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Sample records for pyrazines

  1. Pyrazine Revisited

    NARCIS (Netherlands)

    Drabe, Karel E.; Jonkman, Harry Th.; Kommandeur, Jan

    1986-01-01

    Pyrazine is shown by its Molecular Eigenstate Spectra and by its quantum beats to be a small molecule. The effect of Coriolis coupling and non-resonant light scattering are discussed. This paper further treats the so-called "fast component". Its existence with a decay time of about 100 psec has by n

  2. Synthesis of substituted pyrazines

    Energy Technology Data Exchange (ETDEWEB)

    Pagoria, Philip F.; Zhang, Mao Xi

    2016-10-04

    A method for synthesizing a pyrazine-containing material according to one embodiment includes contacting an iminodiacetonitrile derivative with a base and a reagent selected from a group consisting of hydroxylamine, a hydroxylamine salt, an aliphatic primary amine, a secondary amine, an aryl-substituted alkylamine a heteroaryl-substituted alkyl amine, an alcohol, an alkanolamine and an aryl alcoholamine. Additional methods and several reaction products are presented. ##STR00001##

  3. Transition metal-catalyzed functionalization of pyrazines

    NARCIS (Netherlands)

    Nikishkin, Nicolai I.; Huskens, Jurriaan; Verboom, Willem

    2013-01-01

    Transition metal-catalyzed reactions are generally used for carbon–carbon bond formation on pyrazines and include, but are not limited to, classical palladium-catalyzed reactions like Sonogashira, Heck, Suzuki, and Stille reactions. Also a few examples of carbon–heteroatom bond formation in pyrazine

  4. Novel pyrazine metabolites found in polymyxin biosynthesis by Paenibacillus polymyxa

    DEFF Research Database (Denmark)

    Beck, Hans Christian; Hansen, Anne M; Lauritsen, Frants R

    2003-01-01

    A complex mixture of methyl-branched alkyl-substituted pyrazines was found in the growth medium of the polymyxin-producing bacterium Paenibacillus polymyxa, and of these, seven are new natural compounds. A total of 19 pyrazine metabolites were identified. The dominant metabolite was 2...... supplementation. The other pyrazine metabolites, all related pyrazines with either one, two or three alkyl substituents, were identified by means of their mass spectral data and/or co-elution with authentic standards....

  5. Transition metal-catalyzed functionalization of pyrazines

    NARCIS (Netherlands)

    Nikishkin, N.; Huskens, Jurriaan; Verboom, Willem

    2013-01-01

    Transition metal-catalyzed reactions are generally used for carbon–carbon bond formation on pyrazines and include, but are not limited to, classical palladium-catalyzed reactions like Sonogashira, Heck, Suzuki, and Stille reactions. Also a few examples of carbon–heteroatom bond formation in

  6. Collisional deactivation of highly vibrationally excited pyrazine

    Science.gov (United States)

    Miller, Laurie A.; Barker, John R.

    1996-07-01

    The collisional deactivation of vibrationally excited pyrazine (C4N2H4) in the electronic ground state by 19 collider gases was studied using the time-resolved infrared fluorescence (IRF) technique. The pyrazine was photoexcited with a 308 nm laser and its vibrational deactivation was monitored following rapid radiationless transitions to produce vibrationally excited molecules in the electronic ground state. The IRF data were analyzed by a simple approximate inversion method, as well as with full collisional master equation simulations. The average energies transferred in deactivating collisions (d) exhibit a near-linear dependence on vibrational energy at lower energies and less dependence at higher energies. The deactivation of ground state pyrazine was found to be similar to that of ground state benzene [J. R. Barker and B. M. Toselli, Int. Rev. Phys. Chem. 12, 305 (1990)], but it is strikingly different from the deactivation of triplet state pyrazine [T. J. Bevilacqua and R. B. Weisman, J. Chem. Phys. 98, 6316 (1993)].

  7. Optical Control of Internal Conversion in Pyrazine

    Science.gov (United States)

    Barry, Grant; Singha, Sima; Hu, Zhan; Seideman, Tamar; Gordon, Robert

    2014-03-01

    We apply quantum control schemes previously reserved for atoms and small molecules to more complex polyatomic molecules. Pyrazine was chosen as a model polyatomic molecule for its well-studied conical intersection seam between the S1 and S2 potential energy surfaces (PESs). Using shaped ultraviolet femtosecond laser pulses, we demonstrate optical control of the excited state dynamics of this molecule under collisionless conditions. This was achieved in a pump-probe experiment by employing a genetic algorithm programmed to suppress ionization of the pyrazine molecules at a preselected time. Our findings indicate that the optimized pulses localize the wave packet for times up to 1.5 ps at a location on the coupled S1/S2 PESs where ionization is energetically forbidden. Our approach is general and does not require knowledge of the molecular Hamiltonian. Funding provided by National Science Foundation grant no. CHE-0848198.

  8. 2-Ethyl-3,5,6-triphenyl-pyrazine

    National Research Council Canada - National Science Library

    Anuradha, N; Thiruvalluvar, A; Chitra, S; Devanathan, D; Butcher, R J

    2012-01-01

    In the title mol-ecule, C(24)H(20)N(2), the pyrazine ring is significantly distorted from planarity, presumably due to steric crowding, and its conformation is well described as a flattened twist-boat...

  9. Studies on the Pyrazine Complexes of Some Diaryltellurium Dihalides

    Directory of Open Access Journals (Sweden)

    J. K. Narwal

    2014-01-01

    Full Text Available Nine new Pyrazine Complexes of diaryltelluriumdihalides, R2TeX2.Pyz (R =p-methoxyphenyl, p-hydroxyphenyl and 3-methyl- 4-hydroxy phenyl; X=Cl, Br, I; Pyz = pyrazine have been prepared by reactions of diaryltelluriumdihalides with pyrazine in 1:1 molar ratio. These complexes have been characterized by elemental analysis, conductance and cryoscopic measurements, infrared and proton magnetic resonance spectral studies. Conductance studies in nitrobenzene, acetone and acetonitrile predict their non-electrolyte type behaviour in these solvents, which is well supported by cryoscopic data in nitrobenzene. IR and 1H NMR studies suggest the unidentate nature of pyrazine in these complexes, involving only one nitrogen atom in coordination. Thus, tellurium in R2TeX2.Pyz complexes attains a coordination number of five probably in a square pyramidal.

  10. Pyrazine derivatives in cigarette smoke inhibit hamster oviductal functioning

    Directory of Open Access Journals (Sweden)

    Arey Janet

    2004-05-01

    Full Text Available Abstract Background Our past studies have shown that cigarette smoke inhibits oviductal functioning in vivo and in vitro. The goals in this study were to identify pyrazine derivatives in cigarette smoke solutions that inhibit ciliary beat frequency, oocyte pickup rate, and infundibular smooth muscle contraction in the hamster oviduct and to determine their lowest observable adverse effect levels (LOAELs using in vitro bioassays. Methods MS smoke solutions were fractionated using solid phase extraction cartridges and the fractions were both tested on the hamster oviduct in vitro and analyzed by gas chromatography-mass spectrometry to identify individual pyrazine derivatives. Commercial pyrazine standards were purchased, assayed for purity, and tested in dose-response studies on hamster oviducts. The LOAEL and efficacy were determined for each compound in the in vitro bioassays. Statistical significance was determined using the Student's t-Test where p Results The LOAELs for the most inhibitory pyrazine derivatives in the ciliary beat frequency, oocyte pickup rate, and infundibular smooth muscle contraction assays were as follows: for pyrazine (1 picomolar, 10 picomolar, and 1 nanomolar; for 2-methylpyrazine (1 picomolar, 10 picomolar, and 10 picomolar; and for 2-ethylpyrazine (1 picomolar, 10 picomolar, and 1 picomolar. Six of the seven pyrazine derivatives tested (pyrazine, 2-methylpyrazine, 2-ethylpyrazine, 2-methoxy-3-methylpyrazine, 2,5-dimethylpyrazine, and 2,3,5-trimethylpyrazine were inhibitory in picomolar or nanomolar doses in all three bioassays, while the seventh derivative, 2,6-dimethylpyrazine, had LOAELs in the nanomolar to micromolar range. Conclusion This work shows that very low doses of pyrazines significantly inhibit proper oviductal functioning, raising questions regarding the safety of these compounds in cigarettes and other consumer products.

  11. Pyrazine-based organometallic complex: synthesis, characterization, and supramolecular chemistry.

    Science.gov (United States)

    Bhowmick, Sourav; Chakraborty, Sourav; Das, Atanu; Rajamohanan, P R; Das, Neeladri

    2015-03-16

    The design, synthesis, and characterization of a new pyrazine-based ditopic platinum(II) organometallic complex are reported. The molecular structure of the organoplatinum pyrazine dipod was determined by single-crystal X-ray crystallography. The potential utility of this organometallic ditopic acceptor as a building block in the construction of neutral metallasupramolecular macrocycles containing the pyrazine motif was explored. Pyrazine motifs containing supramolecules were characterized by multinuclear NMR (including (1)H DOSY), mass spectrometry, and elemental analysis. The geometry of each supramolecular framework was optimized by employing the PM6 semiempirical molecular orbital method to predict its shape and size. The ability of the pyrazine-based organoplatinum complex to act as a host for nitroaromatic guest (2,4-dinitrotoluene and PA) molecules was explored by isothermal titration calorimetry (ITC). The binding stoichiometry and thermodynamic parameters of these host-guest complexation reactions were evaluated using ITC. Theoretical calculations were performed to obtain insight into the binding pattern between the organometallic host and nitroaromatic guests. The preferable binding propensity of the binding sites of complex 1 for both nitroaromatics (PA and 2,4-dinitrotoluene) determined by molecular simulation studies corroborates well with the experimental results as obtained by ITC experiments.

  12. N′-[(E-2-Methoxybenzylidene]pyrazine-2-carbohydrazide

    Directory of Open Access Journals (Sweden)

    Marcus V. N. de Souza

    2011-07-01

    Full Text Available In the title compound, C13H12N4O2, all the non-H atoms lie on a crystallographic mirror plane and an intramolecular N—H...N hydrogen bond generates an S(5 ring; the conformation about the imine bond [1.280 (3 Å] is E. In the crystal, molecules assemble into a two-dimensional array via C—H...O(carbonyl and C—H...N(pyrazine contacts. Layers stack along the b-axis direction via weak π–π interactions between pyrazine rings [ring centroid distance = 3.8028 (8 Å].

  13. Hydrogen bonding and multiphonon structure in copper pyrazine coordination polymers.

    Science.gov (United States)

    Brown, S; Cao, J; Musfeldt, J L; Conner, M M; McConnell, A C; Southerland, H I; Manson, J L; Schlueter, J A; Phillips, M D; Turnbull, M M; Landee, C P

    2007-10-15

    We report a systematic investigation of the temperature-dependent infrared vibrational spectra of a family of chemically related coordination polymer magnets based upon bridging bifluoride (HF(2)-) and terminal fluoride (F-) ligands in copper pyrazine complexes including Cu(HF(2))(pyz)(2)BF(4), Cu(HF(2))(pyz)(2)ClO(4), and CuF(2)(H(2)O)(2)(pyz). We compare our results with several one- and two-dimensional prototype materials including Cu(pyz)(NO(3))(2) and Cu(pyz)(2)(ClO(4))(2). Unusual low-temperature hydrogen bonding, local structural transitions associated with stronger low-temperature hydrogen bonding, and striking multiphonon effects that derive from coupling of an infrared-active fundamental with strong Raman-active modes of the pyrazine building-block molecule are observed. On the basis of the spectroscopic evidence, these interactions are ubiquitous to this family of coordination polymers and may work to stabilize long-range magnetic ordering at low temperature. Similar interactions are likely to be present in other molecule-based magnets.

  14. Ammoxidation of 2-methyl pyrazine to 2-cyano pyrazine on MoO3/FePO4 catalysts

    Indian Academy of Sciences (India)

    Nagaraju Pasupulety; Hafedh Driss; Yahia Abobakor Alhamed; Abdulrahim Ahmed Alzahrani; Muhammad A Daous; Lachezar Petrov; N Lingaiah; P S Sai Prasad

    2016-02-01

    The objective of this work is to understand the influence of small amount of Mo=O (1, 3 and 5wt.% MoO3) impregnated on FePO4 and its resultant effect on the acidity was studied for the ammoxidation of 2-methyl pyrazine (2-MP) to 2-cyano pyrazine (2-CP) in the temperature range of 380–420°C. The Mo/FeP catalyst characteristics were evaluated by XRD, HAADF-EDS, TPR and NH3-TPD techniques. Primarily, quartz-type XRD phase was observed for the iron phosphate (FeP). The Mo/FeP exhibits MoO3 and quartztype iron phosphate phase. The interface between Mo particles (20 nm) and FeP was clearly established by HR-TEM in 3Mo/FeP. Furthermore, the average atomic composition revealed by HAADF/EDS for 3Mo/FeP as Fe 30.0%, P 40.0% and Mo 1.6% with Fe/Mo surface XPS ratio 6. The greater 2-CP yield of 68.0% on 3Mo/FeP was attributed to enhanced, moderate acid sites coming from MoO3 and cooperation between Mo and FeP at the interface in terms of oxygen and electron transfer to the reactant (2-MP).

  15. N′-[(E-4-Bromobenzylidene]pyrazine-2-carbohydrazide

    Directory of Open Access Journals (Sweden)

    Shahid Hameed

    2013-07-01

    Full Text Available In the title compound, C12H9BrN4O, the N′-methylidenepyrazine-2-carbohydrazide and 4-bromobenzene groups are oriented at a dihedral angle of 10.57 (7°. The hydrazide N—H group is involved in intramolecular N—H...N interaction, which generates an S(5 motif. A short C—H...O interaction is formed between the methylidene H atom and the carbonyl O atom. It connects molecules into chains extending along [100]. In addition, molecules are arranged into stacks extending along [010] via π–π interactions between pyrazine and benzene rings, with centroid–centroid distances of 3.837 (2 and 3.860 (2 Å.

  16. The Spectrum of the Molecular Eigenstates of Pyrazine and the Reconstruction of Decays of Rotational States of the 1B3u (0-0) Transition of Pyrazine

    NARCIS (Netherlands)

    Meer, Barend J. van der; Jonkman, Harry Th.; Kommandeur, Jan

    1983-01-01

    The spectrum of the molecular eigenstates (ME) belonging to the various rotational members of the 1B3u (0-0) transition of pyrazine was measured with a very narrow band laser in a molecular beam with a Doppler width of 30 MHz. It is shown that, when the ME’s belonging to a single rotational state ar

  17. Characterization of pyrazines in some Chinese liquors and their approximate concentrations.

    Science.gov (United States)

    Fan, Wenlai; Xu, Yan; Zhang, Yanhong

    2007-11-28

    Pyrazines are very important impact aroma compounds in Chinese liquors. The identification of pyrazine derivatives was carried out by liquid-liquid extraction (LLE). The liquor sample was adjusted to the H(+) concentration of 1 N with 12 N HCl and then concentrated by rotatory evaporator under vacuum condition. The concentrated liquor was extracted by diethyl ether, and the residual aqueous phase was adjusted to pH 10. The basic compounds were detected and identified by gas chromatography (GC)-mass spectrometry (MS). A total of 27 pyrazines were identified in Chinese liquors, mainly alkyl- and acetylpyrazines. A method for determining pyrazines in Chinese liquors was developed. It involves extraction by headspace (HS) solid phase microextraction (SPME) and determination using GC-flame thermionic detector (FTD). The optimum method was that the sample alcohol concentration was diluted to 12% vol by freshly redistilled-deionized water, and the diluted samples were saturated with NaCl and equilibrated at 50 degrees C for 15 min and extracted for 30 min at the same temperature. The developed method enabled detection limits of 0.99) and recovery rate were satisfied in all cases. Pyrazines of 12 commercial typical Chinese liquors were quantified by HS-SPME followed by GC-FTD and had a wide range of concentration.

  18. Synthesis, Characterization, and Electropolymerization of Extended Fused-Ring Thieno[3,4-b]pyrazine-Based Terthienyls

    Directory of Open Access Journals (Sweden)

    Kristine L. Konkol

    2016-05-01

    Full Text Available The synthesis, characterization, and electropolymerization of a series of extended fused-ring thieno[3,4-b]pyrazine-based terthienyls are reported. The target terthienyls contain a central extended thieno[3,4-b]pyrazine analogue containing 2-thienyl units at the reactive α-positions of the central thiophene. The extended fused-ring thieno[3,4-b]pyrazine analogues studied include acenaphtho[1,2-b]thieno[3,4-e]pyrazine, dibenzo[f,h]thieno[3,4-b]quinoxaline, and thieno[3′,4′:5,6]-pyrazino[2,3-f][1,10]phenanthroline. Comparison of the electrochemical and photophysical properties to simple thieno[3,4-b]pyrazine-based terthienyls and their polymeric analogues are reported in order to provide structure-function relationships within this series of compounds and materials.

  19. 2,3-Dimethyl-5-(2-methylpropyl)pyrazine, a trail pheromone component of Eutetramorium mocquerysi Emery (1899) (Hymenoptera: Formicidae)

    Science.gov (United States)

    Tentschert, J.; Bestmann, H.-J.; Hölldobler, B.; Heinze, J.

    The ant Eutetramorium mocquerysi (Myrmicinae) is endemic to the island of Madagascar. During foraging and nest emigration the ants lay recruitment trails with secretions from the poison gland. We identified three pyrazine compounds in the poison gland secretion: 2,3-dimethyl-5-(2-methylpropyl)pyrazine 1, 2,3-dimethyl-5-(3-methylbutyl)pyrazine 3, 2,3-dimethyl-5-(2-methylbutyl)pyrazine 4. Only the first component elicited trail-following behavior in the ants. We were unable to investigate whether the other pyrazine components have a synergistic function.

  20. Coherent Phase Control of Internal Conversion in Pyrazine

    CERN Document Server

    Gordon, Robert J; Seideman, Tamar; Singha, Sima; Sukharev, Maxim; Zhao, Youbo

    2014-01-01

    Shaped ultrafast laser pulses were used to study and control the ionization dynamics of electronically excited pyrazine in a pump and probe experiment. For pump pulses created without feedback from the product signal, the ion growth curve (the parent ion signal as a function of pump/probe delay) was described quantitatively by the classical rate equations for internal conversion of the $S_2$ and $S_1$ states. Very different, non-classical behavior was observed when a genetic algorithm (GA) was used to minimize the ion signal at some pre-determined target time, T. Two qualitatively different control mechanisms were identified for early (T$1.5$ ps) target times. In the former case, the ion signal was largely suppressed for $t1.5$ ps the ion growth curve followed the classical rate equations for $t

  1. Novel Halogenated Pyrazine-Based Chalcones as Potential Antimicrobial Drugs

    Directory of Open Access Journals (Sweden)

    Marta Kucerova-Chlupacova

    2016-10-01

    Full Text Available Chalcones, i.e., compounds with the chemical pattern of 1,3-diphenylprop-2-en-1-ones, exert a wide range of bio-activities, e.g., antioxidant, anti-inflammatory, anticancer, anti-infective etc. Our research group has been focused on pyrazine analogues of chalcones; several series have been synthesized and tested in vitro on antifungal and antimycobacterial activity. The highest potency was exhibited by derivatives with electron withdrawing groups (EWG in positions 2 and 4 of the ring B. As halogens also have electron withdrawing properties, novel halogenated derivatives were prepared by Claisen-Schmidt condensation. All compounds were submitted for evaluation of their antifungal and antibacterial activity, including their antimycobacterial effect. In the antifungal assay against eight strains of selected fungi, growth inhibition of Candida glabrata and Trichophyton interdigitale (formerly T. mentagrophytes was shown by non-alkylated derivatives with 2-bromo or 2-chloro substitution. In the panel of selected bacteria, 2-chloro derivatives showed the highest inhibitory effect on Staphylococcus sp. In addition, all products were also screened for their antimycobacterial activity against Mycobacterium tuberculosis H37RV My 331/88, M. kansasii My 235/80, M. avium 152/80 and M. smegmatis CCM 4622. Some of the examined compounds, inhibited growth of M. kansasii and M. smegmatis with minimum inhibitory concentrations (MICs comparable with those of isoniazid.

  2. Synthesis, complexation, and coordination oligomerization of 1,8-pyrazine-capped 5,12-dioxocyclams.

    Science.gov (United States)

    Hegedus, Louis S; Sundermann, Michael J; Dorhout, Peter K

    2003-07-14

    (Methyl)(methoxy)-5,12-dioxocyclam 1 was alkylated on the secondary amines (capped) with 2,6-bis(bromomethyl)pyrazine. The resulting macrocycle was complexed to copper(II) to produce a five-coordinate complex 5a which was fully characterized by a range of spectroscopic methods (IR, UV-vis, ESR) as well as by X-ray crystallography. The structure of this complex is similar to the previously reported pyridine complex, with the five-coordinate copper having distorted square pyramidal geometry and a Cu-Pz bond length of 2.125 A. Attempts to prepare this same complex under microwave irradiation instead produced a trinuclear complex 6a having an octahedral copper(II) center complexed to two pyrazine-cyclam copper units through the amide carbonyl oxygen and the methoxyl group oxygen of the cyclam unit. The X-ray crystal structure of the trinuclear complex showed extensive distortion in the cyclam rings. The remote nitrogen of pyrazine-cyclam complex 5a was capable of coordinating an additional metal. Treatment with RuCl(2)(DMSO)(4) or Rh(2)(OAc)(4), respectively, produced trimetallic Cu-Ru-Cu complex 7 or tetrametallic Cu-Rh-Rh-Cu complex 8. The latter was fully characterized, including an X-ray crystal structure, and had two pyrazine-cyclam complexes bridged by a Rh(2)(OAc)(4) unit through the remote pyrazine nitrogens. There was little distortion in the pyrazine-cyclam copper units as compared to complex 5a: the four metals were collinear, and the two cyclam units were eclipsed. All of the copper complexes were subjected to cyclic voltametry measurements, and no reversible redox changes were observed. Magnetic measurements of 6a and 8 showed the copper atoms to be weakly antiferromagnetically coupled.

  3. Synthesis and Selective Functionalization of [1,2,4]Triazolo[4,3-a]pyrazines

    DEFF Research Database (Denmark)

    Demmer, Charles Sylvain; Jorgensen, Morten; Kehler, Jan

    2015-01-01

    A new tactic for the synthesis and selective functionalization of [1,2,4]triazolo[4,3-a]pyrazines has been developed using an oxidative cyclization as key step. Furthermore, novel strategies for introducing diverse substituents in all positions of the heterocycle were identified.......A new tactic for the synthesis and selective functionalization of [1,2,4]triazolo[4,3-a]pyrazines has been developed using an oxidative cyclization as key step. Furthermore, novel strategies for introducing diverse substituents in all positions of the heterocycle were identified....

  4. Aquadioxidobis(pentane-2,4-dionatouranium(VI pyrazine solvate

    Directory of Open Access Journals (Sweden)

    Takafumi Kitazawa

    2008-05-01

    Full Text Available The asymmetric unit of the title compound, [U(C5H7O22O2(H2O]·C4H4N2, contains one [UO2(acac2(H2O] (where acac is acetylacetonate and two half-molecules of pyrazine. It exhibits a UO7 pentagonal-bipyramidal coordination geometry about the UVI atom, involving two bidentate acetylacetonate ions and one water molecule. The N atoms of the pyrazine molecules are not coordinated to the UVI atom, and are connected with the aqua O atom by hydrogen bonds. This results in a zigzag chain arrangement along the [10overline{1}] direction.

  5. Photophysical characterization of 2,3-difunctionalized thieno[3,4-b]pyrazines

    Energy Technology Data Exchange (ETDEWEB)

    Rasmussen, S.C. E-mail: seth.rasmussen@ndsu.nodak.edu; Sattler, D.J.; Mitchell, K.A.; Maxwell, John

    2004-08-01

    In order to better understand the optical properties of polythieno[3,4-b]pyrazine materials, the photophysical characteristics of a series of monomeric 2,3-difunctionalized thieno[3,4-b]pyrazines (where R=H, CH{sub 3}, C{sub 6}H{sub 13}, C{sub 8}H{sub 17}, C{sub 10}H{sub 21}, C{sub 12}H{sub 25}, and Ph) have been studied. Characterization of the room temperature UV-vis and fluorescence spectra, including solvent and pH dependence, are presented and compared to the related species isothianaphthene and quinoxaline.

  6. A supramolecular ladder-like network from trimesic acid and pyrazine N,N'-dioxide.

    Science.gov (United States)

    Yadav, Vitthal N; Görbitz, Carl Henrik

    2014-01-01

    In the title complex, benzene-1,3,5-tricarboxylic acid-pyrazine N,N'-dioxide (2/1), C9H6O6·0.5C4H4N2O2, cocrystallized trimesic acid (TMA) and pyrazine N,N'-dioxide (PNO) molecules form strong O-H...O hydrogen bonds, but also important weak C-H...O and dipole-dipole intermolecular interactions, to generate a densely packed three-dimensional network. PNO molecules lie on inversion centres where they connect pairs of TMA sheets into distinct two-dimensional hydrogen-bonded layers perpendicular to the crystallographic ab diagonal.

  7. Influence of Free Amino Acids, Oligopeptides, and Polypeptides on the Formation of Pyrazines in Maillard Model Systems.

    Science.gov (United States)

    Scalone, Gustavo Luis Leonardo; Cucu, Tatiana; De Kimpe, Norbert; De Meulenaer, Bruno

    2015-06-10

    Pyrazines are specific Maillard reaction compounds known to contribute to the unique aroma of many products. Most studies concerning the generation of pyrazines in the Maillard reaction have focused on amino acids, while little information is available on the impact of peptides and proteins. The present study investigated the generation of pyrazines in model systems containing whey protein, hydrolyzed whey protein, amino acids, and glucose. The impact of thermal conditions, ratio of reagents, and water activity (a(w)) on pyrazine formation was measured by headspace solid-phase microextraction with gas chromatography/mass spectrometry (HS-SPME-GC/MS. The presence of oligopeptides from hydrolyzed whey protein contributed significantly to an increased amount of pyrazines, while in contrast free amino acids generated during protein hydrolysis contributed to a lesser extent. The generation of pyrazines was enhanced at low a(w) (0.33) and high temperatures (>120 °C). This study showed that the role of peptides in the generation of pyrazines in Maillard reaction systems has been dramatically underestimated.

  8. Coherent phase control of internal conversion in pyrazine

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, Robert J., E-mail: rjgordon@uic.edu; Singha, Sima; Zhao, Youbo [Department of Chemistry (m/c 111), University of Illinois at Chicago, Chicago, Illinois 60680-7061 (United States); Hu, Zhan [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130021 (China); Seideman, Tamar [Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208 (United States); Sukharev, Maxim [Science and Mathematics Faculty, College of Letters and Sciences, Arizona State University, Mesa, Arizona 85212 (United States)

    2015-04-14

    Shaped ultrafast laser pulses were used to study and control the ionization dynamics of electronically excited pyrazine in a pump and probe experiment. For pump pulses created without feedback from the product signal, the ion growth curve (the parent ion signal as a function of pump/probe delay) was described quantitatively by the classical rate equations for internal conversion of the S{sub 2} and S{sub 1} states. Very different, non-classical behavior was observed when a genetic algorithm (GA) employing phase-only modulation was used to minimize the ion signal at some pre-determined target time, T. Two qualitatively different control mechanisms were identified for early (T < 1.5 ps) and late (T > 1.5 ps) target times. In the former case, the ion signal was largely suppressed for t < T, while for t ≫ T, the ion signal produced by the GA-optimized pulse and a transform limited (TL) pulse coalesced. In contrast, for T > 1.5 ps, the ion growth curve followed the classical rate equations for t < T, while for t ≫ T, the quantum yield for the GA-optimized pulse was much smaller than for a TL pulse. We interpret the first type of behavior as an indication that the wave packet produced by the pump laser is localized in a region of the S{sub 2} potential energy surface where the vertical ionization energy exceeds the probe photon energy, whereas the second type of behavior may be described by a reduced absorption cross section for S{sub 0} → S{sub 2} followed by incoherent decay of the excited molecules. Amplitude modulation observed in the spectrum of the shaped pulse may have contributed to the control mechanism, although this possibility is mitigated by the very small focal volume of the probe laser.

  9. Coherent phase control of internal conversion in pyrazine

    Science.gov (United States)

    Gordon, Robert J.; Hu, Zhan; Seideman, Tamar; Singha, Sima; Sukharev, Maxim; Zhao, Youbo

    2015-04-01

    Shaped ultrafast laser pulses were used to study and control the ionization dynamics of electronically excited pyrazine in a pump and probe experiment. For pump pulses created without feedback from the product signal, the ion growth curve (the parent ion signal as a function of pump/probe delay) was described quantitatively by the classical rate equations for internal conversion of the S2 and S1 states. Very different, non-classical behavior was observed when a genetic algorithm (GA) employing phase-only modulation was used to minimize the ion signal at some pre-determined target time, T. Two qualitatively different control mechanisms were identified for early (T 1.5 ps) target times. In the former case, the ion signal was largely suppressed for t 1.5 ps, the ion growth curve followed the classical rate equations for t quantum yield for the GA-optimized pulse was much smaller than for a TL pulse. We interpret the first type of behavior as an indication that the wave packet produced by the pump laser is localized in a region of the S2 potential energy surface where the vertical ionization energy exceeds the probe photon energy, whereas the second type of behavior may be described by a reduced absorption cross section for S0 → S2 followed by incoherent decay of the excited molecules. Amplitude modulation observed in the spectrum of the shaped pulse may have contributed to the control mechanism, although this possibility is mitigated by the very small focal volume of the probe laser.

  10. Two pyrazine derivatives as inhibitors of the cold rolled steel corrosion in hydrochloric acid solution

    Energy Technology Data Exchange (ETDEWEB)

    Deng Shuduan, E-mail: dengshuduan@163.co [Faculty of Wood Science and Decoration Technology, Southwest Forestry University, Kunming 650224 (China); Li Xianghong; Fu Hui [Department of Fundamental Courses, Southwest Forestry University, Kunming 650224 (China)

    2011-02-15

    Research highlights: Two pyrazine derivatives of 2-aminopyrazine (AP) and 2-amino-5-bromopyrazine (ABP) are good inhibitors for the corrosion of steel in 1.0 M HCl solution. The inhibition efficiency follows the order: ABP > AP. The substitution Br of ABP is the additional centre of adsorption and increases the electron density of pyrazine ring, which can facilitate its adsorption on the metal surface. For either ABP or AP, the adsorption obeys Langmuir adsorption isotherm. Both ABP and AP act as mixed-type inhibitors. - Abstract: The inhibition effect of two pyrazine derivatives of 2-aminopyrazine (AP) and 2-amino-5-bromopyrazine (ABP) on the corrosion of cold rolled steel (CRS) in 1.0 M hydrochloric acid (HCl) was studied by weight loss, potentiodynamic polarization curves, and electrochemical impedance spectroscopy (EIS) methods. The results show that both AP and ABP are good inhibitors, and inhibition efficiency follows the order: ABP > AP. The adsorption of each inhibitor on CRS surface obeys Langmuir adsorption isotherm. Potentiodynamic polarization curves show that two pyrazine derivatives act as mixed-type inhibitors. EIS spectra exhibit one capacitive loop and confirm the inhibitive ability.

  11. Synthesis and luminescence modulation of pyrazine-based gold(III) pincer complexes.

    Science.gov (United States)

    Fernandez-Cestau, Julio; Bertrand, Benoît; Blaya, Maria; Jones, Garth A; Penfold, Thomas J; Bochmann, Manfred

    2015-12-04

    The first examples of pyrazine-based gold(III) pincer complexes are reported; their intense photoemissions can be modified by protonation, N-alkylation or metal ions, without the need for altering the ligand framework. Emissions shift from red (77 K) to blue (298 K) due to thermally activated delayed fluorescence (TADF).

  12. The scent of wolves: pyrazine analogs induce avoidance and vigilance behaviors in prey

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    Kazumi eOsada

    2015-10-01

    Full Text Available The common grey wolf (Canis lupus is an apex predator located at the top of the food chain in the Northern Hemisphere. It preys on rodents, rabbits, ungulates, and many other kinds of mammal. However, the behavioral evidence for, and the chemical basis of, the fear-inducing impact of wolf urine on prey are unclear. Recently, the pyrazine analogs 2, 6-dimethylpyrazine, 2, 3, 5-trimethylpyrazine and 3-ethyl-2, 5-dimethyl pyrazine were identified as kairomones in the urine of wolves. When mice were confronted with a mixture of purified pyrazine analogs, vigilance behaviors, including freezing and excitation of neurons at the accessory olfactory bulb, were markedly increased. Additionally, the odor of the pyrazine cocktail effectively suppressed the approach of deer to a feeding area, and for those close to the feeding area elicited fear-related behaviors such as the tail-flag, flight, and jump actions. In this review, we discuss the transfer of chemical information from wolf to prey through the novel kairomones identified in wolf urine and also compare the characteristics of wolf kairomones with other predator-produced kairomones that affect rodents.

  13. Effect of a New Natural Seasoning on the Formation of Pyrazines in Barbecued Beef Patties

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    Javier García-Lomillo

    2016-01-01

    Full Text Available The formation of pyrazines in food cooking is required to obtain satisfactory “roasted” flavor. The aim of this work was to evaluate the effect of a new red wine pomace seasoning (RWPS on the formation of pyrazines in barbecued beef patties. Five pyrazines were successfully identified, 2,5-dimethylpyrazine being the most abundant. Although 2-ethyl-5-methylpyrazine was in lower levels, it presented the highest odor units, due to its low threshold. RWPS enhanced the formation of the five identified pyrazines (2.1 times, without relevant changes in the proportion between them. The highest increase was observed for 2-ethyl-6-methylpyrazine (3 times higher than in control. These results were corroborated by electronic nose analysis, presenting RWPS beef patties higher odor intensities. Mechanisms to explain these effects are also proposed in the present work, and the high content of polyphenols seems to be the major cause of the observed results. The use of RWPS could improve the flavor characteristics of meat products or enable using less intense cooking conditions with no changes in the flavor.

  14. Electrostatic Molecular Interaction from X-ray Diffraction Data. II. Test on Theoretical Pyrazine Data

    NARCIS (Netherlands)

    Feil, Dirk; Moss, Grant

    1983-01-01

    In a previous paper [Moss & Feil (1981). Acta Cryst. A37, 414-421] a method was reported to calculate the electrostatic potential and the electrostatic interaction energy from single-crystal X-ray diffraction data. The method was applied to experimental pyrazine data; however, owing to the relativel

  15. Thermal and chemical decomposition of di(pyrazine)silver(II) peroxydisulfate and unusual crystal structure of a Ag(I) by-product.

    Science.gov (United States)

    Leszczyński, Piotr J; Budzianowski, Armand; Dobrzycki, Lukasz; Cyrański, Michał K; Derzsi, Mariana; Grochala, Wojciech

    2012-01-14

    High purity samples of a [Ag(pyrazine)(2)]S(2)O(8) complex were obtained using modified synthetic pathways. Di(pyrazine)silver(II) peroxydisulfate is sensitive to moisture forming [Ag(pyrazine)(2)](S(2)O(8))(H(2)O) hydrate which degrades over time yielding HSO(4)(-) derivatives and releasing oxygen. One polymorphic form of pyrazinium hydrogensulfate, β-(pyrazineH(+))(HSO(4)(-)), is found among the products of chemical decomposition together with unique [Ag(i)(pyrazine)](5)(H(2)O)(2)(HSO(4))(2)[H(SO(4))(2)]. Chemical degradation of [Ag(pyrazine)(2)]S(2)O(8) in the presence of trace amounts of moisture can explain the very low yield of wet synthesis (11-15%). Attempts have failed to obtain a mixed valence Ag(II)/Ag(I) pyrazine complex via partial chemical reduction of the [Ag(pyrazine)(2)]S(2)O(8) precursor with a variety of inorganic and organic reducing agents, or via controlled thermal decomposition. Thermal degradation of [Ag(pyrazine)(2)]S(2)O(8) containing occluded water proceeds at T > 90 °C via evolution of O(2); simultaneous release of pyrazine and SO(3) is observed during the next stages of thermal decomposition (120-285 °C), while Ag(2)SO(4) and Ag are obtained upon heating to 400-450 °C.

  16. Regioselective synthesis of 3-arylpyrido[2,3-b]pyrazines by reaction of arylglyoxals with 2,3-diaminopyridine

    Directory of Open Access Journals (Sweden)

    Jabbar Khalafy

    2013-01-01

    Full Text Available A series of pyrido[2,3-b]pyrazine derivatives were synthesized in good to excellent yields by condensation reactions of arylglyoxals with 2,3-diaminopyridine in dimethylformamide and ethanol at 90 oC.

  17. Pyrazine analogues are active components of wolf urine that induce avoidance and fear-related behaviors in deer

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    Kazumi eOsada

    2014-08-01

    Full Text Available Our previous studies indicated that a cocktail of pyrazine analogues, identified in wolf urine, induced avoidance and fear behaviors in mice. The effects of the pyrazine cocktail on Hokkaido deer (Cervus nippon yesoensis were investigated in field bioassays at a deer park in Hokkaido, Japan. A set of feeding bioassay trials tested the effects of the pyrazine cocktail odor on the behavior of the deer located around a feeding area in August and September 2013. This odor effectively suppressed the approach of the deer to the feeding area. In addition, the pyrazine cocktail odor provoked fear-related behaviors, such as ‘tail-flag’, ‘flight’ and ‘jump’ actions, of the deer around the feeding area. This study is the first experimental demonstration that the pyrazine analogues in wolf urine have robust and continual fearful aversive effects on ungulates as well as mice. The pyrazine cocktail might be suitable for a chemical repellent that could limit damage to forests and agricultural crops by wild ungulates.

  18. A Convenient Synthesis of Octahydro-pyrazino [ 1,2- a ] pyrazine

    Institute of Scientific and Technical Information of China (English)

    LIANG Feng; WU Xiao-Jun; ZHANG Shi-Wei; WU Cheng-Tai

    2003-01-01

    @@ The recent research results suggest that a series of octahydro-pyrazino[ 1,2-a ]pyrazines are useful as antiallergic agents.[1] Gubert et al. [2] developed a route from 1,4-dibenzyl-2-ethoxycarbonylpiperazine for the synthesis of this ring system. Under their conditions, this ring system was obtained with a low overall yield in six steps. Optimization of synthetic route to this ring system is still desirable. In this paper, we presented an efficient synthesis of octahydropyrazino[1,2-a]pyrazine by a new and efficient method starting from 1,3-dichloro-2-propanol and N-tosylated diethylenetriamine. The structure of title compound was determined by spectroscopy and X-ray diffraction technique.

  19. Multicomponent assembly of diverse pyrazin-2(1H)-one chemotypes.

    Science.gov (United States)

    Azuaje, Jhonny; El Maatougui, Abdelaziz; Pérez-Rubio, José M; Coelho, Alberto; Fernández, Franco; Sotelo, Eddy

    2013-05-03

    An expedient and concise Ugi-based approach for the rapid assembly of pyrazin-2(1H)-one-based frameworks has been developed. This convergent approach encompasses skeletal, functional and stereochemical diversity, exhibiting an unusually high bond-forming efficiency as well as high structure and step economies. The method involves the use of readily available commercial reagents and is an example of the reconciliation of structural complexity with operational simplicity in a time- and cost-effective manner.

  20. TREATMENT BY ALTERNATIVE METHODS OF REGRESSION GAS CHROMATOGRAPHIC RETENTION INDICES OF 35 PYRAZINES

    Directory of Open Access Journals (Sweden)

    Fatiha Mebarki

    2016-02-01

    Full Text Available The study treated two closer alternative methods of which the principal characteristic: a non-parametric method (the least absolute deviation (LAD and a traditional method of diagnosis OLS.This was applied to model, separately, the indices of retention of the same whole of 35 pyrazines (27 pyrazines with 8 other pyrazines in the same unit eluted to the columns OV-101 and Carbowax-20M, by using theoretical molecular descriptors calculated using the software DRAGON. The detection of influential observations for non-parametric method (LAD is a problem which has been extensively studied and offers alternative dicapproaches whose main feature is the robustness.here is presented and compared with the standard least squares regression .The comparison between methods LAD and OLS is based on the equation of the hyperplane, in order to confirm the robustness thus to detect by the meaningless statements and the points of lever and validated results in the state approached by the tests statistics: Test of Anderson-Darling, shapiro-wilk, Agostino, Jarque-Bera, graphic test (histogram of frequency and the confidence interval thanks to the concept of robustness to check if the distribution of the errors is really approximate.

  1. catena-Poly[[(pyrazine-2-carboxamide-κN4copper(I]-μ3-iodido

    Directory of Open Access Journals (Sweden)

    Lukáš Krivosudský

    2014-07-01

    Full Text Available In the title metal–organic polymeric complex, [CuI(C5H5N3O]n, the asymmetric unit is composed of one monomer unit of the polymer and one CuI atom linked to one iodide anion and one pyrazine-2-carboxamide molecule. The CuI atom is in a distorted tetrahedral coordination completed by one pyrazine N atom of the pyrazine-2-carboxamide ligand and three iodide anions. The polymeric structure adopts a well-known ladder-like motif of {CuNI3} tetrahedra running in the b-axis direction. The molecules of the organic ligand are connected via medium-to-strong N—H...O and N—H...N hydrogen bonds and weak π–π interactions [the distance between two parallel planes of the rings is 3.5476 (14 Å and the centroid–centroid contact is 4.080 (2 Å]. The title compound has a relatively high decomposition temperature (564 K as a result of relatively strong covalent and non-covalent interactions inside and between the chains.

  2. A novel three-dimensional coordination polymer constructed from pyrazine and copper(I): poly[[copper(I)-di-mu2-pyrazine-kappa4N:N'] 3,5-dicarboxybenzenesulfonate monohydrate].

    Science.gov (United States)

    Guo, Hong-Xu; Weng, Wen; Li, Xi-Zhong; Liang, Min; Zheng, Cai-Qing

    2008-09-01

    In the title metal-organic framework complex, {[Cu(C(4)H(4)N(2))(2)](C(8)H(5)O(7)S).H(2)O}(n) or {[Cu(I)(pyz)(2)](H(2)SIP).H(2)O}(n) (pyz is pyrazine and H(3)SIP is 5-sulfoisophthalic acid or 3,5-dicarboxybenzenesulfonic acid), the asymmetric unit is composed of one copper(I) center, one whole pyrazine ligand, two half pyrazine ligands lying about inversion centres, one H(2)SIP(-) anion and one lattice water molecule, wherein each Cu(I) atom is in a slightly distorted tetrahedral coordination environment completed by four pyrazine N atoms, with the Cu-N bond lengths in the range 2.017 (3)-2.061 (3) A. The structure features a three-dimensional diamondoid network with one-dimensional channels occupied by H(2)SIP(-) anions and lattice water molecules. Interestingly, the guest-water hydrogen-bonded network is also a diamondoid network, which interpenetrates the metal-pyrazine network.

  3. Poly[aquabis(μ-formato-κ2O:O′(μ-pyrazine-κ2N:N′nickel(II

    Directory of Open Access Journals (Sweden)

    Susanne Wöhlert

    2011-05-01

    Full Text Available In the title compound, [Ni(CHO22(C4H4N2(H2O], the nickel(II cations are coordinated by three O-bonded-formato anions, two N-bonded-pyrazine ligands and one water molecule in an octahedral coordination mode. The nickel(II cations are connected by μ-1,3-bridging formato anions and N,N′-bridging pyrazine ligands into a three dimensional coordination network. The asymmetric unit consists of one nickel(II cation, one water molecule and two crystallographically independent formato anions in general positions as well as two crystallographically independent pyrazine ligands, which are located on centers of inversion.

  4. Bis(triethylammonium bis(μ-pyrazine-2,3-dithiolatobis(pyrazine-2,3-dithiolatodiferrate(III methanol disolvate

    Directory of Open Access Journals (Sweden)

    Toshiki Yamaguchi

    2009-01-01

    Full Text Available In the title compound, (C6H16N2[Fe2(C4H2N2S24]·2CH4O, the [FeIII(pdt2]− anion (pdt is pyrazine-2,3-dithiolate forms a centrosymmetric dimer supported by two FeIII—S bonds [Fe—S = 2.4787 (4 Å]. In the crystal structure, dimers form a one-dimensional stack along the b axis via π–π stacking interactions, the interplanar separation between adjacent dimers being 3.51 (2 Å. The methanol solvent molecule is involved in two hydrogen bonds in which the hydroxyl group acts as a hydrogen-bond donor to the N atom of a pdt ligand and the O atom acts as an acceptor for the NH group of the triethylammonium cation.

  5. Determination cytotoxicity of [1,2,4]triazolo[4,3-a]-pyrazine derivatives

    Directory of Open Access Journals (Sweden)

    Кристина Юріївна Куликовська

    2015-11-01

    Full Text Available With test systems CellTiter-Glo was determined the cytotoxicity of series N7-aryl/benzyl-3-tioxo-2,3-dihydro-7Н-[1,2,4]triazolo-[4,3-а]pyrazin-8-ones, their 3-S- acetamides and 3-S-benzyl derivatives. The synthesis of the compounds performed based on the previously developed and published scheme. Structure and purity of the compounds proved with 1H-NMR and element analysis.Methods. The method is based on determining the number of viable cells in culture by intensity of luminescence mixture of cell suspension of prostate cancer Du145, solution of the substance and CellTiter-Glo reagent. Tubercidin and taxol were used as reference drugs. The parameter СK50, that has been set according to a study, describes the ability of analyzed substances induce cell death.Results. Cytotoxic concentration of synthesized 3-substituted N7-aryl/benzyl-2,3-dihydro-7Н-[1,2,4]triazolo-[4,3-а]pyrazine-8-ones not exceed the maximum concentration of compounds, which were tested, and was above 30 mkM. This demonstrates the complete absence of negative impact of these substances on cells of prostate cancer Du145.Conclusions. Found that these compounds do not exhibit toxic effects on living cells, making the actual possibility of developing new effective and safe drugs on their base. Also inappropriate to search anticancer drugs among of the N7-aryl/benzyl-2,3-dihydro-7Н-[1,2,4]triazolo-[4,3-а]pyrazine-8-one derivatives

  6. A study of the valence shell photoionisation dynamics of pyrimidine and pyrazine

    Energy Technology Data Exchange (ETDEWEB)

    Holland, D.M.P., E-mail: david.holland@stfc.ac.uk [Daresbury Laboratory, Daresbury, Warrington, Cheshire WA4 4AD (United Kingdom); Potts, A.W. [Department of Physics, King' s College, Strand, London WC2R 2LS (United Kingdom); Karlsson, L. [Department of Physics, Uppsala University, Box 530, SE-751 21 Uppsala (Sweden); Stener, M.; Decleva, P. [Dipartimento di Scienze Chimiche, Universita di Trieste, Via L. Giorgieri, I-34127 Trieste (Italy); Consorzio Interuniversitario Nazionale per la Scienze e Tecnologia dei Materiali, INSTM, Unita' di Trieste, Via L. Giorgieri, I-34127 Trieste (Italy); CNR-IOM, Area Science Park - Basovizza, Strada Statale 14 km 163,5, I-34149 Trieste (Italy)

    2011-11-18

    Graphical abstract: The complete valence shell photoelectron spectra of pyrimidine and pyrazine have been recorded with synchrotron radiation and interpreted with the aid of vertical ionisation energies and relative spectral intensities calculated using time-dependent density functional theory. Highlights: Black-Right-Pointing-Pointer Valence shell photoelectron spectra of pyrimidine and pyrazine have been recorded. Black-Right-Pointing-Pointer Many-body effects are important. Black-Right-Pointing-Pointer Photoionisation dynamics are affected by shape resonances. Black-Right-Pointing-Pointer Theoretical predictions for single-hole ionic states are satisfactory. - Abstract: The complete valence shell photoelectron spectra of pyrimidine and pyrazine have been recorded with synchrotron radiation and the observed structure has been interpreted with the aid of vertical ionisation energies and relative spectral intensities calculated using time-dependent density functional theory. The theoretical predictions for the single-hole ionic states due to outer valence shell ionisation agree satisfactorily with the experimental results. Ionisation from the inner valence orbitals is strongly influenced by many-body effects and the intensity associated with a particular orbital is spread amongst numerous satellites. Photoelectron angular distributions and partial cross sections have been determined both experimentally and theoretically, and demonstrate that shape resonances affect the valence shell photoionisation dynamics. In addition to shape resonances occurring a few eV above the ionisation threshold, the calculations indicate that many of the orbitals are influenced by shape resonant processes at much higher energies. Some of these higher energy resonances have been confirmed through a comparison between the relevant theoretical and experimental photoelectron asymmetry parameters. The spectral behaviour of asymmetry parameters associated with {pi}-orbitals has been shown to

  7. Dibromidobis(pyrazine-2-carboxylic acid-κN4mercury(II dihydrate

    Directory of Open Access Journals (Sweden)

    Guo-Wei Wang

    2008-01-01

    Full Text Available The asymmetric unit of the title compound, [HgBr2(C5H4N2O22]·2H2O, contains one half-molecule and one water molecule. The HgII ion, lying on a twofold rotation axis, is four-coordinated by two N atoms of pyrazine-2-carboxylic acid ligands and two bromide ions, forming a highly distorted tetrahedral geometry. In the crystal structure, intermolecular O—H...O and O—H...N hydrogen bonds link the molecules.

  8. The application with tetramethyl pyrazine for antithrombogenicity improvement on silk fibroin surface

    Energy Technology Data Exchange (ETDEWEB)

    Lian Xiaojie [School of Material Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China); Wang Song [School of Material Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China)], E-mail: wangsongbit@126.com; Xu Guoliang; Lin Nini; Li Qian; Zhu Hesun [School of Material Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China)

    2008-11-15

    Chuanxiongqin (tetramethyl pyrazine, TMPZ) is an active ingredient of the Chinese herb and was used to improve the anticoagulant activity of silk fibroin (SF). The side methyl of TMPZ was oxidized, and then linked to polyacrylic acid (PAA) via an ester bond. The prepared conjugate was further mixed with SF solutions at different ratios to make blend films. The resulting products were characterized by FTIR, UV spectrometer and X-ray photoelectron spectroscopy (XPS). The in vitro antithrombogenicity were evaluated by the activated partial thromboplastin time (APTT) and the prothrombin time (PT). It was shown that blend films had longer coagulation time than the pure SF film.

  9. DFT Investigations About Pyrazine Molecules on Si(100)-2×1 Surface

    Institute of Scientific and Technical Information of China (English)

    YU Ang-yang; QU Yong-quan; HAN Ke-li; HE Guo-zhong

    2007-01-01

    It is important to understand the interface of aromatic molecules on semiconductor surfaces because of the rich functionality of such molecules on semiconductor surfaces. The chemisorption of pyrazine molecules on the Si( 100)-2×1 surface has been investigated using the B3LYP density functional theory with Si9H12 one-dimer and Si15H16 twodimer cluster models. The calculated results predict that N-dative bonded-state, C2= C5 [ 4 + 2 ] and the tightbridge1, 2, 5,6 products may coexist on the Si(100)-2×1 surface.

