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Sample records for 1h-1h cosy hmqc

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

    NASA Astrophysics Data System (ADS)

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

    2012-01-01

    Three 1H- 1H homonuclear dipolar decoupling schemes for 1H indirect detection measurements at very fast MAS are compared. The sequences require the following conditions: (i) being operable at very fast MAS, (ii) a long T2' value, (iii) a large scaling factor, (iv) a small number of adjustable parameters, (v) an acquisition window, (vi) a low rf-power requirement, and (vii) a z-rotation feature. To satisfy these conditions a modified sequence named TIlted Magic-Echo Sandwich with zero degree sandwich pulse (TIMES 0) is introduced. The basic elements of TIMES 0 consist of one sampling window and two phase-ramped irradiations, which realize alternating positive and negative 360° rotations of 1H magnetization around an effective field tilted with an angle θ from the B0 axis. The TIMES 0 sequence benefits from very large chemical shift scaling factors at ultra-fast MAS that reach κcs = 0.90 for θ = 25° at νr = 80 kHz MAS and only four adjustable parameters, resulting in easy setup. Long κT2' values, where T2' is a irreversible proton transverse relaxation time, greatly enhance the sensitivity in 1H-{ 13C} through-bond J-HMQC (Heteronuclear Multiple-Quantum Coherence) measurements with 1H- 1H decoupling during magnetization transfer periods. Although similar sensitivity can be obtained with through-space D-HMQC sequences, in which 13C- 1H dipolar interactions are recoupled, J-HMQC experiments incorporating 1H- 1H decoupling benefit from lower t1-noise, more uniform excitation of both CH, CH 2 and CH 3 moieties, and easier identification of through-bond connectivities.

  2. Identification, synthesis and characterization of an unknown process related impurity in eslicarbazepine acetate active pharmaceutical ingredient by LC/ESI-IT/MS, 1H, 13C and 1H-1H COSY NMR.

    PubMed

    Thomas, Saji; Paul, Saroj Kumar; Joshi, Subhash Chandra; Kumar, Vineet; Agarwal, Ashutosh; Vir, Dharam

    2014-10-01

    A new impurity was detected during high performance liquid chromatographic (HPLC) analysis of eslicarbazepine acetate active pharmaceutical ingredient. The structure of unknown impurity was postulated based on liquid chromatography mass spectrometry using electrospray ionization and ion trap analyzer (LC/ESI-IT/MS) analysis. Proposed structure of impurity was unambiguously confirmed by synthesis followed by characterization using 1 H, 13 C nuclear magnetic resonance spectrometry (NMR), 1 H- 1 H correlation spectroscopy (COSY) and infrared spectroscopy (IR). Based on the spectroscopic and spectrometric data, unknown impurity was characterized as 5-carbamoyl-10,11-dihydro-5 H -dibenzo[ b , f ]azepin-10-yl propionate.

  3. Multiplicity-edited1H-1H TOCSY experiment.

    PubMed

    Nolis, Pau; Parella, Teodor

    2017-12-08

    A 1 H- 1 H total correlation spectroscopy (TOCSY) experiment incorporating 13 C multiplicity information is proposed. In addition, broadband 1 H homodecoupling in the indirect dimension can be implemented using a perfect BIRD module that affords exclusive 1 H chemical shift evolution with full decoupling of all heteronuclear and homonuclear (including 2 J HH ) coupling constants. As a complement to the normal TOCSY and the recent PSYCHE-TOCSY experiments, this novel multiplicity-edited TOCSY experiment distinguishes between CH/CH 3 (phased up) and CH 2 (phased down) cross-peaks, which facilitates resonance analysis and assignment. Copyright © 2017 John Wiley & Sons, Ltd.

  4. Systematic Evaluation of Non-Uniform Sampling Parameters in the Targeted Analysis of Urine Metabolites by1H,1H 2D NMR Spectroscopy.

    PubMed

    Schlippenbach, Trixi von; Oefner, Peter J; Gronwald, Wolfram

    2018-03-09

    Non-uniform sampling (NUS) allows the accelerated acquisition of multidimensional NMR spectra. The aim of this contribution was the systematic evaluation of the impact of various quantitative NUS parameters on the accuracy and precision of 2D NMR measurements of urinary metabolites. Urine aliquots spiked with varying concentrations (15.6-500.0 µM) of tryptophan, tyrosine, glutamine, glutamic acid, lactic acid, and threonine, which can only be resolved fully by 2D NMR, were used to assess the influence of the sampling scheme, reconstruction algorithm, amount of omitted data points, and seed value on the quantitative performance of NUS in 1 H, 1 H-TOCSY and 1 H, 1 H-COSY45 NMR spectroscopy. Sinusoidal Poisson-gap sampling and a compressed sensing approach employing the iterative re-weighted least squares method for spectral reconstruction allowed a 50% reduction in measurement time while maintaining sufficient quantitative accuracy and precision for both types of homonuclear 2D NMR spectroscopy. Together with other advances in instrument design, such as state-of-the-art cryogenic probes, use of 2D NMR spectroscopy in large biomedical cohort studies seems feasible.

  5. 1H- 1H double-quantum CRAMPS NMR at very-fast MAS ( νR = 35 kHz): A resolution enhancement method to probe 1H- 1H proximities in solids

    NASA Astrophysics Data System (ADS)

    Mafra, Luís; Gomes, José R. B.; Trébosc, Julien; Rocha, João; Amoureux, Jean-Paul

    2009-01-01

    A High-resolution two-dimensional (2D) 1H double-quantum (DQ) homonuclear recoupling experiments, combined with smooth amplitude-modulation (SAM) homonuclear decoupling is presented. The experiment affords highly resolved and clean 1H DQ-SQ 2D spectra at very-fast MAS rates ( νR = 35 kHz). The method is well suited to probe 1H- 1H distances in powdered solids and demonstrations are applied on a NaH 2PO 4 powdered sample, an inorganic compound having hydrogen bonding networks.

  6. 1H-detected 1H- 1H correlation spectroscopy of a stereo-array isotope labeled amino acid under fast magic-angle spinning

    NASA Astrophysics Data System (ADS)

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

    2010-04-01

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

  7. 1H,13C-1H,1H dipolar cross-correlated spin relaxation in methyl groups.

    PubMed

    Tugarinov, Vitali; Kay, Lewis E

    2004-07-01

    Relaxation in methyl groups is strongly influenced by cross-correlated interactions involving the methyl dipoles. One of the major interference effects results from intra-methyl (1)H-(13)C, (1)H-(1)H dipolar interactions, leading to significant differences in the relaxation of certain multiplet components that contribute to double- and zero-quantum (1)H-(13)C spectra. NMR experiments are presented for the measurement of this differential relaxation effect. It is shown that this difference in relaxation between double- and zero-quantum multiplet components can be used as a sensitive reporter of side chain dynamics and that accurate methyl axis order parameters can be measured in proteins that tumble with correlation times greater than approximately 5 ns.

  8. 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.

  9. 1H- 13C INEPT MAS NMR correlation experiments with 1H- 1H mediated magnetization exchange to probe organization in lipid biomembranes

    NASA Astrophysics Data System (ADS)

    Alam, T. M.; Holland, G. P.

    2006-06-01

    Two-dimensional 1H- 13C INEPT MAS NMR experiments utilizing a 1H- 1H magnetization exchange mixing period are presented for characterization of lipid systems. The introduction of the exchange period allows for structural information to be obtained via 1H- 1H dipolar couplings but with 13C chemical shift resolution. It is shown that utilizing a RFDR recoupling sequence with short mixing times in place of the more standard NOE cross-relaxation for magnetization exchange during the mixing period allowed for the identification and separation of close 1H- 1H dipolar contacts versus longer-range inter-molecular 1H- 1H dipolar cross-relaxation. These 2D INEPT experiments were used to address both intra- and inter-molecular contacts in lipid and lipid/cholesterol mixtures.

  10. 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.

  11. 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. Copyright © 2014 Elsevier Inc. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

    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 1H and 13C signals in isotopically unmodified paramagnetic compounds with moderate hyperfine interactions can be facilitated by the use of two two-dimensional (2D) experiments: (i) 1H-13C correlations with 1H detection and (ii) 1H-1H 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 13C detection, we show that 1H detection leads to a 3-fold enhancement in sensitivity for 1H-13C 2D correlation experiments. By combining 1H-13C and 1H-1H 2D correlation experiments with the analysis of 13C longitudinal relaxation times, we have been able to assign the 1H and 13C signals of each L-alanine ligand.

  13. 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

  14. Measuring 1H-1H and 1H-13C RDCs in methyl groups: example of pulse sequences with numerically optimized coherence transfer schemes

    NASA Astrophysics Data System (ADS)

    Pervushin, Konstantin; Vögeli, Beat; Heinz, Tim N.; Hünenberger, Philippe H.

    2005-01-01

    The optimization of coherence-transfer pulse-sequence elements (CTEs) is the most challenging step in the construction of heteronuclear correlation NMR experiments achieving sensitivity close to its theoretical maximum (in the absence of relaxation) in the shortest possible experimental time and featuring active suppression of undesired signals. As reported in the present article, this complex optimization problem in a space of high dimensionality turns out to be numerically tractable. Based on the application of molecular dynamics in the space of pulse-sequence variables, a general method is proposed for constructing optimized CTEs capable of transferring an arbitrary (generally non-Hermitian) spin operator encoding the chemical shift of heteronuclear spins to an arbitrary spin operator suitable for signal detection. The CTEs constructed in this way are evaluated against benchmarks provided by the theoretical unitary bound for coherence transfer and the minimal required transfer time (when available). This approach is used to design a set of NMR experiments enabling direct and selective observation of individual 1H-transitions in 13C-labeled methyl spin systems close to optimal sensitivity and using a minimal number of spectra. As an illustrative application of the method, optimized CTEs are used to quantitatively measure 1H-1H and 1H-13C residual dipolar couplings (RDCs) in a 17 kDa protein weakly aligned by means of Pf1 phages.

  15. 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.

  16. Photochemical decomposition of 1H,1H,2H,2H-perfluorooctane sulfonate (6:2FTS) induced by ferric ions.

    PubMed

    Jin, Ling; Jiang, Chuanjia; Zhang, Pengyi

    2017-01-01

    Perfluorooctane sulfonate (PFOS) had wide applications, such as in the electroplating industry, but its use was restricted in 2009 by the Stockholm Convention, due to its environmental persistence and potential hazards. As the most common PFOS alternative, 1H,1H,2H,2H-perfluorooctane sulfonic acid (6:2FTS) and its salts have been increasingly used. However, little is known about its photochemical decomposition. This paper reports the ferric ion-induced efficient decomposition and defluorination of 6:2FTS under 254nm ultraviolet (UV) irradiation; the underlying mechanisms were also investigated. In the presence of 100μmol/L ferric ion and at pH3.0, the first-order decomposition rate constant of 6:2FTS (10mg/L) was 1.59/hr, which was 6 times higher than for direct UV photolysis. The effects of the ferric ion concentration and the solution pH on the 6:2FTS photodecomposition were investigated and the optimal reaction conditions were determined. In addition to fluoride and sulfate ions, shorter-chain PFCAs (C2-C7) were detected as major intermediates. The addition of hydrogen peroxide or oxalic acid accelerated the decomposition of 6:2FTS under UV irradiation, but not its defluorination, indicating that hydroxyl radicals can directly react with 6:2FTS but not with the shorter-chain PFCAs. Accordingly, a mechanism for 6:2FTS photochemical decomposition in the presence of ferric ion was proposed, which comprises two reaction pathways. First, hydroxyl radicals can directly attack 6:2FTS, leading to CC bond cleavage. Alternatively, 6:2FTS coordinates with ferric ion to form Fe(III)-6:2FTS complexes, which can undergo ligand-to-metal charge transfer under UV irradiation, causing CS bond cleavage. Copyright © 2016. Published by Elsevier B.V.

  17. 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.

  18. Physics at CELSIUS and COSY

    SciTech Connect

    Machner, H.

    2006-02-11

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

  19. (E)-2,6-Di-bromo-4-{2-[1-(1H,1H,2H,2H-perfluoro-oct-yl)pyridinium-4-yl]ethen-yl}phenolate methanol disolvate, a fluoro-ponytailed solvatochromic dye.

    PubMed

    Fliri, Lukas; Partl, Gabriel; Gelbrich, Thomas; Kahlenberg, Volker; Laus, Gerhard; Schottenberger, Herwig

    2017-10-01

    The title compound, C 21 H 12 Br 2 F 13 NO·2CH 3 OH, was obtained by condensation of 4-methyl-1-(1 H ,1 H ,2 H ,2 H -perfluoro-oct-yl)pyridinium iodide and 3,5-di-bromo-4-hy-droxy-benzaldehyde, followed by deprotonation. It crystallizes as a methanol disolvate and exhibits short O-H⋯O hydrogen bonds and a disordered perfluoro-alkyl chain [occupancy ratio 0.538 (7):0.462 (7)]. Significant π-π stacking inter-actions are observed between the benzene and pyridine rings of neighbouring mol-ecules along the b- axis direction.

  20. 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

    2015-03-07

    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., (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.

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

    NASA Astrophysics Data System (ADS)

    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 13C/13C chemical shift correlation experiments utilizing dipolar recoupling techniques are fully utilized under MAS, correlation of the chemical shifts of 15N nuclei in proteins has been a challenge. Previous studies have shown that the negligible 15N-15N 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 15N/15N correlation experiment. In this study, we show that the use of mixing proton magnetization, instead of 15N, via the recoupled 1H-1H dipolar couplings enable faster 15N/15N correlation. In addition, the use of proton-detection under ultrafast MAS overcomes the sensitivity loss due to multiple magnetization transfer (between 1H and 15N 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 15N/15N/1H experiment can render higher resolution spectra that will be useful in the structural studies of proteins at ultrafast MAS frequencies. 3D 15N/15N/1H and 2D radio frequency-driven dipolar recoupling (RFDR)-based 1H/1H experimental results obtained from a powder sample of N-acetyla-L-15N-valyl-L-15N-leucine at 70 and 100 kHz MAS frequencies are presented.

  2. High efficiency ZnO-based dye-sensitized solar cells with a 1H,1H,2H,2H-perfluorodecyltriethoxysilane chain barrier for cutting on interfacial recombination

    NASA Astrophysics Data System (ADS)

    Xie, Yahong; Zhou, Xiaofeng; Mi, Hongyu; Ma, Junhong; Yang, Jianya; Cheng, Jian

    2018-03-01

    Charge recombination at the ZnO photoanode/electrolyte interface is one of the major limitations for high performance dye-sensitized solar cells (DSSCs) toward their theoretical power conversion efficiency (PCE). Here, we proposed an efficient approach for reducing this interfacial losses and consequently facilitating charge transfer by decorating a hydrophobic thin-film on the surface of the dye-coated zinc oxide photoanode via 1H,1H,2H,2H-perfluorodecyltriethoxysilane (PFDTES) hexane solution immersing. As a result, a high PCE of 8.22% was obtained, which far exceeded the efficiency of 5.40% in a conventional DSSC without PFDTES treatment. Furthermore, PFDTES treatment also largely elongated the lifetime of photogenerated electrons, and maintained a good photo-response at the photoelectrode. This work provides a comprehensive explanation of electron injection, transfer and recombination at the ZnO photoanode/electrolyte interface, and a promising strategy to explore high efficiency ZnO-based DSSCs.

  3. Oligosaccharides display both rigidity and high flexibility in water as determined by 13C NMR relaxation and 1H,1H NOE spectroscopy: evidence of anti-phi and anti-psi torsions in the same glycosidic linkage.

    PubMed

    Höög, C; Landersjö, C; Widmalm, G

    2001-07-16

    The trisaccharide beta-D-Glcp-(1-->2)-beta-D-Glcp-(1-->3)-alpha-D-Glcp-OMe has been investigated by molecular dynamics (MD) simulations and NMR experiments in water. 13C spin-lattice (T1) and spin-spin (T2) relaxation times, together with 1H,13C NOE data were measured at two magnetic field strengths (9.4 and 14.1 T) in a 277 K D2O solution. Relaxation data interpreted by means of the model-free formalism revealed a rigid (S2 approximately 0.9) oligosaccharide tumbling in solution. 1H,1H Cross-relaxation rates were determined at 600 MHz by 1D DPFGSE NOESY and T-ROESY experiments, which provided high quality data and subsequently proton-proton distances within the trisaccharide. The presence of anti conformers at both torsions of a glycosidic linkage is demonstrated for the first time. MD simulations were carried out to facilitate analysis of the NOE data. In total, 15 simulations-starting from five different conformational states--were performed, with production runs of up to 10 ns, resulting in 83 ns of oligosaccharide dynamics in water. anti Conformers were populated to different degrees in the simulations, especially at the phi2 torsion angle. By combining the results from the NOE experiments and the MD simulations, the anti conformers at the (1-->2)-linkage were quantified as 7% anti-phi2 and 2% anti-psi2, revealing a highly flexible trisaccharide in which large conformational changes occur. From the MD simulations, interresidue hydrogen bonding, from HO2" to O2 or O3, was significantly populated (approximately 40%) in both of the anti conformational states. The contentious issue over rigidity versus flexibility in oligosaccharides has thus been thoroughly examined, showing that the dynamics should be taken into account for a relevant description of the molecular system.

  4. 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.

  5. Recording 13C-15N HMQC 2D sparse spectra in solids in 30 s

    NASA Astrophysics Data System (ADS)

    Kupče, Ēriks; Trébosc, Julien; Perrone, Barbara; Lafon, Olivier; Amoureux, Jean-Paul

    2018-03-01

    We propose a dipolar HMQC Hadamard-encoded (D-HMQC-Hn) experiment for fast 2D correlations of abundant nuclei in solids. The main limitation of the Hadamard methods resides in the length of the encoding pulses, which results from a compromise between the selectivity and the sensitivity due to losses. For this reason, these methods should mainly be used with sparse spectra, and they profit from the increased separation of the resonances at high magnetic fields. In the case of the D-HMQC-Hn experiments, we give a simple rule that allows directly setting the optimum length of the selective pulses, versus the minimum separation of the resonances in the indirect dimension. The demonstration has been performed on a fully 13C,15N labelled f-MLF sample, and it allowed recording the build-up curves of the 13C-15N cross-peaks within 10 min. However, the method could also be used in the case of less sensitive samples, but with more accumulations.

  6. (E)-2,6-Di­bromo-4-{2-[1-(1H,1H,2H,2H-perfluoro­oct­yl)pyridinium-4-yl]ethen­yl}phenolate methanol disolvate, a fluoro­ponytailed solvatochromic dye

    PubMed Central

    Fliri, Lukas; Gelbrich, Thomas; Kahlenberg, Volker; Laus, Gerhard; Schottenberger, Herwig

    2017-01-01

    The title compound, C21H12Br2F13NO·2CH3OH, was obtained by condensation of 4-methyl-1-(1H,1H,2H,2H-perfluoro­oct­yl)pyridinium iodide and 3,5-di­bromo-4-hy­droxy­benzaldehyde, followed by deprotonation. It crystallizes as a methanol disolvate and exhibits short O—H⋯O hydrogen bonds and a disordered perfluoro­alkyl chain [occupancy ratio 0.538 (7):0.462 (7)]. Significant π–π stacking inter­actions are observed between the benzene and pyridine rings of neighbouring mol­ecules along the b-axis direction. PMID:29250373

  7. Heteronuclear relayed E.COSY revisited: determination of 3J(H(alpha),C(gamma)) couplings in Asx and aromatic residues in proteins.

    PubMed

    Löhr, F; Pérez, C; Köhler, R; Rüterjans, H; Schmidt, J M

    2000-09-01

    Constant-time 3D heteronuclear relayed E.COSY [Schmidt et al. (1996) J. Biomol. NMR, 7, 142-152], as based on generic 2D small-flip-angle HMQC-COSY [Schmidt et al. (1995) J. Biomol. NMR, 6, 95-105], has been modified to allow for quantitative determination of heteronuclear three-bond 3J(H(alpha),C(gamma)) couplings. The method is applicable to amino acid spin topologies with carbons in the gamma position which lack attached protons, i.e. to asparagine, aspartate, and aromatic residues in uniformly 13C-enriched proteins. The pulse sequence critically exploits heteronuclear triple-quantum coherence (HTQC) of CH2 moieties involving geminal H(beta) proton pairs, taking advantage of improved multiple-quantum relaxation properties, at the same time avoiding scalar couplings between those spins involved in multiple-quantum coherence, thus yielding E.COSY-type multiplets with a splitting structure that is simpler than with the original scheme. Numerical least-squares 2D line-shape simulation is used to extract 3J(H(alpha),C(gamma)) coupling constants which are of relevance to side-chain chi1 dihedral-angle conformations in polypeptides. Methods are demonstrated with recombinant 15N,13C-enriched ribonuclease T1 and Desulfovibrio vulgaris flavodoxin with bound oxidized FMN.

  8. The COSY-TOF barrel detector

    NASA Astrophysics Data System (ADS)

    Böhm, A.; Brinkmann, K.-Th.; Dshemuchadse, S.; Freiesleben, H.; Herrmann, P.; Jakob, B.; Koch, H.; Krug, J.; Kuhlmann, E.; Lange, J. S.; Michel, P.; Möller, K.; Schamlott, A.; Schönmeier, P.; Schülke, A.; Steinke, M.; Sun, G. Y.; Würschig-Pörsel, M.; Zielinski, U.; COSY-TOF-Collaboration

    2000-04-01

    A barrel-shaped scintillator hodoscope was developed as part of the time-of-flight spectrometer TOF operated at an external beam line of the cooler synchrotron COSY. The COSY-TOF spectrometer is used mainly to perform kinematically complete experiments on light meson production and proton-proton bremsstrahlung in proton-proton collisions for laboratory energies up to 2.5 GeV. The newly developed scintillator hodoscope (BARREL1), one of several detector segments of the COSY-TOF spectrometer, consists of one layer of 96 scintillator bars of 15 mm thickness arranged to form a barrel with 3 m in diameter and 2.85 m in length. For any given interaction process the TOF spectrometer allows to determine the velocity vectors of all charged ejectiles emerging from the target by measuring the time of flight between the start and the stop detector as well as the point of impact on the stop detector. For the BARREL1 detector the position information is obtained by two-sided light read-out of the scintillator bars. For minimum ionizing particles the spatial resolution was measured to be Δz( FWHM)=8 cm, corresponding to a polar angle resolution in the range 0.57°≤Δ Θ≤2.86°, depending on the hit position. The binning in azimuthal angular direction amounts to Δ Φ=360°/96=3.75°. For the time-of-flight resolution of minimum ionizing particles a value of Δt( FWHM)=0.61 ns was obtained.

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

    PubMed

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

    2013-03-04

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

  10. COSI: The Compton Spectrometer and Imager Science Program

    NASA Astrophysics Data System (ADS)

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

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

  11. Labdane diterpenes from Marrubium velutinum and Marrubium cylleneum.

    PubMed

    Karioti, Anastasia; Heilmann, Jörg; Skaltsa, Helen

    2005-05-01

    From the aerial parts of Marrubium velutinum and Marrubium cylleneum, seven labdane diterpenes, velutine A, 15-epi-velutine A, velutine B, 15-epi-velutine B, velutine C, cyllenine A and 15-epi-cyllenine A, have been isolated together with five known diterpenes and four known flavones. The structures of the isolated compounds were established by means of NMR [(1)H-(1)H-COSY, (1)H-(13)C-HMQC, HMBC, HMQC-TOCSY, NOESY] and MS spectral analyses. Complete NMR assignments are reported for known compounds.

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

    NASA Astrophysics Data System (ADS)

    Boggs, Steven E.

    2014-08-01

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

  13. N and13C- SOFAST-HMQC editing enhances 3D-NOESY sensitivity in highly deuterated, selectively [1H,13C]-labeled proteins.

    PubMed

    Rossi, Paolo; Xia, Youlin; Khanra, Nandish; Veglia, Gianluigi; Kalodimos, Charalampos G

    2016-12-01

    The ongoing NMR method development effort strives for high quality multidimensional data with reduced collection time. Here, we apply 'SOFAST-HMQC' to frequency editing in 3D NOESY experiments and demonstrate the sensitivity benefits using highly deuterated and 15 N, methyl labeled samples in H 2 O. The experiments benefit from a combination of selective T 1 relaxation (or L-optimized effect), from Ernst angle optimization and, in certain types of experiments, from using the mixing time for both NOE buildup and magnetization recovery. This effect enhances sensitivity by up to 2.4× at fast pulsing versus reference HMQC sequences of same overall length and water suppression characteristics. Representative experiments designed to address interesting protein NMR challenges are detailed. Editing capabilities are exploited with heteronuclear 15 N, 13 C-edited, or with diagonal-free 13 C aromatic/methyl-resolved 3D-SOFAST-HMQC-NOESY-HMQC. The latter experiment is used here to elucidate the methyl-aromatic NOE network in the hydrophobic core of the 19 kDa FliT-FliJ flagellar protein complex. Incorporation of fast pulsing to reference experiments such as 3D-NOESY-HMQC boosts digital resolution, simplifies the process of NOE assignment and helps to automate protein structure determination.

  14. Band structure and unconventional electronic topology of CoSi

    NASA Astrophysics Data System (ADS)

    Pshenay-Severin, D. A.; Ivanov, Y. V.; Burkov, A. A.; Burkov, A. T.

    2018-04-01

    Semimetals with certain crystal symmetries may possess unusual electronic structure topology, distinct from that of the conventional Weyl and Dirac semimetals. Characteristic property of these materials is the existence of band-touching points with multiple (higher than two-fold) degeneracy and nonzero Chern number. CoSi is a representative of this group of materials exhibiting the so-called ‘new fermions’. We report on an ab initio calculation of the electronic structure of CoSi using density functional methods, taking into account the spin-orbit interactions. The linearized \

  15. COSIE: The Coronal Spectrographic Imager in the EUV

    NASA Technical Reports Server (NTRS)

    Savage, Sabrina; Golub, Leon; Deluca, Ed

    2017-01-01

    COSIE is a solar-observing instrument (currently proposed for mounting onto the ISS) which obtains wide field images of the corona and full Sun spectral images with high sensitivity and rapid cadence. The primary purpose of the instrument is to constrain the global field topology and to track coronal mass ejections from the disk through the inner heliosphere.

  16. Symmetries and Hadron Spectroscopy with WASA-at-COSY

    NASA Astrophysics Data System (ADS)

    Wolke, Magnus

    2009-05-01

    Experiments with the WASA detector at COSY Juelich focus both on studies of symmetries and symmetry breaking mechanisms in hadronic systems as well as hadron spectroscopy, to investigate the properties of QCD in the non-perturbative regime, where confinement and chiral symmetry breaking are the characteristic phenomena. Isospin violation and tests of conservation of the fundamental C, P, and T invariances and combinations thereof are the key physics issues in studies of η decays. From the very first production run, results on the Dalitz plot slope parameter in the isospin violating η->3, decay have been obtained. End of 2008, a high statistics data sample of more than 10^7 neutral and charged η decays has been recorded in the reaction pd ->^3He,, in which η tagging can be solely based on ^3He detection and is thus unbiased with respect to the η decay system. Low--mass enhancements in isoscalar ππ invariant mass distributions in nuclear fusion reactions to few--body systems d, ^3He, and ^4He, known as the ABC effect, have been reproduced in exclusive data taken with the WASA detector at CELSIUS. The data indicate the formation of an isoscalar pn resonance coupling to a δδ intermediate state. Follow--up high--statistics experiments have recently been performed on the reactions pn ->dππ and dd ->^4Heππ covering the complete energy range relevant for the ABC effect with WASA-at-COSY. Physics results obtained so far and the physics program with WASA-at-COSY will be presented. The scientific potential for hadron spectroscopy at COSY will be related to activities at Jefferson Lab, and will be discussed in view of future opportunities, e.g. at the FAIR facility at Darmstadt (Germany).

  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. Test of Time-Reversal Invariance at COSY (TRIC)

    NASA Astrophysics Data System (ADS)

    Eversheim, D.; Valdau, Yu.; Lorentz, B.

    2016-02-01

    At the Cooler Synchrotron COSY a novel (P-even, T-odd) null test of time-reversal invariance to an accuracy of 10-6 is planned as an internal target transmission experiment. The parity conserving time-reversal violating observable is the total cross-section asymmetry Ay,xz. This quantity is measured using a polarized proton beam with an energy of 135 MeV and an internal tensor polarized deuteron target from the PAX atomic beam source. The reaction rate will be determined by the lifetime of the beam. Consequently, the accuracy of the current measurement of the circulating proton beam is crucial for this experiment. Thus, the cooler synchroton ring serves as an ideal forward spectrometer, as a detector, and an accelerator.

  19. Flavonol glycosides, nigelflavonosides A-F from the whole plant of Nigella glandulifera (Ranunculaceae).

    PubMed

    Zhang, Yi; Ge, Dandan; Chen, Qiu; He, Wei; Han, Lifeng; Wei, Hongyan; Jia, Xiaoguang; Wang, Tao

    2012-10-01

    Six new flavonol glycosides, nigelflavonosides A-F (1-6), together with a known compound (7) were isolated from the whole plant of Nigella glandulifera Freyn et Sint (Ranunculaceae). Structure elucidation, especially the localization of the glycosyl or acetyl groups, and complete (1)H- and (13)C-NMR assignments of these compounds were carried out using one- and two-dimensional NMR measurements, including (1)H- and (13)C-NMR, (1)H-(1)H COSY, TOCSY, HMQC, HMBC and NOESY, in addition to HRESI-TOF-MS experiments.

  20. Cytotoxicity and immunomodulating characteristics of labdane diterpenes from Marrubium cylleneum and Marrubium velutinum.

    PubMed

    Karioti, Anastasia; Skopeliti, Margarita; Tsitsilonis, Ourania; Heilmann, Jörg; Skaltsa, Helen

    2007-06-01

    From the aerial parts of Marrubium cylleneum, one labdane nor-diterpene has been isolated together with two labdane diterpenes, hitherto not known as natural products. The structures of the isolated compounds were established by means of NMR [(1)H-(1)H-COSY, (1)H-(13)C-HSQC, HMQC-TOCSY, HMBC, NOESY] and MS spectral analyses. Several diterpenoids from M. cylleneum and M. velutinum were tested for their cytotoxic effect against various cancer cell lines and their immunomodulating potential in human peripheral blood mononuclear cells in standard in vitro assays. Our results show a differential cytotoxicity of some compounds as well as their ability to improve selected lymphocyte functions.

  1. Microbial transformation of Isopimpinellin by Glomerella cingulata.

    PubMed

    Marumoto, Shinsuke; Miyazawa, Mitsuo

    2011-01-01

    Microbial transformation studies conducted on isopimpinellin (1) by the fungus Glomerella cingulata have revealed that 1 was metabolized to give the corresponding reduced acid, 5,8-dimethoxy-6,7-furano-hydrocoumaric acid (2). The structure of metabolite 2 was elucidated by high-resolution mass spectrometry (HR-MS), extensive NMR techniques, including (1)H NMR, (13)C NMR, (1)H-(1)H correlation spectroscopy (COSY), heteronuclear multiple quantum coherence (HMQC) and heteonuclear multiple bond coherence (HMBC). The biotransformed product 2 showed weak a in vitro β-secretase (BACE1) inhibitory effect.

  2. 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.

  3. Cosi2: an efficient simulator of exact and approximate coalescent with selection.

    PubMed

    Shlyakhter, Ilya; Sabeti, Pardis C; Schaffner, Stephen F

    2014-12-01

    Efficient simulation of population genetic samples under a given demographic model is a prerequisite for many analyses. Coalescent theory provides an efficient framework for such simulations, but simulating longer regions and higher recombination rates remains challenging. Simulators based on a Markovian approximation to the coalescent scale well, but do not support simulation of selection. Gene conversion is not supported by any published coalescent simulators that support selection. We describe cosi2, an efficient simulator that supports both exact and approximate coalescent simulation with positive selection. cosi2 improves on the speed of existing exact simulators, and permits further speedup in approximate mode while retaining support for selection. cosi2 supports a wide range of demographic scenarios, including recombination hot spots, gene conversion, population size changes, population structure and migration. cosi2 implements coalescent machinery efficiently by tracking only a small subset of the Ancestral Recombination Graph, sampling only relevant recombination events, and using augmented skip lists to represent tracked genetic segments. To preserve support for selection in approximate mode, the Markov approximation is implemented not by moving along the chromosome but by performing a standard backwards-in-time coalescent simulation while restricting coalescence to node pairs with overlapping or near-overlapping genetic material. We describe the algorithms used by cosi2 and present comparisons with existing selection simulators. A free C++ implementation of cosi2 is available at http://broadinstitute.org/mpg/cosi2. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

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

    SciTech Connect

    Singh, Mukhtiyar; Saini, Hardev S.; Thakur, Jyoti

    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 disordersmore » 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.« less

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

    SciTech Connect

    Eschbach, R.; Meyer, M.; Coquelet-Pascal, 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 aimmore » 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.« less

  6. Comparison of Schottky barrier heights of CoSi2 formed from evaporated or crystalline Si

    NASA Astrophysics Data System (ADS)

    Lien, C.-D.; Finetti, M.; Nicolet, M.-A.

    1984-09-01

    Three kinds of samples were used to form Co suicides by thermal annealing: firstly, a Co film of about 370 Å thick, evaporated on a (100) single crystal Si (Si c /Co); secondly, an evaporated boron-containing Si (Si e (B)) layer on the top of the first sample (Si c /Co/Si e (B)). The last sample is in the Co film of the first sample we deposited a Sie(B) layer (Si c /Co/Si e (B)/Co). A laterally uniform CoSi2 layer can be formed from the second and the third samples by annealing at 450 °C. In the first sample, the CoSi2 can be formed only at temperatures above 500 °C and the disilicide is laterally less uniform than in the second and third samples. The Schottky barrier heights of the three samples derived from the forward and reverse I V characteristics show that the barrier height is 0.01 0.02eV higher in the uniform case than in the nonuniform case.

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

    SciTech Connect

    Bavink, S.; Bellemann, F.; Berg, A.

    1997-05-20

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  9. Axiotaxy of CoSi2 thin films on Si(100) substrates and the effects of Ti alloying

    NASA Astrophysics Data System (ADS)

    Özcan, Ahmet S.; Ludwig, Karl F.; Detavernier, Christophe; Lavoie, Christian; Jordan-Sweet, Jean L.

    2004-06-01

    The texture of CoSi2 films on Si(001) substrates has been examined using synchrotron based high-resolution pole figure analysis. We find that axiotaxy, a recently recognized type of texture which was observed in NiSi thin films on Si(001), is also occurring in CoSi2 layers. Typical of axiotaxy texturing, the CoSi2 pole figures show symmetrical patterns of lines. Calculations show that these features on the pole figures are created by three off-normal fiberlike texture components. These off-normal fiber orientations are a consequence of the alignment of CoSi2<110> planes with Si<110> planes because of very similar d spacings, which causes a periodic arrangement along Si<100> directions in the plane of the interface. This one-dimensional periodicity may provide a lower interfacial energy; however, the periodic arrangement along the Si<100> directions may also be indicative of growth anisotropy. The influence of Ti alloying has been investigated by using in situ x-ray diffraction measurements, as well as pole figure analysis. These results show that the nucleation of both the CoSi and CoSi2 phases is delayed to higher temperatures for the 5 at. % Ti alloyed films. The texture of the CoSi2 phase is also influenced by the addition of Ti.

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

    PubMed

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

    2016-04-01

    SABRE (Signal Amplification By Reversible Exchange) nuclear spin hyperpolarization method can provide strongly enhanced NMR signals as a result of the reversible association of small molecules with para-hydrogen (p-H2) at an iridium metal complex. The conversion of p-H2 singlet order to enhanced substrate proton magnetization within such complex is driven by the scalar coupling interactions between the p-H2 derived hydrides and substrate nuclear spins. In the present study these long-range homonuclear couplings are experimentally determined for several SABRE substrates using an NMR pulse sequence for coherent hyperpolarization transfer at high magnetic field. Pyridine and pyrazine derivatives appear to have a similar ∼1.2 Hz (4)J coupling to p-H2 derived hydrides for their ortho protons, and a much lower (5)J coupling for their meta protons. Interestingly, the (4)J hydride-substrate coupling for five-membered N-heterocyclic substrates is well below 1 Hz. Copyright © 2016 Elsevier Inc. All rights reserved.

  12. Co diffusion and growth of buried single-crystal CoSi2 in Si(111) by endotaxy

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

    At a growth temperature of 800 C, Co deposited on a Si capping layer exhibits oriented growth on buried CoSi2 grains on Si(111), 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 of about 100 nm for deposition rates of 0.003-0.01 nm/s. The steady-state process is modeled using known values of the Co diffusion coefficient and solid solubility in Si, allowing some conclusions to be drawn regarding parameters relevant to CoSi2 epitaxy. Using this technique, single-crystal continuous layers of CoSi2 can be formed under a high-quality Si capping layer.

  13. Anomalies in the electronic structure of a Pauli paramagnet, La2CoSi3 and a Kondo lattice, Ce2CoSi3

    NASA Astrophysics Data System (ADS)

    Patil, Swapnil; Saraswat, Garima; Adhikary, Ganesh; Bindu, R.; Sampathkumaran, E. V.; Maiti, Kalobaran

    2014-11-01

    We study the electronic structure of a Pauli paramagnetic compound, La2CoSi3 using photoemission spectroscopy and ab initio band structure calculations. Experimental valence band spectra exhibit signature of electron correlation-induced feature around 2.5 eV —the correlation strength among Co 3d electrons is estimated to be close to 3 eV. The Co 2p core level spectra also exhibit correlation-induced satellite features consistent with the scenario in the valence band spectra suggesting importance of conduction electron correlation in addition to the local moment in Kondo lattice systems. The La2CoSi3 valence band spectra could be utilized to extract Ce 4f related spectral features and thus provide a good reference to study Kondo lattice systems in this class of materials. Temperature evolution of various core level spectra is found to be complex, revealing deviations from a typical Fermi-liquid behavior and emergence of a distinct surface-bulk difference in the electronic structure at finite temperature.

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

    PubMed

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

    2012-04-04

    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). © 2012 IOP Publishing Ltd

  15. High Thermoelectric Power Factor in CoSi1-x B x Alloys

    NASA Astrophysics Data System (ADS)

    Sun, Hui; Morelli, Donald

    2011-03-01

    CoSi 1-x Bx alloys with x ranging from 0 to 0.1 have been prepared by an arc melting and annealing procedure. X-ray diffraction studies suggest the occurrence of minor CoB phase when x >= 0.05 . The thermoelectric (TE) properties were measured from 80 to 300K. The samples with x <= 0.02 showed much lower electrical resistivity than CoSi. The Seebeck coefficient was negative for all samples over the investigated temperature range, indicating dominant transport by electrons in this temperature range. A high TE power factor (70 μ W/K2 cm at room temperature) was obtained in CoSi 0.98 B0.02 , which we ascribe to the appropriate tuning of the Fermi level near the pseudogap in the density of states. In optimized samples the dimensionless figure of merit is in excess of 0.13 due to this enhanced power factor. We will also report on our efforts to further increase the figure of merit by thermal conductivity reduction methods. This work was supported as part of the Center for Revolutionary Materials for Solid State Energy Conversion, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Basic Energy Sciences under Award Number DE-SC0001054.

  16. 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

  17. Magnetic Structure and Dielectric State in the Multiferroic Ca2CoSi2O7

    NASA Astrophysics Data System (ADS)

    Soda, Minoru; Hayashida, Shohei; Yoshida, Toshiya; Akaki, Mitsuru; Hagiwara, Masayuki; Avdeev, Maxim; Zaharko, Oksana; Masuda, Takatsugu

    2017-06-01

    The magnetic structure of the multiferroic Ca2CoSi2O7 was determined by neutron diffraction techniques. A combination of experiments on polycrystalline and single-crystal samples revealed a collinear antiferromagnetic structure with the easy axis along the <100> directions. The dielectric state is discussed in the framework of the spin-dependent d-p hybridization mechanism, leading to the realization of the antiferroelectric structure. The origin of the magnetic anisotropy is discussed in comparison with that of the isostructural Ba2CoGe2O7.

  18. Cryogenic Topics Associated with the Superconducting Linac Proposed for the Cosy-Facility

    NASA Astrophysics Data System (ADS)

    Eichhorn, R.; Esser, F.; Laatsch, B.; Lennartz, M.; Schug, G.; Stassen, R.

    2004-06-01

    An upgrade of the existing proton and deuteron accelerator facility COSY at the Forschungszentrum Jülich, based on a superconducting linac is under investigation. This paper will report on the cryogenic aspects of the project: The cryomodule layout will be shown and special emphasis will put on the short cold-warm transition, the heat transfer of which was calculated using finite element simulation techniques. The cavity tuner, based on fast piezo-electric actuators to adjust the resonators' frequency, will be shown as well as the adjustable power coupler that uses a cold siphon-shaped window to prevent surface contamination of the cavity during assembly and operation.

  19. Cognitive styles in an international perspective: cross-validation of the Cognitive Style Indicator (CoSI).

    PubMed

    Cools, Eva; de Pauw, Ann-Sophie; Vanderheyden, Karlien

    2011-08-01

    This study examines the cross-cultural validity of the Cognitive Style Indicator (CoSI). Measurement equivalence tests were performed on data collected from a Belgian (n = 300) and a South African (n = 246) sample of students and employees. Confirmatory factor analyses within each sample showed the best fit to the data for a three-factor model underlying the CoSI. Measurement invariance tests, using multigroup confirmatory factor analysis, indicated that the relationships among the scales showed equivalence across cultures. Although the study is an important first step toward the cross-validation of the CoSI, further research in other international samples is particularly needed to strengthen these results.

  20. Determination of the Lifetime of Heavy {Lambda}-Hypernuclei at COSY Juelich

    SciTech Connect

    Ohm, H.; Borgs, W.; Cassing, W.

    2000-12-31

    The lifetime of heavy hypernuclei has been determined at COSY Juelich, making use of the (p,K) reaction and the recoil-shadow technique based on the detection of fragments from the {Lambda}-decay induced fission. Hypernuclei were produced by bombarding extremely thin U and Bi targets with protons of 1.5 GeV and 1.9 GeV kinetic energy. High luminosity was achieved due to the multipass technique with the target being exposed to the internal beam of COSY. Position-sensitive low-pressure MWPCs permitted clear identification of fission fragments based on energy loss and TOF information. The lifetime of hypernuclei was deduced from the position distributions ofmore » fission events in the shadow region and from the recoil momentum calculated within the BUU model. Values of 240{+-}60 ps and 161{+-}14(syst.) ps were found with U and Bi targets, respectively. The deduced production cross sections for hot hypernuclei prior to the evaporation process of {sigma}=150{sub {minus}80}{sup +150} {mu}b for U and 350{+-}140 {mu}b for Bi are in agreement with the theoretical predictions.« less

  1. Improving the double quantum filtered COSY experiment by "Moving Tube" NMR.

    PubMed

    Donovan, Kevin J; Allen, Mary; Martin, Rachel W; Shaka, A J

    2012-06-01

    Most 2D NMR spectra show artifacts that become increasingly more prominent as the relaxation delay between transients is decreased. Additionally, "rushing" a 2D experiment may lead to reduced sensitivity. It is shown here how to collect a DQF-COSY spectrum in less time, without artifacts, and with improved sensitivity, by a hardware solution we call Moving Tube NMR (MT NMR): the sample volume is physically moved out of the receiver coil after each transient and replaced by a fresh aliquot that is nearer to the equilibrium magnetization M(0). MT NMR was implemented with an automated mechanism that gave accurate and reproducible vertical tube movement, and a very long 5mm outer diameter (OD) NMR tube to hold a larger sample volume. Comparison of conventional and MT NMR DQF-COSY showed increased sensitivity and far reduced artifacts in the latter. The so-called t(1)-noise in the MT spectrum was no worse than in the conventional spectrum, pointing to the excellent specifications of the long 5mm OD tube, and the good mechanical handling of the automated drive. Thus, MT NMR could improve throughput for routine 2D NMR experiments without reducing sensitivity or adding artifacts, if sufficient sample is available. MT NMR could also be useful in cases of limited solubility, or for nuclei with long T(1) relaxation times. Copyright © 2012 Elsevier Inc. All rights reserved.

  2. CoSi particles on silica support as a highly active and selective catalyst for naphthalene hydrogenation.

    PubMed

    Liang, Changhai; Zhao, Anqi; Zhang, Xiaofei; Ma, Zhiqiang; Prins, Roel

    2009-04-21

    CoSi particles on a silica support, synthesized by metal organic chemical vapor deposition (MOCVD) of Co(SiCl(3))(CO)(4) as a precursor at atmospheric pressure and moderate temperature in a fluidized bed reactor, show high catalytic activity and selectivity in naphthalene hydrogenation.

  3. 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.

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

    NASA Astrophysics Data System (ADS)

    Wrońska, Aleksandra

    2011-10-01

    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→απ0 and np→dπ0 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→απ0 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.

  5. A new ribonucleotide from Cordyceps militaris.

    PubMed

    Sun, Jinfeng; Jin, Mei; Zhou, Wei; Diao, Shengbao; Zhou, Yi; Li, Shuaishuai; Wang, Xin; Pan, Shuai; Jin, Xuejun; Li, Gao

    2017-11-01

    One new ribonucleotide, 5'-(3''-deoxy-β-D-ribofuranosyl)-3'-deoxyadenosine (1), and 14 known compounds (2-15) were isolated from an ethanol extract of Cordyceps militaris. The chemical structures of these compounds were determined from 1D and 2D NMR ( 1 H- 1 H COSY, HMBC, HMQC and NOESY) and HR-ESI-MS spectra, and results were compared with data from the literature. The effects of all isolated compounds were measured on NF-κB activation, with compound 2 exhibiting significant inhibitory activity against TNF-α-induced NF-κB reporter gene expression in HeLa cells from 3 to 100 μM.

  6. 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 [Structure: see text]. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. 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.

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

    PubMed

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

    2017-08-01

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

  9. 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

  10. Study on Dendrobium officinale O-acetyl-glucomannan (Dendronan®): part II. Fine structures of O-acetylated residues.

    PubMed

    Xing, Xiaohui; Cui, Steve W; Nie, Shaoping; Phillips, Glyn O; Goff, H Douglas; Wang, Qi

    2015-03-06

    Main objective of this study was to investigate the detailed structural information about O-acetylated sugar residues in Dendronan(®). A water solution (2%, w/w) of Dendronan(®) was treated with endo-β-mannanase to produce oligosaccharides rich in O-acetylated sugar residues. The oligosaccharides were partly recovered by ethanol precipitation (70%, w/w). The recovered sample (designated Hydrolyzed Dendrobium officinale Polysaccharide, HDOP) had a yield of 24.7% based on the dry weight of Dendronan(®) and was highly O-acetylated. A D2O solution of HDOP (6%, w/w) generated strong signals in (1)H, (13)C, 2D (1)H-(1)H COSY, 2D (1)H-(1)H TOCSY, 2D (1)H-(1)H NOESY, 2D (1)H-(13)C HMQC, and 2D (1)H-(13)C HMBC NMR spectra. Results of NMR analyses showed that the majority of O-acetylated mannoses were mono-substituted with acetyl groups at O-2 or O-3 position. There were small amounts of mannose residues with di-O-acetyl substitution at both O-2 and O-3 positions. Minor levels of mannoses with 6-O-acetyl, 2,6-di-O-acetyl, and 3,6-di-O-acetyl substitutions were also identified. Much information about sugar residue sequence was extracted from 2D (1)H-(13)C HMBC and 2D (1)H-(1)H NOESY spectra. (1)J(C-H) coupling constants of major sugar residues were obtained. Evidences for the existence of branches or O-acetylated glucoses in HDOP were not found. The major structure of Dendronan(®) is shown as follows: [Formula: see text] M: β-D-mannopyranose; G: β-D-glucopyranose; a: O-acetyl group. Crown Copyright © 2014. Published by Elsevier Ltd. All rights reserved.

  11. 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.

  12. Sputtering of NbSi 2 and CoSi 2

    NASA Astrophysics Data System (ADS)

    Hamdi, A. M.; Affolter, K.; Nicolet, M.-A.

    1985-03-01

    Sputtering of niobium and cobalt disilicide films on oxidized Si substrates interposed with an amorphous Si layer has been studied by backscattering spectrometry (BS). Thin NbSi 2 (600 Å) and CoSi 2 (370 Å) films were sputtered by Xe ions at energies of 200 and 260 keV, respectively. The sputtering process was carried out either at room temperature (RT), or at elevated temperatures, placing the samples in the radiation enhanced diffusion regime. The sputtering yields of Si, Ssi, and that of the metals, SNb or SCo, have been calculated from BS spectra. The measured ratios of the sputtering yields for both suicides, {S si}/{S Nb} and {S si}/{S Co}, imply that preferential sputtering of Si with respect to the stoichiometrical composition of these suicides had occurred. {S si}/{S Nb} is found to be about 13 and showed little change with dose and temperature. {S si}/{S Co} increased with both temperature or dose from about 4.3 for a dose of {5 × 10 16}/{cm 2} at RT to about 7.2 for {1 × 10 17}/{cm 2} at elevated temperature. These ratios are in contrast to that reported for CrSi 2 at high temperatures (i.e. {S si}/{S Cr} = 65 ). Possible reasons are thought to be related to the high affinity of Si to oxygen contamination.

  13. 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 necessarymore » 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.« less

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

    NASA Astrophysics Data System (ADS)

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

    2006-05-01

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

  15. 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.

  16. Application with COSI code of gen IV fast reactors introduction in the French park

    SciTech Connect

    Grouiller, Jean-Paul; Boucher, Lionel; Meyer, Maryan

    2007-07-01

    The insertion of a new concept (fuel, reactor, process) must be evaluated in the global electronuclear system with an analysis of the impact on the fuel cycle (Enrichment, Fuel Fabrication, Reactor, Processing, Interim Storage, Waste storage). An approach of scenario studies is used to evaluate different solutions to manage nuclear materials (uranium, plutonium) and wastes (minor actinides and fission products), from the present situation (partially closed cycle) until the total closed cycle with GEN IV systems, in calculating the fluxes and the inventories of these elements in each step of the fuel cycle and to treat the transient period tomore » pass from one situation to the others. For some interesting scenarios, the approach consists on a simulation of transient scenarios from the present situation to the equilibrium situation with a COSI code. The results given at each point of the fuel cycle and for each year permit to demonstrate the technological feasibility and to evaluate the impacts on environmental, economical, proliferation and waste storage aspects. After a presentation of the operational approach, this paper gives an example for a French transient scenario between the present situation and the end of the 21. century with the introduction of GEN IV fast reactors. The results presented in this paper give the impacts on: - The natural uranium resources, - The capacity of different plants (enrichment, fabrication, reprocessing) and interim storages for spent fuels, - The inventory, function of time, of different elements (Pu, Np, Am, Cm) at each stage of the fuel cycle and in the wastes, - The thermal power the high level wastes. (authors)« less

  17. Electronic and magnetic properties of magnetoelectric compound Ca2CoSi2O7: An ab initio study

    NASA Astrophysics Data System (ADS)

    Chakraborty, Jayita

    2018-05-01

    The detailed first principle density functional theory calculations are carried out to investigate the electronic and magnetic properties of magnetoelectric compound Ca2CoSi2O7. The magnetic properties of this system are analyzed by calculating various hopping integrals as well as exchange interactions and deriving the relevant spin Hamiltonian. The dominant exchange path is visualized with Wannier functions plotting. Only intra planer nearest neighbor exchange interaction is strong in this system. The magnetocrystalline anisotropy is calculated for this system, and the results of the calculation reveal that the spin quantization axis lies in the ab plane.

  18. 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. Copyright 2007 John Wiley & Sons, Ltd.

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

    NASA Technical Reports Server (NTRS)

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

    1989-01-01

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

  20. 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.

  1. Recrystallization in Si upon ion irradiation at room temperature in Co/Si(111) thin film systems

    NASA Astrophysics Data System (ADS)

    Banu, Nasrin; Satpati, B.; Dev, B. N.

