoylglucopyranosyl)-(1 --> 2)-O-beta-(6''-malonylgalactopyranoside) (2), cyanidin 3-O-beta-(2''-E-caffeoylglucopyranosyl)-(1 --> 2)-O-beta-(6''-succinylgalactopyranoside) (3), cyanidin 3-O-beta-(2''-E-caffeoylglucopyranosyl)-(1 --> 2)-O-beta-galactopyranoside-3''- O-beta-glucuronopyranoside (4), cyanidin 3-O-beta-(2''-E-caffeoylglucopyranosyl)-(1 --> 2)-O-beta-(6''-malonylgalactopyranoside)-3'-O-beta-glucuronopyranoside (5), and cyanidin 3-O-beta-(2'-E-feruloylglucopyranosyl)-(1 --> 2)-O-beta-(6''-malonylgalactoside)-3' -O-beta-glucuronopyranoside (6), were isolated from the red flowers of two Clematis cultivars, 'Niobe'and 'Madame Julia Correvon'. The chemical structures of the isolated anthocyanins were determined by UV, LC-MS, HPLC, TLC, characterization of hydrolysates, and 1H and 13C NMR spectroscopy, including H-H COSY, C-H COSY, HMBC, HMQC and NOESY. The last three anthocyanins were widely distributed in 37 red flower Clematis cultivars. On the other hand, the first three compounds were found only in two cultivars. Five known flavonol glycosides, kaempferol 3-O-glucoside, kaempferol 3-O-rutinoside, quercetin 3-O-galactoside, quercetin 3-O-glucoside and quercetin 3-O-rutinoside, were isolated from the flowers of'Madame Julia Correvon'. PMID:22224277

  16. 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

  17. [Chemical constituents of Dipsacus asper].

    PubMed

    Wang, Qiang; Liu, Er-Wei; Han, Li-Feng; Zhang, Yi

    2013-07-01

    To study the chemical constituents of Dipsacus asper, chromatographic methods such as D101 macroporous resin, silica gel, octadecylsilyl (ODS) column chromatographic techniques and preparative HPLC were used, and five compounds were isolated from 70% (v/v) ethanol extract of the plant. By using spectroscopic techniques including 1H NMR, 13C NMR, 1H-1H COSY, HSQC, HMBC and TOF-MS, the compounds were identified as 3beta-hydroxy-24-nor-urs-4 (23), 12-dien-28-oic acid (1), ursolic acid (2), oleanolic acid (3), 3-O-alpha-L-rhamnosyl(1 --> 3)-beta-D-glucopyranosyl (1 --> 3)-alpha-L-rhamnosyl (1 --> 2)-alpha-L-arabinopyranosyl hederagenin 28-O-beta-D-glucopyranosyl (1 --> 6)-beta-D-glucopyranosyl ester (4), 3-O-[beta-D-xylopyranosyl (1 --> 4)-beta-D-glucopyranosyl (1 --> 4)] [alpha-L-rhamnosyl(1 --> 3)]-beta-D-glucopyranosyl (1 --> 3)-alpha-L-rhamnosyl(1 --> 2)-alpha-L-arabinopyranosyl hederagenin (5), separately. Among them, 1 is a new compound, and 2 is isolated from this plant for the first time. PMID:24133979

  18. 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. PMID:27115720

  19. Triterpene saponins with anti-inflammatory activity from the stems of Entada phaseoloides.

    PubMed

    Xiong, Hui; Zheng, Yanan; Yang, Guangzhong; Wang, Huixia; Mei, Zhinan

    2015-06-01

    The phytochemical investigation of the ethanol extract from the stems of Entada phaseoloides (L.) Merr (also called "Guo Gang Long") led to the isolation of eleven triterpene saponins (1-11). Their structures were elucidated by extensive spectroscopic methods including 1D- ((1)H and (13)C) and 2D-NMR ((1)H-(1)H COSY, HSQC, HMBC, HSQC-TOCSY and ROESY) experiments as well as ESIMS analysis and hydrolysis. These saponins comprised entagenic acid as the main aglycon, saccharide moieties at C-3 and C-28, and esterification of C-2 or C-3 hydroxyl group of the terminal β-d-glucopyranose unit with a monoterpenic acid. To further explain the clinical applications of "Guo Gang Long" for its anti-inflammatory effect, the inhibitory activities on the production of NO of the saponins and the related aglycon, entagenic acid (12), were evaluated in vitro. The compounds containing a free hydroxyl at C-3 of aglycon (1 and 4) and entagenic acid showed significant activities against NO production in lipopolysaccharide-stimulated mouse macrophage RAW264.7 cells with IC50 values of 25.08, 20.13 and 23.48 μM, respectively. And the three compounds could also inhibit the release of pro-inflammatory cytokines, such as TNF-α, IL-1β, IL-6 and IL-8. PMID:25759122

  20. 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. PMID:27106154

  1. Phenazine-1-carboxylic acid mediated anti-oomycete activity of the endophytic Alcaligenes sp. EIL-2 against Phytophthora meadii.

    PubMed

    Abraham, Amith; Philip, Shaji; Jacob, Manoj Kurian; Narayanan, Sunilkumar Puthenpurackel; Jacob, C Kuruvilla; Kochupurackal, Jayachandran

    2015-01-01

    The oomycete pathogen, Phytophthora meadii, causes various diseases in Hevea brasiliensis at different stages of its life cycle. The study reports the structural characterization of the active principle from the culture filtrate of Alcaligenes sp. EIL-2 (GenBank ID: HQ641257) offering antagonistic activity against P. meadii. Gas Chromatography Mass Spectroscopy (GC-MS) analysis showed the similarity of the compound with phenazine derivatives. The specific representations of FT-IR spectrum such as 3200 cm(-1) (OH stretching, NH stretching and presence of aromatic ring), 1737 cm(-1) (carboxylic acid), 2200-2400 cm(-1) (conjugated dienes) and 1467 cm(-1), and 1422 cm(-1) (CN bonds) were an indicative of phenazine-1-carboxylic acid (PCA). The structure of the compound was further confirmed by (1)H NMR/(13)C NMR spectroscopy, DEPT experiments, and two-dimensional NMR spectral studies, including (1)H-(1)H COSY and (1)H-(13)C HSQC as PCA with the molecular formula of C₁₃H₈N₂O₂. P. meadii was sensitive to purified PCA extract from the endophyte and a concentration of 5 μg/ml completely inhibited the mycelia growth. PCA also showed zoosporicidal activity against P. meadii zoospores. This is the first study of this kind where PCA from an endophyte of H. brasiliensis is being confirmed to carry antagonistic activity against P. meadii. PMID:24985092

  2. Myo-inositol hexakisphosphate, isolated from female gametophyte tissue of loblolly pine, inhibits growth of early-stage somatic embryos.

    PubMed

    Wu, Di; Sullards, M Cameron; Oldham, Charlie D; Gelbaum, Les; Lucrezi, Jacob; Pullman, Gerald S; May, Sheldon W

    2012-01-01

    • Myo-inositol hexakisphosphate (InsP(6)), abundant in animals and plants, is well known for its anticancer activity. However, many aspects of InsP(6) function in plants remain undefined. We now report the first evidence that InsP(6) can inhibit cellular proliferation in plants under growth conditions where phosphorus is not limited. • A highly anionic molecule inhibitory to early-stage somatic embryo growth of loblolly pine (LP) was purified chromatographically from late-stage LP female gametophytes (FGs), and then characterized structurally using mass spectrometry (MS) and nuclear magnetic resonance (NMR) analyses. • Exact mass and mass spectrometry-mass spectrometry (MS-MS) fragmentation identified the bioactive molecule as an inositol hexakisphosphate. It was then identified as the myo-isomer (i.e. InsP(6)) on the basis of (1)H-, (31)P- and (13)C-NMR, (1)H-(1)H correlation spectroscopy (COSY), (1)H-(31)P heteronuclear single quantum correlation (HSQC) and (1)H-(13)C HSQC. Topical application of InsP(6) to early-stage somatic embryos indeed inhibits embryonic growth. • Recently evidence has begun to emerge that InsP(6) may also play a regulatory role in plant cells. We anticipate that our findings will help to stimulate additional investigations aimed at elucidating the roles of inositol phosphates in cellular growth and development in plants. PMID:22023391

  3. Integracides H-J: New tetracyclic triterpenoids from the endophytic fungus Fusarium sp.

    PubMed

    Ibrahim, Sabrin R M; Abdallah, Hossam M; Mohamed, Gamal A; Ross, Samir A

    2016-07-01

    Three new tetracyclic triterpenoids namely, integracides H (1), I (4), and J (5), along with integracides B (3) and F (2) have been isolated from the endophytic fungus Fusarium sp. isolated from the roots of Mentha longifolia L. (Labiatae) growing in Saudi Arabia. The structure elucidation of the isolated compounds was achieved by spectroscopic analysis including UV, IR, 1D ((1)H and (13)C) and 2D ((1)H(1)H COSY, TOCSY, HSQC, HMBC, and NOESY) NMR as well as HRESIMS and comparison with literature data. Integracides H (1) and J (5) showed significant anti-leishmanial activity towards Leishmania donovani with IC50 values of 4.75 and 3.29μM, respectively compared to pentamidine (IC50 6.35μM). Moreover, they displayed potent cytotoxic activity towards BT-549, SKOV-3, and KB cell lines with IC50 values of 1.82, 1.32, and 0.18μM and 2.46, 3.01, and 2.54μM, respectively. PMID:27282207

  4. Determination of astaxanthin and astaxanthin esters in the microalgae Haematococcus pluvialis by LC-(APCI)MS and characterization of predominant carotenoid isomers by NMR spectroscopy.

    PubMed

    Holtin, Karsten; Kuehnle, Maximilian; Rehbein, Jens; Schuler, Paul; Nicholson, Graeme; Albert, Klaus

    2009-11-01

    The oily product ZANTHIN consists of natural astaxanthin, which is manufactured from the microalgae Haematococcus pluvialis by supercritical CO(2) extraction. An HPLC method was developed to separate all of the components of the complex astaxanthin extract using a C(30) column. The separation resulted in different isomers of astaxanthin accompanied by two other carotenoids. The main component consisted of astaxanthin singly esterified with several different fatty acids. C18:3, C18:2, C18:1 and C16:0 were identified as the most commonly occurring fatty acids. Doubly esterified astaxanthin was also found, although in lower concentrations compared to singly esterified astaxanthin. After performing a detailed fatty acid analysis by GC-MS, the peaks from the extract were assigned via HPLC-MS. A trans to cis transmutation of the all-trans compound was performed by thermal treatment in order to obtain an enrichment of cis isomers as the basis for unambiguous identification via NMR experiments. The all-trans as well as the 9- and 13-cis isomers of astaxanthin were characterized in detail by UV/Vis, (1)H, and (1)H,(1)H COSY NMR spectroscopy. PMID:19466394

  5. 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. PMID:25854681

  6. 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.

  7. 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. PMID:26669106

  8. Synthesis and properties of nonlinear optical chromophore containing alkoxy-substituted phenylene as conjugation bridge

    NASA Astrophysics Data System (ADS)

    Kim, Dong Wook; Yoon, Sung Cheol; Lim, Jong-Sun; Lee, Changjin

    2007-07-01

    We designed and synthesized a push-pull type chromophore (St-TCF) containing phenylene ring as a conjugation bridge. Bulky alkyl chain was substituted into the phenylene bridge to minimize intermolecular interaction of the neighbor molecules and to enhance solubility of the chromophore in solvents and polymer host. The chemical structure and purity were verified by 1H NMR, 1H-1H COSY, 13C NMR, DEPT and Mass spectroscopy. The NMR spectra showed that we obtained the chromophore in a trans conformation. In spite of the bulky alkyl chains, St-TCF exhibited fairly high melting point of 167 °C. The chromophore was thermally stable up to 200 °C in the nitrogen atmosphere. The relatively high melting point and decomposition on-set may be attributable to the rigid phenylene ring. The chromophore was blended with an optically transparent polymer host and then the macroscopic electro-optic activity was evaluated. In a preliminary result, the polymer films containing St-TCF as a concentration of 50 wt% exhibited as large as 20-24 pm/V electro-optic coefficient at 1.55 μ.

  9. 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. PMID:23402421

  10. Structural studies of an arabinan from the stems of Ephedra sinica by methylation analysis and 1D and 2D NMR spectroscopy.

    PubMed

    Xia, Yong-Gang; Liang, Jun; Yang, Bing-You; Wang, Qiu-Hong; Kuang, Hai-Xue

    2015-05-01

    Plant arabinan has important biological activity. In this study, a water-soluble arabinan (Mw∼6.15kDa) isolated from the stems of Ephedra sinica was found to consist of (1→5)-Araƒ, (1→3,5)-Araƒ, T-Araƒ, (1→3)-Araƒ and (1→2,5)-Araƒ residues at proportions of 10:2:3:2:1. A tentative structure was proposed by methylation analysis, nuclear magnetic resonance (NMR) spectroscopy ((1)H NMR, (13)C NMR, DEPT-135, (1)H-(1)H COSY, HSQC, HMBC and ROESY) and literature. The structure proposed includes a branched (1→5)-α-Araf backbone where branching occurs at the O-2 and O-3 positions of the residues with 7.7% and 15.4% of the 1,5-linked α-Araf substituted at the O-2 and O-3 positions. The presence of a branched structure was further observed by atomic force microscopy. This polymer was characterized as having a much longer linear (1→5)-α-Araf backbone as a repeating unit. In particular, the presence of α-Araf→3)-α-Araf-(1→3)-α-Araf-(1→ attached at the O-2 is a new finding. This study may facilitate a deeper understanding of structure-activity relationships of biological polysaccharides from the stems of E. sinica. PMID:25659720

  11. 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. PMID:27193305

  12. Steroid constituents from the soft coral Sinularia microspiculata.

    PubMed

    Thanh, Nguyen Van; Ngoc, Ninh Thi; Anh, Hoang Le Tuan; Thung, Do Cong; Thao, Do Thi; Cuong, Nguyen Xuan; Nam, Nguyen Hoai; Kiem, Phan Van; Minh, Chau Van

    2016-10-01

    A methanol extract of the soft coral Sinularia microspiculata revealed five sterols, including two new compounds. Using combined chromatographic and spectroscopic experiments, the new compounds were found to be 7-oxogorgosterol (1) and 16α-hydroxysarcosterol (2). 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 comparing obtained results to the values indicated in previous studies. Among the isolated compounds, 3 showed weak cytotoxic effects against HL-60 (IC50  =  89.02  ±  9.93 μM) cell line, whereas 5 was weakly active against HL-60 (IC50  =  82.80  ±  13.65 μM) and SK-Mel2 (IC50  =  72.32  ±  1.30 μM) cell lines. PMID:27151101

  13. Cytotoxic sesquiterpene lactones from Centaurothamnus maximus and Vicoa pentanema.

    PubMed

    Muhammad, Ilias; Takamatsu, Satoshi; Mossa, Jaber S; El-Feraly, Farouk S; Walker, Larry A; Clark, Alice M

    2003-02-01

    The aerial parts of Centaurothamnus maximus yielded three cytotoxic guaianolides, chlorojanerin (1), cynaropicrin (2) and janerin (3). The structure elucidation of 1-3 was based on (1)H and (13)C NMR data, mainly 2D-NMR (1)H-(1)H COSY and (1)H-(13)C HETCOR experiments. Compounds 1-3 showed in vitro cytotoxic activity against human cancer cell lines of malignant melanoma (SK-MEL), epidermoid (KB), ductal (BT-549) and ovarian (SK-OV-3) carcinomas with IC(50) values of 2-6 microgram/mL. In addition, 12 sesquiterpene lactones (4-15), isolated previously from the aerial parts of Vicoa pentanema, were evaluated for cytotoxic and antimicrobial activities. 2alpha- Acetoxy-3beta-hydroxyalantolactone (10) and 8beta-hydroxyparthenolide (14) were found to be the main cytotoxic agents (IC(50) values of 2-6 microgram/mL against SK-MEL, BT-549 and SK-OV-3), while lactones 4, 5, 11 and 15 selectively inhibited the growth of human malignant melanoma (IC(50) value of 3.6-7.3 microgram/mL). Cell aggregation and cell adhesion assays, using HL-60 and HeLa cell lines, evaluated the effect of cytotoxic constituents 1-3, 10 and 14 on immune response and inflammation. PMID:12601682

  14. Specific synthesis of 5,5'-dicapsaicin by cell suspension cultures of capsicum annuum var. annuum (chili Jalapeño chigol) and their soluble and NaCl-extracted cell wall protein fractions.

    PubMed

    Martínez-Juárez, Víctor M; Ochoa-Alejo, Neftali; Lozoya-Gloria, Edmundo; Villarreal-Ortega, María L; Ariza-Castolo, Armando; Esparza-García, Fernando J; Calva-Calva, Graciano

    2004-02-25

    HPLC-UV, (1)H NMR, (13)C NMR, and (1)H-(1)H COSY analyses revealed that exogenous capsaicin was specifically converted into 5,5'-dicapsaicin by both cell suspension cultures of Capsicum annuum var. annuum (chili Jalapeño chigol) and their soluble and NaCl-extracted cell wall protein fractions under oxidative conditions. In cell suspension cultures 5,5'-dicapsaicin was found only in biomass of capsaicin-fed cultures. This compound has not been detected before either in fresh fruits or in in vitro cultures of Capsicum. The transformation of capsaicin by different protein fractions revealed that most of the enzymatic activity was located in the NaCl-extracted, or ionic cell wall bound, protein, and that it was strictly dependent on H(2)O(2). These results might in part explain some previously described features of capsaicin production by in vitro cultures of Capsicum. The implications of the results regarding the catabolism of capsaicinoids are discussed. PMID:14969559

  15. Systematic phytochemical investigation of Abies spectabilis.

    PubMed

    Wu, Liang; Li, Yong-Li; Li, Su-Mei; Yang, Xian-Wen; Xia, Jia-Han; Zhou, Le; Zhang, Wei-Dong

    2010-12-01

    Systematical phytochemical investigations on Abies spectabilis afforded 72 chemical constituents. On the basis of physical and spectroscopic data, including 1D and 2D homo- and heteronuclear NMR experiments (heteronuclear single quantum coherence (HSQC), (1)H-(1)H correlation spectroscopy (COSY), heteronuclear multiple bond connectivity (HMBC), and nuclear Overhauser effect spectroscopy (NOESY)), and by comparison with the literature references, they were identified as 3 triterpenoids, 23 diterpenoids, 1 sesquiterpenoid, 13 flavonoids, 12 lignans, and 20 other components. Among these compounds, three were identified as new including abieta-7,13-diene-12α-methoxy-18-oic acid (1), 7α-methoxy-dehydroabietic acid (2), and 5-hydroxy-6-methyl-7,4'-dimethoxyflavone-8-O-β-D-glucopyranoside (3). These three new compounds (1-3) and all the known terpenoids (4-28) were tested for cytotoxic activities against four tumor cell lines: A549, COLO-25, QGY-25, and THP-1. However, none of them showed a positive effect (IC₅₀>100 µM). PMID:21139272

  16. 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

    2014-08-01

    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

  17. 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. PMID:26344424

  18. Synthesis, spectral, stereochemical, single crystal XRD and biological studies of 3t-pentyl-2r,6c-diarylpiperidin-4-one picrate derivatives

    NASA Astrophysics Data System (ADS)

    Savithiri, S.; Arockia doss, M.; Rajarajan, G.; Thanikachalam, V.

    2014-10-01

    Various substituted 3t-pentyl-2r,6c-diphenylpiperidin-4-one picrates (1-7) were synthesised and characterised by elemental analysis, FT-IR and NMR spectral studies. NMR spectral assignments were made unambiguously by their one dimensional (1H NMR and 13C NMR) and two dimensional (1H-1H COSY, HSQC, HMBC, NOESY, DEPT) NMR spectra. Single crystal XRD analysis of the compound (1) has confirmed that the complex crystallized in monoclinic system with P21/n space group. The difference in the chemical shifts between equatorial methylene proton and axial proton at C(5) [Δ = δeq - δax] is highly negative in compounds 1-7 in contrast to the value observed for the corresponding parent piperidine-4-one and is indicative of the 1,3-diaxial interaction between the axial NH bond and axial hydrogen at C(5). The chemical shifts of the heterocyclic ring protons are influenced by the picrate anion. All the synthesised compounds exhibited good activity against S. aureus-Staphylococcus aureus bacterial strains and C. albicans fungal strains.

  19. 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.

  20. Teichoic, teichulosonic and teichuronic acids in the cell wall of Brevibacterium aurantiacum VKM Ac-2111(Т).

    PubMed

    Shashkov, Alexander S; Potekhina, Natalia V; Senchenkova, Sofya N; Evtushenko, Lyudmila I

    2016-02-01

    Two different teichoic acids, along with a teichulosonic and a teichuronic acids, were identified in the cell wall of Brevibacterium aurantiacum VKM Ac-2111(Т). One teichoic acid is 1,3-poly(glycerol phosphate) with 2-acetamido-2-deoxy-α-D-galactopyranose and L-glutamic acid as non-stoichiometric substituents at O-2 of the glycerol residue. The second one is a poly(glycosylglycerol phosphate) with -4)-α-D-Galp-(1 → 2)-sn-Gro-(3-P- and/or -6)-α-D-Galp-(1 → 2)-sn-Gro-(3-P- units in the main chain. The structure of the first has not been reported so far, while the latter one is new for actinobacteria. The teichulosonic acid with α-3-deoxy-β-D-glycero-D-galacto-non-2-ulopyranosonic acid (Kdn) and β-D-glucopyranose residues in the backbone represents a novel polymer: → 8)-α-Kdn-(2 → 6)-β-D-Glcp-(1 →. The teichuronic acid has also hitherto unknown structure: → 3)-β-D-Galf(2OAc)0.3-(1 → 3)-β-D-GlcpА-(1 → and is found in members of the genus Brevibacterium for the first time. The polymer structures were elucidated using 1D- and 2D-NMR spectroscopy: (1)H,(1)H COSY, TOCSY, ROESY, (1)H,(13)C HSQC, HSQC-TOCSY, and (1)H,(13)C and (1)H,(31)P HMBC. PMID:26765252

  1. 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. PMID:25803565

  2. 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.

  3. 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).

  4. 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. PMID:22539182

  5. Electronic structure and solvatochromism of merocyanines NMR spectroscopic point of view.

    PubMed

    Kulinich, Andrii V; Ishchenko, Alexander A; Groth, Ulrich M

    2007-09-01

    (1)H and (13)C NMR spectra of two series of malononitrile-based merocyanines, which possess positive and negative solvatochromism have been in detail investigated in low polar chloroform and polar dimethyl sulfoxide (DMSO). Careful attribution of signals in spectra has been made with the help of two-dimensional NMR experiments (COSY, NOESY, HMBC, and HMQC). Hence, the dependence of merocyanines electronic structure on their chemical structure and solvent nature has been studied by this powerful method. It has been shown that there exists a good correlation between the calculated charges on carbon atoms of a polymethine chain and their chemical shifts in (13)C NMR spectra. The influence of solvent polarity on bond orders for dyes with positive and negative solvatochromism is also observed. The comparison of (13)C NMR spectra of merocyanines and corresponding parent ionic dyes allows to determine their sign of solvatochromism irrespectively of electronic spectra, and also to find the key atoms of chromophore whose signals in (13)C NMR spectra are most informative. PMID:17188560

  6. New antimalarials with a triterpenic scaffold from Momordica balsamina.

    PubMed

    Ramalhete, Cátia; Lopes, Dinora; Mulhovo, Silva; Molnár, Joseph; Rosário, Virgílio E; Ferreira, Maria-José U

    2010-07-15

    Bioassay-guided fractionation of the methanol extract of Momordica balsamina led to the isolation of three new cucurbitane-type triterpenoids, balsaminols C-E (1-3). Their structures were elucidated on the basis of spectroscopic methods including 2D NMR experiments (COSY, HMQC, HMBC and NOESY). Balsaminols C-E, together with ten cucurbitacins isolated from the same plant (4-13), were evaluated for their antimalarial activity against the Plasmodium falciparum chloroquine-sensitive strain 3D7 and the chloroquine-resistant clone Dd2. Most of the compounds displayed antimalarial activity. Compounds 9 and 12 revealed the highest antiplasmodial effects against both strains (IC50 values: 4.6, and 7.4 microM, 3D7, respectively; 4.0, and 8.2 microM, Dd2, respectively). Structure-activity relationships are discussed. Furthermore, the preliminary toxicity toward human cells of compounds 1-5 and 9 was investigated in breast cancer cell line (MCF-7). Compounds were inactive or showed weak toxicity (IC50 values>19.0). PMID:20541427

  7. 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

  8. Pyrophen Produced by Endophytic Fungi Aspergillus sp Isolated from Piper crocatum Ruiz and Pav Exhibits Cytotoxic Activity and Induces S Phase Arrest in T47D Breast Cancer Cells.

    PubMed

    Astuti, Puji; Erden, Willy; Wahyono; Wahyuono, Subagus; Hertiani, Triana

    2016-01-01

    Ethyl acetate extracts obtained from culture of endophytic fungi Aspergillus sp isolated from Piper crocatum Ruiz and Pav, have been shown to possess cytotoxic activity against T47D breast cancer cells. Investigations were here conducted to determine bioactive compounds responsible for the activity. Bioassay guided fractionation was employed to obtain active compounds. Structure elucidation was performed based on analysis of LC-MS, 1H-NMR, 13C-NMR, COSY, DEPT, HMQC, HMBC data. Cytotoxity assays were conducted in 96 well plates against T47D and Vero cell lines. Bioassay guided isolation and chemical investigation led to the isolation of pyrophen, a 4-methoxy-6-(1'-acetamido-2'-phenylethyl)-2H-pyran-2-one. Further analysis of its activity against T47D and Vero cells showed an ability to inhibit the growth of T47D cells with IC50 values of 9.2 μg/mL but less cytotoxicity to Vero cells with an IC50 of 109 μg/mL. This compound at a concentration of 400 ng/mL induced S-phase arrest in T47D cells. PMID:26925652

  9. Central to Axial Transfer of Chirality in Menthone or Camphor-Derived 2,2'-Biphenols.

    PubMed

    Fabris, Fabrizio; De Lucchi, Ottorino; Lucchini, Vittorio

    1997-10-17

    A study aimed at defining a molecular arrangement where a chiral fragment derived from menthone or camphor transfers its central chirality to a 2,2'-biphenol residue, inducing an axial chirality, is reported. The menthol or isoborneol groups are attached at the two benzylic positions at 3,3' in order to maximize efficiency in practical applications. A reliable and high-yielding procedure for the synthesis of such C(2)-symmetric molecules substituted at the 3,3'-positions has been developed. The procedure entails Mannich condensation with paraformaldehyde and morpholine, protection of the hydroxylic functions, chlorination, metalation, and addition to (-)-menthone and (+)-camphor. The use of samarium diiodide is essential in the latter step for optimum selectivity and efficiency. The tetrols exhibit intramolecular hydrogen bonding between phenolic and alcoholic hydroxy functions within each monomeric unity, so that they retain their rotational freedom. NOEDS and COSY experiments show that the tetrols are present in more than one rotamer. The tetrols react with tetrachlorosilane to afford siloxanes as pure diastereoisomers, showing that the metal is able to induce preferential helicity at the biphenyl residue; i.e., the central chirality of menthol or isoborneol auxiliary is totally transfered to the axial chirality of the biphenyl. The configurations could be determined by NOEDS and heterocorrelated HMQC experiments. Remarkably, while the menthol derivative induces total M helicity, the camphor induces complementary P helicity. These results suggest that these tetrols may be useful as ligands in catalysts for asymmetric synthesis. PMID:11671820

  10. Analysis of l-DOPA-derived melanin and a novel degradation product formed under alkaline conditions.

    PubMed

    Omotani, Hidetoshi; Yasuda, Makoto; Ishii, Ritsuko; Ikarashi, Tsukasa; Fukuuchi, Tomoko; Yamaoka, Noriko; Mawatari, Ken-Ichi; Kaneko, Kiyoko; Nakagomi, Kazuya

    2016-06-01

    When the therapeutic drug l-DOPA, which is used to treat Parkinson's disease, is combined with magnesium oxide (MgO), a formulation change produces a dark substance. Infrared spectroscopy reveals that this substance is melanin. After allowing the l-DOPA and MgO mixture to stand, the l-DOPA content decreases significantly, and a new degradation product (the final degradation product of l-DOPA, FDP-D) is generated. Formation of this product requires a solution with a pH of >10, and the presence of MgO is not necessary. FDP-D is not produced by tyrosinase decomposition of l-DOPA and is therefore not a melanin-related compound. Pure FDP-D is isolated by adjusting the l-DOPA solution to pH 10 with ammonium hydroxide, allowing it to stand for 3 days at room temperature, adding trifluoroacetic acid (TFA), filtering the precipitate, and separating the supernatant with high-performance liquid chromatography (HPLC). Mass spectrometry indicates that the isolated FDP-D has a molecular formula of C9H9NO7. On the basis of NMR analysis ((1)H NMR, (13)C NMR, DEPT, H-H COSY, HMQC, and HMBC), FDP-D appears to be a substance with the novel structure 7a-hydroxy-5-oxo-1,2,3,5,7,7a-hexahydropyrano [3,4-b]pyrrole-2,7-dicarboxylic acid. PMID:26999318

  11. Potential of Pseudoshikonin I Isolated from Lithospermi Radix as Inhibitors of MMPs in IL-1β-Induced SW1353 Cells.

    PubMed

    Lee, Dae Young; Choi, Soo-Im; Han, Se Hee; Lee, Ye-Joo; Choi, Jong-Gil; Lee, Young-Seob; Choi, Je Hun; Lee, Seung-Eun; Kim, Geum-Soog

    2016-01-01

    Pseudoshikonin I, the new bioactive constituent of Lithospermi radix, was isolated from this methanol extract by employing reverse-phase medium-pressure liquid chromatography (MPLC) using acetonitrile/water solvent system as eluents. The chemical structure was determined based on spectroscopic techniques, including 1D NMR (¹H, (13)C, DEPT), 2D NMR (gCOSY, gHMBC, gHMQC), and QTOF/MS data. In this study, we demonstrated the effect of pseudoshikonin I on matrix-metalloproteinase (MMPs) activation and expression in interleukin (IL)-1β-induced SW1353 chondrosarcoma cells. MMPs are considered important for the maintenance of the extracellular matrix. Following treatment with PS, active MMP-1, -2, -3, -9, -13 and TIMP-2 were quantified in the SW1353 cell culture supernatants using a commercially available ELISA kit. The mRNA expression of MMPs in SW1353 cells was measured by RT-PCR. Pseudoshikonin I treatment effectively protected the activation on all tested MMPs in a dose-dependent manner. TIMP-2 mRNA expression was significantly upregulated by pseudoshikonin I treatment. Overall, we elucidated the inhibitory effect of pseudoshikonin on MMPs, and we suggest its use as a potential novel anti-osteoarthritis agent. PMID:27548143

  12. Sesquiterpene Lactones from Cynara cornigera: Acetyl Cholinesterase Inhibition and In Silico Ligand Docking.

    PubMed

    Hegazy, Mohamed-Elamir F; Ibrahim, Abeer Y; Mohamed, Tarik A; Shahat, Abdelaaty A; El Halawany, Ali M; Abdel-Azim, Nahla S; Alsaid, Mansour S; Paré, Paul W

    2016-01-01

    Wild artichoke (Cynara cornigera), a thistle-like perennial belonging to the Asteraceae family, is native to the Mediterranean region, northwestern Africa, and the Canary Islands. While the pleasant, albeit bitter, taste of the leaves and flowers is attributed to the sesquiterpene lactones cynaropicrin and cynarin, a comprehensive phytochemical investigation still needs to be reported. In this study seven sesquiterpene lactones were isolated from an aqueous methanol plant extract, including a new halogenated metabolite (1), the naturally isolated compound sibthorpine (2), and five metabolites isolated for the first time from C. cornigera. Structures were established by spectroscopic methods, including HREIMS, (1 )H, (13 )C, DEPT, (1 )H-(1 )H COSY, HMQC, and HMBC-NMR experiments as well as by X-ray analysis. The isolated bioactive nutrients were analyzed for their antioxidant and metal chelating activity. Compound 1 exhibited a potent metal chelating activity as well as a high antioxidant capacity. Moreover, select compounds were effective as acetyl cholinesterase inhibitors presenting the possibility for such compounds to be examined for anti-neurodegenerative activity. A computational pharmacophore elucidation and docking study was performed to estimate the pharmacophoric features and binding conformation of isolated compounds in the acetyl cholinesterase active site. PMID:26441064

  13. 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.