  10. Synthesis and molecular modeling of antimicrobial active fluoroquinolone-pyrazine conjugates with amino acid linkers.

    Science.gov (United States)

    Panda, Siva S; Detistov, Oleksandr S; Girgis, Adel S; Mohapatra, Prabhu P; Samir, Ahmed; Katritzky, Alan R

    2016-05-01

    Novel fluoroquinolone-pyrazine conjugates 7a-h with amino acid linkers were synthesized in good yields utilizing benzotriazole chemistry. Antimicrobial bioassay showed that the synthesized bis-conjugates have antimicrobial properties comparable to the parent drugs. Compound 7h showed superior antibacterial activity against Staphylococcus aureus and Streptococcus pyogenes (MIC=74.6 μM and 149.3 μM, respectively). This matched well with the estimated values obtained from 3D-pharmacophore and 2D-QSAR studies (MIC=67 μM and 92.9 μM, respectively). Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Unexpected reversible pyrazine based methylation in a Ru(II) complex bearing a pyrazin-2’-yl-1,2,4-triazolato ligand and its effect on acid/base and photophysical properties

    NARCIS (Netherlands)

    Brennan, Claire; Draksharapu, Apparao; Browne, Wesley R.; McGarvey, John J.; Vos, Johannes G.; Pryce, Mary T.

    2013-01-01

    The regioselective methylation of a ruthenium polypyridyl complex bearing both a 1,2,4-triazolato and a pyrazine moiety is reported. In contrast to previous studies in which methylation of the 1,2,4-triazolato ring was observed, in the present system methylation takes place exclusively at the non-co

  12. Crystal structure of tri-aqua-(2,6-di-methyl-pyrazine-κN (4))bis-(thio-cyanato-κN)manganese(II) 2,5-di-methyl-pyrazine disolvate.

    Science.gov (United States)

    Suckert, Stefan; Wöhlert, Susanne; Jess, Inke; Näther, Christian

    2015-12-01

    In the crystal structure of the title complex, [Mn(NCS)2(C6H8N2)(H2O)3]·2C6H8N2, the Mn(II) cation is coordinated by two terminally N-bonded thio-cyanate anions, three water mol-ecules and one 2,6-di-methyl-pyrazine ligand within a slightly distorted N3O3 octa-hedral geometry; the entire complex mol-ecule is generated by the application of a twofold rotation axis. The asymmetric unit also contains an uncoordinating 2,5-di-methyl-pyrazine ligand in a general position. Obviously, the coordination to the 2,6-di-methyl-pyrazine ligand is preferred because coordination to the 2,5-di-methyl-pyrazine is hindered due to the bulky methyl group proximate to the N atom. The discrete complexes are linked by water-O-H⋯N(2,6-di-methyl-pyzazine/2,5-di-methyl-pyza-zine) hydrogen bonding, forming a three-dimensional network. In the crystal, mol-ecules are arranged in a way that cavities are formed in which unspecified, disordered solvent molecules reside. These were modelled employing the SQUEEZE routine in PLATON [Spek (2015 ▸). Acta Cryst. C71, 9-18]. The composition of the unit cell does not take into account the presence of the unspecified solvent.

  13. Unexpected reversible pyrazine based methylation in a Ru(II) complex bearing a pyrazin-2’-yl-1,2,4-triazolato ligand and its effect on acid/base and photophysical properties

    NARCIS (Netherlands)

    Brennan, Claire; Draksharapu, Apparao; Browne, Wesley R.; McGarvey, John J.; Vos, Johannes G.; Pryce, Mary T.

    2013-01-01

    The regioselective methylation of a ruthenium polypyridyl complex bearing both a 1,2,4-triazolato and a pyrazine moiety is reported. In contrast to previous studies in which methylation of the 1,2,4-triazolato ring was observed, in the present system methylation takes place exclusively at the non-co

  14. Dimethyl and diethyl esters of 5,6-bis-(pyridin-2-yl)pyrazine-2,3-di-carb-oxy-lic acid: a comparison.

    Science.gov (United States)

    Alfonso, Montserrat; Stoeckli-Evans, Helen

    2016-02-01

    In dimethyl 5,6-bis-(pyridin-2-yl)pyrazine-2,3-di-carboxyl-ate, C18H14N4O4, (I), and diethyl 5,6-bis-(pyridin-2-yl)pyrazine-2,3-di-carboxyl-ate, C20H18N4O4, (II), the dimethyl and diethyl esters of 5,6-bis-(pyridin-2-yl)pyrazine-2,3-di-carb-oxy-lic acid, the orientation of the two pyridine rings differ. In (I), pyridine ring B is inclined to pyrazine ring A by 44.8 (2)° and the pyridine and pyrazine N atoms are trans to one another, while pyridine ring C is inclined to the pyrazine ring by 50.3 (2)°, with the pyridine and pyrazine N atoms cis to one another. In compound (II), the diethyl ester, which possesses twofold rotation symmetry, the pyridine ring is inclined to the pyrazine ring by 40.7 (1)°, with the pyridine and pyrazine N atoms trans to one another. In the crystal of (I), mol-ecules are linked by C-H⋯N hydrogen bonds, forming chains along [001]. The chains are linked by C-H⋯π inter-actions, forming a three-dimensional structure. In the crystal of (II), mol-ecules are linked via C-H⋯O hydrogen bonds, forming a three-dimensional framework. There are C-H⋯π inter-actions present within the framework.

  15. Benzothiophen-pyrazine scaffold as a potential membrane targeting drug carrier

    Energy Technology Data Exchange (ETDEWEB)

    Mazuryk, Olga [Department of Inorganic Chemistry, Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow (Poland); Niemiec, Elżbieta [Department of Inorganic Chemistry, Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow (Poland); Institute of Organic and Analytical Chemistry, University of Orléans, UMR-CNRS 7311, rue de Chartres, 45067 Orléans Cedex 2 (France); Stochel, Grażyna [Department of Inorganic Chemistry, Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow (Poland); Gillaizeau, Isabelle, E-mail: isabelle.gillaizeau@univ-orleans.fr [Institute of Organic and Analytical Chemistry, University of Orléans, UMR-CNRS 7311, rue de Chartres, 45067 Orléans Cedex 2 (France); Brindell, Małgorzata, E-mail: brindell@chemia.uj.edu.pl [Department of Inorganic Chemistry, Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow (Poland)

    2013-08-15

    The fluorescent properties of 2,5-di(benzo[b]thiophen-2-yl)pyrazine as a potential membrane targeting drug carrier were characterized and it was shown that its fluorescence intensity was much higher in organic solvent than in water. The embedding of studied compound by liposomes leads to ca. 2 orders of magnitude increase in its fluorescence intensity, suggesting its preferential accumulation in membranes. Preliminary biological studies showed its ability to accumulate in cells, and the concentration of 10 μM was sufficient for homogeneous staining of cells. The treatment of mouse carcinoma CT26 cells with studied compound up to 200 μM resulted in decreasing of viable cells by ca. 30%. Its reactivity towards albumin was found to be moderate with an association constant of 6×10{sup 4} M{sup −1}, while no interaction with DNA was observed. Our findings encourage for further studies on functionalization of this molecule to obtain a new class of anticancer drugs targeting membrane. Highlights: ► The fluorescence of 2,5-di(benzo[b]thiophen-2-yl)pyrazine is solvent dependent. ► Weak fluorescence is found in water while high in organic solvents (DMSO, chloroform). ► Embedding of compound in liposomes remarkably increased its fluorescence. ► No interaction with DNA is observed but moderate reactivity towards albumin is found. ► Homogeneous staining of cells is feasible using nontoxic dose of compound.

  16. Isolation of a pyrazine alarm pheromone component from the fire ant, Solenopsis invicta.

    Science.gov (United States)

    Vander Meer, Robert K; Preston, Catherine A; Choi, Man-Yeon

    2010-02-01

    Alarm pheromones in social insects are an essential part of a complex of pheromone interactions that contribute to the maintenance of colony integrity and sociality. The alarm pheromones of ants were among the first examples of animal pheromones identified, primarily because of the large amount of chemical produced and the distinctive responses of ants to the pheromone. However, the alarm pheromone of the fire ant, Solenopsis invicta, eluded identification for over four decades. We identified 2-ethyl-3,6-dimethylpyrazine as an alarm pheromone component of S. invicta. Worker fire ants detect the pyrazine alarm pheromone at 30 pg/ml, which is comparable to alarm pheromone sensitivities reported for other ant species. The source of this alarm pheromone are the mandibular glands, which, in fire ants, are not well developed and contain only about 300 pg of the compound, much less than the microgram quantities of alarm pheromones reported for several other ant species. Female and male sexuals and workers produce the pyrazine, which suggests that it may be involved in fire ant mating flight initiation, as well as the typical worker alarm response. This is the first report of 2-ethyl-3,6-dimethylpyrazine from a Solenopsis species and the first example of this alkaloid functioning as an alarm pheromone.

  17. Synthesis and characterization of organometallic macrocyclic rhodium (Ⅲ) complex with pyrazine ligands

    Institute of Scientific and Technical Information of China (English)

    WANG Jianqiang; ZHANG Zheng; WENG Linhong; JIN Guoxin

    2004-01-01

    The reaction of half-sandwich complex (Cptt Rh)2Cl2(μ-Cl)2 (1) (Cptt = η5-tBu2C5H3) with 1 equiv. Of AgSO3CF3 in CH2Cl2 affords tri-μ-chloro dirhodium (2) cation compound, with 2 equiv. Of AgSO3CF3 providing di-μ-chloro complex 3. The reaction of 3 with pyrazine gives a novel tetra-nuclear 14-member organometallic macrocyclic complex 4. FT-IR, 1H-NMR, and EA were used to characterize these complexes. The structures of complexes 2 and 4 are confirmed by X-ray analysis. In complex 2, the two Cptt ring and tri-chloro atoms faces are approximately parallel to each other. In complex 4, the complex cation has a rectangular cavity with the dimension of 0.3748 nm×0.7027 nm, and the two-pyrazine rings are parallel to each other with a distance of 0.3510 nm.

  18. Trajectory study of supercollision relaxation in highly vibrationally excited pyrazine and CO2.

    Science.gov (United States)

    Li, Ziman; Sansom, Rebecca; Bonella, Sara; Coker, David F; Mullin, Amy S

    2005-09-01

    Classical trajectory calculations were performed to simulate state-resolved energy transfer experiments of highly vibrationally excited pyrazine (E(vib) = 37,900 cm(-1)) and CO(2), which were conducted using a high-resolution transient infrared absorption spectrometer. The goal here is to use classical trajectories to simulate the supercollision energy transfer pathway wherein large amounts of energy are transferred in single collisions in order to compare with experimental results. In the trajectory calculations, Newton's laws of motion are used for the molecular motion, isolated molecules are treated as collections of harmonic oscillators, and intermolecular potentials are formed by pairwise Lennard-Jones potentials. The calculations qualitatively reproduce the observed energy partitioning in the scattered CO(2) molecules and show that the relative partitioning between bath rotation and translation is dependent on the moment of inertia of the bath molecule. The simulations show that the low-frequency modes of the vibrationally excited pyrazine contribute most to the strong collisions. The majority of collisions lead to small DeltaE values and primarily involve single encounters between the energy donor and acceptor. The large DeltaE exchanges result from both single impulsive encounters and chattering collisions that involve multiple encounters.

  19. 2.2.1. Synthesis, spectroscopic characterization and crystal structure of [ReV(O2(pyz4][ReII(NOBr4(pyz] (pyz = pyrazine

    Directory of Open Access Journals (Sweden)

    Mario Pacheco, Alicia Cuevas, Javier González-Platas, Carlos Kremer*

    2015-03-01

    Full Text Available Abstract: A novel Re(V-Re(II nitrosyl complex, [Re(O2(pyz 4][Re(NOBr4(pyz] (pyz = pyrazine was prepared and characterized by X-ray diffraction, elemental analysis, infrared and ultraviolet-visible absorption spectra. This product is obtained in the initial steps of the reaction of (NBu4[Re(NOBr4(EtOH] with pyrazine. Both, the cation and the anion are mononuclear complexes. The Re(V atom in the cation is six-coordinate with four nitrogen atoms from pyrazine ligands, and two oxo ligands. The Re(II anion is also six-coordinate, with four bromide ligands, a linear nitrosyl group and one nitrogen from pyrazine. The spectroscopic studies are discussed and compared with those already reported separately for the cation and the anion. Supporting information: X-Ray (CIF file

  20. Synthesis of N-Substituted-2-Aminothiazolo[4,5-b]pyrazines by Tandem Reaction of o-Aminohalopyrazines with Isothiocyanates

    Energy Technology Data Exchange (ETDEWEB)

    Kwak, Se Hun; Lee, Geehyung; Gong, Youngdae [Dongguk Univ., Seoul (Korea, Republic of)

    2012-12-15

    In conclusion, a convenient and mild method for the synthesis of N-substituted-2-aminothiazolo[4,5-b]pyrazines, which might either exhibit potential pharmacological activities or be used as building blocks, via tandem reactions of various pyrazines and isothiocyanates has been developed. All substrates were well converted to the desired products. The generality of this reaction could enable its application to other substrates.

  1. Quantifying magnetic exchange in doubly-bridged Cu-X(2)-Cu (X = F, Cl, Br) chains enabled by solid state synthesis of CuF(2)(pyrazine).

    Science.gov (United States)

    Lapidus, Saul H; Manson, Jamie L; Liu, Junjie; Smith, Matthew J; Goddard, Paul; Bendix, Jesper; Topping, Craig V; Singleton, John; Dunmars, Cortney; Mitchell, J F; Schlueter, John A

    2013-05-04

    Solid state techniques involving pressure and temperature have been used to synthesize the fluoride member of the CuX(2)(pyrazine) (X = F, Cl, Br) family of coordination polymers that cannot be crystallized by solution methods. CuF(2)(pyrazine) exhibits unique trans doubly-bridged Cu-F(2)-Cu chains that provide an opportunity to quantify magnetic superexchange in an isostructural Cu-X(2)-Cu series.

  2. Low frequency spin dynamics in the quantum magnet copper pyrazine dinitrate

    Energy Technology Data Exchange (ETDEWEB)

    Kuehne, H.; Klauss, H.H. [Institut fuer Festkoerperphysik, TU Dresden Dresden (Germany); Institut fuer Physik der Kondensierten Materie, TU Braunschweig (Germany); Guenther, M. [Institut fuer Festkoerperphysik, TU Dresden Dresden (Germany); Grossjohann, S.; Brenig, W. [Institut fuer Theoretische Physik, TU Braunschweig (Germany); Litterst, F.J. [Institut fuer Physik der Kondensierten Materie, TU Braunschweig (Germany); Reyes, A.P.; Kuhns, P.L. [National High Magnetic Field Laboratory, Tallahassee, FL (United States); Turnbull, M.M.; Landee, C.P. [Carlson School of Chemistry and Department of Physics, Clark University, Worcester, MA (United States)

    2010-03-15

    The S = 1/2 antiferromagnetic Heisenberg chain exhibits a magnetic field driven quantum critical point. We study the low frequency spin dynamics in copper pyrazine dinitrate (CuPzN), a realization of this model system of quantum magnetism, by means of {sup 13}C-NMR spectroscopy. Measurements of the nuclear spin-lattice relaxation rate T{sub 1}{sup -} {sup 1} in the vicinity of the saturation field are compared with quantum Monte Carlo calculations of the dynamic structure factor. Both show a strong divergence of low energy excitations at temperatures in the quantum regime. The analysis of the anisotropic T{sub 1}{sup -} {sup 1}-rates and frequency shifts allows one to disentangle the contributions from transverse and longitudinal spin fluctuations for a selective study and to determine the transfer of delocalized spin moments from copper to the neighboring nitrogen atoms. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  3. An investigation into electron scattering from pyrazine at intermediate and high energies

    Energy Technology Data Exchange (ETDEWEB)

    Sanz, A. G.; Fuss, M. C. [Instituto de Física Fundamental, Consejo Superior de Investigaciones Científicas, Serrano 113-bis, 28006 Madrid (Spain); Blanco, F. [Departamento de Física Atómica, Molecular y Nuclear, Universidad Complutense de Madrid, Ciudad Universitaria, 28040 Madrid (Spain); Gorfinkiel, J. D. [Department of Physical Sciences, The Open University, Walton Hall, Milton Keynes MK7 6AA (United Kingdom); Almeida, D.; Ferreira da Silva, F.; Limão-Vieira, P. [Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal); Brunger, M. J. [ARC Centre for Antimatter-Matter Studies, School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide, SA 5001 (Australia); Institute of Mathematical Sciences, University of Malaya, 50603 Kuala Lumpur (Malaysia); García, G., E-mail: g.garcia@iff.csic.es [Instituto de Física Fundamental, Consejo Superior de Investigaciones Científicas, Serrano 113-bis, 28006 Madrid (Spain); Centre for Medical Radiation Physics, University of Wollongong, NSW 2522 (Australia)

    2013-11-14

    Total electron scattering cross sections for pyrazine in the energy range 10–500 eV have been measured with a new magnetically confined electron transmission-beam apparatus. Theoretical differential and integral elastic, as well as integral inelastic, cross sections have been calculated by means of a screening-corrected form of the independent-atom representation (IAM-SCAR) from 10 to 1000 eV incident electron energies. The present experimental and theoretical total cross sections show a good level of agreement, to within 10%, in the overlapping energy range. Consistency of these results with previous calculations (i.e., the R-matrix and Schwinger Multichannel methods) and elastic scattering measurements at lower energies, below 10 eV, is also discussed.

  4. Pyrazine motif containing hexagonal macrocycles: synthesis, characterization, and host-guest chemistry with nitro aromatics.

    Science.gov (United States)

    Bhowmick, Sourav; Chakraborty, Sourav; Das, Atanu; Nallapeta, Sivaramaiah; Das, Neeladri

    2015-09-21

    The synthesis and characterization of cationic two-dimensional metallamacrocycles having a hexagonal shape and cavity are described. Both macrocycles utilize a pyrazine motif containing an organometallic acceptor tecton with platinum(II) centers along with different donor ligands. While one macrocycle is a relatively larger [6 + 6], the other is a relatively smaller [2 + 2] polygon. A unique feature of the smaller ensemble is that it is an irregular polygon in which all six edges are not of equal length. Molecular modeling of these macrocycles confirmed the presence of hexagonal cavities. The ability of these π-electron rich macrocycles to act as potential hosts for relatively electron deficient nitroaromatics (DNT = 2,4-dinitrotoluene and PA = picric acid) has been studied using isothermal titration calorimetry (ITC) as a tool. Molecular dynamics simulation studies were subsequently performed to gain critical insight into the binding interactions between the nitroaromatic guest molecules (PA/DNT) and the ionic macrocycles reported herein.

  5. Diaquabis(pyrazine-2-carboxamide-κ2N1,Ocobalt(II dinitrate

    Directory of Open Access Journals (Sweden)

    Ajay Pal Singh Pannu

    2012-04-01

    Full Text Available The asymmetric unit of the title complex, [Co(C5H5N3O2(H2O2](NO32, contains one half of a CoII cationic unit and a nitrate anion. The entire [Co(C5H5N3O2(H2O2]2+ cationic unit is completed by the application of inversion symmetry at the CoII site, generating a six-coordinate distorted octahedral environment for the metal ion. The chelating pyrazine-2-carboxamide molecules are bound to cobalt via N and O atoms, forming a square plane, while the remaining two trans positions in the octahedron are occupied by two coordinated water molecules.

  6. Poly[[tetrakis(μ2-pyrazine N,N′-dioxide-κ2O:O′erbium(III] tris(perchlorate

    Directory of Open Access Journals (Sweden)

    James D. Buchner

    2010-09-01

    Full Text Available The title three-dimensional coordination network, {[Er(C4H4N2O24](ClO43}n, is isostructural to that of other lanthanides. The Er+3 cation lies on a fourfold roto-inversion axis. It is coordinated in a distorted square-antiprismatic fashion by eight O atoms from bridging pyrazine N,N′-dioxide ligands. There are two unique pyrazine N,N′-dioxide ligands. One ring is located around an inversion center, and there is a a twofold rotation axis at the center of the other ring. There are also two unique perchlorate anions. One is centered on a twofold rotation axis and the other on a fourfold roto-inversion axis. The perchlorate anions are located in channels that run perpendicular to (001 and (110 and interact with the coordination network through C—H...O hydrogen bonds.

  7. Hydrothermal Synthesis and Structure of [(PbCl2)(μ-Pyz)1/2]n (Pyz = Pyrazine)

    Institute of Scientific and Technical Information of China (English)

    LIAO Qiu-Xia; ZHANG Jian; QIN Ye-Yan; YAO Yuan-Gen

    2006-01-01

    A novel 2-D lead-containing hybrid compound, [(PbCl2)(μ-Pyz)1/2]n (Pyz = pyrazine) 1, has been synthesized by the hydrothermal assembly of pyrazine with lead chloride.Elemental analysis and X-ray crystal structure analyses were carried out for the structural determination and characterization of the title compound. Compound 1 crystallizes in orthorhombic,space group Ibam, with a = 19.5558(18), b = 7.1939(6), c = 7.5449(6) (A), V = 1061.44(16) (A)3,C2H2Cl2NPb, Mr= 318.14, Z = 8, Dc= 3.982 g/cm3,μ = 32.63 mm-1, F(000) = 1096.0, R = 0.0368and wR = 0.0901 for 623 observed reflections (1 > 2σ(Ⅰ)).

  8. Mechanistic implications of the active species involved in the oxidation of hydrocarbons by Iron complexes of pyrazine-2-carboxylic acid

    NARCIS (Netherlands)

    Tanase, Stefania; Marques-Gallego, Patricia; Browne, Wesley R.; Hage, Ronald; Bouwman, Elisabeth; Feringa, Ben L.; Reedijk, Jan

    2008-01-01

    The reactivity towards H2O2 of the complexes [Fe(pca)(2)(py)(2)]center dot py (1) and Na-2{[Fe(pca(3))](2)O}center dot 2H(2)O center dot CH3CN (2) (where pca(-) is pyrazine-2-carboxylate) and their catalytic activity in the oxidation of hydrocarbons is reported. Addition of H2O2 to 1 results in the

  9. Crystal structure of di-μ-aqua-μ-(pyrazine N,N′-dioxide-κ2O:O-bis(diaquasodium tetraphenylborate dihydrate pyrazine N,N′-dioxide monosolvate

    Directory of Open Access Journals (Sweden)

    Elaine P. Boron

    2015-12-01

    Full Text Available The search for novel lanthanide coordination networks using pyrazine N,N′-dioxide (pzdo, C4H4N2O2 as a structure-directing unit, led to the synthesis and the structure determination of the title compound, [Na2(C4H4N2O2(H2O6][B(C6H54]2·C4H4N2O2·2H2O. The crystal structure is comprised of discrete [{Na(H2O2}2(μ-H2O2(μ-pzdo]2+ cations and tetraphenylborate anions, as well as pzdo and H2O solvent molecules. The dinuclear cation is located about a twofold rotation axis, and the symmetry-related NaI atoms display a distorted square-pyramidal coordination sphere defined by two O atoms of terminal water ligands, two O atoms of bridging water ligands and one O atom of a bridging pzdo ligand. In the crystal, O—H...O hydrogen bonds link the dinuclear cation and solvent pzdo molecules (point-group symmetry -1 into rectangular grid-like layers parallel to the bc plane. Additional C—H...O, O—H...O, C—H...π and O—H...π interactions link the anion and solvent water molecules to the layers. The layers are further linked into a three-dimensional network through a combination of C—H...π and O—H...π hydrogen bonds involving the tetraphenylborate anion.

  10. catena-Poly[[diaquabis(4-formylbenzoato-κO1nickel(II]-μ-pyrazine-κ2N:N′

    Directory of Open Access Journals (Sweden)

    Fatih Çelik

    2014-02-01

    Full Text Available In the title polymeric compound, [Ni(C8H5O32(C4H4N2(H2O2]n, the NiII atom is located on a twofold rotation axis and has a slightly distorted octahedral coordination sphere. In the equatorial plane, it is coordinated by two carboxylate O atoms of two symmetry-related monodentate formylbenzoate anions and by two N atoms of the bridging pyrazine ligand, which is bisected by the twofold rotation axis. The axial positions are occupied by two O atoms of the coordinating water molecules. In the formylbenzoate anion, the carboxylate group is twisted away from the attached benzene ring by 7.0 (6°, while the benzene and pyrazine rings are oriented at a dihedral angle of 66.2 (3°. The pyrazine ligands bridge the NiII cations, forming polymeric chains running along the b-axis direction. Intramolecular O—H...O hydrogen bonds link the water ligands to the carboxylate O atoms. In the crystal, water–water O—H...O hydrogen bonds link adjacent chains into layers parallel to the bc plane. Pyrazine–formyl C—H...O hydrogen bonds link the layers, forming a three-dimensional network. There are also weak C—H...π interactions present. The title compound is isotypic with the copper(II complex [Çelik et al. (2014a. Acta Cryst. E70, m4–m5].

  11. catena-Poly[[diaquabis(4-formylbenzoato-κO1copper(II]-μ-pyrazine-κ2N:N′

    Directory of Open Access Journals (Sweden)

    Fatih Çelik

    2014-01-01

    Full Text Available In the title polymeric compound, [Cu(C8H5O32(C4H4N2(H2O2]n, the CuII atom is located on a twofold rotation axis and has a slightly distorted octahedral coordination sphere. In the equatorial plane, it is coordinated by two carboxylate O atoms of two symmetry-related monodentate formylbenzoate anions and by two N atoms of the bridging pyrazine ligand, which is bisected by the twofold rotation axis. The axial positions are occupied by two O atoms of the coordinating water molecules. In the formylbenzoate anion, the carboxylate group is twisted away from the attached benzene ring by 6.2 (2°, while the benzene and pyrazine rings are oriented at a dihedral angle of 68.91 (8°. The pyrazine ligands bridge the CuII cations, forming polymeric chains running along the b-axis direction. Strong intramolecular O—H...O hydrogen bonds link the water molecules to the carboxylate O atoms. In the crystal, O—Hwater...Owater hydrogen bonds link adjacent chains into layers parallel to the bc plane. The layers are linked via C—Hpyrazine...Oformyl hydrogen bonds, forming a three-dimensional network. There are also weak C—H...π interactions present.

  12. The crystal structures of three pyrazine-2,5-dicarboxamides: three-dimensional supramolecular structures

    Directory of Open Access Journals (Sweden)

    Dilovan S. Cati

    2017-05-01

    Full Text Available The complete molecules of the title compounds, N2,N5-bis(pyridin-2-ylmethylpyrazine-2,5-dicarboxamide, C18H16N6O2 (I, 3,6-dimethyl-N2,N5-bis(pyridin-2-ylmethylpyrazine-2,5-dicarboxamide, C20H20N6O2 (II, and N2,N5-bis(pyridin-4-ylmethylpyrazine-2,5-dicarboxamide, C18H16N6O2 (III, are generated by inversion symmetry, with the pyrazine rings being located about centres of inversion. Each molecule has an extended conformation with the pyridine rings inclined to the pyrazine ring by 89.17 (7° in (I, 75.83 (8° in (II and by 82.71 (6° in (III. In the crystal of (I, molecules are linked by N—H...N hydrogen bonds, forming layers lying parallel to the bc plane. The layers are linked by C—H...O hydrogen bonds, forming a three-dimensional supramolecular structure. In the crystal of (II, molecules are also linked by N—H...N hydrogen bonds, forming layers lying parallel to the (10-1 plane. As in (I, the layers are linked by C—H...O hydrogen bonds, forming a three-dimensional supramolecular structure. In the crystal of (III, molecules are again linked by N—H...N hydrogen bonds, but here form corrugated sheets lying parallel to the bc plane. Within the sheets, neighbouring pyridine rings are linked by offset π–π interactions [intercentroid distance = 3.739 (1 Å]. The sheets are linked by C—H...O hydrogen bonds, forming a three-dimensional supramolecular structure. Compound (I crystallizes in the monoclinic space group P21/c. Another monoclinic polymorph, space group C2/c, has been reported on by Cockriel et al. [Inorg. Chem. Commun. (2008, 11, 1–4]. The molecular structures of the two polymorphs are compared.

  13. Hexaaquacopper(II bis(tetrafluoridoborate–pyrazine 1,4-dioxide (1/3

    Directory of Open Access Journals (Sweden)

    Jan L. Wikaira

    2013-04-01

    Full Text Available The crystal structure of the title compound, [Cu(H2O6](BF42·3C4H4N2O2, comprises discrete [Cu(H2O6]2+ cations and BF4− anions along with three equivalents of pyrazine 1,4-dioxide (pzdo. The hexaaquacopper(II ion and all three pzdo molecules lie about crystallographic inversion centers. The lattice is supported by an extensive hydrogen-bonding network. O—H...O hydrogen bonding between the [Cu(H2O6]2+ and pzdo units creates a pseudo-hexagonal lattice parallel to the bc plane. The BF4− anions lie in the voids of that lattice, held in place by O—H...F hydrogen bonds, and also generate BF4−–pzdo–BF4−–pzdo stacks via short F...N contacts [2.866 (3–3.283 (4 Å].

  14. Full-dimensional control of the radiationless decay in pyrazine using the dynamic Stark effect

    Energy Technology Data Exchange (ETDEWEB)

    Saab, Mohamad, E-mail: mohamad.saab@univ-montp2.fr; Lasorne, Benjamin, E-mail: benjamin.lasorne@univ-montp2.fr; Gatti, Fabien, E-mail: gatti@univ-montp2.fr [CTMM, Institut Charles Gerhardt Montpellier (UMR5253), CC 15001, Université Montpellier 2, F-34095 Montpellier, Cedex 05 (France); Sala, Matthieu; Guérin, Stéphane [Laboratoire Interdisciplinaire Carnot de Bourgogne (UMR 6303) CNRS, Université de Bourgogne, BP 47870, F-21078 Dijon (France)

    2014-10-07

    We present a full quantum-mechanical study of the laser control of the radiationless decay between the B{sub 3u}(nπ{sup *}) and B{sub 2u}(ππ{sup *}) states of pyrazine using the dynamic Stark effect. In contrast to our previous study [Sala et al., J. Chem. Phys. 140, 194309 (2014)], where a four-dimensional model was used, all the 24 degrees of freedom are now included in order to test the robustness of the strategy of control. Using a vibronic coupling Hamiltonian model in a diabatic representation, the multi-layer version of the multi-configuration time-dependent Hartree method is exploited to propagate the corresponding wave packets. We still observe a trapping of the wavepacket on the B{sub 2u}(ππ{sup *}) potential energy surface due to the Stark effect for a longer time than the “non-resonant field-free” B{sub 2u}(ππ{sup *}) lifetime.

  15. Laser control of the radiationless decay in pyrazine using the dynamic Stark effect

    Energy Technology Data Exchange (ETDEWEB)

    Sala, Matthieu, E-mail: matthieu.sala@u-bourgogne.fr; Guérin, Stéphane, E-mail: sguerin@u-bourgogne.fr [Laboratoire Interdisciplinaire Carnot de Bourgogne UMR 6303 CNRS, Université de Bourgogne, BP 47870, F-21078 Dijon (France); Saab, Mohamad; Lasorne, Benjamin; Gatti, Fabien [CTMM, Institut Charles Gerhardt UMR 5253 CNRS, CC 15001, Université Montpellier 2, F-34095 Montpellier (France)

    2014-05-21

    The laser control of the radiationless decay between the B{sub 3u}(nπ*) and B{sub 2u}(ππ*) states of pyrazine using the dynamic Stark effect has been investigated. A vibronic coupling model Hamiltonian in diabatic representation, including potential energy, transition dipole, and static polarizability surfaces as a function of the four most important vibrational modes of the molecule has been parametrized using multi-reference electronic structure calculations. The interaction of the molecule with a strong non-resonant laser pulse has been analyzed in terms of dressed potential energy surfaces. Because of the large polarizability difference between the vibronically coupled B{sub 3u}(nπ*) and B{sub 2u}(ππ*) states, the Stark effect induced by the non-resonant laser pulse shifts the conical intersection away from the Franck-Condon region. We have shown, by solving the time-dependent Schrödinger equation for the molecule interacting with a relatively weak pump pulse driving the electronic excitation from the ground state to the B{sub 2u}(ππ*) state, and a strong non-resonant control pulse, that this control mechanism can be used to trap the wavepacket on the B{sub 2u}(ππ*) potential energy surface for a much longer time than the natural B{sub 2u}(ππ*) lifetime.

  16. Spectroscopic Investigation and Photophysics of a D-π-A-π-D Type Styryl Pyrazine Derivative.

    Science.gov (United States)

    El-Daly, Samy A; Alamry, Khalid A

    2016-01-01

    E,E-2,5-bis(3,4-dimethoxystyryl)pyrazine (BDSP)has been prepared by aldol condensation between 2,5-dimethypyrazine and 3,4-dimthoxybenzaldehyde and characterized by IR, 1HNMR, 13C NMR and X-ray crystallography.The electronic absorption and emission properties of BDSP were studied in different solvents. BDSP displays a strong solvatochromic effect of the emission spectrum that is reflected by large red shifts of its fluorescence emission maximum on increasing the solvent polarity, indicating a large change in dipole moment of BDSP upon excitation due to photoinduced intramolecular charge transfer (PICT). Excited state intermolecular hydrogen bonding affects the energy of emission spectrum and fluorescence quantum yield of BDSP dye. The dye solutions (1×10(-4) M) in DMSO, DMF, CH3CN and dioxane give laser emission in green region upon excitation by a 337.1 nm nitrogen pulse (λ=337 nm). The tuning range, gain coefficient (α), emission cross – section (σe) and half-life energy (E1/2) has been determined. Ground and electronic excited states geometric optimization were performed using density functional theory (DFT) and time-dependent density functional theory (TD-DFT), respectively. A DFT natural bond analysis complemented the ICT. BDSP dye displays fluorescence quenching by colloidal silver nanoparticles(AgNPs). The fluorescence data reveal that radiative and non-radiative energy transfer play a major role in the fluorescence quenching mechanism.

  17. A Combined Experimental and Theoretical Study of the Ammonium Bifluoride Catalyzed Regioselective Synthesis of Quinoxalines and Pyrido[2,3-b]pyrazines

    OpenAIRE

    Lassagne, Frédéric; Chevallier, Floris; Roisnel, Thierry; Dorcet, Vincent; Mongin, Florence; Domingo, Luis .R.

    2015-01-01

    International audience; Ammonium bifluoride was efficiently used (at a 0.5 mol % loading) to catalyze the cyclocondensation between 1,2-arylenediamines and 1,2-dicarbonyl compounds at room temperature in methanol-water, affording quinoxalines and pyrido[2,3-b]pyrazines in excellent yields. Importantly, 2,8-disubstituted quinoxalines and 3-substituted pyrido[2,3-b]pyrazines were regioselectively formed by reacting aryl glyoxals with 3-methyl-1,2-phenylenediamine and 2,3-diaminopyridine, respec...

  18. New Palladium-Catalyzed Domino Reaction with Intramolecular Ring Closure of an N-(2-Chloro-3-heteroaryl) arylamide: First Synthesis of Oxazolo[4,5-b] pyrazines

    DEFF Research Database (Denmark)

    Demmer, Charles S.; Hansen, Jacob C.; Kehler, Jan;

    2014-01-01

    lipophilicity and target interaction points are often desired. In this respect, the oxazolo[4,5-b]pyrazine is an attractive heterocyclic scaffold as it possesses increased water solubility as well as two additional hydrogen bonding acceptors. We here report a new Pd(II)-catalyzed domino reaction comprising...... is required for the domino reaction to proceed. The robustness of the methodology is confirmed by the synthesis of 23 2-substituted oxazolo[4,5-b]pyrazine analogues in good-to-high yields and containing both electron-withdrawing as well as electron-donating substituents on the reacting arylamide....

  19. Synthesis and Properties for Two N-amino Derivatives of 4,8-Dihydrodifurazano[3,4-b,e]pyrazine

    Institute of Scientific and Technical Information of China (English)

    LI Ya-nan; LIU Ning; LIAN Peng; GE Zhong-xue; WANG Bo-zhou

    2014-01-01

    Two energetic compounds---4-aminodifurazano[3,4-b,e]pyrazine(ADFP)and 4,8-diaminodifurazano[3,4-b,e]pyrazine(DADFP) were prepared via N-amination reaction and their structures were characterized by IR,1 H NMR,13 C NMR,MS and elemental analysis. The themal properties of ADFP and DADFP were analyzed by differential scanning calorimetry and thermogravimetry techniques. Results show that DADFP melts concomitantly with decomposition at 284. 3 ℃. The melting point of ADFP is 218. 1 ℃ and its first decomposition temperature is 247. 1 ℃,which in-dicate that ADFP and DADFP have good thermal stability.

  20. Discovery and Biological Evaluation of a Series of Pyrrolo[2,3-b]pyrazines as Novel FGFR Inhibitors.

    Science.gov (United States)

    Zhang, Yan; Liu, Hongchun; Zhang, Zhen; Wang, Ruifeng; Liu, Tongchao; Wang, Chaoyun; Ma, Yuchi; Ai, Jing; Zhao, Dongmei; Shen, Jingkang; Xiong, Bing

    2017-04-05

    Abnormality of fibroblast growth factor receptor (FGFR)-mediated signaling pathways were frequently found in various human malignancies, making FGFRs hot targets for cancer treatment. To address the consistent need for a new chemotype of FGFR inhibitors, here, we started with a hit structure identified from our internal hepatocyte growth factor receptor (also called c-Met) inhibitor project, and conducted a chemical optimization. After exploring three parts of the hit compound, we finally discovered a new series of pyrrolo[2,3-b]pyrazine FGFR inhibitors, which contain a novel scaffold and unique molecular shape. We believe that our findings can help others to further develop selective FGFR inhibitors.

  1. The discovery of novel 3-(pyrazin-2-yl)-1H-indazoles as potent pan-Pim kinase inhibitors.

    Science.gov (United States)

    Wang, Hui-Ling; Cee, Victor J; Chavez, Frank; Lanman, Brian A; Reed, Anthony B; Wu, Bin; Guerrero, Nadia; Lipford, J Russell; Sastri, Christine; Winston, Jeff; Andrews, Kristin L; Huang, Xin; Lee, Matthew R; Mohr, Christopher; Xu, Yang; Zhou, Yihong; Tasker, Andrew S

    2015-02-15

    The three Pim kinases are a small family of serine/threonine kinases regulating several signaling pathways that are fundamental to tumorigenesis. As such, the Pim kinases are a very attractive target for pharmacological inhibition in cancer therapy. Herein, we describe our efforts toward the development of a potent, pan-Pim inhibitor. The synthesis and hit-to-lead SAR development from a 3-(pyrazin-2-yl)-1H-indazole derived hit 2 to the identification of a series of potent, pan-Pim inhibitors such as 13o are described.

  2. Unexpected reversible pyrazine based methylation in a Ru(II) complex bearing a pyrazin-2'-yl-1,2,4-triazolato ligand and its effect on acid/base and photophysical properties.

    Science.gov (United States)

    Brennan, Claire; Draksharapu, Apparao; Browne, Wesley R; McGarvey, John J; Vos, Johannes G; Pryce, Mary T

    2013-02-21

    The regioselective methylation of a ruthenium polypyridyl complex bearing both a 1,2,4-triazolato and a pyrazine moiety is reported. In contrast to previous studies in which methylation of the 1,2,4-triazolato ring was observed, in the present system methylation takes place exclusively at the non-coordinated nitrogen of the pyrazine ring. The monomethylation is confirmed by (1)H NMR spectroscopy and ESI-MS and the electronic properties of the methylated complexes are studied by UV/vis absorption, emission, surface enhanced, resonance and transient resonance Raman spectroscopy. Ligand deuteriation is used to simplify the (1)H NMR spectra and to assign definitively the Raman spectra. Acid-base studies show that the triazolato ring of the N-methylated complexes can be protonated at low pH and that at high pH the N-methyl group can be deprotonated reversibly. Furthermore it is shown that under conditions where the methyl group is deprotonated, demethylation occurs to recover the initial complex.

  3. Theoretical study on S1(1B3u) state electronic structure and absorption spectrum of pyrazine

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Making use of a set of quantum chemistry methods, the harmonic potential surfaces of the ground state (S0(1Ag)) and the first (S1(1B3u)) excited state of pyrazine are investigated, and the electronic structures of the two states are characterized. In the present study, the conventional quantum mechanical method, taking account of the Born-Oppenheimer adiabatic approximation, is adopted to simulate the absorp-tion spectrum of S1(1B3u) state of pyrazine. The assignment of main vibronic transitions is made for S1(1B3u) state. It is found that the spectral profile is mainly described by the Franck-Condon progression of totally symmetric mode ν6a. For the five totally symmetric modes, the present calculations show that the frequency differences between the ground and the S1(1B3u) state are small. Therefore the displaced harmonic oscillator approximation along with Franck-Condon transition is used to simulate S1(1B3u) absorption spectra. The distortion effect due to the so-called quadratic coupling is demonstrated to be unimportant for the absorption spectrum, except the coupling mode ν10a. The calculated S1(1B3u) ab-sorption spectrum is in reasonable agreement with the experimental spectra.

  4. Structural and magnetic properties of quasi-1 and 2D pyrazine-containing spin-1/2 antiferromagnets.

    Energy Technology Data Exchange (ETDEWEB)

    Manson, J. L.; Connor, M. M.; Schlueter, J. A.; Hyzer, K. A.; Kykeem, A.; Materials Science Division; Eastern Washington Univ.

    2007-06-01

    Aqueous reaction of Cu(BF{sub 4}){sub 2}, NH{sub 4}HF{sub 2}, and pyrazine leads to formation of a novel 3D framework, [Cu(HF{sub 2})(pyz){sub 2}]BF{sub 4} (1), where 2D [Cu(pyz){sub 2}]{sup 2+} square layers are connected via HF{sub 2}{sup -}. A second compound, Cu(ReO{sub 4}){sub 2}(H{sub 2}O){sub 2}(pyz) (2), was the result of our attempt to create the perrhenate analog of 1; a linear chain compound consisting of CuO{sub 4}N{sub 2} octahedra linked through pyrazine ligands formed instead. Both compounds exhibit extensive hydrogen bonding interactions where bifluoride, F...H...F{sup -}, and O-H...O link layers and chains together in 1 and 2, respectively. Broad maxima indicative of short-range magnetic ordering (SRO) were observed in the magnetic susceptibility at 5.5 (1) and 7.7 K (2) while no evidence for the transition to long-range magnetic ordering (LRO) was detected above 2 K.

  5. Discovery of pyrazines as pollinator sex pheromones and orchid semiochemicals: implications for the evolution of sexual deception.

    Science.gov (United States)

    Bohman, Björn; Phillips, Ryan D; Menz, Myles H M; Berntsson, Ben W; Flematti, Gavin R; Barrow, Russell A; Dixon, Kingsley W; Peakall, Rod

    2014-08-01

    Sexually deceptive orchids employ floral volatiles to sexually lure their specific pollinators. How and why this pollination system has evolved independently on multiple continents remains unknown, although preadaptation is considered to have been important. Understanding the chemistry of sexual deception is a crucial first step towards solving this mystery. The combination of gas chromatography-electroantennographic detection (GC-EAD), GC-MS, synthesis and field bioassays allowed us to identify the volatiles involved in the interaction between the orchid Drakaea glyptodon and its sexually attracted male thynnine wasp pollinator, Zaspilothynnus trilobatus. Three alkylpyrazines and one novel hydroxymethyl pyrazine were identified as the sex pheromone of Z. trilobatus and are also used by D. glyptodon for pollinator attraction. Given that our findings revealed a new chemical system for plants, we surveyed widely across representative orchid taxa for the presence of these compounds. With one exception, our chemical survey failed to detect pyrazines in related genera. Collectively, no evidence for preadaptation was found. The chemistry of sexual deception is more diverse than previously known. Our results suggest that evolutionary novelty may have played a key role in the evolution of sexual deception and highlight the value of investigating unusual pollination systems for advancing our understanding of the role of chemistry in evolution. © 2014 The Authors. New Phytologist © 2014 New Phytologist Trust.

  6. Enhanced dye-sensitized solar cell photocurrent and efficiency using a Y-shaped, pyrazine-containing heteroaromatic sensitizer linkage.

    Science.gov (United States)

    Watson, Brian L; Sherman, Benjamin D; Moore, Ana L; Moore, Thomas A; Gust, Devens

    2015-06-28

    A new sensitizer motif for dye sensitized solar cells (DSSC) has been developed. A heteroaromatic moiety containing a pyrazine ring links two porphyrin chromophores to the metal oxide surface via two carboxylic acid attachment groups. A test DSSC sensitized with the new molecule was 3.5 times more efficient than a similar cell sensitized by a single porphyrin model compound. The open circuit photovoltage was increased by a modest factor of 1.3, but the photocurrent increased by a factor of 2.7. Most of the increase is attributed to a reduced rate of charge recombination of the charge separated state formed by photoinduced electron transfer from the excited sensitizer to the TiO2, although some of the difference is due to increased light absorption resulting from more dye on the photoanode. Increased light absorption due to the pyrazine-containing group may also play a role. The design illustrated here could also be used to link complementary sensitizers or antenna moieties in order to increase spectral coverage.

  7. Crystal structure of catena-poly[[[trans-bis(acetonitrile-κNdiaquacobalt(II]-μ-pyrazine-κ2N:N′] dinitrate

    Directory of Open Access Journals (Sweden)

    Chen Liu

    2016-02-01

    Full Text Available The central structural motif of the title coordination polymer, [Co(NO32(C4H4N2(CH3CN2(H2O2]n, is a chain composed of CoII ions linked by bis-monodentate bridging pyrazine ligands through their N atoms. The CoII ion is located on an inversion center and is additionally coordinated by two O atoms of water molecules and two N atoms of acetonitrile molecules. The resultant N4O2 coordination sphere is distorted octahedral. The linear cationic chains extend parallel to the a axis and are aligned into layers parallel to the ac plane. Nitrate anions are situated in the space between the CoII chains and form O—H...O hydrogen bonds with the coordinating water molecules, leading to a three-dimensional network structure. Weak C—H...O hydrogen bonds are also present between pyrazine or acetonitrile molecules and the nitrate anions.

  8. Theoretical study on S1(1B3u) state electronic structure and absorption spectrum of pyrazine

    Institute of Scientific and Technical Information of China (English)

    HE RongXing; ZHU ChaoYuan; CHIN Chih-Hao; LIN Sheng-Hsien

    2008-01-01

    Making use of a set of quantum chemistry methods, the harmonic potential surfaces of the ground state (S0(1Ag)) and the first (S1(1B3u)) excited state of pyrazine are investigated, and the electronic structures of the two states are characterized. In the present study, the conventional quantum mechanical method, taking account of the Born-Oppenheimer adiabatic approximation, is adopted to simulate the absorp-tion spectrum of S1(1B3u) state of pyrazine. The assignment of main vibronic transitions is made for S1(1B3u) state. It is found that the spectral profile is mainly described by the Franck-Condon progression of totally symmetric mode v6a. For the five totally symmetric modes, the present calculations show that the frequency differences between the ground and the S1(1B3u) state are small. Therefore the displaced harmonic oscillator approximation along with Franck-Condon transition is used to simulate S1(1B3u)absorption spectra. The distortion effect due to the so-called quadratic coupling is demonstrated to be unimportant for the absorption spectrum, except the coupling mode v10a. The calculated S1(1B3u) ab-sorption spectrum is in reasonable agreement with the experimental spectra.

  9. Magnetic field dependence of rotationally resolved excitation spectra of the 1B3u 000 transition of jet-cooled pyrazine

    NARCIS (Netherlands)

    Jonkman, Harry Th.; Drabe, Karel E.

    1991-01-01

    We report rotationally resolved excitation spectra of the 1B3u 000 transition of jet-cooled pyrazine in magnetic fields up to 50 kG. The emission intensity of every rotational line is found to decrease by a factor of three for magnetic fields larger than about 300 G. For still larger magnetic fields

  10. MAGNETIC-FIELD DEPENDENCE OF ROTATIONALLY RESOLVED EXCITATION-SPECTRA OF THE B-1(3U)0(0)(0) TRANSITION OF JET-COOLED PYRAZINE

    NARCIS (Netherlands)

    DELANGE, PJ; JONKMAN, HT; DRABE, KE

    1991-01-01

    We report rotationally resolved excitation spectra of the 1B3u 0(0)0 transition of jet-cooled pyrazine in magnetic fields up to 50 kG. The emission intensity of every rotational line is found to decrease by a factor of three for magnetic fields larger than about 300 G. For still larger magnetic fiel

  11. Safety and efficacy of pyrazine derivatives including saturated ones belonging to chemical group 24 when used as flavourings for all animal species

    National Research Council Canada - National Science Library

    Rychen, Guido; Aquilina, Gabriele; Azimonti, Giovanna; Bampidis, Vasileios; Lourdes Bastos, Maria; Bories, Georges; Cocconcelli, Pier Sandro; Flachowsky, Gerhard; Gropp, Jürgen; Kolar, Boris; Kouba, Maryline; López Puente, Secundino; López‐Alonso, Marta; Mantovani, Alberto; Mayo, Baltasar; Ramos, Fernando; Saarela, Maria; Villa, Roberto Edoardo; Wallace, Robert John; Wester, Pieter; Brantom, Paul; Dusemund, Birgit; Hogstrand, Christer; Van Beelen, Patrick; Westendorf, Johannes; Gregoretti, Lucilla; Manini, Paola; Chesson, Andrew

    2017-01-01

    ... (pyrazine derivatives). They are currently authorised as flavours in food. The FEEDAP Panel concludes that: 2,3‐diethylpyrazine [14.005], 2‐ethyl‐3‐methylpyrazine [14.006], 5,6,7,8‐tetrahydroquinoxaline...

  12. A practical metal-free homolytic aromatic alkylation protocol for the synthesis of 3-(pyrazin-2-yl)bicyclo[1.1.1]pentane-1-carboxylic acid.

    Science.gov (United States)

    Thirumoorthi, Navanita T; Adsool, Vikrant A

    2016-10-12

    As a part of our ongoing synthetic quest to expand the frontiers of contemporary medicinal chemistry, we now report an expedient synthesis of a potentially useful bicyclo[1.1.1]pentane building block, 3-(pyrazin-2-yl)bicyclo[1.1.1]pentane-1-carboxylic acid. This report also showcases the application of this motif as a probe in a biological study.

  13. Pyrazine-functionalized calix[4]arenes: synthesis by palladium-catalyzed cross-coupling with phosphorus pronucleophiles and metal ion extraction properties

    NARCIS (Netherlands)

    Nikishkin, N.; Huskens, Jurriaan; Ansari, S.A.; Mohapatra, P.K.; Verboom, Willem

    2013-01-01

    A series of pyrazine-based calix[4]arene extractants was prepared by a stepwise functionalization, comprising palladium-catalyzed exhaustive cross-coupling of di- and tetrasubstituted calix[4]arenes bearing chloropyrazine moieties. The extraction behavior of the synthesized ligands was studied on

  14. High Tc ferrimagnetic organic-inorganic hybrid materials with MnII-L-MnII and MnII-NC-NbIV linkages (L=pyrazine, pyrazine-N,N'-dioxide, bipyrimidine).