    2018-04-01

    After several decades of research it was concluded that for a constant flux recrystallization in Si upon ion irradiation is possible only at high temperature. At low temperature or at room temperature only amorphization can take place. However we have observed recrystallization in Si upon ion irradiation at room temperature in a Co/Si thin film system. The Co/Si sample was prepared by deposition of 25 nm Co on clean Si(111) substrate. An oxide layer (˜ 2nm) of cobalt at the top of the film due to air exposure. The ion irradiation was done at room temperature under high vacuum with 1MeV Si+ ion with low beam current < 400 nA. Earlier we have shown similar ion induced recrystallization in Si(100) substrate which had a sandwich Si/Ni/Si structure. This system had an epitaxial buffer Si layer on Si substrate. This study also shows that the phenomenon is independent of substrate orientation and buffer layer. We have used transmission electron microscopy (TEM) to study the recrystallization behavior.

  2. Analysis of closed orbit deviations for a first direct deuteron electric dipole moment measurement at the cooler synchrotron COSY

    NASA Astrophysics Data System (ADS)

    Schmidt, V.; Lehrach, A.

    2017-07-01

    The Jülich Electric Dipole moment Investigations (JEDI) collaboration in Julich is preparing a direct EDM measurement of protons and deuterons first at the storage ring COSY (COoler SYnchrotron) and later at a dedicated storage ring. Ensuring a precise measurement, various beam and spin manipulating effects have to be considered and investigated. A distortion of the closed orbit is one of the major sources for systematic uncertainties. Therefore misalignments of magnets and residual power supply oscillations are simulated using the MAD-X code in order to analyse their effect on the orbit. The underlying model for all simulations includes the dipoles, quadrupoles and sextupoles at COSY as well as the corrector magnets and BPMs (Beam Position Monitors). Since most sextupoles are only used during beam extraction, the sextupole strengths are set to zero resulting in a linear machine. The optics is adjusted in a way that the dispersion is zero in the straight sections. The closed orbit studies are performed for deuterons with a momentum of 970 MeV/c.

  3. Development of a core set of quality indicators for paediatric primary care practices in Europe, COSI-PPC-EU.

    PubMed

    Ewald, Dominik A; Huss, Gottfried; Auras, Silke; Caceres, Juan Ruiz-Canela; Hadjipanayis, Adamos; Geraedts, Max

    2018-04-14

    Paediatric ambulatory healthcare systems in Europe are, because of historical reasons, diverse and show strikingly different outcomes. All across Europe, the benchmarking of structures, processes and outcomes could reveal opportunities for improving Paediatric Primary Care (PPC). The aim of this study was to develop a set of Quality Indicators (QIs) to assess and monitor PPC in Europe. In a three-step process, we used the available external evidence and European expert consensus in a modified RAND/UCLA Appropriateness Method (RAM) to develop an indicator set. (1) A broad literature and online research of published QI and guidelines yielded an inventory of 1516 QI. (2) A collaborative panel of paediatric senior experts from the European Academy of Paediatrics (EAP) and the European Confederation of Primary Care Paediatricians (ECPCP) from 15 European countries participated in a first consensus process to reduce the initial indicator inventory by eliminating not PPC-focused indicators and duplicates. (3) In a second consensus process, the panel rated the QI regarding validity and feasibility. The final QI set "COSI-PPC-EU" consists of 42 indicators in five categories of PPC: (A) health promotion/prevention/screening (13 QI), (B) acute care (9 QI), (C) chronic care (8 QI), (D) practice management (3 QI) and (E) patient safety (9 QI). COSI-PPC-EU represents a consented set of a limited number of valid quality indicators for the application in paediatric primary care in different healthcare systems throughout Europe. What is Known: • Paediatric ambulatory healthcare systems in Europe are diverse and show strikingly different outcomes. • There are known gaps in quality performance measures of paediatric primary care in Europe. Pre-existing sets of quality indicators are predominantly limited to national populations, specific diseases and hospital care. What is New: • A set of 42 quality indicators for primary paediatric care in Europe was developed in a multi

  4. The (2×2) reconstructions on the surface of cobalt silicides: Atomic configuration at the annealed Co/Si(111) interface

    NASA Astrophysics Data System (ADS)

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

    2017-08-01

    We have used scanning tunneling microscopy (STM) and ab initio total-energy calculations to characterize surface and interfacial structure of Co-Si(111) system. It has been found experimentally that two different types of the (2×2) surface structures occur. The coexistence of two phases is demonstrated by the example of STM image of the surface formed at the early stages of cobalt silicide formation under moderate annealing temperatures (500 °C). The measured height difference between the adjacent (2×2) reconstructed patches equal to about 1.0 Å (as determined from the filled-state STM images). In addition, the shift of the atomic rows by half of the row spacing is observed. Two adatom models of the (2×2) surface structures are developed. According to our data, these structures are assigned to CaF2-type CoSi2 and CsCl-type CoSi with a (2×2) array of Si adatoms on their surfaces. If the latter is the case, it has а coherent double interface CoSi/CoSi2/Si(111) with a two-layer CoSi2. Both of these interfaces are characterized by the eightfold cobalt coordination and incorporate a grown-in stacking fault.

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

    PubMed

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

    2014-08-01

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

  6. Charge symmetry breaking in d d →4Heπ0 with WASA-at-COSY

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    Charge symmetry breaking (CSB) observables are a suitable experimental tool to examine effects induced by quark masses on the nuclear level. Previous high precision data from TRIUMF and IUCF are currently used to develop a consistent description of CSB within the framework of chiral perturbation theory. In this work the experimental studies on the reaction dd →4Heπ0 have been extended towards higher excess energies in order to provide information on the contribution of p-waves in the final state. For this, an exclusive measurement has been carried out at a beam momentum of pd = 1.2 GeV / c using the WASA-at-COSY facility. The total cross section amounts to σtot = (118 ±18stat ±13sys ±8ext) pb and first data on the differential cross section are consistent with s-wave pion production.

  7. Shallow junctions formed by BF2(+) implantation into thin CoSi films and rapid thermal annealing

    NASA Astrophysics Data System (ADS)

    Juang, M. H.; Lin, C. T.; Cheng, H. C.

    1994-07-01

    Effects of rapid thermal annealing (RTA) on the shallow p(+) n junctions formed by BF2(+) implantation into thin CoSi films on Si substrates are discussed, with comparison to the implantation into thin Co films. Excellent junctions can be achieved via conventional furnace annealing (CFA) for both the samples prepared by implanting dopant through metal (ITM) and metal silicides (ITS) films. For the RTA process, however, the junction formation for ITS was hindered, with the diodes made by ITM being much better than those by ITS due to a deeper as-implanted profile. Although the problem of knock-on Co induced by heavy dopant impant present in maing n(+) p junctions by ITM can be largely reduced by using ITS, ITS is inferior for forming p(+) n junctions by RTA.

  8. The 2D {31P} Spin-Echo-Difference Constant-Time [13C, 1H]-HMQC Experiment for Simultaneous Determination of 3JH3‧P and 3JC4‧P in 13C-Labeled Nucleic Acids and Their Protein Complexes

    NASA Astrophysics Data System (ADS)

    Szyperski, Thomas; Fernández, César; Ono, Akira; Wüthrich, Kurt; Kainosho, Masatsune

    1999-10-01

    A two-dimensional {31P} spin-echo-difference constant-time [13C, 1H]-HMQC experiment (2D {31P}-sedct-[13C, 1H]-HMQC) is introduced for measurements of 3JC4‧P and 3JH3‧P scalar couplings in large 13C-labeled nucleic acids and in DNA-protein complexes. This experiment makes use of the fact that 1H-13C multiple-quantum coherences in macromolecules relax more slowly than the corresponding 13C single-quantum coherences. 3JC4‧P and 3JH3‧P are related via Karplus-type functions with the phosphodiester torsion angles β and ɛ, respectively, and their experimental assessment therefore contributes to further improved quality of NMR solution structures. Data are presented for a uniformly 13C, 15N-labeled 14-base-pair DNA duplex, both free in solution and in a 17-kDa protein-DNA complex.

  9. Sensitivity-Enhanced MQ-HCN-CCH-TOCSY and MQ-HCN-CCH-COSY Pulse Schemes for 13C/ 15N Labeled RNA Oligonucleotides

    NASA Astrophysics Data System (ADS)

    Hu, Weidong; Jiang, Licong; Gosser, Yuying Q.

    2000-07-01

    Sensitivity enhanced multiple-quantum 3D HCN-CCH-TOCSY and HCN-CCH-COSY experiments are presented for the ribose resonance assignment of 13C/15N-labeled RNA sample. The experiments make use of the chemical shift dispersion of N1/N9 of pyrimidine/purine to distinguish the ribose spin systems. They provide a complementary approach for the assignment of ribose resonance to the currently used HCCH-COSY and HCCH-TOCSY type experiments in which either 13C or 1H is utilized to separate the different ribose spin systems. The pulse schemes have been demonstrated on a 23-mer 13C/15N-labeled RNA aptamer complexed with neomycin and tested on a 32-mer RNA complexed with a 23-residue peptide.

  10. GIAO C-H COSY Simulations Merged with Artificial Neural Networks Pattern Recognition Analysis. Pushing the Structural Validation a Step Forward.

    PubMed

    Zanardi, María M; Sarotti, Ariel M

    2015-10-02

    The structural validation problem using quantum chemistry approaches (confirm or reject a candidate structure) has been tackled with artificial neural network (ANN) mediated multidimensional pattern recognition from experimental and calculated 2D C-H COSY. In order to identify subtle errors (such as regio- or stereochemical), more than 400 ANNs have been built and trained, and the most efficient in terms of classification ability were successfully validated in challenging real examples of natural product misassignments.

  11. 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.

  12. A BEEM study of Schottky barrier height distributions of ultrathin CoSi2/n-Si(100) formed by solid phase epitaxy

    NASA Astrophysics Data System (ADS)

    Zhu, Shiyang; Detavernier, C.; Van Meirhaeghe, R. L.; Qu, Xin-Ping; Ru, Guo-Ping; Cardon, F.; Li, Bing-Zong

    2000-04-01

    The spatial distributions of the Schottky barrier heights of ultrathin CoSi2 films (~10 nm) on n-Si(100), obtained by multilayer solid state reaction of Co/Ti/n-Si, Co/a-Si/Ti/n-Si, Ti/Co/a-Si/Ti/n-Si and Co/n-Si systems, are studied by ballistic electron emission microscopy (BEEM) and spectroscopy (BEES) at low temperature (~-80 °C). The barrier heights determined from BEEM spectra range between 520 meV and 700 meV, with an approximate Gaussian distribution. The mean barrier heights of the epitaxial CoSi2 /Si contacts are 0.60-0.61 eV, lower than the 0.64 eV for polycrystalline CoSi2 /Si contacts. Adding a thin amorphous Si interlayer (1 nm) slightly increases the probability of higher barrier heights, while a thin Ti capping layer (1 nm) has no significant influence on the mean barrier height. The BEEM results are compared to those from I -V /C -V measurements.

  13. Effect of CoSi2 buffer layer on structure and magnetic properties of Co films grown on Si (001) substrate

    NASA Astrophysics Data System (ADS)

    Hu, Bo; He, Wei; Ye, Jun; Tang, Jin; Syed Sheraz, Ahmad; Zhang, Xiang-Qun; Cheng, Zhao-Hua

    2015-01-01

    Buffer layer provides an opportunity to enhance the quality of ultrathin magnetic films. In this paper, Co films with different thickness of CoSi2 buffer layers were grown on Si (001) substrates. In order to investigate morphology, structure, and magnetic properties of films, scanning tunneling microscope (STM), low energy electron diffraction (LEED), high resolution transmission electron microscopy (HRTEM), and surface magneto-optical Kerr effect (SMOKE) were used. The results show that the crystal quality and magnetic anisotropies of the Co films are strongly affected by the thickness of CoSi2 buffer layers. Few CoSi2 monolayers can prevent the interdiffusion of Si substrate and Co film and enhance the Co film quality. Furthermore, the in-plane magnetic anisotropy of Co film with optimal buffer layer shows four-fold symmetry and exhibits the two-jumps of magnetization reversal process, which is the typical phenomenon in cubic (001) films. Project supported by the National Basic Research Program of China (Grant Nos. 2011CB921801 and 2012CB933102), the National Natural Science Foundation of China (Grant Nos. 11374350, 11034004, 11274361, and 11274033), and the Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20131102130005).

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

    SciTech Connect

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

    2016-07-21

    Boron-added CoSi, CoSi 0.98B 0.02, 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 CoSi 0.98B 0.02 has been studied. Here we present a study of themore » substitution of Ge for Si atoms in this compound. Even though Ge and Rh are isovalent with their corresponding host atoms, they play different roles in determining the electrical and thermal transport properties. Through the evaluation of the lattice thermal conductivity by the Debye approximation and the comparison between the high-temperature Seebeck coefficients, we propose that Rh substitution leads to a further overlapping of the conduction and the valence bands while Ge substitution only shifts the Fermi level upward into the conduction band. Lastly, our results show that the influence of isovalent substitution on the electronic structure cannot be ignored when the alloying method is used to improve thermoelectric properties.« less

  15. 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.

    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 inmore » 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.« less

  16. Family socioeconomic status and nutrition habits of 7-8 year old children: cross-sectional Lithuanian COSI study.

    PubMed

    Petrauskienė, Aušra; Žaltauskė, Vilma; Albavičiūtė, Edita

    2015-04-23

    Nutritional habits are a useful way to characterize whole diets and they are also known to be influenced by a wide range of social and economic factors. The above factors in each country may have different effect on children's eating habits. In Lithuania the data of children nutrition in association with socio-economic status of family is poor. There are few studies done, where links between nutrition habits of children and socio-economic status of family was evaluated. The aim of this paper is to evaluate association among nutrition habits of first-formers and family socio-economic status in Lithuania. Data were obtained participating in the international study, which was performed in all ten districts of Lithuania. A cross-sectional study was carried out in 2010, using the protocol and methodology prepared by the experts from the WHO and countries participating in the Initiative. The data were collected by means of COSI standardized questionnaire, which was filled out by parents of selected first-formers'. In this paper a part of questions regarding children nutrition habits and parents' socio-economic status is presented. Statistical analysis was performed by using SPSS 20.0 software for Windows. Correlation among variables was evaluated by χ (2). Links among nutrition habits of first-formers and family socioeconomic status were determined using binary logistic regression to calculate odds ratios (OR) and 95% confidence intervals (CI). For all tests p < 0.05 was considered significant. It was established that the majority (76%) of Lithuanian first-formers eat breakfast every day or 4-6 times a week. Significant differences were found between breakfast consumption and gender - girls eat breakfast less frequently than boys. Odds ratio of children daily breakfast consumption were 1.3 times higher in families where fathers' were older than 30 years comparing with younger fathers. Meanwhile mothers' age had significant influence just on children daily soft drinks

  17. A new rearranged eudesmane sesquiterpene and bioactive sesquiterpenes from the twigs of Lindera glauca (Sieb. et Zucc.) Blume.

    PubMed

    Yu, Jae Sik; Baek, Jiwon; Park, Hyun Bong; Moon, Eunjung; Kim, Sun Yeou; Choi, Sang Un; Kim, Ki Hyun

    2016-12-01

    A new rearranged eudesmane sesquiterpene, named eudeglaucone (1), and five known sesquiterpenes including (+)-faurinone (2) and four eudesmane-type sesquiterpenes (3-6), were isolated from the twigs of Lindera glauca (Sieb. et Zucc.) Blume. The structure of 1 was elucidated by a combination of extensive spectroscopic analyses, including extensive 2D NMR ( 1 H- 1 H COSY, HMQC, HMBC, and NOESY) and HR-MS. Compound 1 was a relatively rare rearranged eudesmane sesquiterpene in terpenoids. All isolates were evaluated for their antiproliferative activities against four human tumor cell lines (A549, SK-OV-3, SK-MEL-2, and HCT-15). Compounds 3 and 6 showed significant cytotoxicity against SK-MEL-2 and HCT-15 cell lines with IC 50 values ranging from 9.98 to 12.20 μM. We also investigated the anti-neuroinflammatory activities of the isolates (1-6) in the lipopolysaccharide (LPS)-stimulated murine microglia BV-2 cell line by measuring nitric oxide (NO) levels. All isolates significantly inhibited NO production with IC 50 values of 3.67-26.48 μM without inducing cell toxicity.

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

    PubMed

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

    2003-10-24

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

  19. 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.

  20. Thermodynamic properties of Ba2CoSi2O6Cl2 in a strong magnetic field: Realization of flat-band physics in a highly frustrated quantum magnet

    NASA Astrophysics Data System (ADS)

    Richter, Johannes; Krupnitska, Olesia; Baliha, Vasyl; Krokhmalskii, Taras; Derzhko, Oleg

    2018-01-01

    The search for flat-band solid-state realizations is a crucial issue to verify or to challenge theoretical predictions for quantum many-body flat-band systems. For frustrated quantum magnets flat bands lead to various unconventional properties related to the existence of localized many-magnon states. The recently synthesized magnetic compound Ba2CoSi2O6Cl2 seems to be an almost perfect candidate to observe these features in experiments. We develop a theory for Ba2CoSi2O6Cl2 by adapting the localized-magnon concept to this compound. We first show that our theory describes the known experimental facts and then we propose new experimental studies to detect a field-driven phase transition related to a Wigner-crystal-like ordering of localized magnons at low temperatures.

  1. Structural stability and electronic behaviors of Co1-xOsxSi and macroscopic magnetic susceptibilities of CoSi and OsSi: GGA-PBEsol, GW-approximation and QTAIM investigations

    NASA Astrophysics Data System (ADS)

    Bouafia, H.; Sahli, B.; Timaoui, M. A.; Djebour, B.; Hiadsi, S.; Abidri, B.

    2018-02-01

    The present work represents a theoretical investigation based on FP-(L)APW + lo method of structural properties, mechanical stability and electronic properties of Co1-xOsxSi as well as the macroscopic magnetic susceptibilities of CoSi and OsSi. The structural properties such as cell parameter, bulk modulus, internal parameters and total energy of non-magnetic NM, ferromagnetic FM and antiferromagnetic AFM phases were predicted by GGA-PBEsol semilocal functional. The obtained results for CoSi and OsSi are in good agreement with those found previously. The spin, orbital and total macroscopic magnetic susceptibilities of CoSi and OsSi have been estimated and confirmed that these compounds are diamagnetic. The total energy of the ferromagnetic phase of Co1-xOsxSi (with x = 0.25, 0.5 and 0.75) is the lowest indicating that they are ferromagnetic materials. The generalized stability criteria indicate that Co1-xOsxSi maintain their mechanical stabilities under a hydrostatic pressure less than 10 GPa. The electronic properties calculated by GW-approximation indicate that CoSi and Co1-xOsxSi (with x = 0.25, 0.50 and 0.75) are semimetals whereas OsSi is a semiconductor with a pseudo-direct band-gap. The topological analysis by QTAIM and the charge density plots indicate that the strong covalent character is predominant for Cosbnd Si, Ossbnd Si and Cosbnd Os bonds.

  2. Quantifying 3D Deformation in the 14 November 2016 MW 7.8 Kaikoura, New Zealand Earthquake Using COSI-Corr Optical Satellite Image Correlation

    NASA Astrophysics Data System (ADS)

    Zinke, R. W.; Hollingsworth, J.; Dolan, J. F.; Van Dissen, R. J.

    2017-12-01

    We determined the 3D surface deformation field for 14 November 2016 MW 7.8 Kaikoura, New Zealand earthquake using a novel version of COSI-Corr optical image correlation software on 20 sets of WorldView satellite images. Our results provide high-precision (better than 1 m) measurements of horizontal and vertical displacement resulting from this event, over areas of 100's of square km. As such, our data set "bridges the gap" between the numerous, high-quality field and lidar-based measurements collected in the very near-field vicinity of the fault (but which may not account for far-field, distributed deformation), and other space-borne techniques such as InSAR that survey a wide spatial aperture but typically decorrelate near the fault. Our results thus provide a clear picture of how surface deformation was manifested in the Kaikoura rupture at a variety of spatial scales, and can aid in understanding how near-fault field measurements reflect broader patterns of strain release in earthquakes, and help us develop a better understanding of the controls on the 3D distribution of near-surface deformation in large earthquakes.

  3. Associations between built environment and physical activity of 7-8-year-old children. Cross-sectional results from the Lithuanian COSI study.

    PubMed

    Žaltauskė, Vilma; Petrauskienė, Aušra

    2016-01-01

    Research shows that regular engagement in physical activity in childhood is associated with multiple physical and psychosocial health benefits. The data on associations between children physical activity level and built environment in Lithuania are limited. The built environment is one of many variables thought to affect children physical activity level. But consequently there is growing interest in how physical environment influences physical activity of school age children. The aim of this paper is to evaluate associations between physical activity of primary school age children and built environment (road safety, travel distance, playgrounds, etc.) in Lithuania. Data were obtained participating in the WHO European Childhood Obesity Surveillance Initiative (COSI). The study protocol was granted ethical approval from Lithuanian Bioethics Committee (No. 6B-10-02). Parents/guardians provided written informed consent. A cross-sectional study was carried out in 2013. A multilevel sampling method was employed for composing a national representative sample. The representing data were collected by means of standardized questionnaires, which were filled out by 3802 parents of the selected first-formers. The mean age of the first-formers was 7.3 years (SD 0.5). More than half (62.2%) of parents stated that roads to schools were safe; most (78.7%) of adults notified that children had where to play and exercise in their living area. Place of residence of family and recreation areas in living environment were significant predictors of children's daily physical activity and possibility to attend sport or dancing clubs. Results from the national survey of 7-8-year-old children of Lithuania reveal that urban living area of families, availability of playgrounds and recreational facilities were associated with higher possibilities of children to be sufficiently physically active. Copyright © 2016 The Lithuanian University of Health Sciences. Production and hosting by Elsevier

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

  7. Measurement of cold fission for 229Th(n th, f), 232U(n th, f) and 239Pu(n th, f) with the Cosi fan tutte spectrometer

    NASA Astrophysics Data System (ADS)

    Asghar, M.; Boucheneb, N.; Medkour, G.; Geltenbort, P.; Leroux, B.

    1993-07-01

    The light-fragment-group mass-energy correlations for 229Th(n th, f), 232U(n th, f) and 239Pu (n th, f) measured with the Cosi fan tutte, have been used to determine the cold fission probability for these fissioning systems. These are the first results on cold fission for 229Th(n th, f) and 232U(n th, f). For 229Th(n th, f) cold fission is realised for the whole mass range ML ≈ 80-99 present in the mass spectrum, but the coldest fission shows up for ML ≈ 85. For 232U(n th, f) cold fission is present for ML ≈ 84-107, with the coldest fission manifesting for ML ≈ 100-105. In the case of 239Pu(n th, f), cold fission exists for ML ≈ 95-112 and here the coldest fission is produced for ML ≈105-110. This systematic study shows that the shells in the nascent fragments seem to play a decisive role in the realisation of cold fission. These results are discussed in terms of the existing concepts and ideas on this phenomenon.

  8. Two new ballonigrin-type diterpenoids from the roots of Ballota limbata.

    PubMed

    Farooq, Umar; Khan, Afsar; Khan, Ather Farooq; Khan, Saleha Suleman; Sarwar, Rizwana; Ahmad, Viqar Uddin; Waseem, Amir

    2012-02-01

    Two new ballonigrin type lactone diterpenoids, named ballonigrin lactone A and B, have been isolated from the roots of Ballota limbata. Structure elucidation of the isolated compounds was based on spectroscopic {IR, 1H- and 3C-NMR, and 2D-NMR (HMQC, HMBC, COSY and NOESY} and EI-MS data.

  9. Structure of the O-specific polysaccharide from the deep-sea marine bacterium Idiomarina abyssalis КММ 227(T) containing a 2-O-sulfate-3-N-(4-hydroxybutanoyl)-3,6-dideoxy-d-glucose.

    PubMed

    Kokoulin, Maxim S; Komandrova, Nadezhda A; Kalinovskiy, Anatoly I; Tomshich, Svetlana V; Romanenko, Lyudmila A; Vaskovsky, Victor V

    2015-09-02

    The O-specific polysaccharide was isolated from the lipopolysaccharide of type strain Idiomarina abyssalis КММ 227(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 I. abyssalis КММ 227(T) containing 2-O-sulfate-3-N-(4-hydroxybutanoyl)-3,6-dideoxy-d-glucose was established. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Stereoselective synthesis and spectral studies of some benzotriazolylacetyl hydrazones of 3-alkyl-2,6-diarylpiperidin-4-ones

    NASA Astrophysics Data System (ADS)

    Pillai, M. Velayutham; Rajeswari, K.; Kumar, C. Udhaya; Krishnan, K. Gokula; Mahendran, S.; Ramalingan, C.; Nagarajan, E. R.; Vidhyasagar, T.

    2017-12-01

    An effort to include biologically potent benzotriazole nucleus into piperidine ring is achieved through hydrazone formation. The characterization of the synthesized compounds was carried out using FT-IR, 1H &13C NMR, 1H-1H COSY, 1H-13C COSY, NOESY spectral techniques and GC-Mass spectrum. The spectral assignments were done without ambiguity using 2D-NMR techniques. The conformational preference of the piperidine ring deduced from the spectral studies is 'chair'. The diastereotopic nature of the methylene protons/methyl groups present in the molecules is revealed clearly in their spectral pattern observed.

  11. Sesquiterpene constituents from the soft coral Sinularia nanolobata.

    PubMed

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

    2017-08-01

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

  12. Limonoids and triterpenoids from the stem bark of Melia toosendan.

    PubMed

    Zhang, Yi; Tang, Chun-Ping; Ke, Chang-Qiang; Yao, Sheng; Ye, Yang

    2010-04-23

    Four new limonoids (1, 3, 4, 6), named meliatoosenins A-D, eight new euphane- and tirucallane-type triterpenoids (8-15), named meliasenins A-H, and 13 known compounds have been isolated from the stem bark of Melia toosendan. The structures of new compounds were established on the basis of 1D and 2D NMR experiments ((1)H-(1)H COSY, HSQC, HMBC, and ROESY).

  13. Limonoids from the fruits of Melia toosendan.

    PubMed

    Zhang, Yi; Tang, Chun-Ping; Ke, Chang-Qiang; Li, Xi-Qiang; Xie, Hua; Ye, Yang

    2012-01-01

    Fifteen limonoids, meliatoosenins E-S (1-15), and 10 known compounds were isolated from the fruits of Melia toosendan. Their structures were elucidated on the basis of extensive spectroscopic methods including DEPT, HSQC, HMBC, (1)H-(1)H COSY, and ROESY experiments. All the compounds were evaluated for antiproliferative activity using A-549 and HL-60 cell lines. Copyright © 2011 Elsevier Ltd. All rights reserved.

  14. New Xanthone from the roots of Swertia cordata (G. Don) Clarke.

    PubMed

    Mishra, Devendra; Joshi, Shivani; Mishra, Shweta; Sah, Mukesh Lal; Ajay, Sama; Shaw, Arun K

    2017-01-01

    The chloroform extract of Swertia cordata (G. Don) roots was subjected to column chromatography, afforded two (one new and one known) xanthones. Both the compounds were isolated for the first time from S. cordata. The structures of the isolated compounds were established on the basis of melting point,1D ( 1 H NMR & 13 C NMR) and 2D ( 1 H 1 H COSY, HSQC & HMBC) NMR spectroscopy, in addition to high-resolution mass spectrometry.

  15. Georatusin, a Specific Antiparasitic Polyketide-Peptide Hybrid from the Fungus Geomyces auratus.

    PubMed

    Shi, Yi-Ming; Richter, Christian; Challinor, Victoria L; Grün, Peter; Girela Del Rio, Antonio; Kaiser, Marcel; Schüffler, Anja; Piepenbring, Meike; Schwalbe, Harald; Bode, Helge B

    2018-03-16

    Georatusin (1), featuring a highly reduced, methylated polyketide moiety fused to a tryptophan by an amide and ester bond forming a 13-membered ring, was produced by the soil fungus Geomyces auratus. An HMQC-COSY spectrum was measured to build up the connectivities despite the overlapping proton signals. DQF-COSY, HETLOC, J-HMBC, and ROESY were implemented to determine the relative configuration of the flexible moiety. Georatusin (1) shows specific antiparasitic activities against Leishmania donovani and Plasmodium falciparum without obvious cytotoxicity. The biosynthesis of 1 was also proposed.

  16. Triterpenoid oligoglycosides from the sea cucumber Stichopus parvimensis.

    PubMed

    Iñiguez-Martinez, Ana María de Moncerrat; Guerra-Rivas, Graciela; Rios, Tirso; Quijano, Leovigildo

    2005-11-01

    Two new holostan-type triterpenoid oligoglycosides, named parvimosides A (1) and B (2), were isolated from the warty sea cucumber Stichopus parvimensis (syn. Parastichopus parvimensis). Their structures and total assignments of the proton and carbon signals were established on the basis of spectral evidence, mainly 1H and 13C 1D and 2D NMR spectroscopy including DEPT, COSY, TOCSY, NOESY/ROESY, HMQC/HSQC, and HMBC experiments, as well as FABMS.

  17. Structural determination of abutilins A and B, new flavonoids from Abutilon pakistanicum, by 1D and 2D NMR spectroscopy.

    PubMed

    Ali, Bakhat; Imran, Muhammad; Hussain, Riaz; Ahmed, Zaheer; Malik, Abdul

    2010-02-01

    Two new flavonoids, abutilin A and B, were isolated from the chloroform soluble fraction of Abutilon pakistanicum and their structures assigned from (1)H and (13)C NMR spectra, DEPT and by 2D COSY, HMQC and HMBC experiments. Ferulic acid (3), (E)-cinnamic acid (4), 5-hydroxy-4',6,7,8-tetramethoxyflavone (5), kaempferol (6), luteolin (7) and luteolin 7-O-beta-D-glucopyranoside (8) have also been reported from this species. Copyright 2009 John Wiley & Sons, Ltd.

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

    PubMed

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

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

  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. C28 sterols with a cyclopentane ring at C-22 and 26 from cape gooseberry (berries of Physalis pubeacens L.).

    PubMed

    Xu, Qiong-Ming; Liu, Yan-Li; Feng, Yu-Lin; Li, Xiao-Ran; Yang, Shi-Lin

    2010-09-01

    Two new C28 sterols with a cyclopentane ring at C-22 and 26, alkesterol A (1) and alkesterol B (2), along with β-sitosterol (3), were isolated from the berries of Physalis pubeacens L. (cape gooseberry). The structures of the new compounds were established by HR-EI-MS, 1D and 2D (1H-1H COSY, HSQC, HMBC) NMR experiments. The known compound was identified by comparison of spectral data with published references. The two new compounds showed some cytotoxic activities by MTT assay.

  1. Brominated aliphatic hydrocarbons and sterols from the sponge Xestospongia testudinaria with their bioactivities.

    PubMed

    Zhou, Xuefeng; Lu, Yanan; Lin, Xiuping; Yang, Bin; Yang, Xianwen; Liu, Yonghong

    2011-10-01

    Four brominated aliphatic hydrocarbons (1-4), including a novel brominated ene-tetrahydrofuran named as mutafuran H (1), and five sterols (5-9) were isolated from the South China Sea sponge Xestospongia testudinaria. The structure of 1 was determined on the basis of NMR ((1)H, (13)C NMR, HSQC, HMBC, (1)H-(1)H COSY, and NOESY), MS, and optical rotation analysis. Known compounds were identified by comparison of their NMR data with those reported in the literature. Compounds 1-4, and 6-9 were evaluated for their toxicity against Artemia salina larvae, and anti-acetylcholinesterase activity. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

  2. Structural and spectral assignment of a new diterpenoid isolated from Ballota undulata and a complete (1)H and (13)C NMR data assignment for three other structurally related compounds.

    PubMed

    Hussein, Ahmed A; Jimeno, María L; Rodríguez, Benjamín

    2007-10-01

    The structure of 3beta-hydroxyballotinone, a new labdane diterpenoid isolated from Ballota undulata, has been established by NMR spectroscopic studies. In addition, complete and unambiguous assignments of the (1)H and (13)C NMR spectra of three other already known labdanes (ballotinone, ballonigrin and ballonigrinone) isolated from the same source have been achieved. The assignments are based on 2D shift-correlated (1)H--(1)H COSY, (1)H--(13)C gHSQC [(1)J(C,H)] and (1)H--(13)C gHMBC [(n)J(C,H) (n = 2 and 3)], and NOE experiments. (c) 2007 John Wiley & Sons, Ltd.

  3. Structural and spectral assignment of three forskolin-like diterpenoids isolated from Plectranthus ornatus.

    PubMed

    Rijo, Patrícia; Simões, M Fátima; Rodríguez, Benjamín

    2005-07-01

    Three labdane diterpenoids were isolated from an acetone extract of Plectranthus ornatus. Their structures, closely related to that of forskolin, were determined by NMR studies. Unambiguous and complete assignments of the 1H and 13C NMR chemical shifts for these substances are presented. The assignments are based on 2D shift-correlated [1H, 1H-COSY, 1H, 13C-gHSQC-1J (C,H), 1H, 13C-gHMBC-(n)J (C,H) (n = 2 and 3)] and NOE experiments. Copyright 2005 John Wiley & Sons, Ltd

  4. 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.

  5. 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.

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

    PubMed

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

    2003-06-23

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

  7. 5-Acetamido-3,5-dideoxy-L-glycero-L-manno-non-2-ulosonic acid-containing O-polysaccharide from marine bacterium Pseudomonas glareae KMM 9500T.

    PubMed

    Kokoulin, Maxim S; Kalinovsky, Anatoly I; Romanenko, Lyudmila A; Mikhailov, Valery V

    2018-03-08

    The O-polysaccharide was isolated from the lipopolysaccharide of a marine bacterium Pseudomonas glareae KMM 9500 T and studied by chemical methods along with 1D and 2D 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 and 1 H, 13 C-HMBC experiments. The O-polysaccharide was found to consist of linear tetrasaccharide repeating units constituted by D-glucuronic acid (D-GlcA), L-rhamnose (L-Rha), D-glucose (D-Glc) and 5-acetamido-7,9-O-[(S)-1-carboxyethylidene]-3,5-dideoxy-L-glycero-L-manno-non-2-ulosonic acid (Sug7,9(S-Pyr)), partially O-acetylated at position 8 (∼70%): →4)-α-D-GlcpA-(1→3)-β-L-Rhap-(1→4)-β-D-Glcp-(1→4)-β-Sugp8Ac(∼70%)7,9(S-Pyr)-(2→. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

    PubMed

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

    2009-11-02

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

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

    PubMed

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

    1999-05-31

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

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

    PubMed

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

    2009-07-27

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

  11. Novel chromone derivatives from the fungus Aspergillus versicolor isolated from the marine sponge Xestospongia exigua.

    PubMed

    Lin, Wenhan; Brauers, Gernot; Ebel, Rainer; Wray, Victor; Berg, Albrecht; Sudarsono; Proksch, Peter

    2003-01-01

    From the marine sponge Xestospongia exigua collected in Indonesia the fungus Aspergillus versicolor was isolated. Following cultivation in a seawater-based medium seven new angular tricyclic chromone derivatives (1-7) were obtained from the mycelia and culture filtrate. Compounds 2-7 contain an additional dihydropyran ring system which is replaced by a pyridine ring in 1. The structures of the new natural products were established on the basis of extensive one- and two-dimensional NMR spectroscopic studies (1H, 13C, COSY, HMQC, HMBC, NOE difference spectra) as well as on mass spectral analysis.

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

    PubMed

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

    2012-12-01

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

  13. 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.

  14. Structure elucidation of five new iridoid glucosides from the leaves of Avicennia marina.

    PubMed

    Sun, Yu; Ouyang, Jie; Deng, Zhiwei; Li, Qingshan; Lin, Wenhan

    2008-07-01

    A chemical examination of the mangrove plant Avicennia marina (Forrsk.) Vierh resulted in the isolation and characterization of five new iridoids, marinoids A-E (1-5), along with 2'-cinnamoyl-mussaenosidic acid (6), 2'-O-(4''-methoxycinnamoyl) mussaenosidic acid (7), 2'-O-(4''-hydroxycinnamoyl) mussaenosidic acid (8), and 3(R)-hydroxy-5-phenyl-4(E)-pentenoic acid (9). The structures of 1-5 were elucidated on the basis of 1D and 2D NMR (COSY, HMQC, HMBC, and NOESY) in association with IR and MS data analysis. Copyright (c) 2008 John Wiley & Sons, Ltd.

  15. 1H and 13C NMR assignments of two new indolic enamide diastereomers from a mangrove endophytic fungus Aspergillus sp.

    PubMed

    Lin, Zhenjian; Zhu, Tianjiao; Fang, Yuchun; Gu, Qianqun

    2008-12-01

    Terpeptin A (1) and B (2), two new members of the indolic enamides, along with three known compounds (3-5) were identified from a strain of Aspergillus sp. (w-6), an endophytic fungus associated with Acanthus ilicifolius. The complete (1)H and (13)C NMR assignments for these compounds were carried out using (1)H, (13)C, DEPT, COSY, HMQC, and HMBC NMR experiments. Terpeptin A and B exhibited modest cytotoxicity against A-549 cell line. Copyright (c) 2008 John Wiley & Sons, Ltd.

  16. A new furostanol glycoside from Tribulus terrestris.

    PubMed

    Xu, Yajuan; Liu, Yonghong; Xu, Tunhai; Xie, Shengxu; Si, Yunshan; Liu, Yue; Zhou, Haiou; Liu, Tonghua; Xu, Dongming

    2010-01-27

    Besides two known glycosides, a new furostanol glycoside was isolated from the Fruits of Tribulus terrestris L. The structure of the new furostanol glycoside was established as 26-O-beta-D-glucopyranosyl-(25S)-5alpha-furostane-20(22)-en-12-one-3beta, 26-diol-3-O-alpha-L-rhamnopyranosyl-(1-->2)-[beta-D-glucopyranosyl-(1-->4)]-beta-D-galactopyranoside (1) on the basis of 1D and 2D-NMR techniques, including COSY, HMBC, and HMQC correlations.

  17. Two new diterpenoids from Ballota limbata.

    PubMed

    Ahmad, Viqar Uddin; Farooq, Umar; Hussain, Javid; Ullah, Farman; Nawaz, Sarfraz Ahmad; Choudhary, Muhammad Iqbal

    2004-04-01

    Two new clerodane-type diterpenoids trivially named as ballotenic acid (1) and ballodiolic acid (2) have been isolated from Ballota limbata along with three the known compounds; beta-amyrin, oleanolic acid, and beta-sitosterol. The structure elucidation of the new compounds was based primarily on two-dimensional (2D)-NMR techniques including correlation spectroscopy (COSY), heteronuclear multiple quantum coherence (HMQC), heteronuclear multiple bond correlation (HMBC), and nuclear Overhauser effect (NOE) experiments. Compounds 1 and 2 displayed inhibitory potential against lipoxygenase enzyme in a concentration-dependent fashion with IC(50) values of 99.6 microM and 38.3 microM, respectively.

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

    DOE PAGES

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

    2014-09-04

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

  19. Simultaneously cycled NMR spectroscopy.

    PubMed

    Parish, David M; Szyperski, Thomas

    2008-04-09

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-06-01

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

  1. 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.

  2. [Chemical constituents of Trichosanthes kirilowii Maxim].

    PubMed

    Sun, Xiao-Ye; Wu, Hong-Hua; Fu, Ai-Zhen; Zhang, Peng

    2012-07-01

    To study the chemical constituents of Trichosanthes kirilowii Maxim., chromatographic methods such as D101 macroporous resin, silica gel column chromatographic technology, Sephadex LH-20, octadecylsilyl (ODS) column chromatographic technique and preparative HPLC were used and nine compounds were isolated from a 95% (v/v) ethanol extract of the plant. By using spectroscopic techniques including 1H NMR, 13C NMR, 1H-1H COSY, HSQC and HMBC, these compounds were identified as 5-ethoxymethyl-1-carboxyl propyl-1H-pyrrole-2-carbaldehyde (1), 5-hydroxymethyl-2-furfural (2), chrysoeriol (3), 4'-hydroxyscutellarin (4), vanillic acid (5), alpha-spinasterol (6), beta-D-glucopyranosyl-a-spinasterol (7), stigmast-7-en-3beta-ol (8), and adenosine (9), separately. Among them, compound 1 is a new compound, and compounds 3, 4 and 5 are isolated from the genus Trichosanthes kirilowii Maxim. for the first time.

  3. 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. 2010 John Wiley & Sons, Ltd.

  4. Enzymatic synthesis and characterization of arbutin glucosides using glucansucrase from Leuconostoc mesenteroides B-1299CB.

    PubMed

    Moon, Young Hwan; Nam, Seung Hee; Kang, Jin; Kim, Young-Min; Lee, Jin-Ha; Kang, Hee-Kyung; Breton, Vincent; Jun, Woo-Jin; Park, Ki-Deok; Kimura, Atsuo; Kim, Doman

    2007-12-01

    Two arbutin glucosides were synthesized via the acceptor reaction of a glucansucrase from Leuconostoc mesenteroides B-1299CB with arbutin and sucrose. The glucosides were purified by Bio-gel P-2 column chromatography and high-performance liquid chromatography, and the structures were elucidated as 4-hydroxyphenyl beta-isomaltoside (arbutin-G1), 4-hydroxyphenyl beta-isomaltotrioside (arbutin-G2), according to the results of (1)H, (13)C, heteronuclear single-quantum coherence, (1)H-(1)H COSY, and heteronuclear multiple-bond correlation analyses. Arbutin glucoside (4-hydroxyphenyl beta-isomaltoside) exhibited slower effects on 1,1-diphenyl-2-picrylhydrazyl radical scavenging and similar effects on tyrosinase inhibition, and increased inhibitory effect on matrix metalloproteinase-1 production induced by UVB than arbutin.

  5. A new megastigmane glycoside from Akebia quinata.

    PubMed

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

    2015-01-01

    A new megastigmane glycoside, 8S*,9R*-megastigman-3-one-4,6-diene-8,9-diol-9-O-β-D-glucopyranoside, named akequintoside D (1), as well as six known compounds, roseoside II (2), 3-O-caffeoylquinic acid (3), methyl-3-O-caffeoylquinate (4), 3,4,5-trimethoxyphenyl-β-D-glucopyranoside (5), cuneataside D (6), 3,4-dimethoxyphenyl-6-O-(α-L-rhamnopyranosyl)-β-D-glucopyranoside (7) were isolated from the stem of Akebia quinata. 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. The inhibitory activity of these isolated compounds against interleukin-6 (IL-6) production in TNF-α stimulated MG-63 cells was also examined.

  6. 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

    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 ofmore » 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.« less

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

    NASA Astrophysics Data System (ADS)

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

    1998-09-01

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

  8. 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.

  9. 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.

  10. 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.

  11. Elemental and Microscopic Analysis of Naturally Occurring C-O-Si Hetero-Fullerene-Like Structures.

    PubMed

    Hullavarad, Nilima V; Hullavarad, Shiva S; Fochesatto, Javier

    2015-03-01

    Carbon exhibits an ability to form a wide range of structures in nature. Under favorable conditions, carbon condenses to form hollow, spheroid fullerenes in an inert atmosphere. Using high resolution FESEM, we have concealed the existence of giant hetero-fullerene like structures in the natural form. Clear, distinct features of connected hexagons and pentagons were observed. Energy dispersive X-ray analysis depth-profile of natural fullerene structures indicates that Russian-doll-like configurations composed of C, 0, and Si rings exist in nature. The analysis is based on an outstanding molecular feature found in the size fraction of aerosols having diameters 150 nm to 1.0 µm. The fullerene like structures, which are ~ 150 nm in diameter, are observed in large numbers. To the best of our knowledge, this is the first direct detailed observation of natural fullerene-like structures. This article reports inadvertent observation of naturally occurring hetero-fullerene-like structures in the Arctic.

  12. Antidepressent Effect of Two New Benzyl Derivatives from Wild Strawberry Fragaria vesca var. nubicola Lindl. ex Hook.f.

    PubMed Central

    Naz, Sadia; Farooq, Umar; Khan, Ajmal; Khan, Haroon; Karim, Nasiara; Sarwar, Rizwana; Hussain, Javid; Rauf, Abdur

    2017-01-01

    Two new benzyl derivatives were isolated from ethyl acetate fraction of wild strawberry, Fragaria vesca var. nubicola Lindl. ex Hook.f. The structures of these compounds were elucidated to be 5-(4-hydroxy-3-methoxyphenethyl)-7-methoxy-2H-chromen-3-ol (1) and 5-(4-hydroxy-3-methoxyphenethyl)-4,7-dimethoxy-2H-chromen-3-ol (2) based on spectroscopic data through IR, UV, 1H-NMR, 13C-NMR along with two dimensional (2D) techniques HMBC, HMQC, and COSY. Both compounds 1 and 2 were studied in tail suspension and forced swim tests for antidepressant like effects. A significant dose dependent antidepressant like effect was observed by causing spontaneous anti-immobility at various test doses upon intraperitoneal administration. PMID:28790915

  13. Cytotoxic tirucallane triterpenoids from the stem bark of Melia toosendan.

    PubMed

    Zhao, Qingjie; Song, Yan; Feng, Chuanwei; Chen, Haisheng

    2012-11-01

    Three new tirucallane triterpenoids, 3β,16-dihydroxy-25-hydroperoxytirucalla-7,23(24)-dien-6-oxo acid (1), 3β,16β-hydroxytirucalla-7,24(25)-dien-21,23-olide (2), and 3β,16β-hydroxytirucalla-7,24(25)-dien-6-oxo-21,23-olide (3) were isolated from the 70% ethanol extract of the stem bark of Melia toosendan. Their structures were determined on the basis of 1D and 2D NMR (COSY, HMQC, HMBC and NOESY) analyses. The isolated compounds were evaluated in vitro for cytotoxic activities against A549, SK-OV-3, SK-MEL-2 and HCT15 tumor cell lines. Compounds 2 and 3 exhibited significant cytotoxic activities against the four tested cell lines with IC(50) values of 3.4-5.7 μg/mL and 3.2-5.0 μg/mL, respectively.

  14. Predicting PSR filters by transverse relaxation enhancements.

    PubMed

    Correa, Juan; Pinto, Luiz F; Riguera, Ricardo; Fernandez-Megia, Eduardo

    2015-01-06

    The paramagnetic spin relaxation (PSR) filter allows the suppression of the NMR resonances of individual components in mixtures according to their Gd(3+)-complexing ability. The difficulty in predicting this property hampers, however, the widespread application of this filter. Herein we describe that the PSR filter is dominated by the transverse relaxation enhancement (R(2p)) experienced by nuclei in the presence of Gd(3+), so that R(2p) represents a reliable predictive tool of suppression in the 1D and 2D PSR filter of complex mixtures. The robustness of R(2p) as a predictive tool in PSR filters has been demonstrated at different magnetic fields and for the (1)H, (13)C, COSY, and HMQC filtering of commercial multicomponent compositions, including beverages and drugs.

  15. (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

  16. Antioxidant activity of Convolvulus hystrix Vahl and its chemical constituents.

    PubMed

    El Raheim Mohammed Donia, Abd; Alqasoumi, Saleh Ibrahim; Awaad, Amani Shafeek; Cracker, Lyle

    2011-04-01

    Total alcohol and successive extracts (diethyl ether, chloroform, ethyl acetate and n-butanol) of Covolvulus hystrix Vahl were screened for their antioxidant activity using free radical 2-2-diphenyl-1-picrylhydrazyl (DPPH) and Trolox as reference substance. The tested extracts showed variable antioxidant activities. The highest antioxidant activity was achieved in total alcohol (48.32%) followed by ethyl acetate (37.8%) and n-butanol (32.96%) extracts. From the ethyl acetate extract four compounds were isolated and identified as quercetin, quercetin 3-0-rutinoside and quercetin-7-O-rhamnoside in addition to ferulic acid using different spectroscopic analysis such as, 1HNMR, 13CNMR, COSY, HMBC and HMQC.

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

    PubMed

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

    2007-08-01

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

  18. Longipetalosides A-C, new steroidal saponins from Tribulus longipetalus.

    PubMed

    Naveed, Muhammad Akram; Riaz, Naheed; Saleem, Muhammad; Jabeen, Bushra; Ashraf, Muhammad; Ismail, Tayaba; Jabbar, Abdul

    2014-05-01

    Longipetalosides A-C (1-3); three new furostane steroidal saponins together with (25S)-5α-furastan-3β,22,26-triol (4) and gitogenin (5) were isolated from the methanolic extract of the whole plant of Tribulus longipetalus. The structures of these compounds (1-5) were established by using 1D ((1)H, (13)C) and 2D NMR (HMQC, HMBC, COSY, NOESY) spectroscopy, and mass spectrometry (ESIMS, HRESIMS), and in comparison with literature data reported for related compounds. Compounds 1-5 were evaluated for their inhibitory activities against enzymes α-glucosidase, lipoxygenase, acetylcholinesterase, and butyrylcholinesterase. Only the compounds 4 and 5 were found as the inhibitors of enzyme α-glucosidase with IC50 values of 33.5±0.22 and 37.2±0.18μM, respectively. Copyright © 2014 Elsevier Inc. All rights reserved.

  19. New anti-inflammatory and anti-proliferative constituents from fermented red mold rice Monascus purpureus NTU 568.

    PubMed

    Hsu, Ya-Wen; Hsu, Li-Chuan; Chang, Chao-Lin; Liang, Yu-Han; Kuo, Yao-Haur; Pan, Tzu-Ming

    2010-11-03

    Six azaphilonoid derivatives, including two new blue fluorescent monapurfluores A (1) and B (2), two known pyridine-containing molecules, monascopyridines C (3) and D (4), and two known monasfluores A (5) and B (6), were isolated and characterized from red mold rice fermented by Monascus purpureus NTU 568. Structural elucidation of new isolates was based on nuclear magnetic resonance (1H- NMR, 13C-NMR, COSY, HMQC, and HMBC) and other spectroscopic analyses. Bioactivity evaluation indicated that 1-6 possessed anti-inflammatory activities with dose-dependent relationships for lipopolysaccharide (LPS)-induced nitric oxide production. Furthermore, 1-4 also showed moderate antiproliferative effects against human laryngeal carcinoma (HEp-2) (IC(50) = 14.81~20.06 μg/mL) and human colon adenocarcinoma (WiDr) (IC(50) = 12.89~21.14 μg/mL).

  20. Penicilazaphilone C, a new antineoplastic and antibacterial azaphilone from the Marine Fungus Penicillium sclerotiorum.

    PubMed

    Zhou, Song-Lin; Wang, Min; Zhao, Huan-Ge; Huang, Yong-Hao; Lin, Ying-Ying; Tan, Guang-Hong; Chen, Shung-Lin

    2016-12-01

    Two azaphilonidal derivatives [penicilazaphilones B (1) and C (2)], have been isolated from the fermented products of marine fungus strain Penicillium sclerotiorum M-22, penicilazaphilones C was a new compound. The compound's structures were identified by the analysis of spectroscopic data including 1D and 2D NMR techniques ( 1 H-NMR, 13 C-NMR, COSY, HMQC, and HMBC). Biological evaluation revealed that penicilazaphilones B and C showed selective cytotoxicity against melanoma cells B-16 and human gastric cancer cells SGC-7901 with IC 50 values of 0.291, 0.449 and 0.065, 0.720 mM, respectively, while exhibiting no significant toxicity to normal mammary epithelial cells M10 at the same concentration. Moreover, penicilazaphilones C also exhibited strong antibacterial activity against Staphylococcus aureus, Pseudomonas aeruginosa, Klebsiella pneumonia and Escherichia coli with MIC values 0.037-0.150 mM, while penicilazaphilones B's bacteriostatic action was weaker.

  1. Assignment of phycocyanobilin in HMPT using triple resonance experiments.

    PubMed

    Röben, Marco; Schmieder, Peter

    2011-09-01

    A complete assignment of all resonances of a small organic molecule is a prerequisite for a structure determination using NMR spectroscopy. This is conventionally obtained using a well-established strategy based on COSY, HMQC and HMBC spectra. In case of phycocyanobilin (PCB) in HMPT this strategy was unsuccessful due to the symmetry of the molecule and extreme signal overlap. Since (13)C and (15)N labeled material was available, an alternative strategy for resonance assignment was used. Triple resonance experiments derived from experiments conventionally performed for proteins are sensitive and easy to analyze. Their application led to a complete and unambiguous assignment using three types of experiments. Copyright © 2011 John Wiley & Sons, Ltd.