  14. 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. PMID:23952497

  15. 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

    2008-11-01

    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. PMID:18841929

  16. A crystal lapiferin derived from Ferula vesceritensis induces apoptosis pathway in MCF-7 breast cancer cells.

    PubMed

    Gamal-Eldeen, Amira M; Hegazy, M-E F

    2010-02-01

    Ferula vesceritensis is a plant that is used in the traditional medicine in Algeria. Chromatographic investigation of the methylene chloride/methanol extract of the aerial parts of F. vesceritensis afforded a crystal carotene sesquiterpene designed lapiferin (10alpha-acetoxy-6alpha-angeloyloxy-8alpha,9alpha-epoxy-trans-caxotan-4beta-ol) for the first time from this species. The structure was determined by comprehensive NMR studies, including DEPT, COSY, NOE, HMQC, HMBC and HRMS, and X-ray data of lapiferin. We report here for the first time the isolation of lapiferin from F. vesceritensis as a new natural source, and we additionally report the first X-ray data for lapiferin. We also report for the first time the specific anti-cancer activity of lapiferin against human breast cancer cells (MCF-7), which is due to apoptosis and not necrosis. Moreover, we have identified for the first time the cell death pathway induced by lapiferin in human breast cancer cells, and also that lapiferin evokes multiple consequences that trigger apoptotic cell death, involving the enhancement of DNA fragmentation, the activation of caspases and the induction of histone acetylation in MCF-7 cells. In conclusion, we record here F. vesceritensis as a new natural source of lapiferin and its first X-ray analysis, and the promising specific anti-cancer activity against human breast cancer of lapiferin and accordingly F. vesceritensis extract. PMID:20140803

  17. Chemical constituents from Tribulus terrestris and screening of their antioxidant activity.

    PubMed

    Hammoda, Hala M; Ghazy, Nabila M; Harraz, Fathalla M; Radwan, Mohamed M; ElSohly, Mahmoud A; Abdallah, Ingy I

    2013-08-01

    Two oligosaccharides (1,2) and a stereoisomer of di-p-coumaroylquinic acid (3) were isolated from the aerial parts of Tribulus terrestris along with five known compounds (4-8). The structures of the compounds were established as O-β-D-fructofuranosyl-(2→6)-α-D-glucopyranosyl-(1→6)-β-D-fructofuranosyl-(2→6)-β-D-fructofuranosyl-(2→1)-α-D-glucopyranosyl-(6→2)-β-D-fructofuranoside (1), O-α-D-glucopyranosyl-(1→4)-α-D-glucopyranosyl-(1→4)-α-D-glucopyranosyl-(1→2)-β-D-fructofuranoside (2), 4,5-di-p-cis-coumaroylquinic acid (3) by different spectroscopic methods including 1D NMR ((1)H, (13)C and DEPT) and 2D NMR (COSY, TOCSY, HMQC and HMBC) experiments as well as ESI-MS analysis. This is the first report for the complete NMR spectral data of the known 4,5-di-p-trans-coumaroylquinic acid (4). The antioxidant activity represented as DPPH free radical scavenging activity was investigated revealing that the di-p-coumaroylquinic acid derivatives possess potent antioxidant activity so considered the major constituents contributing to the antioxidant effect of the plant. PMID:23642392

  18. Synthesis, characterization and antitumor activity of cis-bis(acylthioureato) platinum(II) complexes, cis-[PtL(2)] [HL=N,N-diphenyl-N'-benzoylthiourea or HL=N,N-diphenyl-N'-(p-nitrobenzoyl)thiourea].

    PubMed

    Hernández, Wilfredo; Spodine, Evgenia; 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 (1)H NMR spectrum. At least two downfield shifted and broad paramagnetic signals were apparent in the (1)H 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 (1)H-(13)C 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

  19. 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

    Gaggelli, Elena; D'Amelio, Nicola; Gaggelli, Nicola; Valensin, Gianni; 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 (1)H NMR spectrum. At least two downfield shifted and broad paramagnetic signals were apparent in the (1)H 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 (1)H-(3)C 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

  20. 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. PMID:22624330

  1. Potential of Pseudoshikonin I Isolated from Lithospermi Radix as Inhibitors of MMPs in IL-1β-Induced SW1353 Cells

    PubMed Central

    Lee, Dae Young; Choi, Soo-Im; Han, Se Hee; Lee, Ye-Joo; Choi, Jong-Gil; Lee, Young-Seob; Choi, Je Hun; Lee, Seung-Eun; Kim, Geum-Soog

    2016-01-01

    Pseudoshikonin I, the new bioactive constituent of Lithospermi radix, was isolated from this methanol extract by employing reverse-phase medium-pressure liquid chromatography (MPLC) using acetonitrile/water solvent system as eluents. The chemical structure was determined based on spectroscopic techniques, including 1D NMR (1H, 13C, DEPT), 2D NMR (gCOSY, gHMBC, gHMQC), and QTOF/MS data. In this study, we demonstrated the effect of pseudoshikonin I on matrix-metalloproteinase (MMPs) activation and expression in interleukin (IL)-1β-induced SW1353 chondrosarcoma cells. MMPs are considered important for the maintenance of the extracellular matrix. Following treatment with PS, active MMP-1, -2, -3, -9, -13 and TIMP-2 were quantified in the SW1353 cell culture supernatants using a commercially available ELISA kit. The mRNA expression of MMPs in SW1353 cells was measured by RT-PCR. Pseudoshikonin I treatment effectively protected the activation on all tested MMPs in a dose-dependent manner. TIMP-2 mRNA expression was significantly upregulated by pseudoshikonin I treatment. Overall, we elucidated the inhibitory effect of pseudoshikonin on MMPs, and we suggest its use as a potential novel anti-osteoarthritis agent. PMID:27548143

  2. New lipoxygenase and cholinesterase inhibitory sphingolipids from Carthamus oxyacantha.

    PubMed

    Dilshad, Muhammad; Riaz, Naheed; Saleem, Muhammad; Shafiq, Nusrat; Ashraf, Muhammad; Ismail, Tayaba; Rafiq, Hafiza Mehwish; Jabbar, Abdul

    2016-08-01

    Two new sphingolipids: oxyacanthin A [(2S,3S,4R)-2-{[(2R,5E)-2-hydroxyoctadec-5-enoyl]amino}hexaeicosane-1,3,4-triol; 1] and B [(2S,3S,4R)-2-{[(2R,5E)-2-hydroxyoctadec-5-enoyl]amino}hexaeicosane-1,3,4-triol-1-O-β-D-glucopyranoside; 2], together with 1-octacosanol, β-sitosterol, β-sitosterol 3-O-β-D-glucopyranoside and luteolin 7-O-β-glucopyranoside were isolated from the methanolic extract of the whole plant of Carthamus oxyacantha. Their structures were elucidated using (1)H and (13)C 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 in comparison with the literature data of the related compounds. Both the compounds 1 and 2 showed inhibitory potential against lipoxygenase (LOX) in a concentration-dependent manner with IC50 values 83.3 ± 1.3 and 245.7 ± 1.1 µM, whereas compound 2 showed inhibition against enzymes acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) with IC50 values 65.3 ± 0.1 and 93.6 ± 0.1 µM, respectively. PMID:26285908

  3. Antimicrobial, Antiparasitic and Cytotoxic Spermine Alkaloids from Albizia schimperiana

    PubMed Central

    Samoylenko, Volodymyr; Jacob, Melissa R.; Khan, Shabana I.; Zhao, Jianping; Tekwani, Babu L.; Midiwo, Jacob O.; Walker, Larry A.

    2013-01-01

    Albizia schimperianaOliv. (Leguminosae) is a tree distributed in the highland of Kenya, where it is used as a traditional medicine for the treatment of bacterial and parasitic infections, notably pneumonia and malaria, respectively. Bioassay guided isolation of the CH2Cl2–MeOH 1:1/MeOH-H2O 9:1 (mixed) extract of A. schimperiana afforded the new bioactive macrocyclic spermine alkaloid, namely 5,14-dimethylbudmunchiamine L1 1 and three known budmunchiamine analogs 2-4. The structures of the compounds 1-4 were determined by 1D and 2D NMR data, including COSY, HMQC, and HMBC experiments, and ESI-HRMS. Compounds 1 and 3 exhibited significant in vitro antimicrobial activity against a panel of microorganisms, including C. neoformans, methicillin-resistant S. aureus, E. coli, M. intracellulare, A. fumigatus. In addition, they demonstrated strong in vitro antimalarial activities against chloroquine-susceptible (D6) and -resistant (W2) strains of Plasmodium falciparum with IC50s ranging from 120–270 ng/mL. Compounds 1-4 were also evaluated for cytotoxic activity against selected human cancer cell lines and mammalian kidney fibroblasts (VERO cells). It was observed that hydroxyl substitution of the side chain of the budmunchiamines dramatically reduced the cytotoxicity and antimicrobial activity of the alkaloids 2 and 4 without decreasing antimalarial activity. PMID:19634324

  4. 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. PMID:25835099

  5. Chaetoglobosin U, a cytochalasan alkaloid from endophytic Chaetomium globosum IFB-E019.

    PubMed

    Ding, Gang; Song, Yong C; Chen, Jing R; Xu, Chen; Ge, Hui M; Wang, Xiao T; Tan, Ren X

    2006-02-01

    A new cytotoxic cytochalasan-based alkaloid named chaetoglobosin U (1), along with four known analogues, chaetoglobosins C (2), F (3), and E (5) and penochalasin A (4), has been characterized from the EtOAc extract of a solid culture of Chaetomium globosum IFB-E019, an endophytic fungus residing inside the stem of healthy Imperata cylindrica. The structure of chaetoglobosin U was determined through correlative analyses of its UV, IR, CD, MS, and 1D ((1)H and(13)C NMR and DEPT) and 2D NMR (COSY, NOESY, HMQC, and HMBC) data. Chaetoglobosin U (1) exhibited cytotoxic activity against the human nasopharyngeal epidermoid tumor KB cell line with an IC(50) value of 16.0 microM, comparable to that (14.0 microM) of 5-fluorouracil co-assayed as a positive reference. The known analogues 2-5 were moderately active to the cell line, with IC(50) values of 34.0, 52.0, 48.0, and 40.0 microM, respectively. PMID:16499339

  6. Cucurbitacins-type triterpene with potent activity on mouse embryonic fibroblast from Cucumis prophetarum, cucurbitaceae

    PubMed Central

    Ayyad, Seif-Eldin N.; Abdel-Lateff, Ahmed; Basaif, Salim A.; Shier, Thomas

    2011-01-01

    Background: Higher plants are considered as a well-known source of the potent anticancer metabolites with diversity of chemical structures. For instance, taxol is an amazing diterpene alkaloid had been lunched since 1990. Objective: To isolate the major compounds from the fruit extract of Cucumis prophetarum, Cucurbitaceae, which are mainly responsible for the bioactivities as anticancer. Materials and Methods: Plant material was shady air dried, extracted with equal volume of chloroform/methanol, and fractionated with different adsorbents. The structures of obtained pure compounds were elucidated with different spectroscopic techniques employing 1D (1H and 13C) and 2D (COSY, HMQC and HMBC) NMR (Nuclear Magnetic Resonance Spectrometry) and ESI-MS (Eelectrospray Ionization Mass Spectrometry) spectroscopy. The pure isolates were tested towards human cancer cell lines, mouse embryonic fibroblast (NIH3T3) and virally transformed form (KA3IT). Results: Two cucurbitacins derivatives, dihydocucurbitacin B (1) and cucurbitacin B (2), had been obtained. Compounds 1 and 2 showed (showed potent inhibitory activities toward NIH3T3 and KA31T with IC50 0.2, 0.15, 2.5 and 2.0 μg/ml, respectively. Conclusion: The naturally cucurbitacin derivatives (dihydocucurbitacin B and cucurbitacin B) showed potent activities towards NIH3T3 and KA31T, could be considered as a lead of discovering a new anticancer natural drug. PMID:22022168

  7. 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

  8. Structure of the O-specific polysaccharide of Hafnia alvei PCM 1222 containing 2-aminoethyl phosphate.

    PubMed

    Toukach, F V; Shashkov, A S; Katzenellenbogen, E; Kocharova, N A; Czarny, A; Knirel, Y A; Romanowska, E; Kochetkov, N K

    1996-12-13

    The O-specific polysaccharide of H. alvei strain PCM 1222 has a branched hexasaccharide repeating unit containing D-galactose, L-rhamnose, D-ribose, D-galacturonic acid, and 2-acetamido-2-deoxy-D-glucose in the ratios 1:2:1:1:1, as well as 2-aminoethyl phosphate (EtNP) and O-acetyl groups in nonstoichiometric amounts. The polysaccharide was modified by carboxyl reduction, O-deacetylation, and dephosphorylation with 48% hydrofluoric acid, the last reaction being accompanied by removal of the lateral residue of beta-galactofuranose. The modified polysaccharides were studied by methylation analysis and 1H and 13C NMR spectroscopy, including 2D correlation spectroscopy (COSY), H-detected 1H,13C and 1H,31P heteronuclear multiple-quantum coherence (HMQC), 1D NOE, 2D rotating-frame NOE spectroscopy (ROESY), and 2D combined total correlation spectroscopy (TOCSY) and ROESY (TORO). The following structure of the O-deacetylated polysaccharide was established: [formula: see text] In different batches of the polysaccharide, the content of EtNP varied from 0.35 to 0.55 and that of the O-acetyl groups from 0.05 to 0.4 per repeating unit. It was tentatively suggested that the O-acetyl group is located at position 4 of a rhamnosyl residue. PMID:9002188

  9. 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.

  10. Band-selective excited ultrahigh resolution PSYCHE-TOCSY: fast screening of organic molecules and complex mixtures.

    PubMed

    Kakita, Veera Mohana Rao; Vemulapalli, Sahithya Phani Babu; Bharatam, Jagadeesh

    2016-04-01

    Precise assignments of (1) H atomic sites and establishment of their through-bond COSY or TOCSY connectivity are crucial for molecular structural characterization by using (1) H NMR spectroscopy. However, this exercise is often hampered by signal overlap, primarily because of (1) H-(1) H scalar coupling multiplets, even at typical high magnetic fields. The recent developments in homodecoupling strategies for effectively suppressing the coupling multiplets into nice singlets (pure-shift), particularly, Morris's advanced broadband pure-shift yielded by chirp excitation (PSYCHE) decoupling and ultrahigh resolution PSYCHE-TOCSY schemes, have shown new possibilities for unambiguous structural elucidation of complex organic molecules. The superior broadband PSYCHE-TOCSY exhibits enhanced performance over the earlier TOCSY methods, which however warrants prolonged experimental times due to the requirement of large number of dwell increments along the indirect dimension. Herein, we present fast and band-selective analog of the broadband PSYCHE-TOCSY, which is useful for analyzing complex organic molecules that exhibit characteristic yet crowded spectral regions. The simple pulse scheme relies on band-selective excitation (BSE) followed by PSYCHE homodecoupling in the indirect dimension. The BSE-PSYCHE-TOCSY has been exemplified for Estradiol and a complex carbohydrate mixture comprised of six constituents of closely comparable molecular weights. The experimental times are greatly reduced viz., ~20 fold for Estradiol and ~10 fold for carbohydrate mixture, with respect to the broadband PSYCHE-TOCSY. Furthermore, unlike the earlier homonuclear band-selective decoupling, the BSE-PSYCHE-decoupling provides fully decoupled pure-shift spectra for all the individual chemical sites within the excited band. The BSE-PSYCHE-TOCSY is expected to have significant potential for quick screening of complex organic molecules and mixtures at ultrahigh resolution. Copyright © 2015 John Wiley

  11. 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

  12. Cross-linked supramolecular polymer gels constructed from discrete multi-pillar[5]arene metallacycles and their multiple stimuli-responsive behavior.

    PubMed

    Li, Zhong-Yu; Zhang, Yanyan; Zhang, Chang-Wei; Chen, Li-Jun; Wang, Chao; Tan, Hongwei; Yu, Yihua; Li, Xiaopeng; Yang, Hai-Bo

    2014-06-18

    A new family of discrete hexakis-pillar[5]arene metallacycles with different sizes have been successfully prepared via coordination-driven self-assembly, which presented very few successful examples of preparation of discrete multiple pillar[n]arene derivatives. These newly designed hexakis-pillar[5]arene metallacycles were well characterized with one-dimensional (1-D) multinuclear NMR ((1)H and (31) P NMR), two-dimensional (2-D) (1)H-(1)H COSY and NOESY, ESI-TOF-MS, elemental analysis, and PM6 semiempirical molecular orbital methods. Furthermore, the host-guest complexation of such hexakis-pillar[5]arene hosts with a series of different neutral ditopic guests G1-6 were well investigated. Through host-guest interactions of hexakis-pillar[5]arene metallacycles H2 or H3 with the neutral dinitrile guest G5, the cross-linked supramolecular polymers H2⊃(G5)3 or H3⊃(G5)3 were successfully constructed at the high-concentration region, respectively. Interestingly, these cross-linked supramolecular polymers transformed into the stable supramolecular gels upon increasing the concentrations to a relatively high level. More importantly, by taking advantage of the dynamic nature of metal-ligand bonds and host-guest interactions, the reversible multiple stimuli-responsive gel-sol phase transitions of such polymer gels were successfully realized under different stimuli, such as temperature, halide, and competitive guest, etc. The mechanism of such multiple stimuli-responsive processes was well illustrated by in situ multinuclear NMR investigation. This research not only provides a highly efficient approach to the preparation of discrete multiple pillar[n]arene derivatives but also presents a new family of multiple stimuli-responsive "smart" soft matters. PMID:24571308

  13. Alkynyl triphosphine copper complexes: synthesis and photophysical studies.

    PubMed

    Chakkaradhari, Gomathy; Belyaev, Andrey A; Karttunen, Antti J; Sivchik, Vasily; Tunik, Sergey P; Koshevoy, Igor O

    2015-08-01

    A rigid triphosphine PPh2C6H4-PPh-C6H4PPh2 () reacted with Cu(+) and a stoichiometric amount of terminal alkyne under basic conditions to give a family of copper(i) alkynyl compounds [Cu()C[triple bond, length as m-dash]CR]. The number of terminal -C[triple bond, length as m-dash]CH groups in the starting ligand determines the nuclearity of the resulting complexes giving mono- (, R = Ph; , R = C6H4OMe; , R = C6H4NO2; , R = C6H4CF3; , R = 2-pyridyl), di- (R = -(C6H4)n-, n = 1 (), n = 2, (), n = 3 ()) and trinuclear complexes (, R = 1,3,5-(C6H4)3-C6H3; , R = 1,3,5-(C6H4-4-C2C6H4)3-C6H3). In all the complexes the Cu(i) centers are found in a distorted tetrahedral environment that is achieved by tridentate coordination of the ligand and σ-bonding to the alkynyl function. The crystal structures of , and were estimated by single crystal X-ray diffraction analysis. The (31)P, (1)H and (1)H-(1)H COSY NMR spectroscopy confirms that all the molecules remain intact in solution. The photophysical studies carried out in the solid state at 298 and 77 K revealed moderate to weak orange luminescence (Φem up to 19%), tentatively assigned to thermally activated delayed fluorescence for the mononuclear complexes. The quantum yields of emission of demonstrated strong dependence on the nature of the alkynyl ligand, the role of which in the electronic transitions was elucidated by TD-DFT computational studies. PMID:26129656

  14. Hairpin loops consisting of single adenine residues closed by sheared A.A and G.G pairs formed by the DNA triplets AAA and GAG: solution structure of the d(GTACAAAGTAC) hairpin.

    PubMed

    Chou, S H; Zhu, L; Gao, Z; Cheng, J W; Reid, B R

    1996-12-20

    The DNA undecamers GTACAAAGTAC (AAA 11-mer) and GTACGAGGTAC (GAG 11-mer) have been studied in solution by high-resolution NMR spectroscopy. Both duplexes form stable hairpins containing single deoxyadenosine loops and stems containing five base-pairs that are closed at the loop end by sheared AxA and GxC pairs, respectively. These molecules thus contain new AAA and GAG loop turn motifs. All protons, including the chiral H5'/H5" protons of the loop residues, were assigned using NOESY, DQF-COSY and heteronuclear 1H-31P COSY experiments. The backbone torsion angles were constrained using experimental data from NOE crosspeaks, three-bond 1H-1H coupling constants and four-bond 1H-31P coupling constants and four-bond 1H-31P coupling constants. The AAA and GAG 11-mers form similar structures in solution. The detailed structure of the AAA 11-mer was determined by the combined use of NMR, distance geometry and energy minimization methods. This structure exhibits good stacking of the loop adenosine base on the closing 5Ax7A sheared pair, with the 6A base stacking on the 5A base and the 6A deoxyribose stacking with the 7A base. All sugars in the AAA 11-mer hairpin adopt the typical DNA C2'-endo conformation and a sharp backbone turn occurs between residues 6A and 7A. This loop turn is brought about mainly by a change in the backbone phosphate torsion angles from zeta(g-) alpha(g-) to zeta(g+) alphat(g+) at the turn. The gamma torsion angle of residue 7A in the closing sheared pair also changes from gauche+ to trans. In Pu1NPu2 loop turns of the GCA, AAA and GAG types, the chemical shift of the H4' proton of the loop deoxyribose depends on the nature of Pu2; this reflects the stacking of the loop sugar on the Pu2 base and the different ring current effects of A or G in this position. PMID:9000625

  15. 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…

  16. Isolation, structural characterization, and properties of mattacin (polymyxin M), a cyclic peptide antibiotic produced by Paenibacillus kobensis M.

    PubMed

    Martin, Nathaniel I; Hu, Haijing; Moake, Matthew M; Churey, John J; Whittal, Randy; Worobo, Randy W; Vederas, John C

    2003-04-11

    Mattacin is a nonribosomally synthesized, decapeptide antibiotic produced by Paenibacillus kobensis M. The producing strain was isolated from a soil/manure sample and identified using 16 S rRNA sequence homology along with chemical and morphological characterization. An efficient production and isolation procedure was developed to afford pure mattacin. Structure elucidation using a combination of chemical degradation, multidimensional NMR studies (COSY, HMBC, HMQC, ROESY), and mass spectrometric (MALDI MS/MS) analyses showed that mattacin is identical to polymyxin M, an uncommon antibiotic reported previously in certain Bacillus species by Russian investigators. Mattacin (polymyxin M) is cyclic and possesses an amide linkage between the C-terminal threonine and the side chain amino group of the diaminobutyric acid residue at position 4. It contains an (S)-6-methyloctanoic acid moiety attached as an amide at the N-terminal amino group, one D-leucine, six L-alpha,gamma-diaminobutyric acid, and three L-threonine residues. Transfer NOE experiments on the conformational preferences of mattacin when bound to lipid A and microcalorimetry studies on binding to lipopolysaccharide showed that its behavior was very similar to that observed in previous studies of polymyxin B (a commercial antibiotic), suggesting an identical mechanism of action. It was capable of inhibiting the growth of a wide variety of Gram-positive and Gram-negative bacteria, including several human and plant pathogens with activity comparable with purified polymyxin B. The biosynthesis of mattacin was also examined briefly using transpositional mutagenesis by which 10 production mutants were obtained, revealing a set of genes involved in production. PMID:12569104

  17. Triterpenoids as inhibitors of erythrocytic and liver stages of Plasmodium infections.

    PubMed

    Ramalhete, Cátia; da Cruz, Filipa P; Lopes, Dinora; Mulhovo, Silva; Rosário, Virgílio E; Prudêncio, Miguel; Ferreira, Maria-José U

    2011-12-15

    Bioassay-guided fractionation of the methanol extract of Momordica balsamina led to the isolation of two new cucurbitane-type triterpenoids, balsaminol F (1) and balsaminoside B (2), along with the known glycosylated cucurbitacins, cucurbita-5,24-diene-3β,23(R)-diol-7-O-β-D-glucopyranoside (3) and kuguaglycoside A (4). Compound 1 was acylated yielding two new triesters, triacetylbalsaminol F (5) and tribenzoylbalsaminol F (6). The structures were elucidated based on spectroscopic methods including 2D-NMR experiments (COSY, HMQC, HMBC and NOESY). Compounds 1-6, were evaluated for their antimalarial activity against the erythrocytic stages of the Plasmodium falciparum chloroquine-sensitive strain 3D7 and the chloroquine-resistant clone Dd2. Assessment of compounds (1-3 and 5, 6) activity against the liver stage of Plasmodium berghei was also performed, measuring the luminescence intensity in Huh-7 cells infected with a firefly luciferase-expressing P. berghei line, PbGFP-Luc(con). Active compounds were shown to inhibit the parasite's intracellular development rather than its ability to invade hepatic cells. Toxicity of compounds (1-3 and 5, 6) was assessed on the same cell line and on mouse primary hepatocytes through the fluorescence measurement of cell confluency. Furthermore, toxicity of compounds 1-6 towards human cells was also investigated in the MCF-7 breast cancer cell line, showing that they were not toxic or exhibited weak toxicity. In blood stages of P. falciparum, compounds 1-5 displayed antimalarial activity, revealing triacetylbalsaminol F (5) the highest antiplasmodial effects (IC(50) values: 0.4μM, 3D7; 0.2μM, Dd2). The highest antiplasmodial activity against the liver stages of P.berghei was also displayed by compound 5, with high inhibitory activity and no toxicity. PMID:22071523

  18. New anti-trypanosomal active tetracyclic iridoid isolated from Morinda lucida Benth.

    PubMed

    Suzuki, Mitsuko; Tung, Nguyen Huu; Kwofie, Kofi D; Adegle, Richard; Amoa-Bosompem, Michael; Sakyiamah, Maxwell; Ayertey, Frederick; Owusu, Kofi Baffour-Awuah; Tuffour, Isaac; Atchoglo, Philip; Frempong, Kwadwo Kyereme; Anyan, William K; Uto, Takuhiro; Morinaga, Osamu; Yamashita, Taizo; Aboagye, Frederic; Appiah, Alfred Ampomah; Appiah-Opong, Regina; Nyarko, Alexander K; Yamaoka, Shoji; Yamaguchi, Yasuchika; Edoh, Dominic; Koram, Kwadwo; Ohta, Nobuo; Boakye, Daniel A; Ayi, Irene; Shoyama, Yukihiro

    2015-08-01

    Human African trypanosomiasis (HAT), commonly known as sleeping sickness has remained a serious health problem in many African countries with thousands of new infected cases annually. Chemotherapy, which is the main form of control against HAT has been characterized lately by the viewpoints of toxicity and drug resistance issues. Recently, there have been a lot of emphases on the use of medicinal plants world-wide. Morinda lucida Benth. is one of the most popular medicinal plants widely distributed in Africa and several groups have reported on its anti-protozoa activities. In this study, we have isolated one novel tetracyclic iridoid, named as molucidin, from the CHCl3 fraction of the M. lucida leaves by bioassay-guided fractionation and purification. Molucidin was structurally elucidated by (1)H and (13)C NMR including HMQC, HMBC, H-H COSY and NOESY resulting in tetracyclic iridoid skeleton, and its absolute configuration was determined. We have further demonstrated that molucidin presented a strong anti-trypanosomal activity, indicating an IC50 value of 1.27 μM. The cytotoxicity study using human normal and cancer cell lines indicated that molucidin exhibited selectivity index (SI) against two normal fibroblasts greater than 4.73. Furthermore, structure-activity relationship (SAR) study was undertaken with molucidin and oregonin, which is identical to anti-trypanosomal active components of Alnus japonica. Overlapping analysis of the lowest energy conformation of molucidin with oregonin suggested a certain similarities of aromatic rings of both oregonin and molucidin. These results contribute to the future drug design studies for HAT. PMID:26048790

  19. 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. PMID:25250850

  20. 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. PMID:26020634

  1. Aspergillus fumigatus CY018, an endophytic fungus in Cynodon dactylon as a versatile producer of new and bioactive metabolites.