    Science.gov (United States)

    Podgajny, Robert; Pinkowicz, Dawid; Korzeniak, Tomasz; Nitek, Wojciech; Rams, Michał; Sieklucka, Barbara

    2007-11-26

    A series of heterobimetallic, cyano-bridged 3D inorganic-organic hybrid networks with MnII-L-MnII and MnII-NC-NbIV linkages are reported. Reaction of [Mn(H2O)6]2+ with [Nb(CN)8]4- in the presence of organic linker L (pyrazine (pyz), pyrazine-N,N'-dioxide (pzdo), and 2,2'-bipyrimidine (bpym)) in H2O affords {MnII2(pz)2(H2O)4[NbIV(CN)8]}.pz.3H2O (1), {MnII2(pzdo)(H2O)4[NbIV(CN)8]}.5H2O (2), and {MnII2(bpym)(H2O)2[NbIV(CN)8]} (3), respectively. 1-3 were examined by X-ray crystallography and vibrational and magnetochemical studies. 1 is characterized by the coexistence of 3D inorganic cyano-bridged and 1D organic [Mn-(micro-pyz)]n2n+ sublattices along with the presence of monocoordinated and crystallization molecules of pyrazine. Assemblies 2 and 3 exhibit dimeric {MnII2-(micro-L)}4+ coordination motifs. The magnetic behavior of heterobimetallic 1-3 complexes is dominated by antiferromagnetic coupling between MnII and NbIV centers mediated by cyano bridges, resulting in long-range ferrimagnetic ordering with a high TC of 27 (1), 37 (2), and 50 K (3). The magneto-structural correlation leads to the conclusion that the magnitude of TC is related to the type of coordination polyhedra of [Nb(CN)8] moieties (SAPR (1), intermediate between SAPR and DD (2), and DD (3)), the relative number of cyano bridges per Mn2Nb unit, and coexistence of inorganic and organic connectivity. FC/ZFC responses appear to be sensitive to the degree of organic connectivity. The discussion of magneto-structural correlation is based on the spin-density properties of adequate heterobimetallic systems containing octacyanometalates.

  15. Theoretical Prediction of the Heats of Formation, Densities, and Relative Sensitivities for 1,7-dinitro-3,4,5,8-tetra N-oxide-bis([1,2,3]triazolo)[4,5-b:5’,4’ e]pyrazine, 1,7-dinitro-3,5,8-tri N-oxide bis([1,2,3]triazolo)[4,5-b:5’,4’ e]pyrazine, 1,7-dinitro 3,5-bis N-oxide bis([1,2,3]triazolo)[4,5-b:5’,4’ e]pyrazine, 1,7-dinitro 1,7-dihydrobis([1,2,3]triazolo)[4,5-b:4’,5’-e]pyrazine

    Science.gov (United States)

    2016-09-01

    Sensitivities for 1,7-dinitro- 3,4,5,8-tetra N-oxide-bis([1,2,3]triazolo)[4,5- b:5’,4’- e ]pyrazine, 1,7-dinitro-3,5,8-tri N-oxide- bis([1,2,3]triazolo...4,5-b:5’,4’- e ]pyrazine, 1,7- dinitro-3,5-bis N-oxide-bis([1,2,3]triazolo)[4,5- b:5’,4’- e ]pyrazine, 1,7-dinitro-1,7- dihydrobis([1,2,3]triazolo)[4,5-b:4...8217,5’- e ]pyrazine by Edward FC Byrd Approved for public release; distribution is unlimited. NOTICES Disclaimers The

  16. catena-Poly[[bis(pyrazine-2-carboxamide-κN4mercury(II]-di-μ-bromido

    Directory of Open Access Journals (Sweden)

    Bahareh Mir Mohammad Sadegh

    2010-02-01

    Full Text Available In the crystal structure of the title compound, [HgBr2(C5H5N3O2]n, the HgII cation is located on an inversion center and is coordinated by two N atoms from the pyrazine rings and four bridging Br− anions in a distorted octahedral geometry. The Br− anions bridge the HgII cations with significantly different Hg—Br bond distances of 2.4775 (8 and 3.1122 (8 Å, forming polymeric chains running along the a axis. Intermolecular N—H...O and N—H...N hydrogen bonds are effective in the stabilization of the crystal structure.

  17. Discovery and Biological Evaluation of a Series of Pyrrolo[2,3-b]pyrazines as Novel FGFR Inhibitors

    Directory of Open Access Journals (Sweden)

    Yan Zhang

    2017-04-01

    Full Text Available Abnormality of fibroblast growth factor receptor (FGFR-mediated signaling pathways were frequently found in various human malignancies, making FGFRs hot targets for cancer treatment. To address the consistent need for a new chemotype of FGFR inhibitors, here, we started with a hit structure identified from our internal hepatocyte growth factor receptor (also called c-Met inhibitor project, and conducted a chemical optimization. After exploring three parts of the hit compound, we finally discovered a new series of pyrrolo[2,3-b]pyrazine FGFR inhibitors, which contain a novel scaffold and unique molecular shape. We believe that our findings can help others to further develop selective FGFR inhibitors.

  18. Synthesis, Characterization, and Photochemical Properties of a New Square Mn(I-Ru(II Complex Using Pyrazine as Bridge Ligand

    Directory of Open Access Journals (Sweden)

    Inara de Aguiar

    2013-01-01

    Full Text Available The photochemical properties of the complexes cis,fac- (I, cis-[Ru(phen2(pz2]2+ (II, and fac-Mn(CO3(pz2Br (III where phen is phenanthroline and pz is pyrazine in acetonitrile solution are reported. The three complexes were characterized using 1H NMR, UV-vis and FTIR spectroscopy and electrochemical (cyclic voltammetry and spectroelectrochemical techniques. The complexes show intense absorption in the visible region assigned to the population of MLCT excited states. The absorption spectrum of I is the sum of the spectra of the mononuclear species II and III, and the two oxidation potentials at +1.10 and +1.56 V versus Ag/AGCl observed in I are ascribed to the different coordination environments of metal centers. The photolysis in the acetonitrile solution resulted in the pz dissociation to give the monoacetonitrile complexes for I, II, and III, respectively.

  19. Bistability and the phase transition in 1,3,2-dithiazolo[4,5-b]pyrazin-2-yl.

    Science.gov (United States)

    Brusso, Jaclyn L; Clements, Owen P; Haddon, Robert C; Itkis, Mikhail E; Leitch, Alicea A; Oakley, Richard T; Reed, Robert W; Richardson, John F

    2004-11-17

    The molecular radical 1,3,2-dithiazolo[4,5-b]pyrazin-2-yl (PDTA) exhibits magnetic bistability just above room temperature, undergoing a well-defined hysteretic phase change with TC downward arrow = 297(1) K and TC upward arrow = 343(1) K. The crystal structures of the two phases of PDTA have been determined by single-crystal X-ray diffraction at 323(2) K. LT-PDTA consists of diamagnetic (S = 0) nearly superimposed pi-dimer stacks, while that of HT-PDTA comprises slipped stacks of pi-radicals (S = 1/2). The structural interconversion is suggested to proceed via the cooperative breaking and making of intermolecular S- - -N interactions and an inversion symmetry-preserving "domino cascade" of the pi-stacked rings.

  20. Synthesis, spectral, X-ray diffraction and thermal studies of new ZnII-pyrazine coordination polymers

    Science.gov (United States)

    Marandi, Farzin

    2014-02-01

    Two new zinc(II) coordination polymers with a β-diketone and N-donor ancillary ligands, [Zn(pyz)(ttfa)2]n (1) and [Zn(pyz)(btfa)2]n (2), (Httfa = 2-thenoyltrifluoroacetone, Hbtfa = benzoyltrifluoroacetone and pyz = pyrazine), have been prepared and characterized by elemental analysis, IR, 1H NMR and 13C NMR spectroscopy, and studied by thermal gravimetric analysis as well as single crystal X-ray diffraction. The crystal and molecular structures of 1 and 2 have been solved by X-ray diffraction and they turned out to be one-dimensional polymers with linear dispositions of the metal atoms. These one-dimensional polymers are further connected to form a 3D supramolecular network by CH⋯π (only in 1), CH⋯F, π-π and interesting H⋯H (only in 2) interactions.

  1. Diaquabis[bis(pyrazin-2-yl sulfide-κN4]bis(thiocyanato-κNiron(II monohydrate

    Directory of Open Access Journals (Sweden)

    Susanne Wöhlert

    2013-04-01

    Full Text Available In the title compound [Fe(NCS2(C8H6N4S2(H2O2]·H2O, the FeII cation is coordinated by two N-bonded thiocyanate anions, two N4-bonded bis(pyrazin-2-yl sulfide ligands and two water molecules in an slightly distorted octahedral geometry. The FeII cation is located on a center of inversion and the lattice water molecule on a twofold rotation axis. The thiocyanate anions, the coordinating water molecules and the sulfide ligands occupy general positions. The complex molecules and lattice water molecules are linked into a three-dimensional network by O—H—N and O—H...O hydrogen bonds.

  2. Vinyl azides derived from allenes: thermolysis leading to multisubstituted 1,4-pyrazines and Mn(III)-catalyzed photochemical reaction leading to pyrroles.

    Science.gov (United States)

    Sajna, K V; Kumara Swamy, K C

    2012-10-05

    Thermolysis of phosphorus-based vinyl azides under solvent- and catalyst-free conditions furnished a new route for 1,4-pyrazines. A simple one-pot, Mn(III)-catalyzed photochemical route has been developed for multisubstituted pyrroles starting from allenes and 1,3-dicarbonyls via in situ-generated vinyl azides. The utility of new phosphorus-based pyrroles is also demonstrated in the Horner reaction. The structures of key products are unequivocally confirmed by X-ray crystallography.

  3. Combined in- and ex situ studies of pyrazine adsorption into the aliphatic MOF Al-CAU-13: structures, dynamics and correlations.

    Science.gov (United States)

    Reinsch, Helge; Benecke, Jannik; Etter, Martin; Heidenreich, Niclas; Stock, Norbert

    2017-01-31

    The intercalation of different pyrazines (pyrazine, methylpyrazine, 2,5-dimethylpyrazine, 2,3-dimethylpyrazine, trimethylpyrazine and tetramethylpyrazine) into the trans-1,4-cyclohexanedicarboxylate (CDC(2-)) based Al-MOF [Al(OH)(CDC)], denoted as CAU-13, was investigated. The adsorption of the guest molecules into the flexible MOF was carried out from an aqueous solution or via vapour phase adsorption, starting with the hydrated narrow-pore form of the framework [Al(OH)(O2C-C6H10-CO2)]·H2O (CAU-13-np). The obtained host-guest systems were characterised by thermogravimetry and vibrational spectroscopy and their crystal structures were elucidated using powder X-ray diffraction (PXRD) data. The crystal structures indicate that guest molecules forming hydrogen-bonds with the host framework (pyrazine, methylpyrazine and 2,5-dimethylpyrazine) induce a slight opening of the channels, resulting in a semi-open framework conformation (CAU-13-so). For the bulkier guests 2,3-dimethylpyrazine, trimethylpyrazine and tetramethylpyrazine, only van der Waals interactions can be observed between the host and the guest molecules and a large pore conformation is observed (CAU-13-lp). We carried out in situ PXRD studies using synchrotron radiation during the adsorption of the respective guest molecules from aqueous solutions with various concentrations and at different temperatures. In general, stronger host-guest interactions required milder adsorption conditions while harsher conditions nevertheless accelerated the conversion. The kinetic parameters for the intercalation of pyrazine indicate that the rate limiting step differs, depending on the intercalation temperature.

  4. Crystal structure of catena-poly[[diaquabis(4-formylbenzoato-κO1cobalt(II]-μ-pyrazine-κ2N:N′

    Directory of Open Access Journals (Sweden)

    Gülçin Şefiye Aşkın

    2015-04-01

    Full Text Available In the title polymeric compound, [Co(C8H5O32(C4H4N2(H2O2]n, the CoII atom is located on a twofold rotation axis and has a slightly distorted octahedral coordination sphere. In the equatorial plane, it is coordinated by two carboxylate O atoms of two symmetry-related monodentate formylbenzoate anions and by two N atoms of two bridging pyrazine ligands. The latter are bisected by the twofold rotation axis. The axial positions are occupied by two O atoms of the coordinating water molecules. In the formylbenzoate anion, the carboxylate group is twisted away from the attached benzene ring by 7.50 (8°, while the benzene and pyrazine rings are oriented at a dihedral angle of 64.90 (4°. The pyrazine ligands bridge the CoII cations, forming linear chains running along the b-axis direction. Strong intramolecular O—H...O hydrogen bonds link the water molecules to the carboxylate O atoms. In the crystal, weak O—Hwater...Owater hydrogen bonds link adjacent chains into layers parallel to the bc plane. The layers are linked via C—Hpyrazine...Oformyl hydrogen bonds, forming a three-dimensional network. There are also weak C—H...π interactions present.

  5. Multilayer multiconfiguration time-dependent Hartree method: implementation and applications to a Henon-Heiles hamiltonian and to pyrazine.

    Science.gov (United States)

    Vendrell, Oriol; Meyer, Hans-Dieter

    2011-01-28

    The multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method is discussed and a fully general implementation for any number of layers based on the recursive ML-MCTDH algorithm given by Manthe [J. Chem. Phys. 128, 164116 (2008)] is presented. The method is applied first to a generalized Henon-Heiles (HH) hamiltonian. For 6D HH the overhead of ML-MCTDH makes the method slower than MCTDH, but for 18D HH ML-MCTDH starts to be competitive. We report as well 1458D simulations of the HH hamiltonian using a seven-layer scheme. The photoabsorption spectrum of pyrazine computed with the 24D hamiltonian of Raab et al. [J. Chem. Phys. 110, 936 (1999)] provides a realistic molecular test case for the method. Quick and small ML-MCTDH calculations needing a fraction of the time and resources of reference MCTDH calculations provide already spectra with all the correct features. Accepting slightly larger deviations, the calculation can be accelerated to take only 7 min. When pushing the method toward convergence, results of similar quality than the best available MCTDH benchmark, which is based on a wavepacket with 4.6×10(7)time-dependent coefficients, are obtained with a much more compact wavefunction consisting of only 4.5×10(5) coefficients and requiring a shorter computation time.

  6. 2-(pyrazin-2-yloxy)acetohydrazide analogs QSAR Study: An insight into the structural basis of antimycobacterial activity.

    Science.gov (United States)

    Gupta, Revathi A; Gupta, Arun K; Soni, Love K; Kaskhedikar, Satish Gopalrao

    2010-11-01

    Quantitative structure activity relationship analysis based on classical Hansch approach was adopted on reported novel series of 2-(pyrazin-2-yloxy)acetohydrazide analogs. Various types of descriptors like topological, spatial, thermodynamic, and electronic were used to derive a quantitative relationship between the antitubercular activity and structural properties. The consensus scoring function showed a significant statistics of training and test set. Coefficient of determination (r²) of consensus model and predictive squared correlation coefficient (r²(pred)) were found to be 0.889 and 0.782, respectively. The model is not only able to predict the activity of test compounds but also explained the important structural features of the molecules in a quantitative manner. The study revealed that antimycobacterium activity is predominantly explained by the molecular connectivity indices of length 6, hydrogen donor feature of the analogs, and shape factors of the substituent. The comparative investigation of antibacterial activity against Staphylococcus aureus, Bacillus subtilis, Escherichia coli, and Salmonella typhi provided structural insights on how modulation of the molecular connectivity indices, energy of lowest unoccupied molecular orbital, accessible surface area, and moment of inertia of the analogs could be usefully made to optimize the antibacterial activity.

  7. Two-dimensional photon-echo spectroscopy at a conical intersection: A two-mode pyrazine model with dissipation

    Science.gov (United States)

    Sala, Matthieu; Egorova, Dassia

    2016-12-01

    The multi-dimensional electronic spectroscopy of ultrafast nuclear dynamics at conical intersections (CI) is an emerging field of investigation, which profits also from the recent extension of the techniques to the UV domain. We present a detailed computational study of oscillatory signatures in two-dimensional (2D) photon-echo spectroscopy (also known as 2D electronic spectroscopy, 2DES) for the two-mode pyrazine model with dissipation. Conventional 2D signals as well as the resulting beating maps are considered. Although of a reduced character, the model captures quite well all the main signatures of the excited-state dynamics of the molecule. Due to the ultrafast relaxation via the CI and no excited-state absorption from the low-lying dark state, the oscillatory components of the signal are found to be predominantly determined by the ground state bleach contribution. They reflect, therefore, the ground-state vibrational coherence induced in the Raman active mode. Beating maps provide a way to experimentally differentiate between ground state bleach and stimulated emission oscillatory components. The ultrafast decay of the latter constitutes a clear indirect signature of the CI. In the considered model, because of the sign properties of the involved transition dipole moments, the dominance of the ground-state coherence leads to anti-correlated oscillations of cross peaks located at symmetric positions with respect to the main diagonal.

  8. ANTIMICROBIAL ACTIVITY OF [1,2,4]TRIAZOLO[4,3-а]PYRAZIN-8(7H-ONE DERIVATIVES

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    Kulikovska K. Yu.

    2014-12-01

    Full Text Available Today the problem of microbial resistance to antibacterial agents becomes the global one. Antimicrobial drugs that are in the pharmaceutical market do not satisfy the needs of modern treatment regimens, particularly Hospitalacquired infections. Therefore, the search for new and effective means of this pharmacological group is an important task of medical chemistry. From the literature it is known that derivatives of [1,2,4]triazolo[4,3-a]pyrazine show a wide range of biological actions, including antimicrobial and fungicidal. This makes it relevant microbiological study of primary derivatives of [1,2,4]triazolo[4,3-a]pyrazine for identifying promising compounds of the series and then study it in biological experiment.Using the PASS C&T (Prediction Activity Spectra for Substances: Complex & Training program and based on published data, we have generated virtual library of derivatives of [1,2,4]triazolo[4,3-a]pyrazine. As a result, we have received 35 new synthetic compounds of 7 series that were not previously described in the literature. Materials and methods The research of antimicrobial and fungicidal activity of the synthesized compounds was carried out in the laboratory of antimicrobial agents GA "Mechnikov Institute of microbiology and immunology" under the leadership of PhD, senior scientist V.V.Kazmirchuka. The activity of the synthesized compounds were studied by conventional method of the two-fold serial dilutions in liquid and solid nutrient medium. For primary screening we have used a set of clinical and reference strains of microorganism: Escherichia coli ATCC 25922 (F-50, Staphylococcus aureus ATCC 25923 (F-49, Bacillus anthracoides ATCC 1312, Pseudomonas aeruginosa ATCC 27853, Candida albicans ATCC 885-653. As the reference preparations were chosen Palin - modern antimicrobial agent of class of fluoroquinolones, Nevigramon - nalidixic acid derivative and Fluconazole -38 Annals of Mechnikov Institute, N 4, 2014 www

  9. Silver(I nitrate complexes of three tetrakis-thioether-substituted pyrazine ligands: metal–organic chain, network and framework structures

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    Tokouré Assoumatine

    2017-03-01

    Full Text Available The reaction of the ligand 2,3,5,6-tetrakis[(methylsulfanylmethyl]pyrazine (L1 with silver(I nitrate led to {[Ag(C12H20N2S4](NO3}n, (I, catena-poly[[silver(I-μ-2,3,5,6-tetrakis[(methylsulfanylmethyl]pyrazine] nitrate], a compound with a metal–organic chain structure. The asymmetric unit is composed of two half ligands, located about inversion centres, with one ligand coordinating to the silver atoms in a bis-tridentate manner and the other in a bis-bidentate manner. The charge on the metal atom is compensated for by a free nitrate anion. Hence, the silver atom has a fivefold S3N2 coordination sphere. The reaction of the ligand 2,3,5,6-tetrakis[(phenylsulfanylmethyl]pyrazine (L2 with silver(I nitrate, led to [Ag2(NO32(C32H28N2S4]n, (II, poly[di-μ-nitrato-bis{μ-2,3,5,6-tetrakis[(phenylsulfanylmethyl]pyrazine}disilver], a compound with a metal–organic network structure. The asymmetric unit is composed of half a ligand, located about an inversion centre, that coordinates to the silver atoms in a bis-tridentate manner. The nitrate anion coordinates to the silver atom in a bidentate/monodentate manner, bridging the silver atoms, which therefore have a sixfold S2NO3 coordination sphere. The reaction of the ligand 2,3,5,6-tetrakis[(pyridin-2-ylsulfanylmethyl]pyrazine (L3 with silver(I nitrate led to [Ag3(NO33(C28H24N6S4]n, (III, poly[trinitrato{μ6-2,3,5,6-tetrakis[(pyridin-2-ylsulfanylmethyl]pyrazine}trisilver(I], a compound with a metal–organic framework structure. The asymmetric unit is composed of half a ligand, located about an inversion centre, that coordinates to the silver atoms in a bis-tridentate manner. One pyridine N atom bridges the monomeric units, so forming a chain structure. Two nitrate O atoms also coordinate to this silver atom, hence it has a sixfold S2N2O2 coordination sphere. The chains are linked via a second silver atom, located on a twofold rotation axis, coordinated by the second pyridine N atom. A second nitrate anion

  10. Synthesis and reactivity of iron complexes with a new pyrazine-based pincer ligand, and application in catalytic low-pressure hydrogenation of carbon dioxide.

    Science.gov (United States)

    Rivada-Wheelaghan, Orestes; Dauth, Alexander; Leitus, Gregory; Diskin-Posner, Yael; Milstein, David

    2015-05-04

    A novel pincer ligand based on the pyrazine backbone (PNzP) has been synthesized, (2,6-bis(di(tert-butyl)phosphinomethyl)pyrazine), tBu-PNzP. It reacts with FeBr2 to yield [Fe(Br)2(tBu-PNzP)], 1. Treatment of 1 with NaBH4 in MeCN/MeOH gives the hydride complex [Fe(H)(MeCN)2(tBu-PNzP)][X] (X = Br, BH4), 2·X. Counterion exchange and exposure to CO atmosphere yields the complex cis-[Fe(H)(CO)(MeCN)(tBu-PNzP)][BPh4] 4·BPh4, which upon addition of Bu4NCl forms [Fe(H)(Cl)(CO)(tBu-PNzP)] 5. Complex 5, under basic conditions, catalyzes the hydrogenation of CO2 to formate salts at low H2 pressure. Treatment of complex 5 with a base leads to aggregates, presumably of dearomatized species B, stabilized by bridging to another metal center by coordination of the nitrogen at the backbone of the pyrazine pincer ligand. Upon dissolution of compound B in EtOH the crystallographically characterized complex 7 is formed, comprised of six iron units forming a 6-membered ring. The dearomatized species can activate CO2 and H2 by metal-ligand cooperation (MLC), leading to complex 8, trans-[Fe(PNzPtBu-COO)(H)(CO)], and complex 9, trans-[Fe(H)2(CO)(tBu-PNzP)], respectively. Our results point at a very likely mechanism for CO2 hydrogenation involving MLC.

  11. catena-Poly[[aquabis(4-formylbenzoato-κ2O1,O1′cadmium]-μ-pyrazine-κ2N:N′

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    Fatih Çelik

    2014-02-01

    Full Text Available The polymeric title compound, [Cd(C8H5O32(C4H4N2(H2O]n, contains two 4-formylbenzoate (FB anions, one pyrazine molecule and one coordinating water molecule; the FB anions act as bidentate ligands. The O atom, the aldehyde H atom and the benzene ring of one of the FB anions are disordered over two positions. The O atoms were freely refined [refined occupancy ratio 0.79 (2:0.21 (2], while the aldehyde H atoms and the benzene ring atoms were refined with fixed occupancy ratios of 0.8:0.2 and 0.5:0.5, respectively. In the ordered FB anion, the carboxylate group is twisted away from the attached benzene ring (A by 22.7 (8°. In the disordered FB anion, the corresponding angles are 15.6 (10 and 11.4 (11° for rings B and B′, respectively. Benzene rings A and B are oriented at a dihedral angle of 24.2 (7, A and B′ at 43.0 (8°. The pyrazine ring makes dihedral angles of 67.5 (4, 89.6 (7 and 86.2 (7°, respectively, with benzene rings A, B and B′. The pyrazine ligands bridge the CdII cations, forming polymeric chains running along the b-axis direction. In the crystal, O—Hwater ... Ocarboxylate hydrogen bonds link adjacent chains into layers parallel to the bc plane. These layers are linked via C—Hpyrazine ... Oformyl hydrogen bonds, forming a three-dimensional network. π–π interactions [centroid–centroid distances = 3.870 (11–3.951 (5 Å] further stabilize the crystal structure. There is also a weak C—H...π interaction present.

  12. Three new three-dimensional organic-inorganic hybrid compounds based on PMo12O40(n-) (n = 3 or 4) polyanions and Cu(I)-pyrazine/Cu(I)-pyrazine-Cl porous coordination polymers.

    Science.gov (United States)

    Qi, Ming-Li; Yu, Kai; Su, Zhan-Hua; Wang, Chun-Xiao; Wang, Chun-Mei; Zhou, Bai-Bin; Zhu, Chun-Cheng

    2013-06-07

    Three new organic-inorganic hybrid compounds based on PMo12O40(n-) (n = 3 or 4) polyanions and Cu(I)-pz/Cu(I)-pz-Cl porous coordination polymers: [Cu(I)(pz)]3[PMo(VI)12O40] (1), [Cu(I)(pz)1.5]4[PMo(V)Mo(VI)11O40]·pz·2H2O (2), [Cu(I)3(pz)3Cl][Cu(I)2(pz)3(H2O)][PMo(V)Mo(VI)11O40] (3) (pz = pyrazine) have been hydrothermally prepared and characterized by elemental analysis, IR, TG, XRD, XPS and single-crystal X-ray diffraction. Compound 1 presents a three-dimensional Cu(I)-pz framework with cube-like chambers, into which PMo(VI)12O40(3-) Keggin ions are incorporated. Compound 2 shows a three-dimensional sandwich-like framework, and PMo(V)Mo(VI)11O40(4-) polyanions are located in the octagonal voids of every two-dimensional Cu(I)-pz 4(1)8(2) network structure. Compound 3 exhibits a two-dimensional Cl-bridged Cu(I)-pz-Cl double-layer structure, and two kinds of PMo(V)Mo(VI)11O40(4-) polyanions as bridging linkers connect two adjacent double-layers to form a three-dimensional organic-inorganic framework through Cu(I)-O bonds. Additionally, their electrochemical characters, electrocatalytic behaviors and solid state fluorescent properties at room temperature have been investigated in detail.

  13. Effect of deuteration on the structural and magnetic properties of CuF{sub 2}(H{sub 2}O){sub 2}(pyrazine)

    Energy Technology Data Exchange (ETDEWEB)

    Schlueter, J.A., E-mail: JASchlueter@anl.go [Materials Science Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Park, H. [Materials Science Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Manson, J.L. [Department of Chemistry and Biochemistry, Eastern Washington University, Cheney, WA 99004 (United States); Nakotte, H. [LANSCE, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Physics Department, New Mexico State University, Las Cruces, NM 88003 (United States); Schultz, A.J. [X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439 (United States)

    2010-06-01

    The strongest magnetic exchange interactions in the quasi-two dimensional coordination polymer CuF{sub 2}(H{sub 2}O){sub 2}(pyz) (pyz=pyrazine), lie within the CuF{sub 2}(H{sub 2}O){sub 2} plane and involve F...H-O hydrogen bonds. In order to better understand this novel magnetic exchange pathway, the fully deuterated derivative of this complex was prepared. The structural and magnetic properties of this isotopically substituted derivative are reported. A slight contraction of the unit cell and reduction in the Neel temperature was observed.

  14. Bis[3-(pyrazin-2-yl-5-(pyridin-2-yl-κN-1,2,4-triazol-1-ido-κN1]copper(II

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    Zhi-Liang Liu

    2012-05-01

    Full Text Available In the mononuclear title complex, [Cu(C11H7N62], the CuII atom lies on a crystallographic inversion centre and is coordinated by four N atoms from two bidentate chelate monoanionic 3-(pyrazin-2-yl-5-(pyridin-2-yl-1,2,4-triazol-1-ido ligands, two from the triazolide rings [Cu—N = 1.969 (2 Å] and two from the pyridine rings [Cu—N = 2.027 (2 Å], giving a slightly distorted square-planar geometry.

  15. Coherent quantum control of internal conversion: {S}_{2}\\;\\leftrightarrow \\;{S}_{1} in pyrazine via {S}_{0}\\;\\to \\;{S}_{2}/{S}_{1} weak field excitation

    Science.gov (United States)

    Grinev, Timur; Shapiro, Moshe; Brumer, Paul

    2015-09-01

    Coherent control of internal conversion (IC) between the first (S1) and second (S2) singlet excited electronic states in pyrazine, where the S2 state is populated from the ground singlet electronic state S0 by weak field excitation, is examined. Control is implemented by shaping the laser which excites S2. Excitation and IC are considered simultaneously, using the recently introduced resonance-based control approach. Highly successful control is achieved by optimizing both the amplitude and phase profiles of the laser spectrum. The dependence of control on the properties of resonances in S2 is demonstrated.

  16. Synthesis and in vitro cytotoxic evaluation of 2-hydrazinylpyrido[2,3-6]pyrazin-3(4H)-one derivatives

    Institute of Scientific and Technical Information of China (English)

    Guo Gang Zhang; Ya Jing Liu; Xiao Guang Ma; Hao Dong; Ju Li; Ping Gong

    2011-01-01

    A series of novel 2-hydrazinylpyrido[2,3-b]pyrazin-3(4H)-one derivatives were synthesized and evaluated for their cytotoxic activities against A549, MDA-MB-231 and HT-29 cell lines in vitro. Pharmacological data indicated that compounds 5b, 5c, 10a and 10g possessed marked cytotoxicity, especially 10a (with IC50 values of 0.81, 2.56 and 1.63 μmol/L against A549, MDA-MB-231 and HT29 cell lines, respectively), which had emerged as a lead compound.

  17. Bis[5-(2-pyrid­yl)pyrazine-2-carbonitrile]­silver(I) tetra­fluorido­borate

    OpenAIRE

    Chong-Qing Wan; Fan Zhang; Zi-Jia Wang

    2010-01-01

    In the title mononuclear complex, [Ag(C10H6N4)2]BF4, the AgI atom adopts a square-planar N4 coordination geometry and is surrounded by two 5-(2-pyridyl)pyrazine-2-carbonitrile ligands. The tetrafluoridoborate anions link the mononuclear cations through intermolecular C—H...F hydrogen-bonding interactions, forming an infinite tape structure along [110]. Other weak interactions occur: π–π stacking with centroid–centroid distances of 3.820̳...

  18. Synthesis and Biological Evaluation of Novel 8-Morpholinoimidazo[1,2-a]pyrazine Derivatives Bearing Phenylpyridine/Phenylpyrimidine-Carboxamides

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    Shan Xu

    2017-02-01

    Full Text Available Herein we designed and synthesized three series of novel 8-morpholinoimidazo[1,2-a]pyrazine derivatives bearing phenylpyridine/phenylpyrimidine-carboxamides (compounds 12a–g, 13a–g and 14a–g. All the compounds were evaluated for their IC50 values against three cancer cell lines (A549, PC-3 and MCF-7. Most of the target compounds exhibited moderate cytotoxicity against the three cancer cell lines. Two selected compounds 14b, 14c were further tested for their activity against PI3Kα kinase, and the results indicated that compound 14c showed inhibitory activity against PI3Kα kinase with an IC50 value of 1.25 μM. Structure-activity relationships (SARs and pharmacological results indicated that the replacement of the thiopyranopyrimidine with an imidazopyrazine was beneficial for the activity and the position of aryl group has a significant influence to the activity of these compounds. The compounds 13a–g in which an aryl group substituted at the C-4 position of the pyridine ring were more active than 12a–g substituted at the C-5 position. Moreover, the cytotoxicity of compounds 14a–g bearing phenylpyrimidine-carboxamides was better than that of the compounds 12a–g, 13a–g bearing phenylpyridine-carboxamides. Furthermore, the substituents on the benzene ring also had a significant impact on the cytotoxicity and the pharmacological results showed that electron donating groups were beneficial to the cytotoxicity.

  19. Spectroscopic, quantum chemical studies, Fukui functions, in vitro antiviral activity and molecular docking of 5-chloro-N-(3-nitrophenyl)pyrazine-2-carboxamide

    Science.gov (United States)

    Sebastian, S. H. Rosline; Al-Alshaikh, Monirah A.; El-Emam, Ali A.; Panicker, C. Yohannan; Zitko, Jan; Dolezal, Martin; VanAlsenoy, C.

    2016-09-01

    The molecular structural parameters and vibrational frequencies of 5-chloro-N-(3-nitrophenyl)pyrazine-2-carboxamide have been obtained using density functional theory technique in the B3LYP approximation and CC-pVDZ (5D, 7F) basis set. Detailed vibrational assignments of observed FT-IR and FT-Raman bands have been proposed on the basis of potential energy distribution and most of the modes have wavenumbers in the expected range. In the present case, the NH stretching mode is a doublet in the IR spectrum with a difference of 138 cm-1 and is red shifted by 76 cm-1 from the computed value, which indicates the weakening of NH bond resulting in proton transfer to the neighboring oxygen atom. The molecular electrostatic potential has been mapped for predicting sites and relative reactivities towards electrophilic and nucleophilic attack. The hyperpolarizability values are calculated in order to find its role in nonlinear optics. From the molecular docking study, amino acids Asn161, His162 forms H-bond with pyrazine ring and Trp184, Gln19 shows H-bond with Cdbnd O group and the docked ligand, title compound forms a stable complex with cathepsin K and the results suggest that the compound might exhibit inhibitory activity against cathepsin K. Moderate in vitro antiviral activity with EC50 at tens of μM was detected against feline herpes virus, coxsackie virus B4, and influenza A/H1N1 and A/H3N2.

  20. Synthesis and Crystal Structure of a Three-dimensional Mn(Ⅱ) Coordination Polymer with 3-(Pyrazin-2-yloxy)-pyridine and Azide Anion as Mixed Bridge Ligand

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A three-dimensional coordination polymer [Mn2((1,3-N3)4(μ-PP)2]n (PP = 3-(pyra- zin-2-yloxy)-pyridine) has been synthesized with 3-(pyrazin-2-yloxy)-pyridine and azide anion as mixed bridge ligand, and its crystal structure was determined by X-ray crystallography. The crystal data: triclinic system, space group P, with a = 6.794(4), b = 9.885(6), c = 9.947(6)A, α = 64.170(6),β = 84.190(8),γ = 85.319(8)°, V = 597.7(6)(A)3, Z = 1, C18H14Mn2N18O2, Mr = 624.35, Dc = 1.735 g/cm3, F(000) = 314 andμ= 1.117 mm-1. In the crystal, the azide anion acts as a bridge ligand and makes adjacent Mn(Ⅱ) ions connect into a two-dimensional sheet on the ab plane, then 3-(pyrazin-2-yloxy)-pyridine serves as a bidentate bridge ligand to connect neighboring sheets along the c axis, and finally a three-dimensional structure is formed.

  1. Low Band Gap Donor–Acceptor Type Polymers Containing 2,3-Bis(4-(decyloxyphenylpyrido[4,3-b]pyrazine as Acceptor and Different Thiophene Derivatives as Donors

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    Yan Zhang

    2016-10-01

    Full Text Available Four donor–acceptor type conducting polymers, namely poly(2,3-bis(4-decyloxyphenyl-5,8-bis(4-thiophen-2-ylpyrido[4,3-b]pyrazine (P1, poly(2,3-bis(4-decyloxyphenyl-5,8-bis(4-butylthiophen-2-ylpyrido[4,3-b]pyrazine (P2, poly(2,3-bis(4-(decyloxyphenyl-5,8-bis(4-hexyloxythiophen-2-ylpyrido[4,3-b]pyrazine (P3 and poly(2,3-bis(4-(decyloxyphenyl-5,8-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-ylpyrido[4,3-b]pyrazine (P4, containing thiophene or its derivative as the donor and pyrido[4,3-b]pyrazine as the acceptor were prepared and characterized by cyclic voltammetry, scanning electron microscopy, and UV-Vis spectroscopy to detect the influence of the donor units’ strength on the electrochromic performances. The results demonstrated that all of the polymers could be reversibly reduced and oxidized by p-type doping and n-type doping, and showed near-infrared activities and different color changes in p-type doping process. Especially, P3 and P4 showed lower optical band gap than P1 and P2 due to the strong electron-donating hexyloxythiophen group of P3 and ethylenedioxythiophene group of P4. Besides, P3 and P4 displayed the saturated green color at the neutral state and the desirable transparency at the oxidized state. All the polymers displayed desirable optical contrasts, satisfactory coloration efficiency, excellent stability and short switching time, which made the polymers fascinating candidates in the electrochromic device applications.

  2. Effect of Spin-Crossover-Induced Pore Contraction on CO2–Host Interactions in the Porous Coordination Polymers [Fe(pyrazine)M(CN)4] (M = Ni, Pt)

    Energy Technology Data Exchange (ETDEWEB)

    Culp, Jeffrey T; Chen, De-Li; Liu, Jinchen; Chirdon, Danielle; Kauffman, Kristi; Goodman, Angela; Johnson, J Karl

    2013-02-01

    Variable-temperature in situ ATR-FTIR spectra are presented for the porous spin-crossover compounds [Fe(pyrazine)Ni(CN)4] and [Fe(pyrazine)Pt(CN)4] under CO2 pressures of up to 8 bar. Significant shifts in the ν3 and ν2 IR absorption bands of adsorbed CO2 are observed as the host materials undergo transition between low- and high-spin states. Computational models used to determine the packing arrangement of CO2 within the pore structures show a preferred orientation of one of the adsorbed CO2 molecules with close O=C=O···H contacts with the pyrazine pillar ligands. The interaction is a consequence of the commensurate distance of the inter-pyrazine separations and the length of the CO2 molecule, which allows the adsorbed CO2 to effectively bridge the pyrazine pillars in the structure. The models were used to assign the distinct shifts in the IR absorption bands of the adsorbed CO2 that arise from changes in the O=C=O···H contacts that strengthen and weaken in correlation with changes in the Fe–N bond lengths as the spin state of Fe changes. The results indicate that spin-crossover compounds can function as a unique type of flexible sorbent in which the pore contractions associated with spin transition can affect the strength of CO2–host interactions.

  3. A series of Keggin-based compounds constructed by conjugate ring-rich pyrazine and quinoxaline derivatives.

    Science.gov (United States)

    Tian, Aixiang; Tian, Yan; Ning, Yali; Hou, Xue; Ni, Huaiping; Ji, Xuebin; Liu, Guocheng; Ying, Jun

    2016-09-21

    Through the use of conjugate ring-rich pyrazine and quinoxaline derivatives, five new Keggin polymolybdate based compounds, [Ag(I)3L(1)2(H2O)2(PMo12O40)] (1), [Ag(I)4L(1)5(SiMo12O40)] (2), [Ag(I)6L(2)6(PMo12O40)2] (3), [Ag(I)2L(2)2(C16H36N)2](SiMo12O40)] (4), [Cu(I)3L(2)3(PMo12O40)] (5) (L(1) = 2,3-diphenylpyrazine, L(2) = 2,3-diphenylquinoxaline, C16H36N = tetrabutylammonium), were synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction. In compound 1, three Ag(I) ions are fused by two L(1) molecules to form a [Ag3L(1)2](3+) subunit, and these subunits link the PMo12 anions to construct two kinds of 1D chains (I and II). Chains I and II connect to each other by sharing the same PMo12 anions and a 2D grid-like layer is built. The asymmetric unit of compound 2 is linked to form a dimer by sharing Ag ions, and a 1D double strand is formed. The SiMo12 anions connect adjacent 1D double strands through Ag3-O23 bonds and a 2D network is built. In compound 3, there exists a 1D ladder-like double chain with PMo12 anions as linking bars. A 2D layer is formed by linkage Ag2-O24 between adjacent chains. In compound 4, the PMo12 anions act as inorganic linkages to connect adjacent zigzag chains through Ag1-O3 bonds to construct a 2D grid-like layer. In compound 5 two Cu(I)-L(2) lines are fused by PMo12 anions to build a 1D ladder-like chain. Additionally, the electrochemical and photocatalytic properties of the title compounds have been studied.

  4. Crystal structures of N(2),N(3),N(5),N(6)-tetra-kis-(pyridin-2-ylmeth-yl)pyrazine-2,3,5,6-tetra-carboxamide and N(2),N(3),N(5),N(6)-tetra-kis-(pyridin-4-ylmeth-yl)pyrazine-2,3,5,6-tetra-carboxamide.

    Science.gov (United States)

    Cati, Dilovan S; Stoeckli-Evans, Helen

    2017-02-01

    The title compounds, C32H28N10O4· unknown solvent, (I), and C32H28N10O4, (II), are pyrazine-2,3,5,6-tetra-carboxamide derivatives. In (I), the substituents are (pyridin-2-ylmeth-yl)carboxamide, while in (II), the substituents are (pyridin-4-ylmeth-yl)carboxamide. Both compounds crystallize in the monoclinic space group P21/n, with Z' = 1 for (I), and Z' = 0.5 for (II). The whole mol-ecule of (II) is generated by inversion symmetry, the pyrazine ring being situated about a center of inversion. In (I), the four pyridine rings are inclined to the pyrazine ring by 83.9 (2), 82.16 (18), 82.73 (19) and 17.65 (19)°. This last dihedral angle involves a pyridine ring that is linked to the adjacent carboxamide O atom by an intra-molecular C-H⋯O hydrogen bond. In compound (II), the unique pyridine rings are inclined to the pyrazine ring by 33.3 (3) and 81.71 (10)°. There are two symmetrical intra-molecular C-H⋯O hydrogen bonds present in (II). In the crystal of (I), mol-ecules are linked by N-H⋯O and N-H⋯N hydrogen bonds, forming layers parallel to (10-1). The layers are linked by C-H⋯O and C-H⋯N hydrogen bonds, forming a three-dimensional framework. In the crystal of (II), mol-ecules are linked by N-H⋯N hydrogen bonds, forming chains propagating along the [010] direction. The chains are linked by a weaker N-H⋯N hydrogen bond, forming layers parallel to the (101) plane, which are in turn linked by C-H⋯O hydrogen bonds, forming a three-dimensional structure. In the crystal of compound (I), a region of disordered electron density was treated with the SQUEEZE routine in PLATON [Spek (2015 ▸). Acta Cryst. C71, 9-18]. Their contribution was not taken into account during refinement. In compound (II), one of the pyridine rings is positionally disordered, and the refined occupancy ratio for the disordered Car-Car-Npy atoms is 0.58 (3):0.42 (3).

  5. Crystal structures of N 2,N 3,N 5,N 6-tetra­kis­(pyridin-2-ylmeth­yl)pyrazine-2,3,5,6-tetra­carboxamide and N 2,N 3,N 5,N 6-tetra­kis­(pyridin-4-ylmeth­yl)pyrazine-2,3,5,6-tetra­carboxamide

    Science.gov (United States)

    Cati, Dilovan S.; Stoeckli-Evans, Helen

    2017-01-01

    The title compounds, C32H28N10O4· unknown solvent, (I), and C32H28N10O4, (II), are pyrazine-2,3,5,6-tetra­carboxamide derivatives. In (I), the substituents are (pyridin-2-ylmeth­yl)carboxamide, while in (II), the substituents are (pyridin-4-ylmeth­yl)carboxamide. Both compounds crystallize in the monoclinic space group P21/n, with Z′ = 1 for (I), and Z′ = 0.5 for (II). The whole mol­ecule of (II) is generated by inversion symmetry, the pyrazine ring being situated about a center of inversion. In (I), the four pyridine rings are inclined to the pyrazine ring by 83.9 (2), 82.16 (18), 82.73 (19) and 17.65 (19)°. This last dihedral angle involves a pyridine ring that is linked to the adjacent carboxamide O atom by an intra­molecular C—H⋯O hydrogen bond. In compound (II), the unique pyridine rings are inclined to the pyrazine ring by 33.3 (3) and 81.71 (10)°. There are two symmetrical intra­molecular C—H⋯O hydrogen bonds present in (II). In the crystal of (I), mol­ecules are linked by N—H⋯O and N—H⋯N hydrogen bonds, forming layers parallel to (10-1). The layers are linked by C—H⋯O and C—H⋯N hydrogen bonds, forming a three-dimensional framework. In the crystal of (II), mol­ecules are linked by N—H⋯N hydrogen bonds, forming chains propagating along the [010] direction. The chains are linked by a weaker N—H⋯N hydrogen bond, forming layers parallel to the (101) plane, which are in turn linked by C—H⋯O hydrogen bonds, forming a three-dimensional structure. In the crystal of compound (I), a region of disordered electron density was treated with the SQUEEZE routine in PLATON [Spek (2015 ▸). Acta Cryst. C71, 9–18]. Their contribution was not taken into account during refinement. In compound (II), one of the pyridine rings is positionally disordered, and the refined occupancy ratio for the disordered Car—Car—Npy atoms is 0.58 (3):0.42 (3). PMID:28217363

  6. Microwave-assisted Solvent-free Synthesis and in Vitro Antibacterial Screening of Quinoxalines and Pyrido[2, 3b]pyrazines

    Directory of Open Access Journals (Sweden)

    Javier Peralta-Cruz

    2012-05-01

    Full Text Available We report herein the microwave assisted synthesis, without solvents and catalysts, of 6-substituted quinoxalines and 7-substituted pyrido[2,3b]pyrazines. The compounds were obtained in good yields and short reaction times using the mentioned procedure and two new structures are reported. A complete 1H- and 13C-NMR assignment was performed using 1D and 2D-NMR. Additionally, an in vitro screening was performed on Gram-positive and Gram-negative bacteria using amoxicillin as positive reference. Compounds bearing a pyridyl group tended to have higher antibacterial activity, but the best activity against Bacillus subtilis and Proteus mirabilis was observed with quinoxaline derivatives.

  7. Diaquabis[5-(pyrazin-2-yl-3-(pyridin-4-yl-1H-1,2,4-triazol-1-ido-κN1]zinc

    Directory of Open Access Journals (Sweden)

    Bo Li

    2012-02-01

    Full Text Available The title mononuclear complex, [Zn(C11H7N62(H2O2], is composed of one ZnII ion, two deprotonated ppt ligands [Hppt = 5-(pyrazin-2-yl-3-(pyridin-4-yl-1H-1,2,4-triazole] and two coordinating water molecules. The asymmetric unit consists of one half-molecule that is completed by application of a centre of symmetry. The ZnII atom is six-coordinated in an octahedral environment, surrounded by two O atoms in the axial positions and four N atoms in the equatorial plane. Adjacent mononuclear units are further linked via O—H...N hydrogen-bonding interactions, forming a two-dimensional network along (100.

  8. Synthesis of the new ring system bispyrido[4',3':4,5]pyrrolo [1,2-a:1',2'-d]pyrazine and its deaza analogue.

    Science.gov (United States)

    Parrino, Barbara; Spanò, Virginia; Carbone, Anna; Barraja, Paola; Diana, Patrizia; Cirrincione, Girolamo; Montalbano, Alessandra

    2014-08-29

    Derivatives of the new ring systems bispyrido[4',3':4,5]pyrrolo[1,2-a:1',2'-d] pyrazine-6,13-dione and its deaza analogue pyrido[4'',3'':4',5']pyrrolo-[1',2':4,5]pyrazino [1,2-a]indole-6,13-dione were conveniently synthesized through a four-step sequence. Symmetrical derivatives of the former ring system were obtained through self condensation. On the other hand, condensation of 6-azaindole carboxylic acid with indole 2-carboxylic acid afforded the deaza analogue ring system. Derivatives of the title ring system were tested by the National Cancer Institute (Bethesda, MD, USA) and four of them exhibited modest activity against MCF7 (a breast cancer cell line) and/or UO-31 (a renal cancer cell line).

  9. Synthesis of the New Ring System Bispyrido[4',3':4,5]pyrrolo [1,2-a:1',2'-d]pyrazine and Its Deaza Analogue

    Directory of Open Access Journals (Sweden)

    Barbara Parrino

    2014-08-01

    Full Text Available Derivatives of the new ring systems bispyrido[4',3':4,5]pyrrolo[1,2-a:1',2'-d] pyrazine-6,13-dione and its deaza analogue pyrido[4'',3'':4',5']pyrrolo-[1',2':4,5]pyrazino [1,2-a]indole-6,13-dione were conveniently synthesized through a four-step sequence. Symmetrical derivatives of the former ring system were obtained through self condensation. On the other hand, condensation of 6-azaindole carboxylic acid with indole 2-carboxylic acid afforded the deaza analogue ring system. Derivatives of the title ring system were tested by the National Cancer Institute (Bethesda, MD, USA and four of them exhibited modest activity against MCF7 (a breast cancer cell line and/or UO-31 (a renal cancer cell line.

  10. Discovery of 8-Amino-imidazo[1,5-a]pyrazines as Reversible BTK Inhibitors for the Treatment of Rheumatoid Arthritis.

    Science.gov (United States)

    Liu, Jian; Guiadeen, Deodial; Krikorian, Arto; Gao, Xiaolei; Wang, James; Boga, Sobhana Babu; Alhassan, Abdul-Basit; Yu, Younong; Vaccaro, Henry; Liu, Shilan; Yang, Chundao; Wu, Hao; Cooper, Alan; de Man, Jos; Kaptein, Allard; Maloney, Kevin; Hornak, Viktor; Gao, Ying-Duo; Fischmann, Thierry O; Raaijmakers, Hans; Vu-Pham, Diep; Presland, Jeremy; Mansueto, My; Xu, Zangwei; Leccese, Erica; Zhang-Hoover, Jie; Knemeyer, Ian; Garlisi, Charles G; Bays, Nathan; Stivers, Peter; Brandish, Philip E; Hicks, Alexandra; Kim, Ronald; Kozlowski, Joseph A

    2016-02-11

    Bruton's tyrosine kinase (BTK) is a Tec family kinase with a well-defined role in the B cell receptor (BCR) pathway. It has become an attractive kinase target for selective B cell inhibition and for the treatment of B cell related diseases. We report a series of compounds based on 8-amino-imidazo[1,5-a]pyrazine that are potent reversible BTK inhibitors with excellent kinase selectivity. Selectivity is achieved through specific interactions of the ligand with the kinase hinge and driven by aminopyridine hydrogen bondings with Ser538 and Asp539, and by hydrophobic interaction of trifluoropyridine in the back pocket. These interactions are evident in the X-ray crystal structure of the lead compounds 1 and 3 in the complex with the BTK enzyme. Our lead compounds show desirable PK profiles and efficacy in the preclinical rat collagen induced arthritis model.