  2. Two Novel Cycloartane-Type Triterpenes from Trichilia casaretti C. DC. (Meliaceae).

    PubMed

    Vieira, Ivo Jose Curcino; Figueiredo, Elaine Rodrigues; Vieira, Milena Gonçalves Curcino; Carvalho Junior, Almir Ribeiro de; Passos, Michel de Souza; Boeno, Samyra Imad da Silva; Azevedo, Otoniel Aquino; Braz-Filho, Raimundo

    2018-04-19

    Two new triterpenes cycloartane-type, named 24-methylencycloartan-12-oxo-3β,22α-diol and trichiliol, were isolated from the leaves of Trichilia casaretti C. DC. together with three known triterpenes—24-methylencycloart-3β,22-diol, 22,25-dihydrocycloart-23( E )-en-3β-ol, and 22( R )-hydroxycycloart-24-en-3-ol. These compounds were characterized on the basis of their spectral data, mainly 1D (¹H and 13 C) and 2D NMR (¹H-¹H-COSY, ¹H-¹H-NOESY, HMQC, HSQC, and HMBC), and mass spectra (EI-MS and HR-ESI-MS), also involving comparison with data from the literature.

  3. A prodigiosin from the roseophilin producer Streptomyces griseoviridis.

    PubMed

    Kawasaki, Takashi; Sakurai, Fumi; Hayakawa, Yoichi

    2008-07-01

    Roseophilin is a unique metabolite containing two pyrrole and one furan ring and is structurally related to tripyrrole antibiotics, prodigiosins. Each homologous gene in the roseophilin producer Streptomyces griseoviridis was amplified by PCR using primers designed from the prodigiosin-biosynthesis genes redH, redM, and redW. A search for prodigiosins produced by S. griseoviridis resulted in the isolation of a new prodigiosin designated prodigiosin R1 (1). The molecular formula of 1 was established as C27H37N3O by high-resolution FABMS. The structure of 1 was elucidated by NMR spectroscopic analysis including COSY, HMQC, HMBC, and NOESY. Prodigiosin R1 (1) is a new member of the prodigiosin family possessing a cyclic alkyl side chain.

  4. 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

  5. Diterpenoids from Haplopappus rigidus.

    PubMed

    Morales, G; Sierra, P; Loyola, L A; Borquez, J

    2000-12-01

    Fractionation of the aerial parts of Haplopappus rigidus Phil., directed by the brine shrimp lethality test (BST), has led to the isolation of two new diterpenoids, rigidusol and deacetylrigidusol. Their structures were established as 13-hydroxy-18-acetoxy-cis-cleroda-3,14-diene (8betaH, 10betaH, 19beta, 20alpha form) and 13,18-dihydroxy-cis-cleroda-3,14-diene (8betaH, 10betaH, 19beta, 20alpha form), respectively. Rigidusol exhibit moderate cytotoxic activity against human breast adenocarcinoma cell line MCF-7. Their structures were established by spectral data, in particular using 2D NMR spectroscopy (DEPT, DQF-COSY, HMQC and HMBC).

  6. 1H and 13C NMR assignments of three nitrogen containing compounds from the mangrove endophytic fungus (ZZF08).

    PubMed

    Tao, Yiwen; Zeng, Xianjian; Mou, Chengbo; Li, Jun; Cai, Xiaoling; She, Zhigang; Zhou, Shining; Lin, Yongcheng

    2008-05-01

    A new natural product, named phomopsin A, 1-(meta-hydroxyphenyl)-4-hydroxy-3-isoquinolone (1), together with two known compounds cytochalasin H (2) and glucosylceramide (3), was isolated from the mangrove endophytic fungus Phomopsis sp. (ZZF08) obtained from the South China Sea coast. The structures were elucidated by 1D and 2D NMR experiments including COSY, HMQC, and HMBC. According to NMR and single-crystal X-ray diffraction, it was found that some assignments about (1)H and (13)C NMR data for cytochalasin H (2) were probably uncorrected in the previous reports. In our cytotoxicity assays, compound 1 showed moderate cytotoxicity toward KB cells with IC(50) at 28.0 microg ml(-1) and KBv200 cells with IC(50) at 16.8 microg ml(-1), and compound 2 exhibited strong cytotoxicity toward KB cells and KBv200 cells with IC(50) less than 1.25 microg ml(-1). 2008 John Wiley & Sons, Ltd.

  7. Structure elucidation and NMR assignments for two amide alkaloids from a Mangrove endophytic Fungus (No. ZZF-22).

    PubMed

    Chen, Yiguang; Shao, Changlun; Huang, Zhongjing; Zhang, Ying; Cai, Xiaoling; She, Zhigang; Zhou, Shining; Lin, Yongcheng

    2009-01-01

    The structure elucidations and complete (1)H and (13)C NMR assignments are reported for two new natural products: 3-benzylidene-8,8a-dihydroxy-2-methyl-hexahydro-pyrrolo[1,2-a]pyrazine-1,4-dione(1) and 4-hydroxy-6-(hydroxy-phenyl-methyl)-N-(3-methyl-butyryl)-nicotinamide (2). Both of these secondary metabolites were isolated from the fermentation medium of a Mangrove endophytic fungus. High resolution electron impact mass spectrometry (HREIMS), FT-IR Spectroscopy and NMR experiments including gCOSY, gHMQC, gHMBC and NOE were used for determination of the structures and assignments of the amide alkaloids. 2008 John Wiley & Sons, Ltd.

  8. 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

  9. Antimicrobial compounds from Pimpinella species growing in Turkey.

    PubMed

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

    2003-10-01

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

  10. Isolation and evaluation of the antioxidant activity of phenolic constituents of the Garcinia brasiliensis epicarp.

    PubMed

    Gontijo, Vanessa Silva; de Souza, Thiago Corrêa; Rosa, Isael Aparecido; Soares, Marisi Gomes; da Silva, Marcelo Aparecido; Vilegas, Wagner; Viegas, Cláudio; Dos Santos, Marcelo Henrique

    2012-06-01

    A new glycosylated biflavonone, morelloflavone-4'″-O-β-d-glycosyl, and the known compounds 1,3,6,7-tetrahydroxyxanthone, morelloflavone (fukugetin) and morelloflavone-7″-O-β-d-glycosyl (fukugeside) were isolated from the epicarp of Garcinia brasiliensis collected in Brazil. The structures of these compounds were established using 1 H and 13 C NMR, COSY, gHMQC and gHMBC spectroscopy. The compounds exhibited antioxidant activity. The greatest potency was displayed by morelloflavone (2), with IC 50 =49.5mM against DPPH and absorbance of 0.583 at 400μg/mL for the reduction of Fe 3+ . The weakest potency was displayed by 1,3,6,7-tetrahydroxyxanthone (1), with IC 50 =148mM against DPPH and absorbance of 0.194 at 400μg/mL for the reduction of Fe 3+ . Copyright © 2011 Elsevier Ltd. All rights reserved.

  11. Structural elucidation of a capsular polysaccharide from a clinical isolate of Bacteroides vulgatus from a patient with Crohn's disease.

    PubMed

    Hashimoto, M; Kirikae, F; Dohi, T; Kusumoto, S; Suda, Y; Kirikae, T

    2001-06-01

    The structure of a capsular polysaccharide (CPS) from a clinical isolate of Bacteroides vulgatus was elucidated. B. vulgatus IMCJ 1204 was isolated from feces of a patient with Crohn's disease. CPS was prepared by phenol/water extraction of the bacterial cells followed by hydrophobic interaction chromatography and then gel filtration chromatography of the extract. The structure of CPS was determined by chemical analysis and NMR spectroscopy including DQF-COSY, TOCSY, ROESY, HSQC-TOCSY, HMQC and HMBC to be a polysaccharide composed of the following repeating unit: -->3)beta-D-Glcp(1-->6)[alpha-D-GalpNAc(1-->2)beta-D-Galp(1-->4)]beta-D-GlcpNAc(1-->3)alpha-D-Galp(1-->4)beta-D-Manp(1-->.

  12. Synthesis, spectral and structural characterization of isobutyl 4-(2-chlorophenyl)-5-cyano-6-(((dimethylamino)methylene)amino)-2-methyl-4H-pyran-3-carboxylate

    NASA Astrophysics Data System (ADS)

    Udhaya Kumar, C.; Velayutham Pillai, M.; Gokula Krishnan, K.; Ramalingan, C.

    2017-09-01

    A fascinating selectivity in the direction of the formation of the formamidine was observed upon the reaction of isobutyl 6-amino-4-(2-chlorophenyl)-5-cyano-2-methyl-4H-pyran-3-carboxylate with N,N-dimethyl formamide. A development in selectivity is explored and a probable mechanism for the reaction is also proposed. The formamidine has been analyzed by FT-IR, FT-Raman, LC-MS and NMR (1D and 2D (1H-1H COSY, 1H-13C COSY and HMBC)) spectra. The experimental findings are compared with the theoretical data calculated by using DFT-B3LYP with 6-311++G(d,p) basis set. A good agreement has been observed between experimental and theoretical data. Single crystal X-ray structural analysis of isobutyl 4-(2-chlorophenyl)-5-cyano-6-(((dimethylamino)methylene)amino)-2-methyl-4H-pyran-3-carboxylate (PDMF), evidences the conformation of pyran ring as ;flattened-boat;.

  13. 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

  14. Studies of minute quantities of natural abundance molecules using 2D heteronuclear correlation spectroscopy under 100 kHz MAS.

    PubMed

    Nishiyama, Y; Kobayashi, T; Malon, M; Singappuli-Arachchige, D; Slowing, I I; Pruski, M

    2015-01-01

    Two-dimensional (1)H{(13)C} heteronuclear correlation solid-state NMR spectra of naturally abundant solid materials are presented, acquired using the 0.75-mm magic angle spinning (MAS) probe at spinning rates up to 100 kHz. In spite of the miniscule sample volume (290 nL), high-quality HSQC-type spectra of bulk samples as well as surface-bound molecules can be obtained within hours of experimental time. The experiments are compared with those carried out at 40 kHz MAS using a 1.6-mm probe, which offered higher overall sensitivity due to a larger rotor volume. The benefits of ultrafast MAS in such experiments include superior resolution in (1)H dimension without resorting to (1)H-(1)H homonuclear RF decoupling, easy optimization, and applicability to mass-limited samples. The HMQC spectra of surface-bound species can be also acquired under 100 kHz MAS, although the dephasing of transverse magnetization has significant effect on the efficiency transfer under MAS alone. Published by Elsevier Inc.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  16. Identification of a novel structure in heparin generated by potassium permanganate oxidation

    PubMed Central

    Beccati, Daniela; Roy, Sucharita; Yu, Fei; Gunay, Nur Sibel; Capila, Ishan; Lech, Miroslaw; Linhardt, Robert J.; Venkataraman, Ganesh

    2012-01-01

    The worldwide heparin contamination crisis in 2008 led health authorities to take fundamental steps to better control heparin manufacture, including implementing appropriate analytical and bio-analytical methods to ensure production and release of high quality heparin sodium product. Consequently, there is an increased interest in the identification and structural elucidation of unusually modified structures that may be present in heparin. Our study focuses on the structural elucidation of species that give rise to a signal observed at 2.10 ppm in the N-acetyl region of the 1H NMR spectrum of some pharmaceutical grade heparin preparations. Structural elucidation experiments were carried out using homonuclear (COSY, TOSCY and NOESY) and heteronuclear (HSQC, HSQC-DEPT, HMQC-COSY, HSQC-TOCSY, and HMBC) 2D NMR spectroscopy on both heparin as well as heparin-like model compounds. Our results identify a novel type of oxidative modification of the heparin chain that results from a specific step in the manufacturing process used to prepare heparin. PMID:25147414

  17. Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)PdIIComplexes.

    PubMed

    Mikherdov, Alexander S; Kinzhalov, Mikhail A; Novikov, Alexander S; Boyarskiy, Vadim P; Boyarskaya, Irina A; Dar'in, Dmitry V; Starova, Galina L; Kukushkin, Vadim Yu

    2016-10-04

    The reaction of cis-[PdCl 2 (CNXyl) 2 ] (Xyl = 2,6-Me 2 C 6 H 3 ) with various 1,3-thiazol- and 1,3,4-thiadiazol-2-amines in chloroform gives a mixture of two regioisomeric binuclear diaminocarbene complexes. For 1,3-thiazol-2-amines the isomeric ratio depends on the reaction conditions and kinetically (KRs) or thermodynamically (TRs) controlled regioisomers were obtained at room temperature and on heating, respectively. In CHCl 3 solutions, the isomers are subject to reversible isomerization accompanied with the cleavage of Pd-N and С-N bonds in the carbene fragment XylNCN(R)Xyl. Results of DFT calculations followed by the topological analysis of the electron density distribution within the formalism of Bader's theory (AIM method) reveal that in CHCl 3 solution the relative stability of the regioisomers (∆G exp = 1.2 kcal/mol; ∆G calcd = 3.2 kcal/mol) is determined by the energy difference between two types of the intramolecular chalcogen bonds, viz. S•••Cl in KRs (2.8-3.0 kcal/mol) and S•••N in TRs (4.6-5.3 kcal/mol). In the case of the 1,3,4-thiadiazol-2-amines, the regioisomers are formed in approximately equal amounts and, accordingly, the energy difference between these species is only 0.1 kcal/mol in terms of ∆G exp (∆G calcd = 2.1 kcal/mol). The regioisomers were characterized by elemental analyses (C, H, N), HRESI + -MS and FTIR, 1D ( 1 H, 13 C) and 2D ( 1 H, 1 H-COSY, 1 H, 1 H-NOESY, 1 H, 13 C-HSQC, 1 H, 13 C-HMBC) NMR spectroscopies, and structures of six complexes (three KRs and three TRs) were elucidated by single-crystal X-ray diffraction.

  18. Structural, spectroscopic and passivation properties of a novel binuclear clamshell-type zinc(II) phthalocyanine as gate dielectric for OFET

    NASA Astrophysics Data System (ADS)

    Büyükekşi, Sebile Işık; Altındal, Ahmet; Açar, Nursel; Şengül, Abdurrahman

    A novel clamshell-type binuclear zinc(II) phthalocyanine (2) was synthesized by cross condensation of the bisphthalonitrile (1) with 4-tert-butylphthalonitrile and zinc acetate in 1:10:4 ratio. The structure of the novel compound was characterized by elemental analysis, UV-vis, FT-IR (ATR), HR MALDI-TOF mass, 1H NMR, 13C DEPT NMR and 1H-1H COSY NMR methods. Applying electronic absorption spectroscopy and density functional theory (DFT) revealed that in THF the geometry of 2 is twisted to adopt an intermediate clamshell conformation in which the spacing between the Zn centers is about 8.1Å, providing a very good account of the observed spectrum exhibiting the characteristic B (Soret) band at 347 nm and the Q band at 673 nm. In solution, 2 was found to exist in non-aggregated form. The calculated fluorescence quantum yields (ΦF = 0.23 in THF and 0.10 in DMF) were relatively reduced in comparison to that of std ZnPc. In particular, understanding of leakage current conduction mechanisms in gate dielectrics is crucial for the development of field effect transistors with improved device performance. Analysis of the reverse bias current-voltage data indicated that the origin of leakage current conduction mechanisms in clamshell-type zinc(II) phthalocyanine is Poole-Frenkel emission. The capacitance density of 12.7 nF cm-2 at 5 Hz. and 12.1 nF cm-2 at 13 MHz was obtained with the FTO/Pc/Au sandwich structure. A new clamshell-type binuclear zinc phthalocyanine (2) was synthesized and characterized by microanalysis, 1H NMR, 13C DEPT NMR, 1H1H COSY NMR, HR MALDI TOF MS, UV-vis and fluorescence spectrophotometers. The electronic structure and the nature of the excited states in 2 were correlated with the results obtained by DFT and TDDFT calculations. The performance of 2 as gate dielectric in an organic field effect transistor was investigated and a field effect mobility value of 6.4 × 10‑3 cm2/V s was obtained.

  19. Socioeconomic inequalities in childhood overweight: heterogeneity across five countries in the WHO European Childhood Obesity Surveillance Initiative (COSI-2008).

    PubMed

    Lissner, L; Wijnhoven, T M A; Mehlig, K; Sjöberg, A; Kunesova, M; Yngve, A; Petrauskiene, A; Duleva, V; Rito, A I; Breda, J

    2016-05-01

    Excess risk of childhood overweight and obesity occurring in socioeconomically disadvantaged families has been demonstrated in numerous studies from high-income regions, including Europe. It is well known that socioeconomic characteristics such as parental education, income and occupation are etiologically relevant to childhood obesity. However, in the pan-European setting, there is reason to believe that inequalities in childhood weight status may vary among countries as a function of differing degrees of socioeconomic development and equity. In this cross-sectional study, we have examined socioeconomic differences in childhood obesity in different parts of the European region using nationally representative data from Bulgaria, the Czech Republic, Lithuania, Portugal and Sweden that were collected in 2008 during the first round of the World Health Organization (WHO) European Childhood Obesity Surveillance Initiative. Heterogeneity in the association between parental socioeconomic indicators and childhood overweight or obesity was clearly observed across the five countries studied. Positive as well as negative associations were observed between parental socioeconomic indicators and childhood overweight, with statistically significant interactions between country and parental indicators. These findings have public health implications for the WHO European Region and underscore the necessity to continue documenting socioeconomic inequalities in obesity in all countries through international surveillance efforts in countries with diverse geographic, social and economic environments. This is a prerequisite for universal as well as targeted preventive actions.

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

    DOE Data Explorer

    Kristin Persson

    2014-11-02

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

  1. 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.

  2. New imidazolidineiminothione derivatives: Synthesis, spectral characterization and evaluation of antitumor, antiviral, antibacterial and antifungal activities.

    PubMed

    Moussa, Ziad; El-Sharief, Marwa A M Sh; Abbas, Samir Y

    2016-10-21

    A series of new imidazolidineiminothione derivatives with various halogenated and alkylated aromatic substituents at N-(1) and at N-(3) was synthesized through the reaction of N-arylcyanothioformamides with arylisocyanate derivatives. Structure of imidazolidineiminothione derivatives were established based on spectroscopic IR, (1)H NMR, (13)C NMR, (1)H,(1)H-COSY, HSQC, (19)F NMR, MS and elemental analyses data. Evaluation of antitumor, antiviral, antibacterial and antifungal activities for the synthesized compounds were carried out to probe their activities. Most of the synthesized compounds displayed antitumor activity. The presence of 3,5-dichlorophenyl moiety at N-(1) and trichlorophenyl moiety on N-(3) (2f) resulted the highest cytotoxic activity. The presence of 9H-fluorenyl moiety on N-(3) resulted in the lowest cytotoxic activity. The antiviral screening displayed that 2d and 2f were markedly active against one or two viral strains. Compound 2d (3,5-dichlorophenyl moiety at N-(1) and 4-chlorophenyl moiety on N-(3)) showed 100% antiviral effect toward HAV. Compound 2f showed 96.7% antiviral effect toward HSV1 and 80.3% antiviral effect toward HAV. The antimicrobial activity suggested that all of the imidazolidineiminothione derivatives possess significant antimicrobial activity against most of the test organisms. Some imidazolidineiminothione derivatives showed MIC values of antibacterial and antifungal activities ranged from 0.78 to 6.25 μg/ml. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

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

    PubMed

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

    2016-10-01

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

  4. A hybrid coumarin-thiazole fluorescent sensor for selective detection of bisulfite anions in vivo and in real samples.

    PubMed

    Peng, Meng-Jiao; Yang, Xiao-Feng; Yin, Bing; Guo, Yuan; Suzenet, Franck; En, Da; Li, Jin; Li, Chang-Wei; Duan, Yu-Wei

    2014-07-01

    A hybrid coumarin-thiazole compound was developed as a novel ratiometric and colorimetric sensor for bisulfite anions. Structure identification of the compound was confirmed by (1)H NMR, (13)C NMR, (1)H,(1)H COSY, heteronuclear single quantum coherence (HSQC), IR, and HRMS spectroscopy. The detection of bisulfite anions was performed through the Michael addition of the bisulfite anion toward the hybrid coumarin-thiazole sensor. The reaction between the sensor and bisulfite anion caused the fluorescence intensity to decrease at 600 nm and to increase at 450 nm and simultaneously yielded a visible color change from purplish red to colorless because the π conjugation between thiazole and coumarin was blocked. The sensor possessed high selectivity and sensitivity for bisulfite with respect to other common anions in aqueous solution. Moreover, the practical value of this sensor was confirmed by its application in the detection of bisulfite anion in human breast adenocarcinoma cells and granulated sugar. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Simple efficient synthesis of strongly luminescent polypyrene with intrinsic conductivity and high carbon yield by chemical oxidative polymerization of pyrene.

    PubMed

    Li, Xin-Gui; Liu, You-Wei; Huang, Mei-Rong; Peng, Sai; Gong, Ling-Zhi; Moloney, Mark G

    2010-04-26

    A wholly aromatic polypyrene was synthesized by direct chemical oxidative polymerization of pyrene with ferric chloride as oxidant in hexane/nitromethane. Successful synthesis of polypyrene was thoroughly confirmed by IR, UV/Vis, 1D (1)H NMR, 2D (1)H-(1)H COSY, 2D (1)H-(13)C HSQC, MALDI-TOF MS, elemental analysis, and X-ray diffraction methods. The results indicated that the polypyrene was formed mainly through dehydro coupling between 2- or 1- and 2'- or 1'-positions on pyrene rings having a degree of polymerization of around 24. The polypyrene was purified and then separated into THF-soluble (ca. 10 %) and THF-insoluble (ca. 90 %) fractions. Compared with insulating pyrene monomer, the polypyrene is a controllably conducting polymer that has low conductivity of 3.4x10(-8) S cm(-1) in its virgin state, moderate conductivity of 2.28x10(-4) S cm(-1) upon iodine doping, but much higher conductivity of up to 81.2 S cm(-1) after the insoluble polypyrene was heated up to 1300 degrees C in nitrogen with a high char yield of 70.6 %. In particular, the soluble polypyrene demonstrates much stronger visible color fluorescence and much lower toxicity than pyrene. The soluble polypyrene would be advantageous for detecting Fe(3+) with almost no interference of other metal ions. The soluble and insoluble polypyrene fractions have potential applications as intrinsically luminescent and highly conducting carbon materials, respectively.

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

    PubMed

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

    2014-12-21

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

  7. New sesquiterpene coumarin from the roots of Ferula latisecta

    PubMed Central

    Iranshahi, Mehrdad; Amanolahi, Farjad; Schneider, Bernd

    2012-01-01

    Objective: The genus of Ferula belongs to the tribe Peucedaneae, subfamily of Apioideae and family of Umbelliferae with 133 species distributed throughout the Mediterranean area and central Asia, especially in the former USSR and neighboring countries such as Iran. The popular Persian name of the most of these species is “Koma”. In this research we tried to isolate and elucidate the structure of new sesquiterpene in the root of Ferula latisecta (F. latisecta). Materials and Methods: Dried and powdered roots of F. latisecta were extracted with CH2Cl2 using a Soxhlet apparatus. The extract was concentrated in vacuo to give a red extract. The extract was subjected to column chromatography on silica gel. 1H NMR, 13C NMR, DEPT, 1H-1H COSY, HMBC, HSQC, and NOESY spectra were the methods we used to elucidate the structure of new sesquiterpene in this plant. Results: One new sesquieterpene coumarin, namely Latisectin and IUPAC name [1-(2-Hydroxy-4-methoxy-phenyl)-3,4,8,12-tetramethyl-trideca-4,7,11-trien-1-one ] , together with one known compound , Kopetdaghin C, were isolated from the root of F. latisecta. Conclusion: In this research the structure of one new and one known sesquiterpene in the root of F. latisecta was elucidated. PMID:25050242

  8. Complete 1H NMR spectral analysis of ten chemical markers of Ginkgo biloba

    PubMed Central

    Napolitano, José G.; Lankin, David C.; Chen, Shao-Nong; Pauli, Guido F.

    2013-01-01

    The complete and unambiguous 1H NMR assignments of ten marker constituents of Ginkgo biloba are described. The comprehensive 1H NMR profiles (fingerprints) of ginkgolide A, ginkgolide B, ginkgolide C, ginkgolide J, bilobalide, quercetin, kaempferol, isorhamnetin, isoquercetin, and rutin in DMSO-d6 were obtained through the examination of 1D 1H NMR and 2D 1H,1H-COSY data, in combination with 1H iterative Full Spin Analysis (HiFSA). The computational analysis of discrete spin systems allowed a detailed characterization of all the 1H NMR signals in terms of chemical shifts (δH) and spin-spin coupling constants (JHH), regardless of signal overlap and higher order coupling effects. The capability of the HiFSA-generated 1H fingerprints to reproduce experimental 1H NMR spectra at different field strengths was also evaluated. As a result of this analysis, a revised set of 1H NMR parameters for all ten phytoconstituents was assembled. Furthermore, precise 1H NMR assignments of the sugar moieties of isoquercetin and rutin are reported for the first time. PMID:22730238

  9. Complete 1H NMR spectral analysis of ten chemical markers of Ginkgo biloba.

    PubMed

    Napolitano, José G; Lankin, David C; Chen, Shao-Nong; Pauli, Guido F

    2012-08-01

    The complete and unambiguous (1)H NMR assignments of ten marker constituents of Ginkgo biloba are described. The comprehensive (1)H NMR profiles (fingerprints) of ginkgolide A, ginkgolide B, ginkgolide C, ginkgolide J, bilobalide, quercetin, kaempferol, isorhamnetin, isoquercetin, and rutin in DMSO-d(6) were obtained through the examination of 1D (1)H NMR and 2D (1)H,(1)H-COSY data, in combination with (1)H iterative full spin analysis (HiFSA). The computational analysis of discrete spin systems allowed a detailed characterization of all the (1)H NMR signals in terms of chemical shifts (δ(H)) and spin-spin coupling constants (J(HH)), regardless of signal overlap and higher order coupling effects. The capability of the HiFSA-generated (1)H fingerprints to reproduce experimental (1)H NMR spectra at different field strengths was also evaluated. As a result of this analysis, a revised set of (1)H NMR parameters for all ten phytoconstituents was assembled. Furthermore, precise (1)H NMR assignments of the sugar moieties of isoquercetin and rutin are reported for the first time. Copyright © 2012 John Wiley & Sons, Ltd.

  10. New cytotoxic cycloartane triterpene from Cassia italica aerial parts.

    PubMed

    Mohamed, Gamal A

    2014-01-01

    Phytochemical study of the aerial parts of Cassiaitalica Mill. (family: Fabaceae) growing in Saudi Arabia afforded one new cycloartane triterpene, named (22E)-3-β-hydroxycycloart-22-en-24-one (2), together with eight known compounds: β-sitosterol (1), uvaol (3), daucosterol (4), methyl 3,4-dihydroxybenzoate (5), emodin (6), 4-hydroxypheny-O-β-D-glucopyranoside (7), aloin (8) and rutin (9). The structure of the isolated compounds was determined by physical, chemical and spectral data (UV, IR, MS, 1D ((1)H, (13)C and DEPT) and 2D ((1)H-(1)H COSY, HSQC and HMBC) NMR), as well as by comparing with authentic samples. Compounds 3-5 and 7-9 were isolated for the first time from the plant. Compound 2 was evaluated for its cytotoxic activity against the L5178Y and PC12 cell lines. The total methanolic extract and compounds 5-9 exhibited free radical-scavenging activity using DPPH assay.

  11. A Novel Acylated Anthocyanin with a Linear Trisaccharide from Flowers of Convolvulus althaeoides.

    PubMed

    Cabrita, Luis

    2015-11-01

    An acylated anthocyanin trioside was isolated from pink flowers of Convolvulus althaeoides using a combination of chromatographic techniques. On the basis of MS (MALDI-TOF) and NMR (1H NMR, 1H-1H COSY, 1D TOCSY, HSQC, HMBC, 13C CAPT) its structure was determined as cyanidin 3-O-[6-O-(4-O- (6-O-(E-caffeoyl)-β-D-glucopyranosyl)-β-L-rhamnopyranosyl)-β-D-glucopyranoside]-5-O-β-D-glucopyranoside. The absolute configuration of the aldose enantiomer moieties was determined from the separation of the corresponding thiazolidine diastereoisomer derivatives by HPLC-DAD. This is a novel trisaccharide within the flavonoids, and the first complete characterization of a linear glucosyl-rhamnosyl-glucoside (4'-glucosylrutinoside) within the anthocyanins. Whilst acylation of rhamnose moieties in position 4 is quite common, the occurrence in anthocyanins of a glycosylated rhamnose is a unique trait. Although many complex anthocyanins have been found amongst the Convolvulaceae, the genus Convolvulus had not yet been surveyed for anthocyanins and thus this account could be of significance within the current chemotaxonomy of this family.

  12. Study of spontaneous E/Z isomerization of bis[(Z)-cyanomethylidene]-diazapentacyclodienedicarboxylates by1H,13C, and15N NMR spectroscopy, X-ray, and quantum chemical calculation data.

    PubMed

    Afonin, Andrei V; Vashchenko, Alexander V; Albanov, Alexander I; Nosyreva, Valentina V; Mal'kina, Anastasiya G; Trofimov, Boris A

    2017-06-01

    X-ray data show that the diethyl 6,13-bis[(Z)-cyanomethylidene]-5,5,14,14-tetramethyl-4,15-dioxa-7,12-diazapentacyclo[9.5.2.0 2,10 .0 3,7 .0 12,16 ]octadeca-8,17-diene-10,17-dicarboxylate is formed as the ZZ isomer and diastereomer with the (1R*,2R*,3R*,10S*,11R*,12R*,16R*) configuration. The 1 H, 13 C, and 15 N NMR data exhibit that on standing in chloroform-d solution, there is a spontaneous isomerization of this compound resulting in a thermodynamically stable mixture of the ZZ, ZE, EE, and EZ isomers with the same backbone. Using the 2D [ 1 H- 1 H] COSY, [ 1 H- 13 C] HSQC, and [ 1 H- 13 C, 1 H- 15 N] HMBC NMR techniques and quantum chemical calculations makes it possible a complete assignment of signals in the 1 H, 13 C, and 15 N NMR spectra of each of the isomers. Such isomerization does not occur for similar compounds with the more bulky substituents at the 1,3-oxazolidine rings. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

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

    PubMed

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

    2017-02-01

    The Raman spectrum of tartrazine has been mistakenly reported as being that of Indian yellow in the literature, which has serious consequences for the identification of this pigment in art works regarding their authentication. Unlike tartrazine, Indian yellow (a natural mixture of the magnesium and calcium salts of euxanthic acid) exhibits in its Raman spectrum a strong fluorescent background when visible excitation is used, however, excitation in the near infrared (1064nm) permitted the observation of the Raman bands from the raw pigment with the main features placed at 1346, 1368, 1425, 1441 and 1626cm -1 . Indian yellow identification was assured by 1 H and 13 C Nuclear Magnetic Resonance characterization and the complete assignment of the proton and carbon resonances was accomplished using heteronuclear single quantum correlation (HSQC), heteronuclear multiple bond correlation (HMBC), nuclear overhauser effect spectroscopy (NOESY) and 1 H- 1 H correlation spectroscopy (COSY). Scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and X-ray fluorescence (XRF) analyzes were also conducted on a genuine sample of this historical pigment. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  14. Cytotoxic protobassic acid saponins from the kernels of Palaquium formosanum.

    PubMed

    Chen, Hsin-Yi; Liu, Ju-Fang; Tsai, Sheng-Fa; Lin, Yi-Li; Lee, Shoei-Sheng

    2018-04-01

    Bioassay guided fractionation and separation of the EtOH extract of the kernels of Palaquium formosanum against PC-3 cells via Sephadex LH-20 and reverse phase C-18 columns led to the isolation of 13 protobassic saponins. One of these saponins is new and was characterized as 3‴-O-rhamnopyranosyl-arganin C, a bisdesmoside of 16α-hydroxyprotobassic acid at the C-3 and C-28 positions. The structures of these compounds were determined on the basis of 1D NMR ( 1 H, 13 C), 2D NMR ( 1 H- 1 H COSY, HSQC, HMBC, and NOESY), and selectively excited 1D TOCSY spectroscopic analyses and MS data, and comparison with literature data. Bioassay of these compounds and five additional compounds, isolated from Planchonella obovata leaf, against PC-3 prostate cancer cells indicated arganin C to be the most potent one with the IC 50 value of 13.8 μM. Some structure and activity relationships were also drawn. Copyright © 2017. Published by Elsevier B.V.

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

    PubMed

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

    2006-07-01

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

  16. 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

    2015-05-05

    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. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. Two novel ceramides with a phytosphingolipid and a tertiary amide structure from Zephyranthes candida.

    PubMed

    Wu, Zhi-Ping; Chen, Yu; Xia, Bing; Wang, Ming; Dong, Yun-Fa; Feng, Xu

    2009-01-01

    Two novel ceramides, Candidamide A (1) with a phytosphingolipid structure, and Candidamide B (2) with a tertiary amide structure, together with 12 known compounds (3-14) have been isolated from the bulbs of Zephyranthes candida, The structures of 1 and 2 have been elucidated to be 1,3,5,6-tetrahydroxy-2-(2'-hydroxytetracosanoyl amino)-8-(E)-octadecadiene (1) and (2S,3S,4R,8E,2'R)-2-[N-(2'-hydroxyoctadecanoyl)-N-(1'',2''-dihydroxyethyl)-amino]-8-hexacosene-1,3,4-triol (2) on the basis of spectroscopic evidence including IR, MS, NMR ((1)H-NMR, (13)C-NMR, DEPT, (1)H-(1)H COSY, HSQC, HMBC). The known compounds were identified as (2S)-3',7-dihydroxy-4'-methoxyflavan (3), (2S)-4'-hydroxy-7-methoxyflavan (4), (2S)-4',7-dihydroxyflavan (5), 7-hydroxy-3', 4'-methylenedioxyflavan (6), ambrettolide (7), beta-sitostero1 (8), beta-daucosterin (9), rutin (10), pancratistatin (11), lycorine (12), haemanthidine (13), and haemanthamine (14). In the antimicrobial assay, candidamide A (1) and candidamide B (2) displayed moderate activities against bacteria Staphylococcus aureus and Escherichia coli, and fungi Aspergillus niger, Candida albicans and Trichophyton rubrum.

  18. 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.

  19. Synthetic, spectral and structural study of mono bis(pyridine)dichloro bis(dimethyl sulfoxide- S) ruthenium(II) complex, [RuCl 2(py) 2(dmso- S) 2] and its reactivity with nitrogen donor bases in polar and non-polar solvent

    NASA Astrophysics Data System (ADS)

    Trivedi, Manoj; Sharma, Yogesh K.; Nagarajan, R.; Rath, Nigam P.

    2010-06-01

    Reaction of the cis-[RuCl 2(dmso) 4] with pyridine (py) at room temperature in MeOH/H 2O afforded a neutral mononuclear complex cis,cis, cis-[RuCl 2(py) 2(dmso- S) 2] 1. The complex 1 reacted with nitrogen donor bases such as pyridine (py), pyrazine (pyz), 4,4'-bipyridine (bp) and 1,4-bis(4-pyridyl)ethane (bpeta) in different solvents to give substitution products. The nature of the substitution product was governed by the polarity of the solvents employed in the reaction. Resulting complexes have been characterized by elemental analyses, IR, NMR ( 1H and 1H- 1H COSY), ESI-MS, FAB-MS and electronic spectral studies. Molecular structures of the complexes 1 and 5 have been determined crystallographically. Complex 1 exhibits the strong intra- and inter-molecular C sbnd H⋯X (X = Cl, π) and face-to-face π-π stacking interactions but only intra- and inter-molecular C sbnd H⋯Cl and π-π stacking interactions are present in 5 which play important roles to stabilize crystal packing. Furthermore, the C sbnd H⋯O interactions in 1 and C sbnd H⋯Cl interactions in 5 lead to a single and double-helical motif.

  20. [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.

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

    PubMed

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

    2015-01-25

    The novel azoimine ligand, Ph-NH-N=C(COCH3)-NHPh(C≡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=Ph-N=N-C(COCH3)=N-Ph(COCH3) and an enol (L2=Ph-N=N-C(COCH3)=N-PhC(OH)=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 (1)H NMR, (13)C NMR, (DEPT-135), (DEPT-90), 2D (1)H-(1)H and (13)C-(1)H correlation (HMQC) spectroscopy)). The two complexes exhibit a quasi-reversible one electron Ru(II)/Ru(III) oxidation couple at 604 mV vs. ferrocene/ferrocenium (Cp2Fe(0/+)) 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). Copyright © 2014 Elsevier B.V. All rights reserved.

  2. 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.

  3. Conformation of repaglinide: A solvent dependent structure

    NASA Astrophysics Data System (ADS)

    Chashmniam, Saeed; Tafazzoli, Mohsen

    2017-09-01

    Experimental and theoretical conformational study of repaglinide in chloroform and dimethyl sulfoxide was investigated. By applying potential energy scanning (PES) at B3LYP/6-311++g** and B3LYP-D3/6-311++g** level of theory on rotatable single bonds, four stable conformers (R1-R4) were identified. Spin-spin coupling constant values were obtained from a set of 2D NMR spectra (Hsbnd H COSY, Hsbnd C HMQC and Hsbnd C HMBC) and compared to its calculated values. Interestingly, from 1HNMR and 2D-NOESY NMR, it has been found that repaglinide structure is folded in CDCl3 and cause all single bonds to rotate at an extremely slow rate. On the other hand, in DMSO-d6, with strong solvent-solute intermolecular interactions, the single bonds rotate freely. Also, energy barrier and thermodynamic parameters for chair to chair interconversion was measured (13.04 kcal mol-1) in CDCl3 solvent by using temperature dynamic NMR.

  4. Structural and serological studies of the related O-specific polysaccharides of Proteus vulgaris O21 and Proteus mirabilis O48 having oligosaccharide-phosphate repeating units.

    PubMed

    Bartodziejska, B; Toukach, F V; Vinogradov, E V; Senchenkova, S N; Shashkov, A S; Ziolkowski, A; Czaja, J; Perry, M B; Knirel, Y A; Rozalski, A

    2000-12-01

    The O-specific polysaccharide chains (O-antigens) of the lipopolysaccharides (LPSs) of Proteus mirabilis O48 and Proteus vulgaris O21 were found to have tetrasaccharide and pentasaccharide repeating units, respectively, interlinked by a glycosidic phosphate. Polysaccharides and an oligosaccharide were derived from the LPSs by various degradation procedures and studied by 1H and 13C NMR spectroscopy, including 2D COSY, TOCSY, NOESY, H-detected 1H,13C and 1H,31P HMQC experiments. The following related structures of the repeating units of the O-antigens were established (top: Proteus mirabilis O48; bottom: Proteus vulgaris O21) The O-specific polysaccharide of P. vulgaris O21 has the same structure as that of Hafnia allvei 744 and PCM 1194 [Petersson C., Jachymek, W., Klonowska, A., Lugowski, C., Niedziela, T. & Kenne, L. (1997) Eur. J. Biochem., 245, 668-675], except that the GlcN residue carries the N-acetyl rather than the N-[(R)-3-hydroxybutyryl] group. Serological investigations confirmed the close relatedness of the Proteus and Hafnia O-antigens studied.

  5. Structure of the O-specific polysaccharide of Proteus vulgaris O15 containing a novel regioisomer of N-acetylmuramic acid, 2-acetamido-4-O-[(R)-1-carboxyethyl]-2-deoxy-D-glucose.

    PubMed

    Perepelov, Andrei V; Torzewska, Agnieszka; Shashkov, Alexander S; Ziolkowski, Andrzej; Senchenkova, Sof'ya N; Rozalski, Antoni; Knirel, Yuriy A

    2002-11-29

    An acidic O-specific polysaccharide was obtained by mild acid degradation of the lipopolysaccharide of Proteus vulgaris O15 and studied by sugar and methylation analyses along with 1H and 13C NMR spectroscopy, including 2D COSY, TOCSY, ROESY, and H-detected 1H,(13)C HMQC experiments. The polysaccharide was found to contain an ether of GlcNAc with lactic acid, and the following structure of the repeating unit was established:-->3)-alpha-D-GlcpNAc4(R-Lac)6Ac-(1-->2)-beta-D-GlcpA-(1-->3)-alpha-L-6dTalp2Ac-(1-->3)-beta-D-GlcpNAc-(1-->where L-6dTal and D-GlcNAc4(R-Lac) are 6-deoxy-L-talose and 2-acetamido-4-O-[(R)-1-carboxyethyl]-2-deoxy-D-glucose, respectively. The latter sugar, which to our knowledge has not been hitherto found in nature, was isolated from the polysaccharide by solvolysis with anhydrous triflic acid and identified by comparison with the authentic synthetic compound. Serological studies with the Smith-degraded polysaccharide showed an importance of 2-substituted GlcA for manifesting of the immunospecificity of P. vulgaris O15.

  6. 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.

  7. Investigations on Antioxidant, Antiproliferative and COX-2 Inhibitory Potential of Alkaloids from Anthocephalus cadamba (Roxb.) Miq. Leaves.

    PubMed

    Chandel, Madhu; Kumar, Manish; Sharma, Upendra; Singh, Bikram; Kaur, Satwinderjeet

    2017-04-01

    In the present study, an ayurvedic medicinal plant, Anthocephalus cadamba (Roxb.) Miq. commonly known as 'Kadamb' was explored for its potential against oxidative stress and cancer. The fractions namely AC-4 and ACALK (alkaloid rich fraction) were isolated from A. cadamba leaves by employing two different isolation methods and evaluated for their in vitro antioxidant and antiproliferative activity. The structure of the isolated AC-4 was characterized tentatively as dihydrocadambine by using various spectroscopic techniques such as ESI-QTOF-MS, 1 H- and 13 C-NMR, DEPT, COSY, HMQC, and HMBC. Results of various antioxidant assays viz. 2,2-diphenyl-1-picrylhydrazyl (DPPH), ABTS cation radical, superoxide anion radical scavenging, and plasmid nicking assay demonstrated that both the fractions viz. AC-4 and ACALK possess ability to scavenge DPPH, ABTS radicals and effectively protected plasmid pBR322 DNA from damage caused by hydroxyl radicals. Further, when both fractions were evaluated for their potential to suppress growth of HeLa and COLO 205 cells, only ACALK fraction showed antiproliferative effects. ACALK exhibited GI 50 of 205.98 and 99.54 μg/ml in HeLa and COLO 205 cell lines, respectively. Results of Hoechst staining in cervical carcinoma (HeLa) cells confirmed that ACALK induced cell death in HeLa cells via apoptotic mode. Both the fractions also inhibited COX-2 enzyme activity. © 2017 Wiley-VHCA AG, Zurich, Switzerland.

  8. 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

  9. New acylated flavonoid glycosides from flowers of Aerva javanica.

    PubMed

    Mussadiq, Sara; Riaz, Naheed; Saleem, Muhammad; Ashraf, Muhammad; Ismail, Tayaba; Jabbar, Abdul

    2013-07-01

    Chromatographic purification of ethyl acetate soluble fraction of the methanolic extract of the flowers of Aerva javanica yielded three new acylated flavone glycosides: kaempferol-3-O-β-d-[4‴-E-p-coumaroyl-α-l-rhamnosyl(1 → 6)]-galactoside (1), kaempferol-3-O-β-d-[4‴-E-p-coumaroyl-α-l-rhamnosyl(1 → 6)]-(3″-E-p-coumaroyl)galactoside (2), and kaempferol-3-O-β-d-[4‴-E-p-coumaroyl-α-l-rhamnosyl(1 → 6)]-(4″-E-p-coumaroyl)galactoside (3), along with p-coumaric acid (4), caffeic acid (5), gallic acid (6), eicosanyl-trans-p-coumarate (7), hexadecyl ferulate (8), and hexacosyl ferulate (9). The compounds 1-9 were characterized using 1D ((1)H, (13)C) and 2D NMR (HMQC, HMBC, and COSY) spectroscopy and mass spectrometry (EI-MS, HR-EI-MS, FAB-MS, and HR-FAB-MS) and in comparison with the reported data in the literature. Compound 1 showed weak inhibitory activity against enzymes, such as acetylcholinesterase, butyrylcholinesterase, and lipoxygenase with IC50 values 205.1, 304.1, and 212.3 μM, respectively, whereas compounds 2 and 3 were only weakly active against the enzyme acetylcholinesterase.

  10. Exopolysaccharide from surface-liquid culture of Clonostachys rosea originates from autolysis of the biomass.

    PubMed

    Viccini, Graciele; Martinelli, Thalita Romano; Cognialli, Regielly Caroline Raimundo; de Faria, Rodrigo Otávio; Carbonero, Elaine Rosechrer; Sassaki, Guilherme Lanzi; Mitchell, David Alexander

    2009-04-01

    We describe the purification and chemical characterization of galactomannans that appear both in the biomass and the culture broth during surface-liquid culture of the fungus Clonostachys rosea, a common facultative saprophyte that has potential to be used as a biological control agent against several plant pathogenic fungi, insects and nematodes. The galactomannans from both sources had comparable ratios of Man, Gal and Glc and the similarity were confirmed by (1)H, (13)C NMR, HMQC, and COSY spectra. We propose that the galactomannan in the culture broth originates from autolysis of the biomass, based not only on the similarity that it has with the galactomannan extracted from the biomass but also on the fact that its concentration increased rapidly after glucose depletion from the medium, when biomass concentration was falling. Polysaccharides from C. rosea have not previously been characterized; we show that the characteristics of the galactomannans are consistent with those that have been reported for other members of the Bionectriaceae, the family to which C. rosea belongs.

  11. 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. Georg Thieme Verlag KG Stuttgart · New York.

  12. Two new compounds and anti-HIV active constituents from Illicium verum.

    PubMed

    Song, Wen-Yong; Ma, Yun-Bao; Bai, Xue; Zhang, Xue-Mei; Gu, Qiong; Zheng, Yong-Tang; Zhou, Jun; Chen, Ji-Jun

    2007-04-01

    Two new compounds named illiverin A (1) and tashironin A (8) were isolated from the roots of Illicium verum, together with seven known compounds: 4-allyl-2-(3-methylbut-2-enyl)-1,6-methylenedioxybenzene-3-ol (2), illicinole (3), 3-hydroxy-4,5-methylenedioxyallyl-benzene (4), (-)-illicinone-A (5), 4-allyl-4-(3-methylbut-2-enyl)-1,2-methylenedioxycyclohexa-2,6-dien-5-one (6), 3,4-seco-(24 Z)- cycloart-4(28),24-diene-3,26-dioic acid, 26-methyl ester (7) and tashironin (9). Based on 1D- and 2D-NMR data (COSY, HMQC, HMBC), the structures of the new compounds were deduced to be (E)-1-[(3-methylbut-2-enyl)oxy]-2-methoxy-4-(prop-1-enyl)benzene (1) and 11-O-debenzoyl-11alpha-O-2-methylcyclopent-1-enecarboxyltashironin (8). Compounds 1-9 were screened for anti-HIV activity in vitro whereby compounds 5 and 7 possessed moderate anti-HIV activity with EC50 values of 16.0 and 5.1 microM with SI values of 18.2 and 15.6, respectively.

  13. Identification of a novel triterpenoid saponin from Pisum sativum as a specific inhibitor of the diguanylate cyclase of Acetobacter xylinum.

    PubMed

    Ohana, P; Delmer, D P; Carlson, R W; Glushka, J; Azadi, P; Bacic, T; Benziman, M

    1998-02-01

    A specific and highly potent inhibitor of diguanylate cyclase, the key regulatory enzyme of the cellulose synthesizing apparatus in the bacterium Acetobacter xylinum, was isolated from extracts of etiolated pea shoots (Pisum sativum). The inhibitor has been purified by a multistep procedure, and sufficient amounts of highly purified compound (3-8 mg) for spectral analysis were obtained. The structure of this compound was established as 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-galactopyranosyl-(1--> 2)-beta-D-glucuronopyranosyl soyasapogenol B 22-O-alpha-D-glucopyranoside. The structure was elucidated on the basis of susceptibility to various enzymes, chemical and spectral methods, such as GC-MS, FAB-MS, and the following types of 2D-NMR: COSY, ROESY, TOCSEY, HMQC, HMBC analyses. An identical or a very similar compound with identical biological activity was also isolated from A. xylinum, strongly suggesting that at least certain aspects of cellulose synthesis in the bacteria and in higher plants may be regulated in a similar manner. The content of this saponin in etiolated plants was about 0.04 mumol (g fresh tissue)-1.

  14. Unusual naphthoquinones, catechin and triterpene from Byrsonima microphylla.

    PubMed

    Aguiar, Rosane M; David, Juceni P; David, Jorge M

    2005-10-01

    The new triterpene Delta1-lupenone (1), together with lupeol, beta-amyrin and betulin were isolated from the wood of Byrsonima microphylla (Malpighiaceae). The new compounds 3-hydroxy-2-methoxy-8,8,10-trimethyl-8H-antracen-1,4,5-trione (2), 3,7-dihydroxy-2-methoxy-8,8,10-trimethyl-7,8-dihydro-6H-antracen-1,4,5-trione (3), (2S*,10aR*)-2,8-dihydroxy-6-methoxy-1,1,7-trimethyl-2,3,10, 10a-tetrahydro-1H-fenantren-9-one (4) and (2S,3S)-3'-hydroxy-4',5,7-trimethoxy-flavan-3-ol (5) were also isolated through monitored TLC using the antioxidant beta-carotene reagent. The antioxidant potential of the compounds 2-5 was measured and none of them showed activity. The structures of these compounds were elucidated by chemical and spectroscopic analysis based on NMR techniques (1H, 13C NMR, COSY, nOe difference, HMQC and HMBC), UV and MS.

  15. 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. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. Isolation and biological evaluation of N-(4-aminocyclooctyl)-3, 5-dinitrobenzamide, a new semisynthetic derivative from the Mangrove-associated actinomycete Pseudonocardia endophytica VUK-10.

    PubMed

    Mangamuri, Usha Kiranmayi; Vijayalakshmi, Muvva; Poda, Sudhakar; Manavathi, Bramanandam; Chitturi, Bhujangarao; Yenamandra, Venkateswarlu

    2016-12-01

    The present study was aimed to isolate novel bioactive compounds from actinomycetes species isolated from mangrove habitats. With this connection, Pseudonocardia endophytica (VUK-10) was isolated using dilution plate technique and was examined for its secondary metabolite profiling. After successive purification and spectroscopic characterization viz., FTIR, mass, NMR, DEPT, HMQC, HMBC, and COSY spectroscopy, two compounds were identified including a semi synthetic derivative N-(4-aminocyclooctyl)-3, 5-dinitrobenzamide (1), obtained from the precursor of novel natural product cyclooctane-1,4-diamine (3), along with a known compound 3-((1H-indol-6-yl) methyl) hexahydropyrrolo [1, 2-a] pyrazine-1, 4-dione (2). Anti cancer activities of the characterized compounds against in vitro cancerous cell line models, MDA-MB-231, OAW-42, HeLa, and MCF-7 reveal that HELA cells are most susceptible (IC 50 -10 nM compound 1 and 2) followed by other studied cells. On the other hand, antibacterial and antifungal activities of the studied compounds against tested pathogens revealed that there is a significant antimicrobial activity with all the tested bacterial and fungal species. Moreover, compound 1 showed the lowest MIC values against Streptococcus mutans as 4  and 16 µg/ml for Candida albicans. In conclusion, the identified novel chemical compounds in the present study may have a potential application in anticancer therapy as well as to mitigate the bacterial and fungal pathogens thus to control the infectious diseases.

  17. Synthesis and characterization of N,N'-bis[4-[1-(2-hidroxyethoxy)]salicylidine]-phenyldiamine-nickel(II)] complex

    NASA Astrophysics Data System (ADS)

    Shamsuddin, Roshatiara binti; Karim, Nurul Huda Abd

    2016-11-01

    N,N'-bis[4-[1-(2-hidroxyethoxy)]salicylidine]-phenyldiamine-nickel(II) complex has been synthesized by treating N,N'-bis-4-(hydroxysalicylidene)-phenylenediamine-nickel(II) complex with 2-chloroethanol and nickel(II) acetate tetrahydrate in ethanol solvent. The resulting complex formed was characterized using standard spectroscopic and structural techniques which includes 1H, 13C, COSY and HMQC NMR spectroscopy, FTIR spectroscopy and ESI-MS spectrometry. The 1H NMR spectrum displayed all the expected signals with right integration and multiplicity. The formation of Schiff base can be seen at 8.54 ppm for the formation of diimine and the disappearance of aldehyde peak at 9.88 ppm corresponding to the starting material confirms the full conversion. The presence of resonance peak at 3.76 ppm and 4.00 ppm corresponding to the ethyl group of the hydroxyl side chain also confirm the formation of the complex. The FTIR spectrum of the complex confirmed the expected C=N band at 1577 cm-1 and C-H for sp3 stretching band at 2878 cm-1. The formation of the new complex was also confirmed by ESI(+)-MS spectrometry, which showed the molecular peak with adduct ions at [M+K]+=531 a.m.u and [M+Na]+=515 a.m.u.