    PubMed

    Liu, J Y; Song, Y C; Zhang, Z; Wang, L; Guo, Z J; Zou, W X; Tan, R X

    2004-11-01

    Aspergillus fumigatus CY018 was recognized as an endophytic fungus for the first time in the leaf of Cynodon dactylon. By bioassay-guided fractionation, the EtOAc extract of a solid-matrix steady culture of this fungus afforded two new metabolites, named asperfumoid (1) and asperfumin (2), together with six known bioactive compounds including monomethylsulochrin, fumigaclavine C, fumitremorgin C, physcion, helvolic acid and 5alpha,8alpha-epidioxy-ergosta-6,22-diene-3beta-ol as well as other four known compounds ergosta-4,22-diene-3beta-ol, ergosterol, cyclo(Ala-Leu) and cyclo(Ala-Ile). Through detailed spectroscopic analyses including HRESI-MS, homo- and hetero-nuclear correlation NMR experiments (HMQC, COSY, NOESY and HMBC), the structures of asperfumoid and asperfumin were established to be spiro-(3-hydroxyl-2,6-dimethoxyl-2,5-diene-4-cyclohexone-(1,3')-5'-methoxyl-7'-methyl-(1'H, 2'H, 4'H)-quinoline-2',4'-dione) and 5-hydroxyl-2-(6-hydroxyl-2-methoxyl-4-methylbenzoyl)-3,6-dimethoxyl-benzoic methyl ester, respectively. All of the 12 isolates were subjected to in vitro bioactive assays against three human pathogenic fungi Candida albicans, Tricophyton rubrum and Aspergillus niger. As a result, asperfumoid, fumigaclavine C, fumitremorgin C, physcion and helvolic acid were shown to inhibit C. albicans with MICs of 75.0, 31.5, 62.5, 125.0 and 31.5 microg/mL, respectively. PMID:15522437

  2. Easy oxidative addition of the carbon-halogen bond by dimethylplatinum(II) complexes containing a related series of diimine ligands: Synthesis, spectral characterization and crystal structure

    NASA Astrophysics Data System (ADS)

    Momeni, Badri Z.; Fathi, Nastaran; Mohagheghi, Arezoo

    2015-01-01

    Dimethylplatinum(II) complexes [PtMe2(NN)] {NN = 4,4‧-Me2bpy (4,4‧-dimethyl-2,2‧-bipyridine); 5,5‧-Me2bpy (5,5‧-dimethyl-2,2‧-bipyridine)} were reacted with alkyl halides (RX = EtI, EtBr) to yield the organoplatinum(IV) complexes [PtMe2RX(NN)]. On the basis of NMR data, the platinum(IV) product of each reaction contains almost exclusively the trans isomer but small traces of the cis isomers are also observed. On the other hand, the reaction of [PtMe2(NN)] {NN = bu2bpy (4,4‧-di-tert-butyl-2,2‧-bipyridine); 4,4‧-Me2bpy; 5,5‧-Me2bpy} with CH2Br2 gave a mixture of cis and trans-[PtMe2(CH2Br)Br(NN)] formed by the oxidative addition of one of the C-Br bonds. The formation of the cis isomer increases in the order of 5,5‧-Me2bpy > bu2bpy > 4,4‧-Me2bpy. The reaction of [PtMe2(NN)] {NN = bpy (2,2‧-bipyridine), phen (1,10-phenanthroline)} with 1,8-dibromooctane or 1,9-dibromononane afforded the mononuclear complexes [PtMe2{(CH2)nBr}Br(NN)] (n = 8-9). The products were fully characterized by elemental analysis, 1H, 13C, HH COSY, HMQC, DEPT and DEPTQ-135 NMR spectroscopy. The crystal structure of [PtMe2EtI(4,4‧-Me2bpy)] reveals that Pt(IV) atom is six-coordinated in a slightly distorted octahedral geometry with the ethyl group trans to iodide.

  3. Towards Elucidating Carnosic Acid Biosynthesis in Lamiaceae: Functional Characterization of the Three First Steps of the Pathway in Salvia fruticosa and Rosmarinus officinalis

    PubMed Central

    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. PMID:26020634

  4. Paramagnetic NMR relaxation in polymeric matrixes: sensitivity enhancement and selective suppression of embedded species (1H and 13C PSR filter).

    PubMed

    Fernandez-Megia, Eduardo; Correa, Juan; Novoa-Carballal, Ramon; Riguera, Ricardo

    2007-12-12

    A study of the practical applications of the addition of paramagnetic spin relaxation (PSR) ions to a variety of polymers (PLL, PAA, PGA, PVP, and polysaccharides such as hyaluronic acid, chitosan, mannan, and dextran) in solution (D2O and DMSO-d6) is described. Use of Gd(III), Cu(II), and Mn(II) allows a reduction of up to 500% in the 1H longitudinal relaxation times (T1), and so in the time necessary for recording quantitative NMR spectra (sensitivity enhancement) neither an increase of the spectral line width nor chemical shift changes resulted from addition of any of the PSR agents tested. Selective suppression of the 1H and 13C NMR signals of certain components (low MW molecules and polymers) in the spectrum of a mixture was attained thanks to their different sensitivity [transverse relaxation times (T2)] to Gd(III) (PSR filter). Illustration of this strategy with block copolymers (PGA-g-PEG) and mixtures of polymers and low MW molecules (i.e., lactose-hyaluronic acid, dextran-PAA, PVP-glutamic acid) in 1D and 2D NMR experiments (COSY and HMQC) is presented. In those mixtures where PSR and CPMG filters alone failed in the suppression of certain components (i.e., PVP-mannan-hyaluronic acid) due to their similarity of 1H T2 values and sensitivities to Gd(III), use of the PSR filter in combination with CPMG sequences (PSR-CPMG filter) successfully resulted in the sequential suppression of the components (hyaluronic acid first and then mannan). PMID:18004845

  5. 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

    2008-05-01

    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. PMID:18343385

  6. Complete structure of the polysaccharide from Streptococcus sanguis J22

    SciTech Connect

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

    1990-01-09

    The cell wall polysaccharides of certain oral streptococci such as Streptococcus sanguis strains 34 and J22, although immunologically distinct, act as receptors for the fimbrial lectins of Actinomyces viscosus T14V. The authors report the complete covalent structure of the polysaccharide from S. sanguis J22 which is composed of a heptasaccharide subunit linked by phosphodiester bonds. The repeating subunit, which contains {alpha}-GalNAc, {alpha}-rhamnose, {beta}-rhamnose, {beta}-glucose, and {beta}-galactose all in the pyranoside form and {beta}-galactofuranose, is compared with the previously published structure of the polysaccharide from strain 34. The structure has been determined almost exclusively by high-resolution nuclear magnetic resonance methods. The {sup 1}H and {sup 13}C NMR spectra of the polysaccharides from both strains 34 and J22 have been completely assigned. The stereochemistry of pyranosides was assigned from J{sub H-H} values determined from phase-sensitive COSY spectra, and acetamido sugars were assigned by correlation of the resonances of the amide {sup 1}H with the sugar ring protons. The {sup 13}C spectra were assigned by {sup 1}H-detected multiple-quantum correlation (HMQC) spectra, and the assignments were confirmed by {sup 1}H-detected multiple-bond correlation (HMBC) spectra. The positions of the glycosidic linkages were assigned by detection of three-bond {sup 1}H-{sup 13}C correlation across the glycosidic linkage in the HMBC spectra. The positions of the phosphodiester linkages were determined by splittings observed in the {sup 13}C resonances due to {sup 31}P coupling and also by {sup 1}H-detected {sup 31}P correlation spectroscopy.

  7. 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. PMID:27350550

  8. Reaction of dehydropyrrolizidine alkaloids with valine and hemoglobin.

    PubMed

    Zhao, Yuewei; Wang, Shuguang; Xia, Qingsu; Gamboa da Costa, Gonçalo; Doerge, Daniel R; Cai, Lining; Fu, Peter P

    2014-10-20

    Pyrrolizidine alkaloid-containing plants are probably the most common poisonous plants affecting livestock, wildlife, and humans. Pyrrolizidine alkaloids exert toxicity through metabolism to dehydropyrrolizidine alkaloids that bind to cellular protein and DNA, leading to hepatotoxicity, genotoxicity, and tumorigenicity. To date, it is not clear how dehydropyrrolizidine alkaloids bind to cellular constituents, including amino acids and proteins, resulting in toxicity. Metabolism of carcinogenic monocrotaline, riddelliine, and heliotrine produces dehydromonocrotaline, dehyroriddelliine, and dehydroheliotrine, respectively, as primary reactive metabolites. In this study, we report that reaction of dehydromonocrotaline with valine generated four highly unstable 6,7-dihydro-7-hydroxy-1-hydroxymethyl-5H-pyrrolizine (DHP)-derived valine (DHP-valine) adducts. For structural elucidation, DHP-valine adducts were derivatized with phenyl isothiocyanate (PITC) to DHP-valine-PITC products. After HPLC separation, their structures were characterized by mass spectrometry, UV-visible spectrophotometry, (1)H NMR, and (1)H-(1)H COSY NMR spectral analysis. Two DHP-valine-PITC adducts, designated as DHP-valine-PITC-1 and DHP-valine-PITC-3, had the amino group of valine linked to the C7 position of the necine base, and the other two DHP-valine-PITC products, DHP-valine-PITC-2 and DHP-valine-PITC-4, linked to the C9 position of the necine base. DHP-valine-PITC-1 was interconvertible with DHP-valine-PITC-3, and DHP-valine-PITC-2 was interconvertible with DHP-valine-PITC-4. Reaction of dehydroriddelliine and dehydroheliotrine with valine provided similar results. However, reaction of valine and dehydroretronecine (DHR) under similar experimental conditions did not produce DHP-valine adducts. Reaction of dehydromonocrotaline with rat hemoglobin followed by derivatization with PITC also generated the same four DHP-valine-PITC adducts. This represents the first full structural elucidation of

  9. NMR Investigations of Nitrophorin 2 Belt Side Chain Effects on Heme Orientation and Seating of Native N-terminus NP2 and NP2(D1A)

    PubMed Central

    Muthu, Dhanasekaran; Shokhireva, Tatiana K.; Garrett, Sarah A.; Goren, Allena M.; Zhang, Hongjun

    2014-01-01

    created by replacing a large protein side chain by a much smaller one; the latter was observed for all Tyr→Ala mutants. These relatively small changes in seating have measureable effect on the NMR spectra of the mutants, but are indeed minor in terms of overall seating and reactivity of the NP2(D1A) protein. The 1H NMR resonances of the hemin substituents of the low-spin NMeIm complexes of NP2(D1A,F42L,L105F,I120T) as well as NP2(D1A,I120T), NP2(D1A,Y104A) and NP2(D1A,F42A) have been assigned using natural abundance 1H{13C} HMQC and 1H-1H NOESY spectra. PMID:24292244

  10. 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

  11. Methicillin-resistant Staphylococcus aureus, Vancomycin-resistant Enterococcus faecalis and Enterococcus faecium active Dimeric Isobutyrylphloroglucinol from Ivesia gordonii

    PubMed Central

    Ahmed, Marwa H.; Ibrahim, Mohamed Ali; Zhang, Jin; Melek, Farouk R.; El-Hawary, Seham S.; Jacob, Melissa R.; Muhammad, Ilias

    2014-01-01

    Bioassay-guided fractionation of the chloroform soluble fraction of stem, leave, and flower extracts of the American plant Ivesia gordonii led to the isolation of a new dimeric acylphloroglucinol 3,3′-diisobutyryl-2,6′-dimethoxy-4,6,2′,4′-tetrahydroxy-5,5′dimethyldiphenyl methane (1), to which we have assigned the trivial name of ivesinol (1), together with a known monomeric acylphloroglucinol, 1,5-dihydroxy-2-(2′-methylpropionyl)-3-methoxy-6-methylbenzene (2). The structures of the isolated compounds were characterized using 1D- and 2D NMR spectroscopy, including COSY, HMQC, HMBC, and ROESY experiments as well as mass spectrometery. Ivesinol (1) showed potent activity against Staphylococcus aureus (SA) and methicillin-resistant S. aureus (MRSA) with IC50/MIC/MBC values of 0.10/1.25/>20 µg/mL and 0.05/0.31/>20 µg/mL, respectively (vs. IC50/MIC/MBC 0.133/0.5/1.0 µg/mL and 0.128/0.5/1.0 µg/mL of ciprofloxacin), while the corresponding monomer 2 was found to be less active. Compound 1 also demonstrated strong activity against vancomycin-resistant Enterococcus faecium (VRE) with IC50/MIC/MBC values 0.22/1.25/>20 µg/mL, whereas the reference standard ciprofloxacin was found to be inactive against this strain. In addition, compound 2 showed moderate activity against two species of Candida and Cryptococcus neoformans, while 1 was inactive against these fungi. In order to evaluate the influence of acyl group(s) in phloroglucinol (3) as a ligand, the mono- (4) and diacetylphloroglucinol (5) were prepared from 3, and evaluated for their in vitro SA, MRSA, and VRE activities, where 2,4-diacetylphloroglucinol (5) showed potent activity, like 1, against SA, MRSA, and VRE (ATCC 700221) with IC50/ MIC values of 0.27/2.5 µg/mL, 0.23/2.5 µg/mL, and 0.86/2.5 µg/mL, respectively, while 4 was inactive. PMID:24689296

  12. 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

  13. Variecolactol: A New Sesterterpene Lactone from the Sclerotia of Aspergillus auricomus (Guegen) Saito

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Variecolactol (1), a new sesterterpene lactone related to variecolin (2), has been isolated from the organic extracts of Aspergillus auricomus. Structure determination of this compound was achieved primarily through HMQC, HMBC, and NOESY experiments. The known compounds dihydropenicillic acid (3) ...

  14. 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.

  15. Proton-detected 2D radio frequency driven recoupling solid-state NMR studies on micelle-associated cytochrome-b5

    NASA Astrophysics Data System (ADS)

    Pandey, Manoj Kumar; Vivekanandan, Subramanian; Yamamoto, Kazutoshi; Im, Sangchoul; Waskell, Lucy; Ramamoorthy, Ayyalusamy

    2014-05-01

    Solid-state NMR spectroscopy is increasingly used in the high-resolution structural studies of membrane-associated proteins and peptides. Most such studies necessitate isotopically labeled (13C, 15N and 2H) proteins/peptides, which is a limiting factor for some of the exciting membrane-bound proteins and aggregating peptides. In this study, we report the use of a proton-based slow magic angle spinning (MAS) solid-state NMR experiment that exploits the unaveraged 1H-1H dipolar couplings from a membrane-bound protein. We have shown that the difference in the buildup rates of cross-peak intensities against the mixing time - obtained from 2D 1H-1H radio frequency-driven recoupling (RFDR) and nuclear Overhauser effect spectroscopy (NOESY) experiments on a 16.7-kDa micelle-associated full-length rabbit cytochrome-b5 (cytb5) - can provide insights into protein dynamics and could be useful to measure 1H-1H dipolar couplings. The experimental buildup curves compare well with theoretical simulations and are used to extract relaxation parameters. Our results show that due to fast exchange of amide protons with water in the soluble heme-containing domain of cyb5, coherent 1H-1H dipolar interactions are averaged out for these protons while alpha and side chain protons show residual dipolar couplings that can be obtained from 1H-1H RFDR experiments. The appearance of resonances with distinct chemical shift values in 1H-1H RFDR spectra enabled the identification of residues (mostly from the transmembrane region) of cytb5 that interact with micelles.

  16. Introduction of perfluoroalkyl chain into the esterifying moiety of bacteriochlorophyll c in the green sulfur photosynthetic bacterium Chlorobaculum tepidum by pigment biosynthesis.

    PubMed

    Saga, Yoshitaka; Yamashita, Hayato; Hirota, Keiya

    2016-09-15

    The green sulfur photosynthetic bacterium Chlorobaculum (Cba.) tepidum was grown in liquid cultures containing perfluoro-1-decanol, 1H,1H,2H,2H-heptadecafluoro-1-decanol [CF3(CF2)7(CH2)2OH] or 1H,1H-nonadecafluoro-1-decanol [CF3(CF2)8CH2OH], to introduce rigid and fluorophilic chains into the esterifying moiety of light-harvesting bacteriochlorophyll (BChl) c. Exogenous 1H,1H,2H,2H-heptadecafluoro-1-decanol was successfully attached to the 17(2)-carboxy group of bacteriochlorophyllide (BChlide) c in vivo: the relative ratio of the unnatural BChl c esterified with this perfluoroalcohol over the total BChl c was 10.3%. Heat treatment of the liquid medium containing 1H,1H,2H,2H-heptadecafluoro-1-decanol with β-cyclodextrin before inoculation increased the relative ratio of the BChl c derivative esterified with this alcohol in the total BChl c in Cba. tepidum. In a while, 1H,1H-nonadecafluoro-1-decanol was not attached to BChlide c in Cba. tepidum, which was grown by its supplementation. These results suggest that the rigidity close to the hydroxy group of the esterifying alcohol is not suitable for the recognition by the BChl c synthase called BchK in Cba. tepidum. The unnatural BChl c esterified with 1H,1H,2H,2H-heptadecafluoro-1-decanol participated in BChl c self-aggregates in chlorosomes. PMID:27427396

  17. Proton-Detected 2D Radio Frequency Driven Recoupling Solid-state NMR Studies on Micelle-associated Cytochrome-b5

    PubMed Central

    Pandey, Manoj Kumar; Vivekanandan, Subramanian; Yamamoto, Kazutoshi; Im, Sangchoul; Waskell, Lucy; Ramamoorthy, Ayyalusamy

    2014-01-01

    Solid-state NMR spectroscopy is increasingly used in the high-resolution structural studies of membrane-associated proteins and peptides. Most such studies necessitate isotopically labeled (13C, 15N and 2H) proteins/peptides, which is a limiting factor for some of the exciting membrane-bound proteins and aggregating peptides. In this study, we report the use of a proton-based slow magic angle spinning (MAS) solid-state NMR experiment that exploits the unaveraged 1H-1H dipolar couplings from a membrane-bound protein. We have shown that the difference in the buildup rates of cross peak intensities against the mixing time - obtained from 2D 1H-1H radio frequency-driven recoupling (RFDR) and nuclear Overhauser effect spectroscopy (NOESY) experiments on a 16.7-kDa micelle-associated full-length rabbit cytochrome-b5 (cytb5) - can provide insights into protein dynamics and could be useful to measure 1H-1H dipolar couplings. The experimental buildup curves compare well with theoretical simulations and are used to extract relaxation parameters. Our results show that due to fast exchange of amide protons with water in the soluble heme-containing domain of cyb5, coherent 1H-1H dipolar interactions are averaged out for these protons while alpha and side chain protons show residual dipolar couplings that can be obtained from 1H-1H RFDR experiments. The appearance of resonances with distinct chemical shift values in 1H-1H RFDR spectra enabled the identification of residues (mostly from the transmembrane region) of cytb5 that interact with micelles. PMID:24657390

  18. NMR Investigation of beta-Substituted High-Spin and Low-Spin Iron(III) Tetraphenylporphyrins.

    PubMed

    Wojaczynski, Jacek; Latos-Grazynski, Lechoslaw; Hrycyk, Witold; Pacholska, Ewa; Rachlewicz, Krystyna; Szterenberg, Ludmila

    1996-11-01

    The NMR spectra of a series of beta-substituted iron(III) tetraphenylporphyrin (2-X-TPP) complexes have been studied to elucidate the relationship between the electron donating/withdrawing properties of the 2-substituent and the (1)H NMR spectral pattern. The electronic nature of the substituent has been significantly varied and covered the -0.6 to 0.8 Hammett constant range. Both high-spin and low-spin complexes of the general formula (2-X-TPP)Fe(III)Cl and [(2-X-TPP)Fe(III)(CN)(2)](-) have been investigated. The (1)H NMR data for the following substituents (X) have been reported: py(+), NO(2), CN, CH(3), BzO (C(6)H(5)COO), H, D, Br, Cl, CH(3), NH(2), NH(3)(+), NHCH(3), OH, and O(-). The (1)H NMR resonances for low-spin dicyano complexes have been completely assigned by a combination of two-dimensional COSY and NOESY experiments. In the case of selected high-spin complexes, the 3-H resonance has been identified by the selective deuteration of all but the 3-H position. The pattern of unambiguously assigned seven pyrrole resonances reflects the asymmetry imposed by 2-substitution and has been used as an unique (1)H NMR spectroscopic probe to map the spin density distribution. The pyrrole isotropic shifts of [(2-X-TPP)Fe(III)(CN)(2)](-) are dominated by the contact term. In order to quantify the substituent effect, the dependence of isotropic shift of all low-spin pyrrole resonances and 3-H high-spin pyrrole resonance versus Hammett constants has been studied. The electronic effect is strongly localized at the beta-substituted pyrrole. The major change of the isotropic shift has also been noted for only one of two adjacent pyrrole rings, i.e., at 7-H and 8-H positions. These neighboring protons, located on a single pyrrole ring, experienced opposite shift changes when electron withdrawing/donating properties were modified. Two other pyrrole rings for all investigated derivatives revealed considerably smaller, substituent related, isotropic shift changes. A long

  19. H(C)Ag: a triple resonance NMR experiment for (109) Ag detection in labile silver-carbene complexes.

    PubMed

    Weske, Sebastian; Li, Yingjia; Wiegmann, Sara; John, Michael

    2015-04-01

    In silver complexes, indirect detection of (109) Ag resonances via (1) H,(109) Ag-HMQC frequently suffers from small or absent JHAg couplings or rapid ligand dissociation. In these cases, it would be favourable to employ H(X)Ag triple resonance spectroscopy that uses the large one-bond JXAg coupling (where the donor atom of the ligand X is the relay nucleus). We have applied an HMQC-based version of the H(C)Ag experiment to a labile silver-NHC complex (NHC=N-heterocyclic carbene) at natural (13) C isotopic abundance and variable temperature. In agreement with simulations, H(C)Ag detection became superior to (1) H,(109) Ag-HMQC detection above -20 °C. PMID:25641122

  20. A General Method for Extracting Individual Coupling Constants from Crowded (1)H NMR Spectra.

    PubMed

    Sinnaeve, Davy; Foroozandeh, Mohammadali; Nilsson, Mathias; Morris, Gareth A

    2016-01-18

    Couplings between protons, whether scalar or dipolar, provide a wealth of structural information. Unfortunately, the high number of (1)H-(1)H couplings gives rise to complex multiplets and severe overlap in crowded spectra, greatly complicating their measurement. Many different methods exist for disentangling couplings, but none approaches optimum resolution. Here, we present a general new 2D J-resolved method, PSYCHEDELIC, in which all homonuclear couplings are suppressed in F2, and only the couplings to chosen spins appear, as simple doublets, in F1. This approaches the theoretical limit for resolving (1)H-(1)H couplings, with close to natural linewidths and with only chemical shifts in F2. With the same high sensitivity and spectral purity as the parent PSYCHE pure shift experiment, PSYCHEDELIC offers a robust method for chemists seeking to exploit couplings for structural, conformational, or stereochemical analyses. PMID:26636773

  1. Resolution enhancement in spectra of natural products dissolved in weakly orienting media with the help of 1H homonuclear dipolar decoupling during acquisition: Application to 1H- 13C dipolar couplings measurements

    NASA Astrophysics Data System (ADS)

    Farjon, Jonathan; Bermel, Wolfgang; Griesinger, Christian

    2006-05-01

    In weakly orienting media such as poly-γ-benzyl- L-glutamate (PBLG) a polymer that forms a chiral liquid crystal in organic solvents, the spectral resolution for embedded molecules is usually poor because of numerous 1H, 1H dipolar couplings that generally broaden proton spectra. Therefore 1H, 13C dipolar couplings are difficult or impossible to measure. Here, we incorporate Flip-Flop decoupling during detection into an HSQC experiment. Flip-Flop removes the 1H, 1H dipolar couplings and scales the chemical shifts of the protons as well as the 1H, 13C dipolar couplings during detection. A resolution gain by a factor 1.5-4.2 and improved signal intensity by an average factor of 1.6-1.7 have been obtained. This technique is demonstrated on (+)-menthol dissolved in a PBLG/CDCl 3 phase.

  2. Kinetic Isotope Effects for the Reactions of Muonic Helium and Muonium with H2

    SciTech Connect

    Fleming, Donald G.; Arseneau, Donald J.; Sukhorukov, Oleksandr; Brewer, Jess H.; Mielke, Steven L.; Schatz, George C.; Garrett, Bruce C.; Peterson, Kirk A.; Truhlar, Donald G.

    2011-01-28

    The neutral muonic helium atom may be regarded as the heaviest isotope of the hydrogen atom, with a mass of ~4.1 amu (4.1H), because the negative muon screens one proton charge. We report the reaction rate of 4.1H with 1H2 to produce 4.1H1H + 1H at 295 to 500 K. The experimental rate constants are compared with the predictions of accurate quantum mechanical dynamics calculations carried out on an accurate Born-Huang potential energy surface and with previously measured rate constants of 0.11H (where 0.11H is shorthand for muonium). Kinetic isotope effects can be compared for the unprecedentedly large mass ratio of 36. The agreement with accurate quantum dynamics is quantitative at 500 K, and variational transition state theory is used to interpret the extremely low (large inverse) kinetic isotope effects in the 10-4 to 10-2 range.

  3. Composite-180° pulse-based symmetry sequences to recouple proton chemical shift anisotropy tensors under ultrafast MAS solid-state NMR spectroscopy.

    PubMed

    Pandey, Manoj Kumar; Malon, Michal; Ramamoorthy, Ayyalusamy; Nishiyama, Yusuke

    2015-01-01

    There is considerable interest in the measurement of proton ((1)H) chemical shift anisotropy (CSA) tensors to obtain deeper insights into H-bonding interactions which find numerous applications in chemical and biological systems. However, the presence of strong (1)H/(1)H dipolar interaction makes it difficult to determine small size (1)H CSAs from the homogeneously broadened NMR spectra. Previously reported pulse sequences for (1)H CSA recoupling are prone to the effects of radio frequency field (B1) inhomogeneity. In the present work we have carried out a systematic study using both numerical and experimental approaches to evaluate γ-encoded radio frequency (RF) pulse sequences based on R-symmetries that recouple (1)H CSA in the indirect dimension of a 2D (1)H/(1)H anisotropic/isotropic chemical shift correlation experiment under ultrafast magic angle spinning (MAS) frequencies. The spectral resolution and sensitivity can be significantly improved in both frequency dimensions of the 2D (1)H/(1)H correlation spectrum without decoupling (1)H/(1)H dipolar couplings but by using ultrafast MAS rates up to 70 kHz. We successfully demonstrate that with a reasonable RF field requirement (<200 kHz) a set of symmetry-based recoupling sequences, with a series of phase-alternating 270°0-90°180 composite-180° pulses, are more robust in combating B1 inhomogeneity effects. In addition, our results show that the new pulse sequences render remarkable (1)H CSA recoupling efficiency and undistorted CSA lineshapes. Experimental results on citric acid and malonic acid comparing the efficiencies of these newly developed pulse sequences with that of previously reported CSA recoupling pulse sequences are also reported under ultrafast MAS conditions. PMID:25497846

  4. 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.

  5. High-resolution NMR characterization of low abundance oligomers of amyloid-β without purification

    PubMed Central

    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

    2015-01-01

    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. PMID:26138908

  6. 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.

  7. 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

    2015-01-01

    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 (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. PMID:26138908

  8. Cycloartane triterpenoids from Guarea macrophylla.

    PubMed

    Lago, João Henrique G; Roque, Nídia F

    2002-06-01

    Nine cycloartane triterpenoids, including two new derivatives 22,25-dihydroxy-cycloart-23E-en-3-one and 24-methylenecycloartane-3 beta,22-diol have been isolated from leaves of Guarea macrophylla. The structures were elucidated by interpretation of spectral data, mainly 1H and 13C NMR, including bidimensional analysis (HOMOCOSY, HMQC and HMBC). PMID:12031420

  9. Studies of Systematic Limitations in the EDM Searches at Storage Rings

    NASA Astrophysics Data System (ADS)

    Saleev, Artem; Nikolaev, Nikolai; Rathmann, Frank

    2016-02-01

    Searches of the electric dipole moment (EDM) at a pure magnetic ring, like COSY, encounter strong background coming from magnetic dipole moment (MDM). The most troubling issue is the MDM spin rotation in the so-called imperfection, radial and longitudinal, B-fields. To study the systematic effects of the imperfection fields at COSY we proposed the original method which makes use of the two static solenoids acting as artificial imperfections. Perturbation of the spin tune caused by the spin kicks in the solenoids probes the systematic effect of cumulative spin rotation in the imperfection fields all over the ring. The spin tune is one of the most precise quantities measured presently at COSY at 10‑10 level. The method has been successfully tested in September 2014 run at COSY, unravelling strength of spin kicks in the ring’s imperfection fields at the level of 10‑3rad.

  10. Substitution in ce2tsi3 intermetallic compositions with t = (Cr, Mn, Fe, Co, or Ni) x (Pd or Au) 1-x. Technical report No. 30

    SciTech Connect

    1996-07-10

    Alloys of composition Ce2(3d/T)Si3, with `3d` one of Cr, Mn, Fe, Co or Ni and `T` being Pd or Au, were separated and examined by powder x-ray diffraction. Select single phase compositions were further examined by magnetic susceptibility, by resistivity for the Pd and Co end-members and by specific heat for Ce2CoSi3. For compounds not containing cobalt, effective cerium moments consistent with trivalent cerium were observed. A re-examination of the AlB2 related structure of Ce2CoSi3 by single crystal methods revealed ordering of cobalt within the CoSi3 hexagonal layer. Magnetic susceptibility, resistance and specific heat measurements suggest valence fluctuation behavior of the cerium in Ce2CoSi3. A return to trivalent cerium magnetic behavior occurs on increasing palladium or gold substitution for cobalt.

  11. Storage Ring Based EDM Search — Achievements and Goals

    NASA Astrophysics Data System (ADS)

    Lehrach, Andreas

    2016-02-01

    This paper summarizes the experimental achievements of the JEDI (Jülich Electric Dipole moment Investigations) Collaboration to exploit and demonstrate the feasibility of charged particle Electric Dipole Moment searches with storage rings at the Cooler Synchrotron COSY of the Forschungszentrum Jülich. Recent experimental results, design and optimization of critical accelerator elements, progress in beam and spin tracking, and future goals of the R & D program at COSY are presented.

  12. 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.