  11. Incorporation of Pyrazine and Bipyridine Linkers with High-Spin Fe(II) and Co(II) in a Metal–Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Kawamura, Airi; Greenwood, Arin R.; Filatov, Alexander S.; Gallagher, Audrey T.; Galli, Giulia; Anderson, John S.

    2017-02-27

    A series of isoreticular metal organic frameworks (MOFs) of the formula M(BDC)(L) (M = Fe(II) or Co(II), BDC = 1,4-benzenedicarboxylate, L = pyrazine (pyz) or 4,4'-bipyridine (bipy)) has been synthesized and characterized by N-2 gas uptake Measurements, single crystal and powder X-ray diffraction, magnetometry, X-ray absorption spectroscopy, and Mossbauer spectroscopy. These studies indicate the formation of a permanently porous solid with high-spin Fe(II) and Co(II) centers that are weakly coupled, consistent with first-principles density functional theory calculations. This family of materials represents unusual examples of paramagnetic metal centers coordinated by linkers capable of mediating magnetic or electronic coupling in a porous framework. While only weak interactions are observed, the rigid 3D framework of the MOF dramatically impacts the properties of these materials when compared with close structural analogues.

  12. Property study of poly nitro compounds of cis-syn-cis-2, 6-dioxodecahydro-lH, 5H-diimidazo [4, 5-b: 4', 5'-e] pyrazine

    Science.gov (United States)

    Liu, Yang; Xu, Zhibin; Xu, Yudong; Xu, Liang; Meng, Zihui

    2017-03-01

    Poly nitro group substituted cis-syn-cis-2, 6-dioxodecahydro-lH, 5H-diimidazo [4, 5-b: 4', 5'-e] pyrazine derivatives are synthesized by modified method and adequately characterized. All compounds have good performance both in density (ρ> 1.85 g/cm3) and high detonation velocity (vD > 8800 m/s, calculated). Some representative compounds, for example, 4 (vD: 9405 ms-1; P: 41.6 GPa) and 5 (vD:9781 ms-1; P: 45.6 GPa) exhibit excellent detonation performances, which are comparable with current energetic compounds such as RDX (vD: 8724 ms-1; P: 35.2 GPa) and HMX (vD:9059 ms-1; P: 39.2 GPa). Considering the sensitivity increasing with the number of nitro group, two componds with tetranitro groups (2 and 3) are worthy of deep research.

  13. Design and synthesis of new imidazo[1,2-a]pyridine and imidazo[1,2-a]pyrazine derivatives with antiproliferative activity against melanoma cells.

    Science.gov (United States)

    Garamvölgyi, Rita; Dobos, Judit; Sipos, Anna; Boros, Sándor; Illyés, Eszter; Baska, Ferenc; Kékesi, László; Szabadkai, István; Szántai-Kis, Csaba; Kéri, György; Őrfi, László

    2016-01-27

    Melanoma is an aggressive form of skin cancer and it is generally associated with poor prognosis in patients with late-stage disease. Due to the increasing occurrence of melanoma, there is a need for the development of novel therapies. A new series of diarylamide and diarylurea derivatives containing imidazo[1,2-a]pyridine or imidazo[1,2-a]pyrazine scaffold was designed and synthesized to investigate their in vitro efficacy against the A375P human melanoma cell line. We found several compounds expressing submicromolar IC50 values against the A375P cells, from which 15d, 17e, 18c, 18h, 18i demonstrated the highest potencies with IC50 below 0.06 μM.

  14. Carboxylic acid functionalized ortho-linked oxacalix[2]benzene[2]pyrazine: synthesis, structure, hydrogen bond and metal directed self-assembly.

    Science.gov (United States)

    Kong, Ling-Wei; Ma, Ming-Liang; Wu, Liang-Chun; Zhao, Xiao-Li; Guo, Fang; Jiang, Biao; Wen, Ke

    2012-05-14

    Cyclooligomerization of 2,6-dichloropyrazine 4 and benzyl 2,3-dihydroxybenzoate 5 under microwave irradiation resulted in a racemic pair of ester functionalized ortho-linked oxacalix[2]benzene[2]pyrazine 6, which was further transformed to the corresponding racemic carboxylic acid functionalized ortho-linked oxacalix[2]benzene[2]pyrazine 3. Both enantiomers of 3 adopt 1,3-alternate conformations with their two carboxylic acid groups pointing to opposite directions in the solid state. Enantiomers of 3 form a step-like one-dimensional supramolecular polymer via intermolecular hydrogen bond interactions between the carboxylic acids for crystals obtained in methanol. No hydrogen bonds were formed between the carboxylic acids for crystals of 3 obtained in pyridine and aqueous guanidine solutions; instead, intermolecular hydrogen bonds between the carboxylic acid groups of 3 and pyridine, as well as guanidinium ions were formed. Under metal-mediated self-assembly conditions, the pyrazinyl nitrogen atoms in 3 interacted with transition metal ions, such as Ag(I), Cu(II) and Zn(II), and resulted in the formation of four new metal-containing supramolecular complexes. Metallomacrocycles 7, 8 and 9 were formed by reactions of 3 with Ag(I) or Cu(II) ions by bridging two ligands 3 in the equatorial region via M-N coordination bonds. A one-dimensional coordination polymer 10 was generated by reaction between ligand 3 and Zn(II) ions, and a cage-based structure is presented in 10 by bridging of the cyclophane units by Zn(2+) ions via Zn-N and Zn-O bonds.

  15. Modeling the active site of [FeFe]-hydrogenase: Electro-catalytic hydrogen evolution from acetic acid catalysed by [Fe2(-L)(CO)6] and [Fe2(-L)(CO)5(PPh3)] (L=pyrazine-2, 3-dithiolate, quinoxaline-2, 3-dithiolate and pyrido[2,3-b] pyrazine-2, 3-dithiolate)

    Indian Academy of Sciences (India)

    Gummadi Durgaprasad; Samar K Das

    2015-02-01

    Compounds [Fe2{-pydt}(CO)6] (pydt = pyrazine-2,3-dithiolate) (1), [Fe2{-qdt}(CO)6] (qdt = quinoxaline-2,3-dithiolate) (2), [Fe2{-ppdt}CO)6] (ppdt = pyrido[2,3-b]pyrazine-2,3-dithiolate) (3), [Fe2{-pydt}(CO)5PPh3] (4), [Fe2{-qdt}(CO)5PPh3] (5) and [Fe2{-ppdt}(CO)5PPh3] (6) have been synthesized in order to model the active sites of `[FeFe]-hydrogenase’. Compounds 1–6 have been characterized by routine spectral studies and unambiguously by single crystal X-ray crystallography. Supramolecular chemistry of compounds 1–6 have been described in terms of intermolecular interactions, observed in their respective crystal structures. Electro-catalytic hydrogen evaluation studies (from acetic acid) have been performed using compounds 1–6 as electro-catalysts. The mechanistic aspects of relevant electro–catalytic proton reductions have been discussed in detail.

  16. Hydrothermal Synthesis, Crystal Structure and Thermal Analyses of Pyrazine-2,3-dicarboxylic Acid Bridged Co(II) Coordination Polymer of 2∞[Co(phen) (μ-L)3/3]·H2O (H2L = Pyrazine-2,3-dicarboxylic Acid)

    Institute of Scientific and Technical Information of China (English)

    ZHANG Bi-Song

    2005-01-01

    A novel pyrazine-2,3-dicarboxylic acid bridged Co(II) phen complex2∞[Co- (phen)(μ-L)3/3]·H2O (H2L = pyrazine-2,3-dicarboxylic acid) has been hydrothermally synthesized, and X-ray single-crystal diffraction analysis shows that it crystallizes in the monoclinic system, space group P21/n with a = 11.480(2), b = 11.885(2), c = 12.939(3) (A), β = 110.55(3)°, V = 1653.1(6) (A)3, Mr = 423.25, Dc = 0.425 g/cm3, Z = 4, R = 0.0361 and wR = 0.1011. The title complex consists of 2D 2∞ [Co(phen)(μ-L)3/3] layers and crystal water molecules. Each Co atom is octahedrally coordinated by three N atoms and three O atoms to form 2D 2∞[Co(phen)(μ-L)3/3] polymeric layers. Furthermore, such 2D layers are stacked into 3D supramolecular frameworks via Van der Waals' intermolecular forces, strong and weak hydrogen-bond interactions. The coordination phen and crystal water molecules are resided into cavities of the frameworks.

  17. 1,2,3-Triazolo[4,5,-e]furazano[3,4,-b]pyrazine 6-oxide--a fused heterocycle with a roving hydrogen forms a new class of insensitive energetic materials.

    Science.gov (United States)

    Thottempudi, Venugopal; Yin, Ping; Zhang, Jiaheng; Parrish, Damon A; Shreeve, Jean'ne M

    2014-01-01

    The straightforward synthesis and energetic properties of a new class of energetic materials, 1,2,3-triazolo- [4,5-e]furazano[3,4-b]pyrazine 6-oxide and its energetic salts are described. They were characterized by IR and multinuclear NMR spectroscopy, elemental analysis, differential scanning calorimetry, and single-crystal X-ray diffraction are given. The X-ray structures show that in the title compound, the hydrogen atom is bonded to the nitrogen in the pyrazine ring; however, in the salts, the negative charge is associated with the triazole nitrogen. Heats of formation for all compounds were calculated with the G2 method and then combined with experimentally determined densities to obtain detonation pressures (P) and velocities (D) by using EXPLO5 program. These new materials exhibit good densities and thermal stabilities, high heats of formation, acceptable detonation properties, and are insensitive to impact.

  18. Synthesis, stereochemical, structural, and biological studies of a series of N‧-(2r,4c-diaryl-3-azabicyclo[3.3.1]nonan-9-ylidene)pyrazine-2-carbohydrazides

    Science.gov (United States)

    Mangalam, M.; Sebastian Antony Selvan, C.; Sankar, C.

    2017-02-01

    A new series of N‧-(2r,4c-diaryl-3-azabicyclo[3.3.1]nonan-9-ylidene)pyrazine-2-carbohydrazides (8-14) were synthesized by the corresponding 2r,4c-diaryl-3-azabicyclo[3.3.1]nonan-9-ones (1-7) reaction with pyrazine-2-carbohydrazide. The stereochemistry of the newly synthesized compounds were unambiguously assigned using FT-IR, 1H, 13C, and 2D (COSY, HSQC, HMBC, ROESY) nuclear magnetic resonance (NMR) spectral data. The chemical shifts suggest that all these compounds adopt twin-chair conformation with equatorial orientation of aryl substitutions in solution. Hydrazones were screened for their in vitro antitubercular activity against Mycobacterium tuberculosis H37Rv and antibacterial activity against a set of pathogenic bacteria. Most of the halogenated compounds showed promising antitubercular and antibacterial activities.

  19. Crystal structure of 5-(4,5-dihydro-1H-imidazol-2-yl-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyrazin-6-amine

    Directory of Open Access Journals (Sweden)

    Joel T. Mague

    2014-11-01

    Full Text Available In the title compound, C15H15N7, the phenyl ring is inclined by 19.86 (5° to the mean plane of the pyrazolo[3,4-b]pyrazine core. In the crystal, N—H...N and C—H...N hydrogen bonds form [010] chains, which stack via π–π interactions [centroid–centroid distance between the pyrazole rings = 3.4322 (7 Å].

  20. Isotypic Mn(II) and Fe(II) binuclear complexes of the ligand 5,6-bis-(pyridin-2-yl)-pyrazine-2,3-di-carb-oxy-lic acid.

    Science.gov (United States)

    Alfonso, Monserrat; Stoeckli-Evans, Helen

    2016-10-01

    The title isotypic complexes, bis-[μ-5,6-bis-(pyridin-2-yl)pyrazine-2,3-di-carboxylato]-κ(4)N(1),O(2),N(6):O(3);κ(4)O(3):N(1),O(2),N(6)-bis-[di-aqua-manganese(II)] tetra-hydrate, [Mn2(C16H8N4O4)2(H2O)4]·4H2O, (I), and bis-[μ-5,6-bis-(pyridin-2-yl)pyrazine-2,3-di-carboxyl-ato]-κ(4)N(1),O(2),N(6):O(3);κ(4)O(3):N(1),O(2),N(6)-bis-[di-aqua-iron(II)] tetrahydrate, [Fe2(C16H8N4O4)2(H2O)4]·4H2O, (II), are, respectively, the mangan-ese(II) and iron(II) complexes of the ligand 5,6-bis-(pyridin-2-yl)-pyrazine-2,3-di-carb-oxy-lic acid. The complete mol-ecule of each complex is generated by inversion symmetry. Each metal ion is coordinated by a pyrazine N atom, a pyridine N atom, two carboxyl-ate O atoms, one of which is bridging, and two water O atoms. The metal atoms have MN2O4 coordination geometries and the complexes have a cage-like structure. In the crystals of both compounds, the complexes are linked by O-H⋯O and O-H⋯N hydrogen bonds involving the coordinating water mol-ecules, forming chains along [100]. These chains are linked by O-H⋯O hydrogen bonds involving the non-coordinating water mol-ecules, forming layers parallel to (011). The layers are linked by pairs of C-H⋯O hydrogen bonds and offset π-π inter-actions, so forming a hydrogen-bonded three-dimensional framework.

  1. Crystal structure of poly[[(acetato-κO{μ3-N-[(pyridin-4-ylmethyl]pyrazine-2-carboxamidato-κ4N:N1,N2:N4]copper(II] dihydrate]: a metal–organic framework (MOF

    Directory of Open Access Journals (Sweden)

    Dilovan S. Cati

    2014-07-01

    Full Text Available The title compound, [Cu(C11H9N4O(CH3CO2]·2H2O (CuL, is a hydrated copper acetate complex of the ligand N-[(pyridin-4-ylmethyl]pyrazine-2-carboxamide (HL. Complex CuL has a metal–organic framework (MOF structure with a 10 (3 network topology. The ligand coordinates in a bidentate and a bis-monodentate manner, bridging three equivalent CuII atoms via the pyridine N atom and the second pyrazine N atom. The CuII atom has a fivefold coordination sphere, CuN4O, being coordinated to three N atoms of the ligand and the acetate O atom in the equatorial plane and to the second pyrazine atom in the apical position. This gives rise to a fairly regular square-pyramidal geometry. In the crystal, the water molecules are linked to each other and to the three-dimensional framework via O—H...O hydrogen bonds. There are also a number of C—H...O hydrogen bonds present within the framework.

  2. Crystalline products isolated from solutions with commercially available 2,3-bis(2-pyridyl)pyrazine (dpp) as reactant: Detection of a dimerized form of dpp

    Science.gov (United States)

    Grove, Hilde; Frøystein, Nils Åge; Sæthre, Leif J.; Sletten, Jorunn

    2006-12-01

    From reaction mixtures of commercially available 2,3-bis(2-pyridyl)pyrazine (dpp) and perchloric acid four different solid products have been isolated and structurally characterized by X-ray crystallography; (dppH 2)(ClO 4) 2·3H 2O ( 1), (dppH 2)(ClO 4) 2 ( 2), (ddppH 2)(ClO 4) 2 ( 3) and (dppH)(ClO 4) ( 4) (dppH is monoprotonated dpp, dppH 2 is the diprotonated dication of dpp, ddppH 2 is the dication 5,5'-bis(2,3-bis(2-pyridyl)pyrazinium), i.e. dimerized dppH). In 1 and 2 the nitrogen atom in both of the pyridyl rings in dpp is protonated. Hydrogen bonding and packing arrangements differ in the two compounds. In 3 a protonated and dimerized form of dpp is found; two 2,3-bis(2-pyridyl)pyrazinium units are connected by a C(sp 2) sbnd C(sp 2) bond in the 5-positions of the pyrazine rings, one pyridyl ring in each dpp moiety being protonated at the nitrogen. Strong intra-cation N sbnd H⋯N bonds between pyridyl rings are present. In 4 the monomeric dppH moieties display the same type of intramolecular hydrogen bonds as found in 3. Upon reacting dpp with copper(II) salts and oxalate, a dinuclear copper (II) complex, [Cu 2(ddpp)(ox) 2(H 2O) 2] (ddpp = 5,5'-bis(2,3-bis(2-pyridyl)pyrazine)), as well as mononuclear [Cu(dpp)(ox)(H 2O)] have been obtained in the same reaction mixtures. In one of the isolated crystalline products a dimer of dpp is found, as described in the case of compound 3, but no protonation has occurred. The crystal structure determination reveals a dinuclear complex with the neutral ddpp (dimerized dpp) as bridging ligand. Oxalate occurs as a bidentate, terminal ligand; water completes the copper coordination sphere. The dinuclear complex cocrystallizes with a mononuclear Cu-dpp-ox complex; in the mixed crystal two mononuclear units replace one dinuclear unit in 25% of the unit cells, thus the average formula is [Cu 2(ddpp)(ox) 2(H 2O) 2] 0.75[{Cu(dpp)(ox)(H 2O)} 2] 0.25·8H 2O ( 5). The monomeric species also crystallizes in the form of compound

  3. Fluorescence, Photophysical Behaviour and DFT Investigation of E,E-2,5-bis[2-(3-pyridyl)ethenyl]pyrazine (BPEP).

    Science.gov (United States)

    Al-Soliemy, Amerah M; Osman, Osman I; Hussein, Mahmoud A; Asiri, Abdullah M; El-Daly, Samy A

    2016-07-01

    E,E-2,5-bis[2-(3-pyridyl)ethenyl]pyrazine (BPEP) has been prepared by aldol condensation between 2,5-dimethylpyrazine and pyridine-3-carboxaldehyde. It is characterized by IR, (1)H NMR, and (13)C NMR. The electronic absorption and emission properties of BPEP were studied in different solvents. BPEP displays a slight solvatochromic effect of the absorption and emission spectrum, indicating a small change in dipole moment of BPEP upon excitation. The dye solutions (1 × 10(-4) M) in CHCl3, EtOH and dioxane give laser emission in blue region upon excitation by a 337.1 nm nitrogen pulse (λ = 337 nm). The tuning range, gain coefficient (α) and emission cross - section (σe) have been determined. Ground and excited states electronic geometric optimizations were performed using density functional theory (DFT) and time-dependent density functional theory (TD-DFT), respectively. A DFT natural bond analysis complemented the ICT. The simulated maximum absorption and emission wavelengths are in line the observed ones in trend, and are proportionally red-shifted with the increase of the solvent polarity. The stability, hardness and electrophilicity of BPEP in different solvents were correlated with the polarity of the elected solvents. BPEP dye displays fluorescence quenching by colloidal silver nanoparticles (AgNPs). The fluorescence data reveal that radiative and non-radiative energy transfer play a major role in the fluorescence quenching mechanism.

  4. Synthesis and spectroscopic characterization of tin(II) and tin(IV) complexes containing 2,3,5,6-tetrakis({alpha}-pyridyl)pyrazine as a bridging ligand

    Energy Technology Data Exchange (ETDEWEB)

    Bitzer, Rodrigo S.; Filgueiras, Carlos A.L. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Quimica]. E-mail: calf@iq.ufrj.br; Teles, Wagner M. [Universidade Federal de Juiz de Fora, MG (Brazil). Dept. de Quimica; Abras, Anuar [Universidade Federal de Minas Gerais, Belo Horizonte, MG (Brazil). Dept. de Fisica; Ardisson, Jose Domingos [Centro de Desenvolvimento da Tecnologia Nuclear CDTN/CNEN, Belo Horizonte, MG (Brazil)

    2005-09-15

    In this work we investigated the reactivity of the nitrogen heterocyclic ligand 2,3,5,6-tetrakis({alpha}-pyridyl)pyrazine, TPP, towards six tin-containing reagents, namely SnCl{sub 2}, SnX{sub 4} (X = Cl or Br), SnRCl{sub 3} (R = Ph or Me), and SnPh{sub 2}Cl{sub 2}. The products were characterized by microanalysis (C, H, N, and Sn), IR spectroscopy (4000-200 cm{sup -1}), {sup 1}H, {sup 13}C{l_brace}{sup 1}H{r_brace}, {sup 13}C-CP/MAS, {sup 119}Sn, and {sup 119}Sn-MAS NMR spectroscopy, as well as by {sup 119}Sn Moessbauer spectroscopy. All reactions yielded bimetallic adducts, in which TPP behaved as a bis-bidentate bridging ligand, binding to each metallic center through two pyridine nitrogen atoms. This coordination mode is so far quite rare and, for the first time, is reported for main group metal-TPP complexes. (author)

  5. Effective spectral densities for system-environment dynamics at conical intersections: S{sub 2}-S{sub 1} conical intersection in pyrazine

    Energy Technology Data Exchange (ETDEWEB)

    Martinazzo, Rocco [Department of Physical Chemistry and Electrochemistry, University of Milan, Via Golgi 19, 20122 Milan (Italy); Hughes, Keith H. [School of Chemistry, Bangor University, Bangor, Gwynedd LL57 2UW (United Kingdom); Martelli, Fausto [Department of Physical Chemistry and Electrochemistry, University of Milan, Via Golgi 19, 20122 Milan (Italy); Departement de Chimie, Ecole Normale Superieure, 24 rue Lhomond, F-75231 Paris cedex 05 (France); Burghardt, Irene, E-mail: irene.burghardt@ens.fr [Departement de Chimie, Ecole Normale Superieure, 24 rue Lhomond, F-75231 Paris cedex 05 (France)

    2010-11-25

    Graphical abstract: The effect of high-dimensional environments on conical intersections can be described by hierarchies of approximate spectral densities, which translate to truncated effective-mode chains in the time domain. Abstract: A recently developed effective-mode representation is employed to characterize the influence of a multi-dimensional environment on the S{sub 2}-S{sub 1} conical intersection in pyrazine, taken as a paradigm case of high-dimensional dynamics at a conical intersection. We consider a simplified model by which four modes are strongly coupled to the electronic subsystem while a number of weakly coupled tuning modes, inducing energy gap fluctuations, are sampled from a spectral density. The latter is approximated by a series of simplified spectral densities which can be cast into a continued-fraction form, as previously demonstrated in Hughes et al. (K.H. Hughes, C.D. Christ, I. Burghardt, J. Chem. Phys. 131 (2009) 124108). In the time domain, the hierarchy of spectral densities translates to truncated effective-mode chains with a Markovian or quasi-Markovian (Rubin type) closure. A sequential deconvolution procedure is employed to generate this chain representation. The implications for the ultrafast dynamics and its representation in terms of reduced-dimensional models are discussed.

  6. The effect of changes in {pi}-conjugated terthienyl systems using thienyl and ethylenedioxybenzene functionalized thieno[3,4-b]pyrazine precursors: Multicolored low band gap polymers

    Energy Technology Data Exchange (ETDEWEB)

    Tarkuc, Simge; Unver, Elif Kose [Department of Chemistry and Polymer Science and Technology, Middle East Technical University, 06531 Ankara (Turkey); Udum, Yasemin Arslan [Institute of Science and Technology, Department of Advanced Technologies, Gazi University, 06570 Ankara (Turkey); Tanyeli, Cihangir [Department of Chemistry and Polymer Science and Technology, Middle East Technical University, 06531 Ankara (Turkey); Toppare, Levent, E-mail: toppare@metu.edu.t [Department of Chemistry and Polymer Science and Technology, Middle East Technical University, 06531 Ankara (Turkey)

    2010-10-01

    New classes of thieno[3,4-b]pyrazines containing thienyl and ethylenedioxy phenyl units on electron-withdrawing moieties of {pi}-conjugated terthienyl were synthesized. The effect of structural differences on electrochemical and optoelectronic properties of the resulting polymers was investigated. Changes in the electronic nature of the functional groups enable to tune the electrochemical properties of the {pi}-conjugated terthienyl monomers by lowering oxidation potential from 0.62 V (DTTP) to 0.56 V (DBTP). Spectroelectrochemical analyses revealed that the neutral polymer (PDBTP) is dark green in its neutral state revealing {pi}-{pi}* transitions in two well-separated bands at 410 and 751 nm. The electronic band gap of polymer, defined as the onset of the {pi}-{pi}* transition, is found to be 1.0 eV. Using the thienyl unit instead of ethylenedioxy phenyl, a red shift in the band gap (0.95 eV) is observed. The polymer, PDTTP, exhibits multicolor electrochromism and can be switched between a dark yellow neutral state, a green intermediate state, and a brown oxidized state. PDBTP also shows a multicolored electrochromic behavior with three distinct states: dark green at the neutral state, a brown intermediate state, and a brown-violet oxidized state.

  7. Benzo[1,2-b:4,5-b’]dithiophene-Pyrido[3,4-b]pyrazine Small-Molecule Donors for Bulk Heterojunction Solar Cells

    KAUST Repository

    Wolf, Jannic Sebastian

    2016-01-22

    We report on the synthesis, material properties and BHJ solar cell characteristics of a set of π-conjugated small-molecule (SM) donors composed of benzo[1,2-b:4,5-b′]dithiophene (BDT) and pyrido[3,4-b]pyrazine (PP) units – examining the perspectives of alkyl-substituted PP acceptor motifs in SM designs. In these systems (SM1-4), both the type of side chains derived from the PP motifs and the presence of ring-substituents on BDT critically impact (i) molecular packing, and (ii) thin-film morphologies and charge transport in BHJ solar cells. With the appropriate side-chain pattern, the ring-substituted analogue SM4 stands out: achieving efficiencies of ca. 6.5% with PC71BM, and fine-scale morphologies comparable to those obtained with some of the best-performing polymer donors in BHJ solar cells. 1H-1H DQ-SQ NMR analyses are used to examine the distinct self-assembly pattern of SM4, expected to factor into the development of the BHJ morphology.

  8. Multilayer multi-configuration time-dependent Hartree method: implementation and applications to a Henon-Heiles Hamiltonian and to pyrazine

    CERN Document Server

    Vendrell, Oriol

    2010-01-01

    The multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method is discussed and a fully general implementation for any number of layers based on the recursive ML-MCTDH algorithm given by Manthe [J. Chem. Phys. {\\bf 128}, 164116 (2008)] is presented. The method is applied first to a generalized Henon-Heiles (HH) Hamiltonian. For 6D HH the overhead of ML-MCTDH makes the method slower than MCTDH, but for 18D HH ML-MCTDH starts to be competitive. We report as well 1458D simulations of the HH Hamiltonian using a seven layer scheme. The photoabsorption spectrum of pyrazine computed with the 24D Hamiltonian of Raab {\\em et. al.} [J. Chem. Phys. {\\bf 110}, 936 (1999)] provides a realistic molecular test case for the method. Quick and small ML-MCTDH calculations needing a fraction of the time and resources of reference MCTDH calculations provide already spectra with all the correct features. Accepting slightly larger deviations, the calculation can be accelerated to take only 7 minutes. When pushing the me...

  9. Phenolic compounds reduce formation of N(ε)-(carboxymethyl)lysine and pyrazines formed by Maillard reactions in a model bread system.

    Science.gov (United States)

    Mildner-Szkudlarz, Sylwia; Siger, Aleksander; Szwengiel, Artur; Przygoński, Krzysztof; Wojtowicz, Elżbieta; Zawirska-Wojtasiak, Renata

    2017-09-15

    This study had the objective of determining the antiglycation activity of phenolic compounds (PCs) ((+)-catechin, quercetin, gallic, ferulic, and caffeic acids) added to a model bread with regards to the inhibition of N(ε)-(carboxymethyl)lysine (CML) formation. PCs were found to significantly reduce CML (31.77%-87.56%), even at the lowest concentration, with the exception of ferulic acid (FA). The strongest inhibitory effect of FA (∼62%) appeared when concentration was increased to 1.0g/100g of flour. The available lysine losses (0.00%-90.51%) showed a significant correlation (0.853-0.990) with effectiveness of CML inhibition, except in the case of samples with FA. (+)-Catechin reduced CML levels the most, probably due to its structure-antioxidant activity relationship, its thermal stability (∼51% loss), and its reactivity with ε-lysine side chains (∼40.77% loss). Although the bread supplemented with PCs contained low levels of CML, this process may adversely affect bread flavor, reducing the formation of pyrazines (1.10%-80.77%). Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Bis(arylvinyl)pyrazines, -pyrimidines, and -pyridazines as imaging agents for tau fibrils and β-amyloid plaques in Alzheimer's disease models.

    Science.gov (United States)

    Boländer, Alexander; Kieser, Daniel; Voss, Constantin; Bauer, Silvia; Schön, Christian; Burgold, Steffen; Bittner, Tobias; Hölzer, Jana; Heyny-von Haußen, Roland; Mall, Gerhard; Goetschy, Valérie; Czech, Christian; Knust, Henner; Berger, Robert; Herms, Jochen; Hilger, Ingrid; Schmidt, Boris

    2012-11-08

    The in vivo diagnosis of Alzheimer's disease (AD) is of high socioeconomic interest and remains a demanding field of research. The biopathological hallmarks of the disease are extracellular plaques consisting of aggregated β-amyloid peptides (Aβ) and tau protein derived intracellular tangles. Here we report the synthesis and evaluation of fluorescent pyrazine, pyrimidine,and pyridazine derivatives in vitro and in vivo aiming at a tau-based diagnosis of AD. The probes were pre-evaluated on human brain tissue by fluorescence microscopy and were found to label all known disease-related alterations at high contrast and specificity. To quantify the binding affinity, a new thiazine red displacement assay was developed and selected candidates were toxicologically profiled. The application in transgenic mouse models demonstrated bioavailability and brain permeability for one compound. In the course of histological testing, we discovered an AD-related deposition of tau aggregates in the Bowman's glands of the olfactory epithelium, which holds potential for an endoscopic diagnosis of AD in the olfactory system.

  11. Presence of antioxidative agent, Pyrrolo[1,2-a]pyrazine-1,4-dione, hexahydro- in newly isolated Streptomyces mangrovisoli sp. nov.

    Directory of Open Access Journals (Sweden)

    Hooi-Leng eSer

    2015-08-01

    Full Text Available A novel Streptomyces, strain MUSC 149T was isolated from mangrove soil. A polyphasic approach was used to study the taxonomy of MUSC 149T, which shows a range of phylogenetic and chemotaxonomic properties consistent with those of the members of the genus Streptomyces. The diamino acid of the cell wall peptidoglycan was LL-diaminopimelic acid. The predominant menaquinones were identified as MK9(H8 and MK9(H6. Phylogenetic analysis indicated that closely related strains include Streptomyces rhizophilus NBRC 108885T (99.2 % sequence similarity, Streptomyces gramineus NBRC 107863T (98.7 % and Streptomyces graminisoli NBRC 108883T (98.5 %. The DNA–DNA relatedness values between MUSC 149T and closely related type strains ranged from 12.4 ± 3.3 % to 27.3 ± 1.9 %. The DNA G + C content was determined to be 72.7 mol%. The extract of MUSC 149T exhibited strong antioxidant activity and chemical analysis reported identification of an antioxidant agent, Pyrrolo[1,2-a]pyrazine-1,4-dione, hexahydro-. These data showed that metabolites of MUSC 149T shall be useful as preventive agent against free-radical associated diseases. Based on the polyphasic study of MUSC 149T, the strain merits assignment to a novel species, for which the name Streptomyces mangrovisoli sp. nov. is proposed. The type strain is MUSC 149T (= MCCC 1K00699T = DSM 100438T.

  12. Magnetic ordering and spin excitations in Mn(dca) sub 2 (pyz) [dca=N(CN) sub 2 sup - , pyz=pyrazine

    CERN Document Server

    Manson, J L; Argyriou, D N; Bordallo, H N; Lynn, J W; Huang, Q; Feyerherm, R; Loose, A

    2002-01-01

    We have studied the T- and H-dependent magnetism in Mn(dca) sub 2 (pyz) [dca=N(CN) sub 2 sup - , pyz=pyrazine] using neutron-scattering methods. The crystal structure can be viewed as a molecular analog of ReO sub 3 , where 1D Mn-pyz-Mn chains connect 2D Mn(dca) sub 2 square sheets to form a 3D network. In zero field, the Mn sup 2 sup + moments order antiferromagnetically below 2.53(2) K along the ac diagonal with a magnitude of 4.15(6) mu B at 1.35 K. The field-dependent response of the [111] magnetic reflection is consistent with spin-flop and induced ferromagnetic phase transitions as previously observed in magnetization measurements. Diffuse-scattering studies indicated no evidence for low-dimensional spin correlations. Using quasielastic neutron scattering, a low-energy spin-wave excitation was observed at propor to 0.23 meV, which is propor to 1/6 the momentum transfer observed in Mn(dca) sub 2 owing to a reduced number of magnetic nearest neighbors. (orig.)

  13. Structures and standard molar enthalpies of formation of a series of Ln(III)-Cu(II) heteronuclear compounds with pyrazine-2,3-dicarboxylic acid

    Science.gov (United States)

    Yang, Qi; Xie, Gang; Wei, Qing; Chen, Sanping; Gao, Shengli

    2014-07-01

    Fifteen lanthanide-copper heteronuclear compounds, formulated as [CuLn2(pzdc)4(H2O)6]·xH2O (1-6(x=2), 8(x=3), 9-10(x=4); [CuLn2(pzdc)4(H2O)4]·xH2O (7, 12-13, 15(x=4), 14(x=5), 11(x=8) (Ln(III)=La(1); Ce(2); Pr(3); Nd(4); Sm(5); Eu(6); Gd(7); Tb(8); Dy(9); Ho(10); Er(11); Tm(12); Yb(13); Lu(14); Y(15); H2pzdc (C6H4N2O4)=pyrazine-2,3-dicarboxylic acid) have been hydrothermally synthesized. All compounds were characterized by element analysis, IR spectroscopy, single-crystal X-ray diffraction and thermal analysis. X-ray diffraction analyses confirm that all compounds are isostructural and feature a 3D brick-like framework structure with {4.62}2{42.62.82}{63}2{65.8}2 topology. Using 1 mol cm-3 HCl(aq) as calorimetric solvent, with an isoperibol solution-reaction calorimeter, the standard molar enthalpies of formation of all compounds were determined by a designed thermochemical cycle. In addition, solid state luminescence properties of compounds 5, 6, 8 and 9 were studied in the solid state.

  14. Fused heterocycles bearing bridgehead nitrogen as potent HIV-1 NNRTIs. Part 4: design, synthesis and biological evaluation of novel imidazo[1,2-a]pyrazines.

    Science.gov (United States)

    Huang, Boshi; Liang, Xin; Li, Cuicui; Chen, Wenmin; Liu, Tao; Li, Xiao; Sun, Yueyue; Fu, Lu; Liu, Huiqing; De Clercq, Erik; Pannecouque, Christophe; Zhan, Peng; Liu, Xinyong

    2015-03-26

    Through a structure-guided core-refining approach, a series of novel imidazo[1,2-a]pyrazine derivatives were designed, synthesized and evaluated as HIV-1 non-nucleoside reverse transcriptase inhibitors (NNRTIs). Biological results of antiviral assay in MT-4 cell cultures showed that 12 target compounds displayed moderate activities against wild-type (wt) HIV-1 strain (IIIB) with EC50 values ranging from 0.26 μM to 19 μM. Among them, 4a and 5a were found to be the two most active analogues possessing EC50 values of 0.26 μM and 0.32 μM respectively, comparable to delavirdine (DLV, EC50 = 0.54 μM) and nevirapine (NVP, EC50 = 0.31 μM) in a cell-based assay. Additionally, 9 compounds showed RT inhibitory activity superior to that of NVP. Moreover, some predicted drug-like properties of representative compounds 4a and 5a, as well as the structure-activity relationship (SAR) analysis were discussed in detail. The binding mode of compound 4a was investigated by molecular simulation studies.

  15. Crystal structure of catena-poly[[(dimethyl sulfoxide-κO)(pyridine-2,6-di-carboxyl-ato-κ(3) O,N,O')nickel(II)]-μ-pyrazine-κ(2) N:N'].

    Science.gov (United States)

    Liu, Chen; Thuijs, Annaliese E; Felts, Ashley C; Ballouk, Hamza F; Abboud, Khalil A

    2016-05-01

    The title coordination polymer, [Ni(C7H3NO4)(C4H4N2)(C2H6OS)] n , consists of [010] chains composed of Ni(II) ions linked by bis-monodentate-bridging pyrazine mol-ecules. Each of the two crystallographically distinct Ni(II) ions is located on a mirror plane and is additionally coordinated by a dimethyl sulfoxide (DMSO) ligand through the oxygen atom and by a tridentate 2,6-pyridine-di-carb-oxy-lic acid dianion through one of each of the carboxyl-ate oxygen atoms and the pyridine nitro-gen atom, leading to a distorted octa-hedral coordination environment. The title structure exhibits an inter-esting complementarity between coordinative bonding and π-π stacking where the Ni-Ni distance of 7.0296 (4) Å across bridging pyrazine ligands allows the pyridine moieties on two adjacent chains to inter-digitate at halfway of the Ni-Ni distance, resulting in π-π stacking between pyridine moieties with a centroid-to-plane distance of 3.5148 (2) Å. The double-chain thus formed also exhibits C-H⋯π inter-actions between pyridine C-H groups on one chain and pyrazine mol-ecules on the other chain. As a result, the inter-ior of the double-chain structure is dominated by π-π stacking and C-H⋯ π inter-actions, while the space between the double-chains is occupied by a C-H⋯O hydrogen-bonding network involving DMSO ligands and carboxyl-ate groups located on the exterior of the double-chains. This separation of dissimilar inter-actions in the inter-ior and exterior of the double-chains further stabilizes the crystal structure.

  16. [μ-2,3,5,6-Tetra-kis(2-pyrid-yl)pyrazine-κN,N,N:N,N,N]bis-[diaqua(dihydrogen m-phenylene-diphospho-nato-κO)nickel(II)] dihydrate.

    Science.gov (United States)

    Deburgomaster, Paul; Zubieta, Jon

    2010-10-23

    The title compound [Ni(2)(C(6)H(6)O(6)P(2))(2)(C(24)H(16)N(6))(H(2)O)(4)]·2H(2)O or [Ni(2)(tpyprz)(1,3-HO(3)PC(6)H(4)PO(3)H)(2)(H(2)O)(4)]·2H(2)O [tpyprz = tetra-kis-(2-pyrid-yl)pyrazine, C(24)H(16)N(6)] is a binuclear complex with a crystallographic inversion center located at the center of the pyrazine ring. The equivalent nickel(II) sites exhibit a distorted {NiO(3)N(3)} octa-hedral coordination, with the three nitro-gen donors of each terminus of the tpyprz ligand in a meridional orientation. An aqua ligand occupies the position trans to the pyrazine nitro-gen donor, while the second aqua ligand is trans to the oxygen donor of the dihydrogen-1,3-phenyl-diphospho-nate ligand. The Ni-O and Ni-N bond lengths fall in the range 2.011 (3) to 2.089 (3) Å. The protonation sites on the organo-phospho-nate ligand are evident in the significantly longer P-O bonds compared to the unprotonated sites. In the crystal structure, the complex mol-ecules and the solvent water mol-ecules are linked into a three-dimensional hydrogen-bonded framework through O-H⋯O inter-actions between the aqua ligands, the protonated organo-phospho-nate oxygen atoms and the water mol-ecules of crystallization. Intra-molecular π-stacking between the phenyl group of the phospho-nate ligand and a pyridyl group of the tpyprz ligand, at a distance of 3.244 (5) Å between ring centroids, is also observed.

  17. [Cu(HF{sub 2}){sub 2}(pyrazine)]{sub n} : a rectangular antiferromagnetic lattice with a spin exchange path made up of two different FHF{sup -} bridges.

    Energy Technology Data Exchange (ETDEWEB)

    Manson, J. L.; Warter, M. L.; Schlueter, J. A.; Lancaster, T.; Steele, A. J.; Blundell, S. J.; Pratt, F. L.; Singleton, J.; McDonald, R. D.; Lee, C.; Whangbo, M.-H.; Plonczak, A. (Materials Science Division); (Eastern Washington Univ.); (Oxford Univ.); (Rutherford Appleton Lab.); (LANL); (North Carolina State Univ.)

    2011-01-14

    The two-dimensional antiferromagnet [Cu(HF{sub 2}){sub 2}(pyz)]{sub n} (pyz=pyrazine) has a rectangular lattice (see picture) displaying two types of FHF{sup -} bridging modes. The spin exchange through Cu-(FHF){sub 2}-Cu is about 90% stronger than through Cu-pyz-Cu, and the {mu}{sub 1,1}-coordinated FHF{sup -}, which is close in nature to F{sup -}---HF, is largely responsible for the exchange. C black, Cu red, F green, H cyan.

  18. Crystal structure of catena-poly[[aquabis(4-formylbenzoato-κ2O1,O1′;κO1-zinc]-μ-pyrazine-κ2N:N′

    Directory of Open Access Journals (Sweden)

    Gülçin Şefiye Aşkın

    2015-04-01

    Full Text Available The asymmetric unit of the title polymeric compound, [Zn(C8H5O32(C4H4N2(H2O]n, contains two molecular units. Each unit comprises two 4-formylbenzoate (FB anions, one pyrazine molecule and one coordinating water molecule; the FB anions act either as bidentate or as monodentate ligands. The O atoms of the bidentately coordinating FB anions are disordered over two positions, and they were refined with fixed occupancy ratios of 0.75:0.25 and 0.70:0.30, respectively. In the ordered monodentately coordinating FB anions, the carboxylate groups are twisted away from the attached benzene rings (B and E by 12.1 (2 and 9.2 (2°, respectively. In the disordered FB anions, the corresponding angles are 14.1 (1 and 4.0 (2° for benzene rings A and D, respectively. Benzene rings A and B are oriented at a dihedral angle of 45.7 (1°, D and E at 23.2 (1°. Pyrazine ring C makes dihedral angles of 85.6 (1 and 72.7 (1°, respectively, with benzene rings A and B, and pyrazine ring F makes dihedral angles of 87.0 (1 and 81.3 (1° with benzene rings D and E, respectively. The pyrazine ligands bridge the ZnII cations, forming polymeric chains running parallel to the b-axis direction. Medium-strength intramolecular O—H...O hydrogen bonds link the water molecules to the carboxylate O atoms. In the crystal, water–carboxylate O—H...O hydrogen bonds link adjacent chains into layers parallel to the bc plane. The layers are linked via weak pyrazine–formyl C—H...O and formyl–carboxylate C—H...O hydrogen bonds. π–π contacts between the benzene rings, with centroid-to-centroid distances of 3.7765 (16, 3.7905 (15 and 3.8231 (16 Å, may further stabilize the structure. There are also weak C—H...π interactions present.

  19. Inhibition Mechanism of Novel Pyrazolo[1,5-a]pyrazin-4(5H)-one Derivatives Against Proliferation of A549 and H322 Cancer Cells

    Institute of Scientific and Technical Information of China (English)

    Jin-hui Shao; Gui-hua Feng

    2015-01-01

    Objective To explore the inhibition mechanism and safety of pyrazolo[1,5-a]pyrazin-4(5H)-one derivatives against proliferation of human lung cancer A549 cells, H322 cells, and human umbilical vein endothelial cell (HUVEC). Methods Cells were treated with 40μmol/L of the ppo3a, ppo3b, ppo3i, and 0.1% DMSO (control) for 48 hours, respectively. Apoptosis was determined by Hoechst 33258 staining assay in H322 and A549 cells. Cell cycle distribution was determined by flow cytometry analysis in A549 cell. LC3-II, p53, and heat shock protein (HSP) 70 protein levels were detected by Western blotting in A549 cells treated with ppo3b for 48 hours. The morphology and viability of HUVEC were observed by inverted microscope and sulforhodamine B (SRB) assay. Results Ppo3a, ppo3b, and ppo3i significantly induced apoptosis in H322 and A549 cells. A strong G1-phase arrest was concomitant with the growth inhibitory effect on A549 cells. Ppo3b effectively elevated the p53 protein level, but significantly reduced the HSP70 protein level. There were no significantly inhibitory effect on the morphology and viability of HUVEC when treated with ppo3a, ppo3b, and ppo3i. Conclusions ppo3a, ppo3b, and ppo3i could inhibit H322 proliferation through apoptosis and inhibit A549 through apoptosis and G1-phase arrest. The protein p53 and HSP70 might involve in the inhibition effects. These derivatives might be a clue to find effective and safe drug for lung cancers.

  20. Stimulation of wild-type, F508del- and G551D-CFTR chloride channels by non toxic modified pyrrolo[2,3-b]pyrazine derivatives

    Directory of Open Access Journals (Sweden)

    Luc eDannhoffer

    2011-08-01

    Full Text Available Cystic Fibrosis is a major inherited disorder involving abnormalities of fluid and electrolyte transport in a number of different organs due to abnormal function of Cystic Fibrosis Transmembrane conductance Regulator (CFTR protein. We recently identified a family of CFTR activators, which contains the hit: RP107 [7-n-butyl-6-(4-hydroxyphenyl[5H]-pyrrolo[2,3-b]pyrazine]. Here, we further evaluated the effect of the chemical modifications of the RP107-OH radical on CFTR activation. The replacement of the OH radical by a fluorine atom at position 2 (RP193 or 4 (RP185 significantly decreased the toxicity of the compounds without altering the ability to activate CFTR, especially for RP193. The non-toxic compound RP193 has no effect on cAMP production but stimulates the channel activity of wild-type CFTR in stably transfected CHO cells, in human bronchial epithelial NuLi-1 cells and in primary culture of human bronchial epithelial cells. Whole cell and single patch clamp recordings showed that RP193 induced a linear, time and voltage-independent current, which was fully inhibited by two different and selective CFTR inhibitors (CFTRinh-172 and GPinh-5a. Moreover, RP193 stimulates CFTR in temperature-rescued CuFi-1 (F508del/F508del human bronchial epithelial cells and in CHO cells stably expressing G551D-CFTR. This study shows that it is feasible to reduce cytotoxicity of chemical compounds without affecting their potency to activate CFTR and to rescue the class 2 F508del-CFTR and class 3 G551D-CFTR CF mutant activities.

  1. Switchable Synthesis of Pyrroles and Pyrazines via Rh(II)-Catalyzed Reaction of 1,2,3-Triazoles with Isoxazoles: Experimental and DFT Evidence for the 1,4-Diazahexatriene Intermediate.

    Science.gov (United States)

    Rostovskii, Nikolai V; Ruvinskaya, Julia O; Novikov, Mikhail S; Khlebnikov, Alexander F; Smetanin, Ilia A; Agafonova, Anastasiya V

    2017-01-06

    4-Aminopyrrole-3-carboxylates and pyrazine-2-carboxylates were synthesized from 5-alkoxyisoxazoles and 1-sulfonyl-1,2,3-triazoles by tuning the Rh(II) catalyst and the reaction conditions. The reaction in chloroform at 100 °C under Rh2(OAc)4 catalysis provides 4-aminopyrrole-3-carboxylates in good yields. The use of Rh2(Piv)4 in refluxing toluene results in the formation of 1,2-dihydropyrazine-2-carboxylates as the main products, which can be converted by a one-pot procedure to pyrazine-2-carboxylates by heating with catalytic amounts of TsOH. According to the NMR and DFT investigations of the reaction mechanism, pyrroles and dihydropyrazines are formed, respectively, via 1,5- and 1,6-cyclization of common (5Z)-1,4-diazahexa-1,3,5-triene intermediates. The influence of the nature of the catalyst on the product distribution is rationalized in terms of the Rh-catalyzed isomerization of a pyrrolin-2-ylium-3-aminide zwitterion, the primary product of 1,4-diazahexatriene 1,5-cyclization.

  2. Tetrakis(dimethylammonium trans-dichloridobis[5,5′-(pyrazine-2,3-diylbis(1H-tetrazol-1-ido-κN1]copper(II

    Directory of Open Access Journals (Sweden)

    Ju-Hsiou Liao

    2012-10-01

    Full Text Available The title compound, (C2H8N4[Cu(C6H2N102Cl2], consists of an anionic complex which is composed of a CuII ion surrounded by four N atoms from two pyrazine-2,3-diylbis(1H-tetrazol-1-ide ligands, and two Cl− atoms in a trans-Cl2N4 coordination geometry; the CuII atom lies on a site of symmetry 2/m. The Cu—Cl distance of 2.8719 (5 Å is long due to the Jahn–Teller distortion of the d9 electron configuration of CuII ion. The tetrazole and pyrazine rings make an N—C—C—N torsion angle of 38.25 (17°. The charge of the anionic complex is balanced by four dimethylammonium cations, which interact with the anionic complexes via N—H...N and N—H...Cl hydrogen bonds.

  3. Synthesis and luminescence modulation of pyrazine-based gold(iii) pincer complexes† †Electronic supplementary information (ESI) available: Details of synthesis and characterization, X-ray crystallography, photophysical properties, theoretical calculations. CCDC 1417819–1417822. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5cc07523h

    Science.gov (United States)

    Fernandez-Cestau, Julio; Bertrand, Benoît; Blaya, Maria; Jones, Garth A.

    2015-01-01

    The first examples of pyrazine-based gold(iii) pincer complexes are reported; their intense photoemissions can be modified by protonation, N-alkylation or metal ions, without the need for altering the ligand framework. Emissions shift from red (77 K) to blue (298 K) due to thermally activated delayed fluorescence (TADF). PMID:26425736

  4. Swern Oxidation of Bicyclo[2.2.1]hept-5-ene-2,3-diol and Its Pyrazine-fused Derivatives: An Improved Synthesis of Bicyclo[2.2.1]hept-5-ene-2,3-dione and An Unexpected Ring-Opening Reaction

    Directory of Open Access Journals (Sweden)

    Sayuri Kobayashi

    2000-09-01

    Full Text Available An improved synthesis of bicyclo[2.2.1]hept-5-ene-2,3-dione by Swern oxidation of bicyclo[2.2.1]hept-5-ene-2,3-diol, and an unexpected ring-opening reaction by the Swern oxidation of pyrazine-fused congeners are described.

  5. Crystal structure of a pyrazine-2,3-dicarboxamide ligand and of its silver(I nitrate complex, a three-dimensional coordination polymer

    Directory of Open Access Journals (Sweden)

    Dilovan S. Cati

    2017-06-01

    Full Text Available The title ligand, C18H16N6O2·2H2O (L1 [N2,N3-bis(pyridin-4-ylmethylpyrazine-2,3-dicarboxamide], crystallized as a dihydrate. The molecule is U-shaped with the carboxamide groups being cis to one another, making a dihedral angle of 81.6 (5°. The terminal pyridine rings are inclined to one another by 58.5 (4°. There is an intramolecular N—H...Npyrazine hydrogen bond present, forming an S(5 ring motif. In the crystal, adjacent molecules are linked by N—H...Ocarboxamide hydrogen bonds, forming a chain along [001]. A chain of hydrogen-bonded water molecules is linked to the chain of (L1 molecules by O—H...N hydrogen bonds, forming columns propagating along the c axis. The columns are linked by C—H...O and C—H...N hydrogen bonds, forming a three-dimensional supramolecular structure. The reaction of ligand (L1 with silver(I nitrate led to the formation of a new three-dimensional coordination polymer, {[Ag(C18H16N6O2]NO3}n, poly[[[μ4-N2,N3-bis(pyridin-4-ylmethylpyrazine-2,3-dicarboxamide]silver(I] nitrate] (I. The asymmetric unit is composed of half of one silver ion, located on a twofold rotation axis, half a ligand molecule and half a positionally disordered nitrate anion located about a twofold rotation axis. The full molecule of the ligand is generated by twofold rotational symmetry, with this twofold axis bisecting the Car—Car bonds of the pyrazine ring and the Ag—Ag bond. The carboxamide groups are now trans to one another, making a dihedral angle of 65.8 (4°. The two terminal pyridine rings are inclined to one another by 6.6 (3°. Two ligands wrap around an Ag—Ag bond of 3.1638 (11 Å, forming a figure-of-eight-shaped complex molecule. Each silver ion is coordinated by two pyridine N atoms and by two carboxamide O atoms of neighbouring molecules, hence forming a three-dimensional framework. The nitrate anion is linked to the framework by N—H...O and C—H...O hydrogen bonds.