  18. 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…

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

    PubMed

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

    2012-09-01

    Two novel glucosinolates along with one known glucosinolate were isolated from Broccoli (Brassica oleracea L. var. italica) florets. Their structures were established mainly by 1D ((1)H and (13)C NMR), 2D NMR ((1)H-(1)H COSY, DEPT 135°, HSQC and HMBC), and Tandem MS-MS spectrometric data as 2-mercaptomethyl sulfinyl glucosinolate [(Z)-4-(methylsulfinyl)-N-(sulfooxy)-2-((2'S,3'R,4'S,5'S,6'R)-3',4',5'-trihydroxy-6'(hydroxylmethyl)-2'-mercapto tetrahydro-2H-pyran-2-yl) butane amide] 1, (Z)-1-((2S,5S)-5-hydroxytetra-hydro-2H-pyran-2-ylthio)-2-(1H-indol-3-yl) ethylidene amino sulfate 2 and a known cinnamoyl [6'-O-trans-(4″-hydroxy cinnamoyl)4-(methylsulphinyl)butyl glucosinolate] 3. Compound 1 exhibited scavenging activity against DPPH with an inhibitory concentration IC(50) of 20 mM, whereas compound 3 was a weak antioxidant when compared to the standard quercetin (5 mM) as a positive control. Both the compounds showed a significant and similar antimicrobial activity against Staphylococcus aureus with an IC(50) of <625 μg/mL when compared to antibiotic duricef. Against Salmonella typhimurium the IC(50) of 1 and 3 was determined as <625 μg/mL and <1250 μg/mL, respectively, when compared to ampicillin (IC(50) ≤ 39 μg/mL) as a positive control. Copyright © 2012 Elsevier Ltd. All rights reserved.

  20. NMR Metabolic profiling of green tea (Camellia sinensis L.) leaves grown at Kemuning, Indonesia

    NASA Astrophysics Data System (ADS)

    Wahyuni, D. S. C.; Kristanti, M. W.; Putri, R. K.; Rinanto, Y.

    2017-01-01

    Green tea (Camellia sinensis L.) has been famous as a beverage and natural medicine. It contains a broad range of primary and secondary metabolites i.e. polyphenols. Nuclear Magnetic Resonance (NMR) has been widely used for metabolic profiling in medicinal plants. It provides a very fast and detailed analysis of the biomolecular composition of crude extracts. Moreover, an NMR spectrum is a physical characteristic of a compound and thus highly reproducible. Therefore, this study aims to profile metabolites of three different varieties of green tea C. Sinensis grown in Kemuning, Middle Java. Three varieties of green tea collected on Kemuning (TR1 2025, Gambung 4/5, and Chiaruan 143) were used in this study. 1H-NMR spectra were recorded at 230C on a 400 MHz Agilent WB (Widebore). The analysis was performed on dried green tea leaves and analyzed by 1H-NMR, 2D-J-resolved and 1H-1H correlated spectroscopy (COSY). MestRenova version 11.0.0 applied to identify metabolites in samples. A 1H-NMR spectrum of tea showed amino acids and organic acids signal at the area δ 0.8-4.0. These were theanine, alanine, threonine, succinic acid, aspartic acid, lactic acid. Anomeric protons of carbohydrate were shown by the region of β-glucose, α-glucose, fructose and sucrose. The phenolic region was depicted at area δ 5.5-8.5. Epigallocatechin derivates and caffeine were detected in the tea leaves. The detail compound identification was observed and discussed in the text.

  1. A novel fatty acid, 12,17-dimethyloctadecanoic acid, from the extremophile Thermogemmatispora sp. (Strain T81).

    PubMed

    Vyssotski, M; Ryan, J; Lagutin, K; Wong, H; Morgan, X; Stott, M

    2012-06-01

    The major fatty acids of a novel species of Thermogemmatispora sp. (strain T81) from the phylum Chloroflexi were identified as i18:0 (42.8 % of total fatty acids), i19:0 (9.7 %), and i17:0 (5.9 %). Also observed was a number of unidentified fatty acids, including a major acid (16.3 %) with ECL of 19.04 (BP1), and 18.76 (TG-WAXMS A). GCMS revealed that this compound is a saturated 20-carbon atom fatty acid. (1)H- and (13)C-NMR, with (1)H-(1)H-COSY and (1)H-(13)C-HSQC experiments suggested the structure of dimethyl octadecanoic acid with iso-branching, and an extra middle-chain methyl group. A pyrrolidide derivative demonstrated the characteristic gaps in GCMS indicating methyl branching at C12 and C17, which was eventually confirmed by a (1)H-(13)C-HSQC-TOCSY experiment. This 12,17-dimethyloctadecanoic acid has not been previously detected or described in these organisms. However, a recent description of a phylogenetically related species of Thermogemmatispora (Yabe et al., Int J Syst Evol Microbiol 61:903-910, 2010), noted an unidentified 20:0 fatty acid with matching GC behavior and GCMS data to that of strain T81. These data suggest that Thermogemmatispora share an ability to synthesize the same fatty acid. A number of other dimethyl-branched fatty acids, namely 8,14-diMe 15:0; 12,15-diMe 16:0; 10,15-diMe 16:0; 12,16-diMe 17:0; 10,16-diMe 17:0; 12,17-diMe 18:0; 12,18-diMe 19:0; 14,19-diMe 20:0, were also identified in strain T81.

  2. 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.

  3. Metabolic profiling and biological activities of bioactive compounds produced by Pseudomonas sp. strain ICTB-745 isolated from Ladakh, India.

    PubMed

    Kamal, Ahmed; Shaik, Anver Basha; Kumar, C Ganesh; Mongolla, Poornima; Rani, P Usha; Krishna, K V S Rama; Mamidyala, Suman Kumar; Joseph, Joveeta

    2012-01-01

    In an ongoing survey of the bioactive potential of microorganisms from Ladakh, India, the culture medium of a bacterial strain of a new Pseudomonas sp., strain ICTB-745, isolated from an alkaline soil sample collected from Leh, Ladakh, India, was found to contain metabolites that exhibited broad-spectrum antimicrobial and biosurfactant activities. Bioactivity-guided purification resulted in the isolation of four bioactive compounds. Their chemical structures were elucidated by (1)H and (13)C NMR, 2D-NMR (HMBC, HSQC, (1)H,(1)H-COSY, and DEPT- 135), FT-IR, and mass spectroscopic methods, and were identified as 1-hydroxyphenazine, phenazine-1-carboxylic acid (PCA), rhamnolipid-1 (RL-1), and rhamnolipid-2 (RL-2). These metabolites exhibited various biological activities like antimicrobial and efficient cytotoxic potencies against different human tumor cell lines such as HeLa, HepG2, A549, and MDA MB 231. RL-1 and RL-2 exhibited a dose-dependent antifeedant activity against Spodoptera litura, producing about 82.06% and 73.66% antifeedant activity, whereas PCA showed a moderate antifeedant activity (63.67%) at 60 microgram/cm2 area of castor leaf. Furthermore, PCA, RL-1, and RL-2 exhibited about 65%, 52%, and 47% mortality, respectively, against Rhyzopertha dominica at 20 microgram/ml. This is the first report of rhamnolipids as antifeedant metabolites against Spodoptera litura and as insecticidal metabolites against Rhyzopertha dominica. The metabolites from Pseudomonas sp. strain ICTB-745 have interesting potential for use as a biopesticide in pest control programs.

  4. 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

    2016-02-08

    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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. NMR structure analysis of uniformly 13C-labeled carbohydrates.

    PubMed

    Fontana, Carolina; Kovacs, Helena; Widmalm, Göran

    2014-06-01

    In this study, a set of nuclear magnetic resonance experiments, some of them commonly used in the study of (13)C-labeled proteins and/or nucleic acids, is applied for the structure determination of uniformly (13)C-enriched carbohydrates. Two model substances were employed: one compound of low molecular weight [(UL-(13)C)-sucrose, 342 Da] and one compound of medium molecular weight ((13)C-enriched O-antigenic polysaccharide isolated from Escherichia coli O142, ~10 kDa). The first step in this approach involves the assignment of the carbon resonances in each monosaccharide spin system using the anomeric carbon signal as the starting point. The (13)C resonances are traced using (13)C-(13)C correlations from homonuclear experiments, such as (H)CC-CT-COSY, (H)CC-NOESY, CC-CT-TOCSY and/or virtually decoupled (H)CC-TOCSY. Based on the assignment of the (13)C resonances, the (1)H chemical shifts are derived in a straightforward manner using one-bond (1)H-(13)C correlations from heteronuclear experiments (HC-CT-HSQC). In order to avoid the (1) J CC splitting of the (13)C resonances and to improve the resolution, either constant-time (CT) in the indirect dimension or virtual decoupling in the direct dimension were used. The monosaccharide sequence and linkage positions in oligosaccharides were determined using either (13)C or (1)H detected experiments, namely CC-CT-COSY, band-selective (H)CC-TOCSY, HC-CT-HSQC-NOESY or long-range HC-CT-HSQC. However, due to the short T2 relaxation time associated with larger polysaccharides, the sequential information in the O-antigen polysaccharide from E. coli O142 could only be elucidated using the (1)H-detected experiments. Exchanging protons of hydroxyl groups and N-acetyl amides in the (13)C-enriched polysaccharide were assigned by using HC-H2BC spectra. The assignment of the N-acetyl groups with (15)N at natural abundance was completed by using HN-SOFAST-HMQC, HNCA, HNCO and (13)C-detected (H)CACO spectra.

  6. The Effect of Terminal Substitution on the Helical Carbon Structure of Fluoro-Alkane Chains: a Pure Rotational Study of CH2OH-Cn-1F2n-1 (n = 4, 5,& 6)

    NASA Astrophysics Data System (ADS)

    Schwartz, Aaron Z. A.; Maturo, Mark P.; Obenchain, Daniel A.; Cooke, S. A.

    2016-06-01

    Continuing a series of studies to investigate the change in structure of hydrocarbons as the amount of fluorination is increased to varying degrees of substitution, we present a survey on the change in the helical nature of the fluorinated carbon backbone when a -CH2OH group is substituted for a terminal - CF3 group. Spectra for 1H,1H-heptafluorobutan-1-ol, 1H,1H-nonafluoropentan-1-ol, and 1H,1H-undecafluorohexan-1-ol were collected separately using a chirped-pulse FTMW spectrometer in the range of 7-13 GHz. Only one conformation was observed for each molecule. Additional measurements of the 1H,1H-heptafluorobutan-1-ol were completed using a Balle-Flygare cavity instrument. Assignments of the singly-substituted 13C isotopologues of the 1H,1H-heptafluorobutan-1-ol were also measured. A comparison of both ab initio and experimental structures will be presented.

  7. NMR investigation and theoretical calculations of the solvent effect on the conformation of valsartan

    NASA Astrophysics Data System (ADS)

    Chashmniam, Saeed; Tafazzoli, Mohsen

    2017-11-01

    Structure and conformational properties of valsartan were studied by advanced NMR techniques and quantum calculation methods. Potential energy scanning using B3LYP/6-311++g** and B3LYP-D3/6-311++g** methods were performed and four conformers (V1-V4) at minimum points of PES diagram were observed. According to the NMR spectra in acetone-d6, there are two conformers (M and m) with m/M = 0.52 ratio simultaneously and energy barriers of the two conformers were predicted from chemical shifts and multiplicities. While, intramolecular hydrogen bond at tetrazole ring and carboxylic groups prevent the free rotation on N6sbnd C11 bond in M-conformer, this bond rotates freely in m-conformer. On the other hand, intramolecular hydrogen bond at carbonyl and carboxylic acid can be observed at m-conformer. So, different intramolecular hydrogen bond is the reason for the stability of both M and m structures. Quite interestingly, 1H NMR spectra in CDCl3 show two distinct conformers (N and n) with unequal ratio which are differ from M-m conformers. Also, intramolecular hydrogen bond seven-member ring involving five-membered tetrazole ring and carboxylic acid group observed in both N and n-conformers Solvent effect, by using a set of polar and non-polar solvents including DMSO-d6, methanol-d4, benzene-d6, THF-d8, nitromethane-d3, methylene chloride-d2 and acetonitrile-d3 were investigated. NMR parameters include chemical shifts and spin-spin coupling constants were obtained from a set of 2D NMR spectra (H-H COSY, HMQC and HMBC). For this purpose, several DFT functionals from LDA, GGA and hybrid categories were used which the hybrid method showed better agreement with experiment values.

  8. 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).

  9. Activity in vitro and in vivo against Trypanosoma cruzi of a furofuran lignan isolated from Piper jericoense.

    PubMed

    García-Huertas, Paola; Olmo, Francisco; Sánchez-Moreno, Manuel; Dominguez, Jorge; Chahboun, Rachid; Triana-Chávez, Omar

    2018-04-12

    Piperaceae species are abundant in the tropics and are important components of secondary vegetation. Many of these plants have received considerable attention due to their wide range of biological activities. Here, the trypanocidal activity of extracts and fractions with different polarities obtained from Colombian Piper jericoense plant was evaluated. A furofuran lignan, (1S,3aS,4S,6aS)-1-(3',4'-dimethoxyphenyl)-4-(3″,4″-methylendioxyphenyl)hexahydrofuro[3,4-c]furan, (1), was isolated from Colombian Piper jericoense leaves ethyl acetate extract. Its relative configuration at the stereogenic centers was established on the basis of various spectroscopic analyses, including 1D- (1H, 13C, and DEPT) and 2D-NMR (COSY, NOESY, HMQC and HMBC) and a 2D INADEQUATE NMR experiment as well as by comparison of their spectral data with those of related compounds such as (+)-Kobusin (2). The activity against Trypanosoma cruzi indicated that compound 1 was active against all parasite forms (epimastigote, amastigote and trypomastigote) and presented lower toxicity than the reference drug, benznidazole (Bz), evidenced by a selective index of 18.4 compared to that of Bz, which was 6.7. Moreover, this compound inhibited the infectious process, and it was active in infected mice in the acute phase. This compound significantly inhibited the T. cruzi Fe-SOD enzyme, whereas Cu/Zn-SOD from human cells was not affected. Ultrastructural analyses, together with metabolism-excretion studies in the parasite, were also performed to identify the possible mechanism of action of the tested compound. Interestingly, the lignan affected the parasite structure, but it did not alter the energetic metabolism. Copyright © 2018. Published by Elsevier Inc.

  10. 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.

  11. 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

  12. 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. Copyright © 2011 Elsevier Ltd. All rights reserved.

  13. Synthesis and Cytotoxic Activities of Difluoro-Dimethoxy Chalcones.

    PubMed

    Yamali, Cem; Gul, Halise Inci; Ozgun, Dilan Ozmen; Sakagam, Hiroshi; Umemura, Naoki; Kazaz, Cavit; Gul, Mustafa

    2017-01-01

    Although anticancer chemotherapeutics are available in markets, side effects related to the drugs in clinical use lead to researchers to investigate new drug candidates which are more safe, potent and selective than others. Chalcones are popular with their anticancer activities with the several reported mechanisms including inhibition of angiogenesis, inhibition of tubulin polymerization, and induction of apoptosis etc. This study was focused on to synthesize of 1-(2,4/2,6-difluorophenyl)-3-(2,3/2,4/2,5/3,4- dimethoxyphenyl)-2-propen-1-ones (1-8) and investigate their cytotoxic properties with possible mechanism of action. The compounds were synthesized by Claisen-Schmidt condensation. The chemical structures were confirmed by 1H NMR, 13C NMR, DEPT, COSY, HMQC, HMBC, 19F NMR and HRMS. In vitro cytotoxic effects of the compounds against human tumour cell lines [gingival carcinoma (Ca9-22), oral squamous cell carcinoma (HSC-2)] and human normal oral cells [gingival fibroblasts (HGF), periodontal ligament fibroblasts (HPLF)] were evaluated via MTT test. All compounds had higher cytotoxicity than reference compound 5-Fluorouracil (5-FU). The compounds 3-7 had higher potency selectivity expression values (PSE) than 5-FU and PSE values of the compounds were over 100. All chalcone derivatives seem good candidates for further studies according to very remarkable and high PSE values. It was clearly demonstrated that compound 7 can induce early apoptosis at a concentration of 10 µM and dose-dependent late apoptosis starting at 10 µM. Compound 7 induced cleavage of the apoptosis marker PARP. The results indicate that new chalcones reported here can promote apoptosis in human tumour cell lines. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  14. Identification of antimicrobial compound, diketopiperazines, from a Bacillus sp. N strain associated with a rhabditid entomopathogenic nematode against major plant pathogenic fungi.

    PubMed

    Nishanth Kumar, S; Mohandas, C; Siji, J V; Rajasekharan, K N; Nambisan, Bala

    2012-10-01

    To purify and characterize antimicrobial compounds from Bacillus sp. strain N associated with rhabditid entomopathogenic nematode (EPN). The cell-free culture filtrate of a bacterium associated with an 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 three diketopiperazines (DKPs). 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(l-Pro-l-Leu), cyclo(d-Pro-l-Leu) and cyclo(d-Pro-l-Tyr), respectively. Three DKPs were active against all the five fungi tested (Aspergillus flavus, Candida albicans, Fusarium oxysporum, Rhizoctonia solani and Penicillium expansum) and are more effective than the standard fungicide bavistin. The highest activity of 4 μg ml(-1) by cyclo(l-Pro-l-Leu) and cyclo(d-Pro-l-Tyr) was recorded against P. expansum, a plant pathogen responsible for causing postharvest decay of stored apples and oranges. Cyclo(d-Pro-l-Leu) recorded good antibacterial activity against all the four bacteria tested (Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa), and cyclo(l-Pro-l-Leu) and cyclo(d-Pro-l-Tyr) recorded good activity only against Gram-positive bacteria. To our knowledge, this is the first report of antifungal activity of the DKPs against the plant pathogenic fungi F. oxysporum, R. solani and P. expansum. The production of cyclo(l-Pro-l-Leu), cyclo(d-Pro-l-Leu) and cyclo-(d-Pro-l-Tyr) by a bacterium associated with EPN is also reported here for the first time. Isolated DKPs demonstrated high antimicrobial activity against bacteria and fungi, especially against plant pathogenic fungi. We conclude that the bacterium associated with EPN is a promising source of natural bioactive

  15. Anti-inflammatory sesquiterpenes from Costus speciosus rhizomes.

    PubMed

    Al-Attas, Ahmed A M; El-Shaer, Nagwa S; Mohamed, Gamal A; Ibrahim, Sabrin R M; Esmat, Ahmed

    2015-12-24

    Costus speciosus (Koen ex. Retz.) Sm. (crepe ginger, family Costaceae) is an ornamental plant used in traditional medicine for the treatment of inflammation, rheumatism, bronchitis, fever, headache, asthma, flatulence, constipation, helminthiasis, leprosy, skin diseases, hiccough, anemia, as well as burning sensation on urination. The present study is designed to isolate and identify the active compounds from C. speciosus rhizomes and measure their anti-inflammatory activities. The n-hexane-CHCl3 soluble fraction of the MeOH extract of C. speciosus rhizomes has been subjected to a repeated column chromatography, including normal silica gel and RP-18 column to give eight compounds. The structures of these compounds were established by UV, IR, 1D ((1)H and (13)C), and 2D ((1)H-(1)H COSY, NOESY, HSQC, and HMBC) NMR experiments and HRESIMS data. In addition, the anti-inflammatory activity of compounds 1-8 was evaluated by measuring the levels IL-6, IL-1β, TNF-α, COX-2, lipoxgenase-5, and PGE2 using enzyme-linked immunosorbent assay. The n-hexane-CHCl3 soluble fraction afforded a new eudesmane acid, specioic acid (8), along with seven known compounds, 22,23-dihydrospinasterone (1), dehydrodihydrocostus lactone (mokko lactone) (2), dehydrocostus lactone (3), stigmasterol (4), arbusculin A (5), santamarine (douglanin) (6), and reynosin (7). Compounds 1, 4, and 5-7 were isolated for the first time C. speciosus. Compounds 1-4 displayed potent anti-inflammatory activity, while 7 and 8 showed moderate activity. Compounds 1-8 exhibited a concentration-related decrease in the levels of IL-1β, IL-6, TNF-α, PGE2, lipoxgenase-5, and COX-2. Compounds 5 and 6 did not significantly decrease levels of different cytokines, PGE2, lipoxgenase-5, and COX-2 from PHA treatment at 1 µM. However, all tested compounds significantly decreased cytokines, PGE2, lipoxgenase-5, and COX-2 levels at concentration 100 µM. It is noteworthy that compounds 1-4 had the highest activity, where it

  16. Synthesis and study of the spectroscopic and redox properties of Ru(II),Pt(II) mixed-metal complexes bridged by 2,3,5,6-tetrakis(2-pyridyl)pyrazine.

    PubMed

    Zhao, Shengliang; Arachchige, Shamindri M; Slebodnick, Carla; Brewer, Karen J

    2008-07-21

    The mixed-metal supramolecular complexes [(tpy)Ru(tppz)PtCl](PF6)3 and [ClPt(tppz)Ru(tppz)PtCl](PF6)4 (tpy = 2,2':6',2''-terpyridine and tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine) were synthesized and characterized. These complexes contain ruthenium bridged by tppz to platinum centers to form stereochemically defined linear assemblies. X-ray crystallographic determinations of the two complexes confirm the identity of the metal complexes and reveal intermolecular interactions of the Pt sites in the solid state for [(tpy)Ru(tppz)PtCl](PF6)3 with a Pt...Pt distance of 3.3218(5) A. The (1)H NMR spectra show the expected splitting patterns characteristic of stereochemically defined mixed-metal systems and are assigned with the use of (1)H-(1)H COSY and NOESY. Electronic absorption spectroscopy displays intense ligand-based pi --> pi* transitions in the UV and MLCT transitions in the visible. Electrochemically [(tpy)Ru(tppz)PtCl](PF6)3 and [ClPt(tppz)Ru(tppz)PtCl](PF6)4 display reversible Ru (II/III) couples at 1.63 and 1.83 V versus Ag/AgCl, respectively. The complexes display very low potential tppz (0/-) and tppz(-/2-) couples, relative to their monometallic synthons, [(tpy)Ru(tppz)](PF6)2 and [Ru(tppz)2](PF6)2, consistent with the bridging coordination of the tppz ligand. The Ru(dpi) --> tppz(pi*) MLCT transitions are also red-shifted relative to the monometallic synthons occurring in the visible centered at 530 and 538 nm in CH3CN for [(tpy)Ru(tppz)PtCl](PF6)3 and [ClPt(tppz)Ru(tppz)PtCl](PF6)4, respectively. The complex [(tpy)Ru(tppz)PtCl](PF6)3 displays a barely detectable emission from the Ru(dpi) --> tppz(pi*) (3)MLCT in CH 3CN solution at RT. In contrast, [ClPt(tppz)Ru(tppz)PtCl](PF6)4 displays an intense emission from the Ru(dpi) --> tppz(pi*) (3)MLCT state at RT with lambda max(em) = 754 nm and tau = 80 ns.

  17. Synthesis and phototoxicity of isomeric 7,9-diglutathione pyrrole adducts: Formation of reactive oxygen species and induction of lipid peroxidation.

    PubMed

    Ma, Liang; Zhao, Hengqiang; Xia, Qingsu; Cai, Lining; Fu, Peter P

    2015-09-01

    Pyrrolizidine alkaloids (PAs) are hepatotoxic, genotoxic, and carcinogenic in experimental animals. Because of their widespread distribution in the world, PA-containing plants are probably the most common poisonous plants affecting livestock, wildlife, and humans. Upon metabolism, PAs generate reactive dehydro-PAs and other pyrrolic metabolites that lead to toxicity. Dehydro-PAs are known to react with glutathione (GSH) to form 7-GSH-(+/-)-6,7-dihydro-7-hydroxy-1-hydroxymethyl-5H-pyrrolizine (7-GS-DHP) in vivo and in vitro and 7,9-diGS-DHP in vitro. To date, the phototoxicity of GS-DHP adducts has not been well studied. In this study, we synthesized 7-GS-DHP, a tentatively assigned 9-GS-DHP, and two enantiomeric 7,9-diGS-DHP adducts by reaction of dehydromonocrotaline with GSH. The two 7,9-diGS-DHPs were separated by high performance liquid chromatography (HPLC) and their structures were characterized by 1 H nuclear magnetic resonance (NMR) and 1 H -1 H correlation spectroscopy (COSY) NMR spectral analysis. Photoirradiation of 7-GS-DHP, 9-GS-DHP, and the two 7,9-diGS-DHPs as well as dehydromonocrotaline, dehydroheliotrine, and the 7-R enantiomer of DHP (DHR), by UVA light at 0 J/cm 2 , 14 J/cm 2 , and 35 J/cm 2 in the presence of a lipid, methyl linoleate, all resulted in lipid peroxidation in a light dose-responsive manner. The levels of lipid peroxidation induced by the two isomeric 7,9-diGS-DHPs were significantly higher than that by 7-GS-DHP and 9-GS-DHP. When 7,9-diGS-DHP was irradiated in the presence of sodium azide (NaN 3 ), the level of lipid peroxidation decreased; lipid peroxidation was enhanced when methanol was replaced by deuterated methanol. These results suggest that singlet oxygen is a product induced by the irradiation of 7,9-diGS-DHP. When irradiated in the presence of superoxide dismutase (SOD), the level of lipid peroxidation decreased, indicating that lipid peroxidation is also mediated by superoxide. These results indicate that lipid

  18. Observation and relaxation properties of individual fast-relaxing proton transitions in [13CH3]-methyl-labeled, deuterated proteins

    NASA Astrophysics Data System (ADS)

    Sun, Hechao; Tugarinov, Vitali

    2012-04-01

    A pair of NMR experiments is developed for separation of individual fast-relaxing transitions in 13CH3 methyl groups of methyl-protonated, highly deuterated proteins, and the measurement of their relaxation rates. Intra-methyl 1H-1H/1H-13C dipole-dipole cross-correlated spin relaxation that differentiates the rates of the fast-relaxing transitions depending on the state of 13C spins, is measured in the selectively [13CH3]-methyl-labeled, deuterated ubiquitin at 10, 27, and 40 °C. In contrast with previous observations, the 1H-1H/1H-13C cross-correlated relaxation rates measured from relaxation rates of single-quantum proton transitions serve as good measures of side-chain order even in proteins with global rotational correlation times significantly less than 10 ns.

  19. Neuroprotective Properties of Compounds Extracted from Dianthus superbus L. against Glutamate-induced Cell Death in HT22 Cells.

    PubMed

    Yun, Bo-Ra; Yang, Hye Jin; Weon, Jin Bae; Lee, Jiwoo; Eom, Min Rye; Ma, Choong Je

    2016-01-01

    ) 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.

  20. Anti-inflammatory activity of a new cyclic peptide, citrusin XI, isolated from the fruits of Citrus unshiu.

    PubMed

    Noh, Hyung Jun; Hwang, Dukhyun; Lee, Eun Suk; Hyun, Jae Wook; Yi, Pyoung Ho; Kim, Geum Soog; Lee, Seung Eun; Pang, Changhyun; Park, Yong Joo; Chung, Kyu Hyuck; Kim, Gun Do; Kim, Ki Hyun

    2015-04-02

    Citrus unshiu (Rutaceae) is an easy-peeling citrus fruit, which has been used as a traditional Korean medicine for improving skin elasticity, relieving fatigue and cough, and preventing bronchitis, flu, and various cancers. However, its active components associated with anti-inflammation and underlying mechanisms remain unknown. In this study, we investigated the active constituents from the fruits of Citrus unshiu and evaluated the anti-inflammatory activity in order to support the traditional usage of Citrus unshiu. Repeated column chromatography, together with a semi-preparative HPLC purification was used to separate the bioactive constituent from the EtOAc soluble fraction of the EtOH extract of Citrus unshiu fruits. Anti-inflammatory effects of the isolated compounds on lipopolysaccharide (LPS)-induced production of pro-inflammatory mediators were examined using RAW264.7 macrophage cells. A new cyclic peptide, citrusin XI (1), was isolated and identified from the fruits of Citrus unshiu. The structure of compound 1 was elucidated by spectroscopic analysis, including 1D and 2D nuclear magnetic resonance (NMR) ((1)H, (13)C, COSY, HMQC and HMBC experiments), and high resolution (HR)-mass spectrometry, and its absolute configurations were further confirmed by the Marfey׳s method. Compound 1 decreased NO production in LPS-stimulated RAW264.7 cells in a dose-dependent manner with an IC50 value of 70μM. Compound 1 suppressed NO production by decreasing iNOS expression but COX-2 expression was slightly associated with the reduction by compound 1 in LPS-induced RAW264.7 cells. Furthermore, compound 1 inhibited NF-κB activation by blocking IκBα degradation and NF-κB phosphorylation in LPS-stimulated RAW264.7 cells. These results indicate that a new cyclic peptide, citrusin XI, from Citrus unshiu fruits has anti-inflammatory properties that inhibit the release of pro-inflammatory mediators. Compound 1 decreases NO production by decreasing iNOS expression and NF

  1. Methicillin-resistant Staphylococcus aureus, vancomycin-resistant Enterococcus faecalis and Enterococcus faecium active dimeric isobutyrylphloroglucinol from Ivesia gordonii.

    PubMed

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

    2014-02-01

    Bioassay-guided fractionation of the chloroform soluble fraction of stem, leaf, 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 ofivesinol (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 ROESYexperiments, as well as mass spectrometry. 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 microg/mL and 0.05/0.31/>20 microg/mL, respectively (vs. IC50/MIC/MBC 0.13/0.5/1.0 microg/mL and 0.13/0.5/1.0 microg/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/MlC/MBC values of 0.22/1.25/>20 microg/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 the 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; 2,4-diacetylphloroglucinol (5) showed potent activity, like 1, against SA, MRSA, and VRE (ATCC 700221) with IC50/MIC values of 0.3/2.5, 0.23/2.5, and 0.86/2.5 microg/mL, respectively, while 4 was inactive.

  2. 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

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

    USDA-ARS?s Scientific Manuscript database

    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) ...

  4. 1H Photo-CIDNP Enhancements in Heteronuclear Correlation NMR Spectroscopy

    PubMed Central

    Sekhar, Ashok; Cavagnero, Silvia

    2009-01-01

    Photochemically induced dynamic nuclear polarization (photo-CIDNP) is usually employed as a probe of solvent exposure, in biomolecular NMR. The potential of the photo-CIDNP effect for sensitivity enhancement, however, remains poorly explored. Here, we introduce 1H-photo-CIDNP in heteronuclear correlation spectroscopy at low laser irradiation power (1 W), and compare the sensitivity of various 1H-Photo-CIDNP-enhanced- (HPE) 1H◻15N heteronuclear correlation pulse sequences, including HSQC, HMQC, and SOFAST-HMQC, in terms of their ability to detect the Trp indole Hε1 resonance. Both Trp and the Trp-containing protein apoHmpH were analyzed using flavin mononucleotide as photosensitizer in aqueous solutions either containing or lacking urea. We find that 1H◻15N photo-CIDNP-SOFAST-HMQC, denoted here as HPE-SOFAST-HMQC, yields a two-fold higher signal-to-noise per unit time than the parent SOFAST-HMQC for the solvent-exposed Trp of urea-unfolded apoHmpH. Thus, HPE-SOFAST-HMQC is the most sensitive heteronuclear correlation pulse sequence for the detection of solvent-exposed Trp. PMID:19462951

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

    PubMed

    Zhang, Rongchun; Nishiyama, Yusuke; Ramamoorthy, Ayyalusamy

    2015-10-28

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

  6. 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.

  7. 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

    1996-11-06

    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

  8. Mechanism of adenylate kinase. The "essential lysine" helps to orient the phosphates and the active site residues to proper conformations.

    PubMed

    Byeon, L; Shi, Z; Tsai, M D

    1995-03-14

    Although how Lys21 interacts with the substrate MgATP of muscle adenylate kinase (AK) can now be deduced from the crystal structure of Escherichia coli AK.MgAP5A [P1,P5-bis(5'-adenosyl) pentaphosphate] [Müller, C. W., & Schulz, G. E. (1992) J. Mol. Biol. 224, 159-177], its contribution to catalysis has not yet been demonstrated by functional studies since the proton NMR of the K21M mutant was shown to be perturbed significantly [Tian, G., Yan., H., Jiang, R.-T., Kishi, F., Nakazawa, A., & Tsai, M.-D. (1990) Biochemistry 29, 4296-4304]. We therefore undertook further structural and functional analyses of a conservative mutant K21R and a nonconservative mutant K21A. In addition to kinetic analyses, the structures of the mutants were analyzed by one- and two-dimensional proton NMR spectroscopy and (1H, 15N) heteronuclear multiple-quantum coherence (HMQC) experiments. Detailed assignments were performed in reference to the total backbone assignments of the WT AK.MgAP5A complex [Byeon, I.-J. L., Yan, H., Edison, A. S., Mooberry, E. S., Abildgaard, F., Markley, J. L., & Tsai, M.-D. (1993) Biochemistry 32, 12508-12521]. The analysis showed that the residues located near the active site (Gly15, Thr23, Arg97, Gln101, Arg128, Arg132, Asp140, Asp141, and Tyr153) exhibit greater changes in 1H-15N chemical shifts. Finally, two-dimensional 31P-31P COSY experiments were used to examine the effects of the lysine side chain on the phosphate groups in the bound AP5A. Our data have led to the following conclusions independent of the crystal structure: (i) Because the perturbations in the conformation of the mutants are not global and are mainly localized at active site residues and Tyr153, the side chain of Lys21 can be concluded to stabilize the transition state in the catalysis of AK by up to 7 kcal/mol on the basis of the 10(5)-fold decreases in the kcat/Km of mutants. (ii) The results of 31P NMR analyses suggest that Lys21 functions by orienting the triphosphate chain of Mg

  9. 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. Copyright © 2014 John Wiley & Sons, Ltd.

  10. Simulation of the off-resonance effect in one-dimensional heteronuclear multiple quantum coherence spectroscopy

    NASA Astrophysics Data System (ADS)

    Du, Fei; Zhou, Zhifa; Miao, Xijia; Mao, Xi-an

    2000-03-01

    When a heteronuclear multiple quantum coherence (HMQC) NMR experiment is performed in one-dimensional mode, due to the wide range in chemical shift of the indirectly detected spin and the limited strength of the radio-frequency field, the off-resonance effect on the intensity of the observed signal can be serious. In this paper, the effect is studied using the spin-density-matrix formalism and simulations of the experimental results are presented. The bilinear rotation-decoupling sequence (BIRD), which is usually used in HMQC experiments, is also discussed. It is shown that the BIRD sequence has a negative effect by virtue of narrowing the excitation band.

  11. Spectral analysis of the Crab Nebula and GRB 160530A with the Compton Spectrometer and Imager

    NASA Astrophysics Data System (ADS)

    Sleator, Clio; Boggs, Steven E.; Chiu, Jeng-Lun; Kierans, Carolyn; Lowell, Alexander; Tomsick, John; Zoglauer, Andreas; Amman, Mark; Chang, Hsiang-Kuang; Tseng, Chao-Hsiung; Yang, Chien-Ying; Lin, Chih H.; Jean, Pierre; von Ballmoos, Peter

    2017-08-01

    The Compton Spectrometer and Imager (COSI) is a balloon-borne soft gamma-ray (0.2-5 MeV) telescope designed to study astrophysical sources including gamma-ray bursts and compact objects. As a compact Compton telescope, COSI has inherent sensitivity to polarization. COSI utilizes 12 germanium detectors to provide excellent spectral resolution. On May 17, 2016, COSI was launched from Wanaka, New Zealand and completed a successful 46-day flight on NASA’s new Superpressure balloon. To perform spectral analysis with COSI, we have developed an accurate instrument model as required for the response matrix. With carefully chosen background regions, we are able to fit the background-subtracted spectra in XSPEC. We have developed a model of the atmosphere above COSI based on the NRLMSISE-00 Atmosphere Model to include in our spectral fits. The Crab and GRB 160530A are among the sources detected during the 2016 flight. We present spectral analysis of these two point sources. Our GRB 160530A results are consistent with those from other instruments, confirming COSI’s spectral abilities. Furthermore, we discuss prospects for measuring the Crab polarization with COSI.

  12. (1)H, (13)C and (15)N NMR assignments for N- and O-acylethanolamines, important family of naturally occurring bioactive lipid mediators.

    PubMed

    Ottria, Roberta; Casati, Silvana; Ciuffreda, Pierangela

    2012-12-01

    The complete (1)H, (13)C and (15)N NMR signal assignments of some N- and O-acylethanolamines, important family of naturally occurring bioactive lipid mediators, were achieved using one-dimensional and two-dimensional experiments (gs-HMQC and gs-HMBC). Copyright © 2012 John Wiley & Sons, Ltd.

  13. Improved Performance Accordion Heteronuclear Multiple-Bond Correlation Spectroscopy—IMPEACH-MBC

    NASA Astrophysics Data System (ADS)

    Hadden, Chad E.; Martin, Gary E.; Krishnamurthy, V. V.

    1999-09-01

    A modification of the recently reported ACCORD-HMBC long-range heteronuclear shift correlation experiment is described. The new experiment, IMPEACH-MBC (improved performance accordion heteronuclear multiple-bond correlation), introduces a new pulse sequence element, a constant time variable delay. The incorporation of the constant time variable delay into the IMPEACH-MBC sequence suppresses 1H-1H coupling modulation inherent to the utilization of the accordion principle to sample a broad range of potential long-range heteronuclear couplings. 1H-1H coupling modulation, which introduces an F1 modulation or a "skew" of responses in the second frequency domain of the ACCORD-HMBC experiment, is suppressed in the IMPEACH-MBC experiment. Results of identically optimized IMPEACH-MBC and ACCORD-HMBC experiments performed on a sample of strychnine are compared.

  14. Rapid measurement of multidimensional 1H solid-state NMR spectra at ultra-fast MAS frequencies

    NASA Astrophysics Data System (ADS)

    Ye, Yue Qi; Malon, Michal; Martineau, Charlotte; Taulelle, Francis; Nishiyama, Yusuke

    2014-02-01

    A novel method to realize rapid repetition of 1H NMR experiments at ultra-fast MAS frequencies is demonstrated. The ultra-fast MAS at 110 kHz slows the 1H-1H spin diffusion, leading to variations of 1H T1 relaxation times from atom to atom within a molecule. The different relaxation behavior is averaged by applying 1H-1H recoupling during relaxation delay even at ultra-fast MAS, reducing the optimal relaxation delay to maximize the signal to noise ratio. The way to determine optimal relaxation delay for arbitrary relaxation curve is shown. The reduction of optimal relaxation delay by radio-frequency driven recoupling (RFDR) was demonstrated on powder samples of glycine and ethenzamide with one and multi-dimensional NMR measurements.

  15. 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.

  16. High-resolution 1H homonuclear dipolar recoupling NMR spectra of biological solids at MAS rates up to 67 kHz

    NASA Astrophysics Data System (ADS)

    Mafra, Luis; Siegel, Renée; Fernandez, Christian; Schneider, Denis; Aussenac, Fabien; Rocha, João

    2009-07-01

    Two-dimensional 1H homonuclear correlation NMR spectra of solids of biological interest have been recorded at high magnetic fields (14.1 and 18.8 T) and MAS rates up to 67 kHz, using RNnν symmetry-based homonuclear recoupling and CRAMPS decoupling; this method affords exceptional spectral resolution and is well suited to probe 1H- 1H proximities in powdered solids.

  17. Fluorous synthesis of disubstituted pyrimidines

    PubMed Central

    Zhang, Wei

    2007-01-01

    The fluorous synthesis of disubstituted pyrimidines is carried out by attaching 2,4-dichloro-6-methylpyrimidine with 1H,1H,2H,2H-perfluorodecanethiol. The tagged substrate is substituted with 3-(trifluoromethyl)pyrazole followed by thioether oxidation and tag displacement with amines and thiols. The fluorous ponytail serves as a phase tag for intermediate and product purification over FluoroFlash™ SPE cartridges. PMID:12659561

  18. Fluorous synthesis of disubstituted pyrimidines.

    PubMed

    Zhang, Wei

    2003-04-03

    [reaction: see text] The fluorous synthesis of disubstituted pyrimidines is carried out by attaching 2,4-dichloro-6-methylpyrimidine with 1H,1H,2H,2H-perfluorodecanethiol. The tagged substrate is substituted with 3-(trifluoromethyl)pyrazole followed by thioether oxidation and tag displacement with amines or thiols. The fluorous chain serves as a phase tag for intermediate and product purification over FluoroFlash SPE cartridges.

  19. 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

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

    PubMed

    Kotler, Samuel A; Brender, Jeffrey R; Vivekanandan, Subramanian; Suzuki, Yuta; Yamamoto, Kazutoshi; Monette, Martine; Krishnamoorthy, Janarthanan; Walsh, Patrick; Cauble, Meagan; Holl, Mark M Banaszak; Marsh, E Neil G; Ramamoorthy, Ayyalusamy

    2015-07-03

    Alzheimer's disease is characterized by the misfolding and self-assembly of the amyloidogenic protein amyloid-β (Aβ). The aggregation of Aβ leads to diverse oligomeric states, each of which may be potential targets for intervention. Obtaining insight into Aβ oligomers at the atomic level has been a major challenge to most techniques. Here, we use magic angle spinning recoupling (1)H-(1)H NMR experiments to overcome many of these limitations. Using (1)H-(1)H dipolar couplings as a NMR spectral filter to remove both high and low molecular weight species, we provide atomic-level characterization of a non-fibrillar aggregation product of the Aβ1-40 peptide using non-frozen samples without isotopic labeling. Importantly, this spectral filter allows the detection of the specific oligomer signal without a separate purification procedure. In comparison to other solid-state NMR techniques, the experiment is extraordinarily selective and sensitive. A resolved 2D spectra could be acquired of a small population of oligomers (6 micrograms, 7% of the total) amongst a much larger population of monomers and fibers (93% of the total). By coupling real-time (1)H-(1)H NMR experiments with other biophysical measurements, we show that a stable, primarily disordered Aβ1-40 oligomer 5-15 nm in diameter can form and coexist in parallel with the well-known cross-β-sheet fibrils.

  1. Growth of cobalt and cobalt disilicide on Si(100)

    NASA Astrophysics Data System (ADS)

    Gallego, J. M.; Miranda, R.; Molodtsov, S.; Laubschat, C.; Kaindl, G.

    1990-12-01

    The growth of Co on Si(100) and the initial stages of the formation of cobalt suicides have been studied by means of a multitechnique approach. Adsorption of Co on Si(100) at room temperature does not result in reaction and formation of a few ML-thick CoSi 2 overlayer, contrary to adsorption on (111) surfaces. Rather, a layer-by-layer growth of metallic Co with some Si interdiffused is observed. The formation of CoSi 2 requires annealing to 350°C, a temperature much lower than in the (111) surface. Annealing to 600° C results in additional Si-enrichment at the surface produced by disruption of the CoSi 2 overlayer. The thin CoSi 2 "template" layer, which is crucial to achieve epitaxial growth, contains Si at the outer surface, as demonstrated by chemical titration.

  2. Cobalt silicide formation caused by arsenic ion beam mixing and rapid thermal annealing

    NASA Astrophysics Data System (ADS)

    Ye, Min; Burte, Edmund; Tsien, Pei-Hsin; Ryssel, Heiner

    1991-04-01

    Ion beam mixing and rapid thermal annealing (RTA) were used to prepare low resistivity (≈ 23 μΩ cm) cobalt disilicide, CoSi 2, layers. Through-metal As + ion implantation causes some mixing between Co and Si resulting in the formation of cobalt suicides. By using RTA, the silicide formation happens in the phase sequence Co 2Si, CoSi and CoSi 2. Samples which were only subjected to a one-step high temperature RTA process ( T ≥. 900°C, 1s) show significant lateral growth of cobalt suicides. By ion beam mixing of Co and Si this lateral silicide growth could be reduced efficiently. Furthermore one can get a very homogeneous CoSi 2 layer.

  3. Subsurface Growth Of Silicide Structures In Silicon

    NASA Technical Reports Server (NTRS)

    Fathauer, Robert W.; George, Thomas; Pike, William T.; Schowalter, Leo

    1993-01-01

    Technique shows promise for fabrication of novel electronic, optoelectronic, and electro-optical devices. Experiments demonstrated feasibility of growing microscopic single-crystal CoSi2 structures beneath surfaces of Si substrates.

  4. Phase transformations in ion-irradiated silicides

    NASA Technical Reports Server (NTRS)

    Hewett, C. A.; Lau, S. S.; Suni, I.; Hung, L. S.

    1985-01-01

    The present investigation has three objectives. The first is concerned with the phase transformation of CoSi2 under ion implantation and the subsequent crystallization characteristics during annealing, taking into account epitaxial and nonepitaxial recrystallization behavior. The second objective is related to a study of the general trend of implantation-induced damage and crystallization behavior for a number of commonly used silicides. The last objective involves a comparison of the recrystallization behavior of cosputtered refractory silicides with that of the ion-implanted silicides. It was found that epitaxial regrowth of ion-irradiated CoSi2 occurred for samples with an epitaxial seed left at the Si/CoSi2 interface. A structural investigation of CoSi2 involving transmission electron microscopy (TEM) showed that after high-dose implantation CoSi2 is amorphous.

  5. Polarimetric Analysis of the Long Duration Gamma-Ray Burst GRB 160530A With the Balloon Borne Compton Spectrometer and Imager

    NASA Astrophysics Data System (ADS)

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

    2017-10-01

    A long duration gamma-ray burst, GRB 160530A, was detected by the Compton Spectrometer and Imager (COSI) during the 2016 COSI Super Pressure Balloon campaign. As a Compton telescope, COSI is inherently sensitive to the polarization of gamma-ray sources in the energy range 0.2-5.0 MeV. We measured the polarization of GRB 160530A using (1) a standard method (SM) based on fitting the distribution of azimuthal scattering angles with a modulation curve and (2) an unbinned, maximum likelihood method (MLM). In both cases, the measured polarization level was below the 99% confidence minimum detectable polarization levels of 72.3% ± 0.8% (SM) and 57.5% ± 0.8% (MLM). Therefore, COSI did not detect polarized gamma-ray emission from this burst. Our most constraining 90% confidence upper limit on the polarization level was 46% (MLM).

  6. Field electron emission based on resonant tunneling in diamond/CoSi2/Si quantum well nanostructures

    PubMed Central

    Gu, Changzhi; Jiang, Xin; Lu, Wengang; Li, Junjie; Mantl, Siegfried

    2012-01-01

    Excellent field electron emission properties of a diamond/CoSi2/Si quantum well nanostructure are observed. The novel quantum well structure consists of high quality diamond emitters grown on bulk Si substrate with a nanosized epitaxial CoSi2 conducting interlayer. The results show that the main emission properties were modified by varying the CoSi2 thickness and that stable, low-field, high emission current and controlled electron emission can be obtained by using a high quality diamond film and a thicker CoSi2 interlayer. An electron resonant tunneling mechanism in this quantum well structure is suggested, and the tunneling is due to the long electron mean free path in the nanosized CoSi2 layer. This structure meets most of the requirements for development of vacuum micro/nanoelectronic devices and large-area cold cathodes for flat-panel displays. PMID:23082241

  7. Magnetooptical properties of iron based Heusler alloy epitaxial films on Ge(111)

    NASA Astrophysics Data System (ADS)

    Maeda, Yoshihito; Ikeda, Tatsuya; Ichikawa, Takayuki; Nakajima, Takahito; Matsukura, Bui; Sadoh, Taizoh; Miyao, Masanobu

    We have examined the LMOKE of some Heusler alloy films Fe4Si, Fe3Si, Fe2CoSi, Fe2MnSi (21 at and 9 at.%Mn), Co2FeSi epitaxially grown on Ge(111) and found that Fe3Si, Fe4Si and Fe2CoSi films have larger Kerr rotation and smaller coercive fields than the amorphous Fe film and that they may be promising materials for magnetophotonic applications.

  8. Two-dimensional NMR spectroscopy in Earth's magnetic field.

    PubMed

    Robinson, Jeremy N; Coy, Andrew; Dykstra, Robin; Eccles, Craig D; Hunter, Mark W; Callaghan, Paul T

    2006-10-01

    We demonstrate the first two-dimensional correlation NMR (COSY) spectra obtained at ultra low frequencies (ULF) using the Earth's magnetic field. Using a specially developed spectrometer with multiple audio-frequency pulses under controlled pulse phase, we observe magnetisation transfer arising from heteronuclear J-couplings in trifluoroethanol and para-difluorobenzene. The 2D COSY spectra exhibit all diagonal and off-diagonal multiplets consistent with known J-couplings in these molecules.

  9. In Situ Study of the Formation of Silicide Phases in Amorphous Co–Si Mixed Layers

    SciTech Connect

    Van Bockstael, C.; De Keyser, K; Demeulemeester, J

    2010-01-01

    We investigate Co silicide phase formation when extra Si is added within an as deposited 50 nm Co film. The addition of Si is investigated for both the Co/SiO{sub 2} and Co/Si(1 0 0) system. A series of 10 Co-Si mixed films with a Si content varying from 21 to 59 at.% was prepared and investigated during annealing with in situ X-ray diffraction. The oxide system is used as reference system to identify phases that initially crystallize in an amorphous mixture of a given composition. Multiple phases can nucleate, and the temperature of crystallization depends on the Co-Si atomic ratio.more » Upon heating of the Co(Si)/Si system, the first reaction is a similar crystallization reaction of the Co(Si) mixture. Once the first phase is formed, one has the normal system of a silicide phase in contact with an unlimited amount of Si from the substrate, and the sequential phase formation towards CoSi{sub 2} is established. For deposited layers of composition ranging from 48%Si to 52%Si, the CoSi is the first phase to form and increasing the amount of Si leads to a remarkable improvement of the thermal stability of CoSi on Si(1 0 0). CoSi{sub 2} nucleation was extensively delayed by 150 C compared to the reaction observed from a pure Co film on Si(1 0 0). Electron backscatter diffraction measurements reveal that in this range, the gradual Si increase systematically leads to bigger CoSi grains (up to 20 {micro}m). This shows that the grain size of the CoSi precursor strongly affects the nucleation of the following CoSi{sub 2} phase. Laser-light scattering measurements suggest that adding more than 42%Si reduces the roughness of the CoSi{sub 2} layer.« less

  10. 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.

  11. Large-area Co-silicide nanodot arrays produced by colloidal nanosphere lithography and thermal annealing.

    PubMed

    Cheng, S L; Wong, S L; Lu, S W; Chen, H

    2008-09-01

    We report here the successful fabrication of large-area size-tunable periodic arrays of cobalt and Co-silicide nanodots on silicon substrates by employing the colloidal nanosphere lithography (NSL) technique and heat treatments. The growth of low-resistivity epitaxial CoSi(2) was found to be more favorable for the samples with smaller Co nanodot sizes. The sizes of the epitaxial CoSi(2) nanodots can be tuned from 50 to 100 nm by varying the diameter of the colloidal spheres and annealing temperatures. The epitaxial CoSi(2) nanodots were found to grow with an epitaxial orientation with respect to the (001)Si substrates: [001]CoSi(2)//[001]Si and (200)CoSi(2)//(400)Si. From the results of planview HRTEM, XTEM, and SAED analysis, the epitaxial CoSi(2) nanodots were identified to be inverse pyramids in shape, and the average sizes of the faceted silicide nanodots were measured to decrease with annealing temperature. The observed results present the exciting prospect that with appropriate controls, the colloidal NSL technique promises to facilitate the growth of a variety of well-ordered silicide nanodots with selected shape, size, and periodicity.