  13. Drug solubilization mechanism of α-glucosyl stevia by NMR spectroscopy.

    PubMed

    Zhang, Junying; Higashi, Kenjirou; Ueda, Keisuke; Kadota, Kazunori; Tozuka, Yuichi; Limwikrant, Waree; Yamamoto, Keiji; Moribe, Kunikazu

    2014-04-25

    We investigated the drug solubilization mechanism of α-glucosyl stevia (Stevia-G) which was synthesized from stevia (rebaudioside-A) by transglycosylation. (1)H and (13)C NMR peaks of Stevia-G in water were assigned by two-dimensional (2D) NMR experiments including (1)H-(1)H correlation, (1)H-(13)C heteronuclear multiple bond correlation, and (1)H-(13)C heteronuclear multiple quantum coherence spectroscopies. The (1)H and (13)C peaks clearly showed the incorporation of two glucose units into rebaudioside-A to produce Stevia-G, supported by steviol glycoside and glucosyl residue assays. The concentration-dependent chemical shifts of Stevia-G protons correlated well with a mass-action law model, indicating the self-association of Stevia-G molecules in water. The critical micelle concentration (CMC) was 12.0 mg/mL at 37°C. The aggregation number was 2 below the CMC and 12 above the CMC. Dynamic light scattering and 2D (1)H-(1)H nuclear Overhauser effect spectroscopy (NOESY) NMR experiments demonstrated that Stevia-G self-associated into micelles of a few nanometers in size with a core-shell structure, containing a kaurane diterpenoid-based hydrophobic core and a glucose-based shell. 2D (1)H-(1)H NOESY NMR measurements also revealed that a poorly water-soluble drug, naringenin, was incorporated into the hydrophobic core of the Stevia-G micelle. The Stevia-G self-assembly behavior and micellar drug inclusion capacity can achieve significant enhancement in drug solubility. PMID:24508331

  14. 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. PMID:17019044

  15. New pregnane glycosides from Gymnema sylvestre.

    PubMed

    Xu, Rui; Yang, Yu; Zhang, Yang; Ren, Fengxia; Xu, Jinlong; Yu, Nengjiang; Zhao, Yimin

    2015-01-01

    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. PMID:25685911

  16. 1H and 13C spectral assignment of symmetrical bis[(4-aminosubstituted)quinolinium] derivatives.

    PubMed

    Campos, Joaquín M; Sánchez-Martín, Rosario M; Cruz-López, Olga; Conejo-García, Ana; Gallo, Miguel A; Espinosa, Antonio

    2005-12-01

    1H and 13C NMR spectroscopic data of both the quinolinium ring and the spacers for 32 symmetrical bisquinolinium compounds were assigned by a combination of one- and two-dimensional experiments (DEPT, HMBC, HMQC). The compounds have electron-releasing groups at position 4 of the quinolinium ring, with several arylalkyl linkers such as the 3,3'-, 4,4'-bis(methylene)biphenyl and 4,4'-bis(methylene)bibenzyl moieties. PMID:16114103

  17. 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.

  18. Proton zero-quantum 2D NMR of 2-propenenitrile aligned by an electric field. Determination of the 2H and 14N quadrupole coupling constants

    NASA Astrophysics Data System (ADS)

    Ruessink, B. H.; De Kanter, F. J. J.; MaClean, C.

    Zero-quantum NMR, selectively detected by 2D NMR, is applied to observe small 1H- 1H dipolar couplings in a polar liquid partially oriented by a strong electric field. The normal (single-quantum) 1H spectrum is severely broadened, which prevents the observation of small couplings. The results from the zero-quantum proton spectrum are used to calculate the 2H and 14N quadrupole coupling constants of 2-deutero-2-propenenitrile from the 2H and 14N NMR spectra.

  19. The influence of gold(i) on the mechanism of thiolate, disulfide exchange.

    PubMed

    Garusinghe, Gamage S P; Bessey, S Max; Bruce, Alice E; Bruce, Mitchell R M

    2016-07-28

    The mechanism of gold(i)-thiolate, disulfide exchange was investigated by using initial-rate kinetic studies, 2D ((1)H-(1)H) ROESY NMR spectroscopy, and electrochemical/chemical techniques. The rate law for exchange is overall second order, first order in gold(i)-thiolate and disulfide. 2D NMR experiments show evidence of association between gold(i)-thiolate and disulfide. Electrochemical/chemical investigations do not show evidence of free thiolate and are consistent with a mechanism involving formation of a [Au-S, S-S], four-centered metallacycle intermediate during gold(i)-thiolate, disulfide exchange. PMID:27353236

  20. 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. PMID:27203746

  1. 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.

  2. Bionectriol A, a polyketide glycoside from the fungus Bionectria sp. associated with the fungus-growing ant, Apterostigma dentigerum

    PubMed Central

    Freinkman, Elizaveta; Oh, Dong-Chan; Scott, Jarrod J.; Currie, Cameron R.; Clardy, Jon

    2009-01-01

    A new polyketide glycoside, bionectriol A (1), was produced by a fungal culture of Bionectria sp., which was isolated from a fungus garden of the fungus-growing ant Apterostigma dentigerum, in Costa Rica. The structure of bionectriol A was determined mainly through NMR and mass spectroscopic data, as well as UV and IR spectra. The relative configurations of the main chain, the pyranohexose, and the pentitol moiety were elucidated by 1H-1H coupling constants and ROESY NMR spectral analysis. PMID:20160864

  3. 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.

  4. Fabrication of superhydrophobic polymer films with hierarchical silver microbowl array structures.

    PubMed

    Xu, Miaojun; Lu, Nan; Qi, Dianpeng; Xu, Hongbo; Wang, Yandong; Shi, Shoulei; Chi, Lifeng

    2011-08-01

    Flexible superhydrophobic polyvinyl alcohol (PVA) films with silver bowl-like array structure are fabricated based on the thermal evaporation with sphere monolayer as templates and the modification of 1H, 1H, 2H, 2H-perfluorodecanethiol on silver surface. The silver microbowl arrays were composed of silver nanoparticles with an average diameter size of ca. 10 nm. The polymer films exhibit excellent stability and remarkable superhydrophobicity with a high water contact angle (CA) of about 163° and a low sliding angle (SA) of less than 3°. PMID:21549389

  5. Hydrophobic vertically aligned carbon nanotubes on Corning glass for self cleaning applications

    NASA Astrophysics Data System (ADS)

    Bu, Ian Y. Y.; Oei, Shu Pei

    2010-09-01

    Vertically aligned carbon nanotubes were prepared by Plasma enhanced chemical vapor deposition (PECVD) on inexpensive Corning glass substrates using different under layers. The samples were functionalised by a simple 1H,1H-2H,2H perfluorodecyl-trichlorosilane (FDTS) and hexane mixture. The surface roughness of the CNTs and protective FDTS coating provides an ideal hydrophobic surface of around 141°. Auger spectroscopy analysis was performed to confirm fluorination of the sample. It was also found titanium provides a suitable under layer support for Ni catalyst due to the wetability of the two elements.

  6. Growth and characterization of metal/semiconductor superlattices

    NASA Astrophysics Data System (ADS)

    Henz, J.; Ospelt, M.; Von Känel, H.

    1989-04-01

    Thanks to recent advances in the growth of CoSi 2-layers on Si(111) it has become possible for the first time to fabricate metal/semiconductor superlattices. This is achieved by a combination of solid phase epitaxy (SPE) and molecular beam epitaxy (MBE). We briefly explain the growth of thin ( < 100 Å) type B oriented (i.e. rotated by 180° with respect to the substrate) CoSi 2 layers. We show the effect of the two different surface structures of CoSi 2 on the morphology of the films. Silicon with a reasonable crystal quality can be grown on top of CoSi 2 by using low substrate temperatures for the first few monolayers of growth. We always find the orientation of Si to be the same as the one of the underlying suicide, when the latter is of high quality. Superlattices of CoSi 2 and Si have two periods, one being given by the different materials and the other by the alternating crystal orientations. We show some TEM cross section images as well as first X-ray investigations of these structures.

  7. Comparison of various NMR methods for the indirect detection of nitrogen-14 nuclei via protons in solids.

    PubMed

    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) (14)N coherences via spy (1)H nuclei. These (1)H-{(14)N} D-HMQC sequences differ not only by the order of (14)N 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 (14)N Larmor frequency, ν0((14)N), whereas the DQ coherences are excited and reconverted using rf irradiation either at ν0((14)N) or at the (14)N overtone frequency, 2ν0((14)N). 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 (1)H-{(14)N} D-HMQC sequences, including those with (14)N rectangular pulses at ν0((14)N) for the indirect detection of homo-nuclear (i) (14)N 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 (14)N 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 (14)N sites subject to moderate quadrupole interactions. We demonstrate that the optimum choice of the (1)H-{(14)N} 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 (14)N SQ

  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. Copy number variation of a gene cluster encoding endopolygalacturonase mediates flesh texture and stone adhesion in peach.

    PubMed

    Gu, Chao; Wang, Lu; Wang, Wei; Zhou, Hui; Ma, Baiquan; Zheng, Hongyu; Fang, Ting; Ogutu, Collins; Vimolmangkang, Sornkanok; Han, Yuepeng

    2016-03-01

    Texture is an important attribute affecting consumer perception of fruit quality. Peach melting flesh and flesh adhesion to stone (endocarp) are simply inherited and controlled by the F-M locus on linkage group (LG) 4. Here, we report that two genes encoding endopolygalacturonase (endoPG) in the F-M locus, designated PpendoPGF and PpendoPGM, are associated with the melting flesh and stone adhesion traits. PpendoPGM controls melting flesh while PpendoPGF has pleiotropic effects on both melting flesh and stone adhesion. The F-M locus has three allelic copy number variants of endoPG, H1 (PpendoPGF and PpendoPGM), H2 (PpendoPGM), and H3 (null). The H2 haplotype represents the ancestral one while the H1 and H3 haplotypes are two variants due to duplication and deletion of PpendoPGM, respectively. Accessions with H1H1, H1H2, or H1H3 genotypes show the freestone or semi-freestone and melting flesh phenotype, while both H2H2 and H2H3 accessions have the clingstone and melting flesh phenotype. The H3H3 accessions have the clingstone and non-melting flesh phenotype. Our study not only demonstrates a driving role of gene copy number variations in flesh texture diversification in fruit trees, but also provides a useful diagnostic tool for early seedling selection in peach breeding programmes. PMID:26850878

  10. 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.

  11. Characterization of nanofilm spray products by mass spectrometry.

    PubMed

    Nørgaard, Asger W; Wolkoff, Peder; Lauritsen, Frants R

    2010-09-01

    The use of nanofilm spray products (NFPs) has been associated with a number of severe cases of airway injuries; however, the causative agents are unknown. To identify possible causative agents, 10 products from three different suppliers have been analysed using two mass spectrometric methods: (1) ESI-MS and ESI-MS/MS; (2) GC-MS and GC-MS/MS. The 10 products could be classified into three groups (NFPs 1-3). NFP 1 and NFP 2 contained hydrolysates and condensates of the organo-functionalized silanes 1H,1H,2H,2H-perfluorooctyl triisopropoxysilane and hexadecyl triethoxysilane, respectively. NFP 3 contained non-ionic detergents and abrasive as active ingredients. To verify the fluorosilane solution in NFP 1, a synthetic NFP 1 was prepared by hydrolysis and condensation of 1H,1H,2H,2H-perfluorooctyl triethoxysilane. After about 1month in acidic 2-propanol substitution of the ethoxy groups with isopropoxy groups had taken place and all silane was converted to disiloxanes, trisiloxanes and tetrasiloxanes. PMID:20594580

  12. Copy number variation of a gene cluster encoding endopolygalacturonase mediates flesh texture and stone adhesion in peach

    PubMed Central

    Gu, Chao; Wang, Lu; Wang, Wei; Zhou, Hui; Ma, Baiquan; Zheng, Hongyu; Fang, Ting; Ogutu, Collins; Vimolmangkang, Sornkanok; Han, Yuepeng

    2016-01-01

    Texture is an important attribute affecting consumer perception of fruit quality. Peach melting flesh and flesh adhesion to stone (endocarp) are simply inherited and controlled by the F-M locus on linkage group (LG) 4. Here, we report that two genes encoding endopolygalacturonase (endoPG) in the F-M locus, designated PpendoPGF and PpendoPGM, are associated with the melting flesh and stone adhesion traits. PpendoPGM controls melting flesh while PpendoPGF has pleiotropic effects on both melting flesh and stone adhesion. The F-M locus has three allelic copy number variants of endoPG, H1 (PpendoPGF and PpendoPGM), H2 (PpendoPGM), and H3 (null). The H2 haplotype represents the ancestral one while the H1 and H3 haplotypes are two variants due to duplication and deletion of PpendoPGM, respectively. Accessions with H1H1, H1H2, or H1H3 genotypes show the freestone or semi-freestone and melting flesh phenotype, while both H2H2 and H2H3 accessions have the clingstone and melting flesh phenotype. The H3H3 accessions have the clingstone and non-melting flesh phenotype. Our study not only demonstrates a driving role of gene copy number variations in flesh texture diversification in fruit trees, but also provides a useful diagnostic tool for early seedling selection in peach breeding programmes. PMID:26850878

  13. 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

    2016-08-01

    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. PMID:27480785

  14. High-Resolution Solid-State NMR Investigation of the Phase Transition in Decamethylferrocene-Acenaphthenequinone Charge-Transfer Complex

    NASA Astrophysics Data System (ADS)

    Nakamura, Hideaki; Kuwahara, Daisuke; Mochida, Tomoyuki

    2009-10-01

    A charge-transfer complex composed of decamethylferrocene (D) and acenaphthenequinone (A) was prepared. The material was a 1:1 neutral complex with a mixed-stack structure and exhibited a phase transition at -16 °C. High-resolution 13C and 1H NMR spectroscopy revealed that an inclination of A with respect to D occurs below the phase-transition temperature. The 1H spin-diffusion rates of the complex undergoing high-speed magic-angle spinning (MAS) were measured to determine the shortest 1H-1H distance r between D and A. To analyze the experimental results, we derived the analytical expression of the spin-diffusion rate Wz for a homonuclear multispin system undergoing MAS. It was found that Wz for the complex is proportional only to 1/r6 under high-speed MAS conditions. On the basis of this relationship and the crystal structure at 20 °C, it was determined that the shortest 1H-1H distance r at -27.7 °C (below the phase transition temperature) is 0.4 Å shorter than that at 20 °C. Given this information, a plausible model of the low-temperature structure is discussed.

  15. Heteronuclear 19F-1H statistical total correlation spectroscopy as a tool in drug metabolism: study of flucloxacillin biotransformation.

    PubMed

    Keun, Hector C; Athersuch, Toby J; Beckonert, Olaf; Wang, Yulan; Saric, Jasmina; Shockcor, John P; Lindon, John C; Wilson, Ian D; Holmes, Elaine; Nicholson, Jeremy K

    2008-02-15

    We present a novel application of the heteronuclear statistical total correlation spectroscopy (HET-STOCSY) approach utilizing statistical correlation between one-dimensional 19F/1H NMR spectroscopic data sets collected in parallel to study drug metabolism. Parallel one-dimensional (1D) 800 MHz 1H and 753 MHz 19F{1H} spectra (n = 21) were obtained on urine samples collected from volunteers (n = 6) at various intervals up to 24 h after oral dosing with 500 mg of flucloxacillin. A variety of statistical relationships between and within the spectroscopic datasets were explored without significant loss of the typically high 1D spectral resolution, generating 1H-1H STOCSY plots, and novel 19F-1H HET-STOCSY, 19F-19F STOCSY, and 19F-edited 1H-1H STOCSY (X-STOCSY) spectroscopic maps, with a resolution of approximately 0.8 Hz/pt for both nuclei. The efficient statistical editing provided by these methods readily allowed the collection of drug metabolic data and assisted structure elucidation. This approach is of general applicability for studying the metabolism of other fluorine-containing drugs, including important anticancer agents such as 5-fluorouracil and flutamide, and is extendable to any drug metabolism study where there is a spin-active X-nucleus (e.g., 13C, 15N, 31P) label present. PMID:18211034

  16. Optically transparent superhydrophobic surfaces with enhanced mechanical abrasion resistance enabled by mesh structure.

    PubMed

    Yokoi, Naoyuki; Manabe, Kengo; Tenjimbayashi, Mizuki; Shiratori, Seimei

    2015-03-01

    Inspired by naturally occurring superhydrophobic surfaces such as "lotus leaves", a number of approaches have been attempted to create specific surfaces having nano/microscale rough structures and a low surface free energy. Most importantly, much attention has been paid in recent years to the improvement of the durability of highly transparent superhydrophobic surfaces. In this report, superhydrophobic surfaces are fabricated using three steps. First, chemical and morphological changes are generated in the polyester mesh by alkaline treatment of NaOH. Second, alkaline treatment causes hydrophobic molecules of 1H,1H,2H,2H-perfluorodecyltrichlorosilane to react with the hydroxyl groups on the fiber surfaces forming covalent bonds by using the chemical vapor deposition method. Third, hydrophobicity is enhanced by treating the mesh with SiO2 nanoparticles modified with 1H,1H,2H,2H-perfluorooctyltriethoxysilane using a spray method. The transmittance of the fabricated superhydrophobic mesh is approximately 80% in the spectral range of 400-1000 nm. The water contact angle and the water sliding angle remain greater than 150° and lower than 25°, respectively, and the transmittance remains approximately 79% after 100 cycles of abrasion under approximately 10 kPa of pressure. The mesh surface exhibits a good resistance to acidic and basic solutions over a wide range of pH values (pH 2-14), and the surface can also be used as an oil/water separation material because of its mesh structure. PMID:25625787

  17. Polymer transistors fabricated by painting of metallic nanoparticles

    NASA Astrophysics Data System (ADS)

    Li, S. P.; Russell, D. M.; Newsome, C. J.; Kugler, T.; Shimoda, T.

    2006-09-01

    In this letter the authors describe the fabrication of high performance polymer thin film transistors using an aqueous based silver colloid to form source and drain electrodes patterned by brush painting. The electrode dimensions were controlled by a surface energy pattern defined by soft contact printing of a self-assembled monolayer 1H,1H,2H,2H-perfluorodecyl-trichlorosilane on a SiO2 surface which acted as a dewetting layer for the painted silver particle suspension. Another self-assembled monolayer of 1H ,1H,2H,2H-perfluorodecanethiol was also used to increase the work function of the patterned silver electrodes in order to decrease the barrier for charge injection into the polymer semiconductor. The field-effect mobility of the thin film transistors fabricated by this method approached 0.02cm2V-1s-1 with an on/off current ratio of 105. The relative high mobility may be influenced by the ordering of the poly(3-hexylthiophene) semiconductor layer by the self-assembled monolayer used to define the source and drain electrodes.

  18. 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.

  19. The Reason for Beam Cooling: Some of the Physics that Cooling Allows

    SciTech Connect

    Oelert, W.

    2006-03-20

    There are many examples of achievements in physics which would not be possible without cooling. Different mechanisms for cooling exist and some will be presented in this introductory talk where we distinguish between 'relative' and 'absolute' cooling. A short reminder to high and medium energy physics with antiprotons as performed at the accelerators of CERN will be delineated. The success in applying cooling of beams in hadron physics at the internal COSY-11 experiment installed at the cooler synchrotron COSY will be presented. COSY-11 aims for meson production investigations at threshold in nucleon-nucleon collisions. Again, such investigations would not be feasible without cooling especially regarding the precision required and obtained. The need of cooling for the production and trapping of antihydrogen atoms is demonstrated - as an example - by the ATRAP experiment at the CERN antiproton decelerator AD aiming for a comparison of hydrogen (H0) to antihydrogen (H-bar0) atom spectroscopy.

  20. 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.

  1. Growth of oxide-mediated ternary silicide controlled by a Si cap layer by rapid thermal annealing

    NASA Astrophysics Data System (ADS)

    Xu, M.; Vantomme, A.; Vanormelingen, K.; Yao, S. D.

    2008-01-01

    We reported a simple method to grow good-quality CoSi 2 film by using Si cap technology and introducing moderate Ni. First, a cobalt layer of ∼15 nm with a Si cap layer with a different thickness deposited onto the Si surface with a thin silicon oxide buffer is applied to investigate the formation of CoSi 2 by ex situ rapid thermal annealing. It was found that a 13 nm thick Si cap layer could significantly improve the crystal quality of oxide-mediated CoSi 2 film. Setting the Si cap thickness at 13 nm, we revealed that introduction of Ni can further improve the crystal quality of the silicide film in comparison to the pure Co silicide, and a ratio of Ni to Co at round 1:8 causes the lowest sheet resistance, ∼5 Ω/sq.

  2. Determination of the η'-Proton Scattering Length in Free Space

    NASA Astrophysics Data System (ADS)

    Czerwiński, E.; Moskal, P.; Silarski, M.; Bass, S. D.; Grzonka, D.; Kamys, B.; Khoukaz, A.; Klaja, J.; Krzemień, W.; Oelert, W.; Ritman, J.; Sefzick, T.; Smyrski, J.; Täschner, A.; Wolke, M.; Zieliński, M.

    2014-08-01

    Taking advantage of both the high mass resolution of the COSY-11 detector and the high energy resolution of the low-emittance proton beam of the cooler synchrotron COSY, we determine the excitation function for the pp→ppη' reaction close to threshold. Combining these data with previous results, we extract the scattering length for the η'-proton potential in free space to be Re(apη')=0±0.43 fm and Im(apη')=0.37-0.16+0.40 fm.

  3. Infrared response from metallic particles embedded in a single-crystal Si matrix - The layered internal photoemission sensor

    NASA Technical Reports Server (NTRS)

    Fathauer, R. W.; Iannelli, J. M.; Nieh, C. W.; Hashimoto, Shin

    1990-01-01

    Infrared radiation at wavelengths of 1-2 microns has been detected in a new device labeled the layered internal photoemission sensor. The device structure, which is grown by molecular beam epitaxy, incorporates epitaxial CoSi2 particles with dimensions of 10-50 nm. Radiation absorbed by these particles photoexcites carriers into a surrounding single-crystal silicon matrix. A peak quantum efficiency of 1.3 percent is measured, which is approximately six times higher than in planar CoSi2 Schottky diodes with 5-nm silicide thickness.

  4. 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.

  5. 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.

  6. RUBIDIUM, a program for computer-aided assignment of two-dimensional NMR spectra of polypeptides.

    PubMed

    Yu, C; Hwang, J F; Chen, T B; Soo, V W

    1992-01-01

    Taking advantage of the rule-based expert system technology, a program named RUBIDIUM (Rule-Based Identification In 2D NMR Spectrum) was developed to accomplish the automatic 1H NMR resonance assignments of polypeptides. Besides noise elimination and peak selection capabilities, RUBIDIUM detects the cross-peak patterns of amino acid residues in the COSY spectrum, assigning these patterns to amino acid types, performing sequential assignments using combined COSY/NOESY spectra, and finally, achieving the total assignment of the 1H NMR spectrum. PMID:1607394

  7. Determination of the η(')-proton scattering length in free space.

    PubMed

    Czerwiński, E; Moskal, P; Silarski, M; Bass, S D; Grzonka, D; Kamys, B; Khoukaz, A; Klaja, J; Krzemień, W; Oelert, W; Ritman, J; Sefzick, T; Smyrski, J; Täschner, A; Wolke, M; Zieliński, M

    2014-08-01

    Taking advantage of both the high mass resolution of the COSY-11 detector and the high energy resolution of the low-emittance proton beam of the cooler synchrotron COSY, we determine the excitation function for the pp→ppη(') reaction close to threshold. Combining these data with previous results, we extract the scattering length for the η(')-proton potential in free space to be Re(a(pη(')))=0±0.43  fm and Im(a(pη(')))=0.37(-0.16)(+0.40)  fm. PMID:25148320

  8. NMR analysis of cleaved Escherichia coli thioredoxin (1-73/74-108) and its P76A variant: cis/trans peptide isomerization.

    PubMed Central

    Yu, W. F.; Tung, C. S.; Wang, H.; Tasayco, M. L.

    2000-01-01

    Inspection of high resolution three-dimensional (3D) structures from the protein database reveals an increasing number of cis-Xaa-Pro and cis-Xaa-Yaa peptide bonds. However, we are still far from being able to predict whether these bonds will remain cis upon single-site substitution of Pro or Yaa and/or cleavage of a peptide bond close to it in the sequence. We have chosen oxidized Escherichia coli thioredoxin (Trx), a member of the Trx superfamily with a single alpha/beta domain and cis P76 to determine the effect of single-site substitution and/or cleavage on this isomer. Standard two-dimensional (2D) NMR analysis were performed on cleaved Trx (1-73/74-108) and its P76A variant. Analysis of the NOE connectivities indicates remarkable similarity between the secondary and supersecondary structure of the noncovalent complexes and Trx. Analysis of the 2D version of the HCCH-TOCSY and HMQC-NOESY-HMQC and 13C-filtered HMQC-NOESY spectra of cleaved Trx with uniformly 13C-labeled 175 and P76 shows surprising conservation of both cis P76 and packing of 175 against W31. A similar NMR analysis of its P76A variant provides no evidence for cis A76 and shows only subtle local changes in both the packing of 175 and the interstrand connectivities between its most protected hydrophobic strands (beta2 and beta4). Indeed, a molecular simulation model for the trans P76A variant of Trx shows only subtle local changes around the substitution site. In conclusion, cleavage of R73 is insufficient to provoke cis/trans isomerization of P76, but cleavage and single-site substitution (P76A) favors the trans isomer. PMID:10739243

  9. Line-narrowing in proton-detected nitrogen-14 NMR

    NASA Astrophysics Data System (ADS)

    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) 14N 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 T11IT11S and T21IT11S at the beginning of the evolution interval t1. The spectra obtained by Fourier transformation from t1 to ω1 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 14N 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 14N 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 14N 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 14N in AAG peptide bonds.

  10. Trace level detection of compounds related to the chemical weapons convention by 1H-detected 13C NMR spectroscopy executed with a sensitivity-enhanced, cryogenic probehead.

    PubMed

    Cullinan, David B; Hondrogiannis, George; Henderson, Terry J

    2008-04-15

    Two-dimensional 1H-13C HSQC (heteronuclear single quantum correlation) and fast-HMQC (heteronuclear multiple quantum correlation) pulse sequences were implemented using a sensitivity-enhanced, cryogenic probehead for detecting compounds relevant to the Chemical Weapons Convention present in complex mixtures. The resulting methods demonstrated exceptional sensitivity for detecting the analytes at trace level concentrations. 1H-13C correlations of target analytes at < or = 25 microg/mL were easily detected in a sample where the 1H solvent signal was approximately 58,000-fold more intense than the analyte 1H signals. The problem of overlapping signals typically observed in conventional 1H spectroscopy was essentially eliminated, while 1H and 13C chemical shift information could be derived quickly and simultaneously from the resulting spectra. The fast-HMQC pulse sequences generated magnitude mode spectra suitable for detailed analysis in approximately 4.5 h and can be used in experiments to efficiently screen a large number of samples. The HSQC pulse sequences, on the other hand, required roughly twice the data acquisition time to produce suitable spectra. These spectra, however, were phase-sensitive, contained considerably more resolution in both dimensions, and proved to be superior for detecting analyte 1H-13C correlations. Furthermore, a HSQC spectrum collected with a multiplicity-edited pulse sequence provided additional structural information valuable for identifying target analytes. The HSQC pulse sequences are ideal for collecting high-quality data sets with overnight acquisitions and logically follow the use of fast-HMQC pulse sequences to rapidly screen samples for potential target analytes. Use of the pulse sequences considerably improves the performance of NMR spectroscopy as a complimentary technique for the screening, identification, and validation of chemical warfare agents and other small-molecule analytes present in complex mixtures and environmental

  11. Isolation and characterization of an antimalarial agent of the neem tree Azadirachta indica.

    PubMed

    Khalid, S A; Duddeck, H; Gonzalez-Sierra, M

    1989-01-01

    The isolation and structure elucidation of gedunin [1], the antimalarial agent of Azadirachta indica, are reported. Its 1H- and 13C-nmr spectra were assigned by using one- and two-dimensional nmr spectroscopy, especially homonuclear and heteronuclear COSY, nOe difference, and COLOC experiments. PMID:2607354

  12. 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.

  13. Cobalt silicide formation on a Si(1 0 0) substrate in the presence of an interfacial (Fe90Zr10) interlayer

    NASA Astrophysics Data System (ADS)

    Abrass, Hameda A.; Theron, C. C.; Njoroge, E. G.; van der Berg, N. G.; Botha, A. J.; Yan, X.-L.; Terblans, J. J.

    2015-09-01

    The reaction between a thin film (126 nm) of Co and Si has been studied at 450 °C for 24 h under high vacuum conditions, in the presence of a FeZr barrier layer. Without a diffusion barrier layer between Co and Si, Co2Si forms at 350 °C as the initial phase while CoSi2 forms at 550 °C. The FeZr barrier layer changed the flux of atoms arriving at the reaction interface. Co reacted with the Si from the substrate and formed a mixed layer of CoSi and CoSi2 in the interlayer region. The use of the FeZr diffusion barrier has been demonstrated to lower the temperature formation of CoSi2 to 450 °C. The reactions were characterised by Rutherford backscattering spectrometry, Auger electron spectroscopy depth profiling, X-ray diffraction using CoKα radiation and scanning electron microscopy.

  14. 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," "Guidance-oriented," and…

  15. Characteristics of Cobalt Films Deposited by Metal Organic Chemical Vapor Deposition Method Using Dicobalt Hexacarbonyl tert-Butylacetylene

    NASA Astrophysics Data System (ADS)

    Lee, Keunwoo; Park, Taeyong; Lee, Jaesang; Kim, Jinwoo; Kim, Jeongtae; Kwak, Nohjung; Yeom, Seungjin; Jeon, Hyeongtag

    2008-07-01

    Cobalt films were deposited by metal organic chemical vapor deposition (MOCVD) using C12H10O6(Co)2 (dicobalt hexacarbonyl tert-butylacetylene, CCTBA) as the Co precursor and H2 reactant gas. The impurity content of the Co films was monitored as a function of the partial pressure of H2 reactant gas. The carbon and oxygen content of as-deposited Co films greatly decrease with the increase of H2 partial pressure, and at H2 partial pressure of 10 Torr and a substrate temperature of 150 °C were 2.8 at. % and less than 1 at. %, respectively. As the H2 partial pressure increased, carbon and oxygen content decreased markedly. Excellent conformality of Co film over 80% was achieved on a patterned wafer with aspect ratio of 15:1, 0.12 µm wide and 1.8 µm deep. The phase transition was analyzed with X-ray diffraction (XRD) depending on RTA temperature. CoSi was observed at 500 °C annealing, and was transformed to CoSi2 at 600 °C annealing. In addition, Auger electron spectroscopy (AES) data showed a 1:2 atomic ratio of Co:Si in the CoSi2 layer.

  16. Aligning Olympic Education with the Liberal Arts: A Curriculum Blueprint from Taiwan

    ERIC Educational Resources Information Center

    Hsu, Li-Hong Leo; Kohe, Geoffery Zain

    2015-01-01

    Background: For some time the Olympics have enjoyed a relatively cosy, and quite unsurprising, relationship with Physical Education and its practitioners. Yet, as academics continue their critiques of all matters Olympic, this seemingly symbiotic partnership is being placed under much closer scrutiny. The debates are typically orientated around…

  17. 78 FR 7798 - Privacy Act of 1974; Department of Homeland Security U.S. Immigration and Customs Enforcement-010...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-02-04

    ... Confidential and Other Sources of Information (COSI) System of Records,'' 73 FR 237 (Dec. 9, 2008). This System... the purpose of obtaining information relevant and necessary to ICE's decision whether an individual... published in the Federal Register on August 31, 2009 (74 FR 45083). In the context of this updated SORN,...