  6. Poly[[diaqua-μ4-pyrazine-2,3-dicarboxylato-κ6N,O2:O2′:O3,O3′:O3-strontium(II] monohydrate

    Directory of Open Access Journals (Sweden)

    Vahid Amani

    2008-07-01

    Full Text Available In the title compound, {[Sr(C6H2N2O4(H2O2]·H2O}n, the SrII ions are bridged by the pyrazine-2,3-dicarboxylate ligands with the formation of two-dimensional polymeric layers parallel to the ac plane. Each SrII ion is eight-coordinated by one N and five O atoms from the four ligands and two water molecules. The coordination polyhedron is derived from a pentagonal bipyramid with an O atom at the apex on one side of the equatorial plane and two O atoms sharing the apical site on the other side. The coordinated and uncoordinated water molecules are involved in O—H...O and O—H...N hydrogen bonds, which consolidate the crystal structure.

  7. Pyrazines Attract Catocheilus Thynnine Wasps

    Directory of Open Access Journals (Sweden)

    Bjorn Bohman

    2014-06-01

    Full Text Available Five previously identified semiochemicals from the sexually deceptive Western Australian hammer orchid Drakaea livida, all showing electrophysiological activity in gas chromatography–electroantennogram detection (EAD studies, were tested in field bioassays as attractants for a Catocheilus thynnine wasp. Two of these compounds, (3,5,6-trimethylpyrazin-2-ylmethyl 3-methylbutanoate and 2-(3-methylbutyl-3,5,6-trimethylpyrazine, were attractive to male wasps. Additionally, the semiochemical 3-(3-methylbutyl-2,5-dimethylpyrazine, a close analogue to 2-(3-methylbutyl-3,5,6-trimethylpyrazine, identified in five other species of thynnine wasps, was equally active. The three remaining compounds from D. livida, which were EAD-active against Catocheilus, did not attract the insects in field trials. It is interesting that two structurally similar compounds induce similar behaviours in field experiments, yet only one of these compounds is present in the orchid flower. Our findings suggest the possibility that despite the high specificity normally characterising sex pheromone systems, the evolution of sexual deception may not be entirely constrained by the need to precisely match the sex pheromone constituents and blends. Such evolutionary flexibility may be particularly important during the early stages of speciation.

  8. Hydrothermal synthesis and study of an inorganic-organic hybrid vanadate of a nickel(II) coordination complex with pyrazine, Ni{sub 3}(C{sub 4}H{sub 4}N{sub 2}){sub 3}(V{sub 8}O{sub 23})

    Energy Technology Data Exchange (ETDEWEB)

    Larrea, Edurne S. [Dpto. de Mineralogia y Petrologia, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/Euskal Herriko Unibertsitatea, UPV/EHU, Apdo. 644, E-48080 Bilbao (Spain); Mesa, Jose L., E-mail: joseluis.mesa@ehu.es [Dpto. de Quimica Inorganica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/Euskal Herriko Unibertsitatea, UPV/EHU, Apdo. 644, E-48080 Bilbao (Spain); Arriortua, Maria I. [Dpto. de Mineralogia y Petrologia, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/Euskal Herriko Unibertsitatea, UPV/EHU, Apdo. 644, E-48080 Bilbao (Spain)

    2011-06-15

    Highlights: {yields} A novel inorganic-organic hybrid vanadate of nickel(II) coordination complex with pyrazine has been synthesized hydrothermally. {yields} The thermal and spectroscopic behavior has been studied. {yields} The compound shows AFM interactions which has been fitted to a magnetic model of lineal chains. -- Abstract: The three-dimensional hybrid compound Ni{sub 3}(C{sub 4}H{sub 4}N{sub 2}){sub 3}(V{sub 8}O{sub 23}) has been synthesized by mild hydrothermal methods under autogenous pressure at 170 {sup o}C. The structure of the phase is stable until 380 {sup o}C. The removal of the pyrazine molecules from the structure induces its collapse. The IR spectrum shows the vibration modes of the pyrazine molecule and those of the [VO{sub 4}]{sup 3-} groups. A UV-visible spectrum shows the characteristic bands of the Ni(II) d{sup 8}-high-spin cation in a slightly distorted octahedral coordination. Magnetic measurements indicate the existence of antiferromagnetic interactions that can be fitted with a chain model to give g = 2.31, J/k = -5.3, and zJ'/k = -5.5.

  9. Particle swarm optimization and genetic algorithm as feature selection techniques for the QSAR modeling of imidazo[1,5-a]pyrido[3,2-e]pyrazines, inhibitors of phosphodiesterase 10A.

    Science.gov (United States)

    Goodarzi, Mohammad; Saeys, Wouter; Deeb, Omar; Pieters, Sigrid; Vander Heyden, Yvan

    2013-12-01

    Quantitative structure-activity relationship (QSAR) modeling was performed for imidazo[1,5-a]pyrido[3,2-e]pyrazines, which constitute a class of phosphodiesterase 10A inhibitors. Particle swarm optimization (PSO) and genetic algorithm (GA) were used as feature selection techniques to find the most reliable molecular descriptors from a large pool. Modeling of the relationship between the selected descriptors and the pIC50 activity data was achieved by linear [multiple linear regression (MLR)] and non-linear [locally weighted regression (LWR) based on both Euclidean (E) and Mahalanobis (M) distances] methods. In addition, a stepwise MLR model was built using only a limited number of quantum chemical descriptors, selected because of their correlation with the pIC50 . The model was not found interesting. It was concluded that the LWR model, based on the Euclidean distance, applied on the descriptors selected by PSO has the best prediction ability. However, some other models behaved similarly. The root-mean-squared errors of prediction (RMSEP) for the test sets obtained by PSO/MLR, GA/MLR, PSO/LWRE, PSO/LWRM, GA/LWRE, and GA/LWRM models were 0.333, 0.394, 0.313, 0.333, 0.421, and 0.424, respectively. The PSO-selected descriptors resulted in the best prediction models, both linear and non-linear.

  10. Design, synthesis and antibacterial activities of 5-(pyrazin-2-yl)-4H-1,2,4-triazole-3-thiol derivatives containing Schiff base formation as FabH inhibitory.

    Science.gov (United States)

    Zhang, Fei; Wen, Qing; Wang, She-Feng; Shahla Karim, Baloch; Yang, Yu-Shun; Liu, Jia-Jia; Zhang, Wei-Ming; Zhu, Hai-Liang

    2014-01-01

    A series of novel schiff base derivatives (H(1)-H(20)) containing pyrazine and triazole moiety have been designed and synthesized, and their biological activities were also evaluated as potential inhibitors of β-ketoacyl-acyl carrier protein synthase III (FabH). These compounds were assayed for antibacterial activity against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Bacillus subtilis and Bacillus amyloliquefaciens and selected compounds among them were tested for their Escherichia coli FabH inhibitory activity. Based on the biological data, compound H(17) showed the most potent antibacterial activity with MIC values of 0.39-1.56μg/mL against the tested bacterial strains and exhibited the most potent E. coli FabH inhibitory activity with IC50 of 5.2μM, being better than the positive control Kanamycin B with IC50 of 6.3μM. Furthermore, docking simulation was performed to position compound H(17) into the E. coli FabH active site to determine the probable binding conformation. This study indicated that compound H(17) has demonstrated significant E. coli FabH inhibitory activity as a potential antibacterial agent and provides valuable information for the design of E. coli FabH inhibitors.

  11. catena-Poly[diacridinium [zinc(II-di-μ-pyrazine-2,3-dicarboxylato-κ3N1,O2:O3;O3:N1,O2

    Directory of Open Access Journals (Sweden)

    Hossein Eshtiagh-Hosseini

    2010-08-01

    Full Text Available The crystal structure of the title compound, {(C13H10N2[Zn(C6H2N2O42]}n, consists of polymeric Zn complex anions and discrete acridinium cations. The Zn cation, located on an inversion center, is N,O-chelated by two pyrazine-2,3-dicarboxylate (pyzdc anions in the basal plane, and is further coordinated by two carboxylate O atoms from adjacent pyzdc anions in the axial directions with a longer Zn—O bond distance, forming a distorted ZnN2O4 coordination geometry. The pyzdc anions bridge the Zn cations, forming polymeric chains running along the crystallographic b axis. The acridinium cations are linked to the complex chains via N—H...O and C—H...O hydrogen bonding. Significant π–π stacking between parallel acridinium ring systems is observed in the crystal structure, face-to-face distances being 3.311 (3 and 3.267 (4 Å.

  12. Different Supramolecular Coordination Polymers of [N,N'-di(pyrazin-2-yl-pyridine-2,6-diamine]Ni(II with Anions and Solvent Molecules as a Result of Hydrogen Bonding

    Directory of Open Access Journals (Sweden)

    Hsin-Ta Wang

    2007-04-01

    Full Text Available Ni(II complexes of N,N'–di(pyrazin–2–ylpyridine–2,6–diamine (H2dpzpda with different anions were synthesized and their structures were determined by X-ray diffraction. Hydrogen bonds between the amino groups and anions assembled the mononuclear molecules into different architectures. The perchlorate complex had a 1-D chain structure, whereas switching the anion from perchlorate to nitrate resulted in a corresponding change of the supramolecular structure from 1-D to 3-D. When the nitrate complex packed with the co-crystallized water, a double chain structure was formed through hydrogen bonding. The magnetic studies revealed values of g = 2.14 and D = 3.11 cm-1 for [Ni(H2dpzpda2](ClO42 (1 and g = 2.18 and D = 2.19 cm-1 for [Ni(H2dpzpda2](NO32 (2, respectively.

  13. Detection of Pyrazine Compounds in Cocoa Wort by Gas Chromatography with Headspace Solid Phase Micro-Extraction%顶空-固相微萃取-气相色谱法检测可可麦汁中吡嗪类化合物

    Institute of Scientific and Technical Information of China (English)

    肖天鹏; 郑晓峰; 吕吉鸿; 郭泽峰; 高峰; 刘春凤; 李崎

    2012-01-01

    A headspace solid phase microextraction (HS-SPME), followed by gas chromatographic method was established for the detection of three pyrazine compounds (2,5-dimethyl pyrazine, 2,3,5-trimethyl pyrazine and 2,3, 5, 6-tetramethyl pyrazine) in cocoa wort. Equilibrium temperature and equilibrium time were optimized by using different SPME heads. According to the results of the optimization experiments, the following conclusion can be drawn: The cocoa wort sample was efficiently extracted under 40 ℃ for 40 min with 75 urn CAR/PDMS SPME head. The method had linear response within 1 - 500 mg/L, and the detection limits (S/N=3) were below 0. 023 礸/L. The relative standard deviations were from 3. 6%-6. 4% and the recoveries were from 95. A% to 102. 7%. This method is characterized by rapidly, high sensitivity, good linearity and repeatability for the analysis of cocoa wort samples.%建立了顶空-固相微萃取(HS-SPME)-气相色谱快速测定可可麦汁中3种吡嗪类物质(2,5-二甲基吡嗪、2,3,5-三甲基吡嗪和2,3,5,6-四甲基吡嗪)的方法.选择不同的固相微萃取头对萃取温度和时间进行优化,所得最佳萃取条件为:在60℃下,采用75 μm CAR/PDMS萃取头对麦汁样品萃取40 min.本方法的检出限(S/N=3)为0.023~ 0.056 μg/L,线性范围1~500 mg/L;相对标准偏差为3.6%~6.4%;回收率为95.4%~102.7%.本方法应用于样品检测,发现可可麦汁中吡嗪的浓度与原料中可可粉的添加量正相关,显示了很好灵敏性.

  14. Stimulation of Wild-Type, F508del- and G551D-CFTR Chloride Channels by Non-Toxic Modified pyrrolo[2,3-b]pyrazine Derivatives.

    Science.gov (United States)

    Dannhoffer, Luc; Billet, Arnaud; Jollivet, Mathilde; Melin-Heschel, Patricia; Faveau, Christelle; Becq, Frédéric

    2011-01-01

    Cystic fibrosis (CF) is a major inherited disorder involving abnormalities of fluid and electrolyte transport in a number of different organs due to abnormal function of cystic fibrosis transmembrane conductance regulator (CFTR) protein. We recently identified a family of CFTR activators, which contains the hit: RP107 [7-n-butyl-6-(4-hydroxyphenyl)[5H]-pyrrolo[2,3-b]pyrazine]. Here, we further evaluated the effect of the chemical modifications of the RP107-OH radical on CFTR activation. The replacement of the OH radical by a fluorine atom at position 2 (RP193) or 4 (RP185) significantly decreased the toxicity of the compounds without altering the ability to activate CFTR, especially for RP193. The non-toxic compound RP193 has no effect on cAMP production but stimulates the channel activity of wild-type CFTR in stably transfected CHO cells, in human bronchial epithelial NuLi-1 cells, and in primary culture of human bronchial epithelial cells (HBEC). Whole-cell and single patch-clamp recordings showed that RP193 induced a linear, time- and voltage-independent current, which was fully inhibited by two different and selective CFTR inhibitors (CFTRinh-172 and GP(inh)5a). Moreover, RP193 stimulates CFTR in temperature-rescued CuFi-1 (F508del/F508del) HBEC and in CHO cells stably expressing G551D-CFTR. This study shows that it is feasible to reduce cytotoxicity of chemical compounds without affecting their potency to activate CFTR and to rescue the class 2 F508del-CFTR and class 3 G551D-CFTR CF mutant activities.

  15. Structural modulation and luminescent properties of four CdII coordination architectures based on 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1,2,4-triazole and flexible/rigid dicarboxylate ligands

    Science.gov (United States)

    Xia, Liang; Dong, Wen-Wen; Ye, Xiao; Zhao, Jun; Li, Dong-Sheng

    2016-10-01

    To systematically investigate the influence of the flexible or rigid auxiliary ligands on the structures and properties of transition metal compounds, we synthesized four new d10 coordination polymers (CPs) from 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1,2,4-triazole (4-Hpzpt) and flexible/rigid dicarboxylate ligands, [Cd(4-pzpt)2]n (1), [Cd3(4-pzpt)2(suc)2]n (2), [Cd2(4-Hpzpt)(nbc)2(H2O)]n (3) and {[Cd2(4-pzpt)2(tfbdc)(H2O)4]·H2O}n (4) (H2suc=1,2-ethanedicarboxylic acid, H2nbc=hthalene-1,4-dicarboxylic acid, H2tfbdc =2,3,5,6-tetrafluoroterephthalic acid). Single crystal X-ray analysis indicates that compound 1 shows a 44-sql layer, which is extended to a 3D network via nonclassical C-H…N hydrogen bonds. Compound 2 possesses a 6-connected pcu-4120.63 net composed of trinuclear CdII-clusters. Compound 3 represents a rare 3D (3,4,4,5)-connected topology with a Schläfli symbol of (4·6·7)(4·53·72)(53·6·7·9)(42·55·6·72). Compound 4 exhibits a 2D+2D→2D parallel interpenetrated 63-hcb network. The adjacent 2D networks are interdigitated with each other to form the resulting 3D supramolecular architecture through classical O-H…N and O-H…O hydrogen bonds. Structural diversities indicate that the nature of flexible/rigid-dicarboxlates plays crucial roles in modulating structures of these compounds. Moreover, the luminescent properties of them have been briefly investigated.

  16. Syntheses, Crystal Structures and Fluorescence of Cadmium(Ⅱ) Coordination Polymers with Pyrazine-1,4-dioxide, 2-Methylpyrazine-1,4-dioxide and Thiocyanate as Mixed Bridge Ligands

    Institute of Scientific and Technical Information of China (English)

    SHI Jing-Min; ZHANG Feng-Xia; ZHANG Xia; XU Hai-Yan; LIU Lian-Dong; MA Jian-Ping

    2006-01-01

    Two Cd(Ⅱ) coordination polymers have been synthesized with pyrazine-1,4-dioxide(L1), 2-methylpyrazine-1,4-dioxide (L2), and thiocyanate anion as mixed bridge ligands. Crystal data for complex 1 [Cd(μ13-SCN-)2(L1)]n: monoclinic system, space group P21/n with a =6.8342(11), b = 14.349(2), c = 10.5443(16) (A), β = 98.534(2)°, V = 1022.5(3) (A)3, Z = 4,C6H4CdN4O2S2, Mr = 340.65, Dc. = 2.213 g/cm3, F(000) = 656 andμ = 2.527 mm-1; and those for2: triclinic system, space group P1 with a = 7.877(3), b = 8.693(3), c = 8.754(3) (A), α =102.297(6), β= 102.464(6), γ= 98.480(6)°, V = 560.0(3) (A)3, Z = 2, C7H6CdN4O2S2, Mr = 354.68,Dc = 2.103 g/cm3, F(000) = 344 and μ = 2.311 mm-1. 1 shows a three-dimensional network structure, and along the c direction a one-dimensional chain is constructed by the coordination of Cd(Ⅱ) ions withμ1,3-SCN- ligands, and the L1 bridging ligands made the chains connect each other leading to the formation of a three-dimensional structure. For 2, the one-dimensional chains along the b axis are generated by the coordination of L2 bridging ligands with Cd(Ⅱ) ions, and the chains are further joined byμ1,3-SCN- bridging ligands forming a two-dimensional sheet structure on the (1 0 -1) plane. Both complexes 1 and 2 exhibit strong fluorescence emission.

  17. Formation of thin luminescent Eu{sup 3+}-LB films by in situ coordination with 2,3,5,6-tetra(2 Prime -pyridyl)pyrazine and 1-octadecanol in pure and mixed Langmuir monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Fugisawa, Fernanda P. [Departamento de Quimica, Faculdade de Filosofia, Ciencias e Letras de Ribeirao Preto, Universidade de Sao Paulo, 14040-901 Ribeirao Preto, SP (Brazil); Ramos, Ana P., E-mail: anapr@ffclrp.usp.br [Departamento de Quimica, Faculdade de Filosofia, Ciencias e Letras de Ribeirao Preto, Universidade de Sao Paulo, 14040-901 Ribeirao Preto, SP (Brazil); Sousa Filho, Paulo C. de; Serra, Osvaldo A.; Zaniquelli, Maria E.D. [Departamento de Quimica, Faculdade de Filosofia, Ciencias e Letras de Ribeirao Preto, Universidade de Sao Paulo, 14040-901 Ribeirao Preto, SP (Brazil)

    2012-05-15

    The in situ complexation between 2,3,5,6-tetra(2-pyridyl)pyrazine (tppz) molecules and europium ions at the air-liquid interface by means of mixed 1-octadecanol Langmuir films is reported. These films were transferred to solid supports by means of the Langmuir-Blodgett (LB) technique. The EDS maps attested the homogeneity of the LB films as well as the presence of the europium ions. The mixed alcohol/tppz LB film contained a larger amount of europium ions as compared to the pure octadecanol LB film. This work reports the production of a thin luminescent Eu{sup 3+} film containing europium ions using only alcohol molecules as ligands-an unexpected result, since it is well known that there is an occurrence of non-radiative deactivation of excited europium by hydroxyl groups. Europium ion multiple binding sites were detected from lifetime decay measurements of these films in the presence of tppz molecules. - Highlights: Black-Right-Pointing-Pointer In situ complexation of Eu (III) ions with 1-octadecanol and tppz. Black-Right-Pointing-Pointer Formation of thin luminescent Eu(III)-LB films. Black-Right-Pointing-Pointer EDS and luminescence studies attest to the presence of Eu(III) in the films. Black-Right-Pointing-Pointer Eu(III) coordinates with both tppz and alcohol molecules at air/liquid interface. Black-Right-Pointing-Pointer Relatively strong luminescence is observed in LB-films containing only Eu(III) and O-H oscillators.

  18. Anticancer potential of pyrrole (1, 2, a) pyrazine 1, 4, dione, hexahydro 3-(2-methyl propyl) (PPDHMP) extracted from a new marine bacterium, Staphylococcus sp. strain MB30.

    Science.gov (United States)

    Lalitha, P; Veena, V; Vidhyapriya, P; Lakshmi, Pragna; Krishna, R; Sakthivel, N

    2016-05-01

    Marine bacterium, strain MB30 isolated from the deep sea sediment of Bay of Bengal, India, exhibited antimicrobial activity against human pathogenic bacteria. Based on the 16S rRNA sequence homology and subsequent phylogenetic tree analysis, the strain MB30 was identified as Staphylococcus sp. The bioactive metabolite produced by the strain MB30 was purified through silica gel column chromatography and preparative HPLC. Purified metabolite was further characterized by FT-IR, LC-MS and NMR analyses. On the basis of spectroscopic data, the metabolite was identified as pyrrole (1, 2, a) pyrazine 1, 4, dione, hexahydro 3-(2-methyl propyl) (PPDHMP). The PPDHMP exhibited in vitro anticancer potential against lung (A549) and cervical (HeLa) cancer cells in a dose-dependent manner with the IC50 concentration of 19.94 ± 1.23 and 16.73 ± 1.78 μg ml(-1) respectively. The acridine orange (AO)/ethidium bromide (EB) and 4,6-diamidino-2-phenylindole dihydrochloride (DAPI) staining of the IC50 concentration of PPDHMP-treated cancer cells exhibited an array of morphological changes such as nuclear condensation, cell shrinkage and formation of apoptotic bodies. The PPDHMP-treated cancer cells induced the progressive accumulation of fragmented DNA in a time-dependent manner. Based on the flow cytometric analysis, it has become evident that the compound was also effective in arresting the cell cycle at G1 phase. Further, the Western blotting analysis confirmed the down-regulation of cyclin-D1, cyclin dependent kinase (CDK-2), anti-apoptotic Bcl-2 family proteins (Bcl-2 and Bcl-xL), activation of caspase-9 and 3 with the cleavage of PARP. The PPDHMP-treated cancer cells also showed the inhibition of migration and invasive capacity of cancer cells. In the present investigation, for the first time, we have reported the extraction, purification and characterization of an anticancer metabolite, PPDHMP from a new marine bacterium, Staphylococcus sp. strain MB30.

  19. Mechanical Sensitivity of Composite Modified Double Base Propellant Containing 2,6-diamino-3,5-dinitro Pyrazine-1-oxide%含LLM-105的改性双基推进剂的机械感度

    Institute of Scientific and Technical Information of China (English)

    张超; 张晓宏; 杨立波; 孙志刚; 曹鹏; 王明星

    2014-01-01

    The influence of the 2,6-diamino-3,5-dinitro pyrazine-1-oxide (LLM-105) content and particle size on the impact sensitivity and friction sensitivity of composite modified double base propellant containing LLM-105 (LLM-105-CMDB propellant) was investigated, and these sensitivities of LLM-105-CMDB propellants were compared with those of composite modified double base propellant containing hexanitrohexaazaisowurtzitane (CL-20-CMDB propellant),3,4-dinitro-furazanfuroxan (DNTF-CMDB propellant)and octogen (HMX-CMDB propellant).The results show that after LLM-105 is substituted for RDX, the impact and friction sensitivity of the propellant is decreased obviously, the impact sensitivity value of LLM-105-CMDB propellant is increased form 23.4cm to 39.3cm, the order of mechanical sensitivity of same content high energy density material from low to high is LLM-105-CMDB, DNTF-CMDB, CL-20-CMDB, HMX-CMDB and RDX-CMDB.%研究了2,6-二氨基-3,5-二硝基吡嗪-1-氧化物( LLM-105)的含量和粒度对含LLM-105的改性双基推进剂机械感度的影响,并将LLM-105-CMDB推进剂的机械感度与含六硝基六氮杂异戊兹烷的改性双基推进剂(CL-20-CMDB)、含3,4-二硝基呋咱基氧化呋咱的改性双基推进剂(DNTF-CMDB)及含奥克托今的改性双基推进剂(HMX-CMDB)的感度进行了比较。结果表明:用LLM-105逐步取代改性双基推进剂中的RDX,推进剂的机械感度也随之降低,撞击感度H 50由23.4cm增加至39.3cm;高能量密度材料含量相同的几种改性双基推进剂机械感度由低往高依次为:LLM-105-CMDB、DNTF-CMDB、CL-20-CMDB、HMX-CMDB、RDX-CMDB。

  20. Synthesis and Structural Characterization of 2-Pyrazinecarboxylate Copper Compound {[Cu2 (Pyz) 2 (H2O) 4]·SO4}n (Pyz=2-pyrazinic acid)%2-吡嗪羧酸铜配合物的合成及其结构表征

    Institute of Scientific and Technical Information of China (English)

    禹良才; 赖兰

    2009-01-01

    Solvothermal reaction of 2-pyrazinic acid with Cu(SO4) 2·5H2O yields the title complex {[Cu2 (Pyz) 2 (H2O) 4]·SO4}n (1), which was characterized by elemental analysis, IR and single crystal X-ray diffraction structural analysis. The complex 1 crystallizes in Monoclinic system, space group P21/c, with lattice parameters a=1.126 87(6)nm, b=0.073 511 (4) nm,c=1.185 06(7) nm,β=95.070(2)°,and V=0.977 83(9) nm3,Z=4,Dc=2.172 Mg·m-3. CCDC:692347.

  1. (2R)-4-Oxo-4[3-(Trifluoromethyl)-5,6-diihydro:1,2,4}triazolo[4,3-a}pyrazin-7(8H)-y1]-1-(2,4,5-trifluorophenyl)butan-2-amine: A Potent, Orally Active Dipeptidyl Peptidase IV Inhibitor for the Treatment of Type 2 Diabetes

    Energy Technology Data Exchange (ETDEWEB)

    Kim, D.; Wang, L.; Beconi, M.; Eiermann, G.; Fisher, M.; He, H.; Hickey, G.; Kowalchick, Jennifer; Leiting, Barbara; Lyons, K.; Marsilio, F.; McCann, F.; Patel, R.; Petrov, A.; Scapin, G.; Patel, S.; Roy, R.; Wu, J.; Wyvratt, M.; Zhang, B.; Zhu, L.; Thornberry, N.; Weber, A. (Merck)

    2010-11-10

    A novel series of {beta}-amino amides incorporating fused heterocycles, i.e., triazolopiperazines, were synthesized and evaluated as inhibitors of dipeptidyl peptidase IV (DPP-IV) for the treatment of type 2 diabetes. (2R)-4-Oxo-4-[3-(trifluoromethyl)-5,6-dihydro[1,2,4]triazolo[4,3-a]pyrazin-7(8H)-yl]-1-(2,4,5-trifluorophenyl)butan-2-amine (1) is a potent, orally active DPP-IV inhibitor (IC{sub 50} = 18 nM) with excellent selectivity over other proline-selective peptidases, oral bioavailability in preclinical species, and in vivo efficacy in animal models. MK-0431, the phosphate salt of compound 1, was selected for development as a potential new treatment for type 2 diabetes.

  2. Experimental and Computational Studies of Binding of Dinitrogen, Nitriles, Azides, Diazoalkanes, Pyridine and Pyrazines to M(PR3)2(CO)3 (M=Mo, W; R=Me, iPr)

    Energy Technology Data Exchange (ETDEWEB)

    Hoff, C.D.; Muckerman, J.; Achord, P.; Fujita, E.; Scott, B.; Fortman, G.C.; Temprado, M.; Cai, X.; Captain, B.; Isrow, D.; Weir, J.J.; McDonough, J.E.

    2009-08-17

    The enthalpies of binding of a number of N-donor ligands to the complex Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3} in toluene have been determined by solution calorimetry and equilibrium measurements. The measured binding enthalpies span a range of {approx}10 kcal mol{sup -1}: {Delta}H{sub binding} = -8.8 {+-} 1.2 (N{sub 2}-Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}); -10.3 {+-} 0.8 (N{sub 2}); -11.2 {+-} 0.4 (AdN{sub 3} (Ad = 1-adamantyl)); -13.8 {+-} 0.5 (N{sub 2}CHSiMe{sub 3}); -14.9 {+-} 0.9 (pyrazine = pz); -14.8 {+-} 0.6 (2,6-Me{sub 2}pz); -15.5 {+-} 1.8 (Me{sub 2}NCN); -16.6 {+-} 0.4 (CH{sub 3}CN); -17.0 {+-} 0.4 (pyridine); -17.5 {+-} 0.8 ([4-CH{sub 3}pz][PF{sub 6}] (in tetrahydrofuran)); -17.6 {+-} 0.4 (C{sub 6}H{sub 5}CN); -18.6 {+-} 1.8 (N{sub 2}CHC(=O)OEt); and -19.3 {+-} 2.5 kcal mol{sup -1} (pz)Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}). The value for the isonitrile AdNC (-29.0 {+-} 0.3) is 12.3 kcal mol{sup -1} more exothermic than that of the nitrile AdCN (-16.7 {+-} 0.6 kcal mol{sup -1}). The enthalpies of binding of a range of arene nitrile ligands were also studied, and remarkably, most nitrile complexes were clustered within a 1 kcal mol{sup -1} range despite dramatic color changes and variation of v{sub CN}. Computed structural and spectroscopic parameters for the complexes Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}L are in good agreement with experimental data. Computed binding enthalpies for Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}L exhibit considerable scatter and are generally smaller compared to the experimental values, but relative agreement is reasonable. Computed enthalpies of binding using a larger basis set for Mo(PMe{sub 3}){sub 2}(CO){sub 3}L show a better fit to experimental data than that for Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}L using a smaller basis set. Crystal structures of Mo(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(AdCN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(Me{sub 2}NCN), W(P{sup i}Pr{sub 3}){sub 2}(CO){sub 3}(2,6-F{sub 2}C{sub 6}H

  3. Molecular structure, NMR, UV-Visible, vibrational spectroscopic and HOMO, LUMO analysis of (E)-1-(2, 6-bis (4-methoxyphenyl)-3, 3-dimethylpiperidine-4-ylidene)-2-(3-(3, 5-dimethyl-1H-pyrazol-1-yl) pyrazin-2-yl) hydrazine by DFT method

    Science.gov (United States)

    Alphonsa, A. Therasa; Loganathan, C.; Anand, S. Athavan Alias; Kabilan, S.

    2016-02-01

    We have synthesized (E)-1-(2, 6-bis (4-methoxyphenyl)-3, 3-dimethylpiperidine-4-ylidene)-2-(3-(3, 5-dimethyl-1H-pyrazol-1-yl) pyrazin-2-yl) hydrazine (PM6). It was characterized using FT-IR, FT-Raman, 1H NMR, 13C NMR techniques. To interpret the experimental data, ab initio computations of the vibrational frequencies were carried out using the Gaussian 09 program followed by the full optimizations done using Density Functional Theory (DFT) at B3LYP/6-311 G(d,p) level. The combined use of experiments and computations allowed a firm assignment of the majority of observed bands for the compound. The calculated stretching frequencies have been found to be in good agreement with the experimental frequencies. The electronic and charge transfer properties have been explained on the basis of highest occupied molecular orbitals (HOMOs), lowest unoccupied molecular orbitals (LUMOs) and density of states (DOS). The absorption spectra have been computed by using time dependent density functional theory (TD-DFT). 1H and 13C NMR spectra were recorded and 1H and 13C NMR chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. From the optimized geometry of the molecule, molecular electrostatic potential (MEP) distribution, frontier molecular orbitals (FMOs) of the title compound have been calculated in the ground state theoretically. The theoretical results showed good agreement with the experimental values.

  4. Functionalized pyrazines as ligands for minor actinide extraction and catalysis

    NARCIS (Netherlands)

    Nikishkin, N.

    2013-01-01

    The research presented in this thesis concerns the design of ligands for a wide range of applications, from nuclear waste treatment to catalysis. The strategies employed to design actinide-selective extractants, for instance, comprise the fine tuning of the ligand electronic properties as well as

  5. Functionalized pyrazines as ligands for minor actinide extraction and catalysis

    NARCIS (Netherlands)

    Nikishkin, N.

    2013-01-01

    The research presented in this thesis concerns the design of ligands for a wide range of applications, from nuclear waste treatment to catalysis. The strategies employed to design actinide-selective extractants, for instance, comprise the fine tuning of the ligand electronic properties as well as us

  6. Structural flexibility and role of vicinal 2-thienyl rings in 2,3-dicyano-5,6-di(2-thienyl)-1,4-pyrazine, [(CN)2Th2Pyz], its palladium(II) complex [(CN)2Th2Pyz(PdCl2)2], and the related pentametallic pyrazinoporphyrazines [(PdCl2)4Th8TPyzPzM] (M = Mg(II)(H2O), Zn(II)).

    Science.gov (United States)

    Donzello, Maria Pia; De Mori, Giorgia; Viola, Elisa; Ercolani, Claudio; Bodo, Enrico; Mannina, Luisa; Capitani, Donatella; Rizzoli, Corrado; Gontrani, Lorenzo; Aquilanti, Giuliana; Kadish, Karl M; D'Angelo, Paola

    2011-12-05

    The solid state and solution structure of 2,3-dicyano-5,6-di(2-thienyl)-1,4-pyrazine, [(CN)(2)Th(2)Pyz], and its Pd(II) derivative, [(CN)(2)Th(2)Pyz(PdCl(2))(2)]·H(2)O, formed by reaction of [(CN)(2)Th(2)Pyz] with [(C(6)H(5)CN)(2)PdCl(2)] were characterized by X-ray, UV-visible, (1)H and (13)C NMR, and extended X-ray absorption fine structure (EXAFS) spectral measurements. The X-ray crystal structure of [(CN)(2)Th(2)Pyz] shows the presence of one thienyl ring positioned orthogonal to the rest of the molecule, with the two vicinal thienyl rings lying orthogonal to each other in a rare arrangement. NMR studies of [(CN)(2)Th(2)Pyz] in the solid state and in solutions of dimethylformamide or dimethyl sulfoxide confirm a nonequivalence of the thienyl rings in the solid state and also in solution. EXAFS results indicate that two distinct Pd(II) coordination sites are formed at the di(2-thienyl)pyrazino moiety of [(CN)(2)Th(2)Pyz(PdCl(2))(2)]·H(2)O, with identical Pd-N(pyz) (2.03(3) Å) and Pd-Cl (2.36(3) Å) bond lengths but with different Pd-S1 (2.25(4) Å) and Pd-S2 (3.21(5) Å) bond distances in an overall asymmetric molecular framework. Density functional theory (DFT) and time-dependent DFT (TDDFT) theoretical studies also provide information about the structure and spectral behavior of the precursor and its metalated Pd(II) derivative. (1)H/(13)C NMR and UV-visible spectral measurements were also carried out on two heteropentametallic porphyrazine macrocycles which were prepared by a reaction of PdCl(2) with [Th(8)TPyzPzM] where Th(8)TPyzPz = tetrakis-2,3-[5,6-di-(2-thienyl)-pyrazino]porphyrazinato dianion and M = Mg(II)(H(2)O) or Zn(II). Spectroscopic data on the newly synthesized [(PdCl(2))(4)Th(8)TPyzPzM] compounds suggest that the binding of PdCl(2) involves coordination sites of the type S(2(th))PdCl(2) with the two thienyl rings of each di(2-thienyl)pyrazino fragment bound to Pd(II) in an equivalent manner ("th-th" coordination). This is similar to what was

  7. 含2,4-二氨基-6-(2'-吡嗪)-均三嗪及甘氨酸的铜(Ⅱ)配合物的合成、晶体结构及与DNA作用%Synthesis, Crystal Structure and DNA-Binding Properties of Copper(Ⅱ) Complex with 6-(Pyrazin-2'-yl)-1,3,5-triazine-2,4-diamine and Glycinate

    Institute of Scientific and Technical Information of China (English)

    张雪梅; 区志镔; 陈实; 熊亚红; 周晓华; 刘海峰; 乐学义

    2012-01-01

    以2,4-二氨基-6-(2 '-吡嗪)-均三嗪(PZTA)及甘氨酸为配体与高氯酸铜作用合成了配合物[Cu(H2O)(Gly)(PZTA)]ClO4(Gly=甘氨酸根).通过元素分析、测定摩尔电导率、红外光谱和紫外可见光谱进行表征,并用单晶X-射线衍射方法测定了该配合物的晶体结构.配合物晶体属于单斜晶系,空间群C2/c,晶胞参数:a=2.1896(3) nm,b=1.3083(2) nm,c=1.4654(4) nm,β=131.467(3)°,晶胞体积:V=3.1456(9) nm3,晶胞内结构基元数:Z=8,Dc=1.876 g·cm-3,最后的残差因子:R1=0.0374,wR2=0.1009.应用紫外光谱、溴化乙锭荧光探针及粘度测定等方法研究了配合物与DNA的作用.结果表明,主题配合物以部分插入方式与DNA作用.%The copper(Ⅱ) complex [Cu(H2O)(Gly)(PZTA)]ClO4 (Gly=glycinate) was prepared by the reaction of 6-(pyrazin-2'-yl)-1,3,5-triazine-2,4-diamine (PZTA) and glycine (Gly) with copper(Ⅱ) perchlorate,and characterized by elemental analysis,infrared radiation,UV-Vis,and molar conductance.Its crystal structure was determined by single crystal X-ray diffraction method.The complex crystallizes in the monoclinic system,space group C2/c,with cell parameters: a=2.1896(3) nm,b=1.3083(2) nim,c=1.4654(4) nm,β=131.467(3)°,cell volume: V=3.1456(9)nm3,number of molecules inside the cell: Z=8,final R indices (I>2σ(I)): R1=0.0374,wR2=0.1009.The interaction of the complex to DNA was studied by UV spectroscopy,EtBr fluoescent probe and viscosity measurement.The results indicate that the complex could interact with DNA by partial intercalative mode.CCDC: 848150.

  8. 川芎嗪的临床应用%Clinical application of Tetramethy pyrazine

    Institute of Scientific and Technical Information of China (English)

    都本敏; 荆进红

    2006-01-01

    川芎嗪是由中药伞形科植物川芎(Ligusticum chuanxiong)的根茎提取的有效成分,属于酰胺类生物碱,化学结构为四甲基吡嗪(Tetramethylpyrazine,TMP),现在已可人工合成。近年来川芎嗪在临床应用越来越广泛,笔者现从心血管疾病、脑血管疾病、呼吸系统疾病和糖尿病并发症等几个方面着手,以阐述川芎嗪的临床应用及其作用机制。

  9. catena-Poly[[bis(pyrazine-2-carboxamidemercury(II]-di-μ-chlorido

    Directory of Open Access Journals (Sweden)

    Hamid Reza Khavasi

    2010-03-01

    Full Text Available In the polymeric title compound, [HgCl2(C5H5N3O2]n, the HgII atom (site symmetry overline{1} adopts a distorted trans-HgN2Cl4 octahedral coordination geometry. In the crystal, adjacent mercury ions are bridged by pairs of chloride ions, generating infinite [100] chains, and N—H...O and N—H...(N,N hydrogen bonds help to consolidate the packing.

  10. Hemiterpenoids and Pyrazines in the Odoriferous Urine of the Maned Wolf

    NARCIS (Netherlands)

    Goodwin, T.E.; Songsasen, N.; Broederdorf, L.J.; Burkert, B.A.; Joi Chen, C.; Jackson, S.R.; Keplinger, K.B.; Rountree, M.E.; Waldrip, Z.J.; Wedell, M.E.; Desrochers, L.P.; Baker, W.K.; Helsper, J.P.F.G.

    2013-01-01

    Maned wolves ( Chrysocyon brachyurus ) are endemic to South America, monogamous, solitary, and threatened in the wild. Maned wolf urine has a pungent and powerful odour and is used for scent marking. There is evidence to suggest that the presence of a male may be required to initiate oestrus and/or

  11. High Resolution Infrared Spectroscopy of Pyrazine and Naphthalene in a Molecular Bean

    Science.gov (United States)

    1993-10-26

    3063.3630 0.0108 21021 3063.2963 0.0054 19 118 18 217 3065.7753 0.0027 20 219 19 118 3065.8231 -0.0034 20 2 19 3063.2986 0.0018 211 20 3063.2330 -0.0028 19 1...t3065.88086 49.4 22022 21121 3066.25319 61.7 1175 1064 t 22,22 21021 1174 1065 t3065.84046 55.4 761 652 3066.24955 54.6 981 872 t 762 651 982 871 3065.83923...119 19 218 880 771 t 20219 19118 3066.14407 11.0 1358 1249 3065.82201 38.0 21121 20020 3066.12787 16.0 16512 15411 21021 20120 3066.11461 9.0 1165

  12. Hemiterpenoids and Pyrazines in the Odoriferous Urine of the Maned Wolf

    NARCIS (Netherlands)

    Goodwin, T.E.; Songsasen, N.; Broederdorf, L.J.; Burkert, B.A.; Joi Chen, C.; Jackson, S.R.; Keplinger, K.B.; Rountree, M.E.; Waldrip, Z.J.; Wedell, M.E.; Desrochers, L.P.; Baker, W.K.; Helsper, J.P.F.G.

    2013-01-01

    Maned wolves ( Chrysocyon brachyurus ) are endemic to South America, monogamous, solitary, and threatened in the wild. Maned wolf urine has a pungent and powerful odour and is used for scent marking. There is evidence to suggest that the presence of a male may be required to initiate oestrus and/or

  13. ARTICLES: Microwave Assisted Synthesis of a New Triplet Iridium(III) Pyrazine Complex

    Science.gov (United States)

    Wu, Qiu-hua; Wang, Chuan-hong; Song, Xi-ming; Zhang, Guo-lin

    2010-06-01

    A new cyclometalated iridium(III) complex Ir(DPP)3 (DPP = 2,3-diphenylpyrazine) was prepared by reaction of DPP with iridium trichloride hydrate under microwave irradiation. The structure of the complex was confirmed by elemental analysis, 1H NMR, and mass spectroscopy. The UV-Vis absorption and photoluminescent properties of the complex were investigated. The complex shows strong 1MLCT (singlet metal to ligand charge-transfer) and 3MLCT (triplet metal to ligand charge-transfer) absorption at 382 and 504 nm, respectively. The complex also shows strong photoluminescence at 573 nm at room temperature. These results suggest the complex to be a promising phosphorescent material.

  14. New 1,3,4-thiadiazole compounds including pyrazine moiety: Synthesis, structural properties and antimicrobial features

    Science.gov (United States)

    Gür, Mahmut; Şener, Nesrin; Muğlu, Halit; Çavuş, M. Serdar; Özkan, Osman Emre; Kandemirli, Fatma; Şener, İzzet

    2017-07-01

    In the study, some new 1,3,4-thiadiazole compounds were synthesized and we have reported identification of the structures by using UV-Vis, FT-IR, 1H NMR, 13C NMR and Mass spectroscopic methods. Antimicrobial activities of the compounds against three microorganisms, namely, Candida albicans ATCC 26555, Staphylococcus aureus ATCC 9144, and Escherichia coli ATCC 25922 were investigated by using disk diffusion method. These thiadiazoles exhibited an antimicrobial activity against Staphylococcus aureus and Candida albicans. The experimental data was supported by the quantum chemical calculations. Density functional theory (DFT) calculations were carried out to obtain the ground state optimized geometries of the molecules using the B3LYP, M06 and PBE1PBE methods with 3-21 g, 4-31 g, 6-311++g(2d,2p), cc-pvtz and cc-pvqz basis sets in the different combinations. Frontier molecular orbitals (FMOs) energies, band gap energies and some chemical reactivity parameters were calculated by using the aforementioned methods and basis sets, and the results were also compared with the experimental UV-Vis data.

  15. Analysis of Pyrazine and Volatile Compounds in Cocoa Beans Using Solid Phase Microextraction

    Directory of Open Access Journals (Sweden)

    Misnawi Jati

    2011-05-01

    Full Text Available Analisis pirazin dan senyawa volatil pada biji kakao dilakukan dengan perangkat mikroekstraksi fase padat (solid phase micro extraction, SPME, untuk mengembangkan metode ekstraksi tanpa pelarut yang efisien. Perangkat SPME dilengkapi fiber stableflex dengan polimer DVB/Carboxen/PDMS yang menjerap senyawa volatil di area headspace. Biji kakao terfermentasi disangrai dan diambil lemaknya untuk ditempatkan dalam botol bertutup septa. Sampel dipanaskan pada suhu 70OC dan serat SPME ditusukkan menembus septa untuk mengekstrak senyawa volatil dari lemak kakao selama 30 menit. Senyawa volatil lemak kakao akan dijerap oleh serat SPME dan dilepaskan kembali untuk analisis kromatografi gas. Penelitian menunjukkan pirazin dan senyawa volatil yang diekstrak oleh serat SPME dapat terdeteksi dengan baik oleh kromatografi gas. Area puncak yang dihasilkan SPME meliputi 2,83–5,35% dari area puncak yang dihasilkan syringe, kendati demikian kemampuan ekstraksi SPME dapat disetarakan dengan syringe. Lima jenis pirazin yang sering terdapat di biji kakao telah diidentifikasi, meliputi metil pirazin (2MP; 2,3 dan 2,5-dimetilpirazin (DMP; dan 2,3,5 trimetilpirazin (TrMP dan tetrametil pirazin (TMP. Senyawa lainnya juga terdeteksi meliputi alkohol, asam karboksilat, aldehida, keton, ester, pirazin, amin dan senyawa volatil lainnya, dan diketahui erat kaitannya dengan aroma khas cokelat. Keberhasilan SPME dalam ekstraksi pirazin dan senyawa volatilsemi volatil yang berperan penting dalam pembentukan aroma cokelat menandakan SPME dapat digunakan lebih lanjut untuk analisis citarasa.

  16. Synthesis of Perylene Imide Diones as Platforms for the Development of Pyrazine Based Organic Semiconductors.

    Science.gov (United States)

    de Echegaray, Paula; Mancheño, María J; Arrechea-Marcos, Iratxe; Juárez, Rafael; López-Espejo, Guzmán; López Navarrete, J Teodomiro; Ramos, María Mar; Seoane, Carlos; Ortiz, Rocío Ponce; Segura, José L

    2016-11-18

    There is a great interest in peryleneimide (PI)-containing compounds given their unique combination of good electron accepting ability, high abosorption in the visible region, and outstanding chemical, thermal, and photochemical stabilities. Thus, herein we report the synthesis of perylene imide derivatives endowed with a 1,2-diketone functionality (PIDs) as efficient intermediates to easily access peryleneimide (PI)-containing organic semiconductors with enhanced absorption cross-section for the design of tunable semiconductor organic materials. Three processable organic molecular semiconductors containing thiophene and terthiophene moieties, PITa, PITb, and PITT, have been prepared from the novel PIDs. The tendency of these semiconductors for molecular aggregation have been investigated by NMR spectroscopy and supported by quantum chemical calculations. 2D NMR experiments and theoretical calculations point to an antiparallel π-stacking interaction as the most stable conformation in the aggregates. Investigation of the optical and electrochemical properties of the materials is also reported and analyzed in combination with DFT calculations. Although the derivatives presented here show modest electron mobilities of ∼10(-4) cm(2)V(-1)s(-1), these preliminary studies of their performance in organic field effect transistors (OFETs) indicate the potential of these new building blocks as n-type semiconductors.

  17. Ammoxidation of 2-methyl pyrazine on supported ammonium salt of 12-molybdophosphoric acid catalysts: The influence of nature of support

    Indian Academy of Sciences (India)

    Katabathini Narasimharao; B Hari Babu; N Lingaiah; P S Sai Prasad; Shaeel A Al-Thabaiti

    2014-03-01

    Influence of the nature of support on the formation of catalytically active species was investigated to clarify the key factor for the synthesis of supported ammonium salt of 12-molybdophosphoric acid (AMPA) catalyst which maintains the activity of ammoxidation during 2-methylpyrazine reaction.With this aim, different loadings of niobia-, silica- and alumina-, supported AMPA catalysts were prepared. The AMPA loading was varied in the range of 5-25 wt%. The synthesized solids were characterized by nitrogen adsorption for BET surface area, XRD and 31P MAS NMR techniques. All the AMPA-supported samples are poorly crystalline even after 25 wt% AMPA loading. Investigations using 31P MAS NMR spectroscopy of samples revealed that Keggin ion existed as at least five different species on the supports. The investigated properties were acidity of the support and amount of AMPA loading on the support. Active sites for the ammoxidation of MP on supported AMPA catalysts seem to be the interacted and/or the lacunary species.Maximum catalytic activity could be obtained at lower loadings with AMPA deposited on acidic supports whereas the less acidic supports require higher loading. It was found that in order to efficiently generate the active interactive species, the support must have an acidity which promotes the formation of support-AMPA interactive species. It is possible to enhance the catalytic activity of the supported AMPA catalyst for ammoxidation of 2-methylpyrazine by controlling the acidity of the support and AMPA loading on the support.

  18. CCDC 1505386: Experimental Crystal Structure Determination : catena-[bis(mu-pyrazine)-(mu-fluoro)-(mu-oxido)-tetrafluoro-nickel-niobium carbon dioxide

    KAUST Repository

    Bhatt, Prashant

    2016-01-01

    An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  19. CCDC 970790: Experimental Crystal Structure Determination : catena-[bis(mu~2~-Pyrazine)-(mu~2~-hexafluorosilicate)-copper(ii) hydrate

    KAUST Repository

    Shekhah, Osama

    2014-01-01

    An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  20. Large-Scale Solvent-Free Chlorination of Hydroxy-Pyrimidines, -Pyridines, -Pyrazines and -Amides Using Equimolar POCl3

    Directory of Open Access Journals (Sweden)

    Zhihua Sun

    2012-04-01

    Full Text Available Chlorination with equimolar POCl3 can be efficiently achieved not only for hydroxypyrimidines, but also for many other substrates such as 2-hydroxy-pyridines, -quinoxalines, or even -amides. The procedure is solvent-free and involves heating in a sealed reactor at high temperatures using one equivalent of pyridine as base. It is suitable for large scale (multigram batch preparations.

  1. Formation of Pyrazines and a Novel Pyrrole in Maillard Model Systems of 1,3-Dihydroxyacetone and 2-Oxopropanal

    NARCIS (Netherlands)

    Adams, A.; Polizzi, V.; Boekel, van T.; Kimpe, de N.

    2008-01-01

    Alkylpyrazines are a very important class of Maillard flavor compounds, but their mechanism of formation is complex and consists of different pathways. The model reaction of 20 different amino acids with 1,3-dihydroxyacetone, as a precursor of 2-oxopropanal, was studied by means of SPME-GC-MS to

  2. Aqua(2,2′-bipyridyl(pyrazine-2,6-dicarboxylatonickel(II 1.25-hydrate

    Directory of Open Access Journals (Sweden)

    Yuan-Fang Zhang

    2008-11-01

    Full Text Available The asymmetric unit of the title compound, [Ni(C6H2N2O4(C10H8N2(H2O]·1.25H2O, contains two independent chemically identical NiII complex cations and two and a half solvent water molecules. The NiII ions are in slightly distorted coordination environments. In the crystal structure, intermolecular O—H...O and weak C—H...O hydrogen bonds link cations and water molecules into a three-dimensional network. One of the three uncoordinated water molecules is half-occupied.