  12. Non-uniformly weighted sampling for faster localized two-dimensional correlated spectroscopy of the brain in vivo

    NASA Astrophysics Data System (ADS)

    Verma, Gaurav; Chawla, Sanjeev; Nagarajan, Rajakumar; Iqbal, Zohaib; Albert Thomas, M.; Poptani, Harish

    2017-04-01

    Two-dimensional localized correlated spectroscopy (2D L-COSY) offers greater spectral dispersion than conventional one-dimensional (1D) MRS techniques, yet long acquisition times and limited post-processing support have slowed its clinical adoption. Improving acquisition efficiency and developing versatile post-processing techniques can bolster the clinical viability of 2D MRS. The purpose of this study was to implement a non-uniformly weighted sampling (NUWS) scheme for faster acquisition of 2D-MRS. A NUWS 2D L-COSY sequence was developed for 7T whole-body MRI. A phantom containing metabolites commonly observed in the brain at physiological concentrations was scanned ten times with both the NUWS scheme of 12:48 duration and a 17:04 constant eight-average sequence using a 32-channel head coil. 2D L-COSY spectra were also acquired from the occipital lobe of four healthy volunteers using both the proposed NUWS and the conventional uniformly-averaged L-COSY sequence. The NUWS 2D L-COSY sequence facilitated 25% shorter acquisition time while maintaining comparable SNR in humans (+0.3%) and phantom studies (+6.0%) compared to uniform averaging. NUWS schemes successfully demonstrated improved efficiency of L-COSY, by facilitating a reduction in scan time without affecting signal quality.

  13. Synthesis, potentiometric, kinetic, and NMR Studies of 1,4,7,10-tetraazacyclododecane-1,7-bis(acetic acid)-4,10-bis(methylenephosphonic acid) (DO2A2P) and its complexes with Ca(II), Cu(II), Zn(II) and lanthanide(III) ions.

    PubMed

    Kálmán, Ferenc K; Baranyai, Zsolt; Tóth, Imre; Bányai, István; Király, Róbert; Brücher, Ernö; Aime, Silvio; Sun, Xiankai; Sherry, A Dean; Kovács, Zoltán

    2008-05-05

    an OH (-) assisted process but, unlike formation of Ln(DOTA) complexes, rearrangement of Ln(H 2DO2A2P)* also takes place spontaneously likely as a result of transfer of one of the protons from a ring nitrogen to a phosphonate group. The order of the OH (-) assisted formation rates of complexes is DOTA > DO2A2P > DOTP while the order of the proton assisted dissociation rates of the Gd (3+) complexes is reversed, DOTP > DO2A2P > DOTA. (1)H and (13)C NMR spectra of Eu(DO2A2P) and Lu(DO2A2P) were assigned using two-dimensional correlation spectroscopy (2D COSY), heteronuclear multiple quantum coherence (HMQC), heteronuclear chemical shift correlation (HETCOR), and exchange spectroscopy (EXSY) NMR methods. Two sets of (1)H NMR signals were observed for Eu(DO2A2P) characteristic of the presence of two coordination isomers in solution, a twisted square antiprism (TSAP) and a square antiprism (SAP), in the ratio of ~93% and ~7%, respectively. Line shape analysis of the (1)H NMR spectra of Lu(DO2A2P) gave lower activation parameters compared to La(DOTP) for interconversion between coordination isomers. This indicates that the Ln(DO2A2P) complexes are less rigid probably due to the different size and spatial requirements of the carboxylate and phosphonate groups.

  14. P-O-B(3) linkages in borophosphate glasses evidenced by high field (11)B/(31)P correlation NMR.

    PubMed

    Tricot, G; Raguenet, B; Silly, G; Ribes, M; Pradel, A; Eckert, H

    2015-06-07

    The long-standing debate about the presence of P-O-B(3) linkages in glasses has been solved by high-field scalar correlation NMR. Previously suggested by dipolar NMR methods, the presence of such species has been definitively demonstrated by (11)B((31)P) J-HMQC NMR techniques. The results indicate that borophosphate networks contain P-O-B(3) bonds and thus present a higher degree of atomic homogeneity than previously thought.

  15. Salvinicins A and B, new neoclerodane diterpenes from Salvia divinorum.

    PubMed

    Harding, Wayne W; Tidgewell, Kevin; Schmidt, Matthew; Shah, Kushal; Dersch, Christina M; Snyder, John; Parrish, Damon; Deschamps, Jeffrey R; Rothman, Richard B; Prisinzano, Thomas E

    2005-07-07

    [reaction: see text] Two new neoclerodane diterpenes, salvinicins A (4) and B (5), were isolated from the dried leaves of Salvia divinorum. The structures of these compounds were elucidated by spectroscopic techniques, including (1)H and (13)C NMR, NOESY, HMQC, and HMBC. The absolute stereochemistry of these compounds was assigned on the basis of single-crystal X-ray crystallographic analysis of salvinicin A (4) and a 3,4-dichlorobenzoate derivative of salvinorin B.

  16. Salvinicins A and B, New Neoclerodane Diterpenes from Salvia divinorum

    PubMed Central

    Harding, Wayne W.; Tidgewell, Kevin; Schmidt, Matthew; Shah, Kushal; Dersch, Christina M.; Snyder, John; Parrish, Damon; Deschamps, Jeffrey R.; Rothman, Richard B.

    2008-01-01

    Two new neoclerodane diterpenes, salvinicins A (4) and B (5), were isolated from the dried leaves of Salvia divinorum. The structures of these compounds were elucidated by spectroscopic techniques, including 1H and 13C NMR, NOESY, HMQC, and HMBC. The absolute stereochemistry of these compounds was assigned on the basis of single crystal X-ray crystallographic analysis of salvinicin A (4) and a 3,4-dichlorobenzoate derivative of salvinorin B. PMID:15987194

  17. Chemical shift assignments of two oleanane triterpenes from Euonymus hederaceus *

    PubMed Central

    Hu, He-jiao; Wang, Kui-wu; Wu, Bin; Sun, Cui-rong; Pan, Yuan-jiang

    2005-01-01

    1H-NMR and 13C-NMR assignments of 12-oleanene-3,11-dione (compound 1) were completely described for the first time through conventional 1D NMR and 2D shift-correlated NMR experiments using 1H-1HCOSY, HMQC, HMBC techniques. Based on its NMR data, the assignments of 28-hydroxyolean-12-ene-3,11-dione (compound 2) were partially revised. PMID:16052702

  18. Ballistic-Electron-Emission Microscopy on Epitaxial Silicides

    NASA Astrophysics Data System (ADS)

    von Känel, Hans; Meyer, Thomas; Klemenc, Michaela

    1998-06-01

    Ballistic-electron-emission microscopy (BEEM) andspectroscopy (BEES) applied to epitaxial CoSi2/Si interfaces are reviewed.Interfacial dislocations in 2 3-nm-thick CoSi2(001)/Si(001)films with Burgers vectorb=a/4<111>lower the barrier height by almost 0.1 eV at 77 K. This corresponds to adecrease in the Schottky barrier height ΦB at the metallurgicalinterface from ΦB=0.74±0.03 eV, characteristic of defect-freeregions, to near zero within the range of the strain field of a fewnanometers. In contrast, the dislocations of type\\mbi{b}=a/6≤ft<11\\bar{2}\\right>present at CoSi2/Si(111) interfaces do not affectthe barrier height. CoSi2/Si(111) films are more suitable for studyinginterfacial scattering by BEEM than CoSi2/Si(100) films, because of theirsimpler surface structure and because of band structure effects.Here, individual point defects can beresolved. Their spatial distribution indicates diffusion along the interfaceduring film growth. By analysing the shape of BEES spectra obtained onisolated point defects, and by making use of the projected band structurepredicting the BEES current to set in ˜0.2 eV above the Schottkybarrier, it may be concluded that the defects are located at the interface.

  19. Controlling the rate of shuttling motions in [2]rotaxanes by electrostatic interactions: a cation as solvent-tunable brake.

    PubMed

    Ghosh, Pradyut; Federwisch, Guido; Kogej, Michael; Schalley, Christoph A; Haase, Detlev; Saak, Wolfgang; Lützen, Arne; Gschwind, Ruth M

    2005-08-07

    A series of rotaxanes, with phenolic axle centerpieces and tetralactam macrocycles as the wheels, has been prepared in good yields. The threaded rotaxane structure is confirmed in the gas phase by tandem mass spectrometric experiments through a detailed fragmentation pattern analysis, in solution by NMR spectroscopy, and in the solid state through X-ray crystallography. A close inspection of the 1H,1H NOESY and 1H,1H ROESY NMR data reveals the wheel to travel along the axle between two degenerate diamide "stations" close to the two stoppers. By deprotonation of a phenolic OH group in the axle centerpiece with Schwesinger's P1 base, surprisingly no additional shuttling station is generated at the axle center, although the wheel could form rather strong hydrogen bonds with the phenolate. Instead, the wheel continues to travel between the two diamide stations. Experimental data from 1H,1H NOESY spectra, together with theoretical calculations, show that strong electrostatic interactions between the phenolate moiety and the P1 cation displace the wheel from the "phenolate station". The cation acts as a "brake" for the shuttling movement. Instead of suppressing the shuttling motion completely, as observed in other rotaxanes, our rotaxane is the first system in which electrostatic interactions modulate the speed of the mechanical motion between a fast and a slow motion state as a response to a reversible external stimulus. By tuning these electrostatic interactions through solvent effects, the rate of movement can be influenced significantly, when for example different amounts of DMSO are added to dichloromethane. Besides the shuttling motion, circumrotation of the wheel around the axle is observed and analyzed by variable temperature NMR spectroscopy. Force field and AM1 calculations are in good agreement with the experimental findings.

  20. Determination of fluorotelomer alcohols in selected consumer products and preliminary investigation of their fate in the indoor environment.

    PubMed

    Liu, Xiaoyu; Guo, Zhishi; Folk, Edgar E; Roache, Nancy F

    2015-06-01

    The U.S. Environmental Protection Agency (EPA) has established an ongoing effort to identify the major perfluorocarboxylic acid (PFCA) sources in nonoccupational indoor environments and characterize their transport and fate. This study determined the concentrations of fluorotelomer alcohols (FTOHs), which are the precursors to PFCAs, in fifty-four consumer products collected from the U.S. open market in the years of 2011 and 2013. The products included carpet, commercial carpet-care liquids, household carpet/fabric-care liquids, treated apparel, treated home textiles, treated non-woven medical garments, floor waxes, food-contact paper, membranes for apparel, and thread-sealant tapes. The FTOHs quantified were 1H,1H,2H,2H-perfluoro-1-octanol (6:2 FTOH), 1H,1H,2H,2H-perfluoro-1-decanol (8:2 FTOH), and 1H,1H,2H,2H-perfluoro-1-dodecanol (10:2 FTOH). The content of 6:2 FTOH ranged from non-delectable to 331μgg(-1), 8:2 FTOH from non-delectable to 92μgg(-1), and 10:2 FTOH from non-detectable to 24μgg(-1). In addition, two consumer products from the home textile category were tested in the washing-drying process. One product from the treated apparel category and one from the home textile category were tested in the micro-scale chamber under elevated temperatures. The experimental data show that the washing-drying process with one cycle did not significantly reduce the FTOH concentrations in the tested consumer products. FTOH off-gassing was observed under accelerated aging conditions. Future tests should include air sampling to allow determination of the absolute emission rates at different temperatures. The results of this study should be informative to exposure assessment and risk management. Published by Elsevier Ltd.

  1. Tuning of metal work functions with self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    de Boer, Bert; Hadipour, Afshin; Foekema, Remko; van Woudenbergh, Teunis; Mandoc, Magda M.; Mihailetchi, Valentin D.; Blom, Paul W. M.

    2004-09-01

    Tuning the work functions of metals was demonstrated by chemically modifying the metal surface through the formation of chemisorbed self-assembled monolayers (SAMs) derived from 1H,1H,2H,2H-perfluorinated alkanethiols and hexadecanethiol. The ordering inherent in the SAMs creates an effective, molecular dipole at the metal/SAM interface, which increased the work function of Ag (ΦAg ~4.4 eV) to 5.5 eV (ΔΦ ~ 1.1 eV) for 1H,1H,2H,2H-perfluorinated alkanethiols. Hexadecanethiol on the other hand shifted ΦAg toward 3.8 eV (ΔΦ ~ 0.6 eV) and raised the energy barrier for hole injection. These SAMs on Au were less efficient. 1H,1H,2H,2H-perfluorodecanethiol raised ΦAu (4.9 eV) by 0.5 eV to 5.4 eV, whereas hexadecanethiol decreased ΦAu by only 0.1 eV. These chemically modified electrodes were applied in the fabrication of pLEDs and the hole conduction of MEH-PPV was investigated. An ohmic contact for hole injection between a silver electrode functionalized with the perfluorinated SAMs, and MEH-PPV with a HOMO of 5.2 eV was established. Conversely, a silver electrode modified with a SAM of hexadecanethiol lowered ΦAg to 3.8 eV, creating an efficient energy barrier for hole injection. This method demonstrates a simple and attractive approach to modify and improve metal/organic contacts in organic electronic devices like LEDs and photovoltaic cells.

  2. 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.

  3. The Kagomé topology of the gallium and indium metal-organic framework types with a MIL-68 structure: synthesis, XRD, solid-state NMR characterizations, and hydrogen adsorption.

    PubMed

    Volkringer, Christophe; Meddouri, Mohamed; Loiseau, Thierry; Guillou, Nathalie; Marrot, Jérôme; Férey, Gérard; Haouas, Mohamed; Taulelle, Francis; Audebrand, Nathalie; Latroche, Michel

    2008-12-15

    The vanadium-based terephthalate analogs of MIL-68 have been obtained with gallium and indium (network composition: M(OH)(O(2)C-C(6)H(4)-CO(2)), M = Ga or In) by using a solvothermal synthesis technique using N,N-dimethylformamide as a solvent (10 and 48 h, for Ga and In, respectively, at 100 degrees C). They have been characterized by X-ray diffraction analysis; vibrational spectroscopy; and solid-state (1)H and (1)H-(1)H radio-frequency-driven dipolar recoupling (RFDR), (1)H-(1)H double quantum correlation (DQ), and (13)C{(1)H} cross polarization magic angle spinning (CPMAS) NMR spectroscopy. The three-dimensional network with a Kagomé-like lattice is built up from the connection of infinite trans-connected chains of octahedral units MO(4)(OH)(2) (M = Ga or In), linked to each other through the terephthalate ligands in order to generate triangular and hexagonal one-dimensional channels. The presence of DMF molecules with strong interactions within the channels as well as their departure upon calcination (150 degrees C under a primary vacuum) of the materials has been confirmed by subjecting MIL-68 (Ga) to solid-state (1)H MAS NMR. The (1)H-(1)H RFDR and (1)H-(1)H DQ spectra revealed important information on the spatial arrangement of the guest species with respect to the hybrid organic-inorganic network. (13)C{(1)H} CPMAS NMR of activated samples provided crystallographically independent sites in agreement with X-ray diffraction structure determination. Brunauer-Emmett-Teller surface areas are 1117(24) and 746(31) m(2) g(-1) for MIL-98 (Ga) and MIL-68 (In), respectively. Hydrogen adsorption isotherms have been measured at 77 K, and the storage capacities are found to be 2.46 and 1.98 wt % under a saturated pressure of 4 MPa for MIL-68 (Ga) and MIL-68 (In), respectively. For comparison, the hydrogen uptake for the aluminum trimesate MIL-110, which has an open framework with 16 A channels, is 3 wt % under 4 MPa.

  4. Heavy Lift Helicopter - Cargo Handling ATC Program, Volume III. Results of Tests, Inspections, and Evaluations

    DTIC Science & Technology

    1976-10-01

    Over- Drum Stress Cycles ..... ............... .. 187 81 Kevlar 49, ½-Inch, 3-Strand Rope Specimen After Tensile/Ultimate Test...and stresses . The arrangement of the test specimen and the fixture is shown in Figure 1. The tests were conducted with three differentit wall...1 H >1 H > H &H ,0L 00 )4 E-1 r-IH r-4 H Hr4 I H H rI-4 0 p 4m S 040 040 040 040 040 $ )( C) & 8 O 0 Q 4 H13 fI~ E- W E-1I 0 40 31 HO4 H v 4 * H wO 0

  5. A new C-Glycosylflavone from Encyclia michuacana

    NASA Astrophysics Data System (ADS)

    Tovar-Gijón, Claudia E.; Hernández-Carlos, Beatriz; Burgueño-Tapia, Eleuterio; Cedillo-Portugal, Ernestina; Joseph-Nathan, Pedro

    2006-02-01

    The methanol extracts from Encyclia michuacana tubercles yielded the new 8- C-(6-deoxy-β- D-glucopyranosyl)apigenin ( 1) together with known 1-(3'-hydroxy-5'-methoxyphenyl)-2-(4″-hydroxy-5″-methoxyphenyl)ethane ( 2) and 2-(4-hydroxybenzyl)malic acid ( 3). The new structure was elucidated using spectroscopic methods, mainly 1D and 2D NMR. The β-anomer for 1 was supported by comparison of the experimental 1H- 1H coupling constant values with those generated employing a generalized Karplus-type relationship using dihedral angles extracted from DFT calculations.

  6. 13C-NMR assignments and cytotoxicity assessment of zoanthoxanthin alkaloids from zoanthid corals.

    PubMed

    Jiménez, C; Crews, P

    1993-01-01

    Zoanthoxanthin alkaloids can vary among skeletal types A, B, and C. Three type C zoanthoxanthins were examined, including a new compound 1, previously reported paragracine [2], and zoanthoxanthin 3. Their nmr and cytotoxic properties are reported. We have used 2D nmr data to complete the assignments for 1 and suggest that these benchmark nmr assignments will allow future investigators to establish new metabolites of this class as a member of families A, B, or C with only a 13C APT and a 1H-1H nmr spectra.

  7. 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°. Copyright © 2011 Elsevier Inc. All rights reserved.

  8. Structure of an acidic O-specific polysaccharide of the bacterium Providencia alcalifaciens O7.

    PubMed

    Bystrova, O V; Zatonskii, G V; Borisova, S A; Kocharova, N A; Shashkov, A S; Knirel, Y A; Kholodkova, E V; Stanislavskii, E S

    2000-06-01

    An acidic O-specific polysaccharide was obtained by mild acid degradation of the lipopolysaccharide of the bacterium Providencia alcalifaciens O7 and purified by gel chromatography followed by anion-exchange chromatography. On the basis of full acid hydrolysis, methylation, carboxyl reduction, selective cleavage with anhydrous hydrogen fluoride, and 1H- and 13C-NMR spectroscopy, including two-dimensional 1H,1H homonuclear and H-detected 1H,13C heteronuclear correlation spectroscopy and nuclear Overhauser effect spectroscopy (NOESY), the following structure of the linear tetrasaccharide repeating unit of the polysaccharide was established: [figure], where Rhap2Ac is 2-O-acetylrhamnopyranose.

  9. Fast multidimensional localized parallel NMR spectroscopy for the analysis of samples.

    PubMed

    Vega-Vazquez, Marino; Cobas, Juan Carlos; Martin-Pastor, Manuel

    2010-10-01

    A parallel localized spectroscopy (PALSY) method is presented to speed up the acquisition of multidimensional NMR (nD) spectra. The sample is virtually divided into a discrete number of nonoverlapping slices that relax independently during consecutive scans of the experiment, affording a substantial reduction in the interscan relaxation delay and the total experiment time. PALSY was tested for the acquisition of three experiments 2D COSY, 2D DQF-COSY and 2D TQF-COSY in parallel, affording a time-saving factor of 3-4. Some unique advantages are that the achievable resolution in any dimension is not compromised in any way: it uses conventional NMR data processing, it is not prone to generate spectral artifacts, and once calibrated, it can be used routinely with these and other combinations of NMR spectra. 2010 John Wiley & Sons, Ltd.

  10. Work function characterization of solution-processed cobalt silicide

    DOE PAGES

    Ullah, Syed Shihab; Robinson, Matt; Hoey, Justin; ...

    2012-05-08

    Cobalt silicide thin films were prepared by spin-coating Si6H12-based inks onto various substrates followed by a thermal treatment. The work function of the solution processed Co-Si was determined by both capacitance-voltage (C-V) measurements of metal-oxide-semiconductor (MOS) structures as well as by ultraviolet photoelectron spectroscopy (UPS). The UPS-derived work function was 4.80 eV for a Co-Si film on Si (100) while C-V of MOS structures yielded a work function of 4.36 eV where the metal was solution-processed Co-Si, the oxide was SiO2 and the semiconductor was a B-doped Si wafer.

  11. Implementation of multi-echo-based correlated spectroscopic imaging and pilot findings in human brain and calf muscle.

    PubMed

    Verma, Gaurav; Lipnick, Scott; Ramadan, Saadallah; Nagarajan, Rajakumar; Thomas, M Albert

    2011-08-01

    To implement a spatially encoded correlated spectroscopic imaging (COSI) sequence on 3 Tesla (T) MRI/MR spectroscopy scanners incorporating four echoes to collect four phase-encoded acquisitions per repetition time (TR), and to evaluate the performance and reliability of this four-dimensional (4D) multi-echo COSI (ME-COSI) sequence in brain and calf muscle. Typical scan parameters for the 4D datasets were as follows: repetition time = 1500 ms, 2000 Hz bandwidth, 8 × 8 spatial encoding, one average, 64 Δt(1) increments and the scan duration was 25 min. The performance and test-retest reliability of ME-COSI were evaluated with phantoms and in the occipitoparietal brain tissues and calf of six healthy volunteers (mean age = 32 years old). Regional differences in concentrations of lipids, creatine (Cr), choline (Ch), and carnosine (Car) were observed between spectra from voxels located in tibial marrow, tibialis anterior, and soleus muscle. Diagonal and cross-peak resonances were identified from several brain metabolites including N-acetyl aspartate (NAA), Ch, Cr, lactate (Lac), aspartate (Asp), glutathione (GSH), and glutamine\\glutamate (Glx). Coefficients of variation (CV) in metabolite ratios across repeated measurements were <15% for diagonal and <25% for cross-peaks observed in vivo. The ME-COSI sequence reliably acquired spatially resolved 2D Correlated Spectroscopy (COSY) spectra demonstrating the feasibility of differentiating spatial variation of metabolites in different tissues. Multi-echo acquisition shortens scan duration to clinically feasible times. Copyright © 2011 Wiley-Liss, Inc.

  12. Implementation of Multi-Echo Based Correlated Spectroscopic Imaging and Pilot Findings in Human Brain and Calf Muscle

    PubMed Central

    Verma, Gaurav; Lipnick, Scott; Ramadan, Saadallah; Nagarajan, Rajakumar; Thomas, M. Albert

    2011-01-01

    Purpose To implement a spatially-encoded Correlated Spectroscopic Imaging (COSI) sequence on 3T MRI/MRS scanners incorporating four echoes to collect four phase-encoded acquisitions per repetition time (TR), and to evaluate the performance and reliability of this four-dimensional (4D) Multi-Echo COSI (ME-COSI) sequence in brain and calf muscle. Materials and Methods Typical scan parameters for the 4D datasets were as follows: TR=1500ms, 2000 Hz bandwidth, 8×8 spatial encoding, one average, 64 Δt1 increments and the scan duration was 25 minutes. The performance and test-retest reliability of ME-COSI were evaluated with phantoms and in the occipito-parietal brain tissues and calf of six healthy volunteers (mean age = 32 years old). Results Regional differences in concentrations of lipids, creatine (Cr), choline (Ch) and carnosine (Car) were observed between spectra from voxels located in tibial marrow, tibialis anterior and soleus muscle. Diagonal and cross peak resonances were identified from several brain metabolites including N-acetyl aspartate (NAA), Ch, Cr, lactate (Lac), aspartate (Asp), glutathione (GSH) and glutamine\\glutamate (Glx). Coefficients of variation (CV) in metabolite ratios across repeated measurements were <15% for diagonal and <25% for cross-peaks observed in vivo. Conclusion The ME-COSI sequence reliably acquired spatially-resolved two-dimensional (2D) Correlated Spectroscopy (COSY) spectra demonstrating the feasibility of differentiating spatial variation of metabolites in different tissues. Multi-echo acquisition shortens scan duration to clinically feasible times. PMID:21780221

  13. New irradiation facilities for development of production methods of medical radionuclides at cyclotrons at Forschungszentrum Jülich

    NASA Astrophysics Data System (ADS)

    Spellerberg, S.; Scholten, B.; Spahn, I.; Felden, O.; Gebel, R.; Qaim, S. M.; Bai, M.; Neumaier, B.

    2017-05-01

    An essential basis for research and development work on radiopharmaceuticals is the efficient production of radionuclides of high quality. In this process research-oriented studies aiming for elucidation of biochemical processes require novel products. The radionuclide development at INM-5 entails basic research, e.g. the determination of nuclear reaction data, as well as technical aspects of practical production, such as high-current targetry, chemical separation, formulation and quality control. In this work developments, adaptation and optimization of irradiation facilities at the BC 1710, JULIC as Injector of COSY and COSY itself are summarized, which shall allow the extension of radionuclide production possibilities, aiming at innovations in medical applications.

  14. Epitaxial nickel and cobalt suicide formation by rapid thermal annealing

    NASA Astrophysics Data System (ADS)

    Chevallier, J.; Larsen, A. Nylandsted

    1986-02-01

    Thin films of epitaxial NiSi2 and CoSi2 were formed by short-duration incoherent light exposure of evaporated Ni or Co films on <111> Si single crystals. The crystalline quality of these suicides is comparable to what has been obtained for long-duration furnace annealed suicides, as deduced from channeling measurements. NiSi2 is of high crystalline quality at all temperatures at which it is formed whereas the CoSi2 films recrystallize at a temperature of ˜980°C.

  15. Electron Cooling of Intense Ion Beam

    NASA Astrophysics Data System (ADS)

    Dietrich, J.; Kamerdjiev, V.; Korotaev, Yu.; Maier, R.; Meshkov, I.; Prasuhn, D.; Sidorin, A.; Smirnov, A.; Stein, J.; Stockhorst, H.

    2006-03-01

    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 ♯ 05-02-16320 and INTAS grant ♯03-54-5584.

  16. Polarization-independent dual-band terahertz metamaterial absorbers based on gold/parylene-C/silicide structure.

    PubMed

    Wen, Yongzheng; Ma, Wei; Bailey, Joe; Matmon, Guy; Yu, Xiaomei; Aeppli, Gabriel

    2013-07-01

    We design, fabricate, and characterize dual-band terahertz (THz) metamaterial absorbers with high absorption based on structures consisting of a cobalt silicide (Co-Si) ground plane, a parylene-C dielectric spacer, and a metal top layer. By combining two periodic metal resonators that couple separately within a single unit cell, a polarization-independent absorber with two distinct absorption peaks was obtained. By varying the thickness of the dielectric layer, we obtain absorptivity of 0.76 at 0.76 THz and 0.97 at 2.30 THz, which indicates the Co-Si ground plane absorbers present good performance.

  17. Two-dimensional NMR correlation experiments in the gas phase

    NASA Astrophysics Data System (ADS)

    Marchione, Alexander A.

    2011-05-01

    The application of common two-dimensional NMR correlation experiments to gaseous analytes for structural elucidation is reported. Standard sequences such as COSY, HSQC, and HMBC are readily applied to volatile hydrocarbons and fluorocarbons. In experiments using 19F or 13C as the observed nucleus, it is possible to take advantage of efficient spin-rotation relaxation to perform common experiments swiftly (a 19F COSY acquired in 6 s is shown) or to render insensitive experiments possible on a practical timescale (e.g. a gas phase INADEQUATE at natural isotopic abundance in 14 h). NOE-based experiments were not successful on the gaseous systems studied.

  18. Solid-State NMR Imaging by Tetrahedral-Magic-Echo Time-Suspension Sequences

    NASA Astrophysics Data System (ADS)

    Matsui, S.; Uraoka, A.; Inouye, T.

    A new approach to solid-state imaging using tetrahedral magic echoes (TME) is proposed and compared with the previously reported modified-magic-echo (MME) approaches. The comparison has shown that for common organic solids, where the homonuclear 1H- 1H dipolar interaction is dominant, the degree of TME line narrowing is nearly the same as that of time-suspended MME line narrowing; however, the TME narrowing is substantially superior to the MME narrowing for solids where the heteronuclear dipolar interaction between 1H and a second spin species is comparable in magnitude to the homonuclear 1H- 1H dipolar interaction. This superiority stems from the fact that the homonuclear and hereronuclear interactions do not commute with each other. The TME approach further possesses certain practical advantages over the MME approaches. For example, the optional application of gradient pulses during the RF irradiation periods in the TME sequences increases the scaling factor of the gradient amplitude from {1}/{4} to {1}/{2}, making the gradient switching easier. No apparent deterioration of the TME line-narrowing by the optional gradient application was noted.

  19. New eudesmane derivatives and other sesquiterpenes from the epigeal parts of Dittrichia graveolens.

    PubMed

    Abou-Douh, Ahmad Muhamad

    2008-11-01

    In bioassay-guided searches for novel bioactive natural products from higher plants of the Egyptian flora, two new eudesmane sesquiterpene derivatives, 3alpha-hydroxyilicic acid methyl ester (1) and 2alpha-hydroxy-4-epi-ilicic acid (2), together with 11 known sesquiterpenes were isolated from bioactive fractions of the active epigeal parts extracts of Dittrichia graveolens (L.) GREUTER (Asteraceae) growing in the coastal regions of northwestern Egypt. Four other known sesquiterpene lactones with different carbon skeletons, named 2alpha-hydroxy-2R-xanthalongin (8), 4-epi-isoinuviscolide (9), 8-epi-helenalin (10), and bigelovin (11), were also isolated for the first time from the same source. The stereochemical structures of the isolated compounds were elucidated on the basis of physical and spectroscopic methods including UV, IR, 1H-, 13C-NMR, distortionless enhancement by polarization transfer, 2D NMR, 1H-1H correlation spectroscopy, 1H-13C heteronuclear single-quantum coherence, 1H-13C heteronuclear multiple-bond connectivity, 1H-1H nuclear Overhauser effect spectroscopy experiments, and high-resolution mass spectrometry, as well as some chemical transformations. The antimicrobial, antiinflammatory, and antipyretic activities of D. graveolens extracts and chromatographic fractions were carried out and the various bioactivities of our findings are discussed.

  20. Investigating albendazole desmotropes by solid-state NMR spectroscopy.

    PubMed

    Chattah, Ana K; Zhang, Rongchun; Mroue, Kamal H; Pfund, Laura Y; Longhi, Marcela R; Ramamoorthy, Ayyalusamy; Garnero, Claudia

    2015-03-02

    Characterization of the molecular structure and physicochemical solid-state properties of the solid forms of pharmaceutical compounds is a key requirement for successful commercialization as potential active ingredients in drug products. These properties can ultimately have a critical effect on the solubility and bioavailability of the final drug product. Here, the desmotropy of Albendazole forms I and II was investigated at the atomic level. Ultrafast magic angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) spectroscopy, together with powder X-ray diffraction, thermal analysis, and Fourier transform infrared spectroscopy, were performed on polycrystalline samples of the two solids in order to fully characterize and distinguish the two forms. High-resolution one-dimensional (1)H, (13)C, and (15)N together with two-dimensional (1)H/(1)H single quantum-single quantum, (1)H/(1)H single quantum-double quantum, and (1)H/(13)C chemical shift correlation solid-state NMR experiments under MAS conditions were extensively used to decipher the intramolecular and intermolecular hydrogen bonding interactions present in both solid forms. These experiments enabled the unequivocal identification of the tautomers of each desmotrope. Our results also revealed that both solid forms may be described as dimeric structures, with different intermolecular hydrogen bonds connecting the tautomers in each dimer.

  1. Smart, Sustainable, and Ecofriendly Chemical Design of Fully Bio-Based Thermally Stable Thermosets Based on Benzoxazine Chemistry.

    PubMed

    Froimowicz, Pablo; R Arza, Carlos; Han, Lu; Ishida, Hatsuo

    2016-08-09

    A smart synthetic chemical design incorporating furfurylamine, a natural renewable amine, into a partially bio-based coumarin-containing benzoxazine is presented. The versatility of the synthetic approach is shown to be flexible and robust enough to be successful under more ecofriendly reaction conditions by replacing toluene with ethanol as the reaction solvent and even under solventless conditions. The chemical structure of this coumarin-furfurylamine-containing benzoxazine is characterized by FTIR, (1) H NMR spectroscopy and two-dimensional (1) H-(1) H nuclear Overhauser effect spectroscopy (2D (1) H-(1) H NOESY). The thermal properties of the resin toward polymerization are characterized by differential scanning calorimetry (DSC) and the thermal stability of the resulting polymers by thermogravimetric analysis (TGA). The results reveal that the furanic moiety induces a co-operative activating effect, thus lowering the polymerization temperature and also contributes to a better thermal stability of the resulting polymers. These results, in addition to those of natural renewable benzoxazine resins reviewed herein, highlight the positive and beneficial implication of designing novel bio-based polybenzoxazine and possibly other thermosets with desirable and competitive properties. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Sensitizing solid state nuclear magnetic resonance of dilute nuclei by spin-diffusion assisted polarization transfers

    NASA Astrophysics Data System (ADS)

    Lupulescu, Adonis; Frydman, Lucio

    2011-10-01

    Recent years have witnessed efforts geared at increasing the sensitivity of NMR experiments, by relying on the suitable tailoring and exploitation of relaxation phenomena. These efforts have included the use of paramagnetic agents, enhanced 1H-1H incoherent and coherent transfers processes in 2D liquid state spectroscopy, and homonuclear 13C-13C spin diffusion effects in labeled solids. The present study examines some of the opportunities that could open when exploiting spontaneous 1H-1H spin-diffusion processes, to enhance relaxation and to improve the sensitivity of dilute nuclei in solid state NMR measurements. It is shown that polarization transfer experiments executed under sufficiently fast magic-angle-spinning conditions, enable a selective polarization of the dilute low-γ spins by their immediate neighboring protons. Repolarization of the latter can then occur during the time involved in monitoring the signal emitted by the low-γ nuclei. The basic features involved in the resulting approach, and its potential to improve the effective sensitivity of solid state NMR measurements on dilute nuclei, are analyzed. Experimental tests witness the advantages that could reside from utilizing this kind of approach over conventional cross-polarization processes. These measurements also highlight a number of limitations that will have to be overcome for transforming selective polarization transfers of this kind into analytical methods of choice.

  3. Heteronuclear transverse and longitudinal relaxation in AX4 spin systems: application to (15)N relaxations in (15)NH4(+).

    PubMed

    Werbeck, Nicolas D; Hansen, D Flemming

    2014-09-01

    The equations that describe the time-evolution of transverse and longitudinal (15)N magnetisations in tetrahedral ammonium ions, (15)NH4(+), are derived from the Bloch-Wangsness-Redfield density operator relaxation theory. It is assumed that the relaxation of the spin-states is dominated by (1) the intra-molecular (15)N-(1)H and (1)H-(1)H dipole-dipole interactions and (2) interactions of the ammonium protons with remote spins, which also include the contribution to the relaxations that arise from the exchange of the ammonium protons with the bulk solvent. The dipole-dipole cross-correlated relaxation mechanisms between each of the (15)N-(1)H and (1)H-(1)H interactions are explicitly taken into account in the derivations. An application to (15)N-ammonium bound to a 41kDa domain of the protein DnaK is presented, where a comparison between experiments and simulations show that the ammonium ion rotates rapidly within its binding site with a local correlation time shorter than approximately 1ns. The theoretical framework provided here forms the basis for further investigations of dynamics of AX4 spin systems, with ammonium ions in solution and bound to proteins of particular interest. Copyright © 2014 The Authors. Published by Elsevier Inc. All rights reserved.

  4. Effect of transition metal salts on the initiated chemical vapor deposition of polymer thin films

    SciTech Connect

    Kwong, Philip; Seidel, Scott; Gupta, Malancha, E-mail: malanchg@usc.edu

    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 themore » 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.« less

  5. 6-Acetamidoflavone obtained by microbiological and chemical methods and its antioxidant activity.

    PubMed

    Stompor, Monika

    2016-11-10

    The aim of this research was to select microbial strains capable of transforming flavonoid compounds containing an amino group. 6-Aminoflavone (1) was used as a model compound. Biotransformation of 1 by the cultures of Rhodococcus sp. DSM 364 and Gordonia sp. DSM 44456 bacteria led to 6-acetamidoflavone (2) with the isolated yields in 86% and 93%, respectively. The structure of the product was determined on the basis of spectroscopic data, including NMR spectra ( 1 H, 13 C, 1 H- 1 H, 1 H- 13 C, and DEPT 135°), a UV and IR spectrum and HR ESI-MS analysis. The developed method of microbial replacement of the amino group in 6-aminoflavone (1) by a acetamido one may find application in chemical industry, being an alternative to the reactions involving acetic anhydride. The antioxidant activity of flavone, and its C-6 substituted derivatives: 6-aminoflavone (1), 6-hydroxyflavone and isolated metabolite 6-acetamidoflavone (2) has been examined using the ABTS and DPPH methods. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Thermal stability of thiol and silane monolayers: A comparative study

    NASA Astrophysics Data System (ADS)

    Chandekar, Amol; Sengupta, Sandip K.; Whitten, James E.

    2010-02-01

    The stability of self-assembled monolayers (SAMs) at elevated temperatures is of considerable technological importance. The thermal stability of 1-octadecanethiol (ODT), 16-mercaptohexadecanoic acid (MHDA) and 1H,1H,2H,2H-perfluorodecanethiol (PFDT) SAMs on gold surfaces, and of 4-aminobutyltriethoxysilane (ABTES) and 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane (PFDS) assembled on hydroxylated silicon surfaces, was studied by X-ray photoelectron spectroscopy (XPS). The samples were heated in ultrahigh vacuum to temperatures in excess of that required for SAM degradation. ODT monolayers were stable to ca. 110 °C, while MHDA and PFDT SAMs were stable to ca. 145 °C. ABTES SAMs were found to be indefinitely stable to 250 °C, while PFDS SAMs were stable to 350 °C. These studies demonstrate the advantages of using silane monolayers for moderate to high temperature applications and illustrate differences that arise due to the nature of the tail group. To demonstrate the feasibility of silanes for template-directed patterning, a hydroxylated silicon oxide surface containing microcontact-printed PFDS patterns was spin-coated with a mainly hydrophilic block copolymer. Annealing the surface at 90 °C for 2 h caused the block copolymer to dewet the hydrophobic PFDS-patterned regions and adsorb exclusively on the unpatterned regions of the surface.

  7. 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.

  8. SERF-filtered experiments: New enantio-selective tools for deciphering complex spectra of racemic mixtures dissolved in chiral oriented media

    NASA Astrophysics Data System (ADS)

    Farjon, Jonathan; Merlet, Denis

    2011-05-01

    The use of chiral liquid crystals as NMR solvent is a powerful tool to visualize and quantify enantiomers. This technique is much more robust than traditional liquid state techniques. Recent developments have been performed to simplify proton spectra obtained in these solvents which are usually complex to analyze. In the different published sequences the enantiomeric differentiation can be visualized but none of them rely the different 1H- 1H couplings to have a coherent set for each enantiomer especially in cases of racemic mixtures. In this work to overcome such limitations, we present a new NMR pulse sequence using semi-selective pulses to assign for each enantiomer the different 1H- 1H couplings. The aim is to obtain the signal of only one enantiomer, through a first Selective ReFocussing (SERF) filtering block implemented for the enantio-selection followed by a second SERF block for measuring a chosen coupling. The whole sequence is called 1H SERF-filtered-SERF. These techniques permit for the first time to assign all dipolar couplings to each enantiomer of racemic mixtures dissolved in chiral oriented media. We demonstrate that using this experiment it is possible to visualize enantio-differentiation even in the case where the multiplets are not resolved in the SERF experiments, pushing back the limits of the enantiomeric visualization.

  9. Electronic Structure and Thermoelectric Properties of Transition Metal Monosilicides

    NASA Astrophysics Data System (ADS)

    Pshenay-Severin, D. A.; Ivanov, Yu. V.; Burkov, A. T.; Novikov, S. V.; Zaitsev, V. K.; Reith, H.

    2017-12-01

    We present theoretical and experimental results on electronic structure and thermoelectric properties of cobalt monosilicide (CoSi) and of Co1-x M x Si diluted alloys (M = Fe and Ni) at temperatures from 2 K to 800 K. CoSi crystallizes into a non-centrosymmetric cubic B20 structure, which suggests the possibility of a topologically non-trivial electronic structure. We show that the electronic structure of CoSi exhibits linear band crossings in close vicinity to Fermi energy, confirming the possibility of non-trivial topology. The proximity of the linear-dispersion bands to Fermi energy implies their important contribution to the electronic transport. Calculation of thermopower of CoSi, using ab initio band structure and the constant relaxation time approximation, is carried out. It reveals that many body corrections to the electronic spectrum are important in order to obtain qualitative agreement of theoretical and experimental temperature dependences of thermopower. Phonon dispersion and lattice thermal conductivity are calculated. The phonons give a major contribution to the thermal conductivity of the compound below room temperature.

  10. 3+2-Dipolar cycloaddition of dianhydrohexitol azidoderivatives with N-arylmaleimides

    NASA Astrophysics Data System (ADS)

    Gella, I. M.; Babak, N. L.; Drushlyak, T. G.; Shishkina, S. V.; Musatov, V. I.; Lipson, V. V.

    2015-11-01

    Dianhydrohexitol azides dipolar 3+2 cycloaddition with N-arylmaleimides has been studied with NMR (1H and 13C, COSY, NOESY and HSQC) and X-ray analysis. In spite of low asymmetrical induction in this reaction, diastereomerically pure products have been obtained. These products are interesting over their structural similarity to griseolic acid derivatives and dihydropyrrolotriazoles, significant for pharmaceutics.

  11. Characterization of Bending Magnetostriction in Iron-Gallium Alloys for Nanowire Sensor Applications

    DTIC Science & Technology

    2008-01-01

    ferrimagnets and antiferromagnets), which are so named due to iron be- ing the archetype rather than being a necessary element in the composition. In...Varadwaj, Paritosh Mohanty, Sunghun Lee, Younghun Jo, Myung-Hwa Jung , Jinhee Kim, and Bongsoo Kim. Magnetic properties of single-crystalline CoSi nanowires

  12. The Italian Version of the Cognitive Style Indicator and Its Association with Decision-Making Preferences

    ERIC Educational Resources Information Center

    Miceli, Silvana; de Palo, Valeria; Monacis, Lucia; Cardaci, Maurizio; Sinatra, Maria

    2018-01-01

    The Cognitive Style Indicator (CoSI) includes 3 cognitive dimensions: creating (flexible, open-ended and inventive), knowing (emphasizing facts, details, objectivity, and rationality), and planning (guided by preferences for certainty and well-structured information). The first aim of this research was to validate the 3-factor structure of the…

  13. Unidirectional endotaxial cobalt di-silicide nanowires on Si(110) substrates.

    PubMed

    Mahato, J C; Das, Debolina; Banu, Nasrin; Satpati, Biswarup; Dev, B N

    2017-10-20

    Self-organized growth of well-ordered endotaxial silicide nanowires (NWs) on clean Si(110) surfaces has been investigated by in situ scanning tunneling microscopy (STM) and transmission electron microscopy (TEM). Co deposition on clean Si(110) reconstructed surfaces at ∼600 °C produces unidirectional CoSi 2 NWs by reaction of cobalt with the hot silicon substrate. STM investigations reveal four major types of distinct NWs, all growing along the [-110] in-plane direction except one type growing along the in-plane [-113] direction. There are also some nanodots. The cross-sectional TEM measurements show that the unidirectional NWs are of two types-flat-top and ridged. The NWs grow not only on the substrate but also into the substrate. CoSi 2 in flat top NWs are in the same crystallographic orientation as the substrate Si and the buried interfaces between CoSi 2 and Si are A-type. In the ridged NWs CoSi 2 and Si are in different crystallographic orientations and the interfaces are B-type. The ridged NWs are in general wider and grow deeper into the substrate.

  14. Columnar and subsurface silicide growth with novel molecular beam epitaxy techniques

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

    We have found novel growth modes for epitaxial CoSi2 at high temperatures coupled with Si-rich flux ratios or low deposition rates. In the first of these modes, codeposition of metal and Si at 600-800 C with excess Si leads to the formation of epitaxial silicide columns surrounded by single-crystal Si. During the initial stages of the deposition, the excess Si grows homoepitaxially in between the silicide, which forms islands, so that the lateral growth of the islands is confined. Once a template layer is established by this process, columns of silicide form as a result of selective epitaxy of silicide on silicide and Si on Si. This growth process allows nanometer control over silicide particles in three dimensions. In the second of these modes, a columnar silicide seed layer is used as a template to nucleate subsurface growth of CoSi2. With a 100 nm Si layer covering CoSi2 seeds, Co deposited at 800C and 0.01 nm/s diffuses down to grow on the buried seeds rather than nucleating surface silicide islands. For thicker Si caps or higher deposition rates, the surface concentration of Co exceeds the critical concentration for nucleation of islands, preventing this subsurface growth mode from occurring. Using this technique, single-crystal layers of CoSi2 buried under single-crystal Si caps have been grown.

  15. 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…

  16. 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,"…

  17. 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…

  18. Calibration of the Compton Spectrometer and Imager in preparation for the 2014 balloon campaign

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

    The Compton Spectrometer and Imager (COSI) is a balloon-borne soft gamma-ray (0.2-5 MeV) telescope designed to perform wide-field imaging, high-resolution spectroscopy, and novel polarization measurements of astrophysical sources. COSI employs a compact Compton telescope design, utilizing 12 cross-strip germanium detectors to track the path of incident photons, where position and energy deposits from Compton interactions allow for a reconstruction of the source position in the sky, an inherent measure of the linear polarization, and significant background reduction. The instrument has recently been rebuilt with an updated and optimized design; the polarization sensitivity and effective area have increased due to a change in detector configuration, and the new lightweight gondola is suited to fly on ultra-long duration flights with the addition of a mechanical cryocooler system. COSI is planning to launch from the Long Duration Balloon site at McMurdo Station, Antarctica, in December 2014, where our primary science goal will be to measure gamma-ray burst (GRB) polarization. In preparation for the 2014 campaign, we have performed preliminary calibrations of the energy and 3-D position of interactions within the detector, and simulations of the angular resolution and detector efficiency of the integrated instrument. In this paper we will present the science goals for the 2014 COSI campaign and the techniques and results of the preliminary calibrations.

  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.

  20. 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

  1. 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.

  2. Calculation of incubation period and serial interval from multiple outbreaks of Marburg virus disease.

    PubMed

    Pavlin, Boris I

    2014-12-13

    Marburg viruses have been responsible for a number of outbreaks throughout sub-Saharan Africa, as well as a number of laboratory infections. Despite many years of experience with the viruses, little is known about several important epidemiologic parameters relating to the development of Marburg virus disease. The analysis uses pooled data from all Marburg cases between 1967 and 2008 to develop estimates for the incubation period and the clinical onset serial interval (COSI). Data were obtained from original outbreak investigation forms (n=406) and from published data (n=45). Incubation periods were calculated for person-to-person exposure, for laboratory-acquired infections, and for presumed zoonotic exposures. Similar analysis was conducted for COSI, using only cases with unambiguous person-to-person transmission where both the primary and the secondary case patients had well-defined illness onsets. Seventy-six cases were retained for the incubation period analysis. Incubation periods ranged from a minimum of 2 days in the case of two laboratory workers to a maximum of at least 26 days for a person-to-person household transmission. Thirty-eight cases were retained for COSI analysis. The median COSI was 11 days, with an interquartile range of 8 to 15. This study extends the maximum known incubation period of Marburg virus disease to 26 days. The analysis was severely hampered by a lack of completeness in epidemiologic data. It is necessary to prioritize obtaining more accurate epidemiologic data in future outbreaks; greater use of COSI may facilitate an improved understanding of outbreak dynamics in Marburg and other diseases.

  3. Exploring the functional mealtime associations of older adults through consumer segmentation and a means-end chain approach.

    PubMed

    den Uijl, Louise C; Jager, Gerry; de Graaf, Cees; Kremer, Stefanie

    2016-12-01

    Senior consumers are a rapidly growing and highly heterogeneous part of the world's population. This group does not always meet its recommended protein intake, which can negatively impact on their physical functioning and quality of life. To date, little is known about their motivations to consume protein-rich meals. In the current study, we therefore aim to identify consumer segments within the group of vital community-dwelling older adults on the basis of mealtime functionality (for example 'I eat because I'm hungry', or 'I eat because it is cosy'). To this end, we first conducted an online survey to identify these functional mealtime expectations of older consumers (study I, n = 398, 158 males, mean age 65.8 (y) ± 5.9 (SD)). To obtain further insights regarding mealtime functionality and proteins/protein enrichment, laddering interviews were conducted with a subgroup of the segmentation study participants (study II, n = 40, 20 males, mean age 66.9 (y) ± 4.8 (SD)). The results of the online survey showed three consumer clusters: cosy socialisers, physical nutritioners, and thoughtless rewarders. Thoughtless rewarders tend to eat without having explicit thoughts about it, they eat for the reward, and score highest on environmental awareness. Both the segmentation and the in-depth interviews showed that, for the cosy socialisers, the cosiness and social function of a meal are important motivators, whereas for the physical nutritioners the focus is more on the health and nutrient aspects of a meal. For cosy socialisers, protein enrichment can best be achieved through addition of protein-rich ingredients, whereas, for physical nutritioners, addition of protein powder is preferred. These results provide practical guidelines for the development of protein-rich meals and communication strategies tailored to the needs of specific vital community-dwelling older subgroups. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Helimagnetic order in bulk MnSi and CoSi/MnSi superlattices

    NASA Astrophysics Data System (ADS)

    Loh, G. C.; Khoo, K. H.; Gan, C. K.

    2017-01-01

    Skyrmions are nanoscopic whirls of spins that reside in chiral magnets. It is only fairly recent that a plethora of applications for these quasiparticles emerges, especially in data storage. On the other hand, spin spirals are the periodic analogs of skyrmions, and are equally imperative in the course of exploration to enhance our understanding of helimagnetism. In this study, a new infrastructure based on the B20 compound, MnSi is propounded as a hosting material for spin spirals; alternating thin layers of CoSi and MnSi in the superlattice form provides a facile way of varying the properties of the spin spirals across a continuum. Using first-principles calculations based on full-potential linearized augmented plane-wave (FLAPW)-based density functional theory (DFT), the spin order of bulk MnSi, MnSi film, and the CoSi/MnSi superlattice is investigated. Spin dispersion plots as a function of propagation vectors show that the spiral size changes in the presence of CoSi - we find that the size of the spiral is reduced in the superlattice with thin CoSi layers (CoSi:MnSi=1:1 thickness ratio), whilst at a larger CoSi:MnSi=2:1 thickness ratio, the material behaves as a ferromagnet. In a similar fashion, the spin moment and orbital occupancy depend significantly on the thickness of the CoSi layers. However, the exchange interaction between Mn atoms appears to be generally impervious to the presence of CoSi. Succinctly, the CoSi/MnSi superlattice could be an excellent functional material in data storage applications.

  5. ZSM-5 Zeolite: Complete Al Bond Connectivity and Implications on Structure Formation from Solid-State NMR and Quantum Chemistry Calculations.

    PubMed

    Dib, Eddy; Mineva, Tzonka; Veron, Emmanuel; Sarou-Kanian, Vincent; Fayon, Franck; Alonso, Bruno

    2018-01-04

    Al site distribution in the structurally complex and industrially important ZSM-5 zeolite is determined by studying the spectroscopic response of Al(OSi) 4 units and using a self-consistent combination of up-to-date solid-state NMR correlations ( 29 Si- 27 Al and 1 H- 27 Al D-HMQC) and quantum chemistry methods (DFT-D). To unravel the driving forces behind specific Al sitting positions, our approach focuses on ZSM-5 containing its more efficient OSDA, tetrapropylammonium.

  6. Structural determination of prunusins A and B, new C-alkylated flavonoids from Prunus domestica, by 1D and 2D NMR spectroscopy.