  18. Ion channeling studies of epitaxial Fe and Co silicides on Si

    NASA Astrophysics Data System (ADS)

    Schwarz, C.; Onda, N.; Goncalves-Conto, S.; Sirringhaus, H.; von Kanel, H.; Pixley, R. E.

    1994-12-01

    High quality epitaxial Co and Fe silicides have been grown by molecular beam epitaxy on Si(111) and Si(001) substrates with film thicknesses ranging between 25 and 8400 A. We used Rutherford backscattering spectrometry channeling techniques to measure the lattice distortion as a function of film thickness. The critical thickness h(sub c) corresponding to the film thickness at which strain relieving dislocations begin to appear was determined for CoSi2 on Si(111) and Si(001) as well as for Si on CoSi2(111). For CoSi2 on Si(001), a larger critical thickness was obtained on Si(111), where h(sub c) is about 45A. Epitaxial Si on CoSi2(111) was found to be under a compressive strain up to thicknesses of about 350 a depending on substrate misorientation. Strain measurements were also performed on epitaxially stabilized Co and Fe monosilicides with the CsCl structure. Channeling measurements on thick epitaxial films of bcc-Fe, Fe3Si, FeSi, and Fe0.5Si were used to determine the crystalline quality. Excellent channeling minimum yields of 4.0% were found for bcc-Fe/Si(111). The results are compared with structural information obtained from x-ray diffraction and Brillouin scattering spectroscopy.

  19. Hydrothermal stability investigation of micro- and mesoporous silica containing long-range ordered cobalt oxide clusters by XAS.

    PubMed

    Liu, Liang; Wang, David K; Kappen, Peter; Martens, Dana L; Smart, Simon; Diniz da Costa, João C

    2015-07-15

    This work investigates the hydrothermal stability of cobalt doped silica materials with different Co/Si molar ratios (0, 0.05, 0.10, and 0.25). The resultant materials were characterized by N2 sorption and chemical structures by Raman and X-ray absorption spectroscopy before and after a harsh hydrothermal exposure (550 °C, 75 mol% vapour and 40 h). The cobalt silica materials showed a lower surface area loss from 48% to 12% with increasing Co/Si molar ratio from 0.05 to 0.25 and relatively maintaining their pore size distribution, while pure silica exhibited significant surface area reduction (80%) and pore size broadening. For low cobalt loading sample (Co/Si = 0.05), the cobalt was highly dispersed in the silica network in a tetrahedral coordination with oxygen and a small proportion of Co-Co interaction in the second shell. Long range order Co3O4 was observed when Co/Si molar ratio increased to 0.10 and 0.25. The hydrothermal exposure did not affect the local cobalt environments and no cobalt-silicon interaction was observed by X-ray absorption spectroscopy. The hydrothermal stability of the silica matrix was attributed to the physical barrier of cobalt oxide in opposing densification and silica mobility under harsh hydrothermal conditions. PMID:26145988

  20. Emotion Education without Ontological Commitment?

    ERIC Educational Resources Information Center

    Kristjansson, Kristjan

    2010-01-01

    Emotion education is enjoying new-found popularity. This paper explores the "cosy consensus" that seems to have developed in education circles, according to which approaches to emotion education are immune from metaethical considerations such as contrasting rationalist and sentimentalist views about the moral ontology of emotions. I spell out five…

  1. 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.

  2. Two new glycosides from Conyza bonariensis.

    PubMed

    Zahoor, Aqib; Siddiqui, Imran Nafees; Khan, Afsar; Ahmad, Viqar Uddin; Ahmed, Amir; Hassan, Zahid; Khan, Saleha Suleman; Iqbal, Shazia

    2010-07-01

    Studies on Conyza bonariensis (L.) Cronq. led to the isolation of two new glycosides trivially named as erigeside E and F (1-2), along with two new source compounds; benzyl-beta-D-glucopyranoside (3) and 2-phenylethyl-beta-D-glucopyranoside (4). Compounds 1, 3, and 4 are aromatic glycosides, while compound 2 is an alkyl glycoside. Their structures were elucidated through mass spectrometric, and 1D- and 2D-NMR spectroscopic techniques, including 1H NMR, 13C NMR, HMQC, HSQC and HMBC. PMID:20734949

  3. A new ent-kaurane diterpenoid glycoside from Isodon japonica var. glaucocalyx.

    PubMed

    Xiang, Zhao-Bao; Wang, Guang-Li; Huang, Lan-Zhi; Heng, Lin-Sen; Li, Xiao-Hui

    2013-01-01

    A new ent-kaurane diterpenoid glycoside (1), named glaucocalyxin G, has been isolated from the n-butanol-soluble fraction of the dried whole plants of Isodon japonica var. glaucocalyx along with two known compounds, namely arjunglucoside (2) and kaempferol-3-O-rutinoside (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 HMQC, HMBC, and NOESY experiments and comparison with the literature data. PMID:23614395

  4. 5,8-Epidioxysterols and related derivatives from a Chinese soft coral Sinularia flexibilis.

    PubMed

    Yu, Shanjiang; Deng, Zhiwei; van Ofwegen, Leen; Proksch, Peter; Lin, Wenhan

    2006-11-01

    Chromatographic separation of the methanolic extract of the marine soft coral, Sinularia flexibilis, resulted in the isolation and characterization of four new sterols, 5alpha,8alpha-epidioxygorgosta-6-en-3beta-ol (1), 5alpha,8alpha-epidioxygorgosta-6,9(11)-dien-3beta-ol (2), 22alpha,28-epidioxycholesta-5,23(E)-dien-3beta-ol (3) and its C-22 epimer (4), along with nine known sterols. The structures of the new compounds were determined on the basis of extensive spectroscopic data (IR, MS, 1H and 13C NMR, HMQC, HMBC, and NOESY) analyses. PMID:16930652

  5. 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. PMID:14697274

  6. Fluorous-assisted metal chelate affinity extraction technique for analysis of protein kinase activity.

    PubMed

    Hayama, Tadashi; Kiyokawa, Ena; Yoshida, Hideyuki; Imakyure, Osamu; Yamaguchi, Masatoshi; Nohta, Hitoshi

    2016-08-15

    We have developed a fluorous affinity-based extraction method for measurement of protein kinase activity. In this method, a fluorescent peptide substrate was phosphorylated by a protein kinase, and the obtained phosphopeptide was selectively captured with Fe(III)-immobilized perfluoroalkyliminodiacetic acid reagent via a metal chelate affinity technique. Next, the captured phosphopeptide was selectively extracted into a fluorous solvent mixture, tetradecafluorohexane and 1H,1H,2H,2H-tridecafluoro-1-n-octanol (3:1, v/v), using the specificity of fluorous affinity (fluorophilicity). In contrast, the remained substrate peptide in the aqueous (non-fluorous) phase was easily measured fluorimetrically. Finally, the enzyme activity could be assayed by measuring the decrease in fluorescence. The feasibility of this method was demonstrated by applying the method for measurement of the activity of cAMP-dependent protein kinase (PKA) using its substrate peptide (kemptide) pre-labeled with carboxytetramethylrhodamine (TAMRA). PMID:27260427

  7. Investigation on RAFT Polymerization of a Y-Shaped Amphiphilic Fluorinated Monomer and Anti-Fog and Oil-Repellent Properties of the Polymers.

    PubMed

    Wang, Yun; Dong, Qibao; Wang, Yanxue; Wang, Hu; Li, Guang; Bai, Ruke

    2010-10-18

    A Y-shaped amphiphilic fluorinated monomer, 1-(1H,1H,2H,2H-perfluorodecyloxy)-3-(3,6,9-trioxadecyloxy)-propan-2-yl acrylate has been synthesized and its polymerization by reversible addition-fragmentation chain transfer (RAFT) homopolymerization has been investigated. The results show that the molecular weights of the polymers are controlled and all the molecular weight distributions are lower than 1.4. Well-defined copolymers with 2-(N,N-dimethylamino)ethyl methacrylate have been prepared by RAFT polymerization, and the surface properties of the block and random copolymers have been examined by contact angle measurement for water and hexadecane. It has been found that the surfaces of the block copolymers simultaneously exhibit excellent anti-fog and oil-repellent properties. PMID:21567599

  8. pH-triggered formation of nanoribbons from yeast-derived glycolipid biosurfactants.

    PubMed

    Cuvier, Anne-Sophie; Berton, Jan; Stevens, Christian V; Fadda, Giulia C; Babonneau, Florence; Van Bogaert, Inge N A; Soetaert, Wim; Pehau-Arnaudet, Gérard; Baccile, Niki

    2014-06-14

    In the present paper, we show that the saturated form of acidic sophorolipids, a family of industrially scaled bolaform microbial glycolipids, unexpectedly forms chiral nanofibers only at pH below 7.5. In particular, we illustrate that this phenomenon derives from a subtle cooperative effect of molecular chirality, hydrogen bonding, van der Waals forces and steric hindrance. The pH-responsive behaviour was shown by Dynamic Light Scattering (DLS), pH-titration and Field Emission Scanning Electron Microscopy (FE-SEM) while the nanoscale chirality was evidenced by Circular Dichroism (CD) and cryo Transmission Electron Microscopy (cryo-TEM). The packing of sophorolipids within the ribbons was studied using Small Angle Neutron Scattering (SANS), Wide Angle X-ray Scattering (WAXS) and 2D (1)H-(1)H through-space correlations via Nuclear Magnetic Resonance under very fast (67 kHz) Magic Angle Spinning (MAS-NMR). PMID:24728486

  9. 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.

  10. Synthesis, characterization, and crystal structure of 5,5″-Difluoro-1 H,1″ H-[3,3':3',3″-terindol]-2'(1' H)-one

    NASA Astrophysics Data System (ADS)

    Sharma, Sakshi; Banerjee, Bubun; Brahmachari, Goutam; Kant, Rajni; Gupta, Vivek K.

    2016-03-01

    The new indole derivative, 5,5''-Difluoro-1 H,1'' H-[3,3':3',3''-terindol]-2'(1' H)-one C24H15F2N3O, is synthesized in 87% yield, and its crystal structure is determined by X-ray structure analysis. The crystals are monoclinic, sp. gr. P21/ n, a = 15.4563(7), b = 10.8340(6), c = 16.4718(6) Å, β = 102.403(4)°, Z = 4. Bicyclic indole moieties form dihedral angle of 61.92(5)° with each other; the oxindole ring is twisted with respect to them at angles of 85.70(5)° and 75.62(5)°. The crystal structure is stabilized by N-H···O and C-H···O hydrogen bonds involving both the DMSO solvent molecules. In addition, one C-H···π interaction is observed.

  11. 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.

  12. Non-Uniform Sampling and J-UNIO Automation for Efficient Protein NMR Structure Determination.

    PubMed

    Didenko, Tatiana; Proudfoot, Andrew; Dutta, Samit Kumar; Serrano, Pedro; Wüthrich, Kurt

    2015-08-24

    High-resolution structure determination of small proteins in solution is one of the big assets of NMR spectroscopy in structural biology. Improvements in the 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 [(1)H,(1)H]-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

  13. SpinCouple: Development of a Web Tool for Analyzing Metabolite Mixtures via Two-Dimensional J-Resolved NMR Database.

    PubMed

    Kikuchi, Jun; Tsuboi, Yuuri; Komatsu, Keiko; Gomi, Masahiro; Chikayama, Eisuke; Date, Yasuhiro

    2016-01-01

    A new Web-based tool, SpinCouple, which is based on the accumulation of a two-dimensional (2D) (1)H-(1)H J-resolved NMR database from 598 metabolite standards, has been developed. The spectra include both J-coupling and (1)H chemical shift information; those are applicable to a wide array of spectral annotation, especially for metabolic mixture samples that are difficult to label through the attachment of (13)C isotopes. In addition, the user-friendly application includes an absolute-quantitative analysis tool. Good agreement was obtained between known concentrations of 20-metabolite mixtures versus the calibration curve-based quantification results obtained from 2D-Jres spectra. We have examined the web tool availability using nine series of biological extracts, obtained from animal gut and waste treatment microbiota, fish, and plant tissues. This web-based tool is publicly available via http://emar.riken.jp/spincpl. PMID:26624790

  14. Hybrid organic-inorganic porous semiconductor transducer for multi-parameters sensing.

    PubMed

    Caliò, Alessandro; Cassinese, Antonio; Casalino, Maurizio; Rea, Ilaria; Barra, Mario; Chiarella, Fabio; De Stefano, Luca

    2015-07-01

    Porous silicon (PSi) non-symmetric multi-layers are modified by organic molecular beam deposition of an organic semiconductor, namely the N,N'-1H,1H-perfluorobutyldicyanoperylene-carboxydi-imide (PDIF-CN2). Joule evaporation of PDIF-CN2 into the PSi sponge-like matrix not only improves but also adds transducing skills, making this solid-state device a dual signal sensor for chemical monitoring. PDIF-CN2 modified PSi optical microcavities show an increase of about five orders of magnitude in electric current with respect to the same bare device. This feature can be used to sense volatile substances. PDIF-CN2 also improves chemical resistance of PSi against alkaline and acid corrosion. PMID:26063814

  15. 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-

  16. 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).

  17. 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.

  18. 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. PMID:25250857

  19. 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.

  20. Synthesis, spectroscopic characterization and X-ray structure of [1,2a]benzimidazol-2-yl amidine

    NASA Astrophysics Data System (ADS)

    Hajri, A.; Smirani, W.; Abderrahim, R.

    2011-09-01

    [1,2a]Benzimidazol-2-yl amidine was synthesized by adding cyclopentanamine to iminoester in ethanol. The structure of amidine 1 was characterized by IR, 1H NMR, 1H- 1H NOESY, 13C NMR, DEPT, XHCOR spectra, thermogravimetric analysis (TGA), differential thermal analysis (DTA), differential scanning calorimetry thermograms (DSC), elementary analysis as well as by X-ray diffraction. The single crystals suitable for X-ray measurement were obtained by recrystallization at room temperature. The amidine group of a model was found to have Z configuration in the crystal. This compound crystallizes in a P2 1/n monoclinic unit cell with parameters a = 12.679(2) Å, b = 8.468(3) Å, c = 13.108(2) Å, β = 96.538(2)°, V = 1398.2 Å 3 and Z = 4.

  1. Characterisation of the 1H and 13C NMR spectra of methylcitric acid

    NASA Astrophysics Data System (ADS)

    Krawczyk, Hanna; Martyniuk, Tomasz

    2007-06-01

    Methylcitric acid (MCA) was synthesised in Reformatsky reaction (2 RS, 3 RS stereoisomers) and in the nucleophilic addition (2 RS, 3 SR stereoisomers). The stereoselectivity of these reactions was analysed. 1H and 13C NMR spectra of diastereoisomers of methylcitric acid were recorded and interpreted. The values of 1H chemical shifts and 1H- 1H coupling constants were analysed. Proton-decoupled high-resolution 13C NMR spectra of MCA diastereoisomers were measured in a series of dilute water solutions of various acidities. These data may provide a basis for unequivocal determination of the presence of MCA in the urine samples of patients' suffering from propionic acidemia, methylmalonic aciduria, or holocarboxylase synthetase deficiency. NMR spectroscopy enables determination of MCA diastereoisomers in body fluids and can be a complementary and useful diagnostic tool.

  2. Isolation, characterization, and NO inhibitory activities of sesquiterpenes from Blumea balsamifera.

    PubMed

    Xu, Jing; Jin, Da-qing; Liu, Cuizhou; Xie, Chunfeng; Guo, Yuanqiang; Fang, Lingzhi

    2012-08-15

    Blumea balsamifera belongs to the family Compositae, and its leaves have been used as a flavoring ingredient and a tea. A phytochemical investigation of the aerial parts of B. balsamifera led to the isolation of 10 new (1-10) and 1 known (11) sesquiterpenes. Their structures were elucidated on the basis of extensive one- and two-dimensional nuclear magnetic resonance (heteronuclear multiple-quantum coherence, heteronuclear multiple-bond correlation, (1)H-(1)H correlation spectroscopy, and nuclear Overhauser effect spectrometry) spectroscopic data analyses, and the structure of compound 1 was confirmed by X-ray crystallography. The inhibitory activities on lipopolysaccharide-induced NO production in murine microglial BV-2 cells of these sesquiterpenes were evaluated, and all of the compounds showed inhibitory effects. PMID:22823402

  3. 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.

  4. Synthesis of mono- and dideoxygenated α,α-trehalose analogs

    PubMed Central

    Lin, Fiona L.; van Halbeek, Herman; Bertozzi, Carolyn R.

    2007-01-01

    In this work we describe the synthesis and NMR characterization of four mono- and four dideoxygenated analogs of α,α-d-trehalose. The symmetrical (2,2′-, 3,3′-, 4,4′- and 6,6′-) dideoxy analogs were obtained via selective protection and subsequent radical deoxygenation of the desired hydroxyl group set. The unsymmetrical (2′-, 3′-, 4′- and 6′-) monodeoxy analogs were synthesized by desymmetrization of α,α-trehalose and subsequent deoxygenation under radical conditions. Complete assignment of all 1H and 13C resonances in the spectra of these deoxytrehaloses was achieved through the extensive use of 2D {1H,1H} and {1H,13C} correlation NMR experiments. The synthesis of these trehalose analogs sets the stage for future biochemical and NMR-based studies to probe the substrate interactions of trehalose with the recently identified mycobacterial sulfotransferase Stf0. PMID:17559818

  5. High-Resolution 3D Structure Determination of Kaliotoxin by Solid-State NMR Spectroscopy

    PubMed Central

    Korukottu, Jegannath; Schneider, Robert; Vijayan, Vinesh; Lange, Adam; Pongs, Olaf; Becker, Stefan; Baldus, Marc; Zweckstetter, Markus

    2008-01-01

    High-resolution solid-state NMR spectroscopy can provide structural information of proteins that cannot be studied by X-ray crystallography or solution NMR spectroscopy. Here we demonstrate that it is possible to determine a protein structure by solid-state NMR to a resolution comparable to that by solution NMR. Using an iterative assignment and structure calculation protocol, a large number of distance restraints was extracted from 1H/1H mixing experiments recorded on a single uniformly labeled sample under magic angle spinning conditions. The calculated structure has a coordinate precision of 0.6 Å and 1.3 Å for the backbone and side chain heavy atoms, respectively, and deviates from the structure observed in solution. The approach is expected to be applicable to larger systems enabling the determination of high-resolution structures of amyloid or membrane proteins. PMID:18523586

  6. Hybrid organic–inorganic porous semiconductor transducer for multi-parameters sensing

    PubMed Central

    Caliò, Alessandro; Cassinese, Antonio; Casalino, Maurizio; Rea, Ilaria; Barra, Mario; Chiarella, Fabio; De Stefano, Luca

    2015-01-01

    Porous silicon (PSi) non-symmetric multi-layers are modified by organic molecular beam deposition of an organic semiconductor, namely the N,N′-1H,1H-perfluorobutyldicyanoperylene-carboxydi-imide (PDIF-CN2). Joule evaporation of PDIF-CN2 into the PSi sponge-like matrix not only improves but also adds transducing skills, making this solid-state device a dual signal sensor for chemical monitoring. PDIF-CN2 modified PSi optical microcavities show an increase of about five orders of magnitude in electric current with respect to the same bare device. This feature can be used to sense volatile substances. PDIF-CN2 also improves chemical resistance of PSi against alkaline and acid corrosion. PMID:26063814

  7. Characterisation of the 1H and 13C NMR spectra of N-acetylaspartylglutamate and its detection in urine from patients with Canavan disease.

    PubMed

    Krawczyk, Hanna; Gradowska, Wanda

    2003-03-10

    1H and 13C NMR spectra of N-acetylaspartylglutamate (NAAG) have been recorded and interpreted. The values of the 1H chemical shifts and 1H-(1)H coupling constants at different pH were obtained by iterative computer fitting of 1-D 1H NMR spectra. This provided information on the solution conformation of the investigated molecule. Proton-decoupled high resolution 13C NMR spectra of NAAG have been measured in a series of dilute water solution of various acidity. These data have provided a basis for unequivocal determination of the presence of NAAG in the urine sample of a patient suffering from Canavan disease. NMR spectroscopy provides a possibility of detecting NAAG in body fluids. PMID:12615232

  8. Structural Studies of Glutamine-Binding Protein of Escherichia Coli Using Multinuclear and Multidimensional Magnetic Resonance

    NASA Astrophysics Data System (ADS)

    Tjandra Leksana, Nico

    1993-01-01

    Multinuclear and multidimensional nuclear magnetic resonance (NMR) spectroscopy along with molecular biology techniques were utilized in studying the structure of glutamine -binding protein (GlnBP). Uniform and specific labeling of the GlnBP with ^{15}N and ^{13}C provided filtering of the otherwise overlapping ^ 1H resonances and markers along the GlnBP primary sequence. These facts are important in creating a possibility of sequentially assigning the ^ 1H backbone resonances, which is the first step in elucidating a protein structure. In parallel with this effort, specific distance measurement were done using ^ 1H-^ 1H nuclear Overhauser effect (NOE) measurement and solid-state rotational echo double resonance (REDOR) spectroscopy. These distances can be used as constraints in building all possible structures of GlnBP. The consequences of the structural features observed are noted and discussed in this thesis.

  9. Controlling film topography to form highly hydrophobic waterborne coatings.

    PubMed

    López, Ana B; de la Cal, José C; Asua, José M

    2016-08-17

    Coatings have a tremendous impact on economy as they reduce corrosion that has an estimated cost of 3% of the world's GDP. Hydrophobic coatings are particularly efficient for this purpose and the challenge is to produce cost effective and environmentally friendly, highly hydrophobic, cohesive and non-porous coatings applicable to large and irregular surfaces. This work shows that this goal can be achieved by forming wrinkles on the surface of waterborne coatings through fine-tuning of the film forming conditions. The proof of concept was demonstrated by using waterborne dispersions of copolymers of 1H,1H,2H,2H-perfluorodecyl acrylate and 2-ethylhexyl acrylate, and using the temperature and hardness of the copolymer as control variables during film formation. This allowed the formation of transparent films with a wrinkled surface that had a contact angle of 133°, which represents an increase of 20° with respect to the film cast under standard conditions. PMID:27476531

  10. 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

    2016-04-01

    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. PMID:26845749

  11. 3D ¹⁵N/¹⁵N/¹H chemical shift correlation experiment utilizing an RFDR-based ¹H/¹H mixing period at 100 kHz MAS.

    PubMed

    Nishiyama, Yusuke; Malon, Michal; Ishii, Yuji; Ramamoorthy, Ayyalusamy

    2014-07-01

    Homonuclear correlation NMR experiments are commonly used in the high-resolution structural studies of proteins. While (13)C/(13)C chemical shift correlation experiments utilizing dipolar recoupling techniques are fully utilized under MAS, correlation of the chemical shifts of (15)N nuclei in proteins has been a challenge. Previous studies have shown that the negligible (15)N-(15)N dipolar coupling in peptides or proteins necessitates the use of a very long mixing time (typically several seconds) for effective spin diffusion to occur and considerably slows down a (15)N/(15)N correlation experiment. In this study, we show that the use of mixing proton magnetization, instead of (15)N, via the recoupled (1)H-(1)H dipolar couplings enable faster (15)N/(15)N correlation. In addition, the use of proton-detection under ultrafast MAS overcomes the sensitivity loss due to multiple magnetization transfer (between (1)H and (15)N nuclei) steps. In fact, less than 300 nL (∼1.1 micromole quantity) sample is sufficient to acquire the 3D spectrum within 5 h. Our results also demonstrate that a 3D (15)N/(15)N/(1)H experiment can render higher resolution spectra that will be useful in the structural studies of proteins at ultrafast MAS frequencies. 3D (15)N/(15)N/(1)H and 2D radio frequency-driven dipolar recoupling (RFDR)-based (1)H/(1)H experimental results obtained from a powder sample of N-acetyla-L-(15)N-valyl-L-(15)N-leucine at 70 and 100kHz MAS frequencies are presented. PMID:24801998

  12. 1H and 13C NMR spectra, structure and physicochemical features of phenyl acridine-9-carboxylates and 10-methyl-9-(phenoxycarbonyl)acridinium trifluoromethanesulphonates--alkyl substituted in the phenyl fragment.

    PubMed

    Krzymiński, K; Malecha, P; Zadykowicz, B; Wróblewska, A; Błażejowski, J

    2011-01-01

    The 1H and 13C NMR spectra of twelve phenyl acridine-9-carboxylates--alkyl-substituted in the phenyl fragment--and their 10-methyl-9-(phenoxycarbonyl)acridinium salts dissolved in CD3CN, CD3OD, CDCl3 and DMSO-d6 were recorded in order to examine the influence of the structure of these compounds and the properties of the solvents on chemical shifts and 1H-(1)H coupling constants. Experimental data were compared with 1H and 13C chemical shifts predicted at the GIAO/DFT level of theory for DFT(B3LYP)/6-31G** optimised geometries of molecules, as well as with values of 1H chemical shifts and 1H-(1)H coupling constants, estimated using ACD/HNMR database software to ensure that the assignment was correct. To investigate the relations between chemical shifts and selected structural or physicochemical characteristics of the target compounds, the values of several of these parameters were determined at the DFT or HF levels of theory. The HOMO and LUMO energies obtained at the HF level yielded the ionisation potentials and electron affinities of molecules. The DFT method provided atomic partial charges, dipole moments, LCAO coefficients of pz LUMO of selected C atoms, and angles reflecting characteristic structural features of the compounds. It was found that the experimentally determined 1H and 13C chemical shifts of certain atoms relate to the predicted dipole moments, the angles between the acridine and phenyl moieties, and the LCAO coefficients of the pz LUMO of the C atoms believed to participate in the initial step of the oxidation of the target compounds. The spectral and physicochemical characteristics of the target compounds were investigated in the context of their chemiluminogenic ability. PMID:21134782

  13. 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. PMID:25279932

  14. 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

  15. 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

    2013-08-01

    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. PMID:23810980

  16. Selective observation of biologically important 15N-labeled metabolites in isolated rat brain and liver by 1H-detected multiple-quantum-coherence spectroscopy

    NASA Astrophysics Data System (ADS)

    Kanamori, Keiko; Ross, Brian D.; Parivar, Farhad

    Four cerebral metabolites of importance in neurotransmission, serotonin, L-tryptophan, L-glutamine, and N-acetyl- L-aspartate, and two hepatic urea-cycle intermediates, citrulline and urea, were found to be observable by 1H- 15N heteronuclear multiple-quantum-coherence (HMQC) spectroscopy in aqueous solution at physiological pH and temperature, through the protons spin-coupled to their indole, amide, or ureido nitrogen. Their 1H chemical shifts were well dispersed over a 5-10 ppm region while the 1J 15N- 1H values were 87-99 Hz. For [γ- 15N]glutamine, a 50- to 100-fold increase in sensitivity over direct 15N detection was achieved, in contrast to a 2-fold increase by the polarization-transfer method. In the isolated brain of portacaval-shunted rats, the amide protons of biologically 15N-enriched [γ- 15N]glutamine were observed in 2 min of acquisition, with suppression of proton signals from all other cerebral metabolites. In isolated liver of 15N-enriched control rats, [ 15NIurea protons were observed in 16 min. The HMQC method is likely to be effective for the in vivo study of cerebral and hepatic nitrogen metabolism.

  17. Facilitating unambiguous NMR assignments and enabling higher probe density through selective labeling of all methyl containing amino acids.

    PubMed

    Proudfoot, Andrew; Frank, Andreas O; Ruggiu, Fiorella; Mamo, Mulugeta; Lingel, Andreas

    2016-05-01

    The deuteration of proteins and selective labeling of side chain methyl groups has greatly enhanced the molecular weight range of proteins and protein complexes which can be studied using solution NMR spectroscopy. Protocols for the selective labeling of all six methyl group containing amino acids individually are available, however to date, only a maximum of five amino acids have been labeled simultaneously. Here, we describe a new methodology for the simultaneous, selective labeling of all six methyl containing amino acids using the 115 kDa homohexameric enzyme CoaD from E. coli as a model system. The utility of the labeling protocol is demonstrated by efficiently and unambiguously assigning all methyl groups in the enzymatic active site using a single 4D (13)C-resolved HMQC-NOESY-HMQC experiment, in conjunction with a crystal structure. Furthermore, the six fold labeled protein was employed to characterize the interaction between the substrate analogue (R)-pantetheine and CoaD by chemical shift perturbations, demonstrating the benefit of the increased probe density. PMID:27130242

  18. Stable isotope-enhanced two- and three-dimensional diffusion ordered 13C NMR spectroscopy (SIE-DOSY 13C NMR)

    NASA Astrophysics Data System (ADS)

    Vermillion, Karl; Price, Neil P. J.

    2009-06-01

    The feasibility of obtaining high quality homonuclear or heteronuclear diffusion-ordered 13C NMR data is shown to be greatly improved by using 13C isotopically-enriched samples. Stable isotope-enhanced diffusion ordered (SIE-DOSY) 13C NMR has been applied to 13C-enriched carbohydrates, and has been used to determine diffusion coefficients for pentose and hexose monosaccharides, and a disaccharide and trisaccharide. These 2D spectra were obtained with as little as 8 min of acquisition time. Fully resolved 3D DOSY-HMQC NMR spectra of [U- 13C]xylose, [U- 13C]glucose, and [1- 13C gal]lactose were obtained in 5 h. Sample derivatization with [ carbonyl- 13C]acetate (peracetylation) extends the usefulness of the technique to included non-labeled sugars; the 13C-carbonyl - carbohydrate ring proton 1H- 13C correlations also provide additional structural information, as shown for the 3-D DOSY-HMQC analysis of a mixture of maltotriose and lactose per-[ carbonyl- 13C]acetates.

  19. Convenient analytical methods for endo-type glycosidase that acts on glycoconjugates and their application in glycotechnology.