  3. CCDC 1404097: Experimental Crystal Structure Determination : catena-((mu2-Hexafluorosilicato)-bis(mu2-pyrazine)-nickel dihydrate)

    KAUST Repository

    Shekhah, Osama

    2015-01-01

    An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  4. CCDC 1477136: Experimental Crystal Structure Determination : catena-[bis(mu-pyrazine)-(mu-oxido)-(mu-fluoro)-tetrafluoro-nickel-niobium dihydrate

    KAUST Repository

    Cadiau, Amandine

    2016-01-01

    An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  5. Synthesis of New Perhydropyrrolo[1,2-a]pyrazine Derivatives and Their Evaluation in Animal Models of Epilepsy

    Directory of Open Access Journals (Sweden)

    Maciej Dawidowski

    2014-10-01

    Full Text Available A series of novel stereochemically pure derivatives of the investigative broad-spectrum anticonvulsant ADD408003 was designed and synthesized. Five-center four-component (U-5C-4CR and four-center three-component (U-4C-3CR variants of Ugi reaction were used in the key step of the synthetic pathways. The compounds obtained were evaluated for the anticonvulsant activitiy in the maximal electroshock seizure (MES, subcutaneous Metrazole (scMET and minimal clonic seizure (6 Hz animal models of epilepsy. The efficacies of most derivatives in the 6 Hz model of pharmacoresistant partial seizures were markedly higher than in the ‘classical’ MES and scMET models. The most active compounds, (4R,8aR-3a, and (4S,8aS-6 displayed median effective doses (ED50 of 47.90 and 126.19 mg/kg, respectively, for the 6 Hz test.

  6. (3R,8aS-3-Ethylperhydropyrrolo[1,2-a]pyrazine-1,4-dione

    Directory of Open Access Journals (Sweden)

    Adailton J. Bortoluzzi

    2010-02-01

    Full Text Available In the title compound, C9H14N2O2, the pyrrolidine and piperazine rings adopt envelope and boat conformations, respectively. The chiral centers were assigned on the basis of the known stereogenic center of an enantiomerically pure starting material and the trans relationship between the H atoms attached to these centers. The crystal packing is stabilized by an intermolecular hydrogen bond between the N—H group and a carbonyl O atom of the diketopiperazine group, forming zigzag C(5 chains along [010].

  7. Electrostatic Molecular Interaction from X-ray Diffraction Data. I. Development of the Method; Test on Pyrazine

    NARCIS (Netherlands)

    Moss, Grant; Feil, Dirk

    1981-01-01

    Electrostatic interaction is often an important part of the total interaction between molecules. It depends on the electron density distribution in the participating molecules, which can, in principle, be determined by X-ray diffraction methods. A method is described to calculate the electrostatic i

  8. Diaquabis[bis(pyrazin-2-yl) sulfide-κN4]bis(thiocyanato-κN)iron(II) monohydrate

    National Research Council Canada - National Science Library

    Wöhlert, Susanne; Jess, Inke; Näther, Christian

    2013-01-01

    ...) sulfide ligands and two water molecules in an slightly distorted octahedral geometry. The FeII cation is located on a center of inversion and the lattice water molecule on a twofold rotation axis...

  9. CCDC 1505385: Experimental Crystal Structure Determination : catena-[bis(mu-pyrazine)-(mu-oxido)-(mu-fluoro)-tetrafluoro-nickel(ii)-niobium(v) dihydrate

    KAUST Repository

    Bhatt, Prashant

    2016-01-01

    An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  10. Antiferromagnetism in a Family of S = 1 Square Lattice Coordination Polymers NiX2(pyz)2 (X = Cl, Br, I, NCS; pyz = Pyrazine).

    Science.gov (United States)

    Liu, Junjie; Goddard, Paul A; Singleton, John; Brambleby, Jamie; Foronda, Francesca; Möller, Johannes S; Kohama, Yoshimitsu; Ghannadzadeh, Saman; Ardavan, Arzhang; Blundell, Stephen J; Lancaster, Tom; Xiao, Fan; Williams, Robert C; Pratt, Francis L; Baker, Peter J; Wierschem, Keola; Lapidus, Saul H; Stone, Kevin H; Stephens, Peter W; Bendix, Jesper; Woods, Toby J; Carreiro, Kimberly E; Tran, Hope E; Villa, Cecelia J; Manson, Jamie L

    2016-04-01

    The crystal structures of NiX2(pyz)2 (X = Cl (1), Br (2), I (3), and NCS (4)) were determined by synchrotron X-ray powder diffraction. All four compounds consist of two-dimensional (2D) square arrays self-assembled from octahedral NiN4X2 units that are bridged by pyz ligands. The 2D layered motifs displayed by 1-4 are relevant to bifluoride-bridged [Ni(HF2)(pyz)2]EF6 (E = P, Sb), which also possess the same 2D layers. In contrast, terminal X ligands occupy axial positions in 1-4 and cause a staggered packing of adjacent layers. Long-range antiferromagnetic (AFM) order occurs below 1.5 (Cl), 1.9 (Br and NCS), and 2.5 K (I) as determined by heat capacity and muon-spin relaxation. The single-ion anisotropy and g factor of 2, 3, and 4 were measured by electron-spin resonance with no evidence for zero-field splitting (ZFS) being observed. The magnetism of 1-4 spans the spectrum from quasi-two-dimensional (2D) to three-dimensional (3D) antiferromagnetism. Nearly identical results and thermodynamic features were obtained for 2 and 4 as shown by pulsed-field magnetization, magnetic susceptibility, as well as their Néel temperatures. Magnetization curves for 2 and 4 calculated by quantum Monte Carlo simulation also show excellent agreement with the pulsed-field data. Compound 3 is characterized as a 3D AFM with the interlayer interaction (J⊥) being slightly stronger than the intralayer interaction along Ni-pyz-Ni segments (J(pyz)) within the two-dimensional [Ni(pyz)2](2+) square planes. Regardless of X, J(pyz) is similar for the four compounds and is roughly 1 K.

  11. Diaqua-bis-[bis-(pyrazin-2-yl) sulfide-κN (4)]bis-(thio-cyanato-κN)iron(II) monohydrate

    National Research Council Canada - National Science Library

    Wöhlert, Susanne; Jess, Inke; Näther, Christian

    2013-01-01

    ...) sulfide ligands and two water mol-ecules in an slightly distorted octa-hedral geometry. The Fe(II) cation is located on a center of inversion and the lattice water mol-ecule on a twofold rotation axis...

  12. EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF); Scientific Opinion on Flavouring Group Evaluation 50, Revision 1 (FGE.50Rev1): Consideration of pyrazine derivatives evaluated by JECFA (57th meeting) structurally related to pyrazine derivatives evaluated by EFSA in FGE.17Rev2 (2010)

    DEFF Research Database (Denmark)

    Larsen, John Christian; Nørby, Karin Kristiane; Beltoft, Vibe Meister;

    The Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids of the European Food Safety Authority was requested to consider evaluations of flavouring substances assessed since 2000 by the Joint FAO/WHO Expert Committee on Food Additives (the JECFA), and to decide whether further...... concern at estimated levels of intake as flavouring substances” based on the MSDI approach. Adequate specifications for the materials of commerce are available for all 41 flavouring substances....

  13. Molecular recognition effects in atomistic models of imprinted polymers.

    Science.gov (United States)

    Dourado, Eduardo M A; Herdes, Carmelo; van Tassel, Paul R; Sarkisov, Lev

    2011-01-01

    In this article we present a model for molecularly imprinted polymers, which considers both complexation processes in the pre-polymerization mixture and adsorption in the imprinted structures within a single consistent framework. As a case study we investigate MAA/EGDMA polymers imprinted with pyrazine and pyrimidine. A polymer imprinted with pyrazine shows substantial selectivity towards pyrazine over pyrimidine, thus exhibiting molecular recognition, whereas the pyrimidine imprinted structure shows no preferential adsorption of the template. Binding sites responsible for the molecular recognition of pyrazine involve one MAA molecule and one EGDMA molecule, forming associations with the two functional groups of the pyrazine molecule. Presence of these specific sites in the pyrazine imprinted system and lack of the analogous sites in the pyrimidine imprinted system is directly linked to the complexation processes in the pre-polymerization solution. These processes are quite different for pyrazine and pyrimidine as a result of both enthalpic and entropic effects.

  14. Molecular Recognition Effects in Atomistic Models of Imprinted Polymers

    Directory of Open Access Journals (Sweden)

    Carmelo Herdes

    2011-07-01

    Full Text Available In this article we present a model for molecularly imprinted polymers, which considers both complexation processes in the pre-polymerization mixture and adsorption in the imprinted structures within a single consistent framework. As a case study we investigate MAA/EGDMA polymers imprinted with pyrazine and pyrimidine. A polymer imprinted with pyrazine shows substantial selectivity towards pyrazine over pyrimidine, thus exhibiting molecular recognition, whereas the pyrimidine imprinted structure shows no preferential adsorption of the template. Binding sites responsible for the molecular recognition of pyrazine involve one MAA molecule and one EGDMA molecule, forming associations with the two functional groups of the pyrazine molecule. Presence of these specific sites in the pyrazine imprinted system and lack of the analogous sites in the pyrimidine imprinted system is directly linked to the complexation processes in the pre-polymerization solution. These processes are quite different for pyrazine and pyrimidine as a result of both enthalpic and entropic effects.

  15. Marine natural product, Pyrrolo[1,2-a]pyrazine-1,4-dione, hexahydro-(C7H10N2O2) of antioxidant properties from Bacillus species at Lakshadweep archipelago

    Institute of Scientific and Technical Information of China (English)

    Mohan Gopi; Karuppaiah Nanthini Devi

    2014-01-01

    Objective:To investigate the antioxidant property of purified bioactive compound from sponge associated bacteria Bacillus species. Methods:The potential active compound was subjected for assay of total antioxidant activity,α,α-diphenyl-α-picrylhydrazyl (DPPH) radical scavenging activity, nitric oxide radical scavenging activity, hydrogen peroxide (H2O2) scavenging activity and total reducing power. Further, the 16S rRNA gene sequence was carried out to identify the sponge symbiotic bacteria. Results:The results showed linear increase of total antioxidant activity, DPPH radical scavenging activity, nitric oxide radical scavenging activity, H2O2 scavenging activity and total reducing power. IC50 value of the active compound for DPPH activity, H2O2 scavenging activity, nitric oxide scavenging activity was recorded as 15.025μg/mL, 23.73μg/mL, and 41.70μg/mL respectively. The potential strain was identified as Bacillus species from GenBank database (GenBank Accession number JX985748). Conclusions: The present study has reported the antioxidant property of purified bioactive compound from sponge associated Bacillus species. The report will be helpful to pharmaceutical and antioxidant researchers for further studies.

  16. Poly[di-μ-thiocyanato-κ2N:S;κ2S:N-bis[2-(1H-1,2,3-triazol-1-yl-κN3pyrazine]cadmium(II

    Directory of Open Access Journals (Sweden)

    Cheng Qi Liu

    2009-10-01

    Full Text Available In the title two-dimensional coordination polymer, [Cd(NCS2(C6H5N52]n, the CdII ion (site symmetry overline1 is coordinated by two N atoms from two 2-(1H-1,2,3-triazol-1-ylpyrazine ligands and two N and two S atoms from four thiocyanate anions. The N—Cd bond lengths range from 2.323 (2 to 2.3655 (19 Å and the S—Cd bond length is 2.7117 (7 Å. The associated cisoid angles vary from 84.99 (7 to 95.01 (7°, indicating that the CdII ion assumes a distorted octahedral geometry. In the complex, each thiocyanate anion functions as a bridging ligand, linking adjacent CdII ions with a separation of 6.4919 (6 Å, resulting in the formation of a two-dimensional sheet structure in the bc plane.

  17. EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF); Scientific Opinion on Flavouring Group Evaluation 17, Revision 3 (FGE.17Rev3): Pyrazine derivatives from chemical group 24

    DEFF Research Database (Denmark)

    Larsen, John Christian; Nørby, Karin Kristiane; Beltoft, Vibe Meister

    The Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids of the European Food Safety Authority was requested to evaluate 28 flavouring substances in the Flavouring Group Evaluation 17, including seven additional substances considered in this Revision 3, using the Procedure...... in Commission Regulation (EC) No 1565/2000. From the in vitro data available, genotoxic potential is indicated for the flavouring substances quinoxaline [FL-no: 14.147] and 2- methylquinoxaline [FL-no: 14.139]. Therefore, the Panel decided that the Procedure could not be applied to these two substances, until.......126, 14.127, 14.128, 14.129, 14.148, 14.161 and 14.170] do not give rise to safety concerns at their levels of dietary intake, estimated on the basis of the MSDI approach. For the remaining substance [FL-no: 14.052], additional toxicity data are required. Besides the safety assessment of these flavouring...

  18. Low-T magnetometry study of S = 1 Q2D [Ni(pyz)2(H2O)2](BF4)2 (pyz = pyrazine)

    Energy Technology Data Exchange (ETDEWEB)

    Manson, J. L. [Eastern Washington Univ., Cheney, WA (United States); Villa, D. Y. [Eastern Washington Univ., Cheney, WA (United States); Blackmore, W. J. A. [Univ. of Warwick, Coventry (United Kingdom); Brambleby, J. [Univ. of Warwick, Coventry (United Kingdom); Goddard, P. A. [Univ. of Warwick, Coventry (United Kingdom); Singleton, John [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-02-13

    [Ni(pyz)2(H2O)2](BF4)2 (pyz = N2C4H4) was synthesized by a solvent-free technique and its structure solved by synchrotron X-ray powder diffraction.1 The compound contains S = 1 Ni(II) ions and has tetragonal symmetry. Two-D [Ni(pyz)2(H2O)2]2+ square lattices propagate in the ab-plane and stack along the c-axis (Fig. 1). Water ligands occupy axial sites and form H-bonds with interlayer BF4- ions. SQUID magnetometry shows a possible transition to long-range magnetic order near 3 K. We measured the magnetization of [Ni(pyz)2(H2O)2](BF4)2 as a function of temperature to search for field-induced phase transitions and briefly report those findings here.

  19. 3,4-二(吡嗪-2′-基)氧化呋咱的合成与表征%Synthesis and Characterization of 3,4-Bis(pyrazine-2′-yl)furoxan

    Institute of Scientific and Technical Information of China (English)

    李亚南; 张志忠; 周彦水; 陈斌; 王伯周

    2009-01-01

    以2-氰基吡嗪为原料,经肟化、重氮化、脱氮、环化四步反应合成出-3,4-二(吡嗪-2′-基)氧化呋咱(DPF),总收率为51.0%,纯度99.3%;利用红外光谱、核磁共振、质谱、元素分析等手段对中间体与目标化合物的结构进行表征;探讨了氧化呋咱成环反应机理以及肟化、重氮化/脱氮及氧化呋咱成环的影响因素.氧化呋咱成环的最佳反应条件:Na_2CO_3摩尔量为理论值的1.10~1.25倍,反应温度2~10℃,反应时间4 h,收率75.6%,纯度不小于99.0%(HPLC).

  20. Synthesis and Crystal Structure of a Three-dimensional Cd(Ⅱ) Coordination Polymer [Cd(μ1,3-SCN)(μ3-pco)]n (pco = Pyrazine-2-carboxylate 4-oxide Anion)

    Institute of Scientific and Technical Information of China (English)

    SHI Jing-Min; XU Hong-Kun; WU Chang-Ju; LIU Lian-Dong

    2006-01-01

    The three-dimensional complex [Cd(μ1,3-SCN)(μ3-pco)]n has been synthesized with μ1,3-SCN- and pco as mixed bridged ligands. The crystal belongs to monoclinic, space group P21/n with a = 10.3777(16), b = 6.2592(9), c = 13.150(2) (A), β= 97.317(2)°, V=847.2(2) (A)3, Z= 4,C6H3CdN3O3S, Mr = 309.575, Dc = 2.427 g/cm3, F(000) = 592 and μ = 2.804 mm-1. The structure was refined to R = 0.0255 and wR = 0.0550 for 1712 observed reflections (I>2σ(I)). In the crystal the Cd(Ⅱ) ions are coordinated by μ1,3-SCN- and μ3-pco bridge ligands to form a three-dimensional structure.

  1. Analysis of the interfacial admittance in the case of a two-step two-electron electrode reaction with a diffusing intermediate, with application to the reduction of pyrazine

    NARCIS (Netherlands)

    Rueda, M.; Sluyters-Rehbach, M.; Sluyters, J.H.

    1987-01-01

    A critical evaluation is presented of the analysis of impedance or admittance data in the case of an electrode reaction proceeding by two consecutive one-electron transfers with a stable, solution-soluble intermediate. It is shown that the expression for this case, as derived by Armstrong and

  2. Structures and detonation performance for nitro derivatives of pyrazine by density functional theory%吡嗪类硝基衍生物结构与爆轰性能的DFT研究

    Institute of Scientific and Technical Information of China (English)

    陈铁旦; 王卷刚

    2011-01-01

    采用B3LYP/6-311++G**方法对26种硝基吡嗪类衍生物体系进行了全优化,几何优化结果表明所有优化后的化合物结构均无虚频,为势能面上的稳定结构;采用Monte-Carlo方法理论估算了26种化合物的密度,随着硝基数目的增加,密度增加;并设计等键等电子反应计算了其生成焓及其热力学性质,硝基数目逐渐增加时,Cp、Sm、Hm值都逐渐增大;运用Kamlet-Jacobs预测了爆速、爆压,其爆速在(6.52~9.72)km.s-1之间.结果表明:吡嗪环上有一定的芳香性,所设计的系列硝基吡嗪类化合物能量较高,是有潜力的含能材料候选物.%Twenty-six nitropyrazine compounds and its derivatives have been calculated by density functional theory. Their optimized geometries and electronic structures were computed at the B3LYP/6-311++G(d, p) level. Optimized geometries of these compounds show that they have no inmaginary frequencies, and they are stable on the potential energy surface. The heat capacity and enthalpy of some representative compounds at different temperatures were obtained by statistic thermodynamics. In order to calculate standard enthalpies of formation for the derivatives of nitrotriazole, isodesmic reactions were designed. The average molar volume and theoretical density were estimated using the Monte-Carlo method based on 0.001 ebohr-3 density space. Furthermore, the detonation velocity and pressure of the derivatives were estimated by the Kamlet-Jacbos equation. The results show that the ring of triazole has some aromaticity and the detonation velocities of these compounds are between 6.52 and 9.72 km·s-1. Detonation performance shows that these compounds are very good candidates for energetic materials.

  3. Generation, characterization, and reactivity of the transition metal-o-benzne analog of pyrazine (Fe{sup +}-2,3-didehydropyrazine) in the gas phase: An experimental and theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Chen, H.; Jacobson, D.B.; Freiser, B.S. [Purdue Univ., West Lafayette, IN (United States). H.C. Brown Lab. of Chemistry

    1999-04-26

    Fe{sup +}-2,3-didehydropyrazine (2) has been generated and its reactivity with simple olefins and alkynes studied by using Fourier transform ion cyclotron resonance (FTICR) mass spectrometry. 2, which is prepared by dehalogenation of chloropyrazine by Fe{sup +}, undergoes a simple adduct formation (no ligand coupling) with ethene and ethene-d{sub 4}. Ethyne also yields adduct formation; however, ligand coupling has clearly occurred in this reaction. Interestingly, reactions with propene and isobutene yield the same products with similar product distributions. Again, ligand coupling is involved and a metal-centered mechanism featuring activation of the allylic carbon-hydrogen bonds is proposed. Propyne, allene, 1-butene, and cis-2-butene yield a variety of products with 2. However, 2 yields exclusive dehydrogenation with 1,3-butadiene to generate FeC{sub 8}H{sub 6}N{sub 2}{sup +}. CID results suggest that this FeC{sub 8}H{sub 6}N{sub 2}{sup +} ion consists of quinoxaline bound to Fe{sup +}. Ligand displacement reactions yield a bond dissociation energy of 47 {+-} 5 kcal/mol for D{degree}(Fe{sup +}-quinoxaline). FeC{sub 4}H{sub 2}N{sub 2}{sup +} ion (2) has also been investigated theoretically. Density functional calculations predicted that the ground state of 2,3-didehydropyrazine is the triplet state, with the singlet state being 9.9 kcal/mol higher than the triplet state. 2 has C{sub 2{nu}} symmetry with the metal center coplanar with the 2,3-didehydropyrazine ring. 2 has a sextet ground state with doublet and quartet states 4.9 and 6.8 kcal/mol higher, respectively. The bond dissociation energy D{degree}(Fe{sup +}-C{sub 4}H{sub 2}N{sub 2}) for the sextet ground state is computed to be 87 {+-} 10 kcal/mol.

  4. 川芎嗪及其配伍对犬肺动脉高压血流动力学的影响%Effect of tetramelthyl pyrazine and its prescription on hemodynamics of pulmonary hypertension in dogs

    Institute of Scientific and Technical Information of China (English)

    崔勤; 赵建斌; 杨景学; 朱海龙

    2000-01-01

    目的探讨川芎嗪等药物对动力性肺动脉高压犬血流动力学影响. 方法利用幼犬肺动脉高压模型,经Swan-Ganz导管输入川芎嗪及其配伍,观察其对体、肺循环血流动力学影响. 结果单用川芎嗪可降低肺动脉压,但作用较弱,川芎嗪与黄芪、参麦等配伍后,降低肺动脉压作用增强,且降低体动脉压作用不及肺动脉压显著. 结论川芎嗪与黄芪、参麦合用,对肺循环有较好选择性.

  5. EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF); Scientific Opinion on Flavouring Group Evaluation 17, Revision 2 (FEG.17Rev2): Pyrazine derivatives from chemical group 24

    DEFF Research Database (Denmark)

    Larsen, John Christian; Nørby, Karin Kristiane; Beltoft, Vibe Meister;

    intake, estimated on the basis of the MSDI approach. For the remaining substance [FL-no: 14.052] additional toxicity data are required. Besides the safety assessment of these flavouring substances, the specifications for the materials of commerce have also been considered and for two substances...

  6. Palladium-catalyzed cross-coupling of various phosphorus pronucleophiles with chloropyrazines: synthesis of a novel Am(III)-selective extractants

    NARCIS (Netherlands)

    Nikishkin, N.; Huskens, Jurriaan; Assenmacher, J.; Wilden, A.; Modolo, G.; Verboom, Willem

    2012-01-01

    Palladium-catalyzed cross-coupling of (di)chloropyrazines with phosphorus pronucleophiles in the presence of a base gave the phosphorylated pyrazines in 81–95% yields. Based on this methodology a series of appropriately functionalized pyrazines was prepared as potential extractants of trivalent

  7. New parameters for evaluating the quality of commercial krill oil capsules from the aspect of lipid oxidation and non-enzymatic browning reactions

    DEFF Research Database (Denmark)

    Lu, Henna Fung Sieng; Bruheim, Inge; Jacobsen, Charlotte

    2015-01-01

    different commercial krill oil capsules through parameters such as: investigation of chemical compositions (bioactive compounds such as phospholipids, n-3 polyunsaturated fatty acids, antioxidants), hydrophobic pyrroles, and volatile profiles (lipid and Strecker-derived volatiles, pyridines, pyrazines...

  8. Componentes voláteis do café torrado. Parte I: compostos heterocíclicos Volatile components in roasted coffee. Part I: heterocyclic compounds

    Directory of Open Access Journals (Sweden)

    Carlos Alberto Bastos De Maria

    1999-04-01

    Full Text Available A review of heterocyclic compounds in roasted coffee is presented. The contents, precursors and sensorial properties of furans, pyrroles, oxazoles, thiazoles, thiophenes, pyrazines and pyridines are discussed. The impact heterocyclic compounds of coffee aroma are described.

  9. Structural and photophysical characterisation of coordination and optical isomers of mononuclear ruthenium(II) polypyridyl 1,2,4-triazole complexes

    NARCIS (Netherlands)

    Browne, Wesley R.; Hesek, Dusan; Gallagher, John F.; O’Connor, Christine M.; Killeen, J. Scott; Aoki, Fumiko; Ishida, Hitoshi; Inoue, Yoshihisa; Villani, Claudio; Vos, Johannes G.

    2003-01-01

    The X-ray crystal structure of the N2 isomers of the Ru(bipy)2 complexes of Hphpztr (1) and Hpztr (2), (bipy = 2,2'-bipyridine, Hphpztr = 2-(5'-phenyl-4'H-[1,2,4]triazol-3'-yl)pyrazine and Hpztr = 2-(4'H-[1,2,4]triazol-3'-yl)pyrazine) are reported. The molecular structure obtained for 2 demonstrates

  10. One-pot three-component synthesis of quinoxaline and phenazine ring systems using Fischer carbene complexes

    Directory of Open Access Journals (Sweden)

    Priyabrata Roy

    2010-05-01

    Full Text Available One-pot three-component coupling of o-alkynylheteroaryl carbonyl derivatives with Fischer carbene complexes and dienophiles leading to the synthesis of quinoxaline and phenazine ring systems has been investigated. This involves the generation of furo[3,4-b]pyrazine and furo[3,4-b]quinoxaline as transient intermediates, which were trapped with Diels–Alder dienophiles. This is the first report on furo[3,4-b]pyrazine intermediates.

  11. Highly efficient synthesis of quinoxaline derivatives from 1,2-benzenediamine and α-aminoxylated 1,3-dicarbonyl compounds.

    Science.gov (United States)

    Yan, Jianwei; Xu, Yanhong; Zhuang, Fangfang; Tian, Jie; Zhang, Guisheng

    2016-05-01

    Simple and efficient synthetic procedures for the preparation of quinoxaline, pyrazine, pyridopyrazine, and benzoxazin-2-one derivatives were developed. The one-pot cascade process involves the acidic elimination of α-aminoxylated dicarbonyl compounds to generate 1,2,3-tricarbonyl compounds and subsequent condensation with 1,4-N,N or -N,O dinucleophiles to afford quinoxaline, pyrazine, pyridopyrazine, and benzoxazin-2-one scaffolds. All the proposed processes do not need extra catalysts, dry solvents, or harsh reaction conditions.

  12. (1R,2R,3S,6aS,7R,8R,9S,12aS-1,2,3,7,8,9-Hexahydroxyperhydrodipyrido[1,2-a:1′,2′-d]pyrazine-6,12-dione

    Directory of Open Access Journals (Sweden)

    S. F. Jenkinson

    2010-04-01

    Full Text Available The crystal structure of the title compound, C12H18N2O8, exists as O—H...O hydrogen-bonded layers of molecules running parallel to the ab plane. Each molecule is a donor and acceptor for six hydrogen bonds. The absolute stereochemistry was determined by the use of d-glucuronolactone as the starting material.

  13. Bimetallic MOFs (H3O)x[Cu(MF6)(pyrazine)2]·(4 - x)H2O (M = V4+, x = 0; M = Ga3+, x = 1)

    DEFF Research Database (Denmark)

    Manson, Jamie L.; Schlueter, John A.; Garrett, Kerry E.

    2016-01-01

    The title compounds are bimetallic MOFs containing [Cu(pyz)2]2+ square lattices linked by MF6 n- octahedra. In each, only the Cu2+ spins exhibit long-range magnetic order below 3.5 K (M = V4+) and 2.6 K (M = Ga3+). The V4+ spins remain disordered down to 0.5 K....

  14. Conversion of Tobacco Biomass to Flavor Components by Means of Microwave and Parr Reactors

    Directory of Open Access Journals (Sweden)

    Ara Katayoun Mahdavi

    2017-04-01

    Full Text Available In the present work, microwave and Parr reactors were utilized for synthesis of pyrazines from plant-based biomass in the presence of ammonia and different amino acids. Using these techniques led to synthesis of a relatively wide range of pyrazines with sweet odor and chocolate-like smell. The optimum synthetic conditions to have maximum pyrazine yield for both the microwave and Parr reactions were 41 g of fructose/glucose syrup derived from cellulosic biomass, 28 mL NH4OH (30%, and 0.96 g L-threonine, 0.56 g L-valine, 0.5 g L-leucine, and 0.5 g L-isoleucine at 120 °C for 30 min. Quantitative results obtained via gas chromatography-mass spectrometry (GC-MS using the traditional open-heated oil bath method have been compared with data obtained via microwave and Parr reactors. In these two latter methods, sealed vessels under high pressure and higher temperature were used. The yield of synthesized pyrazines increased dramatically with both microwave and Parr reactors. Surprisingly, the yield of synthesized pyrazines was both reproducible and nearly two times higher via the Parr reactor than that observed with the microwave reactor under comparable conditions.

  15. Substituted N-Phenylpyrazine-2-carboxamides, Their Synthesis and Evaluation as Herbicides and Abiotic Elicitors

    Directory of Open Access Journals (Sweden)

    Katarína Kráľová

    2007-12-01

    Full Text Available The condensation of substituted pyrazine-2-carboxylic acid chlorides with ring-substituted anilines yielded five substituted pyrazine-2-carboxylic acid amides. Thesynthesis, and analytical, lipophilicity and biological data of the newly synthesizedcompounds are presented in this paper. The photosynthesis inhibition, antialgal activityand the effect of a series of pyrazine derivatives as abiotic elicitors on the accumulation offlavonoids in a callus culture of Ononis arvensis (L. were investigated. The most activeinhibitor of the oxygen evolution rate in spinach chloroplasts was 6-chloro-pyrazine-2-carboxylic acid (3-iodo-4-methylphenyl-amide (2, IC50 = 51.0 μmol·L-1. The highestreduction of chlorophyll content in Chlorella vulgaris was found for 5-tert-butyl-N-(4-chloro-3-methylphenyl-pyrazine-2-carboxamide (3, IC50 = 44.0 μmol·L-1. The maximalflavonoid production (about 900% was reached after a twelve-hour elicitation processwith 6-chloropyrazine-2-carboxylic acid (3-iodo-4-methylphenyl-amide (2.

  16. Comparison of natural and roasted Turkish tombul hazelnut (Corylus avellana L.) volatiles and flavor by DHA/GC/MS and descriptive sensory analysis.

    Science.gov (United States)

    Alasalvar, Cesarettin; Shahidi, Fereidoon; Cadwallader, Keith R

    2003-08-13

    Natural (raw) and roasted hazelnuts were compared for their differences in volatile components and sensory responses. A total of 79 compounds were detected in both hazelnuts, of which 39 (27 positive, 5 tentative, and 7 unknown) were detected in natural hazelnut and 71 (40 positive, 14 tentative, and 17 unknown) were detected in roasted hazelnut. These included ketones, aldehydes, pyrazines, alcohols, aromatic hydrocarbons, furans, pyrroles, terpenes, and acids. Pyrazines, pyrroles, terpenes, and acids were detected in roasted hazelnut only. Concentrations of several compounds increased as a result of roasting and these may play significant roles in the flavor of roasted hazelnut. Pyrazines together with ketones, aldehydes, furans, and pyrroles may contribute to the characteristic roasted aroma of hazelnut. Descriptive sensory analysis (DSA) showed that some flavor attributes such as "aftertaste", "burnt", "coffee/chocolate-like", "roasty", and "sweet" were rated significantly higher in roasted hazelnut compared to its natural counterpart. Natural and roasted hazelnuts can be distinguished using these attributes.

  17. Volatile compounds of black cumin seeds (Nigella sativa L.) from microwave-heating and conventional roasting.

    Science.gov (United States)

    Kiralan, Mustafa

    2012-04-01

    The volatile compounds in raw, conventionally roasted and microwave roasted black cumin (Nigella sativa L.) seeds at 0.45 kW for 2, 4, and 8 min, were analyzed by headspace-SPME gas chromatography-mass spectrometry. Among the 38 volatile compounds identified, the major compounds were thymoquinone and p-cymene in all samples. The levels of these compounds decreased with roasting. However, concentrations of pyrazines and furans increased significantly as a result of roasting and these compounds may affect the flavor of roasted black cumin seeds. Methyl pyrazine and 2,5-dimethylpyrazine were major pyrazines, formed at high concentration in seeds roasted for 8 min and in conventional roasting.

  18. Controlled synthesis of MoO{sub 3} microcrystals by subsequent calcination of hydrothermally grown pyrazine–MoO{sub 3} nanorod hybrids and their photodecomposition properties

    Energy Technology Data Exchange (ETDEWEB)

    Rajagopal, S., E-mail: raja2001s@gmail.com [Thin Films and Nanomaterials Research Laboratory, Department of Physics, Bharathiar University, Coimbatore 641 046 (India); Department of Chemical Engineering and Division of Energy Systems Research, Ajou University, San 5, Woncheon-dong, Yeontong-gu, Suwon 443-749 (Korea, Republic of); Department of Metallurgical and Materials Engineering, National Institute of Technology, Tiruchirappalli 620 015 (India); Nataraj, D., E-mail: de.natraj2011@gmail.com [Thin Films and Nanomaterials Research Laboratory, Department of Physics, Bharathiar University, Coimbatore 641 046 (India); Khyzhun, O.Y. [Frantsevych Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, 3 Krzhyzhanivsky Street, UA-03142 Kyiv (Ukraine); Djaoued, Yahia; Robichaud, Jacques [Laboratoire de Micro-spectroscopies Raman et FTIR, Université de Moncton-Campus de Shippagan, 218 boul. J.-D. Gauthier, Shippagan, NB E8S 1P6 (Canada); Kim, Chang-Koo [Department of Chemical Engineering and Division of Energy Systems Research, Ajou University, San 5, Woncheon-dong, Yeontong-gu, Suwon 443-749 (Korea, Republic of)

    2013-08-15

    We present our results on successful synthesis of pyrazine–MoO{sub 3} nanorod hybrids by using pyrazine and MoO{sub 3} nanorods. On the first stage, MoO{sub 3} nanorods were grown hydrothermally and, on the second stage, their mixture with pyrazine was again involved in a hydrothermal reaction to produce organic–inorganic hybrids. To understand the growth mechanism of the hybrids we varied time and temperature of the hydrothermal process. Intercalation of pyrazine was confirmed through X-ray diffraction analysis, X-ray photoelectron spectroscopy, X-ray emission spectroscopy, scanning electron microscopy methods. Upon calcinations, pyrazine was deintercalated, i.e. removed from the MoO{sub 3} hybrid system, and the MoO{sub 3} nanorods were found to bind together resulting in formation of MoO{sub 3} microslabs with increased surface area. Photodecomposition performance of the MoO{sub 3} nanorods, pyrazine–MoO{sub 3} hybrids and MoO{sub 3} microcrystals was studied against Procion Red MX-5B textile dye. A high photodecomposition performance was found to decrease when going from MoO{sub 3} nanorods to MoO{sub 3} microcrystal and, further, to pyrazine–MoO{sub 3} hybrids. - Graphical abstract: Display Omitted - Highlights: • High aspect ratio MoO{sub 3} nanorods were prepared through a new hydrothermal method. • Hybrids of pyrazine–MoO{sub 3} were formed by intercalating pyrazine into MoO{sub 3} nanorods. • Intercalation of pyrazine was confirmed in X-ray spectroscopic analysis. • After calcinations, MoO{sub 3} crystal was retained by binding MoO{sub 3} nanorods together. • High photodegradation performance was noticed from MoO{sub 3} nanorods.

  19. 6,7-Dichloro-3-(2,4-dichlorobenzylquinoxalin-2(1H-one

    Directory of Open Access Journals (Sweden)

    Jinpeng Zhang

    2012-08-01

    Full Text Available In the title compound, C15H8Cl4N2O, the quinoxaline ring system is almost planar, with a dihedral angle between the benzene and pyrazine rings of 3.1 (2°. The 2,4-dichlorophenyl ring is approximately perpendicular to the pyrazine ring, with a dihedral angle of 86.47 (13° between them. The crystal packing features intermolecular N—H...O hydrogen bonds and π–π stacking interactions, with centroid–centroid distances in the range 3.699 (3–4.054 (3 Å.

  20. 4-Pyridylnitrene and 2-pyrazinylcarbene

    Science.gov (United States)

    Reisinger, Ales; Kvaskoff, David

    2013-01-01

    Summary Both flash vacuum thermolysis (FVT) and matrix photolysis generate 2-diazomethylpyrazine (22) from 1,2,3-triazolo[1,5-a]pyrazine (24). FVT of 4-azidopyridine (18) as well as of 24 or 2-(5-tetrazolyl)pyrazine (23) affords the products expected from the nitrene, i.e., 4,4’-azopyridine and 2- and 3-cyanopyrroles. Matrix photolyses of both 18 and 24 result in ring expansion of 4-pyridylnitrene/2-pyrazinylcarbene to 1,5-diazacyclohepta-1,2,4,6-tetraene (20). Further photolysis causes ring opening to the ketenimine 27. PMID:23766787

  1. Heteroaromatic-based electrolytes for lithium and lithium-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Gang; Abraham, Daniel P.

    2017-04-18

    The present invention provides an electrolyte for lithium and/or lithium-ion batteries comprising a lithium salt in a liquid carrier comprising heteroaromatic compound including a five-membered or six-membered heteroaromatic ring moiety selected from the group consisting of a furan, a pyrazine, a triazine, a pyrrole, and a thiophene, the heteroaromatic ring moiety bearing least one carboxylic ester or carboxylic anhydride substituent bound to at least one carbon atom of the heteroaromatic ring. Preferred heteroaromatic ring moieties include pyridine compounds, pyrazine compounds, pyrrole compounds, furan compounds, and thiophene compounds.

  2. Ruthenium(II) and osmium(II) polypyridyl complexes of an asymmetric pyrazinyl- and pyridinyl-containing 1,2,4-triazole based ligand. Connectivity and physical properties of mononuclear complexes

    NARCIS (Netherlands)

    Browne, Wesley R.; O’Connor, Christine M.; Hughes, Helen P.; Hage, Ronald; Walter, Olaf; Doering, Manfred; Gallagher, John F.; Vos, Johannes G.

    2002-01-01

    The synthesis, purification and characterisation of two coordination isomers of ruthenium(II) and osmium (II) complexes containing the ligand 3-(pyrazin-2'-yl)-5-(pyridin-2"-yl)-1,2,4-triazole (Hppt) are described. The X-ray and molecular structure of the complex [Ru(bipy)(2) (ppt)] PF6.CH3OH (1a) i

  3. Extended quantum critical phase in a magnetized spin-1/2 antiferromagnetic chain

    DEFF Research Database (Denmark)

    Stone, M.B.; Reich, D.H.; Broholm, C.

    2003-01-01

    Measurements are reported of the magnetic field dependence of excitations in the quantum critical state of the spin S=1/2 linear chain Heisenberg antiferromagnet copper pyrazine dinitrate (CuPzN). The complete spectrum was measured at k(B)T/Jless than or equal to0.025 for H=0 and H=8.7 T, where...

  4. Synthesis of Novel Pyrazinamide Derivatives Based on 3-Chloropyrazine-2-carboxamide and Their Antimicrobial Evaluation

    Directory of Open Access Journals (Sweden)

    Ondrej Jandourek

    2017-02-01

    Full Text Available Aminodehalogenation of 3-chloropyrazine-2-carboxamide with variously substituted benzylamines yielded a series of fifteen 3-benzylaminopyrazine-2-carboxamides. Four compounds possessed in vitro whole cell activity against Mycobacterium tuberculosis H37Rv that was at least equivalent to that of the standard pyrazinamide. MIC values ranged from 6 to 42 μM. The best MIC (6 μM was displayed by 3-[(4-methylbenzylamino]pyrazine-2-carboxamide (8 that also showed low cytotoxicity in the HepG2 cell line (IC50 ≥ 250 μM. Only moderate activity against Enterococcus faecalis and Staphylococcus aureus was observed. No activity was detected against any of tested fungal strains. Molecular docking with mycobacterial enoyl-ACP reductase (InhA was performed to investigate the possible target of the prepared compounds. Active compounds shared common binding interactions of known InhAinhibitors. Antimycobacterial activity of the title compounds was compared to the previously published benzylamino-substituted pyrazines with differing substitution on the pyrazine core (carbonitrile moiety. The title series possessed comparable activity and lower cytotoxicity than molecules containing a carbonitrile group on the pyrazine ring.

  5. Mechanism of the self-condensation of GlcNH2

    DEFF Research Database (Denmark)

    Jia, Lingyu; Liu, Xingchen; Qiao, Yan

    2017-01-01

    dihydrofructosazine [2,5-bis(d-arabino-tetrahydroxybutyl)dihydropyrazine], which subsequently is converted to the corresponding pyrazine ring carbons of DOF and FZ respectively. The isotopic-labelling experiments disclose that there are two parallel reaction pathways open to the intermediate dihydrofructosazine, when...

  6. [Sigma]-Adducts of pteridines and 3-deazapteridines, structure and reactivity

    NARCIS (Netherlands)

    Nagel, A.

    1978-01-01

    In the introduction of this thesis the reactions of pteridines and pyrido[2,3- b ]-pyrazines with nucleophiles are reviewed. In the following chapters the results of an NMR investigation on the formation of σ-adducts between these azaaromatic ring systems and nitrogen

  7. Revision of outcome and mechanism of a new multicomponent reaction.

    Science.gov (United States)

    Carballares, Santiago; Espinosa, Juan F

    2005-06-09

    [reaction: see text] A recently reported multicomponent reaction (MCR) produces pyrido[1,2-a]pyrazines and not the previously described 1H-imidazol-4-yl-pyridines. This different structure is proposed on the basis of a new mechanism of formation and the spectroscopic data.

  8. Enhanced sensitivity of Cypridina luciferin analog (CLA) chemiluminescence for the detection of O2- with non ionic detergents

    NARCIS (Netherlands)

    Osman, A.M.; Laane, C.; Hilhorst, R.

    2000-01-01

    Superoxide anion-triggered chemiluminescence of Cypridina luciferin analogue (CLA), 2-methyl-6-phenyl-3,7-dohydroimidazo[1,2-]pyrazin-3-one, is enhanced by non-ionic detergents such as Tween 20, Triton X-100 and Tween 80. At the concentration of 0.6øv/v) the largest increase (2.7-fold) of CLA light

  9. Highly Selective Water Adsorption in a Lanthanum Metal-Organic Framework

    NARCIS (Netherlands)

    Plessius, R.; Kromhout, R.; Dantas Ramos, A.L.; Ferbinteanu, M.; Mittelmeijer-Hazeleger, M.C.; Krishna, R.; Rothenberg, G.; Tanase, S.

    2014-01-01

    We present a new metal-organic framework (MOF) built from lanthanum and pyrazine-2,5-dicarboxylate (pyzdc) ions. This MOF, [La(pyzdc)(1.5)(H2O)(2)]center dot 2H(2)O, is microporous, with 1D channels that easily accommodate water molecules. Its framework is highly robust to dehydration/hydration

  10. In situ co-crystallisation as a tool for low-temperature crystal engineering

    DEFF Research Database (Denmark)

    Bond, Andrew D

    2003-01-01

    Synthesis and single-crystal X-ray diffraction of a series of low-melting co-crystals of pyrazine and n-alkyl carboxylic acids demonstrates in situ co-crystallisation as a versatile tool for low-temperature crystal engineering....

  11. Sigma-Adducts of pteridines and 3-deazapteridines : structure and reactivity

    NARCIS (Netherlands)

    Nagel, A.

    1978-01-01

    In the introduction of this thesis the reactions of pteridines and pyrido[2,3- b ]-pyrazines with nucleophiles are reviewed. In the following chapters the results of an NMR investigation on the formation of σ-adducts between these azaaromatic ring systems and nitrogen nucleophiles, especially KNH

  12. Ruthenium(II) and osmium(II) polypyridyl complexes of an asymmetric pyrazinyl- and pyridinyl-containing 1,2,4-triazole based ligand. Connectivity and physical properties of mononuclear complexes

    NARCIS (Netherlands)

    Browne, Wesley R.; O’Connor, Christine M.; Hughes, Helen P.; Hage, Ronald; Walter, Olaf; Doering, Manfred; Gallagher, John F.; Vos, Johannes G.

    2002-01-01

    The synthesis, purification and characterisation of two coordination isomers of ruthenium(II) and osmium (II) complexes containing the ligand 3-(pyrazin-2'-yl)-5-(pyridin-2"-yl)-1,2,4-triazole (Hppt) are described. The X-ray and molecular structure of the complex [Ru(bipy)(2) (ppt)] PF6.CH3OH (1a) i

  13. Chemistry around imidazopyrazine and ibuprofen: discovery of novel fatty acid amide hydrolase (FAAH) inhibitors.

    Science.gov (United States)

    De Wael, Frédéric; Muccioli, Giulio G; Lambert, Didier M; Sergent, Thérèse; Schneider, Yves-Jacques; Rees, Jean-François; Marchand-Brynaert, Jacqueline

    2010-09-01

    Based on the imidazo-[1,2-a]-pyrazin-3-(7H)-one scaffold, a dual action prodrug has been designed for combining antioxidant and anti-inflammatory activities, possibly unmasked upon oxidation. The construction of the target-molecule requires two building blocks, namely a 2-amino-1,4-pyrazine and a 2-ketoaldehyde. Attempts to synthesize the 2-ketoaldehyde (5a) derived from ibuprofen failed, but led to the corresponding 2-ketoaldoxime (7a) which could not be condensed with the pyrazine synthons. However, a model compound, i.e. phenylglyoxal aldoxime, reacted well under microwave activation to furnish novel imidazo[1,2-a]-pyrazine-3-(7H)-imine derivatives (18a,b). These heterobicycles behave as antioxidants by inhibiting the lipid peroxidation, and one compound (18b) is endowed with a significant anti-inflammatory effect in a cellular test. Unexpectedly, all the synthetic intermediates derived from ibuprofen are good inhibitors of FAAH, the most active compound (4a) featuring the 1,3-dithian-2-yl motif.

  14. A novel and simple synthetic route for a piperazine derivative

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Maria A.S. da; Pinheiro, Solange de O.; Francisco, Thiago dos S.; Silva, Francisco O.N. da; Carvalho, Idalina M.M.; Sousa, Jackson R. de; Dias-Filho, Francisco A.; Diogenes, Izaura C.N. [Universidade Federal do Ceara (UFC), Fortaleza, CE (Brazil). Dept. de Quimica Organica e Inorganica; Batista, Alzir A. [Universidade Federal de Sao Carlos (UFSCAR), Sao Carlos, SP (Brazil). Dept. de Quimica; Ellena, Javier [Universidade de Sao Paulo (USP), Sao Carlos, SP (Brazil). Inst. de Fisica; Longhinottid, Elisane, E-mail: izaura@dqoi.ufc.b [Universidade Federal do Ceara (UFC), Fortaleza, CE (Brazil). Dept. de Quimica Analitica e Fisico-Quimica

    2010-07-01

    A new derivative of piperazine, 5-oxopiperazinium-3-sulfonate monohydrate, was produced from a simple synthetic route as a result of the nucleophilic addition to HSO{sub 3} - bisulphite ion and of the nucleophilic attack of water molecules on pyrazine molecules. The isolated material was characterized by means of NMR, mass spectrometry, infrared, and X-ray diffraction. (author)

  15. The effect of peripheral bipyridine ligands on the photocatalytic hydrogen production activity of Ru/Pd catalysts

    NARCIS (Netherlands)

    Bindra, Gurmeet Singh; Schulz, Martin; Paul, Avishek; Soman, Suraj; Groarke, Robert; Inglis, Jane; Pryce, Mary T.; Browne, Wesley R.; Rau, Sven; Maclean, Brian J.; Vos, Johannes G.

    2011-01-01

    A pyrazine bridged ruthenium/palladium bimetallic photocatalyst with peripheral 4,4'-dicarboxyethyl-2,2'-bipyridine ligands, EtOOC-RuPd, is reported, together with its 2,2'-bipyridine analogue. Upon irradiation with visible light, EtOOC-RuPd catalyses the production of hydrogen gas whereas the compl

  16. Water soluble (Eta sup (6) - arene) ruthenium (II) complexes incorporating marine derived bioligand: Synthesis, spectral and structural studies

    Digital Repository Service at National Institute of Oceanography (India)

    Singh, K.S.; Svitlyk, V.; PrabhaDevi; Mozharivskyj, Y.

    ) or L sub(2) in the presence of AgBF sub(4) (L sub(1) = PyCN, DMAP; L sub(2) = 4,4`-bipy, pyrazine). The complexes are characterized on the basis of spectroscopic data and molecular structures of three representative compounds have been determined...

  17. Pressure-induced local structure distortions in Cu(pyz)F{sub 2}(H{sub 2}O){sub 2}.

    Energy Technology Data Exchange (ETDEWEB)

    Musfeldt, J. L.; Liu, Z.; Li, S.; Kang, J.; Lee, C.; Jena, P.; Manson, J. L.; Schlueter, J. A.; Carr, G. L.; Whangbo, M.-H. (Materials Science Division); (Univ. of Tennessee); (Carnegie Inst. of Washington); (Virginia Commonwealth Univ.); (North Carolina State Univ.); (Eastern Washington Univ.); (BNL)

    2011-06-06

    We employed infrared spectroscopy along with complementary lattice dynamics and spin density calculations to investigate pressure-driven local structure distortions in the copper coordination polymer Cu(pyz)F{sub 2}(H{sub 2}O){sub 2}. Here, pyz is pyrazine. Our study reveals rich and fully reversible local lattice distortions that buckle the pyrazine ring, disrupt the bc-plane O-H {hor_ellipsis} F hydrogen-bonding network, and reinforce magnetic property switching. The resiliency of the soft organic ring is a major factor in the stability of this material. Interestingly, the collective character of the lattice vibrations masks direct information on the Cu-N and Cu-O linkages through the series of pressure-induced Jahn-Teller axis switching transitions, although Cu-F bond softening is clearly identified above 3 GPa. These findings illustrate the importance of combined bulk and local probe techniques for microscopic structure determination in complex materials.

  18. Pressure-Induced Local Structure Distortions in Cu(pyz)F(2)(H(2)O)(2)

    Energy Technology Data Exchange (ETDEWEB)

    J Musfeldt; Z Liu; S Li; J Kang; C Lee; P Jena; J Manson; J Schlueter; G Carr; M Whangbo

    2011-12-31

    We employed infrared spectroscopy along with complementary lattice dynamics and spin density calculations to investigate pressure-driven local structure distortions in the copper coordination polymer Cu(pyz)F{sub 2}(H{sub 2}O){sub 2}. Here, pyz is pyrazine. Our study reveals rich and fully reversible local lattice distortions that buckle the pyrazine ring, disrupt the bc-plane O-H {hor_ellipsis} F hydrogen-bonding network, and reinforce magnetic property switching. The resiliency of the soft organic ring is a major factor in the stability of this material. Interestingly, the collective character of the lattice vibrations masks direct information on the Cu-N and Cu-O linkages through the series of pressure-induced Jahn-Teller axis switching transitions, although Cu-F bond softening is clearly identified above 3 GPa. These findings illustrate the importance of combined bulk and local probe techniques for microscopic structure determination in complex materials.