    PubMed

    Mahmood, Azhar; Fatima, Itrat; Kosar, Shaheen; Ahmed, Rehana; Malik, Abdul

    2010-02-01

    Prunusins A (1) and B (2), the new C-alkylated flavonoids, have been isolated from the seed kernels of Prunus domestica. Their structures were assigned from (1)H and (13)C nuclear magnetic resonating spectra, DEPT and by correlation spectroscopy, HMQC and HMBC experiments. 3, 5, 7, 4'-Tetrahydroxyflavone (3) and 3, 5, 7-trihydroxy-8, 4'-dimethoxyflavone (4) have also been reported from this species. Both compounds (1) and (2) showed significant antifungal activity against pathogenic fungus Trichophyton simmi. Copyright 2009 John Wiley & Sons, Ltd.

  7. Kaempferol triosides from Reseda muricata.

    PubMed

    El-Sayed, N H; Omara, N M; Yousef, A K; Farag, A M; Mabry, T J

    2001-06-01

    A flavonoid trioside and its coumaryl ester together with seven known flavonoids and five phenolic acids were isolated from the leaves of Reseda muricata. Their structures were elucidated by spectroscopic methods including UV, FAB MS, 1H, 13C and 2D-NMR, DEPT, HMBC and HMQC experiments. The two compounds were identified as kaempferol 3-O-beta-D-glucopyranosyl-(1''' --> 2'')-O-alpha-L-rhamnopyranoside 7-O-beta-D-glucopyranoside and kaempferol 3-O-beta-D-glucopyranosyl-(1''' --> 2'')-O-alpha-L rhamnopyranoside 7-O-beta-D-(6''''-O-E-coumarylglucopyranoside), respectively.

  8. Kaempferol triosides from Silphium perfoliatum.

    PubMed

    el-Sayed, Nabil H; Wojcińska, Małgorzata; Drost-Karbowska, Krystyna; Matławska, Irena; Williams, Jeffrey; Mabry, Tom J

    2002-08-01

    Two apiose-containing kaempferol triosides, together with nine known flavonoids were isolated from the leaves of Silphium perfoliatum L. Their structures were elucidated by acid hydrolysis and spectroscopic methods including UV, LSI MS, FAB MS, CI MS, (1)H, (13)C and 2D-NMR, DEPT, HMQC and HMBC experiments. The two new compounds were identified as kaempferol 3-O-beta-D-apiofuranoside 7-O-alpha-L-rhamnosyl-(1"-->6"')-O-beta-D-galactopyranoside and kaempferol 3-O-beta-D-apiofuranoside 7-O-alpha-L-rhamnosyl-(1''''--> 6"')-O-beta-D (2"'-O-E-caffeoylgalactopyranoside).

  9. 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.

  10. Constituents of the leaves of Woodfordia fruticosa Kurz. I. Isolation, structure, and proton and carbon-13 nuclear magnetic resonance signal assignments of woodfruticosin (woodfordin C), an inhibitor of deoxyribonucleic acid topoisomerase II.

    PubMed

    Kadota, S; Takamori, Y; Nyein, K N; Kikuchi, T; Tanaka, K; Ekimoto, H

    1990-10-01

    Woodfruticosin (woodfordin C), a new cyclic dimeric hydrolyzable tannin having an inhibitory activity toward deoxyribonucleic acid (DNA) topoisomerase II, has been isolated from the leaves of Woodfordia fruticosa Kurz (Lythraceae) along with three known flavonol glycosides and three known flavonol glycoside gallates. The structure of wood fruticosin (woodfordin C) was determined by the use of two-dimensional nuclear magnetic resonance (2-D NMR) spectroscopy including heteronuclear multiple quantum coherence (HMQC) and heteronuclear multiple bond connectivity (HMBC) techniques. Detailed analyses of the proton and carbon-13 NMR (1H- and 13C-NMR) spectra of six known flavonoids were performed.

  11. Melanogenesis inhibitory bisabolane-type sesquiterpenoids from the roots of Angelica koreana.

    PubMed

    Lee, Jin Woo; Yun, Cheong-Yong; Roh, Eunmiri; Lee, Chul; Jin, Qinghao; Bang, Kwon Ki; Jung, Sang-Hun; Lee, Dongho; Lee, Mi Kyeong; Kim, Youngsoo; Hwang, Bang Yeon

    2012-04-15

    Bioactivity-guided isolation of the methanolic extract of the roots of Angelica koreana led to the isolation of four new bisabolane-type sesquiterpenoids, osterivolones A-D (1-4) together with four known compounds, bisabolangelone (5), decursinol angelate (6), psoralen (7), and falcarindiol (8). Their structures were elucidated on the basis of spectroscopic data interpretation, especially 2D NMR spectra such as HMQC, HMBC, and NOESY. All compounds were evaluated for their inhibitory effects of the melanogenesis against α-melanocyte stimulating hormone (α-MSH)-activated B16 melanoma cells. Copyright © 2012 Elsevier Ltd. All rights reserved.

  12. 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

  13. Indirect detection of infinite-speed MAS solid-state NMR spectra

    NASA Astrophysics Data System (ADS)

    Perras, Frédéric A.; Venkatesh, Amrit; Hanrahan, Michael P.; Goh, Tian Wei; Huang, Wenyu; Rossini, Aaron J.; Pruski, Marek

    2017-03-01

    Heavy spin-1/2 nuclides are known to possess very large chemical shift anisotropies that can challenge even the most advanced magic-angle-spinning (MAS) techniques. Wide manifolds of overlapping spinning sidebands and insufficient excitation bandwidths often obfuscate meaningful spectral information and force the use of static, low-resolution solid-state (SS)NMR methods for the characterization of materials. To address these issues, we have merged fast-magic-angle-turning (MAT) and dipolar heteronuclear multiple-quantum coherence (D-HMQC) experiments to obtain D-HMQC-MAT pulse sequences which enable the rapid acquisition of 2D SSNMR spectra that correlate isotropic 1H chemical shifts to the indirectly detected isotropic "infinite-MAS" spectra of heavy spin-1/2 nuclides. For these nuclides, the combination of fast MAS and 1H detection provides a high sensitivity, which rivals the DNP-enhanced ultra-wideline SSNMR. The new pulse sequences were used to determine the Pt coordination environments in a complex mixture of decomposition products of transplatin and in a metal-organic framework with Pt ions coordinated to the linker ligands.

  14. Indirect detection of infinite-speed MAS solid-state NMR spectra

    SciTech Connect

    Perras, Frédéric A.; Venkatesh, Amrit; Hanrahan, Michael P.

    2017-01-18

    Heavy spin-1/2 nuclides are known to possess very large chemical shift anisotropies that can challenge even the most advanced magic-angle-spinning (MAS) techniques. Wide manifolds of overlapping spinning sidebands and insufficient excitation bandwidths often obfuscate meaningful spectral information and force the use of static, low-resolution solid-state (SS)NMR methods for the characterization of materials. In order to address these issues, we have merged fast-magic-angle-turning (MAT) and dipolar heteronuclear multiple-quantum coherence (D-HMQC) experiments to obtain D-HMQC-MAT pulse sequences which enable the rapid acquisition of 2D SSNMR spectra that correlate isotropic 1H chemical shifts to the indirectly detected isotropic “infinite-MAS” spectra of heavy spin-1/2more » nuclides. Furthermore, for these nuclides, the combination of fast MAS and 1H detection provides a high sensitivity, which rivals the DNP-enhanced ultra-wideline SSNMR. The new pulse sequences were used to determine the Pt coordination environments in a complex mixture of decomposition products of transplatin and in a metal-organic framework with Pt ions coordinated to the linker ligands.« less

  15. A ‘just-in-time’ HN(CA)CO experiment for the backbone assignment of large proteins with high sensitivity

    NASA Astrophysics Data System (ADS)

    Werner-Allen, Jon W.; Jiang, Ling; Zhou, Pei

    2006-07-01

    Among the suite of commonly used backbone experiments, HNCACO presents an unresolved sensitivity limitation due to fast 13CO transverse relaxation and passive 13Cα-13Cβ coupling. Here, we present a high-sensitivity 'just-in-time' (JIT) HN(CA)CO pulse sequence that uniformly refocuses 13Cα-13Cβ coupling while collecting 13CO shifts in real time. Sensitivity comparisons of the 3-D JIT HN(CA)CO, a CT-HMQC-based control, and a HSQC-based control with selective 13Cα inversion pulses were performed using a 2H/13C/15N labeled sample of the 29 kDa HCA II protein at 15 °C. The JIT experiment shows a 42% signal enhancement over the CT-HMQC-based experiment. Compared to the HSQC-based experiment, the JIT experiment is 16% less sensitive for residues experiencing proper 13Cα refocusing and 13Cα-13Cβ decoupling. However, for the remaining residues, the JIT spectrum shows a 106% average sensitivity gain over the HSQC-based experiment. The high-sensitivity JIT HNCACO experiment should be particularly beneficial for studies of large proteins to provide 13CO resonance information regardless of residue type.

  16. Improving reliability of chemometric models for authentication of species origin of heparin by switching from 1D to 2D NMR experiments.

    PubMed

    Monakhova, Yulia B; Fareed, Jawed; Yao, Yiming; Diehl, Bernd W K

    2018-05-10

    Nuclear magnetic resonance (NMR) spectroscopy is regarded as one of the most powerful and versatile analytical approaches to assure the quality of heparin preparations. In particular, it was recently demonstrated that by using 1 H NMR coupled with chemometrics heparin and low molecular weight heparin (LMWH) samples derived from three major animal species (porcine, ovine and bovine) can be differentiated [Y.B. Monakhova et al. J. Pharm. Anal. 149 (2018) 114-119]. In this study, significant improvement of existing chemometric models was achieved by switching to 2D NMR experiments (heteronuclear multiple-quantum correlation (HMQC) and diffusion-ordered spectroscopy (DOSY)). Two representative data sets (sixty-nine heparin and twenty-two LMWH) belonged to different batches and distributed by different commercial companies were investigated. A trend for animal species differentiation was observed in the principal component analysis (PCA) score plot built based on the DOSY data. A superior model was constructed using HMQC experiments, where individual heparin (LMWH) clusters as well as their blends were clearly differentiated. The predictive power of different classification methods as well as unsupervised techniques (independent components analysis, ICA) clearly proved applicability of the model for routine heparin and LMWH analysis. The switch from 1D to 2D NMR techniques provides a wealth of additional information, which is beneficial for multivariate modeling of NMR spectroscopic data for heparin preparations. Copyright © 2018 Elsevier B.V. All rights reserved.

  17. 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.

  18. Morphological analysis of the oribatid mite species Scutovertex pannonicus Schuster and description of its juvenile stages (Acari: Oribatida: Scutoverticidae).

    PubMed

    Mccullough, Elke; Krisper, Günther

    2013-01-01

    This paper provides a detailed redescription of the adult as well as the first morphological description of all juvenile instars (inclusive egg, prelarva and earlier larval stages) of Scutovertex pannonicus. The adults are characterized by their relatively large size (692-892 μm), their well developed sharply bordered foveae which are regularly distributed on the whole notogaster, except in the central field and the posterior notogastral brush-like setae ps1, h1,-h3. The exochorion of the eggs shows the typical structures for the genus Scutovertex like 'mushrooms' and granules with the species-specific expression of the 'mushrooms' and its substructures. The exochorion is covered with an extra thin layer which is typical for this species. The larva and the nymphs can be distinguished from those of S. sculptus and S. minutus mainly by their lateral setae l' and l" on tibia I which are strongly serrated and slightly broadened.

  19. Gas-forming liposomes prepared using a liposomal magnetoporation method.

    PubMed

    Lee, Jae Min; Kwag, Dong Sup; Youn, Yu Seok; Lee, Eun Seong

    2017-07-01

    In this study, we report a gas-forming drug carrier engineered using the liposomal magnetoporation method. The liposomes that were magnetoporated under a magnetic shear stress possessed an opened lipid bilayer hole. A photosensitizing model drug (chlorin e6: Ce6) and 1H-1H-2H-perfluoro-1-hexene (PFH, as a volatile gas-forming agent) were efficiently loaded into the opened holes of the magnetoporated liposomes. PFH in the liposomes is vaporized at 50°C and can initiate liposome destabilization. The experimental results demonstrated that the liposomes were destabilized at 50°C efficiently released Ce6 and enhanced Ce6-mediated phototoxicity against KB tumor cells. As a result, these liposomes induced a significantly increased in vitro and in vivo photodynamic tumor inhibition. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Electrowetting properties of atomic layer deposited Al{sub 2}O{sub 3} decorated silicon nanowires

    SciTech Connect

    Rajkumar, K.; Rajavel, K.; Cameron, D. C.

    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°.more » Electrowetting induced a maximum reversible decrease of the contact angle of 20°at 150V in air.« less

  1. 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.

  2. The second lightest CP-even Higgs boson signals in the NMSSM at the LHC

    NASA Astrophysics Data System (ADS)

    Almarashi, M. M.

    2018-04-01

    We study the signal rates of the second lightest CP-even Higgs boson, h2, of the NMSSM produced in gluon fusion, in association with bottom quarks and in association with top quarks, which is not the SM-like Higgs boson, at the LHC. We evaluate the production rates of h2 in the SM fermionic and bosonic final states in addition to a1a1, h1h1 and Za1 final states. It is observed that the size of the signal rates in some regions of the NMSSM parameter space is quite large and that could help extracting h2 signals at the LHC through a variety of decay channels.

  3. Impact of surface wettability on S-layer recrystallization: a real-time characterization by QCM-D

    PubMed Central

    Vianna, Ana C; Moreno-Cencerrado, Alberto; Pum, Dietmar; Sleytr, Uwe B

    2017-01-01

    Quartz crystal microbalance with dissipation monitoring (QCM-D) has been employed to study the assembly and recrystallization kinetics of isolated SbpA bacterial surface proteins onto silicon dioxide substrates of different surface wettability. Surface modification by UV/ozone oxidation or by vapor deposition of 1H,1H,2H,2H-perfluorododecyltrichlorosilane yielded hydrophilic or hydrophobic samples, respectively. Time evolution of frequency and dissipation factors, either individually or combined as the so-called Df plots, showed a much faster formation of crystalline coatings for hydrophobic samples, characterized by a phase-transition peak at around the 70% of the total mass adsorbed. This behavior has been proven to mimic, both in terms of kinetics and film assembly steps, the recrystallization taking place on an underlying secondary cell-wall polymer (SCWP) as found in bacteria. Complementary atomic force microscopy (AFM) experiments corroborate these findings and reveal the impact on the final structure achieved. PMID:28144568

  4. Extending the Lifetime of Perovskite Solar Cells using a Perfluorinated Dopant.

    PubMed

    Salado, Manuel; Ramos, F Javier; Manzanares, Valentin M; Gao, Peng; Nazeeruddin, Mohammad Khaja; Dyson, Paul J; Ahmad, Shahzada

    2016-09-22

    The principle limitation of perovskite solar cells is related to their instability and, hence, their limited lifetime. Herein, we employ an imidazolium iodide dopant, 1-methyl-3-(1H,1H,2H,2H-nonafluorohexyl)-imidazolium iodide, containing a perfluorous appendage, which leads to prolonged (unencapsulated, under Ar atmosphere) device activities exceeding 100 days without compromising the power conversion efficiency and other photovoltaic parameters. The extended lifetime of the device can be attributed, at least in part, to the hydrophobic nature of the imidazolium iodide salt. The functionalization of the perovskite material was found to have negligible influence on the perovskite crystal structure. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Biotransformation of bergapten and xanthotoxin by Glomerella cingulata.

    PubMed

    Marumoto, Shinsuke; Miyazawa, Mitsuo

    2010-07-14

    The biotransformation of bergapten (1) by the fungus Glomerella cingulata gave the corresponding reduced acid, 6,7-furano-5-methoxy hydrocoumaric acid (2), a new compound. Xanthotoxin (3) was also converted to the corresponding reduced acid cnidiol b (4) and demethylated metabolite xanthotoxol (5) by G. cingulata. The structure of the new compound 2 was elucidated by high-resolution mass spectrometry, extensive NMR techniques, including (1)H NMR and (13)C NMR, (1)H-(1)H correlation spectroscopy, heteronuclear multiple quantum coherence, and heteonuclear multiple bond coherence. The methyl ester or methyl ether or methyl ester and ether derivatives of 2 and 4 were synthesized. All compounds were tested for the beta-secretase (BACE1) inhibitory activity in vitro. The methyl ester and ether derivative 8 was shown to possess BACE1 inhibitory activity, and a IC(50) value was 0.64 +/- 0.04 mM.

  6. Impact of surface wettability on S-layer recrystallization: a real-time characterization by QCM-D.

    PubMed

    Iturri, Jagoba; Vianna, Ana C; Moreno-Cencerrado, Alberto; Pum, Dietmar; Sleytr, Uwe B; Toca-Herrera, José Luis

    2017-01-01

    Quartz crystal microbalance with dissipation monitoring (QCM-D) has been employed to study the assembly and recrystallization kinetics of isolated SbpA bacterial surface proteins onto silicon dioxide substrates of different surface wettability. Surface modification by UV/ozone oxidation or by vapor deposition of 1 H ,1 H ,2 H ,2 H -perfluorododecyltrichlorosilane yielded hydrophilic or hydrophobic samples, respectively. Time evolution of frequency and dissipation factors, either individually or combined as the so-called Df plots, showed a much faster formation of crystalline coatings for hydrophobic samples, characterized by a phase-transition peak at around the 70% of the total mass adsorbed. This behavior has been proven to mimic, both in terms of kinetics and film assembly steps, the recrystallization taking place on an underlying secondary cell-wall polymer (SCWP) as found in bacteria. Complementary atomic force microscopy (AFM) experiments corroborate these findings and reveal the impact on the final structure achieved.

  7. 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.

  8. 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

    2016-01-05

    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.

  9. Poly(isobutylene) nanoparticles via cationic polymerization in nonaqueous emulsions.

    PubMed

    Schuster, Thomas; Golling, Florian E; Krumpfer, Joseph W; Wagner, Manfred; Graf, Robert; Alsaygh, Abdulhamid A; Klapper, Markus; Müllen, Klaus

    2015-01-01

    The preparation of poly(isobutylene) (PIB) nanoparticles via cationic emulsion polymerization is presented. As a requirement, an oil-in-perfluoroalkane nonaqueous emulsion is developed, which is inert under the carbocationic polymerization conditions. To stabilize the dichloromethane/hexane droplets in the fluorinated, continuous phase, an amphiphilic block copolymer emulsifier is prepared containing PIB and 1H,1H-perfluoroalkylated poly(pentafluorostyrene) blocks. This system allows for the polymerization of isobutylene with number-average molecular weights (Mn) up to 27,000 g mol(-1). The particle morphologies are characterized via dynamic light scattering and electron microscopy. For Mn > 20,000 g mol(-1), the particles exhibit shape-persistence at room temperature and are ≈100 nm in diameter. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Janus cyclic peptide-polymer nanotubes

    NASA Astrophysics Data System (ADS)

    Danial, Maarten; My-Nhi Tran, Carmen; Young, Philip G.; Perrier, Sébastien; Jolliffe, Katrina A.

    2013-11-01

    Self-assembled nanotubular structures have numerous potential applications but these are limited by a lack of control over size and functionality. Controlling these features at the molecular level may allow realization of the potential of such structures. Here we report a new generation of self-assembled cyclic peptide-polymer nanotubes with dual functionality in the form of either a Janus or mixed polymeric corona. A ‘relay’ synthetic strategy is used to prepare nanotubes with a demixing or mixing polymeric corona. Nanotube structure is assessed in solution using 1H-1H nuclear Overhauser effect spectroscopy NMR, and in bulk using differential scanning calorimetry. The Janus nanotubes form artificial pores in model phospholipid bilayers. These molecules provide a viable pathway for the development of intriguing nanotubular structures with dual functionality via a demixing or a mixing polymeric corona and may provide new avenues for the creation of synthetic transmembrane protein channel mimics.

  11. Versatile superamphiphobic cotton fabrics fabricated by coating with SiO2/FOTS

    NASA Astrophysics Data System (ADS)

    Li, Deke; Guo, Zhiguang

    2017-12-01

    A multifunctional superamphiphobic cotton fabric was fabricated by coating silica nanoparticles on the cotton fabric surface and further modification by 1H,1H,2H,2H-perfluorooctyltrichlorosilane (FOTS). The fluctuant woven fabric and the fluffy spherical SiO2 nanoparticles constructed a dual micro/nano-structures. The surface free energy of the fabric composite was reduced by FOTS modifier. The interplay of the structured and perfluorinated SiO2 nanoparticles could not only endow the fabric highly liquid repellent ability, but could also to enhance the coating stability. The prepared cotton fabrics exhibited high liquid repellency to water, colza oil and n-hexadecane with lower surface tension, showing a contact angle of 158°, 152°, and 153°, respectively. The results demonstrated that superamphiphobic cotton fabric possessed desirable chemical and mechanical durability, self-cleaning and self-healing property, the robust and multifunctional fabric would find innovative opportunities for practical applications.

  12. Anomalous vapor sensor response of a fluorinated alkylthiol-protected gold nanoparticle film.

    PubMed

    Im, Jisun; Chandekar, Amol; Whitten, James E

    2009-04-21

    Monolayer-protected gold nanoparticle films generally swell and increase their electrical resistance when exposed to organic vapors. Films of gold nanoparticles protected by 1H,1H,2H,2H-perfluorodecanethiol (PFDT) exhibit an anomalous response in which the resistance decreases for all vapors investigated. Electron microscopy illustrates that the PFDT-functionalized gold nanoparticles are hexagonally ordered with an interparticle separation of 3 nm. Quartz crystal microbalance measurements confirm substantial mass uptake, but the relatively large interparticle separation and insulating properties of the gold particles lead to a porous film whose electrical resistance is strongly influenced by changes in the relative permittivity and reversible, vapor-induced changes in film morphology.

  13. Thiol-yne click reactions on alkynyl-dopamine-modified reduced graphene oxide.

    PubMed

    Kaminska, Izabela; Qi, Wang; Barras, Alexandre; Sobczak, Janusz; Niedziolka-Jonsson, Joanna; Woisel, Patrice; Lyskawa, Joel; Laure, William; Opallo, Marcin; Li, Musen; Boukherroub, Rabah; Szunerits, Sabine

    2013-06-24

    The large-scale preparation of graphene is of great importance due to its potential applications in various fields. We report herein a simple method for the simultaneous exfoliation and reduction of graphene oxide (GO) to reduced GO (rGO) by using alkynyl-terminated dopamine as the reducing agent. The reaction was performed under mild conditions to yield rGO functionalized with the dopamine derivative. The chemical reactivity of the alkynyl function was demonstrated by post-functionalization with two thiolated precursors, namely 6-(ferrocenyl)hexanethiol and 1H,1H,2H,2H-perfluorodecanethiol. X-ray photoelectron spectroscopy, UV/Vis spectrophotometry, Raman spectroscopy, conductivity measurements, and cyclic voltammetry were used to characterize the resulting surfaces. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Rapid fabrication and characterization of superhydrophobic tri-dimensional Ni/Al coatings

    NASA Astrophysics Data System (ADS)

    Guo, Xiaogang; Li, Xueming; Wei, Zhibo; Li, Xiaolin; Niu, Lidan

    2016-11-01

    Superhydrophobic tri-dimensional Ni/Al coatings (3DNACs) with great application value have been successfully fabricated via a simple two-step method combined with hydrogen bubble dynamic template and electrophoretic deposition technique after 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane treatment. The surface morphologies and chemical compositions were analyzed by FE-SEM, EDS, XRD, AFM and FT-IR in detail. The water contact angle of superhydrophobic 3DNACs surface was as high as 156 ± 2° (>150) much larger than that of unmodified samples. Moreover, the obtained samples exhibited great thermal properties and combustion performance. Thus, the superhydrophobic 3DNACs with prominent exothermic capability turn out to be a promising novel energy in field of mirco/nano energy materials for longer-term storage or transportation, especially in high humid environment.

  15. 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. Copyright © 2010 Elsevier B.V. All rights reserved.

  16. High-throughput aided synthesis of the porous metal-organic framework-type aluminum pyromellitate, MIL-121, with extra carboxylic acid functionalization.

    PubMed

    Volkringer, Christophe; Loiseau, Thierry; Guillou, Nathalie; Férey, Gérard; Haouas, Mohamed; Taulelle, Francis; Elkaim, Erik; Stock, Norbert

    2010-11-01

    A new porous metal-organic framework (MOF)-type aluminum pyromellitate (MIL-121 or Al(OH)[H(2)btec]·(guest), (guest = H(2)O, H(4)btec = pyromellitic acid) has been isolated by using a high-throughput synthesis method under hydrothermal conditions. Its structure was determined from powder X-ray diffraction analysis using synchrotron radiation (Soleil, France) and exhibits a network closely related to that of the MIL-53 series. It is a three-dimensional (3D) framework containing one-dimensional (1D) channels delimited by infinite trans-connected aluminum-centered octahedra AlO(4)(OH)(2) linked through the pyromellitate ligand. Here the organic ligand acts as tetradendate linker via two of the carboxylate groups. The two others remain non-bonded in their protonated form, and this constitutes a rare case of the occurrence of both bonding and non-bonding organic functionalities of the MOF family. The non-coordinated -COOH groups points toward the channels to get them an open form configuration. Within the tunnels are located unreacted pyromellitic acid and water species, which are evacuated upon heating, and a porous MIL-121 phase is obtained with a Brunauer-Emmett-Teller (BET) surface area of 162 m(2) g(-1). MIL-121 has been characterized by IR, thermogravimetry (TG) analyses, and solid state NMR spectroscopy employing a couple of two-dimensional (2D) techniques such as (1)H-(1)H SQ-DQ BABA, (1)H-(1)H SQ-SQ RFDR, (27)Al{(1)H} CPHETCOR and (27)Al MQMAS.

  17. 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.

  18. Study of Perfluorophosphonic Acid Surface Modifications on Zinc Oxide Nanoparticles

    PubMed Central

    Shoup, Deben; Behnke, Grayce; Peck, Cynthia; Agarwal, Sushant; Gupta, Rakesh K.; Fagan, Jonathan W.; Iuliucci, Robbie J.; Wang, Qiang

    2017-01-01

    In this study, perfluorinated phosphonic acid modifications were utilized to modify zinc oxide (ZnO) nanoparticles because they create a more stable surface due to the electronegativity of the perfluoro head group. Specifically, 12-pentafluorophenoxydodecylphosphonic acid, 2,3,4,5,6-pentafluorobenzylphosphonic acid, and (1H,1H,2H,2H-perfluorododecyl)phosphonic acid have been used to form thin films on the nanoparticle surfaces. The modified nanoparticles were then characterized using infrared spectroscopy, X-ray photoelectron spectroscopy, and solid-state nuclear magnetic resonance spectroscopy. Dynamic light scattering and scanning electron microscopy-energy dispersive X-ray spectroscopy were utilized to determine the particle size of the nanoparticles before and after modification, and to analyze the film coverage on the ZnO surfaces, respectively. Zeta potential measurements were obtained to determine the stability of the ZnO nanoparticles. It was shown that the surface charge increased as the alkyl chain length increases. This study shows that modifying the ZnO nanoparticles with perfluorinated groups increases the stability of the phosphonic acids adsorbed on the surfaces. Thermogravimetric analysis was used to distinguish between chemically and physically bound films on the modified nanoparticles. The higher weight loss for 12-pentafluorophenoxydodecylphosphonic acid and (1H,1H,2H,2H-perfluorododecyl)phosphonic acid modifications corresponds to a higher surface concentration of the modifications, and, ideally, higher surface coverage. While previous studies have shown how phosphonic acids interact with the surfaces of ZnO, the aim of this study was to understand how the perfluorinated groups can tune the surface properties of the nanoparticles. PMID:29182559

  19. (¹⁵N ± ¹³C') edited (4, 3)D-H(CC)CONH TOCSY and (4, 3)D-NOESY HNCO experiments for unambiguous side chain and NOE assignments of proteins with high shift degeneracy.

    PubMed

    Kumar, Dinesh; Arora, Ashish

    2011-11-01

    Well-resolved and unambiguous through-bond correlations and NOE data are crucial for high-quality protein structure determination by NMR. In this context, we present here (4, 3)D reduced dimensionality (RD) experiments: H(CC)CONH TOCSY and NOESY HNCO--which instead of (15)N shifts exploit the linear combination of (15)N(i) and (13)C'(i-1) shifts (where i is a residue number) to resolve the through-bond (1)H-(1)H correlations and through-space (1)H-(1)H NOEs. The strategy makes use of the fact that (15)N and (13)C' chemical shifts when combined linearly provide a dispersion which is better compared to those of the individual chemical shifts. The extended dispersion thus available in these experiments will help to obtain the unambiguous side chain and accurate NOE assignments especially for medium-sized alpha-helical or partially unstructured proteins [molecular weight (MW) between 12-15 kDa] as well as higher MW (between 15-25 kDa) folded proteins where spectral overlap renders inaccurate and ambiguous NOEs. Further, these reduced dimensionality experiments in combination with routinely used (15)N and (13)C' edited TOCSY and NOESY experiments will provide an alternative way for high-quality NMR structure determination of large unstable proteins (with very high shift degeneracy), which are not at all amenable to 4D NMR. The utility of these experiments has been demonstrated here using (13)C/(15)N labeled ubiquitin (76 aa) protein. Copyright © 2011 John Wiley & Sons, Ltd.

  20. Structure of the Mesophases Formed by a Perfluoroalkyl/Biphenyl Compound. Amphiphilic and Steric Effects

    NASA Astrophysics Data System (ADS)

    Pensec, Sandrine; Tournilhac, François-Genès; Bassoul, Pierre

    1996-11-01

    We describe the synthesis and mesomorphic behaviour of 4-(1H,1H-perfluorooctyloxy)- 4'-methoxy biphenyl. Two mesophases of smectic E and smectic A types were observed. X-ray diffraction study of the smectic E phase indicates a herringbone arrangement of the biphenyl cores, the perfluoroalkyl chains being in a molten state. The {S_E to S_A} transition is related to the melting of the biphenyl sublattice. In both phases, the flexibility of perfluoroalkyl chains permits the area matching between the two segregated sublayers. Nous décrivons la synthèse et les propriétés mésomorphes du 4-(1H,1H-perfluorooctyloxy)- 4'-méthoxy biphényle. Ce composé forme deux mésophases de type smectique E et smectique A. L'analyse par diffraction des rayons X révèle, dans le cas de la phase smectique E un arrangement en chevrons des coeurs biphényles, les chaînes perfluoroalkyles se trouvant dans un état désordonné. La transition {S_E to S_A} correspond à la fusion partielle de la sous-couche biphényle. Dans les deux phases smectiques, la flexibilité des chaînes perfluoroalkyles permet l'adéquation des aires moléculaires entre les deux sous-couches ségrégées.

  1. Hydrazine 5,5'-bitetrazole-1,1'-diolate: a promising high density energetic salt with good properties.

    PubMed

    Zhang, Zhi-Bin; Xu, Cai-Xia; Yin, Xin; Zhang, Jian-Guo

    2016-12-21

    The development of new environmentally friendly energetic compounds with reasonable detonation performance and safety is a long-term target in energetic materials research. A new energetic eco-friendly salt of hydrazine 5,5'-bitetrazole-1,1'-diolate (HA·BTO) is developed based on the reaction of 1H,1'H-5,5'-bitetrazole-1,1'-diolate (BTO) with hydrazine hydrochloride (HA·HCl), and fully characterized. The monocrystal of the title salt is obtained and the structure is determined by powder X-ray diffraction and single crystal X-ray diffraction. Results show that the salt belongs to the triclinic space group P1[combining macron] with a relatively high density of 1.912 g cm -3 under 298 K. The properties of the salt are discussed in detail. The thermal decomposition behaviors of the salt are tested, indicating that the salt has good thermal stability with a decomposition temperature above 200 °C. The enthalpy of formation for the salt is dependent on the combustion heat date measured by oxygen bomb calorimetry with a result of 425.6 kJ mol -1 , which is the same level as TKX-50, and four times higher than that of RDX. The detonation pressure (P) and detonation velocity (D) of the salt are calculated as 8931 m s -1 and 36.1 GPa, which are higher than those of RDX. In addition, the impact and friction sensitivities are tested through a relevant standard method with a result of 28 J and 120 N, which are better than those of TKX-50. We can draw the conclusion that the salt could provide a promising future in use as a kind of insensitive explosive alternative. The discovery also contributes significantly to the expansion and application of the chemistry of 1H,1'H-5,5'-bitetrazole-1,1'-diolate, as well as N-heterocyclic compounds.

  2. Salt Segregation and Sample Cleanup on Perfluoro-Coated Nanostructured Surfaces for Laser Desorption Ionization Mass Spectrometry of Biofluid Samples.

    PubMed

    Zhou, Ya; Peng, Chen; Harris, Kenneth D; Mandal, Rupasri; Harrison, D Jed

    2017-03-21

    We present a surface assisted laser desorption ionization (SALDI) technique, coupled with fluorocarbon coating, to achieve selective segregation of ionic and/or hydrophilic analytes from background biofluid electrolytes for quantiatve mass spectrometric analysis. By controlling the contact angle of (1H,1H,2H,2H-perfluorooctyl) trichlorosilane or (1H,1H,2H,2H-perfluorooctyl) dimethylchlorosilane to a specific range (105-120°), background electrolytes can be made to segregate from hydrophilic analytes during a drying step on the surface of a highly nanoporous thin film. Nanoporous silicon films were prepared using glancing angle deposition (GLAD) thin film technology, then coated with fluorcarbon. This desalting method directly separates highly polar, ionic metabolites, such as amino acids, from salty biofluids such as aritificial cerebrospinal fluid (aCSF) and serum. Derivatization, extraction and rinsing steps are not required to separate the analytes from the bioelectrolytes. With on-chip desalting, the limit of quantitation for histidine spiked in aCSF is ∼1 μM, and calibration curves with internal standards can achieve a precision of 1-9% within a 1 to 50 μM range. Five highly polar organic acids in serum were successfully quantified, and the SALDI-MS results obtained on the desalted serum sample spots show both good reproducibility and compare well to results from NMR and liquid chromatography-mass spectrometry. Putative identification of a total of 32 metabolites was accomplished in blood using time-of-flight MS with perfluoro coated Si-GLAD SALDI, by comparison to tabulated data.

  3. Overall structure and sugar dynamics of a DNA dodecamer from homo- and heteronuclear dipolar couplings and 31P chemical shift anisotropy.

    PubMed

    Wu, Zhengrong; Delaglio, Frank; Tjandra, Nico; Zhurkin, Victor B; Bax, Ad

    2003-08-01

    The solution structure of d(CGCGAATTCGCG)(2) has been determined on the basis of an exceptionally large set of residual dipolar couplings. In addition to the heteronuclear (13)C-(1)H and (15)N-(1)H and qualitative homonuclear (1)H-(1)H dipolar couplings, previously measured in bicelle medium, more than 300 quantitative (1)H-(1)H and 22 (31)P-(1)H dipolar restraints were obtained in liquid crystalline Pf1 medium, and 22 (31)P chemical shift anisotropy restraints. High quality DNA structures can be obtained solely on the basis of these new restraints, and these structures are in close agreement with those calculated previously on the basis of (13)C-(1)H and (15)N-(1)H dipolar couplings. In the newly calculated structures, (31)P-(1)H dipolar and (3)JsubH3(')Psub couplings and (31)P CSA data restrain the phosphodiester backbone torsion angles. The final structure represents a quite regular B-form helix with a modest bending of approximately 10 degrees, which is essentially independent of whether or not electrostatic terms are used in the calculation. Combined, the number of homo- and heteronuclear dipolar couplings significantly exceeds the number of degrees of freedom in the system. Results indicate that the dipolar coupling data cannot be fit by a single structure, but are compatible with the presence of rapid equilibria between C2(')-endo and C3(')-endo deoxyribose puckers (sugar switching). The C2(')-H2(')/H2(") dipolar couplings in B-form DNA are particularly sensitive to sugar pucker and yield the largest discrepancies when fit to a single structure. To resolve these discrepancies, we suggest a simplified dipolar coupling analysis that yields N/S equilibria for the ribose sugar puckers, which are in good agreement with previous analyses of NMR J(HH) couplings, with a population of the minor C3(')-endo form higher for pyrimidines than for purines.

  4. Association between FASN gene polymorphisms ultrasound carcass traits and intramuscular fat in Qinchuan cattle.

    PubMed

    Raza, Sayed Haidar Abbas; Gui, Linsheng; Khan, Rajwali; Schreurs, Nicola M; Xiaoyu, Wang; Wu, Sen; Mei, Chugang; Wang, Li; Ma, Xueyao; Wei, Dawei; Guo, Hongfang; Zhang, Song; Wang, Xingping; Kaleri, Hubdar Ali; Zan, Linsen

    2018-03-01

    Fatty acid synthase (FASN) is an enzyme involved with fat deposition and fatty acid composition in cattle. This study was conducted to detect single nucleotide polymorphisms (SNPs) of the FASN gene and explore their relationships with ultrasound carcass traits in order to assess the potential use of the FASN gene for the breeding selection of Qinchuan cattle for desirable carcass traits. The frequencies of SNP g.12740C>T, g.13192T>C and g.13232C>T were identified in 525 individual Qinchuan cattle which were also assessed for backfat depth, eye muscle area and intramuscular fat by ultrasound. According to the PIC values, g.13192T>C possessed an intermediate polymorphism (0.25T, g.12740C>T possessed low polymorphism (PIC<0.25). Chi-square tests showed that g.13192T>C were in Hardy-Weinberg disequilibrium (c21 H 1 , H 1 H 4 and H 1 H 2 (P<0.01). The TT genotype at g.13192T>C was associated with a greater eye muscle area and the TT genotype at g.13232C>T was associated with greater intramuscular fat. When these genotypes were combined there was no difference in eye muscle area and intramuscular fat between the diplotypes. The H 2 H 2 diplotype was associated with carcass traits that are likely to provide economic advantage in Qinchuan cattle. Variations in the FASN genes and their corresponding genotypes may be considered as molecular markers for economic traits in cattle breeding. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Tantalum and cobalt suicides: Temperature sensor applications

    NASA Astrophysics Data System (ADS)

    Collins, R. A.; Johnston, D. F. C.; Dearnaley, G.

    1986-06-01

    Ion bombardment induced mixing of Ta-Si films has been studied using 400 keV argon ions. Doses varied from 7×1014 to 1×1017 Ar+ cm-2 with post-bombardment anneals of 180 900 s at temperatures in the range 600 860 °C using radiant heating. Silicide uniformity and stoichiometry were determined using alpha backscattering spectrometry. Optimum fabrication parameters were determined with regard to subsequent material sheet resistivity, temperature coefficient of resistance and application as a temperature sensing material. Similar measurements were made on CoSi2 layers prepared by annealing ion bombarded samples and comparison with silicide films arising from purely thermal annealing was made. CoSi2 was found to be the more suitable material for temperature-sensor applications, showing a positive linear variation in sheet resistivity in the range 0 400 °C for samples which could be prepared simply and reproducibly.

  6. Materials aspects of ion beam synthesis of epitaxial suicides

    NASA Astrophysics Data System (ADS)

    Mantl, S.

    1994-02-01

    Ion beam synthesis of epitaxial suicides involves high dose ion implantation and subsequent annealing. In this short review the formation of suicide precipitates during the hot implantation and the layer formation during the high temperature anneal are discussed. Diffusivity and solid solubility of the transition metals in Si are crucial material properties for the formation of a uniform buried layer. Recent X-ray reflectivity measurements on buried CoSi 2 layers provided different interface roughnesses depending on suicide orientation and annealing conditions. A new 2 × 1 ordered structure of the CoSi 2/Si(001) interface was found using Z-contrast imaging. In addition, the carrier mobilities of the semiconducting suicides β-FeSi 2 and CrSi 2 are discussed.

  7. 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.

  8. Composition-tuned Co(n)Si nanowires: location-selective simultaneous growth along temperature gradient.

    PubMed

    Seo, Kwanyong; Lee, Sunghun; Yoon, Hana; In, Juneho; Varadwaj, Kumar S K; Jo, Younghun; Jung, Myung-Hwa; Kim, Jinhee; Kim, Bongsoo

    2009-05-26

    We report the simultaneous and selective synthesis of single-crystalline Co(n)Si NWs (n = 1-3) and their corresponding crystal structures--simple cubic (CoSi), orthorhombic (Co(2)Si), and face-centered cubic (Co(3)Si)--following a composition change. Co(n)Si NWs were synthesized by placing the sapphire substrates along a temperature gradient. The synthetic process is a successful demonstration of tuning the chemical composition in Co(n)Si NWs. The synthesis and detailed crystal structure of single-crystalline Co(2)Si and Co(3)Si are reported for the first time including the bulk and the nanostructure phases. The electrical and magnetic properties of Co(2)Si NWs are investigated and compared with those of CoSi NWs.

  9. 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

  10. 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.

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

    PubMed

    Lu, Chi-Ming; Hsu, Han-Fu; Lu, Kuo-Chang

    2013-07-03

    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.

  12. Microgravity

    NASA Image and Video Library

    2001-04-26

    The first NASA Dropping In a Microgravity Environment (DIME) student competition pilot project came to a conclusion at the Glenn Research Center in April 2001. The competition involved high-school student teams who developed the concept for a microgravity experiment and prepared an experiment proposal. The two student teams - COSI Academy, sponsored by the Columbus Center of Science and Industry, and another team from Cincinnati, Ohio's Sycamore High School, designed a microgravity experiment, fabricated the experimental apparatus, and visited NASA Glenn to operate their experiment in the 2.2 Second Drop Tower. Students from Sycamore High School in Cincinnati, Ohio (girls), and the COSI Academy, Columbus, Ohio (boys), participated. This image is from a digital still camera; higher resolution is not available.

  13. Spin Dependence of η Meson Production in Proton-Proton Collisions Close to Threshold.

    PubMed

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

    2018-01-12

    Taking advantage of the high acceptance and axial symmetry of the WASA-at-COSY detector, and the high polarization degree of the proton beam of COSY, the reaction p[over →]p→ppη has been measured close to threshold to explore the analyzing power A_{y}. The angular distribution of A_{y} is determined with the precision improved by more than 1 order of magnitude with respect to previous results, allowing a first accurate comparison with theoretical predictions. The determined analyzing power is consistent with zero for an excess energy of Q=15  MeV, signaling s-wave production with no evidence for higher partial waves. At Q=72  MeV the data reveal strong interference of Ps and Pp partial waves and cancellation of (Pp)^{2} and Ss^{*}Sd contributions. These results rule out the presently available theoretical predictions for the production mechanism of the η meson.

  14. A self optimizing synthetic organic reactor system using real-time in-line NMR spectroscopy† †Electronic supplementary information (ESI) available: Details about the methodology, LabView scripts, experimental set-ups, additional spectra and self-optimization can be found in the SI. See DOI: 10.1039/c4sc03075c Click here for additional data file.

    PubMed Central

    Sans, Victor; Porwol, Luzian; Dragone, Vincenza

    2015-01-01

    A configurable platform for synthetic chemistry incorporating an in-line benchtop NMR that is capable of monitoring and controlling organic reactions in real-time is presented. The platform is controlled via a modular LabView software control system for the hardware, NMR, data analysis and feedback optimization. Using this platform we report the real-time advanced structural characterization of reaction mixtures, including 19F, 13C, DEPT, 2D NMR spectroscopy (COSY, HSQC and 19F-COSY) for the first time. Finally, the potential of this technique is demonstrated through the optimization of a catalytic organic reaction in real-time, showing its applicability to self-optimizing systems using criteria such as stereoselectivity, multi-nuclear measurements or 2D correlations. PMID:29560211

  15. New Methylene Specific Experiments for the Measurement of Scalar Spin-Spin Coupling Constants between Protons Attached to 13C

    NASA Astrophysics Data System (ADS)

    Carlomagno, T.; Schwalbe, H.; Rexroth, A.; Sørensen, O. W.; Griesinger, C.

    1998-11-01

    New two- and three-dimensional NMR methods are proposed for the measurement of3J(H, H) coupling constants between two adjacent methylene moieties. The new experiment, which is based on a combination of the E.COSY principle and double/zero quantum heteronuclear spectroscopy, has been applied to diaceton-glucose and to the protein rhodniin. The coupling constants of CH-CH2groups have been compared with those obtained from a HCCH-E.COSY experiment to check the reliability of the results. An analysis of the coupling constants derived by comparison between experimental and simulated spectra is presented. Simulations were done with the program wtest considering fully correlated dipolar relaxation. Side-chain conformations in amino acids with adjacent methylene groups can be determined by the new experiment.

  16. Spin Dependence of η Meson Production in Proton-Proton Collisions Close to Threshold

    NASA Astrophysics Data System (ADS)

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

    2018-01-01

    Taking advantage of the high acceptance and axial symmetry of the WASA-at-COSY detector, and the high polarization degree of the proton beam of COSY, the reaction p → p →p p η has been measured close to threshold to explore the analyzing power Ay. The angular distribution of Ay is determined with the precision improved by more than 1 order of magnitude with respect to previous results, allowing a first accurate comparison with theoretical predictions. The determined analyzing power is consistent with zero for an excess energy of Q =15 MeV , signaling s -wave production with no evidence for higher partial waves. At Q =72 MeV the data reveal strong interference of P s and P p partial waves and cancellation of (P p )2 and S s*S d contributions. These results rule out the presently available theoretical predictions for the production mechanism of the η meson.

  17. Neutron-proton scattering in the context of the d*(2380) resonance

    NASA Astrophysics Data System (ADS)

    Adlarson, P.; Augustyniak, W.; Bardan, W.; Bashkanov, M.; Bergmann, F. S.; Berłowski, M.; Bhatt, H.; Büscher, M.; Calén, H.; Ciepał, I.; Clement, H.; Coderre, D.; Czerwiński, E.; Demmich, K.; Doroshkevich, E.; Engels, R.; Erven, A.; Erven, W.; Eyrich, W.; Fedorets, P.; Föhl, K.; Fransson, K.; Goldenbaum, F.; Goslawski, P.; Goswami, A.; Grigoryev, K.; Gullström, C.-O.; Hauenstein, F.; Heijkenskjöld, L.; Hejny, V.; Hodana, M.; Höistad, B.; Hüsken, N.; Jany, A.; Jany, B. R.; Jarczyk, L.; Johansson, T.; Kamys, B.; Kemmerling, G.; Khan, F. A.; Khoukaz, A.; Kirillov, D. A.; Kistryn, S.; Kleines, H.; Kłos, B.; Krapp, M.; Krzemień, W.; Kulessa, P.; Kupść, A.; Lalwani, K.; Lersch, D.; Lorentz, B.; Magiera, A.; Maier, R.; Marciniewski, P.; Mariański, B.; Mikirtychiants, M.; Morsch, H.-P.; Moskal, P.; Ohm, H.; Ozerianska, I.; Perez del Rio, E.; Piskunov, N. M.; Podkopał, P.; Prasuhn, D.; Pricking, A.; Pszczel, D.; Pysz, K.; Pyszniak, A.; Redmer, C. F.; Ritman, J.; Roy, A.; Rudy, Z.; Sawant, S.; Schadmand, S.; Sefzick, T.; Serdyuk, V.; Serdyuk, V.; Siudak, R.; Skorodko, T.; Skurzok, M.; Smyrski, J.; Sopov, V.; Stassen, R.; Stepaniak, J.; Stephan, E.; Sterzenbach, G.; Stockhorst, H.; Ströher, H.; Szczurek, A.; Täschner, A.; Trzciński, A.; Varma, R.; Wagner, G. J.; Wolke, M.; Wrońska, A.; Wüstner, P.; Wurm, P.; Yamamoto, A.; Yurev, L.; Zabierowski, J.; Zieliński, M. J.; Zink, A.; Złomańczuk, J.; Żuprański, P.; Żurek, M.; Workman, R. L.; Briscoe, W. J.; Strakovsky, I. I.; WASA-at-COSY Collaboration

    2014-09-01

    New data on quasifree polarized neutron-proton scattering in the region of the recently observed d* resonance structure are obtained by exclusive and kinematically complete high-statistics measurements with WASA at COSY. This paper details the determination of the beam polarization, checks of the quasifree character of the scattering process, on all obtained Ay angular distributions and on the new partial-wave analysis, which includes the new data producing a resonance pole in 3D3-3G3 coupled partial waves at (2380±10-i40±5) MeV—in accordance with the d* dibaryon resonance hypothesis. The effect of the new partial-wave solution on the description of total and differential cross-section data as well as specific combinations of spin-correlation and spin-transfer observables available from COSY-ANKE measurements at Td=2.27 GeV is discussed.

  18. 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.

  19. Electrical properties and magnetic response of cobalt germanosilicide nanowires.

    PubMed

    Tsai, Chun-I; Wang, Chiu-Yen; Tang, Jianshi; Hung, Min-Hsiu; Wang, Kang L; Chen, Lih-Juann

    2011-12-27

    The effects of partial substitution of Ge for Si in cobalt germanosilicide (CoSi(1-x)Ge(x) and Co(2)Si(1-x)Ge(x)) nanowires (NWs) on the electrical transport, magnetic properties, and magnetoresistance (MR) have been investigated. Cobalt germanosilicide NWs were synthesized by a spontaneous chemical vapor transport growth method. The Ge concentration can be selectively controlled from 0 to 15% and 0-50% for CoSi(1-x)Ge(x) and Co(2)Si(1-x)Ge(x) NWs, respectively, by varying the reaction temperature. Electrical measurements showed that the resistivities of CoSi(1-x)Ge(x) NWs are 90, 60, 30, and 23 μΩ-cm for x = 0, 0.01, 0.05, and 0.15, respectively. Therefore, the electrical resistivity of CoSi(1-x)Ge(x) NWs was found to decrease significantly with an increasing Ge concentration, which is believed to be a result of the band gap narrowing. On the other hand, the Co(2)Si(1-x)Ge(x) (x ≤ 0.5) NWs exhibited ferromagnetism at 300 K, which is attributed to the uncoordinated Co atoms on the NW surface and spin-glass behavior at low temperature. The highest MR response of Co(2)Si(1-x)Ge(x) NWs occurred at x = 0.5, where a MR ratio of 11.7% can be obtained at 10-25 K with a magnetic field of 8 T. The enhanced physical properties of cobalt germanosilicide NWs with Ge substitution shall lead to promising application in the fabrication of nanodevices, including spintronics and serving as the gate and interconnect material.

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

    DOE PAGES

    Guidoboni, G.; Stephenson, E.; Andrianov, S.; ...

    2016-07-28

    Here, 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.

  1. 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.

    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-membraneousmore » 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.« less

  2. Dinoflagellate Toxins Responsible for Ciguatera Food Poisoning

    DTIC Science & Technology

    1991-03-30

    D DINOF[AGELIATE TO:XruNS RESPONSIBLE FOR CIGUATERA FOOD POISONING Final Report Donald M. Miller March 30, 1991 Supported by US ARMY MEDICAL RESEARCH...NO. NO. N. ACCESSION NO. 11. TITLE (iclude Security Classification) DINOFLAGELLATE TOXINS RESPONSIBLE FOR CIGUATERA POISONING 12. PERSONAL AUTHOR(S...GROUP SUB-GROUP 06 03 Ciguatera ; Toxins; Inhibitor; NMR; 10H COSY; 06 01 1 Dinoflagellates: Mass Culture: Purification: RAT 19. ABSTRACT (Continue on

  3. Atomic-Scale Variations of the Tunneling Distribution in a Scanning Tunneling Microscope Observed by Ballistic-Electron-Emission Microscopy

    NASA Astrophysics Data System (ADS)

    Sirringhaus, H.; Lee, E. Y.; von Känel, H.

    1995-05-01

    In situ ballistic-electron-emission microscopy (BEEM) and spectroscopy (BEES) have been performed at 77 K on epitaxial CoSi2/Si (100) and (111). BEEM images reflect the atomic-scale periodicity of the surface topography. Atomically resolved BEES is correlated with tunneling spectroscopy and the apparent tunneling barrier height. The effect is due to variations of the energy distribution of the tunneling electrons on an atomic scale.

  4. 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.