    PubMed

    Ishii-Karakasa, Ikuko

    2003-01-01

    The following procedures were established in order to develop useful degradation enzymes of glycoconjugate for developing postgenome and postproteome research: (1) Enzyme activity with a short time reliability was measured using small amounts by HPLC. (2) The structures of the sugar chains liberated from the glycoconjugate were non-destructively analyzed using small amounts of sugar chains only by 1D 1H-NMR and H-H COSY spectrometry and a computer simulation of the spectrum. (3) The conformations of the sugar chains liberated from a glycoconjugate in aqueous solution were estimated using 1D 1H-NMR and H-H COSY spectrometry and the anisotropic effect. Endo-alpha-N-acetylgalactosaminidase from the culture medium of Streptomyces sp. OH-11242 developed using the above methods transferred the sugar chain to sugars and peptides; therefore, it was also an effective enzyme when synthesizing sugar chains and glycopeptides. PMID:12558030

  20. Proton NMR assignments and regular backbone structure of bovine pancreatic ribonuclease A in aqueous solution

    SciTech Connect

    Robertson, A.D. ); Purisima, E.O. Cornell Univ., Ithaca, NY ); Eastman, M.A.; Scheraga, H.A. )

    1989-07-11

    Proton NMR assignments have been made for 121 of the 124 residues of bovine pancreatic ribonuclease A (RNase A). During the first stage of assignment, COSY and relayed COSY data were used to identify 40 amino acid spin systems belonging to alanine, valine, threonine, isoleucine, and serine residues. Approximately 60 other NH-{alpha}CH-{beta}CH systems were also identified but not assigned to specific amino acid type. NOESY data then were used to connect sequentially neighboring spin systems; approximately 475 of the possible 700 resonances in RNase A were assigned in this way. The authors' assignments agree with those for 20 residues assigned previously. NOESY correlations were used to identify regular backbone structure elements in RNase A, which are very similar to those observed in X-ray crystallographic studies.

  1. 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.

  2. The PREMOS/PICARD Radiometer: An Overview after 3 Years of Observations

    NASA Astrophysics Data System (ADS)

    Cessateur, Gaël; Schmutz, Werner; Shapiro, Alexander

    2014-05-01

    Total and Spectral Solar Irradiance are key input parameters to atmospheric/oceanic and space weather models. We present here spectral solar irradiance data from the radiometer PREMOS onboard the PICARD satellite for three years. This instrument covers the solar spectrum from the Ultraviolet to near-infrared, and provide valuable information, which helps to constrain theoretical models. An overview of the results involving PREMOS result will be presented including observations and modelling. We use the radiative transfer code COSI to model the variability of the irradiance. We will then introduce the COCOSIS model (for Combination of COSI Spectra) which assumes that the variability is determined by the evolution of the solar surface magnetic field as seen with SDO/HMI data. A direct comparison shows a very good correlation for most of channels from PREMOS. Those data could also been used for reconstructing the whole solar spectrum using then the PREMOS radiometer as a spectrometer.

  3. Growth of single-crystalline cobalt silicide nanowires and their field emission property

    PubMed Central

    2013-01-01

    In this work, cobalt silicide nanowires were synthesized by chemical vapor deposition processes on Si (100) substrates with anhydrous cobalt chloride (CoCl2) as precursors. Processing parameters, including the temperature of Si (100) substrates, the gas flow rate, and the pressure of reactions were varied and studied; additionally, the physical properties of the cobalt silicide nanowires were measured. It was found that single-crystal CoSi nanowires were grown at 850°C ~ 880°C and at a lower gas flow rate, while single-crystal Co2Si nanowires were grown at 880°C ~ 900°C. The crystal structure and growth direction were identified, and the growth mechanism was proposed as well. This study with field emission measurements demonstrates that CoSi nanowires are attractive choices for future applications in field emitters. PMID:23819795

  4. 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.

  5. Controllable surface-plasmon resonance in engineered nanometer epitaxial silicide particles embedded in silicon

    NASA Technical Reports Server (NTRS)

    Fathauer, R. W.; Ksendzov, A.; Iannelli, J. M.; George, T.

    1991-01-01

    Epitaxial CoSi2 particles in a single-crystal silicon matrix are grown by molecular-beam epitaxy using a technique that allows nanometer control over particle size in three dimensions. These composite layers exhibit resonant absorption predicted by effective-medium theory. Selection of the height and diameter of disklike particles through a choice of growth conditions allows tailoring of the depolarization factor and hence of the surface-plasmon resonance energy. Resonant absorption from 0.49 to 1.04 eV (2.5 to 1.2 micron) is demonstrated and shown to agree well with values predicted by the Garnett (1904, 1906) theory using the bulk dielectric constants for CoSi2 and Si.

  6. Formation of cobalt silicide by ion beam mixing

    NASA Astrophysics Data System (ADS)

    Min, Ye; Burte, Edmund P.; Ryssel, Heiner

    1991-07-01

    The formation of cobalt silicides by arsenic ion implantation through a cobalt film which causes a mixing of the metal with the silicon substrate was investigated. Furthermore, cobalt suicides were formed by rapid thermal annealing (RTA). Sheet resistance and silicide phases of implanted Co/Si samples depend on the As dose. Ion beam mixing at doses higher than 5 × 10 15 cm -2 and RTA at temperatures T ⩾ 900° C result in almost equal values of Rs. RBS and XRD spectra of these samples illustrate the formation of a homogeneous CoSi 2 layer. Significant lateral growth of cobalt silicide beyond the edge of patterned SiO 2 was observed in samples which were only subjected to an RTA process ( T ⩾ 900 ° C), while this lateral suicide growth could be reduced efficiently by As implantation prior to RTA.

  7. DIME Fluid Payload on Student Platform

    NASA Technical Reports Server (NTRS)

    2002-01-01

    Colored oil flow toy was part of a student-designed apparatus used in 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.

  8. How to Reach a Thousand-Second in-Plane Polarization Lifetime with 0.97 -GeV /c Deuterons in a Storage Ring

    NASA Astrophysics Data System (ADS)

    Guidoboni, G.; Stephenson, E.; Andrianov, S.; Augustyniak, W.; Bagdasarian, Z.; Bai, M.; Baylac, M.; Bernreuther, W.; Bertelli, S.; Berz, M.; Böker, J.; Böhme, C.; Bsaisou, J.; Chekmenev, S.; Chiladze, D.; Ciullo, G.; Contalbrigo, M.; de Conto, J.-M.; Dymov, S.; Engels, R.; Esser, F. M.; Eversmann, D.; Felden, O.; Gaisser, M.; Gebel, R.; Glückler, H.; Goldenbaum, F.; Grigoryev, K.; Grzonka, D.; Hahnraths, T.; Heberling, D.; Hejny, V.; Hempelmann, N.; Hetzel, J.; Hinder, F.; Hipple, R.; Hölscher, D.; Ivanov, A.; Kacharava, A.; Kamerdzhiev, V.; Kamys, B.; Keshelashvili, I.; Khoukaz, A.; Koop, I.; Krause, H.-J.; Krewald, S.; Kulikov, A.; Lehrach, A.; Lenisa, P.; Lomidze, N.; Lorentz, B.; Maanen, P.; Macharashvili, G.; Magiera, A.; Maier, R.; Makino, K.; Mariański, B.; Mchedlishvili, D.; Meißner, Ulf-G.; Mey, S.; Morse, W.; Müller, F.; Nass, A.; Natour, G.; Nikolaev, N.; Nioradze, M.; Nowakowski, K.; Orlov, Y.; Pesce, A.; Prasuhn, D.; Pretz, J.; Rathmann, F.; Ritman, J.; Rosenthal, M.; Rudy, Z.; Saleev, A.; Sefzick, T.; Semertzidis, Y.; Senichev, Y.; Shmakova, V.; Silenko, A.; Simon, M.; Slim, J.; Soltner, H.; Stahl, A.; Stassen, R.; Statera, M.; Stockhorst, H.; Straatmann, H.; Ströher, H.; Tabidze, M.; Talman, R.; Thörngren Engblom, P.; Trinkel, F.; Trzciński, A.; Uzikov, Yu.; Valdau, Yu.; Valetov, E.; Vassiliev, A.; Weidemann, C.; Wilkin, C.; Wrońska, A.; Wüstner, P.; Zakrzewska, M.; Zuprański, P.; Zyuzin, D.; JEDI Collaboration

    2016-07-01

    We observe a deuteron beam polarization lifetime near 1000 s in the horizontal plane of a magnetic storage ring (COSY). This long spin coherence time is maintained through a combination of beam bunching, electron cooling, sextupole field corrections, and the suppression of collective effects through beam current limits. This record lifetime is required for a storage ring search for an intrinsic electric dipole moment on the deuteron at a statistical sensitivity level approaching 10-29 e cm .

  9. 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.

  10. Role of Spin in NN → NNπ

    NASA Astrophysics Data System (ADS)

    Baru, Vadim

    2016-02-01

    The recent measurements of the reactions pp → ppπ0 and pn → ppπ‑ by the ANKE collaboration at COSY are analyzed with the focus on the p-wave pion production amplitudes. These amplitudes are known to provide an important connection between NN → NNπ and other low-energy few-nucleon reactions. The results of the recent partial wave analysis of the ANKE data are discussed and compared with the theoretical predictions.

  11. 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.

  12. Correcting Aberrations in Complex Magnet Systems for Muon Cooling Channels

    SciTech Connect

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

    2011-03-01

    Designing and simulating complex magnet systems needed for cooling channels in both neutrino factories and muon colliders requires innovative techniques to correct for both chromatic and spherical aberrations. Optimizing complex systems, such as helical magnets for example, is also difficult but essential. By using COSY INFINITY, a differential algebra based code, the transfer and aberration maps can be examined to discover what critical terms have the greatest influence on these aberrations.

  13. 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.

  14. New tricyclic and tetracyclic pyranocoumarins with an unprecedented C-4 substituent. Structure elucidation of tamanolide, tamanolide D and tamanolide P from Calophyllum inophyllum of French Polynesia.

    PubMed

    Leu, T; Raharivelomanana, P; Soulet, S; Bianchini, J P; Herbette, G; Faure, R

    2009-11-01

    Three new pyranocoumarin derivatives, tamanolide (1), tamanolide D (2) and tamanolide P (3), were isolated from the almond seeds of Calophyllum inophyllum L. (Clusiaceae) grown in French Polynesia. These compounds, having an unprecedented C-4 isobutyl substituent, have been characterized as a new class of pyranocoumarins called tamanolides. Their structures were elucidated on the basis of 1D and 2D NMR techniques (COSY, NOESY, HSQC and HMBC) in association with MS (HR-ESI-MS) data analysis. PMID:19603395

  15. Dynamics of Hyperon Production

    SciTech Connect

    Sibirtsev, A.

    2007-11-07

    The progress of strangeness physics at COSY in both experimental and theoretical aspects is reviewed. It is argued that the dynamics of hyperon production involves excitation of baryons and that it is feasible to study their properties such as mass and total width. It is shown that under certain kinematical cuts the resonance signal can be isolated from the effect due to the final state interaction. Recent puzzles concerning the {sigma}-hyperon production are discussed.

  16. Isolation and structure elucidation of rebaudioside D2 from bioconversion reaction of rebaudioside A to rebaudioside D.

    PubMed

    Prakash, Indra; Bunders, Cynthia; Devkota, Krishna P; Charan, Romila D; Ramirez, Catherine; Parikh, Maunik; Markosyan, Avetik

    2014-08-01

    We report the isolation and complete structure of an isomer of rebaudioside D, known as rebaudioside D2. This novel steviol glycoside was isolated from a bioconversion reaction of rebaudioside A to rebaudioside D. Rebaudioside D2 possesses a relatively rare 1 --> 6 sugar linkage, which was discovered by extensive analysis of NMR (1H, 13C, COSY, HSQC-DEPT, HMBC, 1D TOCSY and NOESY) and mass spectral data. PMID:25233591

  17. DIME Students Share Comments About Experiments

    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. DIME Students Waiting for Their Turn to Drop Experiment

    NASA Technical Reports Server (NTRS)

    2002-01-01

    Students pause while waiting their turn at the 2.2-second Drop Tower 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.

  19. Complete NMR assignment of a bisecting hybrid-type oligosaccharide transferred by Mucor hiemalis endo-β-N-acetylglucosaminidase.

    PubMed

    Yamanoi, Takashi; Oda, Yoshiki; Katsuraya, Kaname; Inazu, Toshiyuki; Yamamoto, Kenji

    2016-06-01

    This study describes the complete nuclear magnetic resonance (NMR) spectral assignment of a bisecting hybrid-type oligosaccharide 1, transferred by Mucor hiemalis endo-β-N-acetylglucosaminidase (Endo-M). Through (1)H- and (13)C-NMR, DQF-COSY, HSQC, HMBC, TOCSY, and NOESY experiments, we determine the structure of the glycoside linkage formed by the Endo-M transglycosylation, i.e., the connection between GlcNAc and GlcNAc in oligosaccharide 1. PMID:27131291

  20. Studies on η meson production in dp collisions at the ANKE spectrometer

    NASA Astrophysics Data System (ADS)

    Fritzsch, Christopher; Guderian, Daniel; Khoukaz, Alfons; Mielke, Malte; Papenbrock, Michael; Schröer, Daniel

    2016-03-01

    Current investigations at the internal fixed target experiment ANKE at the storage ring COSY, located at the Forschungszentrum Jülich in Germany, focus on the behaviour of the η meson production process as well as on the study of angular distributions in the reactions d + p → 3He+ η and p+d → d + η + psp. The recent analysis status for both reactions will be presented and discussed.

  1. A new cassane diterpenoid from the seeds of Caesalpinia decapetala.

    PubMed

    Wei, Hua; Liu, Xiao-Qian; Zhu, Jing-Jing; Gao, Liang-Liang; Wang, Zhi-Min; Yan, Li-Hua

    2016-04-01

    Phytochemical investigation on the seeds of Caesalpinia decapetala led to the isolation of a new cassane diterpenoid with an unusual O bridge between C-19 and C-20, named phanginin Q (1), together with three known cassane diterpenoids, caesaljapin (2), caesaldekarin A (3), and caesaldekarin B (4). The structure of the new compound was elucidated by spectroscopic methods, including (1)H NMR, (13)C NMR, HSQC, (1)H - (1)H COSY, HMBC, NOESY, and HR-ESI-MS. PMID:26268793

  2. 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.

  3. 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. PMID:8450315

  4. 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). PMID:18348057

  5. Mimicking the membrane-mediated conformation of dynorphin A-(1-13)-peptide: Circular dichroism and nuclear magnetic resonance studies in methanolic solution

    SciTech Connect

    Lancaster, C.R.D.; Hughes, D.W.; Epand, R.M. ); Mishra, P.K.; Bothner-By, A.A. ); St.Pierre, S.A. )

    1991-05-14

    The structural requirements for the binding of dynorphin to the {kappa}-opioid receptor are of profound clinical interest in the search for a powerful nonaddictive analgesic. These requirements are thought to be met by the membrane-mediated conformation of the opioid peptide dynorphin A-(1-13)-peptide, Tyr{sup 1}-Gly{sup 2}-Gly{sup 3}-Phe{sup 4}-Leu{sup 5}-Arg{sup 6}-Arg{sup 7}-Ile{sup 8}-Arg{sup 9}-Pro{sup 10}-Lys{sup 11}-Leu{sup 12}-Lys{sup 13}. Schwyzer has proposed an essentially {alpha}-helical membrane-mediated conformation of the 13 amino acid peptide. In the present study, circular dichroism (CD) studies on dynorphin A-(1-13)-peptide bound to an anionic phospholipid signified negligible helical content of the peptide. CD studies also demonstrated that the aqueous-membraneous interphase may be mimicked by methanol. The 500- and 620-MHz {sup 1}H nuclear magnetic resonance (NMR) spectra of dynorphin A-(1-13)-peptide in methanolic solution were sequence-specifically assigned with the aid of correlated spectroscopy (COSY), double-quantum filtered phase-sensitive COSY (DQF-COSY), relayed COSY (RELAY), and nuclear Overhauser enhancement spectroscopy (NOESY). 2-D CAMELSPIN/ROESY experiments indicated that at least the part of the molecule from Arg{sup 7} to Arg{sup 9} was in an extended or {beta}-strand conformation, which agreed with deuterium-exchange and temperature-dependence studies of the amide protons and analysis of the vicinal spin-spin coupling constants {sup 3}J{sub HN{alpha}}. The results clearly demonstrated the absence of extensive {alpha}-helix formation. {chi}{sub 1} rotamer analysis of the {sup 3}J{sub {alpha}{beta}} demonstrated no preferred side-chain conformations.

  6. 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.

  7. Cytotoxic and antimalarial bisbenzylisoquinoline alkaloids from Cyclea barbata.

    PubMed

    Lin, L Z; Shieh, H L; Angerhofer, C K; Pezzuto, J M; Cordell, G A; Xue, L; Johnson, M E; Ruangrungsi, N

    1993-01-01

    An alkaloid extract derived from the roots of Cyclea barbata demonstrated cytotoxic and antimalarial activities, and five bisbenzylisoquinoline alkaloids, (+)-tetrandrine [1], (-)-limacine [2], (+)-thalrugosine [3], (+)-homoaromoline [4], and (-)-cycleapeltine [5], were isolated as the active principles. The complete and unambiguous assignments of the 1H- and 13C-nmr data of these substances were made by 1D and 2D nmr techniques (COSY, phase-sensitive ROESY, HETCOR, and FLOCK). PMID:8450318

  8. Rapid microwaves synthesis of CoSix/CNTs as novel catalytic materials for hydrogenation of phthalic anhydride

    NASA Astrophysics Data System (ADS)

    Zhang, Liangliang; Chen, Xiao; Jin, Shaohua; Guan, Jingchao; Williams, Christopher T.; Peng, Zhijian; Liang, Changhai

    2014-09-01

    CoSix/CNTs catalysts with different CoSix phases (CoSi, CoSi2) 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 CoSix/CNTs catalysts exhibited excellent activity and good selectivity to phthalide under mild reaction conditions (180-220 °C and 4.0 MPa H2). This novel methodology can be applied to the synthesis of other transition metal silicides such as FeSi, Ni2Si, and Cu4Si.

  9. Low-power adiabatic sequences for in-vivo localized two-dimensional chemical shift correlated MR spectroscopy

    PubMed Central

    Andronesi, Ovidiu C.; Ramadan, Saadallah; Mountford, Carolyn E.; Sorensen, A. Gregory

    2011-01-01

    Novel low-power adiabatic sequences are demonstrated for in-vivo localized two-dimensional (2D) correlated MR spectroscopy, such as COSY (Correlated Spectroscopy) and TOCSY (Total Correlated Spectroscopy). The design is based on three new elements for in-vivo 2D MRS: the use of gradient modulated constant adiabaticity GOIA-W(16,4) pulses for i) localization (COSY and TOCSY) and ii) mixing (TOCSY), and iii) the use of longitudinal mixing (z-filter) for magnetization transfer during TOCSY. GOIA-W(16,4) provides accurate signal localization, and more importantly, lowers the SAR for both TOCSY mixing and localization. Longitudinal mixing improves considerably (five-folds) the efficiency of TOCSY transfer. These are markedly different from previous 1D editing TOCSY sequences using spatially non-selective pulses and transverse mixing. Fully adiabatic (adiabatic mixing with adiabatic localization) and semi-adiabatic (adiabatic mixing with non-adiabatic localization) methods for 2D TOCSY are compared. Results are presented for simulations, phantoms, and in-vivo 2D spectra from healthy volunteers and patients with brain tumors obtained on 3T clinical platforms equipped with standard hardware. To the best of our knowledge this is the first demonstration of in-vivo adiabatic 2D TOCSY and fully adiabatic 2D COSY. It is expected that these methodological developments will advance the in-vivo applicability of multi(spectrally)dimensional MRS to reliably identify metabolic biomarkers. PMID:20890988

  10. New SSI and TSI reconstruction suggests large value of the radiative solar forcing

    NASA Astrophysics Data System (ADS)

    Shapiro, A.; Schmutz, W. K.; Thuillier, G.; Rozanov, E.; Haberreiter, M.; Schoell, M.; Shapiro, A.; Nyeki, S.

    2010-12-01

    We have developed and published the COde for Solar Irradiance (COSI) which allows us to calculate the entire solar spectrum. COSI reproduces the spectral irradiance measured by SOLSTICE (up to 320 nm) and SIM (from 320 nm onward) onboard the SORCE satellite during the 2008 solar minimum as well as SOLSPEC during the ATLAS 3 mission in 1994 with high accuracy. COSI is also used as a tool for modeling the variability of the solar irradiance. In our new reconstruction we represent the quiet Sun as a combination of two components. The first corresponds to the least active areas of the Sun as presently observed, while the second component is responsible for the magnetic activity of the quiet Sun. The time-dependent filling factors of these components are calculated based on the solar activity as derived from cosmogenic isotope concentrations in natural archieves. This allows us to obtain a time-dependent reconstructed solar spectrum from 7000 BC to the present with a temporal resolution of 22 years. From 1610 onward we have additional information from sunspot numbers, which allows the reconstruction of the spectral solar irradiance with a yearly resolution. These basic assumptions lead to a total and spectral solar irradiance that was substantially lower during the Maunder minimum than observed today. The difference is remarkably larger than other estimations published in the recent literature. Using our reconstruction as an input to a chemistry-climate model we show that the enhanced UV variability results in significant variations of stratospheric ozone and temperature.

  11. First stage of CoSi{sub 2} formation during a solid-state reaction

    SciTech Connect

    Delattre, R.; Thomas, O.; Perrin-Pellegrino, C.; Rivero, C.; Simola, R.

    2014-12-28

    The kinetics of CoSi{sub 2} formation via a solid-state reaction between CoSi and single crystal Si has been the object of many studies in the past. Because of the importance of nucleation, complex kinetics has been reported. In this work, we investigate CoSi{sub 2} formation kinetics with in-situ diffraction during isothermal annealing of CoSi films on Si (100). In-situ measurements allow capturing the initial stage of CoSi{sub 2} formation. An initial t{sup 3/2} time-dependent evolution is observed and attributed to 3D growth of individual nuclei. This first regime is followed after the coalescence of the nuclei by a classical parabolic t{sup 1/2} one-dimensional film growth. We evidence a marked influence of the initial Co thickness (50 nm vs 10 nm) on the growth kinetics. A significant slowdown of the CoSi{sub 2} formation kinetics is observed for the thinnest film, whereas the activation energy remains the same. These results shine a new light on the complex formation kinetics of CoSi{sub 2} during solid-state reaction between CoSi and single crystal silicon and bring new knowledge about what occurs in the ultra-thin film regime, which is important for nanotechnologies.

  12. Ultrafast double-quantum NMR spectroscopy with optimized sensitivity for the analysis of mixtures.

    PubMed

    Rouger, Laetitia; Gouilleux, Boris; Pourchet-Gellez, Mariane; Dumez, Jean-Nicolas; Giraudeau, Patrick

    2016-03-01

    Ultrafast (UF) 2D NMR enables the acquisition of 2D spectra within a single-scan. This methodology has become a powerful analytical tool, used in a large array of applications. However, UF NMR spectroscopy still suffers from the need to compromise between sensitivity, spectral width and resolution. With the commonly used UF-COSY pulse sequence, resolution issues are compounded by the presence of strong auto-correlation signals, particularly in the case of samples with high dynamic ranges. The recently proposed concept of UF Double Quantum Spectroscopy (DQS) allows a better peak separation as it provides a lower spectral peak density. This paper presents the detailed investigation of this new NMR tool in an analytical chemistry context. Theoretical calculations and numerical simulations are used to characterize the modulation of peak intensities as a function of pulse-sequence parameters, and thus enable a significant enhancement of the sensitivity. The analytical comparison of UF-COSY and UF-DQS shows similar performances, however the ultrafast implementation of the DQS approach is found to have some sensitivity advantages over its conventional counterpart. The analytical performance of the pulse sequence is illustrated by the quantification of taurine in complex mixtures (homemade and commercial energy drinks). The results demonstrate the high potential of this experiment, which forms a valuable alternative to UF-COSY spectra when the latter are characterized by strong overlaps and high dynamic ranges. PMID:26865359

  13. New C20-diterpenoid alkaloids from Aconitum vilmorrianum and structural revision of 2-O-acetylorochrine and orochrine.

    PubMed

    Tang, Tian-Xing; Chen, Qi-Feng; Liu, Xiao-Yu; Jian, Xi-Xian; Wang, Feng-Peng

    2016-04-01

    Three new C20-diterpenoid alkaloids vilmorrianines E (1), F (2), and G (3) were isolated from the whole plants of Aconitum vilmorrianum, along with one artifact N-chloromethyl vilmorrianine E hydrochloride (4), as well as two known alkaloids hemsleyaconitines F (5) and G (6). The structures of 1-4 were established by HR-ESI-MS, 1D-, 2D-NMR (HMQC, HMBC, and NOESY), and single-crystal X-ray diffraction analysis. In addition, the structures of naturally occurring 2-O-acetylorochrine (7) and orochrine (8) were revised to be the known alkaloids heterophylloidine (9) and deacetyl heterophylloidine (10), respectively, on the basis of consideration of transannular effect and chemical correlations. PMID:26479584

  14. Synthesis and characterization of higher amino acid Schiff bases, as monosodium salts and neutral forms. Investigation of the intramolecular hydrogen bonding in all Schiff bases, antibacterial and antifungal activities of neutral forms

    NASA Astrophysics Data System (ADS)

    Güngör, Özlem; Gürkan, Perihan

    2014-09-01

    Schiff bases derived from 5-nitro-salicylaldehyde and 4-aminobutyric acid, 5-aminopentanoic acid and 6-aminohexanoic acid were synthesized both as monosodium salts (1a-3a) and neutral forms (1b-3b). The monosodium-Schiff bases were characterized by elemental analysis, 1H/13C NMR, IR, powder XRD, UV-vis spectra and conductivity measurements. The neutral-Schiff bases were characterized by elemental analysis, 1H/13C NMR, 2D NMR (HMQC), mass, IR, powder XRD, UV-vis spectra and conductivity measurements. The intramolecular hydrogen bonding and related tautomeric equilibria in all the Schiff bases were studied by UV-vis and 1H NMR spectra in solution. Additionally, the neutral-Schiff bases were screened against Staphylococcus aureus-EB18, S. aureus-ATCC 25923, Escherichia coli-ATCC 11230, Candida albicans-M3 and C. albicans-ATCC 16231.

  15. Cardenolides and bufadienolide glycosides from Kalanchoe tubiflora and evaluation of cytotoxicity.

    PubMed

    Huang, Hui-Chi; Lin, Ming-Kuem; Yang, Hsin-Ling; Hseu, You-Cheng; Liaw, Chih-Chuang; Tseng, Yen-Hsueh; Tsuzuki, Minoru; Kuo, Yueh-Hsiung

    2013-09-01

    Two new cardenolides, kalantubolide A (1) and kalantubolide B (2), and two bufadienolide glycosides, kalantuboside A (3) and kalantuboside B (4), as well as eleven known compounds were isolated and characterized from the EtOH extract of Kalanchoe tubiflora. The structures of compounds were assigned based on 1D and 2D NMR spectroscopic analyses including HMQC, HMBC, and NOESY. Biological evaluation indicated that cardenolides (1-2) and bufadienolide glycosides (3-7) showed strong cytotoxicity against four human tumor cell lines (A549, Cal-27, A2058, and HL-60) with IC50 values ranging from 0.01 µM to 10.66 µM. Cardenolides (1-2) also displayed significant cytotoxicity toward HL-60 tumor cell line. In addition, compounds 3, 4, 5, 6, and 7 blocked the cell cycle in the G2/M-phase and induced apoptosis in HL-60 cells. PMID:23877916

  16. Isolation and structural characterization of a new minor diterpene glycoside from Stevia rebaudiana.

    PubMed

    Chaturvedula, Venkata Sai Prakash; Zamora, Julian

    2014-12-01

    From the commercial extract of the leaves of the sweet plant Stevia rebaudiana Bertoni obtained from Sinochem Qingdao Co. Ltd., a new diterpene glycoside having three β-D-glucopyranosyl units of which two of them were connected in a relatively rare linkage of 3-β-D-glucobiosyl substitution at C-19 position of the aglycone steviol. The structure of the new compound has been characterized as 13-β-D-glucopyranosyloxy ent-kaur-16-en-19-oic acid-[(3-O-β-D- glucopyranosyl-β-D-glucopyranosyl) ester (1) on the basis of extensive 1D (1H and 13C) and 2D NMR (TOCSY, HMQC, and HMBC), and High Resolution mass spectroscopic data as well as hydrolysis studies. PMID:25632456

  17. Study on ferrocenes, part 9 [1] substrate selective transformations of some ferrocenylhydrazones

    NASA Astrophysics Data System (ADS)

    Abrán, Á.; Csámpai, A.; Kotschy, A.; Barabás, O.; Sohár, P.

    2001-07-01

    Different ferrocenyl-substituted hydrazones of heteroaryl/arylhydrazines ( 1a- e, 3 and 10) were reacted with dimethyl fumarate and gave two epimeric pairs of pyrazolidines ( t, c- 2a and t, c- 2c), pyrazolines ( 5a, c, 6, 11), pyrazoles ( 8, 12) and condensed triazoles ( 4a, 7). On treatment with dicyanodichloroquinone (DDQ) the pyrido[2,3- d]pyridazinyl-substituted hydrazones ( 1b, e) were cyclized to condensed triazoles 4b, e. The reactivity of 1a- e in the cycloaddition process and oxidation level of the products were found to be highly dependent on the temperature and on the heteroaryl/aryl group. The significant difference was explained by theoretical calculations. The structures of products were determined by IR, 1D and 2D NMR methods (including HMQC, HMBC and DNOE) and single crystal X-ray analysis.