  19. Pressure Induced Local Structure Distortions in Cu(pyz)F2(H2O)2

    Energy Technology Data Exchange (ETDEWEB)

    Musfeldt, J.L.; Carr, G.; Liu, Z.; Li, S.; Kang, C.L., Jena, P.; Manson, J.L.; Schlueter, J.A. Whangbo, M.H.

    2011-06-06

    We employed infrared spectroscopy along with complementary lattice dynamics and spin density calculations to investigate pressure-driven local structure distortions in the copper coordination polymer Cu(pyz)F{sub 2}(H{sub 2}O){sub 2}. Here, pyz is pyrazine. Our study reveals rich and fully reversible local lattice distortions that buckle the pyrazine ring, disrupt the bc-plane O-H {hor_ellipsis} F hydrogen-bonding network, and reinforce magnetic property switching. The resiliency of the soft organic ring is a major factor in the stability of this material. Interestingly, the collective character of the lattice vibrations masks direct information on the Cu-N and Cu-O linkages through the series of pressure-induced Jahn-Teller axis switching transitions, although Cu-F bond softening is clearly identified above 3 GPa. These findings illustrate the importance of combined bulk and local probe techniques for microscopic structure determination in complex materials.

  20. 2,5-Bis[4-(dimethylaminophenyl]-3,6-dimethylpyrazine

    Directory of Open Access Journals (Sweden)

    Sebastian Moschel

    2011-06-01

    Full Text Available The title compound, C22H26N4, was prepared from p-dimethylaminopropiophenone in six steps. The molecule has no crystallographic symmetry. The dihedral angles between the pyrazine ring and the phenyl rings are 35.81 (6 and 37.11 (8°. The dimethylamino groups are essentially planar (sum of the bond angles at N = 359.3 and 359.9° and nearly coplanar with the adjacent aromatic ring [dihedral angles = 5.54 (11 and 7.40 (3°]. This effect and the short aniline C—N bonds can be rationalised in terms of charge transfer from the amino groups to the central pyrazine ring.

  1. Analysis of the volatiles in the headspace above the plasmodium and sporangia of the slime mould (Physarum polycephalum) by SPME-GCMS

    CERN Document Server

    Kateb, Huda al

    2013-01-01

    Solid phase micro-extraction (SPME) coupled with Gas Chromatography Mass Spectrometry (GC-MS) was used to extract and analyse the volatiles in the headspace above the plasmodial and sporulating stages of the slime mould Physarum Polycephalum. In total 115 compounds were identified from across a broad range of chemical classes. Although more (87) volatile organic compounds (VOCs) were identified when using a higher incubation temperature of 75oC, a large number of compounds (79) were still identified at the lower extraction temperature of 30oC and where the plasmodial stage was living. Far fewer compounds were extracted after sporulation at the two extraction temperatures. There were some marked differences between the VOCs identified in the plasmodial stage and after sporulation. In particular the nitrogen containing compounds acetonitrile, pyrrole, 2, 5-dimethyl-pyrazine and trimethyl pyrazine seemed to be associated with the sporulating stage. There were many compounds associated predominantly with the plas...

  2. Uso de perfis cromatográficos de voláteis de cafés arábicas torrados para a diferenciação das amostras segundo o sabor, o aroma e a qualidade global da bebida

    Directory of Open Access Journals (Sweden)

    Juliano S. Ribeiro

    2010-01-01

    Full Text Available In this work, the volatile chromatographic profiles of roasted Arabica coffees, previously analyzed for their sensorial attributes, were explored by principal component analysis. The volatile extraction technique used was the solid phase microextraction. The correlation optimized warping algorithm was used to align the gas chromatographic profiles. Fifty four compounds were found to be related to the sensorial attributes investigated. The volatiles pyrrole, 1-methyl-pyrrole, cyclopentanone, dihydro-2-methyl-3-furanone, furfural, 2-ethyl-5-methyl-pyrazine, 2-etenyl-n-methyl-pyrazine, 5-methyl-2-propionyl-furan compounds were important for the differentiation of coffee beverage according to the flavour, cleanliness and overall quality. Two figures of merit, sensitivity and specificity (or selectivity, were used to interpret the sensory attributes studied.

  3. Theoretical Studies on the Interactions of Cations with Diazine

    Institute of Scientific and Technical Information of China (English)

    CHEN Xing; WU Wen-Peng; ZHANG Jing-Lai; CAO Ze-Xing

    2006-01-01

    Density functional theory and MP2 calculations have been used to determine the geometries, stabilities, binding energies, and dissociative properties of cation-diazine complexes Mn+-C4H4N2 (Mn+ = Li+, B+, Al+, Be2+, Mg2+, Ca2+). The calculated results indicate that most complexes are stable except the π complexes of Ca2+-pyridazine, Ca2+-pyrazine, Al+-pyrimidine and Al+-pyrimidine. The σ complexes are generally much more stable than their π counterparts. Among the π complexes, the cation-pyrazine π complexes have slightly higher stability. The nature of the ion-molecule interactions has been discussed by the natural bond orbital analysis and frontier molecular orbital interactions. In these σ complexes, there is stronger covalent interaction between B+ and diazine. In the selected π complexes, B+ and Be2+ have stronger covalent interaction with diazine, while the other cations mainly have electrostatic interaction with diazine.

  4. N-(3-Methylphenylquinoxalin-2-amine monohydrate

    Directory of Open Access Journals (Sweden)

    Azila Idris

    2010-09-01

    Full Text Available The quinoxaline system in the title hydrate, C15H13N3·H2O, is roughly planar, the r.m.s. deviation for the 18 non-H atoms being 0.188 Å; this conformation features a short intramolecular C—H...N(pyrazine interaction. In the crystal, the amine H atom forms an N—H...O hydrogen bond to the water molecule, which in turn forms two O—H...N hydrogen bonds to the pyrazine N atoms of different organic molecules. These interactions lead to supramolecular arrays in the bc plane that are two molecules thick; additional π–π interactions stabilize the layers [ring centroid–centroid distance = 3.5923 (7 Å]. The layers stack along the a-axis direction via C—H...π contacts.

  5. A metal-organic framework-based splitter for separating propylene from propane

    KAUST Repository

    Cadiau, A.

    2016-07-07

    The chemical industry is dependent on the olefin/paraffin separation, which is mainly accomplished by using energy-intensive processes. We report the use of reticular chemistry for the fabrication of a chemically stable fluorinated metal-organic framework (MOF) material (NbOFFIVE-1-Ni, also referred to as KAUST-7). The bridging of Ni(II)-pyrazine square-grid layers with (NbOF5)2- pillars afforded the construction of a three-dimensional MOF, enclosing a periodic array of fluoride anions in contracted square-shaped channels. The judiciously selected bulkier (NbOF5)2- caused the looked-for hindrance of the previously free-rotating pyrazine moieties, delimiting the pore system and dictating the pore aperture size and its maximum opening. The restricted MOF window resulted in the selective molecular exclusion of propane from propylene at atmospheric pressure, as evidenced through multiple cyclic mixed-gas adsorption and calorimetric studies.

  6. [Hypertensive action of 5-(beta-aminoethyl)aminoisoxazoles: synthesis and screening of isoxazolopyrazines and isoxazolodiazepines].

    Science.gov (United States)

    Dannhardt, G; Dominiak, P; Laufer, S

    1991-03-01

    The 5-aminoisoxazole 1 is converted via the 4-nitro derivative to the 4,5-diamino compound 4, which cyclises with glyoxal to yield the isoxazolo[4,5-b)pyrazine 5. Decomposition of the isoxazole moiety is always observed in experiments to hydrogenate partially the pyrazine ring and to phenylate the N-atom, respectively. Therefore, the corresponding tetrahydro derivative 6 is prepared from 4 and 1,2-ethandiol ditosylate. Starting with benzohydroxamic acid chloride and a cyanoacetic acid amide the tetrahydro isoxazolo[5,4-e]1,4-diazepinone-4 18 is synthesized. All new compounds are characterized by their spectroscopic data, the reaction mechanisms are discussed. Using the model of the pithed and the anaesthetized rat, resp., the pyrazino- and diazepino-isoxazoles (compounds 5, 6, 13, 18) have less or no hypertensive activity as compared to the corresponding derivatives with fully flexible side chains.

  7. Rh(II) Catalyzed High Order Cycloadditions of 8-Azaheptafulvenes with N-Sulfonyl 1,2,3-Triazloes or α-Oxo Diazocompounds.

    Science.gov (United States)

    Chen, Wei; Bai, Ya-Li; Luo, Yong-Chun; Xu, Peng-Fei

    2017-01-20

    A novel strategy was developed for the application of Rh carbenes generated from readily accessible N-sulfonyl 1,2,3,-triazoles or diazocompouds in the high order cycloadditions, which offered an efficient route to a variety of N-containing medium-sized rings. The process provided a wide range of cyclohepta[b]pyrazine and cyclohepta[b]pyrrolone derivatives with high yields.

  8. Mechanical properties of a metal-organic framework containing hydrogen-bonded bifluoride linkers.

    Science.gov (United States)

    Li, Wei; Kiran, M S R N; Manson, Jamie L; Schlueter, John A; Thirumurugan, A; Ramamurty, U; Cheetham, Anthony K

    2013-05-18

    We report the mechanical properties of a framework structure, [Cu2F(HF)(HF2)(pyz)4][(SbF6)2]n (pyz = pyrazine), in which [Cu(pyz)2](2+) layers are pillared by HF2(-) anions containing the exceptionally strong F-H···F hydrogen bonds. Nanoindentation studies on single-crystals clearly demonstrate that such bonds are extremely robust and mechanically comparable with coordination bonds in this system.

  9. Structure-based discovery of antagonists for GluN3-containing N-methyl-D-aspartate receptors

    DEFF Research Database (Denmark)

    Kvist, Trine; Greenwood, Jeremy R; Hansen, Kasper B

    2013-01-01

    . In the subsequent pharmacological evaluation of 99 selected compounds, we identified 6-hydroxy-[1,2,5]oxadiazolo[3,4-b]pyrazin-5(4H)-one (TK80) a novel competitive antagonist with preference for the GluN3B subunit. Serendipitously, we also identified [2-hydroxy-5-((4-(pyridin-3-yl)thiazol-2-yl)amino]benzoic acid...

  10. Supramolecular Architecture from a Sodium Coordination Polymer with a 3D Net Containing 3-Aminopyrazine-2-carb oxylic acid (APZC): Synthesis, Characterization and Crystal Structure of [Na2(APZC)2(μ-H2O)2(μ3-H2O)]n

    Institute of Scientific and Technical Information of China (English)

    TAYEBEE Reza; AMANI Vahid; KHAVASI Hamid Reza

    2008-01-01

    The synthesis and spectroscopic properties of a Na+ complex with ligand 3-aminopyrazine-2-carboxylic acid were described. The resulting complex was characterized by elemental analysis, IR, UV-Vis, NMR spectroscopy and single crystal X-ray diffraction method. The title compound crystallizes in the triclinic system with space group P1. The crystalline structure of this compound consists of supramolecular architectures involving strong inbonds between substituted pyrazine and water molecules.

  11. Substituted Pyrazinecarboxamides: Synthesis and Biological Evaluation

    Directory of Open Access Journals (Sweden)

    Katarina Kralova

    2006-03-01

    Full Text Available Condensation of the corresponding chlorides of some substituted pyrazine-2-carboxylic acids (pyrazine-2-carboxylic acid, 6-chloropyrazine-2-carboxylic acid, 5-tert-butylpyrazine-2-carboxylic acid or 5-tert-butyl-6-chloropyrazine-2-carboxylic acid withvarious ring-substituted aminothiazoles or anilines yielded a series of amides. Thesyntheses, analytical and spectroscopic data of thirty newly prepared compounds arepresented. Structure-activity relationships between the chemical structures and the anti-mycobacterial, antifungal and photosynthesis-inhibiting activity of the evaluatedcompounds are discussed. 3,5-Bromo-4-hydroxyphenyl derivatives of substitutedpyrazinecarboxylic acid, 16-18, have shown the highest activity against Mycobacteriumtuberculosis H37Rv (54-72% inhibition. The highest antifungal effect againstTrichophyton mentagrophytes, the most susceptible fungal strain tested, was found for5-tert-butyl-6-chloro-N-(4-methyl-1,3-thiazol-2-ylpyrazine-2-carboxamide (8, MIC =31.25 μmol·mL-1. The most active inhibitors of oxygen evolution rate in spinachMolecules 2006, 11 243 chloroplasts were the compounds 5-tert-butyl-6-chloro-N-(5-bromo-2-hydroxyphenyl- pyrazine-2-carboxamide (27, IC50 = 41.9 μmol·L-1 and 5-tert-butyl-6-chloro-N-(1,3- thiazol-2-yl-pyrazine-2-carboxamide (4, IC50 = 49.5 μmol·L-1.

  12. A new compound from liquid fermentation broth of Armillaria mellea and the determination of its absolute configuration.

    Science.gov (United States)

    Wang, Yun-Chao; Zhang, Yu-Wei; Zheng, Li-Hua; Bao, Yong-Li; Wu, Yin; Yu, Chun-Lei; Sun, Lu-Guo; Zhang, Yu; Huang, Yan-Xin; Sun, Ying; Li, Yu-Xin

    2013-01-01

    A new 2,5-diketopiperazine, (R)-2-(2-(furan-2-yl)-oxoethyl)-octahydropyrrolo[1,2-a]pyrazine-1,4-dione, and seven known compounds were isolated from the ethyl acetate extract of liquid fermentation broth of Armillaria mellea. The structures of the isolated compounds were established from NMR and HR-MS data. The absolute configuration of the new compound was established by comparing the experimental electronic circular dichroism (ECD) spectrum with the calculated ECD data.

  13. Development of Non-prey Baits for Delivery of Acetaminophen to Brown Treesnakes (Boiga irregularis) on Guam. Version 3

    Science.gov (United States)

    2012-03-14

    set at 150oC, and the transfer line at 280oC. Total run time was 21.4 min. Peak identification/ quantification was determined with a 37 compound...Fatty acid Isobutyric Acid 40 mL 15 mL Alcohol n-Butanol 14 mL 9 mL Aldehyde Hexanal 11 mL 13.5 mL Alkaloid 2,6-Dimethyl Pyrazine 0.5 g 0.2 g

  14. Ozonation of pyridine and other N-heterocyclic aromatic compounds: Kinetics, stoichiometry, identification of products and elucidation of pathways.

    Science.gov (United States)

    Tekle-Röttering, Agnes; Reisz, Erika; Jewell, Kevin S; Lutze, Holger V; Ternes, Thomas A; Schmidt, Winfried; Schmidt, Torsten C

    2016-10-01

    Pyridine, pyridazine, pyrimidine and pyrazine were investigated in their reaction with ozone. These compounds are archetypes for heterocyclic aromatic amines, a structural unit that is often present in pharmaceuticals, pesticides and dyestuffs (e.g., enoxacin, pyrazineamide or pyrimethamine). The investigated target compounds react with ozone with rate constants ranging from 0.37 to 57 M(-1) s(-1), hampering their degradation during ozonation. In OH radical scavenged systems the reaction of ozone with pyridine and pyridazine is characterized by high transformation (per ozone consumed) of 55 and 54%, respectively. In non scavenged system the transformation drops to 52 and 12%, respectively. However, in the reaction of pyrimidine and pyrazine with ozone this is reversed. Here, in an OH radical scavenged system the compound transformation is much lower (2.1 and 14%, respectively) than in non scavenged one (22 and 25%, respectively). This is confirmed by corresponding high N-oxide formation in the ozonation of pyridine and pyridazine, but probably low formation in the reaction of pyrimidine and pyrazine with ozone. With respect to reaction mechanisms, it is suggested that ozone adduct formation at nitrogen is the primary step in the ozonation of pyridine and pyridazine. On the contrary, ozone adduct formation to the aromatic ring seems to occur especially in the ozonation of pyrimidine as inferred from hydrogen peroxide yield. However, also OH radical reactions are supposed processes in the case of pyrimidine and in particular for pyrazine, albeit negligible OH radical yields are obtained. The low compound transformation in OH radical scavenged system can prove this. As a result of negligible OH radical yields in all cases (less than 6%) electron transfer as primary reaction pathway plays a subordinate role.

  15. Crystal structure of methyl 3′-benzamido-4′-(4-methoxyphenyl-1′-methylspiro[indeno[1,2-b]quinoxaline-11,2′-pyrrolidine]-3′-carboxylate

    Directory of Open Access Journals (Sweden)

    Kuppan Chandralekha

    2016-09-01

    Full Text Available In the title compound, C35H30N4O3, the spiro C atom connects the five-membered pyrrolidine ring and the indenoquinoxaline ring system. The pyrrolidine ring adopts a twist conformation. An intramolecular N—H...N interaction between the amino group and the pyrazine ring is observed. In the crystal, molecules are linked by a pairs of C—H...O hydrogen bonds, forming inversion dimers.

  16. Nanomolar inhibitors of Mycobacterium tuberculosis glutamine synthetase 1: synthesis, biological evaluation and X-ray crystallographic studies.

    Science.gov (United States)

    Couturier, Cédric; Silve, Sandra; Morales, Renaud; Pessegue, Bernard; Llopart, Sylvie; Nair, Anil; Bauer, Armin; Scheiper, Bodo; Pöverlein, Christoph; Ganzhorn, Axel; Lagrange, Sophie; Bacqué, Eric

    2015-04-01

    A series of imidazo[1,2-a]indeno[1,2-e]pyrazin-4-ones that potently inhibit M. tuberculosis glutamine synthetase (GlnA1) has been identified by high throughput screening. Exploration of this series was performed owing to a short chemistry program. Despite possibly nanomolar inhibitions, none of these compounds was active on whole cell Mtb, suggesting that GlnA1 may not be a suitable target to find new anti-tubercular drugs.

  17. Proton controlled intramolecular communication in dinuclear ruthenium(II) polypyridine complexes

    NARCIS (Netherlands)

    Pietro, Cinzia Di; Serroni, Scolastica; Campagna, Sebastiano; Gandolfi, Maria Teresa; Ballardini, Roberto; Fanni, Stefano; Browne, Wesley R.; Vos, Johannes G.

    2002-01-01

    The synthesis and characterization of two dinuclear ruthenium polypyridyl complexes based on the bridging ligands 5,5'-bis(pyridin-2"-yl)-3,3'-bis(1H-1,2,4-triazole) and 5,5'-bis(pyrazin-2"-yl)-3,3'-bis(1H-1,2,4-triazole) and of their mononuclear precursors are reported. The dinuclear compounds have

  18. Identification of characteristic flavor compounds in cocoa powder by gas chromatography-olfactometry-mass spectrometry with headspace solid phase micro-extraction%顶空固相微萃取结合GC-O与GC-MS技术鉴定可可粉中特征风味化合物

    Institute of Scientific and Technical Information of China (English)

    肖天鹏; 郑晓峰; 吕吉鸿; 郭泽峰; 高峰; 刘春凤; 李崎

    2012-01-01

    A method for headspace solid-phase microextraction(HS-SPME),followed by gas chromatography-olfactometry-mass spectrometry analysis was established for the identification of the characteristic flavor compounds in cocoa powder.According to the results,39 compounds which gave contribution to the flavor of cocoa powder were detected,including 7 aldehydes,3 alcohols,3 ketones,8 esters,2 acids,4 pyrazines,2 amines and any other special volatile substances.Among the flavor compounds,three compounds had key odorant(nutty,cocoa flavor),they were 2,5-dimethyl pyrazine,2,3,5-trimethyl pyrazine and 2,3,5,6-tetramethyl pyrazine.%利用顶空固相微萃取(HS-SPME)结合GC-O与GC-MS技术鉴定可可粉中的特征致香成分,鉴定出有39种化合物参与构成可可风味,分别是:7种醛、3种醇、3种酮、8种酯、2种酸、4种吡嗪、2种胺以及其他一些特殊的挥发性物质。其中具有典型可可风味(坚果,可可香)的关键化合物有3种,分别为2,5-二甲基吡嗪、2,3,5-三甲基吡嗪以及2,3,5,6-四甲基吡嗪。

  19. {sup 57}Fe Moessbauer Spectroscopic Study on the Assembled Iron Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Nakashima, S. [Hiroshima University, Natural Science Center for Basic Research and Development (N-BARD) (Japan); Asada, Y.; Okuda, T. [Hiroshima University, Department of Chemistry, Graduate School of Science (Japan)

    2004-12-15

    {sup 57}Fe Moessbauer spectroscopy was carried out to know the electronic states of the assembled iron complexes. The IS value revealed a high-spin Fe{sup II} state in the bipyridine and pyrazine iron complexes with NCS or NCSe. The dissociation behavior of ligand was investigated by TG, and the resultant change in the coordination sphere around iron atom was reflected in the change in QS value.

  20. Integration of enabling methods for the automated flow preparation of piperazine-2-carboxamide.

    Science.gov (United States)

    Ingham, Richard J; Battilocchio, Claudio; Hawkins, Joel M; Ley, Steven V

    2014-01-01

    Here we describe the use of a new open-source software package and a Raspberry Pi(®) computer for the simultaneous control of multiple flow chemistry devices and its application to a machine-assisted, multi-step flow preparation of pyrazine-2-carboxamide - a component of Rifater(®), used in the treatment of tuberculosis - and its reduced derivative piperazine-2-carboxamide.

  1. Integration of enabling methods for the automated flow preparation of piperazine-2-carboxamide

    Directory of Open Access Journals (Sweden)

    Richard J. Ingham

    2014-03-01

    Full Text Available Here we describe the use of a new open-source software package and a Raspberry Pi® computer for the simultaneous control of multiple flow chemistry devices and its application to a machine-assisted, multi-step flow preparation of pyrazine-2-carboxamide – a component of Rifater®, used in the treatment of tuberculosis – and its reduced derivative piperazine-2-carboxamide.

  2. Potential of multisyringe chromatography for the on-line monitoring of the photocatalytic degradation of antituberculosis drugs in aqueous solution.

    Science.gov (United States)

    Guevara-Almaraz, E; Hinojosa-Reyes, L; Caballero-Quintero, A; Ruiz-Ruiz, E; Hernández-Ramírez, A; Guzmán-Mar, J L

    2015-02-01

    In this study, a multisyringe chromatography system (MSC) using a C18 monolithic column was proposed for the on-line monitoring of the photocatalytic degradation of isoniazid (INH, 10 mg L(-1)) and pyrazinamide (PYRA, 5mgL(-1)) mixtures in aqueous solution using a small sample volume (200 μL) with an on-line filtration device in a fully automated approach. During the photocatalytic oxidation using TiO2 or ZnO semiconductor materials, total organic carbon (TOC) and the formed intermediates were analyzed off-line using ion chromatography, ion exclusion HPLC, and ESI-MS/MS. The results showed that TiO2 exhibits a better photocatalytic activity than ZnO under UV irradiation (365 nm) for the degradation of INH and PYRA mixtures, generating 97% and 92% degradation, respectively. The optimal oxidation conditions were identified as pH 7 and 1.0 g L(-1) of TiO2 as catalyst. The mineralization of the initial organic compounds was confirmed by the regular decrease in TOC, which indicated 63% mineralization, and the quantitative release of nitrate and nitrite ions, which represent 33% of the nitrogen in these compounds. The major intermediates of INH degradation included isonicotinamide, isonicotinic acid, and pyridine, while the ESI-MS/MS analysis of PYRA aqueous solution after photocatalytic treatment showed the formation of pyrazin-2-ylmethanol, pyrazin-2-ol, and pyrazine. Three low-molecular weight compounds, acetamide, acetic acid and formic acid, were detected during INH and PYRA decomposition. PYRA was more resistant to photocatalytic degradation due to the presence of the pyrazine ring, which provides greater stability against OH attack.

  3. 新产品集锦(110)

    Institute of Scientific and Technical Information of China (English)

    2013-01-01

    AMT0dd公司推出的“天然吡嗪18号混合物”(natural pyrazines mixture No.18,FEMA#3244、3919、3154和3155),具有坚果味,焙烘和可可香调,可用于食品香精中,推荐用量为0.05~5.00ppm。

  4. Effect of ring rotation upon gas adsorption in SIFSIX-3-M (M = Fe, Ni) pillared square grid networks

    Energy Technology Data Exchange (ETDEWEB)

    Elsaidi, Sameh K.; Mohamed, Mona H.; Simon, Cory M.; Braun, Efrem; Pham, Tony; Forrest, Katherine A.; Xu, Wenqian; Banerjee, Debasis; Space, Brian; Zaworotko, Michael J.; Thallapally, Praveen K.

    2017-01-01

    The study of the mobility/rotation of the organic linkers in porous metal-organic frameworks could provide a valuable information about the guest/framework interaction and the factors control the kinetics of adsorption. Here, we analyzed the dynamics of pyrazine ring rotation in a series of pillared square grid frameworks, namely SIFSIX-3-M (M = Fe, Ni). It was found that the rotation of pyrazine ring is influenced by the variation of metal cation, temperature and the guest molecule. The Fe-analogue, [Fe(pz)2(SiF6)2] (pz= Pyrazine), , showed no pronounced ring rotation and exhibited a high affinity toward Xe gas over Kr as exemplified by the sharp Xe uptake at low loading (~0.1 bar) and its high isosteric heat of adsorption (Qst~ 27.4 kJmol-1) compared to the current benchmark materials. The Ni analogue, on the contrary, showed a two-regime adsorption isotherm for Xe with a temperature-dependent inflection point. However, this behavior is not observed with the other gases such as CO2, N2, and Kr which showed one-step adsorption isotherms without any inflection. Using molecular models and simulations, we hypothesize that the inflection point is due to a disordered to ordered transition of the rotational configurations of the pz rings in SIFSIX-3-Ni. These results further support the impact of tuning the pore size and chemistry on the adsorption behavior of porous materials.

  5. Chemical Annealing of Zinc Tetraphenylporphyrin Films: Effects on Film Morphology and Organic Photovoltaic Performance

    KAUST Repository

    Trinh, Cong

    2012-07-10

    We present a chemical annealing process for organic thin films. In this process, a thin film of a molecular material, such as zinc tetraphenylporphyrin (ZnTPP), is exposed to a vapor of nitrogen-based ligand (e.g., pyrazine, pz, and triazine, tz), forming a film composed of the metal-ligand complex. Fast and quantitative formation of the complex leads to marked changes in the morphology and optical properties of the film. X-ray diffraction studies show that the chemical annealing process converts amorphous ZnTPP films to crystalline ZnTPP•ligand films, whose porphryin planes lie nearly parallel to the substrate (average deviation is 8° for the ZnTPP•pz film). Organic solar cells were prepared with ZnTPP donor and C 60 acceptor layers. Devices were prepared with and without chemical annealing of the ZnTPP layer with a pyrazine ligand. The devices with chemically annealed ZnTPP donor layer show an increase in short-circuit current (J SC) and fill factor (FF) relative to analogous unannealed devices, presumably because of enhanced exciton diffusion length and improved charge conductivity. The open circuit voltages (V OC) of the chemically annealed devices are lower than their unannealed counterpart because of enhanced polaron pair recombination at the donor/acceptor heterojunction. A net improvement of 5-20% in efficiency has been achieved, after chemical annealing of ZnTPP films with pyrazine. © 2012 American Chemical Society.

  6. Ligational behavior of Schiff bases towards transition metal ion and metalation effect on their antibacterial activity.

    Science.gov (United States)

    Devi, Jai; Batra, Nisha; Malhotra, Rajesh

    2012-11-01

    New Schiff bases pyrazine-2-carboxylicacid (phenyl-pyridin-2-yl-methylene)-hydrazide (Hpch-bp) HL(1) and pyrazine-2-carboxylicacid (pyridin-2-ylmethylene)-hydrazide (Hpch-pc) HL(2) derived from condensation of pyrazine carboxylic hydrazide (Hpch) with 2-benzoyl pyridine (bp) or pyridine 2-carbaldehyde (pc) and their transition metal complexes of type ML((1-2)2) have been synthesized, where M=Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). Characterization of ligands and their metal complexes was carried out by elemental analysis, conductimetric studies, magnetic susceptibility, spectroscopic techniques (IR, UV-VIS, NMR, ESR, Mass) and thermogravimetric analysis. The physico-chemical studies revealed octahedral geometry or distorted octahedral geometry around metal ion. These azomethine Schiff base ligands acted as tridentate coordinating through carbonyl, azomethine and pyridine nitrogen present in the ligand. The thermodynamic and thermal properties of the complexes have been investigated and it was observed on the basis of these studies that thermal stability of complexes follows the order Mnantibacterial activity at different concentrations against bacteria viz. Gram positive Bacillus subtilis, Micrococcus luteus and Gram negative Pseudomonas aeruginosa, Pseudomonas mendocina. A marked enhancement in biocidal activity of the ligands under similar experimental conditions was observed as a consequence of coordination with metal ions. The trend of growth inhibition in the complexes was found to be in the order: Cu>Mn>Ni>Co>Zn.

  7. Ligational behavior of Schiff bases towards transition metal ion and metalation effect on their antibacterial activity

    Science.gov (United States)

    Devi, Jai; Batra, Nisha; Malhotra, Rajesh

    2012-11-01

    New Schiff bases pyrazine-2-carboxylicacid (phenyl-pyridin-2-yl-methylene)-hydrazide (Hpch-bp) HL1 and pyrazine-2-carboxylicacid (pyridin-2-ylmethylene)-hydrazide (Hpch-pc) HL2 derived from condensation of pyrazine carboxylic hydrazide (Hpch) with 2-benzoyl pyridine (bp) or pyridine 2-carbaldehyde (pc) and their transition metal complexes of type ML(1-2)2 have been synthesized, where M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II). Characterization of ligands and their metal complexes was carried out by elemental analysis, conductimetric studies, magnetic susceptibility, spectroscopic techniques (IR, UV-VIS, NMR, ESR, Mass) and thermogravimetric analysis. The physico-chemical studies revealed octahedral geometry or distorted octahedral geometry around metal ion. These azomethine Schiff base ligands acted as tridentate ? coordinating through carbonyl, azomethine and pyridine nitrogen present in the ligand. The thermodynamic and thermal properties of the complexes have been investigated and it was observed on the basis of these studies that thermal stability of complexes follows the order Mn complexes were tested for in vitro antibacterial activity at different concentrations against bacteria viz. Gram positive Bacillus subtilis, Micrococcus luteus and Gram negative Pseudomonas aeruginosa, Pseudomonas mendocina. A marked enhancement in biocidal activity of the ligands under similar experimental conditions was observed as a consequence of coordination with metal ions. The trend of growth inhibition in the complexes was found to be in the order: Cu > Mn > Ni > Co > Zn.

  8. High Field Magnetization Studies of Low Dimensional Heisenberg S = 1/2 Antiferromagnets

    Science.gov (United States)

    Landee, C. P.; Turnbull, M. M.

    1998-03-01

    The magnetization curves of a number of low dimensional S=1/2 Heisenberg antiferromagnets have been determined in fields up to 30 tesla at low temperatures at the National High Magnetic Fields Laboratory. Materials studied include a family of 1D materials, based upon Cu(pyrazine)(NO_3)_2, 2D magnets consisting of pyrazine-bridged copper layers, and several spin ladders with singlet ground states. All of the magnetization data show upward curvature and are well described by T = 0 calculations based upon finite cluster models(Bonner and Fisher, Phys. Rev. A135, 640 (1964); Yang and Mutter, NANL cond-mat/9610092.). Chemical substitution on the pyrazine rings permits the variation of exchange constants by more than 25 percent for the family of well isolated chains. The spin ladder systems consist of ferromagnetic dimers weakly connected by antiferromagnetic intradimer interactions. Field induced transitions are seen at fields of less than one tesla for each of the three compounds.

  9. Geographical matching of volatile signals and pollinator olfactory responses in a cycad brood-site mutualism.

    Science.gov (United States)

    Suinyuy, Terence N; Donaldson, John S; Johnson, Steven D

    2015-10-07

    Brood-site mutualisms represent extreme levels of reciprocal specialization between plants and insect pollinators, raising questions about whether these mutualisms are mediated by volatile signals and whether these signals and insect responses to them covary geographically in a manner expected from coevolution. Cycads are an ancient plant lineage in which almost all extant species are pollinated through brood-site mutualisms with insects. We investigated whether volatile emissions and insect olfactory responses are matched across the distribution range of the African cycad Encephalartos villosus. This cycad species is pollinated by the same beetle species across its distribution, but cone volatile emissions are dominated by alkenes in northern populations, and by monoterpenes and a pyrazine compound in southern populations. In reciprocal choice experiments, insects chose the scent of cones from the local region over that of cones from the other region. Antennae of beetles from northern populations responded mainly to alkenes, while those of beetles from southern populations responded mainly to pyrazine. In bioassay experiments, beetles were most strongly attracted to alkenes in northern populations and to the pyrazine compound in southern populations. Geographical matching of cone volatiles and pollinator olfactory preference is consistent with coevolution in this specialized mutualism.

  10. Optimization of potent DFG-in inhibitors of platelet derived growth factor receptorβ (PDGF-Rβ) guided by water thermodynamics.

    Science.gov (United States)

    Horbert, Rebecca; Pinchuk, Boris; Johannes, Eugen; Schlosser, Joachim; Schmidt, Dorian; Cappel, Daniel; Totzke, Frank; Schächtele, Christoph; Peifer, Christian

    2015-01-08

    In this study we report on the hit optimization of substituted 3,5-diaryl-pyrazin-2(1H)-ones toward potent and effective platelet-derived growth factor receptor (PDGF-R) β-inhibitors. Originally, the 3,5-diaryl-pyrazin-2-one core was derived from the marine sponge alkaloid family of hamacanthins. In our first series compound 2 was discovered as a promising hit showing strong activity against PDGF-Rβ in the kinase assay (IC50 = 0.5 μM). Furthermore, 2 was shown to be selective for PDGF-Rβ in a panel of 24 therapeutically relevant protein kinases. Molecular modeling studies on a PDGF-Rβ homology model using prediction of water thermodynamics suggested an optimization strategy for the 3,5-diaryl-pyrazin-2-ones as DFG-in binders by using a phenolic OH function to replace a structural water molecule in the ATP binding site. Indeed, we identified compound 38 as a highly potent inhibitor with an IC50 value of 0.02 μM in a PDGF-Rβ enzymatic assay also showing activity against PDGF-R dependent cancer cells.

  11. Analyzing the flavor compounds in Chinese traditional fermented shrimp pastes by HS-SPME-GC/MS and electronic nose

    Science.gov (United States)

    Fan, Yan; Yin, Li'ang; Xue, Yong; Li, Zhaojie; Hou, Hu; Xue, Changhu

    2017-04-01

    Shrimp paste is a type of condiments with high nutritional value. However, the flavors of shrimp paste, particularly the non-uniformity flavors, have limited its application in food processing. In order to identify the characteristic flavor compounds in Chinese traditional shrimp pastes, five kinds of typical commercial products were evaluated in this study. The differences in the volatile composition of the five products were investigated. Solid phase micro-extraction method was employed to extract the volatile compounds. GC-MS and electronic nose were applied to identify the compounds, and the data were analyzed using principal component analysis (PCA). A total of 62 volatile compounds were identified, including 8 alcohols, 7 aldehydes, 3 ketones, 7 ethers, 7 acids, 3 esters, 6 hydrocarbons, 12 pyrazines, 2 phenols, and 7 other compounds. The typical volatile compounds contributing to the flavor of shrimp paste were found as follows: dimethyl disulfide, dimethyl tetrasulfide, dimethyl trisulfide, 2, 3, 5-trimethyl-6-ethyl pyrazine, ethyl-2, 5-dimethyl-pyrazine, phenol and indole. Propanoic acid, butanoic acid, furans, and 2-hydroxy-3-pentanone caused unpleasant odors, such as pungent and rancid odors. Principal component analysis showed that the content of volatile compounds varied depending on the processing conditions and shrimp species. These results indicated that the combinations of multiple analysis and identification methods could make up the limitations of a single method, enhance the accuracy of identification, and provide useful information for sensory research and product development.

  12. Spectral and Kinetic Properties of Radicals Derived from Oxidation of Quinoxalin-2-One and Its Methyl Derivative

    Directory of Open Access Journals (Sweden)

    Konrad Skotnicki

    2014-11-01

    Full Text Available The kinetics and spectral characteristics of the transients formed in the reactions of •OH and •N3 with quinoxalin-2(1H-one (Q, its methyl derivative, 3-methylquinoxalin-2(1H-one (3-MeQ and pyrazin-2-one (Pyr were studied by pulse radiolysis in aqueous solutions at pH 7. The transient absorption spectra recorded in the reactions of •OH with Q and 3-MeQ consisted of an absorption band with λmax = 470 nm assigned to the OH-adducts on the benzene ring, and a second band with λmax = 390 nm (for Q and 370 nm (for 3-MeQ assigned, inter alia, to the N-centered radicals on a pyrazin-2-one ring. The rate constants of the reactions of •OH with Q and 3-MeQ were found to be in the interval (5.9–9.7 × 109 M–1·s–1 and were assigned to their addition to benzene and pyrazin-2-one rings and H-abstraction from the pyrazin-2-one nitrogen. In turn, the transient absorption spectrum observed in the reaction of •N3 exhibits an absorption band with λmax = 350 nm. This absorption was assigned to the N-centered radical on the Pyr ring formed after deprotonation of the respective radical cation resulting from one-electron oxidation of 3-MeQ. The rate constant of the reaction of •N3 with 3 MeQ was found to be (6.0 ± 0.5 × 109 M–1·s–1. Oxidation of 3-MeQ by •N3 and Pyr by •OH and •N3 confirms earlier spectral assignments. With the rate constant of the •OH radical with Pyr (k = 9.2 ± 0.2 × 109 M–1·s‒1, a primary distribution of the •OH attack was estimated nearly equal between benzene and pyrazin-2-one rings.

  13. Laser enhanced chemical reaction studies. Technical report, January 1, 1994--February 28, 1995

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-07-01

    The relaxation of vibrationally excited pyrazine (E=40,640 cm{sup -1}) by collisions which populate the high J tail (J=58-82) of the vibrationless ground state (00{sup 0}0) of CO{sub 2} has been studied using tunable infrared diode lasers to probe the scattered CO{sub 2} molecules. The nascent rotational populations and translational recoil velocities for a series of rotational states in the high J tail of the 00{sup 0}0 level of CO{sub 2} were measured at five collision cell temperatures: 243, 263, 298, 339, and 364 K. Both the rate constants describing these V-R/T processes and the translational temperatures describing the recoiling CO{sub 2} molecules exhibit a very weak positive temperature dependence indicating that the high energy CO{sub 2} molecules must originate from near the center of the pre-collision energy distribution. Quantitative estimates of the actual amount of energy transferred in collisions between CO{sub 2} and vibrationally excited pyrazine, based on an angular momentum and translational energy exponential gap model of the cross section, indicate that {triangle}E{sub total} can be as large as 7090 cm{sup -1} ({approximately}20 kcal/mol). These experiments offer compelling evidence that these energy transfer events can indeed be classified as supercollisions since they involve unusually large, single collision energy transfer magnitudes; and despite their relative infrequency, they play a most important role in the collisional deactivation of vibrationally excited pyrazine by a CO{sub 2} bath.

  14. The Anaphase-Promoting Complex (APC ubiquitin ligase affects chemosensory behavior in C. elegans

    Directory of Open Access Journals (Sweden)

    Julia Wang

    2016-05-01

    Full Text Available The regulation of fundamental aspects of neurobiological function has been linked to the ubiquitin signaling system (USS, which regulates the degradation and activity of proteins and is catalyzed by E1, E2, and E3 enzymes. The Anaphase-Promoting Complex (APC is a multi-subunit E3 ubiquitin ligase that controls diverse developmental and signaling processes in post-mitotic neurons; however, potential roles for the APC in sensory function have yet to be explored. In this study, we examined the effect of the APC ubiquitin ligase on chemosensation in Caenorhabditis elegans by testing chemotaxis to the volatile odorants, diacetyl, pyrazine, and isoamyl alcohol, to which wild-type worms are attracted. Animals with loss of function mutations in either of two alleles (g48 and ye143 of the gene encoding the APC subunit EMB-27 APC6 showed increased chemotaxis towards diacetyl and pyrazine, odorants sensed by AWA neurons, but exhibited normal chemotaxis to isoamyl alcohol, which is sensed by AWC neurons. The statistically significant increase in chemotaxis in the emb-27 APC6 mutants suggests that the APC inhibits AWA-mediated chemosensation in C. elegans. Increased chemotaxis to pyrazine was also seen with mutants lacking another essential APC subunit, MAT-2 APC1; however, mat-2 APC1 mutants exhibited wild type responses to diacetyl. The difference in responsiveness of these two APC subunit mutants may be due to differential strength of these hypomorphic alleles or may indicate the presence of functional sub-complexes of the APC at work in this process. These findings are the first evidence for APC-mediated regulation of chemosensation and lay the groundwork for further studies aimed at identifying the expression levels, function, and targets of the APC in specific sensory neurons. Because of the similarity between human and C. elegans nervous systems, the role of the APC in sensory neurons may also advance our understanding of human sensory function and

  15. Peculiar reactivity of a di-imine copper(II) complex regarding its binding to albumin protein.

    Science.gov (United States)

    Silveira, Vivian C; Abbott, Mariana P; Cavicchioli, Maurício; Gonçalves, Marcos B; Petrilli, Helena M; de Rezende, Leandro; Amaral, Antonia T; Fonseca, David E P; Caramori, Giovanni F; Ferreira, Ana M da Costa

    2013-05-14

    A set of four di-imine copper(II) complexes containing pyridine, pyrazine and/or imidazole moieties, [Cu(apyhist)H2O](2+) 1 (apyhist = 2-(1H-imidazol-4-yl)-N-(1-(pyridin-2-yl)ethylidene)ethanamine), [Cu(apzhist)OH](+) 2 (apzhist = 2-(1H-imidazol-4-yl)-N-(1-(pyrazin-2-yl)ethylidene)ethanamine), [Cu(apyepy)OH](+) 3 (apyepy = 2-(pyridin-2-yl)-N-(1-(pyridin-2-yl)ethylidene)ethanamine), and [Cu(apzepy)H2O](2+) 4 (apzepy = N-(1-(pyrazin-2-yl)ethylidene)-2-(pyridin-2-yl)ethanamine), were investigated regarding their capability of interacting with serum albumin (human, HSA and bovine, BSA), by using spectroscopic techniques, CD, UV/Vis and EPR. Like other similar di-imine copper(II) complexes, most of them showed an expected preferential insertion of the metal ion at the primary N-terminal site of the protein, very selective for copper and characterized by a CD band at 560 nm. Further insertion of the copper ion at a secondary site is expected when using an excess of the metal. However, one of these studied complexes, [Cu(apyhist)H2O](2+) 1, exhibited anomalous behaviour interacting only at this secondary metal binding site of albumin, characterized by a CD band at 370 nm, and attributed to the coordination of copper at the Cys34 pocket. Analogous experiments with HSA previously treated with N-ethyl-maleimide (NEM), that oxidizes the protein Cys34 residue and obstructs the metal coordination, verified these results. Additional data obtained by EPR spectroscopy complemented those results. DFT calculations, considering some structural and electronic characteristics of such series of di-imine ligands and of the corresponding copper complexes, suggested molecular recognition of the apyhist ligand at the protein cavity as a feasible explanation for this unexpected and peculiar behaviour of complex 1.

  16. Synthesis and photo-/electro-catalytic properties of a 3D POMOF material based on an interpenetrated copper coordination polymer linked by in situ dual ligands and Dawson-type phosphotungstates.

    Science.gov (United States)

    Fan, Ling-Yu; Yu, Kai; Lv, Jing-Hua; Zhang, He; Su, Zhan-Hua; Wang, Lu; Wang, Chun-Mei; Zhou, Bai-Bin

    2017-08-08

    A novel 3D polyoxometalate metal organic framework (POMOF), [{CuCu (H2O)5(pzc)10(pz)6}{P2W18O62}2]·4H2O (1) (Hpzc = pyrazine-2-carboxylic acid, pz = pyrazine) has been hydrothermally synthesized and characterized by IR, TG, XRD, UV-vis and elemental analyses. In compound 1, the pzc and pz ligands are generated through in situ transformation from pyrazine-2,3-dicarboxylic acid (pzdc) to remove one or two CO2 molecules. The ligands with four coordination modes connect nine crystallographically independent Cu atoms to form a super-big circle unit. Each ring unit is connected to the adjacent six rings via an edge-sharing way to form a 2-D Cu/pz/pzc MOF layer, which is further extended along two spatial directions by two kinds of insert modes to generate an interpenetrating and staggered 3-D metal organic network. The {P2W18} clusters as nine-node inorganic guest molecules are grafted on the Cu/pz/pzc framework forming a complex 3D POMOF with a new topology {4·6·8(3)·10}2 {4·6·8}2 {4·6(2)·8(2)·10}2{4·6(3)·8(2)}2{4·8(5)}2{4(2)·6(2)·8(2)}2{4(2)·6(3)·8}{4(3)·6(7)·8(13)·10(10)·12(3)}2 {4}6{6·8(2)}2{6(2)·8}2 {6(4)·8·10}{6}2{8}4. Additionally, compound 1 exhibits good electrocatalytic activity for the reduction of H2O2 and effective photocatalytic degradation ability for three azo dyes under UV irradiation.

  17. Ultrafast Internal Conversion of Aromatic Molecules Studied by Photoelectron Spectroscopy using Sub-20 fs Laser Pulses

    Directory of Open Access Journals (Sweden)

    Toshinori Suzuki

    2014-02-01

    Full Text Available This article describes our recent experimental studies on internal conversion via a conical intersection using photoelectron spectroscopy. Ultrafast S2(ππ*–S1(nπ* internal conversion in pyrazine is observed in real time using sub-20 fs deep ultraviolet pulses (264 and 198 nm. While the photoelectron kinetic energy distribution does not exhibit a clear signature of internal conversion, the photoelectron angular anisotropy unambiguously reveals the sudden change of electron configuration upon internal conversion. An explanation is presented as to why these two observables have different sensitivities to internal conversion. The 198 nm probe photon energy is insufficient for covering the entire Franck-Condon envelopes upon photoionization from S2/S1 to D1/D0. A vacuum ultraviolet free electron laser (SCSS producing 161 nm radiation is employed to solve this problem, while its pulse-to-pulse timing jitter limits the time resolution to about 1 ps. The S2–S1 internal conversion is revisited using the sub-20 fs 159 nm pulse created by filamentation four-wave mixing. Conical intersections between D1(π−1 and D0(n−1 and also between the Rydberg state with a D1 ion core and that with a D0 ion core of pyrazine are studied by He(I photoelectron spectroscopy, pulsed field ionization photoelectron spectroscopy and one-color resonance-enhanced multiphoton ionization spectroscopy. Finally, ultrafast S2(ππ*–S1(ππ* internal conversion in benzene and toluene are compared with pyrazine.

  18. Determining single-ion and spatial exchange anisotropies by pulsed-field magnetometry

    Energy Technology Data Exchange (ETDEWEB)

    Manson, J. L. [Chemistry, Eastern Wash. U.; Villa, J. A. [Chemistry, Eastern Wash. U.; Singleton, John [Los Alamos National Laboratory; Brambleby, J. [Physics, U. of Warwick; Goddard, P. A. [Physics, U. of Warwick

    2017-02-13

    The magnetic ground-state of the Q1D S = 1 antiferromagnetic (AFM) chain is sensitive to the single-ion anisotropy (D) and the relative strength of intra- (J) and interchain (J’) exchange interactions. The ratios D/J and J’/J dictate the material’s placement on the phase diagram for which three competing phases are known to theoretically exist: Haldane, XY and quantum paramagnetic. We identified [Ni(HF2)(pyz)2]SbF6 (pyz = pyrazine) as a candidate in which to explore proximity to these phases.

  19. Alkaloids from Marine Invertebrates as Important Leads for Anticancer Drugs Discovery and Development

    Directory of Open Access Journals (Sweden)

    Concetta Imperatore

    2014-12-01

    Full Text Available The present review describes research on novel natural antitumor alkaloids isolated from marine invertebrates. The structure, origin, and confirmed cytotoxic activity of more than 130 novel alkaloids belonging to several structural families (indoles, pyrroles, pyrazines, quinolines, and pyridoacridines, together with some of their synthetic analogs, are illustrated. Recent discoveries concerning the current state of the potential and/or development of some of them as new drugs, as well as the current knowledge regarding their modes of action, are also summarized. A special emphasis is given to the role of marine invertebrate alkaloids as an important source of leads for anticancer drug discovery.

  20. "Abnormal" salt and solvent effects on anion/cation electron-transfer reactions: an interpretation based on Marcus-Hush treatment.

    Science.gov (United States)

    Garcia-Fernandez, E; Prado-Gotor, R; Sanchez, F

    2005-08-11

    Salt and solvent effects on the kinetics of the reactions [Fe(CN)6]3- + [Ru(NH3)5pz](2+) right arrow over left arrow [Fe(CN)6]4- + [Ru(NH3)5pz]3+ (pz = pyrazine) have been studied through T-jump measurements. The forward and reverse reactions show different behaviors: "abnormal" salt and solvent effects in the first case and normal effects in the second one. These facts imply an asymmetric behavior of anion/cation reactions depending on the charge of the oxidant. The results can be rationalized by using the Marcus-Hush treatment for electron-transfer reactions.

  1. Pressure-induced sequential orbital reorientation in a magnetic framework material.

    Energy Technology Data Exchange (ETDEWEB)

    Halder, G. J.; Chapman, K. W.; Schlueter, J. A.; Manson, J. L. (Materials Science Division); ( XSD); (Eastern Washington Univ.)

    2011-01-20

    Pressure has been applied to manipulate the structure-property relationship of the copper(II)-based coordination network CuF{sub 2}(H{sub 2}O){sub 2}(pyz) (pyz=pyrazine). The elongated Jahn-Teller axis was found to switch sequentially from the NCuN (<0.9 GPa), to the O-Cu-O (0.9-3.1 GPa), to the F-Cu-F bonds (>3.1 GPa; see picture). This orbital reordering leads to a drastic change in the magnetic properties, whereby the magnetic structure changes from two-dimensional to one-dimensional above 0.9 GPa.

  2. Chemical reactivity of ethyl 4-(1-ethyl-1,2-dihydro-4-hydroxy-2-oxoquinolin-3-yl-2,4-dioxobutanoate towards some nucleophilic reagents

    Directory of Open Access Journals (Sweden)

    Hany Hassanin

    2016-02-01

    Full Text Available AbstractA novel series of heterocyclic systems linked with quinolin-2-one was efficiently synthesized from reaction of ethyl 4-(1-ethyl-1,2-dihydro-4-hydroxy-2-oxoquinolin-3-yl -2,4-dioxobutanoate (1 with a variety of nitrogen and/or carbon nucleophiles. A variety of heterocyclic systems such as pyrazoles, pyrimidines, pyrazines, oxazines and triazines containing quinoline moiety were synthesized. Structures of the new synthesized products were deduced on basis of their analytical and spectral data.