  5. A Novel Multivoxel-Based Quantitation of Metabolites and Lipids Noninvasively Combined with Diffusion-Weighted Imaging in Breast Cancer

    DTIC Science & Technology

    2013-10-01

    0743 TITLE: A Novel Multivoxel-Based Quantitation of Metabolites and Lipids Noninvasively Combined with Diffusion-Weighted Imaging in Breast ...Multivoxel-Based Quantitation of Metabolites and Lipids Noninvasively Combined with Diffusion-Weighted Imaging in Breast Cancer 5a. CONTRACT NUMBER...implement a Matlab-based post-processing algorithm in order to process the 2D COSY data recorded in breast cancer, iii) To record DWI and to calculate

  6. Polar secondary metabolites of Ferula persica roots.

    PubMed

    Iranshahi, Mehrdad; Mojarab, Mehdi; Sadeghian, Hamid; Hanafi-Bojd, Mohammad Yahya; Schneider, Bernd

    2008-01-01

    Phytochemical investigation of the methanolic extract of the dried roots of Ferula persica resulted in four sesquiterpene coumarin glycosides, persicaosides A-D, and two known phytosterol glucosides, sitosterol 3-O-beta-glucoside and stigmasterol 3-O-beta-glucoside. The structures of these compounds were elucidated by extensive spectroscopic methods including 1D-((1)H and (13)C) and 2D NMR experiments (DQF-COSY, HSQC, HMBC, and ROESY) as well as ESIMS and TOFMS analyses.

  7. Microgravity

    NASA Image and Video Library

    2002-08-07

    Students prepare to load fluids in their experiment apparatus during the 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. Microgravity

    NASA Image and Video Library

    2002-08-07

    Students prepare to load fluids in their experiment apparatus during the 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.

  9. 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.

  10. Kaempferol-3,4'-di-O-beta-glucopyranoside-7-O-alpha-rhamnopyranoside as a new flavonoid from Iberis amara L.

    PubMed

    Kroll, U; Reif, K; Lederer, I; Förster, G; Zapp, J

    2009-02-01

    A new flavonol glycoside, kaempferol-3,4'-di-O-beta-glucopyranoside-7-O-alpha-rhamno-pyranoside, was isolated from the ethanolic extract of the whole fresh plant of Iberis amara L., an European plant used in gastrointestinal medicine. The structure was established by a combination of 1D and 2D NMR techniques (COSY, HSQC, HMBC, NOESY) as well as UV, IR and mass spectral data.

  11. 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).

  12. Microgravity

    NASA Image and Video Library

    2002-08-08

    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.

  13. Microgravity

    NASA Image and Video Library

    2002-08-07

    Students prepare their experiment apparatus for free-fall 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.

  14. Microgravity

    NASA Image and Video Library

    2002-08-08

    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.

  15. Microgravity

    NASA Image and Video Library

    2002-08-07

    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.

  16. Microgravity

    NASA Image and Video Library

    2002-08-08

    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.

  17. Half-metallicity and magnetism of Ti2Ni1-x CoxAl1-y Siy inverse Heusler alloys

    NASA Astrophysics Data System (ADS)

    Zhou, Ting; Feng, Yu; Chen, Xiaorui; Yuan, Hongkuan; Chen, Hong

    2017-02-01

    Half-metallicity and magnetism of Ti2Ni1-x CoxAl1-y Siy, which are obtained by Co/Si substitutions for Ni/Al of inverse Heusler alloy Ti2NiAl, are investigated by first-principle calculations based on density functional theory (DFT). The optimized lattice constants of the doped systems all conform to the Vegard law as the increase of the impurity concentration, and the magnetic moments obey the Slater-Pauling rule when the half-metallicity is retained. The defect formation energies of the codoped systems are lower than those of the monodoped systems due to the charge compensation effects, thus the Co+Si codoping is more favorable in energy than the Co/Si monodoping. Furthermore, for the Co and Si monodoped systems, the Co monodoping retains the minority-spin bandgap unchanged although the Fermi level moves towards high energy region, and the Si monodoping leads to the minority-spin bandgap narrowing and even the loss of half-metallicity at the high concentration, while for the Co+Si codoped systems, the majority of the codoped compounds obviously show more stable half-metallicity and the minority-spin gap get widened. In particular, the minority-spin band gap of the codoped compounds Ti2Ni0.5Co0.5Al0.5Si0.5 , Ti2Ni0.25Co0.75Al0.5Si0.5 , and Ti2NiCo Al0.25Si0.75 are widened distinctly and their Fermi level are adjusted to the middle of the minority-spin gap, indicating that they possess robust half-metallicity and thus they are promising candidates for spintronics applications.

  18. Fluid Physics

    NASA Image and Video Library

    2002-08-07

    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.

  19. 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 .

  20. Thermoelectric properties of Si/CoSi2 sub-micrometer composites prepared by melt-spinning technique

    NASA Astrophysics Data System (ADS)

    Xie, Jun; Ohishi, Yuji; Ichikawa, Satoshi; Muta, Hiroaki; Kurosaki, Ken; Yamanaka, Shinsuke

    2017-05-01

    We here report on the influence of CoSi2 precipitates on the thermoelectric properties of heavily doped p-type Si. A simple self-assembly process using a melt-spinning technique followed by spark plasma sintering is introduced to prepare bulk Si/CoSi2 composites with a nominal composition of (Si0.99B0.01)95Co5. Scanning and transmission electron microscopy observations present clear evidence of a sub-micrometer CoSi2 phase with a size ranging from 50 to 500 nm. These sub-micrometer precipitates resulted in a retention of the high electrical performance of heavily doped Si, while simultaneously reducing thermal conductivity by over 20% compared to a coarse CoSi2 phase (1-10 μm) in a comparative sample prepared by arc melting and spark plasma sintering. As a result, a figure of merit ZT value of 0.21 at 1073 K was achieved in the sub-micrometer Si/CoSi2, an increase of 16% compared with the ZT value for homogeneous p-type Si with a similar carrier concentration. This suggests that the self-assembled sub-micrometer inclusions effectively enhanced the thermoelectric performance of Si-based thermoelectric materials.

  1. Cobalt silicide nanocables grown on Co films: synthesis and physical properties.

    PubMed

    Hsin, Cheng-Lun; Yu, Shih-Ying; Wu, Wen-Wei

    2010-12-03

    Single-crystalline cobalt silicide/SiO(x) nanocables have been grown on Co thin films on an SiO(2) layer by a self-catalysis process via vapor-liquid-solid mechanism. The nanocables consist of a core of CoSi nanowires and a silicon oxide shell with a length of several tens of micrometers. In the confined space in the oxide shell, the CoSi phase is stable and free from agglomeration in samples annealed in air ambient at 900 °C for 1 h. The nanocable structure came to a clear conclusion that the thermal stability of the silicide nanowires can be resolved by the shell encapsulation. Cobalt silicide nanowires were obtained from the nanocable structure. The electrical properties of the CoSi nanowires have been found to be compatible with their thin film counterpart and a high maximum current density of the nanowires has been measured. One way to obtain silicate nanowires has been demonstrated. The silicate compound, which is composed of cobalt, silicon and oxygen, was achieved. The Co silicide/oxide nanocables are potentially useful as a key component of silicate nanowires, interconnects and magnetic units in nanoelectronics.

  2. Changes in the neurochemistry of athletes with repetitive brain trauma: preliminary results using localized correlated spectroscopy.

    PubMed

    Lin, Alexander P; Ramadan, Saadallah; Stern, Robert A; Box, Hayden C; Nowinski, Christopher J; Ross, Brian D; Mountford, Carolyn E

    2015-01-01

    The goal was to identify which neurochemicals differ in professional athletes with repetitive brain trauma (RBT) when compared to healthy controls using a relatively new technology, in vivo Localized COrrelated SpectroscopY (L-COSY). To achieve this, L-COSY was used to examine five former professional male athletes with 11 to 28 years of exposure to contact sports. Each athlete who had had multiple symptomatic concussions and repetitive sub concussive trauma during their career was assessed by an experienced neuropsychologist. All athletes had clinical symptoms including headaches, memory loss, confusion, impaired judgment, impulse control problems, aggression, and depression. Five healthy men, age and weight matched to the athlete cohort and with no history of brain trauma, were recruited as controls. Data were collected from the posterior cingulate gyrus using a 3 T clinical magnetic resonance scanner equipped with a 32 channel head coil. The variation of the method was calculated by repeated examination of a healthy control and phantom and found to be 10% and 5%, respectively, or less. The L-COSY measured large and statistically significant differences (P ≤0.05), between healthy controls and those athletes with RBT. Men with RBT showed higher levels of glutamine/glutamate (31%), choline (65%), fucosylated molecules (60%) and phenylalanine (46%). The results were evaluated and the sample size of five found to achieve a significance level P = 0.05 and a power of 90%. Differences in N-acetyl aspartate and myo-inositol between RBT and controls were small and were not statistically significance. A study of a small cohort of professional athletes, with a history of RBT and symptoms of chronic traumatic encephalopathy when compared with healthy controls using 2D L-COSY, showed elevations in brain glutamate/glutamine and choline as recorded previously for early traumatic brain injury. For the first time increases in phenylalanine and fucose are recorded in the

  3. N- versus O-alkylation: utilizing NMR methods to establish reliable primary structure determinations for drug discovery.

    PubMed

    LaPlante, Steven R; Bilodeau, François; Aubry, Norman; Gillard, James R; O'Meara, Jeff; Coulombe, René

    2013-08-15

    A classic synthetic issue that remains unresolved is the reaction that involves the control of N- versus O-alkylation of ambident anions. This common chemical transformation is important for medicinal chemists, who require predictable and reliable protocols for the rapid synthesis of inhibitors. The uncertainty of whether the product(s) are N- and/or O-alkylated is common and can be costly if undetermined. Herein, we report an NMR-based strategy that focuses on distinguishing inhibitors and intermediates that are N- or O-alkylated. The NMR strategy involves three independent and complementary methods. However, any combination of two of the methods can be reliable if the third were compromised due to resonance overlap or other issues. The timely nature of these methods (HSQC/HMQC, HMBC. ROESY, and (13)C shift predictions) allows for contemporaneous determination of regioselective alkylation as needed during the optimization of synthetic routes. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. Cytotoxic constituents of Diadema setosum.

    PubMed

    Minh, Chau Van; Kiem, Phan Van; Huong, Le Mai; Kim, Young Ho

    2004-07-01

    5,8-Epidioxycholest-6-en-3-ol (1), cholesterol (2), glycerol 1-palmitate (3) and glycerol 1,3-dioleate-2-stearate (4) were isolated from the methanol extract of the sea urchin Diadema setosum, which was collected from the Halong sea, Vietnam. Chemical structures were established based on extensive 1D, 2D-NMR, FAB-MS, El-MS spectroscopic data and GC-MS analysis. The NMR spectral data of compound 1 were reassigned by using HMQC and HMBC. Compound 1 was found to have strong cytotoxic effect against various cancer cell lines, such as KB (IC50, 2.0 microg/mL), FL (ICso, 3.93 microg/mL), and Hep-2 (IC50, 2.4 microg/mL) by in vitro assay.

  5. 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. Georg Thieme Verlag KG Stuttgart · New York.

  6. Synthetic, 119Sn NMR spectroscopic, electrochemical, and reactivity study of organotin A3 corrolates including chiral and ferrocenyl derivatives.

    PubMed

    Tsay, Olga G; Kim, Byung-Kwon; Luu, Tuong Loan; Kwak, Juhyoun; Churchill, David G

    2013-02-18

    Various R/Ar-functionalized tin 5,10,15-tris(pentafluorophenyl)corrolate derivatives are reported herein including the first ferrocenyltin corrolate species. The isopropyl, sec-butyl-, 2-methyl-n-butyl-, phenyl-, 2-thienyl-, and ferrocenyltin species have been prepared and characterized through (1)H, (13)C, and (119)Sn HMQC NMR spectroscopy, mass spectrometry, UV-vis and photoluminescent spectroscopy, and cyclic voltammetry studies. J(C/H-Sn) NMR spectroscopic couplings and ring-current effects (upfield shifting) were determined for the R-Sn axial hydrogen and carbon atoms. This report adds to older conceptually similar reports, by, i.e., Janson et al. (J. Am. Chem. Soc. 1969, 91, 5210) and Walker et al. (J. Am. Chem. Soc.1983, 105, 6923-6929), as discussed herein. Such NMR spectroscopic aspects are discussed for these model systems. Compound Sn-Ph bond cleavage was achieved by treatment with I(2).

  7. 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.

  8. Novel method of estimating proton proton dipolar couplings to aid the analyses of NMR spectra of oriented molecules using two-dimensional inverse experiment

    NASA Astrophysics Data System (ADS)

    Vivekanandan, S.; Suryaprakash, N.

    2001-04-01

    NMR spectroscopy of molecules oriented in liquid crystalline matrices provides information on the molecular structure and order parameters. Analyses of such spectra are generally carried out by numerical iterative calculations. The iterative analysis requires an initial estimate of proton-proton dipolar couplings. In the present study it is shown, for an AA 'MM 'X spin system, the two-dimensional HMQC experiment provides the magnitude of proton-proton dipolar couplings. In the case of an AA 'A″A ‴X spin system the experiment provides the initial starting dipolar couplings values for the iterative analysis. The use of this experiment in combination with two-dimensional HSQC experiments has been demonstrated for the analyses of 1,1-difluoro-1,2-dibromoethane and p-dibromobenzene.

  9. A New Two-Dimensional Pulse Sequence for T2* Measurements of Protons in 13C Isotopomers

    NASA Astrophysics Data System (ADS)

    Lambert, Jörg; Haiber, Stephan; Herzog, Helmut

    2001-06-01

    A new two-dimensional pulse sequence for T2* measurement of protons directly coupled to 13C spins is proposed. The sequence measures the tranverse relaxation time of heteronuclear proton single-quantum coherence under conditions of free precession and is therefore well suited to evaluate relaxation losses of proton magnetization during preparation delays of heteronuclear pulse experiments in analytical NMR. The relevant part of the pulse sequence can be inserted as a "building block" into any direct or inverse detecting H,C correlation pulse sequence if proton spin-spin relaxation is to be investigated. In this contribution, the building block is inserted into a HETCOR as well as into a HMQC pulse sequence. Experimental results for the HETCOR-based sequence are given.

  10. Structural elucidation and NMR assignments of four aromatic lactones from a mangrove endophytic fungus (No. GX4-1B).

    PubMed

    Huang, Hongbo; Li, Qing; Feng, Xiaojun; Chen, Bin; Wang, Jun; Liu, Lan; She, Zhigang; Lin, Yongcheng

    2010-06-01

    Two new aromatic lactones, 6-hydroxy-4-hydroxymethyl-8-methoxy-3- methylisocoumarin (1) and 1,10-dihydroxy-8-methyl-dibenz[b, e]oxepin-6,11-dione (2), together with two known compounds, 1,10-dihydroxy-dibenz[b, e]oxepin-6,11-dione (3) and 3-hydroxymethyl-6,8-dimethoxycoumarin (4), were isolated from a mangrove endophytic fungus (No. GX4-1B) collected from the South China Sea. Their structures were elucidated and the data of (1)H and (13)C NMR were assigned completely by HREIMS, 1D and 2D NMR experiments including HMQC, HMBC and NOESY. Copyright (c) 2010 John Wiley & Sons, Ltd.

  11. Characterization and Fungal Inhibition Activity of Siderophore from Wheat Rhizosphere Associated Acinetobacter calcoaceticus Strain HIRFA32.

    PubMed

    Maindad, D V; Kasture, V M; Chaudhari, H; Dhavale, D D; Chopade, B A; Sachdev, D P

    2014-09-01

    Acinetobacter calcoaceticus HIRFA32 from wheat rhizosphere produced catecholate type of siderophore with optimum siderophore (ca. 92 % siderophore units) in succinic acid medium without FeSO4 at 28 °C and 24 h of incubation. HPLC purified siderophore appeared as pale yellow crystals with molecular weight [M(+1)] m/z 347.18 estimated by LCMS. The structure elucidated by (1)H NMR, (13)C NMR, HMQC, HMBC, NOESY and decoupling studies, revealed that siderophore composed of 2,3-dihydroxybenzoic acid with hydroxyhistamine and threonine as amino acid subunits. In vitro study demonstrated siderophore mediated mycelium growth inhibition (ca. 46.87 ± 0.5 %) of Fusarium oxysporum. This study accounts to first report on biosynthesis of acinetobactin-like siderophore by the rhizospheric strain of A. calcoaceticus and its significance in inhibition of F. oxysporum.

  12. The first fulleropyrrolidine derivative of Sc3N@C80: pronounced chemical shift differences of the geminal protons on the pyrrolidine ring.

    PubMed

    Cardona, Claudia M; Kitaygorodskiy, Alex; Ortiz, Angy; Herranz, M Angeles; Echegoyen, Luis

    2005-06-24

    The first pyrrolidine adduct on Sc(3)N@C(80) was synthesized and fully characterized. Addition of the N-ethylazomethine ylide occurs regioselectively on a [5,6] double bond on the surface of the icosahedral symmetry Sc(3)N@C(80), exactly in the same position as that described previously for a Diels-Alder adduct of the same compound.(11a,b) This addition pattern results in symmetric pyrrolidine carbons and unsymmetric geminal hydrogens on the pyrrolidine ring, as confirmed by (1)H and (13)C NMR spectroscopy, especially by HMQC. The shielding environment experienced by these geminal hydrogens differs by 1.26 ppm, indicative of pronounced ring current effects on the surface of this endohedral fullerene. This represents the first fully characterized pyrrolidine adduct on an endohedral metallofullerene.

  13. 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.

  14. Flavonoids from the stems of Croton caudatus Geisel. var. tomentosus Hook.

    PubMed

    Zou, Guo-An; Su, Zhi-Heng; Zhang, Hong-Wu; Wang, Yuan; Yang, Jun-Shan; Zou, Zhong-Mei

    2010-02-26

    A new flavone, named crotoncaudatin (1), was isolated from the stems of Croton caudatus Geisel. var. tomentosus Hook., together with nine known analogues: 3,5,6,7,8,3',4'-heptamethoxyflavone (2), tangeretin (3), nobiletin (4), 5,6,7,4'-tetramethoxy-flavone (5), sinensetin (6), kaempferol (7), tiliroside (8), kaempferol-3-O-rutinoside (9) and rutin (10). The structures of the above compounds were established by a combination of spectroscopic methods, including HR-ESI-MS, 1H-NMR, 13C-NMR, HMQC and HMBC spectra. All compounds were isolated from and identified in this species for the first time and compounds 1-6 are new for the genus Croton.

  15. 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. Copyright © 2010 Elsevier Masson SAS. All rights reserved.

  16. 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.

  17. Dual allosteric activation mechanisms in monomeric human glucokinase.

    PubMed

    Whittington, A Carl; Larion, Mioara; Bowler, Joseph M; Ramsey, Kristen M; Brüschweiler, Rafael; Miller, Brian G

    2015-09-15

    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 (1)H-(13)C heteronuclear multiple quantum coherence (HMQC) spectrum of (13)C-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 (1)H-(13)C 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.

  18. 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.

  19. Lack of sleep is associated with internet use for leisure.

    PubMed

    Kim, So Young; Kim, Min-Su; Park, Bumjung; Kim, Jin-Hwan; Choi, Hyo Geun

    2018-01-01

    Previous studies have suggested that excessive internet use may cause lack of sleep. However, recent studies have hypothesized that lack of sleep may instigate internet use for leisure. To elucidate the potential effects of sleep time on internet use, we explored the different associations between sleep time and internet use according to its purpose. The population-based, cross-sectional study group from the Korea Youth Risk Behavior Web-based Survey (KYRBWS) collected data from 57,425 middle school students in 2014 and 2015. Sleep time over the past 7 days was classified into the following groups: < 7 h (6 h); ≥ 7 h, < 8 h (7 h); ≥ 8 h, < 9 h (8 h); and ≥ 9 h (9+ h). Internet use time per day was separately surveyed for leisure and for study and categorized as follows: 0 h; > 0 h, ≤ 1 h (1 h); > 1 h, ≤ 2 h (2 h); and > 2 h (2+ h) per day. Information on age, sex, region of residence, body mass index (BMI), economic level, parental education level, stress level, school performance level, and sleep satisfaction were retrieved. The relationships between sleep time and internet use time for leisure/study were analyzed using multinomial logistic regression with complex sampling. In the subgroup analysis according to sleep satisfaction (good, normal, and poor), the associations of sleep time with internet use for leisure were analyzed using the same methods. Compared to 9+ h of sleep, less sleep was related to a long internet use time (2+ h) for leisure (adjusted odds ratio, AOR [95% confidence interval, CI] of sleep: 8 h = 1.23 [1.14-1.32]; 7 h = 1.42 [1.31-1.54]; and 6 h = 1.56 [1.44-1.70]; P < 0.001). Conversely, a relationship between less sleep and a long internet use time (2+ h) for study was evident only for 6 h of sleep (AOR of sleep: 8 h = 0.84 [0.84-1.04]; 7 h = 1.05 [0.94-1.17]; and 6 h = 1.32 [1.27-1.59]; P < 0.001). In the subgroup analysis according to sleep satisfaction, less sleep was associated with a long internet use time for leisure in all

  20. 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

  1. 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

  2. A Bivalent Heterologous DNA Virus-Like-Particle Prime-Boost Vaccine Elicits Broad Protection against both Group 1 and 2 Influenza A Viruses

    PubMed Central

    Jiang, Wenbo; Wang, Shuangshuang; Chen, Honglin; Ren, Huanhuan; Huang, Xun; Wang, Guiqin; Chen, Ling; Chen, Zhiwei

    2017-01-01

    ABSTRACT Current seasonal influenza vaccines are efficacious when vaccine strains are matched with circulating strains. However, they do not protect antigenic variants and newly emerging pandemic and outbreak strains. Thus, there is a critical need for developing so-called “universal” vaccines that protect against all influenza viruses. In the present study, we developed a bivalent heterologous DNA virus-like particle prime-boost vaccine strategy. We show that mice immunized with this vaccine were broadly protected against lethal challenge from group 1 (H1, H5, and H9) and group 2 (H3 and H7) viruses, with 94% aggregate survival. To determine the immune correlates of protection, we performed passive immunizations and in vitro assays. We show that this vaccine elicited antibody responses that bound HA from group 1 (H1, H2, H5, H6, H8, H9, H11, and H12) and group 2 (H3, H4, H7, H10, H14, and H15) and neutralized homologous and intrasubtypic H5 and H7 and heterosubtypic H1 viruses and hemagglutinin-specific CD4 and CD8 T cell responses. As a result, passive immunization with immune sera fully protected mice against H5, H7, and H1 challenge, whereas with both immune sera and T cells the mice survived heterosubtypic H3 and H9 challenge. Thus, it appears that (i) neutralizing antibodies alone fully protect against homologous and intrasubtypic H5 and H7 and (ii) neutralizing and binding antibodies are sufficient to protect against heterosubtypic H1, (iii) but against heterosubtypic H3 and H9, binding antibodies and T cells are required for complete survival. We believe that this vaccine regimen could potentially be a candidate for a “universal” influenza vaccine. IMPORTANCE Influenza virus infection is global health problem. Current seasonal influenza vaccines are efficacious only when vaccine strains are matched with circulating strains. However, these vaccines do not protect antigenic variants and newly emerging pandemic and outbreak strains. Because of this

  3. A Bivalent Heterologous DNA Virus-Like-Particle Prime-Boost Vaccine Elicits Broad Protection against both Group 1 and 2 Influenza A Viruses.

    PubMed

    Jiang, Wenbo; Wang, Shuangshuang; Chen, Honglin; Ren, Huanhuan; Huang, Xun; Wang, Guiqin; Chen, Ze; Chen, Ling; Chen, Zhiwei; Zhou, Paul

    2017-05-01

    Current seasonal influenza vaccines are efficacious when vaccine strains are matched with circulating strains. However, they do not protect antigenic variants and newly emerging pandemic and outbreak strains. Thus, there is a critical need for developing so-called "universal" vaccines that protect against all influenza viruses. In the present study, we developed a bivalent heterologous DNA virus-like particle prime-boost vaccine strategy. We show that mice immunized with this vaccine were broadly protected against lethal challenge from group 1 (H1, H5, and H9) and group 2 (H3 and H7) viruses, with 94% aggregate survival. To determine the immune correlates of protection, we performed passive immunizations and in vitro assays. We show that this vaccine elicited antibody responses that bound HA from group 1 (H1, H2, H5, H6, H8, H9, H11, and H12) and group 2 (H3, H4, H7, H10, H14, and H15) and neutralized homologous and intrasubtypic H5 and H7 and heterosubtypic H1 viruses and hemagglutinin-specific CD4 and CD8 T cell responses. As a result, passive immunization with immune sera fully protected mice against H5, H7, and H1 challenge, whereas with both immune sera and T cells the mice survived heterosubtypic H3 and H9 challenge. Thus, it appears that (i) neutralizing antibodies alone fully protect against homologous and intrasubtypic H5 and H7 and (ii) neutralizing and binding antibodies are sufficient to protect against heterosubtypic H1, (iii) but against heterosubtypic H3 and H9, binding antibodies and T cells are required for complete survival. We believe that this vaccine regimen could potentially be a candidate for a "universal" influenza vaccine. IMPORTANCE Influenza virus infection is global health problem. Current seasonal influenza vaccines are efficacious only when vaccine strains are matched with circulating strains. However, these vaccines do not protect antigenic variants and newly emerging pandemic and outbreak strains. Because of this, there is an urgent

  4. Polarized Sources, Targets and Polarimetry

    NASA Astrophysics Data System (ADS)

    Ciullo, Guiseppe; Contalbrigo, Marco; Lenisa, P.

    2011-01-01

    Remarks on the history of workshops on "spin tools" / E. Steffens -- Polarized proton beams in RHIC / A. Zelenski -- The COSY/Julich polarized H[symbol] and D[symbol] ion source / O. Felden -- The new source of polarized ions for the JINR accelerator complex / V. V. Fimushkin -- Resonance effects in nuclear dichroism - an inexpensive source of tensor-polarized deuterons / H. Seyfarth -- Polarized electrons and positrons at the MESA accelerator / K. Aulenbacher -- Status report of the Darmstadt polarized electron injector / Y. Poltoratska -- The Mott polarimeter at MAMI / V. Tioukine -- Proton polarimetry at the relativistic heavy ion collider / Y. Makdisi -- Polarisation and polarimetry at HERA / B. Sobloher -- Polarisation measurement at the ILC with a Compton polarimeter / C. Bartels -- Time evolution of ground motion-dependent depolarisation at linear colliders / A. Hartin -- Electron beam polarimetry at low energies and its applications / R. Barday -- Polarized solid targets: recent progress and future prospects / C. D. Keith -- HD gas distillation and analysis for HD frozen spin targets / A. D'Angelo -- Electron spin resonance study of hydrogen and alkyl free radicals trapped in solid hydrogen aimed for dynamic nuclear polarization of solid HD / T. Kumada -- Change of ultrafast nuclear-spin polarization upon photoionization by a short laser pulse / T. Nakajima -- Radiation damage and recovery in polarized [symbol]NH[symbol] ammonia targets at Jefferson lab / J. D. Maxwell.Polarized solid proton target in low magnetic field and at high temperature / T. Uesaka -- Pulse structure dependence of the proton spin polarization rate / T. Kawahara -- Proton NMR in the large COMPASS [symbol]NH[symbol] target / J. Koivuniemi -- DNP with TEMPO and trityl radicals in deuterated polystyrene / L. Wang -- The CLIC electron and positron polarized sources / L. Rinolfi -- Status of high intensity polarized electron gun at MIT-Bates / E. Tsentalovich -- Target section for spin

  5. WHO European Childhood Obesity Surveillance Initiative in Serbia: a prevalence of overweight and obesity among 6-9-year-old school children.

    PubMed

    Djordjic, Visnja; Radisavljevic, Snezana; Milanovic, Ivana; Bozic, Predrag; Grbic, Miljana; Jorga, Jagoda; Ostojic, Sergej M

    2016-09-01

    The World Health Organization (WHO) European Childhood Obesity Surveillance Initiative (COSI) is a public health program established in order to understand the progress of the obesity epidemic in young populations and gain inter-country comparisons within the European region, yet the data from a number of East European countries, including Serbia, were not available then. Therefore, the main aim of this cross-sectional study was to collect data about the prevalence of overweight and obesity among 6-9-year-old school children in Serbia according to the standardized protocol during the Fourth COSI Implementation Round. From September 2015 to November 2015, 5102 first- and second-grade primary-school children (age 7.7±0.6 years) were assessed for weight, height, and body mass index (BMI) in 14 Serbian school districts. The prevalence rates of obesity, as calculated using the International Obesity Task Force (IOTF) cut-off points, vary across different age groups, with the lowest obesity rates reported in 7-year-old boys (6.2%), while the highest obesity prevalence rates were observed in 6-year-old boys (9.7%). In addition, being overweight was strongly associated with poor local community development and lower level of urbanization. The overall prevalence of overweight (23.1%, including obesity) and obesity (6.9%) in Serbian primary-school children seem to be comparable to rather high rates previously reported in other countries participating in the COSI program, indicating an obesity epidemic in Serbian children. This surveillance system should be regularly implemented throughout Europe, providing comparable data on rates of overweight/obesity in primary schools that might drive prudent actions to reverse the pandemic trend of childhood obesity.

  6. WHO European Childhood Obesity Surveillance Initiative: body mass index and level of overweight among 6-9-year-old children from school year 2007/2008 to school year 2009/2010.

    PubMed

    Wijnhoven, Trudy M A; van Raaij, Joop M A; Spinelli, Angela; Starc, Gregor; Hassapidou, Maria; Spiroski, Igor; Rutter, Harry; Martos, Éva; Rito, Ana I; Hovengen, Ragnhild; Pérez-Farinós, Napoleón; Petrauskiene, Ausra; Eldin, Nazih; Braeckevelt, Lien; Pudule, Iveta; Kunešová, Marie; Breda, João

    2014-08-07

    The World Health Organization (WHO) Regional Office for Europe has established the Childhood Obesity Surveillance Initiative (COSI) to monitor changes in overweight in primary-school children. The aims of this paper are to present the anthropometric results of COSI Round 2 (2009/2010) and to explore changes in body mass index (BMI) and overweight among children within and across nine countries from school years 2007/2008 to 2009/2010. Using cross-sectional nationally representative samples of 6-9-year-olds, BMI, anthropometric Z-scores and overweight prevalence were derived from measured weight and height. Significant changes between rounds were assessed using variance and t-tests analyses. At Round 2, the prevalence of overweight (including obesity; WHO definitions) ranged from 18% to 57% among boys and from 18% to 50% among girls; 6 - 31% of boys and 5 - 21% of girls were obese. Southern European countries had the highest overweight prevalence. Between rounds, the absolute change in mean BMI (range: from -0.4 to +0.3) and BMI-for-age Z-scores (range: from -0.21 to +0.14) varied statistically significantly across countries. The highest significant decrease in BMI-for-age Z-scores was found in countries with higher absolute BMI values and the highest significant increase in countries with lower BMI values. The highest significant decrease in overweight prevalence was observed in Italy, Portugal and Slovenia and the highest significant increase in Latvia and Norway. Changes in BMI and prevalence of overweight over a two-year period varied significantly among European countries. It may be that countries with higher prevalence of overweight in COSI Round 1 have implemented interventions to try to remedy this situation.

  7. In vivo 1D and 2D correlation MR spectroscopy of the soleus muscle at 7T

    NASA Astrophysics Data System (ADS)

    Ramadan, Saadallah; Ratai, Eva-Maria; Wald, Lawrence L.; Mountford, Carolyn E.

    2010-05-01

    AimThis study aims to (1) undertake and analyse 1D and 2D MR correlation spectroscopy from human soleus muscle in vivo at 7T, and (2) determine T1 and T2 relaxation time constants at 7T field strength due to their importance in sequence design and spectral quantitation. MethodSix healthy, male volunteers were consented and scanned on a 7T whole-body scanner (Siemens AG, Erlangen, Germany). Experiments were undertaken using a 28 cm diameter detunable birdcage coil for signal excitation and an 8.5 cm diameter surface coil for signal reception. The relaxation time constants, T1 and T2 were recorded using a STEAM sequence, using the 'progressive saturation' method for the T1 and multiple echo times for T2. The 2D L-Correlated SpectroscopY (L-COSY) method was employed with 64 increments (0.4 ms increment size) and eight averages per scan, with a total time of 17 min. ResultsT1 and T2 values for the metabolites of interest were determined. The L-COSY spectra obtained from the soleus muscle provided information on lipid content and chemical structure not available, in vivo, at lower field strengths. All molecular fragments within multiple lipid compartments were chemically shifted by 0.20-0.26 ppm at this field strength. 1D and 2D L-COSY spectra were assigned and proton connectivities were confirmed with the 2D method. ConclusionIn vivo 1D and 2D spectroscopic examination of muscle can be successfully recorded at 7T and is now available to assess lipid alterations as well as other metabolites present with disease. T1 and T2 values were also determined in soleus muscle of male healthy volunteers.

  8. DIME Students Show Off their Lego(TM) Challenge Creation

    NASA Technical Reports Server (NTRS)

    2002-01-01

    Two students show the Lego (TM) Challenge device they designed and built to operate in the portable drop tower demonstrator as part of 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.

  9. Dimeric sesquiterpene and thiophenes from the roots of Echinops latifolius.

    PubMed

    Jin, Qinghao; Lee, Jin Woo; Jang, Hari; Choi, Ji Eun; Kim, Hyung Sik; Lee, Dongho; Hong, Jin Tae; Lee, Mi Kyeong; Hwang, Bang Yeon

    2016-12-15

    Phytochemical investigation of the roots of Echinops latifolius led to the isolation of a new carbon skeleton dimeric sesquiterpene (1) and a new thiophene (2), along with six known compounds (3-8). Their structures and relative stereochemistry were elucidated by spectroscopic and spectrometric methods ( 1 H and 13 C NMR, COSY, HSQC, HMBC, ROESY, and MS). All isolates were evaluated for their inhibition of LPS-induced NO production in RAW 264.7 cells. Compounds 4 and 5 exhibited the most potent inhibitory effects on NO production. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Intermolecular Interactions between Eosin Y and Caffeine Using 1H-NMR Spectroscopy

    PubMed Central

    Okuom, Macduff O.; Wilson, Mark V.; Jackson, Abby; Holmes, Andrea E.

    2014-01-01

    DETECHIP has been used in testing analytes including caffeine, cocaine, and tetrahydrocannabinol (THC) from marijuana, as well as date rape and club drugs such as flunitrazepam, gamma-hydroxybutyric acid (GHB), and methamphetamine. This study investigates the intermolecular interaction between DETECHIP sensor eosin Y (DC1) and the analyte (caffeine) that is responsible for the fluorescence and color changes observed in the actual array. Using 1H-NMR, 1H-COSY, and 1H-DOSY NMR methods, a proton exchange from C-8 of caffeine to eosin Y is proposed. PMID:25018772

  11. Labdane diterpenes from Marrubium thessalum.

    PubMed

    Argyropoulou, Catherine; Karioti, Anastasia; Skaltsa, Helen

    2009-03-01

    From the aerial parts of Marrubium thessalum, four labdane diterpenes, 13S-preperegrinine, 3alpha-hydroxymarrubiin, 9alpha,13R-15,16-bisepoxy-15beta-methoxy-3-oxo-labdan-6beta,19-olide and 15-methoxyvelutine C, have been isolated together with four known diterpenes and one methoxylated flavone, ladanein. The structures of the isolated compounds were established by means of NMR (COSY, HSQC, HMBC, NOESY, and ROESY) and MS spectral analyses. Complete NMR assignments are reported for 13R-preperegrinine. Characteristic compounds of the plant were peregrinine and ladanein.

  12. Penicilloitins A and B, new antimicrobial fatty acid esters from a marine endophytic Penicillium species.

    PubMed

    Mourshid, Samar S A; Badr, Jihan M; Risinger, April L; Mooberry, Susan L; Youssef, Diaa T A

    2016-11-01

    Two new antimicrobial fatty acid esters, penicilloitins A and B (1 and 2), along with α-cyclopiazonic acid (3), tryptamine (4) and indole-3-carbaldehyde (5), were isolated from mycelial extracts and the culture broth of a marine endophytic Penicillium species and their structures established by spectroscopic techniques including 1D (1H NMR and 13C NMR) and 2D NMR (COSY, multiplicity-edited HSQC, and HMBC) as well as HRESIMS. Of these compounds, 1, 3 and 4 displayed modest antimicrobial activity.

  13. Inophyllin A, a new pyranoxanthone from Calophyllum inophyllum (Guttiferae).

    PubMed

    Ee, G C L; Kua, A S M; Lim, C K; Jong, V; Lee, H L

    2006-05-10

    In the authors' continuing search for new natural products, their recent studies on the roots of Calophyllum inophyllum (Guttiferae) have yielded a new prenylated pyranoxanthone, Inophyllin A together with the common triterpenes friedelin and stigmasterol. Structural elucidations of these compounds were achieved through (1)H, (13)C, DEPT, COSY, HSQC and HMBC experiments. The molecular mass was determined using MS techniques. The authors report here the isolation of and structural elucidation for Inophyllin A as well as its toxicity test result. The discovery of this new natural product from the unexploited Malaysian forest will certainly contribute to the search for potential natural larvicides.

  14. A Novel Multi-voxel Based Quantitation of Metabolites and Lipids Non-invasively Combined with Diffusion Weighted Imaging in Breast Cancer

    DTIC Science & Technology

    2011-09-01

    COSI sequence is demonstrated in Fig.5B. A metabolite map of the fat peak at 1.3ppm is shown in Fig.4B. 2D MR spectra were recorded in multiple...contrast enhanced magnetic resonance imaging. Brit J Radiology 1994; 67(793):14-20. 12. Kerslake RW, et al. A dynamic contrast-enhanced and fat ...weighted imaging. European journal of radiology. 2003 Mar;45(3):169-84. 18. Belli P, Constantini M, Bufi E, et al. Diffusion weighted imaging in

  15. Bayesian Neural Networks for Ray Reconstruction of Spectrographs

    NASA Astrophysics Data System (ADS)

    Kuchera, M. P.; Bazin, D.; Sherrill, B. M.

    2014-09-01

    Spectrograph ray reconstruction is an important consideration for data analysis of many modern spectrometer experiments. Typically, calculated inverse ion-optical maps are used to reconstruct ion trajectories through a magnetic system. A standard practice is to calculate ion-optical maps using programs such as COSY Infinity and then use a procedure to invert these maps. The inverse maps are used to reconstruct ion parameters at the object location from measurements at the spectrograph focal plane. This presentation will present our exploration of an alternate method, namely, the use of Bayesian Neural Networks, BNN, for the construction of transport maps using experimental data. In order to study the effectiveness of the training of the neural network, COSY Infinity maps were used to generate training data for the S800 spectrograph at the National Superconducting Cyclotron Laboratory. BNNs were trained from this generated data, where the exact map is known, and a study of the method will be presented. Among the factors that will be reported are an accuracy of the BNN mapping, a study of the amount of training data necessary to construct an accurate BNN, and what level of precision in the training data is necessary for an accurate mapping. Spectrograph ray reconstruction is an important consideration for data analysis of many modern spectrometer experiments. Typically, calculated inverse ion-optical maps are used to reconstruct ion trajectories through a magnetic system. A standard practice is to calculate ion-optical maps using programs such as COSY Infinity and then use a procedure to invert these maps. The inverse maps are used to reconstruct ion parameters at the object location from measurements at the spectrograph focal plane. This presentation will present our exploration of an alternate method, namely, the use of Bayesian Neural Networks, BNN, for the construction of transport maps using experimental data. In order to study the effectiveness of the training

  16. One new 19-nor cucurbitane-type triterpenoid from the stems of Momordica charantia.

    PubMed

    Li, Yong-chao; Xu, Xin-juan; Yang, Jing; Wu, Xing-gang; Fu, Qing-yun

    2016-01-01

    One new 19-nor cucurbitane-type triterpenoid (3β,9β,25-trihydroxy-7β-methoxy-19-nor-cucurbita-5,23(E)-diene) (1), together with other six known cucurbitane-type triterpenoids (2-7), were isolated from the stems of Momordica charantia L. The chemical structure of 1 was elucidated by extensive 1D NMR and 2D NMR (HSQC, HMBC, COSY and ROESY), MS experiments. Using MTT assay, compound 1 exhibited weak cytotoxicity against HL-60, A-549, and SK-BR-3 cell lines with the IC50 values at 27.3, 32.7 and 26.6 μM, respectively.

  17. Triterpene saponins from the sea cucumber Stichopus chloronotus.

    PubMed

    Thao, Nguyen Phuong; Luyen, Bui Thi Thuy; Le Vien, Thi; Tai, Bui Huu; Le Dat, Duc; Cuong, Nguyen Xuan; Nam, Nguyen Hoai; Van Kiem, Phan; Van Minh, Chau; Kim, Young Ho

    2014-05-01

    Sea cucumbers have been used as a dietary delicacy and important ingredient in Asian traditional medicine and functional foods over many centuries. Using combined chromatographic methods, six triterpene saponins (1-6), including a new compound, stichloroside F (1), were isolated from a methanol extract of the sea cucumber Stichopus chloronotus Brandt. Their structures were determined on the basis of spectroscopic (1H and 13C NMR, HSQC, HMBC, 1H-1lH COSY, ROESY) and FTICR-MS data and by comparison with literature values.

  18. Microgravity

    NASA Image and Video Library

    2002-08-07

    Test tubes to hold different types of fluids while in free-fall were among the student-designed items for the second Dropping in a Microgravity Environment (DIME) competition held April 23-25, 2002, at NASA's Glenn Research Center. Competitors included two teams from Sycamore High School, Cincinnati, OH, and one each from Bay High School, Bay Village, OH, and COSI Academy, Columbus, OH. DIME is part of NASA's education and outreach activities. Details are on line at http://microgravity.grc.nasa.gov/DIME_2002.html.

  19. Electromagnetic Simulation and Design of a Novel Waveguide RF Wien Filter for Electric Dipole Moment Measurements of Protons and Deuterons

    NASA Astrophysics Data System (ADS)

    Slim, J.; Gebel, R.; Heberling, D.; Hinder, F.; Hölscher, D.; Lehrach, A.; Lorentz, B.; Mey, S.; Nass, A.; Rathmann, F.; Reifferscheidt, L.; Soltner, H.; Straatmann, H.; Trinkel, F.; Wolters, J.

    2016-08-01

    The conventional Wien filter is a device with orthogonal static magnetic and electric fields, often used for velocity separation of charged particles. Here we describe the electromagnetic design calculations for a novel waveguide RF Wien filter that will be employed to solely manipulate the spins of protons or deuterons at frequencies of about 0.1-2 MHz at the COoler SYnchrotron COSY at Jülich. The device will be used in a future experiment that aims at measuring the proton and deuteron electric dipole moments, which are expected to be very small. Their determination, however, would have a huge impact on our understanding of the universe.

  20. Design of interior-functionalized fully acetylated dendrimers for anticancer drug delivery.

    PubMed

    Hu, Jingjing; Su, Yunzhang; Zhang, Hongfeng; Xu, Tongwen; Cheng, Yiyun

    2011-12-01

    In this study, dendrimers was synthesized by introducing functional groups into the interior pockets of fully acetylated dendrimers. NMR techniques including COSY and 2D-NOESY revealed the molecular structures of the synthesized dendrimers and the encapsulation of guest molecule such as methotrexate within their interior pockets. The synthesized polymeric nanocarriers showed much lower cytotoxicity on two cell lines than cationic dendrimers, and exhibited better performance than fully acetylated dendrimers in the sustained release of methotrexate. The results provided a new strategy in the design of non-toxic dendrimers with high performance in the delivery of anti-cancer drugs for clinical applications. Copyright © 2011 Elsevier Ltd. All rights reserved.

  1. Growing Cobalt Silicide Columns In Silicon

    NASA Technical Reports Server (NTRS)

    Fathauer, Obert W.

    1991-01-01

    Codeposition by molecular-beam epitaxy yields variety of structures. Proposed fabrication process produces three-dimensional nanometer-sized structures on silicon wafers. Enables control of dimensions of metal and semiconductor epitaxial layers in three dimensions instead of usual single dimension (perpendicular to the plane of the substrate). Process used to make arrays of highly efficient infrared sensors, high-speed transistors, and quantum wires. For fabrication of electronic devices, both shapes and locations of columns controlled. One possible technique for doing this electron-beam lithography, see "Making Submicron CoSi2 Structures on Silicon Substrates" (NPO-17736).

  2. Difficulties in determining factors that influence effective groundwater recharge in Ohio

    USGS Publications Warehouse

    Ashooh, J.; Liu, J.; Mueller, E.; Sherer, S.; Woggon, N.; Dumouchelle, D.H.; Eberle, M.

    2003-01-01

    As part of a COSI Academy research project, data from a recent statewide analysis of effective groundwater recharge were reexamined by students to further discern relations between recharge and selected environmental characteristics of individual drainage basins: 1) location of the main stem of a river relative to coarse and fine surficial sediments and 2) influence of land use. Lack of sufficiently detailed data was the principal difficulty in most phases of the examination. Other than a potential relation between recharge and the percentages of agricultural and forested land, no relations were found in visual comparisons of mapped and tabulated data.

  3. Improved Measurement of Brain Phenylalanine and Tyrosine Related to Neuropsychological Functioning in Phenylketonuria.

    PubMed

    Waisbren, Susan E; Prabhu, Sanjay P; Greenstein, Patricia; Petty, Carter; Schomer, Donald; Anastasoaie, Vera; Charette, Kalin; Rodriguez, Daniel; Merugumala, Sai; Lin, Alexander P

    2017-01-01

    Researchers hypothesized that in phenylketonuria (PKU) high brain phenylalanine (Phe) levels and low brain tyrosine (Tyr) levels affect neuropsychological functioning. However, traditional magnetic resonance spectroscopy (MRS) yielded uncertain results of brain Phe and could not adequately measure brain Tyr. This pilot study examined the potential of correlated spectroscopy (COSY) to quantify these biomarkers and explain variability in neuropsychological functioning. Nine adults with early treated classic PKU received magnetic resonance imaging (MRI) with COSY and a battery of neuropsychological tests. Brain Phe and Tyr in parietal white matter (PWM) were compared to results in gray matter of the posterior cingulate gyrus (PCG). Brain Phe ranged from 101 to 182 (mean = 136.76 ± 23.77) μmol/L in PCG and 76 to 185 (mean = 130.11 ± 37.88) μmol/L in PWM. Brain Tyr ranged from 4.0 to 7.4 (mean = 5.44 ± 1.01) μmol/L in PCG and 4.1 to 8.4 (mean = 5.90 ± 1.48) μmol/L in PWM. Correlation coefficients were largest for brain Phe PWM and measures of auditory memory (rho = -0.79), anxiety (rho = 0.79), and executive functioning (rho = 0.69). Associations were in the expected direction, with higher brain Phe and lower brain Tyr related to poorer functioning. The two participants with severe structural MRI abnormalities had low brain Tyr levels in PCG and 3/5 of the participants with moderate to severe MRI abnormalities had higher than average brain Phe levels. COSY has the potential to quantify brain Phe and Tyr at low concentrations and in specific brain regions. In this pilot study, these biomarkers were associated with indices of neuropsychological functioning. Additional studies are needed to validate the COSY results.

  4. Combustion Science

    NASA Image and Video Library

    2002-08-07

    Interior of a combustion experiment apparatus used in the 2.2-second drop tower at NASA's Glenn Research Center. This was shown to students participating 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.

  5. Microgravity

    NASA Image and Video Library

    2002-08-07

    A Bay High School team member prepares the oil and water samples for their next drop operation as part of 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.

  6. Microgravity

    NASA Image and Video Library

    2002-08-07

    Students watch a test run on their experiment before the actual drop. They designed and built their apparatus to fit within a NASA-provided drop structure. This was part of 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.

  7. Microgravity

    NASA Image and Video Library

    2002-08-07

    A NASA test conductor at the top of the 2.2-second Drop Tower monitors a student lecture at a lower level. This was part of the 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. Microgravity

    NASA Image and Video Library

    2002-08-07

    A student assembles a Lego (TM) Challenge device designed to operate in the portable drop tower demonstrator as part of 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.

  9. Microgravity

    NASA Image and Video Library

    2002-08-07

    Members from all four teams were mixed into pairs to work on a Lego (TM) Challenge device to operate in the portable drop tower demonstrator (background). These two team members are about to try out their LEGO (TM) creation. This was part of 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.

  10. Microgravity

    NASA Image and Video Library

    2002-08-07

    Two students show the Lego (TM) Challenge device they designed and built to operate in the portable drop tower demonstrator as part of 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.

  11. Microgravity

    NASA Image and Video Library

    2002-08-07

    Students from the four teams pose in front of he NASA Glenn Administration Building alongside the NASA Glenn Time Capsule. The students participated 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.

  12. Results of the Juelich Accelerator Module Based on Super-Conducting Half-Wave Resonators

    NASA Astrophysics Data System (ADS)

    Eichhorn, R.; Esser, F.; Laatsch, B.; Lennartz, M.; Schug, G.; Stassen, R.

    2006-04-01

    In the context of upgrading the existing proton and deuteron accelerator facility COSY at the Forschungszentrum Juelich, an accelerator module based on superconducting cavities is prototyped. Two rf cavities have been delivered and extensively tested. The design of the cryostat was finished in 2004, the construction has started and the first cool-down of the module was scheduled for early summer 2005. This paper will review the design constraints, report the results obtained from the superconducting accelerator cavities and their ancillary parts (power coupler, tuner etc) and present the status of the almost finished work.

  13. A recoil detector for the measurement of antiproton-proton elastic scattering at angles close to 90°

    NASA Astrophysics Data System (ADS)

    Hu, Q.; Bechstedt, U.; Gillitzer, A.; Grzonka, D.; Khoukaz, A.; Klehr, F.; Lehrach, A.; Prasuhn, D.; Ritman, J.; Sefzick, T.; Stockmanns, T.; Täschner, A.; Wuestner, P.; Xu, H.

    2014-10-01

    The design and construction of a recoil detector for the measurement of recoil protons of antiproton-proton elastic scattering at scattering angles close to are described. The performance of the recoil detector has been tested in the laboratory with radioactive sources and at COSY with proton beams by measuring proton-proton elastic scattering. The results of laboratory tests and commissioning with beam are presented. Excellent energy resolution and proper working performance of the recoil detector validate the conceptual design of the KOALA experiment at HESR to provide the cross section data needed to achieve a precise luminosity determination at the PANDA experiment.

  14. Novel phenyl-1-benzoxepinols from butcher's broom (Rusci rhizoma).

    PubMed

    Barbič, Matej; Schmidt, Thomas J; Jürgenliemk, Guido

    2012-06-01

    Two novel compounds, (3S)-2,3-dihydro-3-(4-hydroxyphenyl)-1-benzoxepin-8-ol (ruscozepine A) and (3S)-2,3-dihydro-3-(4-hydroxyphenyl)-8-methoxy-1-benzoxepin-7-ol (ruscozepine B) were isolated from butcher's broom (Rusci rhizoma) together with a biosynthetically possible phenylethanoid precursor, hydroxytyrosol. The structures were elucidated by spectroscopic methods such as 1D- and 2D-NMR (COSY, HSQC, HMBC, ROESY), and HR-EI-MS experiments. The absolute configuration of the ruscozepines was determined by electronic circular dichroism. Copyright © 2012 Verlag Helvetica Chimica Acta AG, Zürich.

  15. Microgravity

    NASA Image and Video Library

    2002-08-08

    In addition to drop tower activities, students assembled a plastic pipe structure underwater in a SCUBA exercise similar to training astronauts receive at NASA Johnson Space Center. This was part of 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.

  16. Measurement of the overrightarrow{n} p→ dπ0π0 reaction with polarized beam in the region of the d*(2380) resonance

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    We report on a high-statistics measurement of the most basic double-pionic fusion reaction overrightarrow{n} p→ dπ0π0 over the energy region of the d *(2380) resonance by use of a polarized deuteron beam and observing the double fusion reaction in the quasifree scattering mode. The measurements were performed with the WASA detector setup at COSY. The data reveal substantial analyzing powers and confirm conclusions about the d* resonance obtained from unpolarized measurements. We also confirm the previous unpolarized data obtained under complementary kinematic conditions.

  17. Measurements of branching ratios for η decays into charged particles

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

    The WASA-at-COSY experiment has collected 3 ×107 events with η mesons produced via the reaction p d →3He η at T =1.0 GeV . Using this data set, we evaluate the branching ratios of the decays η →π+π-γ , η →e+e-γ , η →π+π-e+e- , and η →e+e-e+e- . The branching ratios are normalized to the η →π+π-π0 decay. In addition an upper limit on a C P -violating asymmetry in η →π+π-e+e- is extracted.