  18. Jatrophane diterpenoid esters from Euphorbia sororia serving as multidrug resistance reversal agents.

    PubMed

    Lu, Dongli; Liu, Yongqiang; Aisa, Haji Akber

    2014-01-01

    Six (1-6) new jatrophane diterpenoid esters together with four known compounds (7-10) were isolated from the acetone extract of fructus Euphorbia sororia. Their structures were elucidated by the spectral technology, including the 2D NMR experiments (HMQC, HMBC and NOESY). The absolute configuration of compound 1 and compound 7 were first confirmed by X-ray crystallographic analysis. Compounds 1-7 were assayed for their antiproliferative activity in human cancer cell lines: human mammary adenocarcinoma (MCF-7) and human lung adenocarcinoma (A549). All the compounds were inactive for the cell lines. The multidrug-resistance reversal activity was also tested on KBv200 cells and compound 2 displayed strong multidrug resistance reversal activity, outperforming verapamil at 10 μM. PMID:24291755

  19. Canna indica flower: New source of anthocyanins.

    PubMed

    Srivastava, Jyoti; Vankar, Padma S

    2010-12-01

    In this study the red flowers of Canna indica (Cannaceae) were extracted by using sonicator and isolation of anthocyanins have been carried out. Four anthocyanin pigments have been isolated apart from quercetin and lycopene. They are Cyanidin-3-O-(6''-O-α-rhamnopyranosyl)-β-glucopyranoside (1), Cyanidin-3-O-(6''-O-α-rhamnopyranosyl)-β-galactopyranoside (2), Cyanidin-3-O-β-glucopyranoside (3) and Cyanidin-O-β-galactopyranoside (4). These compounds were isolated by using HPLC and their structures were subsequently determined on the basis of spectroscopic analyses, i.e., (1)H NMR, (13)C NMR, HMQC, HMBC, ESI-MS, FTIR, UV-Visible etc. The isolated compounds showed good antioxidant activity thus makes it suitable for use in food coloration and as a nutraceutical. Thus it is a promising pigment source for food applications. PMID:20926305

  20. Sesamolinol glucoside, disaminyl ether, and other lignans from sesame seeds.

    PubMed

    Grougnet, Raphael; Magiatis, Prokopios; Laborie, Helene; Lazarou, Despina; Papadopoulos, Athanasios; Skaltsounis, Alexios-Leandros

    2012-01-11

    The application of a procedure based on XAD-4 adsorption resin permitted the obtainment of an enriched polyphenolic extract from Sesamum indicum seeds. Chemical analysis of the obtained extract led to the identification of 12 lignans. Among them, 2 lignans, (+)-sesamolinol-4'-O-β-D-glucoside and disaminyl ether, are reported for the first time as natural compounds. Their structure has been determined by spectroscopic methods, mainly by the application of one-dimensional (1D) and two-dimensional (2D) nuclear magnetic resonance (NMR) techniques [heteronuclear multiple-quantum coherence (HMQC), heteronuclear multiple-bond correlation (HMBC), and nuclear Overhauser effect spectrometry (NOESY)] and mass spectroscopy. The isolated compounds were evaluated for their antimutagenic activity. Among the tested lignans, the most active lignan was found to be sesamolin, followed by sesamolinol and samin, against H(2)O(2). Additionally, some of the tested lignans showed desmutagenic activity against benzo[a]pyrene (BaP). PMID:22148167

  1. A new flavane acid from the fruits of Illicium verum.

    PubMed

    Wu, Liang-Deng; Xiong, Chun-Lan; Chen, Zi-Zhan; He, Rui-Jie; Zhang, Yan-Jun; Huang, Yan; Deng, Sheng-Ping; Yang, Rui-Yun; Li, Jun

    2016-07-01

    A new compound, illiciumflavane acid (1), along with 13 known compounds (2-14), were isolated from the fruits of Illicium verum Hook. F. Their structures were elucidated through various spectroscopic methods, including 1D NMR ((1)H NMR, (13)C NMR), 2D NMR (HMQC, HMBC and NOESY) and HRMS. The stereochemistry at the chiral centres was determined using CD spectrum as well as analyses of coupling constants and optical rotation data. Cytotoxicity evaluation of four compounds showed that illiciumflavane acid and (E)-1,2-bis(4-methoxyphenyl)ethene exhibited potential against A549 activities with IC50 values of 4.63 μM and 9.17 μM, respectively. PMID:26734839

  2. 5β,19-epoxycucurbitane triterpenoids from Momordica charantia and their anti-inflammatory and cytotoxic activity.

    PubMed

    Liaw, Chia-Ching; Huang, Hui-Chi; Hsiao, Ping-Chun; Zhang, Li-Jie; Lin, Zhi-Hu; Hwang, Syh-Yuan; Hsu, Feng-Lin; Kuo, Yao-Haur

    2015-01-01

    Five new 5β,19-epoxycucurbitane triterpenoids, taikugausins A-E (1-5), together with 5β,19-epoxy-25-methoxycucurbita-6,23-diene-3β,19-diol (6), have been isolated and characterized from the 70 % EtOH extract of the fresh fruits of Momordica charantia. The chemical structures of compounds 1-6 were elucidated on the basis of extensive spectroscopic analyses, especially 2D NMR (HMQC, HMBC, and NOESY) experiments and HRESIMS data. The relationship between NMR chemical shifts and the configuration of C-19 with an OMe group in 5β,19-epoxycucurbitane are described. Among them, compounds 3 and 4 exhibited remarkable anti-inflammatory activities by the inhibition of nitric oxide production at the concentration of 10 µg/mL. In addition, 3 and 4 also showed moderate cytotoxicity against WiDr, Hep G2, MCF-7, and HEp-2 human tumor cell lines. PMID:25469855

  3. Biochemical classification of kidney carcinoma biopsy samples using magic-angle-spinning 1H nuclear magnetic resonance spectroscopy.

    PubMed

    Moka, D; Vorreuther, R; Schicha, H; Spraul, M; Humpfer, E; Lipinski, M; Foxall, P J; Nicholson, J K; Lindon, J C

    1998-05-01

    High resolution 1H nuclear magnetic resonance (NMR) spectra using spinning at the magic angle (1H MAS NMR) have been obtained on intact normal and pathological kidney tissue samples from patients undergoing surgery for renal cell carcinoma (RCC). The spectra were measured on ca. 80 mg samples and provided high resolution 1H NMR spectra in which effects of dipolar couplings, chemical shift anisotropy and magnetic susceptibility differences are minimised thus yielding high spectral resolution. Conventional one-dimensional and spin-echo spectra and two-dimensional J-resolved, TOCSY and 1H-13C HMQC spectra were also measured on selected samples and these allowed the assignment of resonances of endogenous substances comprising both cytosolic and membrane components. The tumour tissues were characterised principally by an increased lipid content. These are the first reported results on human tumour tissues using this technique and the approach offers potential for the rapid classification of different types of tumour tissue. PMID:9608434

  4. NMR analyses of deuterated phospholipids isolated from Pichia angusta

    NASA Astrophysics Data System (ADS)

    Massou, S.; Augé, S.; Tropis, M.; Lindley, N. D.; Milon, A.

    1998-02-01

    The phospholipid composition of methylotrophic yeasts grown on deuterated and hydrogenated media has been determined by proton and phosphorus NMR. By using a line narrowing solvent, we could obtain linewidth lower than 2 Hz, and all the resonances could be resolved. Phospholipids were identified on the basis of their chemical shift and by 31P - H correlations (HMQC - HOHAHA gradient enhanced experiments). We have thus analysed qualitatively and quantitatively lipids mixtures directly after chloroform-methanol extraction. The lipid composition is deeply modified after growth in deuterated medium were phosphatidyl Inositol (PI) becomes the major lipid, instead of a PC, PS, PI mixture in hydrogenated conditions. La composition en phospholipides de levures méthylotrophes ayant poussé sur des milieux de cultures hydrogénés et deutériés a été déterminée par RMN du proton et du phosphore31. L'utilisation d'un solvant d'affinement a permis d'obtenir des largeurs de raies inférieures à 2Hz et de résoudre toutes les classes de phospholipides. Ils sont ensuite identifiés par leur déplacement chimique et par des corrélations phosphore - proton spécifiques (expériences HMQC-HOHAHA gradients). Cette approche a permis une analyse qualitative et quantitative de mélanges de phospholipides directement après extraction au chloroforme-méthanol. La composition en phospholipides est profondément modifiée lors de la croissance en milieu perdeutérié où l'on observe un lipide majoritaire, le phosphatidyl Inositol (PI), au lieu d'un mélange PC, PS PI en milieu hydrogéné.

  5. The tautomeric state of histidines in myoglobin.

    PubMed Central

    Bhattacharya, S; Sukits, S F; MacLaughlin, K L; Lecomte, J T

    1997-01-01

    1H-15N HMQC spectra were collected on 15N-labeled sperm whale myoglobin (Mb) to determine the tautomeric state of its histidines in the neutral form. By analyzing metaquoMb and metcyanoMb data sets collected at various pH values, cross-peaks were assigned to the imidazole rings and their patterns interpreted. Of the nine histidines not interacting with the heme in sperm whale myoglobin, it was found that seven (His-12, His-48, His-81, His-82, His-113, His-116, and His-119) are predominantly in the N epsilon2H form with varying degrees of contribution from the Ndelta1 H form. The eighth, His-24, is in the Ndelta1H state as expected from the solid state structure. 13C correlation spectra were collected to probe the state of the ninth residue (His-36). Tentative interpretation of the data through comparison with horse Mb suggested that this ring is predominantly in the Ndelta1H state. In addition, signals were observed from the histidines associated with the heme (His-64, His-93, and His-97) in the 1H-15N HMQC spectra of the metcyano form. In several cases, the tautomeric state of the imidazole ring could not be derived from inspection of the solid state structure. It was noted that hydrogen bonding of the ring was not unambiguously reflected in the nitrogen chemical shift. With the experimentally determined tautomeric state composition in solution, it will be possible to broaden the scope of other studies focused on the electrostatic contribution of histidines to the thermodynamic properties of myoglobin. PMID:9414234

  6. Sequence-specific {sup 1}H, {sup 13}C, and {sup 15}N resonance assignments for intestinal fatty-acid-binding protein complexed with palmitate (15.4 kDA)

    SciTech Connect

    Hodsdon, M.E.; Toner, J.J.; Cistola, D.P.

    1994-12-01

    Intestinal fatty-acid-binding protein (I-FABP) belongs to a family of soluble, cytoplasmic proteins that are thought to function in the intracellular transport and trafficking of polar lipids. Individual members of this protein family have distinct specificities and affinities for fatty acids, cholesterol, bile salts, and retinoids. We are comparing several retinol- and fatty-acid-binding proteins from intestine in order to define the factors that control molecular recognition in this family of proteins. We have established sequential resonance assignments for uniformly {sup 13}C/{sup 15}N-enriched I-FABP complexed with perdeuterated palmitate at pH7.2 and 37{degrees}C. The assignment strategy was similar to that introduced for calmodulin. We employed seven three-dimensional NMR experiments to establish scalar couplings between backbone and sidechain atoms. Backbone atoms were correlated using triple-resonance HNCO, HNCA, TOCSY-HMQC, HCACO, and HCA(CO)N experiments. Sidechain atoms were correlated using CC-TOCSY, HCCH-TOCSY, and TOCSY-HMQC. The correlations of peaks between three-dimensional spectra were established in a computer-assisted manner using NMR COMPASS (Molecular Simulations, Inc.) Using this approach, {sup 1}H, {sup 13}C, and {sup 15}N resonance assignments have been established for 120 of the 131 residues of I-FABP. For 18 residues, amide {sup 1}H and {sup 15}N resonances were unobservable, apparently because of the rapid exchange of amide protons with bulk water at pH 7.2. The missing amide protons correspond to distinct amino acid patterns in the protein sequence, which will be discussed. During the assignment process, several sources of ambiguity in spin correlations were observed. To overcome this ambiguity, the additional inter-residue correlations often observed in the HNCA experiment were used as cross-checks for the sequential backbone assignments.

  7. Dual allosteric activation mechanisms in monomeric human glucokinase

    PubMed Central

    Whittington, A. Carl; Larion, Mioara; Bowler, Joseph M.; Ramsey, Kristen M.; Brüschweiler, Rafael; Miller, Brian G.

    2015-01-01

    Cooperativity in human glucokinase (GCK), the body’s primary glucose sensor and a major determinant of glucose homeostatic diseases, is fundamentally different from textbook models of allostery because GCK is monomeric and contains only one glucose-binding site. Prior work has demonstrated that millisecond timescale order-disorder transitions within the enzyme’s small domain govern cooperativity. Here, using limited proteolysis, we map the site of disorder in unliganded GCK to a 30-residue active-site loop that closes upon glucose binding. Positional randomization of the loop, coupled with genetic selection in a glucokinase-deficient bacterium, uncovers a hyperactive GCK variant with substantially reduced cooperativity. Biochemical and structural analysis of this loop variant and GCK variants associated with hyperinsulinemic hypoglycemia reveal two distinct mechanisms of enzyme activation. In α-type activation, glucose affinity is increased, the proteolytic susceptibility of the active site loop is suppressed and the 1H-13C heteronuclear multiple quantum coherence (HMQC) spectrum of 13C-Ile–labeled enzyme resembles the glucose-bound state. In β-type activation, glucose affinity is largely unchanged, proteolytic susceptibility of the loop is enhanced, and the 1H-13C HMQC spectrum reveals no perturbation in ensemble structure. Leveraging both activation mechanisms, we engineer a fully noncooperative GCK variant, whose functional properties are indistinguishable from other hexokinase isozymes, and which displays a 100-fold increase in catalytic efficiency over wild-type GCK. This work elucidates specific structural features responsible for generating allostery in a monomeric enzyme and suggests a general strategy for engineering cooperativity into proteins that lack the structural framework typical of traditional allosteric systems. PMID:26283387

  8. Selectively Labeling the Heterologous Protein in Escherichia coli for NMR Studies: A Strategy to Speed Up NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Almeida, F. C. L.; Amorim, G. C.; Moreau, V. H.; Sousa, V. O.; Creazola, A. T.; Américo, T. A.; Pais, A. P. N.; Leite, A.; Netto, L. E. S.; Giordano, R. J.; Valente, A. P.

    2001-01-01

    Nuclear magnetic resonance is an important tool for high-resolution structural studies of proteins. It demands high protein concentration and high purity; however, the expression of proteins at high levels often leads to protein aggregation and the protein purification step can correspond to a high percentage of the overall time in the structural determination process. In the present article we show that the step of sample optimization can be simplified by selective labeling the heterologous protein expressed in Escherichia coli by the use of rifampicin. Yeast thioredoxin and a coix transcription factor Opaque 2 leucine zipper (LZ) were used to show the effectiveness of the protocol. The 1H/15N heteronuclear correlation two-dimensional NMR spectrum (HMQC) of the selective 15N-labeled thioredoxin without any purification is remarkably similar to the spectrum of the purified protein. The method has high yields and a good 1H/15N HMQC spectrum can be obtained with 50 ml of M9 growth medium. Opaque 2 LZ, a difficult protein due to the lower expression level and high hydrophobicity, was also probed. The 15N-edited spectrum of Opaque 2 LZ showed only the resonances of the protein of heterologous expression (Opaque 2 LZ) while the 1H spectrum shows several other resonances from other proteins of the cell lysate. The demand for a fast methodology for structural determination is increasing with the advent of genome/proteome projects. Selective labeling the heterologous protein can speed up NMR structural studies as well as NMR-based drug screening. This methodology is especially effective for difficult proteins such as hydrophobic transcription factors, membrane proteins, and others.

  9. The effect of polar end of long-chain fluorocarbon oligomers in promoting the superamphiphobic property over multi-scale rough Al alloy surfaces

    NASA Astrophysics Data System (ADS)

    Saifaldeen, Zubayda S.; Khedir, Khedir R.; Camci, Merve T.; Ucar, Ahmet; Suzer, Sefik; Karabacak, Tansel

    2016-08-01

    Rough structures with re-entrant property and their subsequent surface energy reduction with long-chain fluorocarbon oligomers are both critical in developing superamphiphobic (SAP, i.e. both super hydrophobic and superoleophobic) surfaces. However, morphology of the low-surface energy layer on a rough re-entrant substrate can strongly depend on the fluorocarbon oligomers used. In this study, the effect of polar end of different kinds of long-chain fluorocarbon oligomers in promoting a self-assembled monolayer with close packed molecules and robust adhesion on multi-scale rough Al alloy surfaces was investigated. Hierarchical Al alloy surfaces with microgrooves and nanograss structures were developed by a simple combination of one-directional mechanical sanding and post treatment in boiling de-ionized water (DIW). Three types of long-chain fluorocarbon oligomers of 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane (PFDTS), 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane (PFDCS), and perfluorooctanoic acid (PFOA) were chemically vaporized onto these rough Al alloy surfaces. The PFDCS exhibited the lowest surface free energy of less than 10 mN/m. The contact angle and sliding angle measurements for water, ethylene glycol, and peanut oil verified the SAP property of hierarchical rough Al alloy surfaces treated with alkylsilane oligomers (PFDTS, PFDCS). However, the hierarchical surfaces treated with fluorocarbon oligomer with polar acidic tail (PFOA) showed highly amphiphobic properties but could not reach the threshold for SAP. Chemical stability of the hierarchical Al alloy surfaces treated with the fluorocarbon oligomers was tested under the harsh conditions of ultra-sonication in acetone and annealing at high temperature after different treatment times. Contact angle measurements revealed the robustness of the alkylsilane oligomers and deterioration of the PFOA coating particularly for low surface tension liquids. The robust adhesion and close-packing of the alkylsilane

  10. Control and characterization of textured, hydrophobic ionomer surfaces

    NASA Astrophysics Data System (ADS)

    Wang, Xueyuan

    Polymer thin films are of increasing interest in many industrial and technological applications. Superhydrophobic, self-cleaning surfaces have attracted a lot of attention for their application in self-cleaning, anti-sticking coatings, stain resistance, or anti-contamination surfaces in diverse technologies, including medical, transportation, textiles, electronics and paints. This thesis focuses on the preparation of nanometer to micrometer-size particle textured surfaces which are desirable for super water repellency. Textured surfaces consisting of nanometer to micrometer-sized lightly sulfonated polystyrene ionomer (SPS) particles were prepared by rapid evaporation of the solvent from a dilute polymer solution cast onto silica. The effect of the solvent used to spin coat the film, the molecular weight of the ionomer, and the rate of solvent evaporation were investigated. The nano-particle or micron-particle textured ionomer surfaces were prepared by either spin coating or solution casting ionomer solutions at controlled evaporation rates. The surface morphologies were consistent with a spinodal decomposition mechanism where the surface first existed as a percolated-like structure and then ripened into droplets if molecular mobility was retained for sufficient time. The SPS particles or particle aggregates were robust and resisted deformation even after annealing at 120°C for one week. The water contact angles on as-prepared surfaces were relatively low, ~ 90° since the polar groups in ionomer reduce the surface hydrophobicity. After chemical vapor deposition of 1H,1H,2H,2H-perfluorooctyltrichlorosilane, the surface contact angles increased to ~ 109° on smooth surfaces and ~140° on the textured surfaces. Water droplets stuck to these surfaces even when tilted 90 degrees. Superhydrophobic surfaces were prepared by spraying coating ionomer solutions and Chemical Vapor Deposition (CVD) of 1H,1H,2H,2H-perfluorooctyltrichlorosilane onto textured surfaces. The

  11. Hydrazine N-N Bond Cleavage over Silica-Supported Tantalum-Hydrides.

    PubMed

    Jia, Hong-Peng; Gouré, Eric; Solans-Monfort, Xavier; Llop Castelbou, Jessica; Chow, Catherine; Taoufik, Mostafa; Eisenstein, Odile; Quadrelli, Elsje Alessandra

    2015-12-21

    Hydrazine reacts with silica-supported tantalum-hydrides [(≡SiO)2TaHx] (x = 1, 3), 1, under mild conditions (100 °C). The IR in situ monitoring of the reaction with N2H4 or (15)N2H4, and the solid-state MAS NMR spectra of the fully (15)N labeled compounds (CP (15)N, (1)H-(15)N HETCOR, (1)H-(1)H double-quantum, and (1)H-(1)H triple-quantum spectra) were used to identify stable intermediates and products. DFT calculations were used for determining the reaction pathway and calculating the (15)N and (1)H NMR chemical shifts. Combining the experimental and computational studies led to the following results. At room temperature, only hydrazine adducts, 1-N2H4, are formed. Upon heating at 100 °C, the hydrazine adducts are converted to several species among which [(≡SiO)2Ta(═NH)(NH2)], 2, [(≡SiO)2TaH(NH2)2], 3, and [(≡SiO)2TaH2(NH-NH2)], 4, were identified. The final product 2 is also formed in the reaction of N2 with the same silica-supported tantalum-hydride complexes, and the species identified as 3 and 4 had been previously suggested by DFT studies as intermediates on the reaction pathway for N-N cleavage in N2. The present computational studies (cluster models with M06 functional complemented by selected calculations with periodic calculations) show that 2 is formed via 3 and 4, with either N2 or N2H4. This strengthens the previous proposal of the existence of 3 and 4 as intermediates in the reaction of N2 with the tantalum-hydrides. However, the reaction of N2 does not imply the formation of N2H4 or its hydrazido monoanionic or dianionic ligand as an intermediate. For this reason, this study informs both on the similarities and differences of the reaction pathways involving N2 and N2H4 with tantalum-hydrides. PMID:26650850

  12. Functional Genetic Variants in DC-SIGNR Are Associated with Mother-to-Child Transmission of HIV-1

    PubMed Central

    Boily-Larouche, Geneviève; Iscache, Anne-Laure; Zijenah, Lynn S.; Humphrey, Jean H.; Mouland, Andrew J.; Ward, Brian J.; Roger, Michel

    2009-01-01

    Background Mother-to-child transmission (MTCT) is the main cause of HIV-1 infection in children worldwide. Given that the C-type lectin receptor, dendritic cell-specific ICAM-grabbing non-integrin-related (DC-SIGNR, also known as CD209L or liver/lymph node–specific ICAM-grabbing non-integrin (L-SIGN)), can interact with pathogens including HIV-1 and is expressed at the maternal-fetal interface, we hypothesized that it could influence MTCT of HIV-1. Methods and Findings To investigate the potential role of DC-SIGNR in MTCT of HIV-1, we carried out a genetic association study of DC-SIGNR in a well-characterized cohort of 197 HIV-infected mothers and their infants recruited in Harare, Zimbabwe. Infants harbouring two copies of DC-SIGNR H1 and/or H3 haplotypes (H1-H1, H1-H3, H3-H3) had a 3.6-fold increased risk of in utero (IU) (P = 0.013) HIV-1 infection and a 5.7-fold increased risk of intrapartum (IP) (P = 0.025) HIV-1 infection after adjusting for a number of maternal factors. The implicated H1 and H3 haplotypes share two single nucleotide polymorphisms (SNPs) in promoter region (p-198A) and intron 2 (int2-180A) that were associated with increased risk of both IU (P = 0.045 and P = 0.003, respectively) and IP (P = 0.025, for int2-180A) HIV-1 infection. The promoter variant reduced transcriptional activity in vitro. In homozygous H1 infants bearing both the p-198A and int2-180A mutations, we observed a 4-fold decrease in the level of placental DC-SIGNR transcripts, disproportionately affecting the expression of membrane-bound isoforms compared to infant noncarriers (P = 0.011). Conclusion These results suggest that DC-SIGNR plays a crucial role in MTCT of HIV-1 and that impaired placental DC-SIGNR expression increases risk of transmission. PMID:19809496

  13. Superhydrophobic surfaces on light alloy substrates fabricated by a versatile process and their corrosion protection.

    PubMed

    Ou, Junfei; Hu, Weihua; Xue, Mingshan; Wang, Fajun; Li, Wen

    2013-04-24

    After hydrothermally treated in H2O (for Mg alloy and Al alloy) or H2O2 (for Ti alloy), microstructured oxide or hydroxide layers were formed on light alloy substrates, which further served as the active layers to boost the self-assembling of 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFOTES) and finally endowed the substrates with unique wettability, that is, superhydrophobicity. For convenience, the so-fabricated superhyrdophobic surfaces (SHS) were abridged as HT-SHS. For comparison, SHS coded as CE-SHS were also prepared based on chemical etching in acid and succedent surface passivation with PFOTES. To reveal the corrosion protection of these SHS, potentiodynamic polarization measurements in NaCl solution (3.5 wt %) were performed. Moreover, to reflect the long-term stability of these SHS, SHS samples were immersed into NaCl solution and the surface wettability was monitored. Experimental results indicated that HT-SHS was much more stable and effective in corrosion protection as compared with CE-SHS. The enhancement was most likely due to the hydrothermally generated oxide layer by the following tow aspects: on one hand, oxide layer itself can lower the corrosion due to its barrier effect; on the other hand, stronger interfacial bonding is expected between oxide layer and PFOTES molecules. PMID:23496751

  14. Complement Factor H and Simian Virus 40 bind the GM1 ganglioside in distinct conformations.

    PubMed

    Blaum, Bärbel S; Frank, Martin; Walker, Ross C; Neu, Ursula; Stehle, Thilo

    2016-05-01

    Mammalian cell surfaces are decorated with a variety of glycan chains that orchestrate development and defense and are exploited by pathogens for cellular attachment and entry. While glycosidic linkages are, in principle, flexible, the conformational space that a given glycan can sample is subject to spatial and electrostatic restrictions imposed by its overall chemical structure. Here, we show how the glycan moiety of the GM1 ganglioside, a branched, monosialylated pentasaccharide that serves as a ligand for various proteins, undergoes differential conformational selection in its interactions with different lectins. Using STD NMR and X-ray crystallography, we found that the innate immune regulator complement Factor H (FH) binds a previously not reported GM1 conformation that is not compatible with the GM1-binding sites of other structurally characterized GM1-binding lectins such as the Simian Virus 40 (SV40) capsid. Molecular dynamics simulations of the free glycan in explicit solvent on the 10 μs timescale reveal that the FH-bound conformation nevertheless corresponds to a minimum in the Gibbs free energy plot. In contrast to the GM1 conformation recognized by SV40, the FH-bound GM1 conformation is associated with poor NOE restraints, explaining how it escaped(1)H-(1)H NOE-restrained modeling in the past and highlighting the necessity for ensemble representations of glycan structures. PMID:26715202

  15. Advanced Structural Determination of Diterpene Esters Using Molecular Modeling and NMR Spectroscopy.

    PubMed

    Nothias-Scaglia, Louis-Félix; Gallard, Jean-François; Dumontet, Vincent; Roussi, Fanny; Costa, Jean; Iorga, Bogdan I; Paolini, Julien; Litaudon, Marc

    2015-10-23

    Three new jatrophane esters (1-3) were isolated from Euphorbia amygdaloides ssp. semiperfoliata, including an unprecedented macrocyclic jatrophane ester bearing a hemiketal substructure, named jatrohemiketal (3). The chemical structures of compounds 1-3 and their relative configurations were determined by spectroscopic analysis. The absolute configuration of compound 3 was determined unambiguously through an original strategy combining NMR spectroscopy and molecular modeling. Conformational search calculations were performed for the four possible diastereomers 3a-3d differing in their C-6 and C-9 stereocenters, and the lowest energy conformer was used as input structure for geometry optimization. The prediction of NMR parameters ((1)H and (13)C chemical shifts and (1)H-(1)H coupling constants) by density functional theory (DFT) calculations allowed identifying the most plausible diastereomer. Finally, the stereostructure of 3 was solved by comparison of the structural features obtained by molecular modeling for 3a-3d with NMR-derived data (the values of dihedral angles deduced from the vicinal proton-proton coupling constants ((3)JHH) and interproton distances determined by ROESY). The methodology described herein provides an efficient way to solve or confirm structural elucidation of new macrocyclic diterpene esters, in particular when no crystal structure is available. PMID:26431312

  16. Evaluation of potential performance additives for the advanced lithium bromide chiller

    SciTech Connect

    Reiner, R.H.; Del Cul, W.; Perez-Blanco, H.; Ally, M.R.; Zaltash, A.

    1991-04-01

    The effectiveness and stability of potential heat-and-mass transfer (performance) additives for an advanced lithium bromide (LiBr) chiller were evaluated in a series of experimental studies. These studies of additive effectiveness and stability were necessary because many currently used performance additives decompose at the high generator temperatures (220{degrees}C to 260{degrees}C) desired for this particular advanced LiBr chiller. For example, one common performance additive, 2-ethyl-l-hexanol (2EH), reacts with the corrosion inhibitor, lithium chromate (Li{sub 2}CrO{sub 4}), even at moderate generator temperatures ({ge}180{degrees}C). These stability problems can be mitigated by using less reactive corrosion inhibitors such as lithium molybdate (Li{sub 2}MoO{sub 4}) and by using more stable performance additives such as 1-heptanol (HEP) or 1H,1H,7H-dodecafluoro-1-heptanol (DFH). There seems to be a trade-off between additive stability and effectiveness: the most effective performance additives are not the most stable additives. These studies indicate that HEP or DFH may be effective additives in the advanced LiBr chiller if Li{sub 2}MoO{sub 4} is used as a corrosion inhibitor.

  17. The amyloidogenic SEVI precursor, PAP248-286, is highly unfolded in solution despite an underlying helical tendency

    PubMed Central

    Brender, Jeffrey R.; Nanga, Ravi Prakash Reddy; Popovych, Nataliya; Soong, Ronald; Macdonald, Peter M.; Ramamoorthy, Ayyalusamy

    2011-01-01

    Amyloid fibers in human semen known as SEVI (Semen-derived Enhancer of Viral Infection) dramatically increase the infectivity of HIV and other enveloped viruses, which appears to be linked to the promotion of bridging interactions and the neutralization of electrostatic repulsion between the host and the viral cell membranes. The SEVI precursor PAP248-286 is mostly disordered when bound to detergent micelles, in contrast to the highly α-helical structures found for most amyloid proteins. To determine the origin of this difference, the structures of PAP248-286 were solved in aqueous solution and with 30% and 50% trifluoroethanol. In solution, pulsed field gradient (PFG)-NMR and 1H-1H NOESY experiments indicate that PAP248-286 is unfolded to an unusual degree for an amyloidogenic peptide but adopts significantly helical structures in TFE solutions. The clear differences between the structures of PAP248-286 in TFE and SDS indicate electrostatic interactions play a large role in the folding of the peptide, consistent with the slight degree of penetration of PAP248-286 into the hydrophobic core of the micelle. This is another noticeable difference between PAP248-286 and other amyloid peptides, which generally show penetration into at least the headgroup region of the bilayer, and may explain some of the unusual properties of SEVI. PMID:21262195

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

    PubMed

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

    2010-01-01

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

  19. Wettability modification of rock cores by fluorinated copolymer emulsion for the enhancement of gas and oil recovery

    NASA Astrophysics Data System (ADS)

    Feng, Chunyan; Kong, Ying; Jiang, Guancheng; Yang, Jinrong; Pu, Chunsheng; Zhang, Yuzhong

    2012-07-01

    The fluorine-containing acrylate copolymer emulsion was prepared with butyl acrylate, methacrylic acid and 1H, 1H, 2H, 2H-perfluorooctyl acrylate as monomers. Moreover, the structure of the copolymer was verified by Fourier transform infrared (FTIR), nuclear magnetic resonance (1H NMR and 19F NMR) and X-ray photoelectron spectroscopy (XPS) analyses. The results showed that all the monomers had been copolymerized and the presence of fluorine moieties. The contact angle (CA) analyses, capillary rise and imbibition spontaneous tests were used to estimate the influence of the copolymer emulsion on the wettability of gas reservoirs. It was observed that the rock surface was of large contact angles of water, oilfield sewage, hexadecane and crude oil after treatment with the emulsion. The capillary rise results indicated that the contact angles of water/air and oil/air systems increased from 60° and 32° to 121° and 80°, respectively, due to the emulsion treatment. Similarly, because of wettability alteration by the fluoropolymer, the imbibition of water and oil in rock core decreased significantly. Experimental results demonstrated that the copolymer emulsion can alter the wettability of porous media from strong liquid-wetting to gas-wetting. This work provides a cost-effective method to prepare the fluoropolymer which can increase gas deliverability by altering the wettability of gas-condensate reservoirs and mitigating the water block effect.