  18. ABC effect and resonance d*(2380)

    NASA Astrophysics Data System (ADS)

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

    2017-11-01

    A new state in the two-baryon system with mass 2380 MeV and width 80 MeV has been detected in the experiments at the Juelich Cooler Synchrotron (COSY). The new particle denoted now d*(2380) has quantum numbers I( J p ) = 0(3+). The total cross sections for the d and 4He fusion reactions show similar to each other resonance-like energy dependence. The resonance-like structure is sensed in the double-pionic fusion channels and polarized np scattering.

  19. Bioconversion of rebaudioside I from rebaudioside A.

    PubMed

    Prakash, Indra; Bunders, Cynthia; Devkota, Krishna P; Charan, Romila D; Ramirez, Catherine; Snyder, Tara M; Priedemann, Christopher; Markosyan, Avetik; Jarrin, Cyrille; Halle, Robert Ter

    2014-10-28

    To supply the increasing demand of natural high potency sweeteners to reduce the calories in food and beverages, we have looked to steviol glycosides. In this work we report the bioconversion of rebaudioside A to rebaudioside I using a glucosyltransferase enzyme. This bioconversion reaction adds one sugar unit with a 1→3 linkage. We utilized 1D and 2D NMR spectroscopy (1H, 13C, COSY, HSQC-DEPT, HMBC, 1D TOCSY and NOESY) and mass spectral data to fully characterize rebaudioside I.

  20. Intermolecular Interactions between Eosin Y and Caffeine Using 1H-NMR Spectroscopy.

    PubMed

    Okuom, Macduff O; Wilson, Mark V; Jackson, Abby; Holmes, Andrea E

    2013-12-31

    DETECHIP has been used in testing analytes including caffeine, cocaine, and tetrahydrocannabinol (THC) from marijuana, as well as date rape and club drugs such as flunitrazepam, gamma-hydroxybutyric acid (GHB), and methamphetamine. This study investigates the intermolecular interaction between DETECHIP sensor eosin Y (DC1) and the analyte (caffeine) that is responsible for the fluorescence and color changes observed in the actual array. Using 1 H-NMR, 1 H-COSY, and 1 H-DOSY NMR methods, a proton exchange from C-8 of caffeine to eosin Y is proposed.

  1. Monoterpenoid glucoindole alkaloids and iridoids from Pterocephalus pinardii.

    PubMed

    Gülcemal, Derya; Masullo, Milena; Alankuş-Calişkan, Ozgen; Karayildirim, Tamer; Senol, Serdar G; Piacente, Sonia; Bedir, Erdal

    2010-03-01

    A new secondary metabolite, pterocephaline, along with the known cantleyoside, 7alpha-morroniside, 3beta,5alpha-tetrahydrodesoxycordifoline lactam, 5S-5-carboxyvincoside, sweroside, and loganin have been isolated from the aerial parts of P. pinardii (Dipsacaceae). Moreover, cantleyoside-methyl-hemiacetal and cantleyoside-dimethyl-acetal were obtained as seco-iridoid artifacts. The structures were elucidated by extensive spectroscopic methods including 1D-((1)H, (13)C and TOCSY) and 2D-NMR (DQF-COSY, HSQC and HMBC). Monoterpenoid glucoindole alkaloids were encountered for the first time in Dipsacaceae family. Copyright (c) 2010 John Wiley & Sons, Ltd.

  2. Complete assignments of 1H and 13C NMR spectra of leucanthoside A, a new triterpenoid saponin from Cephalaria leucantha L.

    PubMed

    Godevac, D; Mandić, B; Vajs, V; Menković, N; Macura, S; Milosavljević, S

    2006-07-01

    Leucanthoside A, a new allose-containing triterpenoid saponin (1), was isolated from the aerial parts of Cephalaria leucantha L. Its structure was determined by electrospray ionization mass spectrometry and NMR spectroscopy. Complete assignments of the 1H and 13C NMR chemical shifts were achieved by two-dimensional NMR experiments: DQF-COSY, NOESY, TOCSY, HSQC, DINE-HSQC, HMBC, 13C-1H 2D-J-resolved spectroscopy, and 1,1-ADEQUATE. Copyright (c) 2006 John Wiley & Sons, Ltd.

  3. Advanced wave field sensing using computational shear interferometry

    NASA Astrophysics Data System (ADS)

    Falldorf, Claas; Agour, Mostafa; Bergmann, Ralf B.

    2014-07-01

    In this publication we give a brief introduction into the field of Computational Shear Interferometry (CoSI), which allows for determining arbitrary wave fields from a set of shear interferograms. We discuss limitations of the method with respect to the coherence of the underlying wave field and present various numerical methods to recover it from its sheared representations. Finally, we show experimental results on Digital Holography of objects with rough surface using a fiber coupled light emitting diode and quantitative phase contrast imaging as well as numerical refocusing in Differential Interference Contrast (DIC) microscopy.

  4. NMR spectra and potentiometry studies of aluminum(III) binding with coenzyme NAD+ in acidic aqueous solutions.

    PubMed

    Yang, Xiaodi; Bi, Shuping; Yang, Xiaoliang; Yang, Li; Hu, Jun; Liu, Jian; Yang, Zhengbiao

    2003-06-01

    Complexation and conformational studies of coenzyme NAD+ with aluminum were conducted in acidic aqueous solutions (pH 2-5) by means of potentiometry as well as multinuclear (1H, 13C, 31P, 27Al) and two-dimensional (1H, 1H-NOESY) NMR spectroscopy. These led to the following results: (1) Al could coordinate with NAD+ through the following binding sites: N7' of adenine and pyrophosphate free oxygen (O(A)1, O(N)1,O(A)2) to form various mononuclear 1:1 (AlLH23+, AlLH2+) and 2:1 (AlL2-) species, and dinuclear 2:2 (Al2L22+) species. (2) The conformations of NAD+ and Al-NAD+ depended on the solvents and different species in the complexes. The results suggest the occurrence of an Al-linked complexation, which causes structural changes at the primary recognition sites and secondary conformational alterations for coenzymes. This finding will help us to understand role of Al in biological enzyme reaction systems.

  5. Improved characteristics of conventional and inverted polymer photodetectors using phosphonic acid-based self-assembled monolayer treatment for interfacial engineering of Ga-doped ZnO electrodes

    NASA Astrophysics Data System (ADS)

    Kajii, Hirotake; Mohri, Yoshinori; Okui, Hiyuto; Kondow, Masahiko; Ohmori, Yutaka

    2018-03-01

    The characteristics of conventional and inverted polymer photodetectors based on a blend of a donor, poly(3-hexylthiophene) (P3HT), and an acceptor, fullerene derivative [6,6]phenyl-C61-butyric acid methyl ester (PCBM) using Ga-doped ZnO (GZO) electrodes modified by phosphonic acid-based self-assembled monolayer (SAM) treatment in a short time are investigated. Fluoroalkyl SAM, 1H,1H,2H,2H-perfluorooctane phosphonic acid (FOPA) treatment leads to efficient hole extraction from the active layer. The characteristics of the conventional device with GZO modified by FOPA treatment are almost the same as those with indium tin oxide modified by FOPA. Cs2CO3 and aminoalkyl SAM, 11-aminoundecylphosphonic acid (11-AUPA) treatments suppress the hole injection from GZO to the organic layer. For the inverted devices with GZO cathodes using Cs2CO3 and 11-AUPA, the dark current decreases, which results in the improved photodetector detectivity. An inverted device with both Cs2CO3 and 11-AUPA exhibits incident-photon-to-current conversion efficiency (IPCE) of approximately 65% (80%) at 0 V (-6 V) under light irradiation (λ = 500 nm), high on/off ratio, and improved durability. Improved open-circuit voltage and IPCE at low voltages are achieved by these treatments, which are related with the improved internal built-in field, the reduction of recombination probability in the vicinity of GZO, and the modified charge collection efficiency.

  6. An intercalation-locked parallel-stranded DNA tetraplex.

    PubMed

    Tripathi, Shailesh; Zhang, Daoning; Paukstelis, Paul J

    2015-02-18

    DNA has proved to be an excellent material for nanoscale construction because complementary DNA duplexes are programmable and structurally predictable. However, in the absence of Watson-Crick pairings, DNA can be structurally more diverse. Here, we describe the crystal structures of d(ACTCGGATGAT) and the brominated derivative, d(AC(Br)UCGGA(Br)UGAT). These oligonucleotides form parallel-stranded duplexes with a crystallographically equivalent strand, resulting in the first examples of DNA crystal structures that contains four different symmetric homo base pairs. Two of the parallel-stranded duplexes are coaxially stacked in opposite directions and locked together to form a tetraplex through intercalation of the 5'-most A-A base pairs between adjacent G-G pairs in the partner duplex. The intercalation region is a new type of DNA tertiary structural motif with similarities to the i-motif. (1)H-(1)H nuclear magnetic resonance and native gel electrophoresis confirmed the formation of a parallel-stranded duplex in solution. Finally, we modified specific nucleotide positions and added d(GAY) motifs to oligonucleotides and were readily able to obtain similar crystals. This suggests that this parallel-stranded DNA structure may be useful in the rational design of DNA crystals and nanostructures. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

  7. Mussel-inspired superhydrophobic surfaces with enhanced corrosion resistance and dual-action antibacterial properties.

    PubMed

    Qian, Hongchang; Li, Minglu; Li, Zhong; Lou, Yuntian; Huang, Luyao; Zhang, Dawei; Xu, Dake; Du, Cuiwei; Lu, Lin; Gao, Jin

    2017-11-01

    In this study, a multilayer antibacterial film was assembled onto 316L stainless steel via mussel-inspired depositions of polydopamine (PDA) and silver (Ag) nanoparticles followed by post-modification with 1H, 1H, 2H, 2H-perfluorodecanethiol. The resulting surface exhibited excellent superhydrophobicity with hierarchical micro/nanostructures that were constructed by both PDA and Ag nanoparticles. The crystal structure and chemical composition of these surfaces were investigated using X-ray photoelectron spectroscopy (XPS) analysis. Potentiodynamic polarization measurements revealed that the corrosion resistance of the as-prepared surfaces were sequentially increased after each step of the fabrication process. Compared with the surface covered with only Ag nanoparticles, the superhydrophobic surfaces exhibited substantially enhanced antibacterial activity against the Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus, resulting from the synergistic antibacterial actions of the superhydrophobic surface and Ag nanoparticles. The superhydrophobic surface exhibited lower cytotoxicity, compared to the surface covered with Ag nanoparticles. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Revealing the metabolome of animal tissues using 1H nuclear magnetic resonance spectroscopy.

    PubMed

    Viant, Mark R

    2007-01-01

    The measurement of tissue-specific metabolic fingerprints can be of particular interest when investigating disease processes, mechanisms of toxicity, or when knowledge of the metabolic interactions between different organs is required. This chapter presents several optimized protocols for the extraction of metabolites from animal tissues, their analysis by 1H nuclear magnetic resonance (NMR) spectroscopy, and the subsequent spectral preprocessing required for an NMR-based metabolomics experiment. First, the three critical steps in the preparation of tissue extracts for NMR analysis are described, including both a perchloric acid protocol for the extraction of polar metabolites, and a methanol:chloroform protocol for extraction of polar and lipophilic metabolites. Then a series of NMR experiments are described including a standard one-dimensional (1D) 1H NMR study, a 1D 1H Carr-Purcell-Meiboom-Gill spin-echo experiment, and a two-dimensional 1H-1H J-resolved NMR experiment. The advantages and limitations of each experiment for metabolomics research are discussed. Analysis of the resulting NMR datasets is typically conducted in two phases comprising "low level" spectral preprocessing and "high level" multivariate analysis. NMR spectral preprocessing is a critical step that converts raw NMR spectra into an appropriate data format for multivariate analysis. A detailed protocol for preprocessing NMR data, using ProMetab software, is presented. Because a plethora of algorithms exist for multivariate analyses, which can be used to construct classification models or for biomarker discovery, this is beyond the scope of the current chapter.

  9. Monitoring self-sorting by electrospray ionization mass spectrometry: formation intermediates and error-correction during the self-assembly of multiply threaded pseudorotaxanes.

    PubMed

    Jiang, Wei; Schäfer, Andreas; Mohr, Parveen Choudhary; Schalley, Christoph A

    2010-02-24

    Three binary pseudorotaxanes, which are based on two different secondary ammonium/crown ether binding motifs, have been studied by (1)H NMR and (1)H,(1)H EXSY NMR experiments with respect to their thermodynamic stabilities and their axle exchange kinetics. The stability ranking does not follow the order of axle exchange rates, and the thermodynamically most stable axle-wheel combinations assemble only slowly. On the basis of these binding motifs, a series of self-sorting systems have been studied ranging from simple four-component mixtures through sequence-specific pseudorotaxanes to multiply threaded complexes. Because of the mismatch of kinetic and thermodynamic order, wrongly assembled structures are unavoidable, which require error-correction steps to yield the final thermodynamically controlled self-sorted products. These error-correction steps can easily be monitored by electrospray mass spectrometry, when a mixed-flow microreactor is coupled to the ion source to cover second time scales. Self-assembly intermediates, wrongly assembled structures, and the final thermodynamic products can be simultaneously identified. The determination of preferred assembly pathways as well as the formation of dead-end structures provides a clear picture of a rich kinetic behavior of the self-sorting systems under study.

  10. Probing intermolecular interactions in a diethylcarbamazine citrate salt by fast MAS1H solid-state NMR spectroscopy and GIPAW calculations.

    PubMed

    Venâncio, Tiago; Oliveira, Lyege Magalhaes; Ellena, Javier; Boechat, Nubia; Brown, Steven P

    2017-10-01

    Fast magic-angle spinning (MAS) NMR is used to probe intermolecular interactions in a diethylcarbamazine salt, that is widely used as a treatment against adult worms of Wuchereria bancrofti which cause a common disease in tropical countries named filariasis. Specifically, a dihydrogen citrate salt that has improved thermal stability and solubility as compared to the free form is studied. One-dimensional 1 H, 13 C and 15 N and two-dimensional 1 H- 13 C and 14 N- 1 H heteronuclear correlation NMR experiments under moderate and fast MAS together with GIPAW (CASTEP) calculations enable the assignment of the 1 H, 13 C and 14 N/ 15 N resonances. A two-dimensional 1 H- 1 H double-quantum (DQ) -single-quantum (SQ) MAS spectrum recorded with BaBa recoupling at 60kHz MAS identifies specific proton-proton proximities associated with citrate-citrate and citrate-diethylcarbamazine intermolecular interactions. Copyright © 2017 Elsevier Inc. All rights reserved.

  11. Hybridization of Deoxyribonucleic Acid and Immobilization of Green Fluorescent Protein on Nanostructured Organosilane Templates

    NASA Astrophysics Data System (ADS)

    Tanii, Takashi; Hosaka, Takumi; Miyake, Takeo; Kanari, Yuzo; Zhang, Guo-Jun; Funatsu, Takashi; Ohdomari, Iwao

    2005-07-01

    We propose a novel process for preferential immobilization of deoxyribonucleic acid (DNA) and green fluorescent protein (GFP) onto organosilane self-assembled monolayer (SAM) templates. One of the advantages of using the organosilane SAM as the template is that it is electron-beam sensitive and, by utilizing the SAM as an alternative resist film, we can make nanopatterns on a molecular scale because the proximity effect is negligible owing to the film’s thinness. An other advantage is that the organosilane SAM is repellent to both DNA and GFP. Thus, the patterned SAM can be utilized as the passivation film covering the outside of the pattern while DNA and GFP are immobilized within the pattern. We investigate two kinds of organosilane SAMs for the template. One is n-octadecyltrimethoxysilane (ODS) SAM, and the other is 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FDS) SAM. Our results indicate that the ODS SAM is more repellent to DNA than the FDS SAM and is suitable for DNA immobilization, while the FDS SAM template is suitable for GFP immobilization via biotin-avidin coupling because the FDS SAM surface prevents the nonspecific adsorption of streptavidin. Although the nonspecific adsorption of DNA and GFP on a SAM is also recognized, by controlling both the concentration and the incubation time, we can immobilize DNA and GFP preferentially onto nanopatterns of 100 nm diameter.

  12. 1H and 15N nuclear magnetic resonance assignment and secondary structure of the cytotoxic ribonuclease alpha-Sarcin.

    PubMed Central

    Campos-Olivas, R.; Bruix, M.; Santoro, J.; Martínez del Pozo, A.; Lacadena, J.; Gavilanes, J. G.; Rico, M.

    1996-01-01

    The ribosome-inactivating protein alpha-Sarcin (alpha S) is a 150-residue fungal ribonuclease that, after entering sensitive cells, selectively cleaves a single phosphodiester bond in an universally conserved sequence of the major rRNA to inactivate the ribosome and thus exert its cytotoxic action. As a first step toward establishing the structure-dynamics-function relationships in this system, we have carried out the assignment of the 1H and 15N NMR spectrum of alpha S on the basis of homonuclear (1H-1H) and heteronuclear (1H-15N) two-dimensional correlation spectra of a uniformly 15N-labeled sample, and two selectively 15N-labeled (Tyr and Phe) samples, as well as a single three-dimensional experiment. The secondary structure of alpha S, as derived from the characteristic patterns of dipolar connectivities between backbone protons, conformational chemical shifts, and the protection of backbone amide protons against exchange, consists of a long N-terminal beta-hairpin, a short alpha-helical segment, and a C-terminal beta-sheet of five short strands arranged in a + 1, + 1, + 1, + 1 topology, connected by long loops in which the 13 Pro residues are located. PMID:8732769

  13. Synthesis, configuration, and (15)n NMR spectra of iminoaziridines. Synthons equivalent to three components of the Ugi reaction.

    PubMed

    Quast, Helmut; Aldenkortt, Sven; Freudenreich, Bernd; Schäfer, Peter; Hagedorn, Manfred; Lehmann, Jens; Banert, Klaus

    2007-03-02

    Monocyclic iminoaziridines and exo-endo diastereomers of spirocyclic iminoaziridines that are derived from norbornane are prepared in batches of up to 10 g to foster applications as building blocks in syntheses. N,N'-Disubstituted alpha-haloamidines, which are readily available in two steps from N-substituted alpha-halocarboxamides, are 1,3-dehydrohalogenated by strong bases such as alkali-metal hydrides or tert-butoxides to afford distillable oils or low-melting solids, which consist of slowly interconverting E-Z diastereomers of the title compounds. The scope and limitations are outlined for this reaction. The configurations E and Z that were assigned on the basis of homoallylic 1H-1H coupling and asymmetric solvent-induced shifts required that, in 13C NMR spectra, the observed gamma-effects of substitutents at the imino nitrogens were deshielding, contrary to the well-known shielding gamma-effects in all other types of C=N compounds. However, an NOE NMR study demonstrated unequivocally that the previous assignments are correct and hence the observed gamma-effects actually deshielding. The ranges of 15N NMR chemical shifts span more than 60 ppm. Neither the beta- nor the gamma-effects of substituents on both types of nitrogen follow a uniform increment pattern.

  14. Preparation of Superhydrophobic Film on Ti Substrate and Its Anticorrosion Property

    PubMed Central

    Zhu, Min; Tang, Wenchuan; Huang, Luyao; Zhang, Dawei; Du, Cuiwei; Yu, Gaohong; Chen, Ming; Chowwanonthapunya, Thee

    2017-01-01

    Superhydrophobic films were fabricated on a titanium substrate with or without anodizing by using a self-assembling method. Firstly, the pretreatments of mechanical polishing/anodizing or mechanical polishing only were conducted, respectively. Subsequently, the preparation of polydopamine film layer, deposition of nano-silver particles, and post modification of 1H,1H,2H,2H-perfluorodecanethiol were performed on the surface of the pretreated substrate. The surface morphologies, compositions, wettability, and corrosion resistance of the films were investigated with scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), water contact angle measurements, and electrochemical tests, respectively. Meanwhile, the effect of the deposition time in the silver nitrate solution on the hydrophobicity of the specimen surface was investigated. The result showed that with the increase of deposition time, the hydrophobic property enhanced gradually. The surface deposited for 7 h exhibited an optimum hydrophobic effect, which was characterized with a large water contact angle (WCA) of 154°, and the surface was rather rough and covered by a relatively uniform layer of micro-nano silver particles. The excellent hydrophobicity was attributed to a rough stratified microstructure along with the low surface energy. The electrochemical measurements showed that the existence of the superhydrophobic film can effectively enhance the corrosion resistance of Ti samples. PMID:28772987

  15. Preparation of Superhydrophobic Film on Ti Substrate and Its Anticorrosion Property.

    PubMed

    Zhu, Min; Tang, Wenchuan; Huang, Luyao; Zhang, Dawei; Du, Cuiwei; Yu, Gaohong; Chen, Ming; Chowwanonthapunya, Thee

    2017-06-08

    Superhydrophobic films were fabricated on a titanium substrate with or without anodizing by using a self-assembling method. Firstly, the pretreatments of mechanical polishing/anodizing or mechanical polishing only were conducted, respectively. Subsequently, the preparation of polydopamine film layer, deposition of nano-silver particles, and post modification of 1H,1H,2H,2H-perfluorodecanethiol were performed on the surface of the pretreated substrate. The surface morphologies, compositions, wettability, and corrosion resistance of the films were investigated with scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), water contact angle measurements, and electrochemical tests, respectively. Meanwhile, the effect of the deposition time in the silver nitrate solution on the hydrophobicity of the specimen surface was investigated. The result showed that with the increase of deposition time, the hydrophobic property enhanced gradually. The surface deposited for 7 h exhibited an optimum hydrophobic effect, which was characterized with a large water contact angle (WCA) of 154°, and the surface was rather rough and covered by a relatively uniform layer of micro-nano silver particles. The excellent hydrophobicity was attributed to a rough stratified microstructure along with the low surface energy. The electrochemical measurements showed that the existence of the superhydrophobic film can effectively enhance the corrosion resistance of Ti samples.

  16. Increasing active surface area to fabricate ultra-hydrophobic surface by using "Black silicon" with bosch etching process.

    PubMed

    Atthi, Nithi; Supadech, Jakrapong; Dupuy, Gaëtan; Nimittrakoolchai, On-Uma; Pankiew, Apirak; Supothina, Sitthisuntorn; Jeamsaksiri, Wutthinan; Hruanun, Charndet; Poyai, Amporn; Brachais, Claire-Helene

    2012-06-01

    Needle-shaped pillars so-called "Black silicon" (B-Si) were fabricated by etching cleaned silicon wafer with fluorine-based deep reactive ion etching plasma. The B-Si pillar with the pillar size (a) and spacing (b) of 250 nm, and height (h) of 6.47 microm, coated with SiOxFy film had water contact angle (WCA) and ethylene glycol contact angle (ECA) of 159.8 degrees and 135.5 degrees, respectively. After coating the pillar with trichloro(1H,1H, 2H,2H-perfluorooctyl)silane (TPFS), the WCA and ECA increased to 166.2 degrees and 161.8 degrees, respectively. At the optimum etching condition, the B-Si pillar with the size a = 376 nm, b = 576 nm, h = 6.47microm, and the aspect ratio of 14.80 showed the WCA and ECA of 4.25 degrees and 14.77 degrees, respectively. After coating with the TPFS, liquid droplets ran across the sample's surface rapidly and the WCA and ECA could not be measured. Moreover, when the pillar height was increased twice, the WCA and ECA of the B-Si with and without the TPFS coating were greater than 170 degrees, indicating excellent water-and-oil repellency and can be applied for Micro-Electro-Mechanical Systems (MEMS).

  17. Low-cost self-cleaning room temperature SnO2 thin film gas sensor on polymer nanostructures

    NASA Astrophysics Data System (ADS)

    Huo, Haibin; Yan, Fadong; Wang, Cong; Ren, Haizhou; Shen, Mengyan

    2010-04-01

    We have successfully fabricated SnO2 thin film CO gas sensors on nanospiked polyurethane (PU) polymer surfaces that are replicated with a low-cost soft nanolithography method from nanospiked silicon surfaces formed with femtosecond laser irradiations. The sensors show sensitive responses to the CO gas at room temperature because of the sharp structures of the nanospikes. This is much different from the sensors of SnO2 thin film coated on smooth surfaces that show no response to the CO gas at room temperature. To make the nanostructure sensor surface behave self-cleaning like lotus leaves, we deposited a silane monolayer on the surface of the sensors with the 1H,1H,2H,2H-perfluorooctyltrichlorosilane (PFOTS) which has low surface energy. The contact angle measurement conducted on the PFOTS monolayer-coated SnO2 gas sensors indicates that a super-hydrophobic surface formed on the nanospike sensor. The CO gas response sensitivity of the PFOTS-coated SnO2 sensors is almost the same to that of the as-fabricated SnO2 sensors without the PFOTS coating. Such a super-hydrophobic surface can protect the sensors exposed to moisture and heavy particulates, and can perform cleaning-in-place operations to prolong the lifetime of the sensors. These results show a great potential to fabricate thousands of identical gas sensors at low cost.

  18. Failure study of SnO2 room temperature gas sensors fabricated on nanospike substrates

    NASA Astrophysics Data System (ADS)

    Wang, Pengtao; Ren, Haizhou; Huo, Haibin; Shen, Mengyan; Sun, Hongwei; Ruths, Marina

    2012-04-01

    SnO2 gas sensors were fabricated on polyurethane (PU) polymer surfaces with nanospike structures. These nanospikes are replicated with a low-cost soft nanolithography method from silicon nanospike surfaces formed by femtosecond pulsed laser irradiation. The hydrophobicity of the sensing surface was enhanced by a monolayer coating of silane (1H,1H,2H,2H-perfluorooctyltrichlorosilane, PFOTS). The resulting self-cleaning behavior enabled sensing in environments with high moisture and heavy particulate content, while performing cleaning-in-place operations to prolong the lifetime of the sensors. Failure studies were performed to quantify the effects on the sensitivity of water washing. Contact angle measurements showed that the hydrophobicity was weakened after many cycles of droplet washing due to wear of the PFOTS film and/or damage of the nanoscale spike structure. It was also found that the baseline signal increased with droplet washing, while the sensitivity changed randomly within about 7.5%, so that the sensitivity of the gas sensor remained at a constant level after several thousand cycles of water washing.

  19. Crosslinked superhydrophobic films fabricated by simply casting poly(methyl methacrylate-butyl acrylate-hydroxyethyl methacrylate)-b-poly(perfluorohexylethyl methacrylate) solution

    NASA Astrophysics Data System (ADS)

    Wen, Xiufang; Ye, Chao; Cai, Zhiqi; Xu, Shouping; Pi, Pihui; Cheng, Jiang; Zhang, Lijuan; Qian, Yu

    2015-06-01

    This study focuses on the preparation of superhydrophobic films by crosslinkable polymer material-Poly(methyl methacrylate-butyl acrylate-hydroxyethyl methacrylate)-b-Poly(perfluorohexylethyl methacrylate) (P (MMA-BA-HEMA)-b-PFMA) with a simple one-step casting process. Nanoscale micelle particles with core-shell structure was obtained by dissolving the polymer and curing agent in the mixture of acetone and 1H, 1H, 5H octafluoropentyl-1,1,2,2 tetrafluoroethyl ether (FHT). Superhydrophobic films were fabricated by casting the micelle solution on the glass slides. By controlling the polymer concentration and acetone/FHT volume ratio, superhydrophobic polymer film with water contact angle of 153.2 ± 2.1° and sliding angle of 4° was obtained. By introducing a curing agent into the micelle solution, mechanical properties of the films can be improved. The adhension grade and hardness of the crosslinked superhydrophobic films reached 2 grade and 3H, respectively. The hydrophobicity is attributed to the synergistic effect of micro-submicro-nano-meter scale roughness by nanoscale micelle particles and low surface energy of fluoropolymer. This procedure makes it possible for widespread applications of superhydrophobic film due to its simplicity and practicability.

  20. 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.

  1. Surface-segregated monolayers: a new type of ordered monolayer for surface modification of organic semiconductors.

    PubMed

    Wei, Qingshuo; Tajima, Keisuke; Tong, Yujin; Ye, Shen; Hashimoto, Kazuhito

    2009-12-09

    We report a new type of ordered monolayer for the surface modification of organic semiconductors. Fullerene derivatives with fluorocarbon chains ([6,6]-phenyl-C(61)-buryric acid 1H,1H-perfluoro-1-alkyl ester or FC(n)) spontaneously segregated as a monolayer on the surface of a [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) film during a spin-coating process from the mixture solutions, as confirmed by X-ray photoelectron spectroscopy (XPS). Ultraviolet photoelectron spectroscopy (UPS) showed the shift of ionization potentials (IPs) depending on the fluorocarbon chain length, indicating the formation of surface dipole moments. Surface-sensitive vibrational spectroscopy, sum frequency generation (SFG) revealed the ordered molecular orientations of the C(60) moiety in the surface FC(n) layers. The intensity of the SFG signals from FC(n) on the surface showed a clear odd-even effect when the length of the fluorocarbon chain was changed. This new concept of the surface-segregated monolayer provides a facile and versatile approach to modifying the surface of organic semiconductors and is applicable to various organic optoelectronic devices.

  2. High resolution deuterium NMR studies of bacterial metabolism

    SciTech Connect

    Aguayo, J.B.; Gamcsik, M.P.; Dick, J.D.

    1988-12-25

    High resolution deuterium NMR spectra were obtained from suspensions of five bacterial strains: Escherichia coli, Clostridium perfringens, Klebsiella pneumoniae, Proteus mirabilis, and Staphylococcus aureus. Deuterium-labeled D-glucose at C-1, C-2, and C-6 was used to monitor dynamically anaerobic metabolism. The flux of glucose through the various bacterial metabolic pathways could be determined by following the disappearance of glucose and the appearance of the major end products in the 2H NMR spectrum. The presence of both labeled and unlabeled metabolites could be detected using 1H NMR spectroscopy since the proton resonances in the labeled species are shifted upfield due to an isotopicmore » chemical shift effect. The 1H-1H scalar coupling observed in both the 2H and 1H NMR spectra was used to assign definitively the resonances of labeled species. An increase in the intensity of natural abundance deuterium signal of water can be used to monitor pathways in which a deuteron is lost from the labeled metabolite. The steps in which label loss can occur are outlined, and the influence these processes have on the ability of 2H NMR spectroscopy to monitor metabolism are assessed.« less

  3. Effect of chemical and physical heterogeneities on colloid-facilitated cesium transport

    SciTech Connect

    Rod, Kenton; Um, Wooyong; Chun, Jaehun

    2018-03-31

    A set of column experiments was conducted to investigate the chemical and physical heterogeneity effect on colloid facilitated transport under slow pore velocity conditions. Pore velocities were kept below 100 cm d -1 for all experiments. Glass beads were packed into columns establishing four different conditions: 1) homogeneous, 2) mixed physical heterogeneity, 3) sequentially layered physical heterogeneity, and 4) chemical heterogeneity. The homogeneous column was packed with glass beads (diameter 500–600 μm), and physical heterogeneities were created by sequential layering or mixing two sizes of glass bead (500–600 μm and 300–400 μm). A chemical heterogeneity was created using 25% ofmore » the glass beads coated with hydrophobic molecules (1H-1H-2H-2H-perfluorooctyltrichlorosilane) mixed with 75% pristine glass beads (all 500–600 μm). Input solution with 0.5 mM CsI and 50 mg L -1 colloids (1-μm diameter SiO 2) was pulsed into columns under saturated conditions. The physical heterogeneity in the packed glass beads retarded the transport of colloids compared to homogeneous (R = 25.0), but showed only slight differences between sequentially layered (R = 60.7) and mixed heterogeneity(R = 62.4). The column with the chemical, hydrophobic/hydrophilic, heterogeneity removed most of the colloids from the input solution. All column conditions stripped Cs from colloids onto the column matrix of packed glass beads.« less

  4. Simplified calculation approaches designed to reproduce the geometry of hydrogen bonds in molecular complexes in aprotic solvents.

    PubMed

    Shenderovich, Ilya G

    2018-03-28

    The impact of the environment onto the geometry of hydrogen bonds can be critically important for the properties of the questioned molecular system. The paper reports on the design of calculation approaches capable to simulate the effect of aprotic polar solvents on the geometric and NMR parameters of intermolecular hydrogen bonds. A hydrogen fluoride and pyridine complex has been used as the main model system because the experimental estimates of these parameters are available for it. Specifically, F-H, F⋯N, and H-N distances, the values of 15 N NMR shift, and spin-spin coupling constants 1 J( 19 F 1 H), 1h J( 1 H 15 N), and 2h J( 19 F 15 N) have been analyzed. Calculation approaches based on the gas-phase and the Polarizable Continuum Model (PCM) approximations and their combinations with geometric constraints and additional noncovalent interactions have been probed. The main result of this work is that the effect of an aprotic polar solvent on the geometry of a proton-donor⋯H⋯proton-acceptor complex cannot be reproduced under the PCM approximation if no correction for solvent-solute interactions is made. These interactions can be implicitly accounted for using a simple computational protocol.

  5. Methoxyflavones from New Lingzhi Medicinal Mushroom, Ganoderma lingzhi (Agaricomycetes).

    PubMed

    Shimizu, Kuniyoshi; Amen, Yhiya M; Kaifuchi, Satoru

    2016-01-01

    Ganoderma lingzhi is one of the most famous medicinal fungi in the world. It has been used in folk medicine, especially in East Asian countries. It is also a white-rot fungus with strong wood degradation ability, especially against lignin. Different classes of bioactive natural products have been reported in Ganoderma, including triterpenes, polysaccharides, sterols, and peptides. The triterpenes and polysaccharides are the primary bioactive compounds of Ganoderma. We report for the first time the presence of 3 methoxyflavones as minor constituents in G. linghzi. The 3 compounds were identified based on different spectroscopic techniques, including 1- and 2-dimensional nuclear magnetic resonance (1H-1H correlation spectroscopy, heteronuclear single quantum coherence, and heteronuclear multiple bond correlation) and mass spectrometry (high-resolution electrospray ionization mass spectrometry). Our report provides an approach to a possible biosynthetic pathway for biosynthetic genes in the mushrooms. Another great possibility is that these compounds may exist or be formed through degradation of the components in the woody substrate, such as lignin, and then subsequently translocate to the fruiting bodies.

  6. Effects of Intermittent Training on Anaerobic Performance and MCT Transporters in Athletes

    PubMed Central

    Millet, Grégoire; Bentley, David J.; Roels, Belle; Mc Naughton, Lars R.; Mercier, Jacques; Cameron-Smith, David

    2014-01-01

    This study examined the effects of intermittent hypoxic training (IHT) on skeletal muscle monocarboxylate lactate transporter (MCT) expression and anaerobic performance in trained athletes. Cyclists were assigned to two interventions, either normoxic (N; n = 8; 150 mmHg PIO2) or hypoxic (H; n = 10; ∼3000 m, 100 mmHg PIO2) over a three week training (5×1 h-1h30.week−1) period. Prior to and after training, an incremental exercise test to exhaustion (EXT) was performed in normoxia together with a 2 min time trial (TT). Biopsy samples from the vastus lateralis were analyzed for MCT1 and MCT4 using immuno-blotting techniques. The peak power output (PPO) increased (p<0.05) after training (7.2% and 6.6% for N and H, respectively), but VO2max showed no significant change. The average power output in the TT improved significantly (7.3% and 6.4% for N and H, respectively). No differences were found in MCT1 and MCT4 protein content, before and after the training in either the N or H group. These results indicate there are no additional benefits of IHT when compared to similar normoxic training. Hence, the addition of the hypoxic stimulus on anaerobic performance or MCT expression after a three-week training period is ineffective. PMID:24797797

  7. Functionalization of AlN surface and effect of spacer density on Escherichia coli pili-antibody molecular recognition.

    PubMed

    Cao, Ting; Wang, Anfeng; Liang, Xuemei; Tang, Haiying; Auner, Gregory W; Salley, Steven O; Ng, K Y Simon

    2008-06-01

    The immobilization of antibodies to sensor surfaces is critical in biochemical sensor development. In this study, Jeffamine spacers were employed to tether Escherichia coli K99 pilus antibody to AlN/sapphire surfaces which may allow the antibody to freely reorient and potentially improving the antigen capture efficiency. Spacer density was one of the key parameters to be optimized in studying its effect on the immobilization of antibody. The spacer density was controlled by functionalizing AlN/sapphire surfaces with a mixed (3-glycidyloxypropyl)trimethoxysilane (GPTMS) and trichloro(1H,1H,2H,2H-perfluoroctyl)silane (FAS) self-assembled monolayer (SAM) through a step-wise method. Contact angle measurement and X-ray photoelectron spectroscopy (XPS) were used to characterize the surface coverage of GPTMS and surface chemical composition. Compared to spacer fully covered samples, the capture efficiency was improved by approximately 28% with optimal Jeffamine ED 600 spacer density, which depends on the spacer properties such as the number of monomer units and its size.

  8. Comprehensive Metabolite Identification Strategy Using Multiple Two-Dimensional NMR Spectra of a Complex Mixture Implemented in the COLMARm Web Server

    SciTech Connect

    Bingol, Kerem; Li, Da-Wei; Zhang, Bo

    2016-12-06

    Identification of metabolites in complex mixtures represents a key step in metabolomics. A new strategy is introduced, which is implemented in a new public web server, COLMARm, that permits the co-analysis of up to three 2D NMR spectra, namely 13C-1H HSQC, 1H-1H TOCSY, and 13C-1H HSQC-TOCSY for the comprehensive, accurate, and efficient performance of this task. The highly versatile and interactive nature of COLMARm permits its application to a wide range of metabolomics samples independent of the magnetic field. Database query is performed using the HSQC spectrum and the top metabolite hits are then validated against the TOCSY-type experiment(s) bymore » superimposing the expected cross-peaks on the mixture spectrum. In this way the user can directly accept or reject candidate metabolites by taking advantage of the complementary spectral information offered by these experiments and their different sensitivities. The power of COLMARm is demonstrated for a human serum sample uncovering the existence of 14 metabolites that hitherto were not identified by NMR.« less

  9. 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

  10. Superamphiphobic cotton fabrics with enhanced stability

    NASA Astrophysics Data System (ADS)

    Xu, Bi; Ding, Yinyan; Qu, Shaobo; Cai, Zaisheng

    2015-11-01

    Superamphiphobic cotton fabrics were prepared by alternately depositing organically modified silica alcogel (ormosil) particles onto chitosan precoated cotton fabrics and subsequent 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane (PFOTMS) modification. Transmission electron microscopy and scanning electron microscopy images reveal that the ormosil particles display a fluffy, sponge-like nanoporous structure, and the entire cotton fiber surface is covered with highly porous networks. PFOTMS acts as not only a modifier to lower the surface energy of the cotton fabric but also a binder to enhance the coating stability against abrasion and washing. The treated cotton fabrics show highly liquid repellency with the water, cooking oil and hexadecane contact angels reaching to 164.4°, 160.1° and 156.3°, respectively. Meanwhile, the treated cotton fabrics exhibit good abrasion resistance and high laundering durability, which can withstand 10,000 cycles of abrasion and 30 cycles of machine wash without apparently changing the superamphiphobicity. The superamphiphobic cotton fabric also shows high acid stability, and can withstand 98% H2SO4. Moreover, the superamphiphobic coating has almost no influence on the other physical properties of the cotton fabrics including tensile strength, whiteness and air permeability. This durable non-wetting surface may provide a wide range of new applications in the future.

  11. Estimation of hydraulic jump characteristics of channels with sudden diverging side walls via SVM.

    PubMed

    Roushangar, Kiyoumars; Valizadeh, Reyhaneh; Ghasempour, Roghayeh

    2017-10-01

    Sudden diverging channels are one of the energy dissipaters which can dissipate most of the kinetic energy of the flow through a hydraulic jump. An accurate prediction of hydraulic jump characteristics is an important step in designing hydraulic structures. This paper focuses on the capability of the support vector machine (SVM) as a meta-model approach for predicting hydraulic jump characteristics in different sudden diverging stilling basins (i.e. basins with and without appurtenances). In this regard, different models were developed and tested using 1,018 experimental data. The obtained results proved the capability of the SVM technique in predicting hydraulic jump characteristics and it was found that the developed models for a channel with a central block performed more successfully than models for channels without appurtenances or with a negative step. The superior performance for the length of hydraulic jump was obtained for the model with parameters F 1 (Froude number) and (h 2- h 1 )/h 1 (h 1 and h 2 are sequent depth of upstream and downstream respectively). Concerning the relative energy dissipation and sequent depth ratio, the model with parameters F 1 and h 1 /B (B is expansion ratio) led to the best results. According to the outcome of sensitivity analysis, Froude number had the most significant effect on the modeling. Also comparison between SVM and empirical equations indicated the great performance of the SVM.

  12. Epoxynemanione A, nemanifuranones A-F, and nemanilactones A-C, from Nemania serpens, an endophytic fungus isolated from Riesling grapevines.

    PubMed

    Ibrahim, Ashraf; Sørensen, Dan; Jenkins, Hilary A; Ejim, Linda; Capretta, Alfredo; Sumarah, Mark W

    2017-08-01

    Ten polyketide specialized metabolites, epoxynemanione A, nemanifuranones A-F, and nemanilactones A-C, were isolated from the culture filtrate of Nemania serpens (Pers.) Grey (1821), an endophytic fungus from a Riesling grapevine (Vitis vinifera) found in Canada's Niagara region. Additionally, four known metabolites 2-(hydroxymethyl)-3-methoxy-benzoic acid, phyllostine, 5-methylmellein and a nordammarane triterpenoid were isolated. A related known metabolite 2,3-dihydro-2-hydroxy-2,4-dimethyl-5-trans-propenylfuran-3-one has also been included for structural and biological comparison to the nemanifuranones. The latter was isolated from the culture filtrates of Mollisia nigrescens, an endophytic fungus from the leaves and stems of lowbush blueberry (Vaccinium angustifolium) found in the Acadian forest of Nova Scotia, Canada. Their structures were elucidated based on 1D and 2D NMR, HRESIMS measurements, X-ray crystallographic analysis of nemanifuranone A, the nordammarane triterpenoid and 2,3-dihydro-2-hydroxy-2,4-dimethyl-5-trans-propenylfuran-3-one compounds, and comparison of NOE and vicinal 1 H- 1 H coupling constants to literature data for relative stereochemical assignments. Nemanifuranone A possesses a rare C2 hemiacetal and was active against both Gram-negative and Gram-positive bacteria. Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.

  13. Superamphiphobic Surfaces Prepared by Coating Multifunctional Nanofluids.

    PubMed

    Esmaeilzadeh, Pouriya; Sadeghi, Mohammad Taghi; Bahramian, Alireza; Fakhroueian, Zahra; Zarbakhsh, Ali

    2016-11-23

    Construction of surfaces with the capability of repelling both water and oil is a challenging issue. We report the superamphiphobic properties of mineral surfaces coated with nanofluids based on synthesized Co-doped and Ce-doped Barium Strontium Titanate (CoBST and CeBST) nanoparticles and fluorochemicals of trichloro(1H,1H,2H,2H-perfluorooctyl)silane (PFOS) and polytetrafluoroethylene (PTFE). Coating surfaces with these nanofluids provides both oil (with surface tensions as low as 23 mN/m) and water repellency. Liquids with high surface tension (such as water and ethylene glycol) roll off the coated surface without tilting. A water drop released from 8 mm above the coated surface undergoes first a lateral displacement from its trajectory and shape deformation, striking the surface after 23 ms, bouncing and rolling off freely. These multifunctional coating nanofluids impart properties of self-cleaning. Applications include coating surfaces where cleanliness is paramount such as in hospitals and domestic environments as well as the maintenance of building facades and protection of public monuments from weathering. These superamphiphobic-doped nanofluids have thermal stability up to 180 °C; novel industrial applications include within fracking and the elimination of condensate blockage in gas reservoirs.

  14. Air-stable solution-processed n-channel organic thin film transistors with polymerenhanced morphology

    DOE PAGES

    He, Zhengran; Shaik, Shoieb; Bi, Sheng; ...

    2015-05-04

    N,N 0-1H,1H-perfluorobutyl dicyanoperylenecarboxydiimide (PDIF-CN 2) is an n-type semiconductor exhibiting high electron mobility and excellent air stability. However, the reported electron mobility based on spin-coated PDIF-CN 2 film is much lower than the value of PDIF-CN 2 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) (PaMS), are pre-coated on silicon substrate aiming to enhance the morphology of the PDIF-CN 2 thin film, thereby improving the charge transport and air stability. Atomic force microscopy images reveal that with the pre-deposition of PaMSmore » or PMMA polymers, the morphology of the PDIF-CN 2 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 cm 2/V s has been achieved from OTFTs based on the PDIF-CN 2 film with the pre-deposition of PaMS polymer.« less

  15. Improvements, extensions, and practical aspects of rapid ASAP-HSQC and ALSOFAST-HSQC pulse sequences for studying small molecules at natural abundance

    NASA Astrophysics Data System (ADS)

    Schulze-Sünninghausen, David; Becker, Johanna; Koos, Martin R. M.; Luy, Burkhard

    2017-08-01

    Previously we introduced two novel NMR experiments for small molecules, the so-called ASAP-HSQC and ALSOFAST-HSQC (Schulze-Sünninghausen et al., 2014), which allow the detection of heteronuclear one-bond correlations in less than 30 s at natural abundance. We propose an improved symmetrized pulse scheme of the basic experiment to minimize artifact intensities and the combination with non-uniform sampling to enable the acquisition of conventional HSQC spectra in as short as a couple of seconds and extremely 13C-resolved spectra in less than ten minutes. Based on steady state investigations, a first estimate to relative achievable signal intensities with respect to conventional, ASAP-, and ALSOFAST-HSQC experiments is given. In addition, we describe several extensions to the basic pulse schemes, like a multiplicity-edited version, a revised symmetrized CLIP-ASAP-HSQC, an ASAP-/ALSOFAST-HSQC sequence with broadband BIRD-based 1H,1H decoupling, and a symmetrized sequence optimized for water suppression. Finally, RF-power considerations with respect to the high duty cycle of the experiments are given.

  16. Ionic Liquid-Solute Interactions Studied by 2D NOE NMR Spectroscopy.

    PubMed

    Khatun, Sufia; Castner, Edward W

    2015-07-23

    Intermolecular interactions between a Ru(2+)(bpy)3 solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {(1)H-(19)F} HOESY and {(1)H-(1)H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru(2+)(bpy)3 solute is rather different from the bulk IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru(2+)(bpy)3 solute interacts with both the polar head and the nonpolar tail groups of the 1-butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.

  17. GFT projection NMR based resonance assignment of membrane proteins: application to subunit C of E. coli F(1)F (0) ATP synthase in LPPG micelles.

    PubMed

    Zhang, Qi; Atreya, Hanudatta S; Kamen, Douglas E; Girvin, Mark E; Szyperski, Thomas

    2008-03-01

    G-matrix FT projection NMR spectroscopy was employed for resonance assignment of the 79-residue subunit c of the Escherichia coli F(1)F(0) ATP synthase embedded in micelles formed by lyso palmitoyl phosphatidyl glycerol (LPPG). Five GFT NMR experiments, that is, (3,2)D HNNCO, L-(4,3)D HNNC (alphabeta) C (alpha), L-(4,3)D HNN(CO)C (alphabeta) C (alpha), (4,2)D HACA(CO)NHN and (4,3)D HCCH, were acquired along with simultaneous 3D (15)N, (13)C(aliphatic), (13)C(aromatic)-resolved [(1)H,(1)H]-NOESY with a total measurement time of approximately 43 h. Data analysis resulted in sequence specific assignments for all routinely measured backbone and (13)C(beta) shifts, and for 97% of the side chain shifts. Moreover, the use of two G(2)FT NMR experiments, that is, (5,3)D HN{N,CO}{C (alphabeta) C (alpha)} and (5,3)D {C (alphabeta) C (alpha)}{CON}HN, was explored to break the very high chemical shift degeneracy typically encountered for membrane proteins. It is shown that the 4D and 5D spectral information obtained rapidly from GFT and G(2)FT NMR experiments enables one to efficiently obtain (nearly) complete resonance assignments of membrane proteins.

  18. Local Structural Preferences and Dynamics Restrictions in the Urea-Denatured State of SUMO-1: NMR Characterization

    PubMed Central

    Kumar, Ashutosh; Srivastava, Sudha; Mishra, Ram Kumar; Mittal, Rohit; Hosur, Ramakrishna V.

    2006-01-01

    We have investigated by multidimensional NMR the structural and dynamic characteristics of the urea-denatured state of activated SUMO-1, a 97-residue protein belonging to the growing family of ubiquitin-like proteins involved in post-translational modifications. Complete backbone amide and 15N resonance assignments were obtained in the denatured state by using HNN and HN(C)N experiments. These enabled other proton assignments from TOCSY-HSQC spectra. Secondary Hα chemical shifts and 1H-1H NOE indicate that the protein chain in the denatured state has structural preferences in the broad β-domain for many residues. Several of these are seen to populate the (φ,ψ) space belonging to polyproline II structure. Although there is no evidence for any persistent structures, many contiguous stretches of three or more residues exhibit structural propensities suggesting possibilities of short-range transient structure formation. The hetero-nuclear 1H-15N NOEs are extremely weak for most residues, except for a few at the C-terminal, and the 15N relaxation rates show sequence-wise variation. Some of the regions of slow motions coincide with those of structural preferences and these are interspersed by highly flexible residues. The implications of these observations for the early folding events starting from the urea-denatured state of activated SUMO-1 have been discussed. PMID:16415059

  19. Antibacterial and antifouling properties of a polyurethane surface modified with perfluoroalkyl and silver nanoparticles.

    PubMed

    Xu, Deqiu; Su, Yuling; Zhao, Lili; Meng, Fancui; Liu, Chang; Guan, Yayuan; Zhang, Jiya; Luo, Jianbin

    2017-02-01

    Inspired by mussel-adhesion phenomena in nature, a simple, mild surface modification process was elaborated to endow the polyurethane (PU) substrate with antibacterial/antifouling properties. In the present study, polydopamine was coated directly onto polyurethane surfaces. AgNO 3 was then added and absorbed onto the surface by the active catechol and amine groups of the polydopamine coating. Meanwhile, the adsorbed Ag + ions were reduced in situ into metallic silver nanoparticles by the "bridge" of the polydopamine coating which yielded a coating with good antimicrobial properties. Finally, 1H, 1H, 2H, 2H-perfluorodecanethiol (CF 3 (CF 2 ) 7 CH 2 CH 2 SH, F-SH) was attached on the PDA coating via the Michael addition reaction. The hydrophobic F-SH layer above the antibacterial layer yielded a surface with excellent antifouling properties. Preliminary antibacterial assays indicate that the coated surfaces show enhanced antibacterial activity against Escherichia coli (Gram-negative bacteria) and Staphylococcus aureus (Gram-positive bacteria). Platelet adhesion was significantly reduced for the F-SH-coated PU film. These results suggest that the modified PU could be used as an antibacterial material for future biomedical applications. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 531-538, 2017. © 2016 Wiley Periodicals, Inc.

  20. CFA-1: the first chiral metal-organic framework containing Kuratowski-type secondary building units.

    PubMed

    Schmieder, Phillip; Denysenko, Dmytro; Grzywa, Maciej; Baumgärtner, Benjamin; Senkovska, Irena; Kaskel, Stefan; Sastre, German; van Wüllen, Leo; Volkmer, Dirk

    2013-08-14

    The novel homochiral metal-organic framework CFA-1 (Coordination Framework Augsburg-1), [Zn5(OAc)4(bibta)3], containing the achiral linker {H2-bibta = 1H,1'H-5,5'-bibenzo[d][1,2,3]triazole}, has been synthesised. The reaction of H2-bibta and Zn(OAc)2·2H2O in N-methylformamide (NMF) (90 °C, 3 d) yields CFA-1 as trigonal prismatic single crystals. CFA-1 serves as a convenient precursor for the synthesis of isostructural frameworks with redox-active metal centres, which is demonstrated by the postsynthetic exchange of Zn(2+) by Co(2+) ions. The framework is robust to solvent removal and has been structurally characterized by synchrotron single-crystal X-ray diffraction and solid state NMR measurements ((13)C MAS- and (1)H MAS-NMR at 10 kHz). Results from MAS-NMR and IR spectroscopy studies are corroborated by cluster and periodic DFT calculations performed on CFA-1 cluster fragments.