  20. Multi-dimensional 1H- 13C HETCOR and FSLG-HETCOR NMR study of sphingomyelin bilayers containing cholesterol in the gel and liquid crystalline states

    NASA Astrophysics Data System (ADS)

    Holland, Gregory P.; Alam, Todd M.

    2006-08-01

    13C cross polarization magic angle spinning (CP-MAS) and 1H MAS NMR spectra were collected on egg sphingomyelin (SM) bilayers containing cholesterol above and below the liquid crystalline phase transition temperature ( Tm). Two-dimensional (2D) dipolar heteronuclear correlation (HETCOR) spectra were obtained on SM bilayers in the liquid crystalline ( Lα) state for the first time and display improved resolution and chemical shift dispersion compared to the individual 1H and 13C spectra and significantly aid in spectral assignment. In the gel ( Lβ) state, the 1H dimension suffers from line broadening due to the 1H- 1H homonuclear dipolar coupling that is not completely averaged by the combination of lipid mobility and MAS. This line broadening is significantly suppressed by implementing frequency switched Lee-Goldburg (FSLG) homonuclear 1H decoupling during the evolution period. In the liquid crystalline ( Lα) phase, no improvement in line width is observed when FSLG is employed. All of the observed resonances are assignable to cholesterol and SM environments. This study demonstrates the ability to obtain 2D heteronuclear correlation experiments in the gel state for biomembranes, expands on previous SM assignments, and presents a comprehensive 1H/ 13C NMR assignment of SM bilayers containing cholesterol. Comparisons are made to a previous report on cholesterol chemical shifts in dimyristoylphosphatidylcholine (DMPC) bilayers. A number of similarities and some differences are observed and discussed.

  1. Chemical stability of nonwetting, low adhesion self-assembled monolayer films formed by perfluoroalkylsilanization of copper

    NASA Astrophysics Data System (ADS)

    Hoque, E.; DeRose, J. A.; Hoffmann, P.; Bhushan, B.; Mathieu, H. J.

    2007-03-01

    A self-assembled monolayer (SAM) has been produced by reaction of 1H,1H,2H,2H-perfluorodecyldimethylchlorosilane (PFMS) with an oxidized copper (Cu) substrate and investigated by x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), friction force microscopy (FFM), a derivative of AFM, and contact angle measurement. FFM showed a significant reduction in the adhesive force and friction coefficient of PFMS modified Cu (PFMS/Cu) compared to unmodified Cu. The perfluoroalkyl SAM on Cu is found to be extremely hydrophobic, yielding sessile drop static contact angles of more than 130° for pure water and a "surface energy" (which is proportional to the Zisman critical surface tension for a Cu surface with 0rms roughness) of 14.5mJ/m2(nM/m). Treatment by exposure to harsh conditions showed that PFMS/Cu SAM can withstand boiling nitric acid (pH=1.8), boiling water, and warm sodium hydroxide (pH =12, 60°C) solutions for at least 30min. Furthermore, no SAM degradation was observed when PFMS/Cu was exposed to warm nitric acid solution for up to 70min at 60°C or 50min at 80°C. Extremely hydrophobic (low surface energy) and stable PFMS/Cu SAMs could be useful as corrosion inhibitors in micro/nanoelectronic devices and/or as promoters for antiwetting, low adhesion surfaces or dropwise condensation on heat exchange surfaces.

  2. NMR approach for monitoring post-mortem changes in Atlantic salmon fillets stored at 0 and 4°C.

    PubMed

    Shumilina, Elena; Ciampa, Alessandra; Capozzi, Francesco; Rustad, Turid; Dikiy, Alexander

    2015-10-01

    High resolution NMR technique has been used to monitor post-mortem changes in salmon (Salmo salar) fillets upon storage at 4 and 0°C. Thirty-one different fish metabolites influencing freshness and taste properties have been unequivocally assigned by NMR using either available standard compounds or ad hoc acquired 2D (1)H-(1)H TOCSY and (1)H-(13)С HSQC spectra. The monitored fish metabolites include amino acids, dipeptides, sugars, vitamins, biogenic amines, as well as different products of the ATP degradation. The detection and monitoring of biogenic amines by NMR, upon fish storage, is information of interest for consumers, since some of these compounds are toxic. The data from this study shows that NMR spectroscopy also provides the amount of all metabolites necessary for the calculation of the K-index used to express fish freshness. A good correlation was found between the K-index increase and the formation of the undesired biogenic amines. The metabolite concentrations and the K-index found in this work were compared and found coherent with literature data. The performed study reveals the strengths and the suitability of the NMR approach to monitor different biochemical processes occurring during fish storage and qualitatively and quantitatively characterise fish metabolites determining fish quality. PMID:25872421

  3. Air-stable solution-processed n-channel organic thin film transistors with polymer-enhanced morphology

    NASA Astrophysics Data System (ADS)

    He, Zhengran; Shaik, Shoieb; Bi, Sheng; Chen, Jihua; Li, Dawen

    2015-05-01

    N,N'-1H,1H-perfluorobutyl dicyanoperylenecarboxydiimide (PDIF-CN2) is an n-type semiconductor exhibiting high electron mobility and excellent air stability. However, the reported electron mobility based on spin-coated PDIF-CN2 film is much lower than the value of PDIF-CN2 single crystals made from vapor phase deposition, indicating significant room for mobility enhancement. In this study, various insulating polymers, including poly(vinyl alcohol), poly(methyl methacrylate) (PMMA), and poly(alpha-methylstyrene) (PαMS), are pre-coated on silicon substrate aiming to enhance the morphology of the PDIF-CN2 thin film, thereby improving the charge transport and air stability. Atomic force microscopy images reveal that with the pre-deposition of PαMS or PMMA polymers, the morphology of the PDIF-CN2 polycrystalline films is optimized in semiconducting crystal connectivity, domain size, and surface roughness, which leads to significant improvement of organic thin-film transistor (OTFT) performance. Particularly, an electron mobility of up to 0.55 cm2/V s has been achieved from OTFTs based on the PDIF-CN2 film with the pre-deposition of PαMS polymer.

  4. Nanostructure protein repellant amphiphilic copolymer coatings with optimized surface energy by Inductively Excited Low Pressure Plasma.

    PubMed

    Bhatt, Sudhir; Pulpytel, Jérome; Ceccone, Giacomo; Lisboa, Patricia; Rossi, François; Kumar, Virendra; Arefi-Khonsari, Farzaneh

    2011-12-01

    Statistically designed amphiphilic copolymer coatings were deposited onto Thermanox, Si wafer, and quartz crystal microbalance (QCM) substrates via Plasma Enhanced Chemical Vapor Deposition of 1H,1H,2H,2H-perfluorodecyl acrylate and diethylene glycol vinyl ether in an Inductively Excited Low Pressure Plasma reactor. Plasma deposited amphiphilic coatings were characterized by Field Emission Scanning Electron Microscopy, X-ray Photoelectron Spectroscopy, Atomic Force Microscopy, and Water Contact Angle techniques. The surface energy of the coatings can be adjusted between 12 and 70 mJ/m(2). The roughness of the coatings can be tailored depending on the plasma mode used. A very smooth coating was deposited with a CW (continuous wave) power, whereas a rougher surface with R(a) in the range of 2 to 12 nm was deposited with the PW (pulsed wave) mode. The nanometer scale roughness of amphiphilic PFDA-co-DEGVE coatings was found to be in the range of the size of the two proteins namely BSA and lysozyme used to examine for the antifouling properties of the surfaces. The results show that the statistically designed surfaces, presenting a surface energy around 25 mJ/m(2), present no adhesion with respect to both proteins measured by QCM. PMID:22029599

  5. Aldosterone, corticosterone, and thyroid hormone and their influence on respiratory control development in Lithobates catesbeianus: An in vitro study.

    PubMed

    Rousseau, Jean-Philippe; Bairam, Aida; Kinkead, Richard

    2016-04-01

    The emergence of air breathing during Lithobates catesbeianus development requires significant changes to the brainstem circuits that generate and regulate breathing; however, the mechanisms responsible for initiating this transformation remain largely unknown. Because amphibian metamorphosis is regulated by hormones such as aldosterone, corticosterone, and thyroid hormone (T3), we tested the hypothesis that exposing the brainstem to these hormones augments the fictive air breathing frequency in pre-metamorphic tadpoles. Brainstems were isolated and were placed either in the recording chamber (acute; 1h+1h recovery) or in a bottle (chronic exposure; 24h) for treatment. Brainstems were exposed to artificial cerebrospinal fluid (aCSF; sham treatment) or one of the following hormones: aldosterone (100nM), corticosterone (100nM), or T3 (100nM). While acute exposure had limited effects on respiratory motor output, chronic incubation with any hormone significantly increased fictive air breathing; the burst frequencies observed following treatment were similar to those observed in adult bullfrogs. We conclude that through their long term effects, hormones regulating metamorphosis can initiate the maturation of the neural circuits that generate and regulate breathing in this species. PMID:25476838

  6. Strong interfacial attrition developed by oleate/layered double hydroxide nanoplatelets dispersed into poly(butylene succinate).

    PubMed

    Zhou, Qian; Verney, Vincent; Commereuc, Sophie; Chin, In-Joo; Leroux, Fabrice

    2010-09-01

    Poly(butylene succinate) (PBS) nanocomposite structure was studied as a function of the filler percentage loading. The resulting state of dispersion was evaluated by XRD and TEM, and the interfacial attrition between PBS chain and lamellar platelets by the melt rheological properties. Hybrid organic inorganic (O/I) layered double hydroxide (LDH) organo-modified by oleate anions was used as filler. It was found that the confinement supplied by the LDH framework forces the interleaved organic molecule to be more distant from each other than in the case of oleate salt, this having as an effect to decrease strongly the homonuclear intermolecular (1)H(1)H dipolar interaction. An additional consequence of this relatively free molecular rotation, affecting the (13)C CPMAS response as well, is to facilitate the delamination of the 2D-stacked layers during extrusion since an quasi-exfoliated PBS:Mg(2)Al/oleate structure is observed for filler loading lower than 5% w/w. This is in association to a non-linear viscoelasticity in the low-omega region and the observed shear-thinning tendency compares better than other PBS:silicate nanocomposite derivatives and is here explained by the presence of a percolated LDH nanoparticle network. Indeed the plastic deformation in the low-omega region is found to be restricted by well-dispersed LDH tactoids in association with a rather strong attrition phenomenon between tethered oleate anions and PBS chains. PMID:20605578

  7. Protein and polysaccharide-composite sol-gel silicate film for an interference-free amperometric glucose biosensor.

    PubMed

    Matsuhisa, Hironori; Tsuchiya, Munenori; Hasebe, Yasushi

    2013-11-01

    A novel permselective, organic-inorganic-hybrid, sol-gel silicate-film was chemically modified on an anodized platinum (Pt) electrode surface to form a selective, sensitive and interference-free amperometric glucose biosensor. This permselective hybrid sol-gel film consists of three organo-silanes [i.e., 3-aminopropyltriethoxysilane (APTES); tetraethoxysilane (TEOS); triethoxy-1H,1H,2H,2H-tridecafluoro-n-octylsilane (FAS)] and two biomacromolecules [i.e., bovine serum albumin (BSA) and a chitosan (CHIT)]. After the addition of the film to the Pt electrode, glucose oxidase (GOx) was covalently immobilized within the film with glutaraldehyde. The incorporation of the BSA and CHIT not only enhanced the permselectivity of H2O2 but also improved the activity of the immobilized GOx. The CHIT effectively suppressed any swelling of the film. Moreover, the conjugation of the FAS was especially effective in reducing the interference currents of AA and UA to levels less than 1/400 and 1/300 of the current of H2O2. The resulting organic-inorganic-hybrid sol-gel-film-based amperometric glucose biosensor exhibited rapid and sensitive responses to glucose (100% response in <3s, sensitivity: 1.84 μA mM(-1), detection limit: 0.032 mM), and the highly selective determination of glucose was possible, even in the presence of 0.1mM AA and UA. PMID:23886787

  8. Desalination by Membrane Distillation using Electrospun Polyamide Fiber Membranes with Surface Fluorination by Chemical Vapor Deposition.

    PubMed

    Guo, Fei; Servi, Amelia; Liu, Andong; Gleason, Karen K; Rutledge, Gregory C

    2015-04-22

    Fibrous membranes of poly(trimethyl hexamethylene terephthalamide) (PA6(3)T) were fabricated by electrospinning and rendered hydrophobic by applying a conformal coating of poly(1H,1H,2H,2H-perfluorodecyl acrylate) (PPFDA) using initiated chemical vapor deposition (iCVD). A set of iCVD-treated electrospun PA6(3)T fiber membranes with fiber diameters ranging from 0.25 to 1.8 μm were tested for desalination using the air gap membrane distillation configuration. Permeate fluxes of 2-11 kg/m2/h were observed for temperature differentials of 20-45 °C between the feed stream and condenser plate, with rejections in excess of 99.98%. The liquid entry pressure was observed to increase dramatically, from 15 to 373 kPa with reduction in fiber diameter. Contrary to expectation, for a given feed temperature the permeate flux was observed to increase for membranes of decreasing fiber diameter. The results for permeate flux and salt rejection show that it is possible to construct membranes for membrane distillation even from intrinsically hydrophilic materials after surface modification by iCVD and that the fiber diameter is shown to play an important role on the membrane distillation performance in terms of permeate flux, salt rejection, and liquid entry pressure. PMID:25835769

  9. Organic-inorganic hybrid fluorous monolithic capillary column for selective solid-phase microextraction of perfluorinated persistent organic pollutants.

    PubMed

    Xiong, Xiyue; Yang, Zihui; Huang, Yongbin; Jiang, Linbo; Chen, Yingzhuang; Shen, Yao; Chen, Bo

    2013-03-01

    A novel construction strategy of monolithic capillary column for selectively enriching perfluorinated persistent organic pollutants was proposed. The organic-inorganic hybrid fluorous monolithic capillary column was synthesized by a "one-pot" approach via the polycondensation of γ-methacryloxypropyltrimethoxy-silane, then in situ copolymerization of 1H,1H,7H-dodecafluoroheptyl methacrylate and vinyl group on the precondensed siloxanes. The obtained monolithic columns were systematically characterized. The results demonstrated that the optimal column possessed good mechanical stability and high permeability. The adsorption capacities of the optimized monolithic column for perfluorooctanoic acid and perfluorooctane sulfonate were 0.257 and 0.513 μg/mg, respectively. Adsorption capacities of the monoliths were proved to increasing with increasing the amounts of fluorinated monomers in the fluorous monoliths. Sodium 1-octanesulfonate, as a comparison compound, was hardly adsorbed on the fluorous monolith. In addition, the trace amounts of perfluorooctanoic acid and perfluorooctane sulfonate in water samples can be successfully concentrated about 160 times to their original concentrations by this monolithic column. These results demonstrated that the capacity and selectivity of the affinity fluorous column is high and can be applied to the selective enrichment for the perfluorinated persistent organic pollutants from environmental samples. PMID:23378177

  10. Characterization of the selenotrisulfide formed by reaction of selenite with end-capped phytochelatin-2.

    PubMed

    Spain, Stephen M; Rabenstein, Dallas L

    2004-03-01

    The phytochelatins are a family of peptides synthesized by plants in response to exposure to heavy metals and metalloids, including selenium in the form of selenite. The amino acid sequence of the phytochelatin (PC) peptides is (gamma-Glu-Cys)n-Gly, where n typically ranges from 2 to 5. In this paper, the products of the reaction of selenite with an end-capped analogue of PC2, Ac-(gamma-Glu-Cys)2-Gly-NH2, are characterized. Selenite reacts with Ac-(gamma-Glu-Cys)2-Gly-NH2 (Ac-PC2-NH2) to form a compound that contains an intramolecular selenotrisulfide (-SSeS-)-linkage (Se[Ac-PC2-NH2]) and oxidized Ac-PC2-NH2. Both Se[Ac-PC2-NH2] and oxidized Ac-PC2-NH2 were isolated by HPLC and were characterized by MALDI-TOF mass spectrometry, by two-dimensional 1H and 13C NMR and, in the case of Se[Ac-PC2-NH2], by 77Se NMR. Using dihedral angles determined from vicinal 1H-1H coupling constants as constraints for the conformations around the Cys(CalphaH)-Cys(CbetaH) bonds, structures were predicted for the most abundant form of both compounds by Monte Carlo molecular mechanics simulations. PMID:15214417

  11. Measurements of gas hydrate formation probability distributions on a quasi-free water droplet

    NASA Astrophysics Data System (ADS)

    Maeda, Nobuo

    2014-06-01

    A High Pressure Automated Lag Time Apparatus (HP-ALTA) can measure gas hydrate formation probability distributions from water in a glass sample cell. In an HP-ALTA gas hydrate formation originates near the edges of the sample cell and gas hydrate films subsequently grow across the water-guest gas interface. It would ideally be desirable to be able to measure gas hydrate formation probability distributions of a single water droplet or mist that is freely levitating in a guest gas, but this is technically challenging. The next best option is to let a water droplet sit on top of a denser, immiscible, inert, and wall-wetting hydrophobic liquid to avoid contact of a water droplet with the solid walls. Here we report the development of a second generation HP-ALTA which can measure gas hydrate formation probability distributions of a water droplet which sits on a perfluorocarbon oil in a container that is coated with 1H,1H,2H,2H-Perfluorodecyltriethoxysilane. It was found that the gas hydrate formation probability distributions of such a quasi-free water droplet were significantly lower than those of water in a glass sample cell.

  12. Structural studies of a polysaccharide from Vibrio parahaemolyticus strain AN-16000.

    PubMed

    Fontana, Carolina; Zaccheus, Mona; Weintraub, Andrej; Ansaruzzaman, Mohammad; Widmalm, Göran

    2016-09-01

    The structure of a polysaccharide from Vibrio parahaemolyticus strain AN-16000 has been investigated. The sugar and absolute configuration analysis revealed d-Glc, d-GalN, d-QuiN and l-FucN as major components. The PS was subjected to dephosphorylation with aqueous 40% HF to obtain an oligosaccharide that was analyzed by (1)H and (13)C NMR spectroscopy. The HR-MS spectrum of the oligosaccharide revealed a pentasaccharide composed of two Glc residues, one QuiNAc and one GalNAc, one FucNAc, as well as a glycerol moiety. The structure of the PS was determined using (1)H, (13)C, (15)N and (31)P NMR spectroscopy; inter-residue correlations were identified by (1)H,(13)C-heteronuclear multiple-bond correlation, (1)H,(1)H-NOESY and (1)H,(31)P-hetero-TOCSY experiments. The PS backbone has the following teichoic acid-like structure: →3)-d-Gro-(1-P-6)-β-d-Glcp-(1→4)-α-l-FucpNAc-(1→3)-β-d-QuipNAc-(1→ with a side-chain consisting of α-d-Glcp-(1→6)-α-d-GalpNAc-(1→ linked to the O3 position of the FucNAc residue. PMID:27392309

  13. Proton-detected solid-state NMR spectroscopy of fully protonated proteins at slow to moderate magic-angle spinning frequencies

    NASA Astrophysics Data System (ADS)

    Mote, Kaustubh R.; Madhu, Perunthiruthy K.

    2015-12-01

    1H -detection offers a substitute to the sensitivity-starved experiments often used to characterize biomolecular samples using magic-angle spinning solid-state NMR spectroscopy (MAS-ssNMR). To mitigate the effects of the strong 1H -1H dipolar coupled network that would otherwise severely broaden resonances, high MAS frequencies (>40 kHz) are often employed. Here, we have explored the alternative of stroboscopic 1H -detection at moderate MAS frequencies of 5-30 kHz using windowed version of supercycled-phase-modulated Lee-Goldburg homonuclear decoupling. We show that improved resolution in the 1H dimension, comparable to that obtainable at high spinning frequencies of 40-60 kHz without homonuclear decoupling, can be obtained in these experiments for fully protonated proteins. Along with detailed analysis of the performance of the method on the standard tri-peptide f-MLF, experiments on micro-crystalline GB1 and amyloid- β aggregates are used to demonstrate the applicability of these pulse-sequences to challenging biomolecular systems. With only two parameters to optimize, broadbanded performance of the homonuclear decoupling sequence, linear dependence of the chemical-shift scaling factor on resonance offset and a straightforward implementation under experimental conditions currently used for many biomolecular studies (viz. spinning frequencies and radio-frequency amplitudes), we expect these experiments to complement the current 13C -detection based methods in assignments and characterization through chemical-shift mapping.

  14. ARTSY-J: Convenient and precise measurement of (3)JHNHα couplings in medium-size proteins from TROSY-HSQC spectra.

    PubMed

    Roche, Julien; Ying, Jinfa; Shen, Yang; Torchia, Dennis A; Bax, Ad

    2016-07-01

    A new and convenient method, named ARTSY-J, is introduced that permits extraction of the (3)JHNHα couplings in proteins from the relative intensities in a pair of (15)N-(1)H TROSY-HSQC spectra. The pulse scheme includes (3)JHNHα dephasing of the narrower TROSY (1)H(N)-{(15)N} doublet component during a delay, integrated into the regular two-dimensional TROSY-HSQC pulse scheme, and compares the obtained intensity with a reference spectrum where (3)JHNHα dephasing is suppressed. The effect of passive (1)H(α) spin flips downscales the apparent (3)JHNHα coupling by a uniform factor that depends approximately linearly on both the duration of the (3)JHNHα dephasing delay and the (1)H-(1)H cross relaxation rate. Using such a correction factor, which accounts for the effects of both inhomogeneity of the radiofrequency field and (1)H(α) spin flips, agreement between prior and newly measured values for the small model protein GB3 is better than 0.3Hz. Measurement for the HIV-1 protease homodimer (22kDa) yields (3)JHNHα values that agree to better than 0.7Hz with predictions made on the basis of a previously parameterized Karplus equation. Although for Gly residues the two individual (3)JHNHα couplings cannot be extracted from a single set of ARTSY-J spectra, the measurement provides valuable ϕ angle information. PMID:27179455

  15. ARTSY-J: Convenient and precise measurement of 3JHNHα couplings in medium-size proteins from TROSY-HSQC spectra

    NASA Astrophysics Data System (ADS)

    Roche, Julien; Ying, Jinfa; Shen, Yang; Torchia, Dennis A.; Bax, Ad

    2016-07-01

    A new and convenient method, named ARTSY-J, is introduced that permits extraction of the 3JHNHα couplings in proteins from the relative intensities in a pair of 15N-1H TROSY-HSQC spectra. The pulse scheme includes 3JHNHα dephasing of the narrower TROSY 1HN-{15N} doublet component during a delay, integrated into the regular two-dimensional TROSY-HSQC pulse scheme, and compares the obtained intensity with a reference spectrum where 3JHNHα dephasing is suppressed. The effect of passive 1Hα spin flips downscales the apparent 3JHNHα coupling by a uniform factor that depends approximately linearly on both the duration of the 3JHNHα dephasing delay and the 1H-1H cross relaxation rate. Using such a correction factor, which accounts for the effects of both inhomogeneity of the radiofrequency field and 1Hα spin flips, agreement between prior and newly measured values for the small model protein GB3 is better than 0.3 Hz. Measurement for the HIV-1 protease homodimer (22 kDa) yields 3JHNHα values that agree to better than 0.7 Hz with predictions made on the basis of a previously parameterized Karplus equation. Although for Gly residues the two individual 3JHNHα couplings cannot be extracted from a single set of ARTSY-J spectra, the measurement provides valuable ϕ angle information.

  16. Synthesis of TiO2 nanoparticles utilizing hydrated reverse micelles in CO2.

    PubMed

    Lim, Kwon Taek; Hwang, Ha Soo; Ryoo, Won; Johnston, Keith P

    2004-03-16

    Titanium dioxide nanoparticles were produced by the controlled hydrolysis of titanium tetraisopropoxide (TTIP) in the presence of reverse micelles formed in CO2 with the surfactants ammonium carboxylate perfluoropolyether (PFPECOO-+NH4) (Mw = 587) and poly(dimethyl amino ethyl methacrylate-block-1H,1H,2H,2H-perfluorooctyl methacrylate) (PDMAEMA-b-PFOMA). Based on dynamic light scattering measurements, the amorphous TiO2 particles formed by injection of TTIP are larger than the reverse micelles, indicating surfactant reorganization. The size of the particles and the stability of dispersions in CO2 were affected by the molar ratio of water to surfactant headgroup (w(o)), precursor concentration, and injection rate. The amorphous particle size did not change upon depressurization and redispersion in CO2. PDMAEMA-b-PFOMA provided greater stability against particle aggregation at higher reactant concentration compared with PFPECOO-+NH4. The crystallite size after calcination, which was examined by X-ray diffraction and transmission electron microscopy, increased with w(o). PMID:15835711

  17. Pure Rotational Spectroscopy of Asymmetric Tops in the Undergraduate Classroom or Laboratory

    NASA Astrophysics Data System (ADS)

    Minei, A. J.; Cooke, S. A.

    2013-06-01

    Due to concerns of complexity, the asymmetric top, for which κ = {(2B - A - C) / (A - C)} ≠ ± 1, is feared, or at least avoided, by many instructors when explaining the rigid rotor. However, the spectral patterns formed by cold} asymmetric rigid rotors in the centimeter-wave} region of the electromagnetic spectrum can be easily identified. We will present some techniques for spectral analyses that we have successfully employed with undergraduate students who are either ``pre-quantum mechanics" or are currently enrolled in a chemical quantum mechanics class. The activities are simple, requiring the students to first locate repeating patterns and then apply simple algebraic expressions in order to determine all three rotational constants. The method will be illustrated using the spectra of 2,2,3,3-tetrafluoropropyl trifluoroacetate (CF_3C(=O)OCH_2CF_2CHF_2), (E)-1,3,3,3-tetrafluoropropene (CF_3CH=CHF), 1H,1H,2H-perfluorocyclobutane (CF_2CF_2CHFCH_2), and 2H-nonafluorobutane (CF_3CHFCF_2CF_3). The first two of these species have predominantly a-type spectra, the third has a predominantly b-type spectrum, the fourth has a predominantly c-type spectrum.

  18. Super-efficient surfactant for stabilizing water-in-carbon dioxide microemulsions.

    PubMed

    Sagisaka, Masanobu; Iwama, Shuho; Hasegawa, Satoshi; Yoshizawa, Atsushi; Mohamed, Azmi; Cummings, Stephen; Rogers, Sarah E; Heenan, Richard K; Eastoe, Julian

    2011-05-17

    The fluorinated double-tailed glutarate anionic surfactant, sodium 1,5-bis[(1H,1H,2H,2H-perfluorodecyl)oxy]-1,5-dioxopentane-2-sulfonate (8FG(EO)(2)), was found to stabilize water-in-supercritical CO(2) microemulsions with high water-to-surfactant molar ratios (W(0)). Studies were carried out here to obtain detailed information on the phase stability and nanostructure of the microemulsions by using a high-pressure UV-vis dye probe and small-angle neutron scattering (SANS) measurements. The UV-vis spectra, with methyl orange as a reporter dye, indicated a maximum attainable W(0) of 60 at 45 and 75 °C, and SANS profiles indicated regular droplet swelling with a linear relationship between the water core nanodroplet radius and W(0). This represents the highest water solubilization reported to date for any water-in-CO(2) microemulsion. Further analysis of the SANS data indicated critical packing parameters for 8FG(EO)(2) at the microemulsion interface >1.34, representing approximately 1.1 times the value for common aerosol-OT in water-in-heptane microemulsions under equivalent conditions. PMID:21486003

  19. Real-time monitoring of the progress of polymerization reactions directly on surfaces at open atmosphere by ambient mass spectrometry.

    PubMed

    Nørgaard, Asger W; Vaz, Boniek G; Lauritsen, Frants R; Eberlin, Marcos N

    2010-12-15

    The progress of an on-surface polymerization process involving alkyl and perfluoroalkyl silanes and siloxanes was monitored in real-time via easy ambient sonic spray ionization mass spectrometry (EASI-MS). When sprayed on surfaces, the organosilicon compounds present in commercially available nanofilm products (NFPs) react by condensation to form a polymeric coating. A NFP for coating of floor materials (NFP-1) and a second NFP for coating tiles and ceramics (NFP-2) were applied to glass, filter paper or cotton surfaces and the progress of the polymerization was monitored by slowly scanning the surface. Via EASI(+)-MS monitoring, significant changes in the composition of hydrolysates and condensates of 1H,1H,2H,2H-perfluorooctyl triisopropoxysilane (NFP-1) and hexadecyl triethoxysilane (NFP-2) were observed over time. The abundances of the hydrolyzed species decreased compared with those of the non-hydrolysed species for both NFP-1 and NFP-2 and the heavier oligomers became relatively more abundant over a period of 15-20 min. A similar tendency favouring the heavier oligomers was observed via EASI(-)-MS. This work illustrates the potential of ambient mass spectrometry for the direct monitoring of polymerization reactions on surfaces. PMID:21072800

  20. Structure of fully protonated proteins by proton-detected magic-angle spinning NMR.

    PubMed

    Andreas, Loren B; Jaudzems, Kristaps; Stanek, Jan; Lalli, Daniela; Bertarello, Andrea; Le Marchand, Tanguy; Cala-De Paepe, Diane; Kotelovica, Svetlana; Akopjana, Inara; Knott, Benno; Wegner, Sebastian; Engelke, Frank; Lesage, Anne; Emsley, Lyndon; Tars, Kaspars; Herrmann, Torsten; Pintacuda, Guido

    2016-08-16

    Protein structure determination by proton-detected magic-angle spinning (MAS) NMR has focused on highly deuterated samples, in which only a small number of protons are introduced and observation of signals from side chains is extremely limited. Here, we show in two fully protonated proteins that, at 100-kHz MAS and above, spectral resolution is high enough to detect resolved correlations from amide and side-chain protons of all residue types, and to reliably measure a dense network of (1)H-(1)H proximities that define a protein structure. The high data quality allowed the correct identification of internuclear distance restraints encoded in 3D spectra with automated data analysis, resulting in accurate, unbiased, and fast structure determination. Additionally, we find that narrower proton resonance lines, longer coherence lifetimes, and improved magnetization transfer offset the reduced sample size at 100-kHz spinning and above. Less than 2 weeks of experiment time and a single 0.5-mg sample was sufficient for the acquisition of all data necessary for backbone and side-chain resonance assignment and unsupervised structure determination. We expect the technique to pave the way for atomic-resolution structure analysis applicable to a wide range of proteins. PMID:27489348