  3. 4-Pyridylnitrene and 2-pyrazinylcarbene

    Directory of Open Access Journals (Sweden)

    Curt Wentrup

    2013-04-01

    Full Text Available Both flash vacuum thermolysis (FVT and matrix photolysis generate 2-diazomethylpyrazine (22 from 1,2,3-triazolo[1,5-a]pyrazine (24. FVT of 4-azidopyridine (18 as well as of 24 or 2-(5-tetrazolylpyrazine (23 affords the products expected from the nitrene, i.e., 4,4’-azopyridine and 2- and 3-cyanopyrroles. Matrix photolyses of both 18 and 24 result in ring expansion of 4-pyridylnitrene/2-pyrazinylcarbene to 1,5-diazacyclohepta-1,2,4,6-tetraene (20. Further photolysis causes ring opening to the ketenimine 27.

  4. Crystal structures of N2,N3,N5,N6-tetrakis(pyridin-2-ylmethylpyrazine-2,3,5,6-tetracarboxamide and N2,N3,N5,N6-tetrakis(pyridin-4-ylmethylpyrazine-2,3,5,6-tetracarboxamide

    Directory of Open Access Journals (Sweden)

    Dilovan S. Cati

    2017-02-01

    Full Text Available The title compounds, C32H28N10O4· unknown solvent, (I, and C32H28N10O4, (II, are pyrazine-2,3,5,6-tetracarboxamide derivatives. In (I, the substituents are (pyridin-2-ylmethylcarboxamide, while in (II, the substituents are (pyridin-4-ylmethylcarboxamide. Both compounds crystallize in the monoclinic space group P21/n, with Z′ = 1 for (I, and Z′ = 0.5 for (II. The whole molecule of (II is generated by inversion symmetry, the pyrazine ring being situated about a center of inversion. In (I, the four pyridine rings are inclined to the pyrazine ring by 83.9 (2, 82.16 (18, 82.73 (19 and 17.65 (19°. This last dihedral angle involves a pyridine ring that is linked to the adjacent carboxamide O atom by an intramolecular C—H...O hydrogen bond. In compound (II, the unique pyridine rings are inclined to the pyrazine ring by 33.3 (3 and 81.71 (10°. There are two symmetrical intramolecular C—H...O hydrogen bonds present in (II. In the crystal of (I, molecules are linked by N—H...O and N—H...N hydrogen bonds, forming layers parallel to (10-1. The layers are linked by C—H...O and C—H...N hydrogen bonds, forming a three-dimensional framework. In the crystal of (II, molecules are linked by N—H...N hydrogen bonds, forming chains propagating along the [010] direction. The chains are linked by a weaker N—H...N hydrogen bond, forming layers parallel to the (101 plane, which are in turn linked by C—H...O hydrogen bonds, forming a three-dimensional structure. In the crystal of compound (I, a region of disordered electron density was treated with the SQUEEZE routine in PLATON [Spek (2015. Acta Cryst. C71, 9–18]. Their contribution was not taken into account during refinement. In compound (II, one of the pyridine rings is positionally disordered, and the refined occupancy ratio for the disordered Car—Car—Npy atoms is 0.58 (3:0.42 (3.

  5. Intrinsic Semiconducting Materials on Phthalocyanine Basis

    OpenAIRE

    Hanack, Michael

    2014-01-01

    Stacked transition metal macrocycles [MacM(L)]n with M e.g. Fe, Ru, Os, Co, Rh and Mac = phthalocyanine (Pc) 1,2- or 2,3-naphthalocyanine (1,2-, 2,3-Nc) were synthesized. The bridging ligands (L) may be e.g. pyrazine (pyz) or s-tetrazine (tz). In general, these complexes [MacM(L)]n are insoluble in organic solvents; however, soluble oligomers [R4PcM(L)]n can be prepared using metallomacrocycles RnPcM, R = t-bu, et, OR, M = Fe, Ru, which are substituted in the peripheric positions. A systemati...

  6. Recent progress in electron scattering from atoms and molecules

    Energy Technology Data Exchange (ETDEWEB)

    Brunger, M. J. [Centre for Antimatter-Matter Studies, CAPS, Flinders University, GPO Box 2100, Adelaide, SA 5001, Australia and Institute of Mathematical Sciences, University of Malaya, Kuala Lumpur (Malaysia); Buckman, S. J. [Institute of Mathematical Sciences, University of Malaya, Kuala Lumpur, Malaysia and Centre for Antimatter-Matter Studies, AMPL, Australian National University, Canberra, ACT 0200 (Australia); Sullivan, J. P.; Palihawadana, P. [Centre for Antimatter-Matter Studies, AMPL, Australian National University, Canberra, ACT 0200 (Australia); Jones, D. B. [School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide, SA 5001 (Australia); Chiari, L.; Pettifer, Z. [Centre for Antimatter-Matter Studies, CAPS, Flinders University, GPO Box 2100, Adelaide, SA 5001 (Australia); Silva, G. B. da [Centre for Antimatter-Matter Studies, CAPS, Flinders University, GPO Box 2100, Adelaide, SA 5001, Australia and Universidade Federal de Mato Grosso, Barra do Garças, Mato Grosso (Brazil); Lopes, M. C. A. [Centre for Antimatter-Matter Studies, CAPS, Flinders University, GPO Box 2100, Adelaide, SA 5001, Australia and Departamento de Fisica, Universidade Federal de Juiz de Fora, Juiz de Fora, MG (Brazil); Duque, H. V. [Departamento de Fisica, Universidade Federal de Juiz de Fora, Juiz de Fora, MG (Brazil); Masin, Z.; Gorfinkiel, J. D. [Department of Physical Sciences, The Open University, Walton Hall, Milton Keynes, MK7 6AA (United Kingdom); Garcia, G. [Instituto de Fisica Fundamental, CSIC, Madrid E-28006 (Spain); Hoshino, M.; Tanaka, H. [Department of Physics, Sophia University, Tokyo, 102-8554 (Japan); Limão-Vieira, P. [Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal)

    2014-03-05

    We present and discuss recent results, both experimental and theoretical (where possible), for electron impact excitation of the 3s[3/2 ]{sub 1} and 3s′[1/2 ]{sub 1} electronic states in neon, elastic electron scattering from the structurally similar molecules benzene, pyrazine, and 1,4-dioxane and excitation of the electronic states of the important bio-molecule analogue α-tetrahydrofurfuryl alcohol. While comparison between theoretical and experimental results suggests that benchmarked cross sections for electron scattering from atoms is feasible in the near-term, significant further theoretical development for electron-molecule collisions, particularly in respect to discrete excitation processes, is still required.

  7. Analysis of volatile flavour compounds and acrylamide in roasted Malaysian tropical almond (Terminalia catappa) nuts using supercritical fluid extraction.

    Science.gov (United States)

    Lasekan, Ola; Abbas, Kassim

    2010-01-01

    Considering the importance of tropical almond nuts as a snack item, a study was conducted to identify the flavour volatiles and acrylamide generated during the roasting of the nuts. The supercritical fluid extracted flavour components revealed 74 aroma active compounds made up of 27 hydrocarbons, 12 aldehydes, 11 ketones, 7 acids, 4 esters, 3 alcohols, 5 furan derivatives a pyrazine, and 2 unknown compounds. While low levels of acrylamide (8-86 microg/kg) were obtained in the roasted nuts, significant (P0.05) concentration of acrylamide was generated with mild roasting and shorter roasting period.

  8. Effect of the addition of a fused donor-acceptor ligand on a Ru(II) complex: synthesis, characterization, and photoinduced electron transfer reactions of [Ru(TTF-dppz)2(Aqphen)]2+.

    Science.gov (United States)

    Dupont, Nathalie; Ran, Ying-Fen; Jia, Hong-Peng; Grilj, Jakob; Ding, Jie; Liu, Shi-Xia; Decurtins, Silvio; Hauser, Andreas

    2011-04-18

    The synthesis and the photophysical properties of the complex [Ru(TTF-dppz)(2)(Aqphen)](2+) (TTF = tetrathiafulvalene, dppz = dipyrido-[3,2-a:2',3'-c]phenazine, Aqphen = anthraquinone fused to phenanthroline via a pyrazine bridge) are described. In this molecular triad excitation into the metal-ligand charge transfer bands results in the creation of a long-lived charge separated state with TTF acting as electron donor and anthraquinone as terminal acceptor. The lifetime of the charge-separated state is 400 ns in dichloromethane at room temperature. A mechanism for the charge separation involving an intermediate charge-separated state is proposed based on transient absorption spectroscopy.

  9. Determination of volatile components in fresh, frozen, and freeze-dried Padrón-type peppers by gas chromatography-mass spectrometry using dynamic headspace sampling and microwave desorption.

    Science.gov (United States)

    Oruña-Concha, M J; López-Hernández, J; Simal-Lozano, J A; Simal-Gándara, J; González-Castro, M J; de la Cruz García, C

    1998-12-01

    "Padrón-type" peppers are a small variety of Capsicum annuum cultivated mainly in Galicia, Spain. To compare the effects of freezing and freeze-drying on the volatile components of Padrón-type peppers, preserved samples are analyzed by means of dynamic headspace sampling on an adsorbent followed by microwave desorption into a gas chromatograph equipped with a mass spectrometric detector. Sixty-five compounds are identified, including hydrocarbons, terpenes, alcohols, phenols, ethers, aldehydes, ketones, esters, pyrroles, pyrazines, and sulfurous compounds. Fresh whole, homogenized, and freeze-dried peppers have characteristic volatile-component profiles, whereas frozen peppers have a highly variable volatile-component profile.

  10. Poly[aqua-μ-bromido-(μ2-5-methylpyrazine-2-carboxylato-κ4N1,O2:O2,O2′lead(II

    Directory of Open Access Journals (Sweden)

    Pan Yang

    2012-09-01

    Full Text Available In the title coordination polymer, [PbBr(C6H5N2O2(H2O]n, the PbII atom is coordinated by one pyrazine N atom, two bridging Br atoms, a water molecule and three carboxylate O atoms. Bridging by the two anions generates a layer structure parallel to (001; the layers are linked by O—H...N and O—H...Br hydrogen bonds, forming a three-dimensional network. The lone pair is stereochemically active, resulting in a Ψ-dodecahedral coordination environment for PbII.

  11. Dragmacidin G, a Bioactive Bis-Indole Alkaloid from a Deep-Water Sponge of the Genus Spongosorites

    Science.gov (United States)

    Wright, Amy E.; Killday, K. Brian; Chakrabarti, Debopam; Guzmán, Esther A.; Harmody, Dedra; McCarthy, Peter J.; Pitts, Tara; Pomponi, Shirley A.; Reed, John K.; Roberts, Bracken F.; Rodrigues Felix, Carolina; Rohde, Kyle H.

    2017-01-01

    A deep-water sponge of the genus Spongosorites has yielded a bis-indole alkaloid which we have named dragmacidin G. Dragmacidin G was first reported by us in the patent literature and has recently been reported by Hitora et al. from a sponge of the genus Lipastrotheya. Dragmacidin G is the first in this series of compounds to have a pyrazine ring linking the two indole rings. It also has a rare N-(2-mercaptoethyl)-guanidine side chain. Dragmacidin G shows a broad spectrum of biological activity including inhibition of methicillin-resistant Staphylococcus aureus, Mycobacterium tuberculosis, Plasmodium falciparum, and a panel of pancreatic cancer cell lines. PMID:28085024

  12. Vibrational Spectra of the Azabenzenes Revisited: Anharmonic Force Fields

    CERN Document Server

    Boese, A D; Martin, Jan M.L.

    2003-01-01

    Anharmonic force fields and vibrational spectra of the azabenzene series (pyridine, pyridazine, pyrimidine, pyrazine, s-triazine, 1,2,3-triazine, 1,2,4-triazine and s-tetrazine) and benzene are obtained using density functional theory (DFT) with the B97-1 exchange-correlation functional and a triple-zeta plus double polarization (TZ2P) basis set. Overall, the fundamental frequencies computed by second-order rovibrational perturbation theory are in excellent agreement with experiment. The resolution of the presently calculated anharmonic spectra is such that they represent an extremely useful tool for the assignment and interpretation of the experimental spectra, especially where resonances are involved.

  13. Resonant femtosecond stimulated Raman spectroscopy with an intense actinic pump pulse: Application to conical intersections

    Science.gov (United States)

    Rao, B. Jayachander; Gelin, Maxim F.; Domcke, Wolfgang

    2017-02-01

    We theoretically investigate the feasibility of characterizing conical intersections with time-resolved resonant femtosecond stimulated Raman spectroscopy (FSRS) using an intense actinic pump pulse. We perform nonperturbative numerical simulations of FSRS signals for a three-electronic-state two-vibrational-mode model, which is inspired by the S 2 ( π π * )- S 1 ( n π * ) conical intersection in pyrazine. Our results show that moderately strong actinic pulses increase the intensity of vibrational fingerprint lines in FSRS transients. They facilitate the extraction of useful spectroscopic information by enhancing peaks revealing the coupling and tuning modes of the conical intersection.

  14. Characterization of cocoa liquors by GC-MS and LC-MS/MS: focus on alkylpyrazines and flavanols.

    Science.gov (United States)

    Magi, Emanuele; Bono, Luca; Di Carro, Marina

    2012-09-01

    Flavor is one of the most important characteristics of chocolate products and is due to a complex volatile fraction, depending both on the cocoa bean genotype and the several processes occurring during chocolate production (fermentation, drying, roasting and conching). Alkylpyrazines are among the most studied volatiles, being one of the main classes of odorant compounds in cocoa products. In this work, a mass spectrometric approach was used for the comparison of cocoa liquors from different countries. A headspace solid-phase microextraction gas chromatography-mass spectrometry method was developed for the qualitative study of the volatile fraction; the standard addition method was then used for the quantitative determination of five pyrazines (2-methylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,3,5-trimethylpyrazine and tetramethylpyrazine). Satisfactory figures of merit were obtained: Limits of quantitation were in the range 0.1-2.7 ng/g; repeatability and reproducibility varied between 3% and 7% and between 8% and 14%, respectively. The total content of the pyrazines was remarkably different in the considered samples, ranging from 99 to 708 ng/g. Tetramethylpyrazine showed the highest concentration in all samples, with a maximum value of 585 ng/g. A preliminary study was also performed on the nonvolatile fraction using LC-MS/MS, identifying some flavanols such as catechin, epicatechin and procyanidins.

  15. Discovery of Inhibitors of Trypanosoma brucei by Phenotypic Screening of a Focused Protein Kinase Library.

    Science.gov (United States)

    Woodland, Andrew; Thompson, Stephen; Cleghorn, Laura A T; Norcross, Neil; De Rycker, Manu; Grimaldi, Raffaella; Hallyburton, Irene; Rao, Bhavya; Norval, Suzanne; Stojanovski, Laste; Brun, Reto; Kaiser, Marcel; Frearson, Julie A; Gray, David W; Wyatt, Paul G; Read, Kevin D; Gilbert, Ian H

    2015-11-01

    A screen of a focused kinase inhibitor library against Trypanosoma brucei rhodesiense led to the identification of seven series, totaling 121 compounds, which showed >50 % inhibition at 5 μm. Screening of these hits in a T. b. brucei proliferation assay highlighted three compounds with a 1H-imidazo[4,5-b]pyrazin-2(3H)-one scaffold that showed sub-micromolar activity and excellent selectivity against the MRC5 cell line. Subsequent rounds of optimisation led to the identification of compounds that exhibited good in vitro drug metabolism and pharmacokinetics (DMPK) properties, although in general this series suffered from poor solubility. A scaffold-hopping exercise led to the identification of a 1H-pyrazolo[3,4-b]pyridine scaffold, which retained potency. A number of examples were assessed in a T. b. brucei growth assay, which could differentiate static and cidal action. Compounds from the 1H-imidazo[4,5-b]pyrazin-2(3H)-one series were found to be either static or growth-slowing and not cidal. Compounds with the 1H-pyrazolo[3,4-b]pyridine scaffold were found to be cidal and showed an unusual biphasic nature in this assay, suggesting they act by at least two mechanisms.

  16. Photophysics of organic molecules at high pressure

    Energy Technology Data Exchange (ETDEWEB)

    Mitchell, Dean James

    1978-01-01

    The pressure dependence of emission intensities, energies, and lifetimes of several classes of organic compounds in plastic media were investigated over the range 0-140 kilobars. The fluorescence intensity of 9-anthraldehyde, 9-acetylanthracene, and 9-benzoylanthracene increases remarkably with increasing pressure, accompanied by a large red shift in the emission spectrum. For azulene and several derivatives, the efficiency of fluorescence from both the second and first excited singlet states was pressure dependent as was the relative energy of these states. The rate of internal conversion depended strongly on the energy separating the relevant states. The energy and quantum efficiency of fluorescence for fluorenone in crystalline form and in several polymeric matrices was measured as a function of pressure. The quantum yield, ranged from 0.001 at low pressure to a maximum of about 0.1 at high pressure in paraffinic plastics. Fluorescence quantum yields and phosphorescence quantum yields and lifetimes were measured for pyrazine (P) 2,6-dimethylpyrazine and tetramethylpyrazine (TMP) in PMMA over the pessure range 20-120 kbar. An additional emission, which is attributed to excimer fluorescence, was also observed for these samples and for crystalline pyrazine. The phosphorescence radiative lifetime for P and TMP was about 18 ms.

  17. Hydrogen Bonding and Multiphonon Structure in One- and Two-Dimensional Polymeric Magnets

    Science.gov (United States)

    Musfeldt, J. L.; Brown, S.; Cao, J.; Conner, M. M.; McConnell, A. C.; Southerland, H. I.; Manson, J. L.; Schlueter, J. A.; Phillips, M. D.; Turnbull, M. M.; Landee, C. P.

    2007-03-01

    We report a systematic investigation of the temperature dependent infrared vibrational spectra of a family of chemically related coordination polymeric magnets based upon two different bridging anions, fluoride (F^-) and bifluoride (HF2^-), in copper-pyrazine complexes including Cu(HF2)(pyz)2BF4, Cu(HF2)(pyz)2ClO4, and CuF2(H2O)(pyz)). We compare our results with several one- and two-dimensional prototype materials including Cu(NO3)2(pyz) and Cu(ClO4)(pyz) 2. Unusual low temperature hydrogen bonding, local structural transitions associated with stronger low-temperature hydrogen bonding, and striking multiphonon effects that derive from coupling of an infrared-active fundamental with strong Raman-active modes of the pyrazine building-block molecule are observed. Based on the spectroscopic evidence, these interactions are common to this family of coordination polymers and work to stabilize the low temperature magnetic state. Similar interactions are likely to be present in other molecule-based magnets.

  18. Cu(I)-N heterocyclic carbene complexes: Synthesis, catalysis and DFT studies

    Science.gov (United States)

    Dinda, Joydev; Roymahapatra, Gourisankar; Sarkar, Deblina; Mondal, Tapan K.; Al-Deyab, Salem S.; Sinha, Chittaranjan; Hwang, Wen-Shu

    2017-01-01

    The structural, spectroscopic and catalytic properties of the two Cu(I) complexes [Cu2(L1)2](PF6)2;(1) and [Cu2(L2)2](PF6)2; (2), bearing proligands 2,6-bis-(N-methylimidazolium)pyrazine hexafluorophosphate (L1) and 2,6-bis-(N-methylbenzimidazolium)pyrazine hexafluorophosphate (L2), have been investigated. The solid state structure of 1 has been determined by X-ray diffraction studies, while DFT computation technique has been used to optimize structure 2. From molecular orbital calculations using TD-DFT, the absorption bands are assigned to metal to ligand charge transfer(MLCT) along with some inter ligand charge transfer (ILCT) transitions. Complexes 1 and 2 possess very weak Cu(I)sbnd Cu(I) interactions within the reported distance 2.947-3.020 Å. They are expected to have luminescent properties due to Cu(I)sbnd Cu(I) interactions. Preliminary studies revealed both complexes to possess catalytic efficiency in general hydrosilylation reactions.

  19. [Pyrolysates of novel latent fragrant compound 3,6-dimethyl-2,5-pyrazinedicarboxylic acid menthol ester].

    Science.gov (United States)

    Lai, Miao; Zhao, Boya; Bao, Xiaorong; Zhao, Mingqin; Ji, Xiaoming; Fu, Peipei; Zhang, Yujie

    2015-01-01

    In order to develop a new tobacco flavor released at high-temperature, the novel latent fragrant compound 3,6-dimethyl-2,5-pyrazinedicarboxylic acid menthol ester (DPAME) was synthesized by esterification using 2,3,5,6-tetramethylpyrazine and menthol as raw materials. In air atmosphere, the pyrolysis behavior of DPAME was investigated using an on-line pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) method at three temperature levels of 300, 600 and 900 degrees C, separately. The pyrolysis products were directly introduced into GC-MS and were qualitatively and semi-quantitatively analyzed. The results showed that a variety of aroma compounds of aldehydes, 3-p-menthene and menthol were released and identified at 300 degrees C. While at 600 degrees C and 900 degrees C, flavor alkene class, the alkyl pyrazines, menthol and 3-p-menthene were generated. And the types and relative amounts of pyrazines were significantly increased, at these two temperatures. Combined the analytical results of DPAME pyrolysates and the results of sensory evaluation of the cigarette, the possible pyrolysis mechanism was preliminarily speculated. The Py-GC-MS technique for the study of the pyrolysis products of DPAME was convenient and rapid. The investigation provided a reliable theoretical foundation for the perfume reinforcement technology in tobacco products, contributing to the development of cigarette products with better aroma and taste. This method is an accurate and quick way to study the pyrolysis products of latent fragrant substance.

  20. Structure and magnetic properties of heterometallic coordination carboxylate polymers with cobalt and lithium atoms

    Energy Technology Data Exchange (ETDEWEB)

    Evstifeev, I. E.; Kiskin, M. A., E-mail: mkiskin@igic.ras.ru [Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry (Russian Federation); Bogomyakov, A. S. [Russian Academy of Sciences, International Tomography Center, Siberian Branch (Russian Federation); Sidorov, A. A.; Novotortsev, V. M.; Eremenko, I. L. [Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry (Russian Federation)

    2011-09-15

    Reactions between lithium pivalate and cobalt coordination polymers [Co{sub 5}(OH{sub 2})(OH)(Piv){sub 9})L{sup 1}){sub 4}]{sub n} (I) and [Co{sub 2}(OH{sub 2})(Piv){sub 4}(L{sup 2}){sub 2}]{sub n} (II), where Piv-is the pivalate anion, L{sup 1} is pyrazine, and L{sup 2} is pyrimidine, result in new heterometallic polymers {l_brace}[Li{sub 2}Co{sub 2}(Piv){sub 6}(L{sup 1}){sub 2}]{sub 2}MeCN{r_brace}{sub n} (III), {l_brace}[Li{sub 2}Co{sub 2}(Piv){sub 6}(L{sup 2})]{sub 0.5}MeCN{r_brace}{sub n} (IV), and [Li{sub 2}Co{sub 2}(Piv){sub 6}(L{sup 2}){sub 2}]{sub n} (V). The resulting compounds contain tetra-nuclear {l_brace}Li{sub 2}Co{sub 2}(Piv){sub 6}{r_brace} fragments connected by neutral bridging ligands (pyrazine or pyrimidine) into layer structures. Crystal structures III-V are determined, and the magnetic properties of III and IV are studied.

  1. Domino reactions of 2H-azirines with acylketenes from furan-2,3-diones: Competition between the formation of ortho-fused and bridged heterocyclic systems

    Directory of Open Access Journals (Sweden)

    Alexander F. Khlebnikov

    2014-04-01

    Full Text Available 3-Aryl-2H-azirines react with acylketenes, generated by thermolysis of 5-arylfuran-2,3-diones, to give bridged 5,7-dioxa-1-azabicyclo[4.4.1]undeca-3,8-diene-2,10-diones and/or ortho-fused 6,6a,12,12a-tetrahydrobis[1,3]oxazino[3,2-a:3′,2′-d]pyrazine-4,10-diones. The latter compounds, with a new heterocyclic skeleton, are the result of the coupling of two molecules of azirine and two molecules of acylketene and can be prepared only from 3-aryl-2H-azirines having no electron-withdrawing groups in the aryl substituent. Calculations at the DFT B3LYP/6-31G(d level for the various routes of bis[1,3]oxazino[3,2-a:3′,2′-d]pyrazine skeleton formation revealed a new domino reaction of 3-aryl-2H-azirines occurring in the presence of furandiones: acid-catalyzed dimerization to dihydropyrazine followed by consecutive cycloaddition of the latter to two molecules of acylketenes.

  2. Investigating a persistent odor at an aircraft seat manufacturer.

    Science.gov (United States)

    Broadwater, Kendra; de Perio, Marie A; Roberts, Jennifer; Burton, Nancy C; Lemons, Angela R; Green, Brett J; Brueck, Scott E

    2016-10-01

    An aircraft seat manufacturing company requested a NIOSH health hazard evaluation to help identify a strong odor that had persisted throughout the facility for over a year. Employees reported experiencing health effects thought to be related to the odor. We collected and analyzed area air samples for volatile organic compounds, endotoxin, bacterial and fungal metagenome, and metalworking fluid aerosol. Bulk metalworking fluid samples were analyzed for endotoxin, bacterial and fungal metagenome, and viable bacteria and fungus. We also evaluated the building ventilation systems and water diversion systems. Employees underwent confidential medical interviews about work practices, medical history, and health concerns. Based on our analyses, the odor was likely 2-methoxy-3,5-dimethylpyrazine. This pyrazine was found in air samples across the facility and originated from bacteria in the metalworking fluid. We did not identify bacteria known to produce the compound but bacteria from the same Proteobacteria order were found as well as bacteria from orders known to produce other pyrazines. Chemical and biological contaminants and odors could have contributed to health symptoms reported by employees, but it is likely that the symptoms were caused by several factors. We provided several recommendations to eliminate the odor including washing and disinfecting the metalworking machines and metalworking fluid recycling equipment, discarding all used metalworking fluid, instituting a metalworking fluid maintenance program at the site, and physically isolating the metalworking department from other departments.

  3. Theoretical Design of High-spin Organic Molecules with-. N-S-as a Spin-containing Fragment and Heterocycle as End Groups

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Novel stable high-spin molecules possessing three different arranging fashions were designed with -(.) N-S-as a spin-containing (SC) fragment, an aromatic group, such as benzene (1), pyridine (2), pyridazine (3), pyrimidine (4), pyrazine (5) or triazine (6) as end groups (EG), and phenyl as a ferromagnetic coupling (FC) unit.The effects of different EG on the spin multiplicities of the ground states and their stabilities were investigated by means of the AM1-CI approach. All the investigated molecules corresponded to the FC and possessed high-spin ground states. The spin on the two atoms of the SC fragment was not in agreement with the delocalization results in the specific stability of -(.) N-S-. In those molecules, the stabilities of the triplet states decreased when the distance between the atoms of central SC fragments (-N-) increased. The stabilities of the triplet states of compounds 1a-n, 1b-n and 1c-n, with heterocycles as EG were higher than those of the triplet states of those compounds with phenyl as EG. Furthermore, the stabilities of the triplet states of the compounds with pyrimidine and triazine as EG were higher than those with pyridine, pyridazine or pyrazine as EG.

  4. Theoretical design of high-spin biradical molecules with heterocycles as coupling unit

    Institute of Scientific and Technical Information of China (English)

    WANG Li-min; CHU De-qing; ZHANG Jing-ping; WANG Rong-shun

    2006-01-01

    Computational studies of a class of potentially stable high-spin biradicals that two-atom-three-electron spin centers SC units connected by heterocycles FC and phenyl EG were described. The geometry and character of the spin exchange interaction were obtained by means of UB3LYP/6-31G*. The results show that the molecules possessing three different arranged fashions are designed with—·N—S as SC fragment,pyridine as FC and phenyl as EG,the spin densities on the two atoms of the SC fragment are different from the delocalization results in the specific stability of—·N—S. In these molecules,the stabilities of the triplet states decrease when the distance between the atoms of central SC (—N—) increases. Molecules with—·N—S as SC fragment,pyridine,pyrazine and triazine as FC and phenyl as EG are designed,the stability of triplet states for the molecule with pyridine as FC is the highest,and that for the molecule with pyrazine as FC is the lowest. Molecules with—·N—S,— ··N—O and—·N—NH as SC fragment,pyridine as FC and phenyl as EG are designed,the stability of triplet states for the molecule with—·N—S as SC is the highest,that for the molecule with—·N—NH as SC is the lowest.

  5. Elucidation of the aroma compositions of Zhenjiang aromatic vinegar using comprehensive two dimensional gas chromatography coupled to time-of-flight mass spectrometry and gas chromatography-olfactometry.

    Science.gov (United States)

    Zhou, Zhilei; Liu, Shuangping; Kong, Xiangwei; Ji, Zhongwei; Han, Xiao; Wu, Jianfeng; Mao, Jian

    2017-03-03

    In this work, a method to characterize the aroma compounds of Zhenjiang aromatic vinegar (ZAV) was developed using comprehensive two dimensional gas chromatography (GC×GC) coupled with time-of-flight mass spectrometry (TOFMS) and gas chromatography olfactometry (GC-O). The column combination was optimized and good separation was achieved. Structured chromatograms of furans and pyrazines were obtained and discussed. A total of 360 compounds were tentatively identified based on mass spectrum match factors, structured chromatogram and linear retention indices comparison. The most abundant class in number was ketones. A large number of esters, furans and derivatives, aldehydes and alcohols were also detected. The odor-active components were identified by comparison of the reported odor of the identified compounds with the odor of corresponding GC-O region. The odorants of methanethiol, 2-methyl-propanal, 2-methyl-butanal/3-methyl-butanal, octanal, 1-octen-3-one, dimethyl trisulfide, trimethyl-pyrazine, acetic acid, 3-(methylthio)-propanal, furfural, benzeneacetaldehyde, 3-methyl-butanoic acid/2-methyl-butanoic acid and phenethyl acetate were suspected to be the most potent. About half of them were identified as significant aroma constituents in ZAV for the first time. Their contribution to specific sensory attribute of ZAJ was also studied. The results indicated that the presented method is suitable for characterization of ZAV aroma constituents. This study also enriches our knowledge on the components and aroma of ZAV.

  6. Copper inorganic-organic hybrid coordination compound as a novel L-cysteine electrochemical sensor: Synthesis, characterization, spectroscopy and crystal structure

    Indian Academy of Sciences (India)

    Zohreh Derikvand; Azadeh Azadbakht

    2015-11-01

    Dinuclear coordination compound of Cu(II), namely, [Cu2(pydc)2(pz)(H2O)2]·2H2O, where pydc = pyridine-2,6-dicarboxylic acid (dipicolinic acid) and pz = pyrazine has been synthesized and characterized by elemental analysis, spectra (IR, UV-Vis), thermal (TG/DTG) analysis, magnetic measurements and single crystal X-ray diffraction. In the dimeric structure, the planar tridentate pyridine-2,6-dicarboxylic acid dianion coordinates to a Cu(II) ion in a meridional fashion and defines the basal plane of the complex. The fourth equatorial coordination site is then occupied by a pyrazine molecule that functions as a linear bidentate ligand bridging two Cu(II) complexes to form a dimer. The axial positions of each Cu(II) complex are occupied by one water molecule to form a distorted square pyramidal geometry. The complicated hydrogen bonding network accompanied with C–O· · · and C–H· · · stacking interactions assemble the crystal structure of 1 into a fascinating supramolecular architecture. Electrochemical behavior of [Cu2(pydc)2(pz)(H2O)2] (Cu-PDAP) on the surface of carbon nanotube (CNTs) glassy carbon electrode (GCE) is described. Oxidation of cysteine on the surface of modified electrode was investigated with cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The results show that the Cu-PDAP/CNTs film displays excellent electrochemical catalytic activities towards L-cysteine oxidation.

  7. Volatiles and Water- and Fat-Soluble Precursors of Saanen Goat and Cross Suffolk Lamb Flavour

    Directory of Open Access Journals (Sweden)

    Luciana Brasil

    2013-02-01

    Full Text Available This paper evaluates the concentrations of water- and fat-soluble precursors of meat flavour, with the aim of characterising the effect of species on the volatile profile of grilled goat and lamb meat. Compared to goat, lamb meat had higher levels of saturated fatty acids—SFA, monounsaturated fatty acids—MUFA and polyunsaturated fatty acids—PUFA and similar levels of sugars and free amino acids, except for lysine and glycine, which were higher in goat. Major differences were detected in lipid-derived volatiles; only pyrazine, thiazole, and some Strecker aldehydes were at different concentrations in these species. Volatile compounds derived from the oxidation of linoleic acid were at higher levels in meat from lamb due to the higher concentration of the latter, while compounds formed from α-linolenic acid were at higher levels in goat. It can be concluded that lamb meat has a stronger flavour profile compared to goat meat because it has the highest concentrations of lipid-derived volatile compounds, primarily straight saturated alkanals, pyrazines and thiazole.

  8. Comparative Study of the Effect of Glucosamine and Free Ammonium on 4-Methylimidazole Formation.

    Science.gov (United States)

    Yu, Pei; Xu, Xian-Bing; Yu, Shu-Juan

    2015-09-16

    The effect of glucosamine analogues (glucosamine and acetylglucosamine) and free ammonium on the formation of 4-methylimidazole (4-MeI) was investigated in the caramel model reaction systems. Methylglyoxal (MGO) was detected after derivatization by high-performance liquid chromatography with a diode array detector (HPLC-DAD). 4-MeI in the Maillard reaction was tested using a high-performance cation exchange chromatography coupled with APCI-MS (HPCEC-MS). The levels of pyrazines tested by gas chromatography (GC) coupled with MS were applied to mark the condensation reaction between dicarbonyls and free ammonium. Results showed that the formation of 4-MeI and its precursor MGO was inhibited in glucosamine analogue model reaction systems. Besides, the results from pyrazines and brown intensity in glucosamine analogues model reaction systems indicated that glucosamine analogues mainly underwent the reaction of intra-intermolecular polymerization into melanoidins rather than the degradation reaction into MGO. Using glucosamine analogues to produce the caramel color with a low level of 4-MeI was applicable.

  9. The silver(I nitrate complex of the ligand N-(pyridin-2-ylmethylpyrazine-2-carboxamide: a metal–organic framework (MOF structure

    Directory of Open Access Journals (Sweden)

    Dilovan S. Cati

    2017-04-01

    Full Text Available The reaction of silver(I nitrate with the mono-substituted pyrazine carboxamide ligand, N-(pyridin-2-ylmethylpyrazine-2-carboxamide (L, led to the formation of the title compound with a metal–organic framework (MOF structure, [Ag(C11H10N4O(NO3]n, poly[μ-nitrato-[μ-N-(pyridin-2-ylmethyl-κNpyrazine-2-carboxamide-κN4]silver(I]. The silver(I atom is coordinated by a pyrazine N atom, a pyridine N atom, and two O atoms of two symmetry-related nitrate anions. It has a fourfold N2O2 coordination sphere, which can be described as distorted trigonal–pyramidal. The ligands are bridged by the silver atoms forming –Ag–L–Ag–L– zigzag chains along the a-axis direction. The chains are arranged in pairs related by a twofold screw axis. They are linked via the nitrate anions, which bridge the silver(I atoms in a μ2 fashion, forming the MOF structure. Within the framework there are N—H...O and C—H...O hydrogen bonds present.

  10. Dynamics of Activated Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Mullin, Amy S. [Univ. of Maryland, College Park, MD (United States)

    2016-11-16

    Experimental studies have been performed to investigate the collisional energy transfer processes of gas-phase molecules that contain large amounts of internal energy. Such molecules are prototypes for molecules under high temperature conditions relevant in combustion and information about their energy transfer mechanisms is needed for a detailed understanding and modeling of the chemistry. We use high resolution transient IR absorption spectroscopy to measure the full, nascent product distributions for collisions of small bath molecules that relax highly vibrationally excited pyrazine molecules with E=38000 cm-1 of vibrational energy. To perform these studies, we developed new instrumentation based on modern IR light sources to expand our experimental capabilities to investigate new molecules as collision partners. This final report describes our research in four areas: the characterization of a new transient absorption spectrometer and the results of state-resolved collision studies of pyrazine(E) with HCl, methane and ammonia. Through this research we have gained fundamental new insights into the microscopic details of relatively large complex molecules at high energy as they undergo quenching collisions and redistribute their energy.

  11. Crystal engineering of energetic materials: co-crystals of Ethylenedinitramine (EDNA) with modified performance and improved chemical stability.

    Science.gov (United States)

    Aakeröy, Christer B; Wijethunga, Tharanga K; Desper, John

    2015-07-27

    In the area of energetic materials, co-crystallization is emerging as a new technology for modifying or enhancing the properties of existing energetic substances. Ethylenedinitramine (EDNA) is a known energetic material which requires attention partly due to its chemical instability originating with its two highly acidic protons. In order to stabilize EDNA, a co-crystallization approach targeting the acidic protons using a series of co-crystallizing agents with suitable hydrogen-bond acceptors was employed. Fifteen attempted co-crystallizations resulted in eight successful outcomes and six of these were crystallographically characterized and all showed evidence of hydrogen bonds to the intended protons. Calculated detonation properties and experimental thermal and impact data for the co-crystals were obtained and compared with those of pure EDNA. The co-crystal of EDNA and 1,2-bis(4-pyridyl)ethylene was recognized as a more thermally stable alternative to EDNA while the co-crystal of EDNA and pyrazine N,N'-dioxide showed comparable detonation strengths (and much improved chemical stability) compared with that of EDNA. The co-crystals EDNA:4,4'-bipyridine and EDNA:pyrazine N,N'-dioxide were found to be about 50 % less impact sensitive than EDNA, all of which illustrate how co-crystallizations can be utilized for successfully modifying specific aspects of energetic materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Comparison of the structure of (E)-2-(2-benzylidenehydrazinylidene)quinoxaline with those of its chloro- and bromobenzylidene analogues.

    Science.gov (United States)

    Gomes, Ligia Rebelo; Low, John Nicolson; Rodrigues, Ana S M C; Wardell, James L; de Souza, Marcus V N; Noguiera, Thais C M; Pinheiro, Alessandra C

    2013-08-01

    (E)-2-(2-Benzylidenehydrazinylidene)quinoxaline, C₁₅H₁₂N₄, crystallized with two molecules in the asymmetric unit. The structures of six halogen derivatives of this compound were also investigated: (E)-2-[2-(2-chlorobenzylidene)hydrazinylidene]quinoxaline, C₁₅H₁₁ClN₄; (E)-2-[2-(3-chlorobenzylidene)hydrazinylidene]quinoxaline, C₁₅H₁₁ClN₄; (E)-2-[2-(4-chlorobenzylidene)hydrazinylidene]quinoxaline, C₁₅H₁₁ClN₄; (E)-2-[2-(2-bromobenzylidene)hydrazinylidene]quinoxaline, C₁₅H₁₁BrN₄; (E)-2-[2-(3-bromobenzylidene)hydrazinylidene]quinoxaline, C₁₅H₁₁BrN₄; (E)-2-[2-(4-bromobenzylidene)hydrazinylidene]quinoxaline, C₁₅H₁₁BrN₄. The 3-Cl and 3-Br compounds are isomorphous, as are the 4-Cl and 4-Br compounds. In all of these compounds, it was found that the supramolecular structures are governed by similar predominant patterns, viz. strong intermolecular N-H...N(pyrazine) hydrogen bonds supplemented by weak C-H∙∙∙N(pyrazine) hydrogen-bond interactions in the 2- and 3-halo compounds and by C-H∙∙∙Cl/Br interactions in the 4-halo compounds. In all compounds, there are π-π stacking interactions.

  13. Reduction of carcinogenic 4(5)-methylimidazole in a caramel model system: influence of food additives.

    Science.gov (United States)

    Seo, Seulgi; Ka, Mi-Hyun; Lee, Kwang-Geun

    2014-07-09

    The effect of various food additives on the formation of carcinogenic 4(5)-methylimidazole (4-MI) in a caramel model system was investigated. The relationship between the levels of 4-MI and various pyrazines was studied. When glucose and ammonium hydroxide were heated, the amount of 4-MI was 556 ± 1.3 μg/mL, which increased to 583 ± 2.6 μg/mL by the addition of 0.1 M of sodium sulfite. When various food additives, such as 0.1 M of iron sulfate, magnesium sulfate, zinc sulfate, tryptophan, and cysteine were added, the amount of 4-MI was reduced to 110 ± 0.7, 483 ± 2.0, 460 ± 2.0, 409 ± 4.4, and 397 ± 1.7 μg/mL, respectively. The greatest reduction, 80%, occurred with the addition of iron sulfate. Among the 12 pyrazines, 2-ethyl-6-methylpyrazine with 4-MI showed the highest correlation (r = -0.8239).

  14. Methoxypyrazine analysis and influence of viticultural and enological procedures on their levels in grapes, musts, and wines.

    Science.gov (United States)

    Sidhu, Davinder; Lund, Jensen; Kotseridis, Yorgos; Saucier, Cedric

    2015-01-01

    This review discusses the factors that affect the concentrations of methoxypyrazines (MPs) and the techniques used to analyze MPs in grapes, musts, and wines. MPs are commonly studied pyrazines in food science due to their contribution of aroma and flavor to numerous vegetables such as peas and asparagus. They are described as highly odorous compounds with a very low olfactory threshold. The grape varietals that exhibit green or herbaceous aromas that are characteristic of MPs are predominantly Vitis vinifera cv. Cabernet Sauvignon and Sauvignon Blanc, but include others. The most extensively studied MPs include 3-isobutyl-2-methoxypyrazine, 3-isopropyl-2-methoxypyrazine, and 3-sec-butyl-2-methoxypyrazine. It outlines the significance of methoxypyrazines in grapes, musts, and wines in terms of the concentrations that are capable of contributing their sensory characteristics to wines. This review discusses methods for analyzing MPs including gas chromatography-mass spectroscopy (one or two dimension) and high-performance liquid chromatography, the appropriate extraction techniques, and the efficacy of these methods. Additionally, this review explores factors that affect pyrazine content of grapes, must, and wines, such as the effects of different viticultural practices, effects of light exposure and grape maturation, climate, soil, the multi-colored Asian lady beetle and the effects of different vinification processes.

  15. Control of Reactivity and Regioselectivity for On-Surface Dehydrogenative Aryl-Aryl Bond Formation.

    Science.gov (United States)

    Kocić, Nemanja; Liu, Xunshan; Chen, Songjie; Decurtins, Silvio; Krejčí, Ondřej; Jelínek, Pavel; Repp, Jascha; Liu, Shi-Xia

    2016-05-04

    Regioselectivity is of fundamental importance in chemical synthesis. Although many concepts for site-selective reactions are well established for solution chemistry, it is not a priori clear whether they can easily be transferred to reactions taking place on a metal surface. A metal will fix the chemical potential of the electrons and perturb the electronic states of the reactants because of hybridization. Additionally, techniques to characterize chemical reactions in solution are generally not applicable to on-surface reactions. Only recent developments in resolving chemical structures by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) paved the way for identifying individual reaction products on surfaces. Here we exploit a combined STM/AFM technique to demonstrate the on-surface formation of complex molecular architectures built up from a heteroaromatic precursor, the tetracyclic pyrazino[2,3-f][4,7]phenanthroline (pap) molecule. Selective intermolecular aryl-aryl coupling via dehydrogenative C-H activation occurs on Au(111) upon thermal annealing under ultrahigh vacuum (UHV) conditions. A full atomistic description of the different reaction products based on an unambiguous discrimination between pyrazine and pyridine moieties is presented. Our work not only elucidates that ortho-hydrogen atoms of the pyrazine rings are preferentially activated over their pyridine equivalents, but also sheds new light onto the participation of substrate atoms in metal-organic coordination bonding during covalent C-C bond formation.

  16. Effects of heterocyclic aromatic substituents on binding affinities at two distinct sites of somatostatin receptors. Correlation with the electrostatic potential of the substituents.

    Science.gov (United States)

    Prasad, Vidya; Birzin, Elizabeth T; McVaugh, Cheryl T; Van Rijn, Rachel D; Rohrer, Susan P; Chicchi, Gary; Underwood, Dennis J; Thornton, Edward R; Smith, Amos B; Hirschmann, Ralph

    2003-05-08

    In our continuing program exploring glucose-based peptidomimetics of somatostatin (SRIF-14), we sought to improve the water solubility of our glycosides. This led to insights into the nature of the ligand binding sites at the SRIF receptor. Replacement of the C4 benzyl substituent in glucoside (+)-2 with pyridinylmethyl or pyrazin-2-ylmethyl congeners increased water solubility and enhanced affinity for the human SRIF subtype receptor 4 (sst4). We attribute this effect to hydrogen bond formation. The pyridin-3-ylmethyl substituent at C4, when combined with the imidazol-4-ylmethyl group at C2, generated (-)-19, which has the highest affinity of a glucose-based peptidomimetic at a human SRIF receptor to date (K(i) 53 +/- 23 nM, n = 6 at sst4). The C4 heterocyclic congeners of glucosides bearing a 1-methoxy substituent rather than an indole side chain at the anomeric carbon, such as (+)-16, also provided information about the Trp(8) binding pocket. We correlated the SARs at both the C4 and the Trp(8) binding pockets with calculations of the electrostatic potentials of the diverse C4 aromatic substituents using Spartan 3-21G(*) MO analysis. These calculations provide an approximate analysis of a molecule's ability to interact within a receptor binding site. Our binding studies show that benzene and indole rings, but not pyridinylmethyl nor pyrazin-2-ylmethyl rings, can bind the hydrophobic Trp(8) binding pocket of sst4. The Spartan 3-21G(*) MO analysis reveals significant negative electrostatic potential in the region of the pi-clouds for the benzene and indole rings but not for the pyridinylmethyl or pyrazin-2-ylmethyl congeners. Our data further demonstrate that the replacement of benzene or indole side chains by heterocyclic aromatic rings typified by pyridine and pyrazine not only enhances water solubility and hydrogen bonding capacity as expected, but can also profoundly diminish the ability of the pi-cloud of the aromatic substituent to interact with side chains

  17. Ligand effects on the structures and magnetic properties of tricyanomethanide-containing copper(II) complexes.

    Science.gov (United States)

    Yuste, Consuelo; Bentama, Abdeslem; Stiriba, Salah-Eddine; Armentano, Donatella; De Munno, Giovanni; Lloret, Francesc; Julve, Miguel

    2007-11-28

    The preparation, crystal structure and magnetic properties of four heteroleptic copper(II) complexes with the tricyanomethanide (tcm(-)) and the heterocyclic nitrogen donors 3,6-bis(2-pyridyl)pyridazine (dppn), 2,5-bis(2-pyridyl)pyrazine (2,5-dpp), 2,3-bis(2-pyridyl)pyrazine (2,3-dpp) and 2,3-bis(2-pyridyl)quinoxaline (2,3-dpq) are reported, {[Cu(2)(dppn)(OH)(tcm)(2)] x tcm}(n) (1), {[Cu(2,5-dpp)(tcm)] x tcm}(n) (2), {[Cu(2)(2,3-dpp)(2)(tcm)(3)(H(2)O)(0.5)] x tcm x 0.5H(2)O}(n) (3) and [Cu(2,3-dpq)(tcm)(2)](n) (4). 1 has a ladder-like structure with single mu-1,5-tcm ligands forming the sides and a bis-bidentate dppn and a single mu-hydroxo providing the rung. Each copper atom in 1 exhibits a distorted square pyramidal CuN(4)O surrounding: the basal plane is built by the hydroxo-oxygen, a nitrile-nitrogen atom from a tcm group and one pyrazine and a pyridyl nitrogen atoms from the dppn whereas the apical position is filled by a nitrile-nitrogen atom from a symmetry-related tcm ligand. The structures of 2-4 consists of zig-zag (2 and 3)/linear (4) chains of copper(II) ions which are bridged by either bis-bidentate 2,5-dpp (2) and 2,3-dpp (3) molecules or single mu-1,5-tcm (4) groups. The copper atoms in 2 and 4 are five coordinated with distorted trigonal bipyramidal (2) and square pyramidal (4) CuN(5) surroundings. The axial positions in 2 are occupied by two pyridyl-nitrogen atoms from two 2,5-dpp ligands whereas the trigonal plane is built by a nitrile-nitrogen from a terminally bound tcm group and two pyrazine nitrogen atoms from two 2,5-dpp molecules. The basal plane in 4 is defined by a pyridyl and a pyrazine nitrogen atoms from the bidentate 2,3-dpq ligand and two nitrile nitrogen atoms from two tcm groups (one terminal and the other bridging) whereas the apical position is filled by a nitrile nitrogen from another tcm ligand. The crystallographically independent copper atoms in 3 [Cu(1) and Cu(2)] exhibit elongated octahedral geometries being defined by four

  18. Photoanodic reactions at natural pyrite(100) studied by photocalorimetry: internal quantum and energy efficiencies and Peltier heats after different surface treatment

    Energy Technology Data Exchange (ETDEWEB)

    Schaaf, N.-S.; Dohrmann, J.K. [Freie Univ. Berlin (Germany). Inst. fuer Physikalische und Theoretische Chemie; Seeliger, W.; Tributsch, H. [Hahn-Meitner-Inst., Berlin (Germany). Abt. Solare Energetik

    1996-12-31

    Photoanodic oxidation of I{sup -}, Fe(CN){sup 4-}{sub 6}, and Fe{sup 2+} at the (100)-face of a natural pyrite electrode (n-type FeS{sub 2}) has been investigated by photocalorimetry at 633 nm. The internal and external quantum efficiencies, {eta}{sub a} and {eta}{sub c}, respectively, the maximal internal efficiency, L{sub G}, for conversion of optical into electrical energy, the Peltier heat, Q{sub PE}, of the electrode process, and the reflectivity, R, of the electrode-solution interface have been determined at cathodically activated pyrite and (for I{sup -}, and Fe{sup 2+}) after additional treatment of the electrode with pyrazine or (1 H-benzotriazol-1-yl)-methylisocyanide (btic), L{sub G}, {eta}{sub a}, and {eta}{sub c} decrease in the order I{sup -} > Fe(CN){sup 4}{sub 6} > Fe{sup 2+}. At the bare electrode L{sub G} was 0.6% for I{sup -} 0.2% for Fe(CN){sup 4}{sub 6}, and 0.02% for Fe{sup 2+}. Adsorption of pyrazine and btic affects {eta}{sub a} and L{sub G} for oxidation of I{sup -}, without changing Q{sub PE} (-0.09 eV) and R (67%). With btic, L{sub G} increased to 0.9%. For oxidation of Fe{sup 2+}, the adsorbates diminish {eta}{sub a} and L{sub G} and shift Q{sub PE} from -0.24 eV at the bare electrode to -0.13 eV (pyrazine) and +0.23 eV (btic). The effects demonstrate different pathways for charge transfer from I{sup -} and Fe{sup 2+} to the electrode. The shift of Q{sub PE} for oxidation of Fe{sup 2+} is attributed to adsorbate-induced differences in the hydration entropies of the pyrite surface. (orig.) 27 refs.

  19. Water-soluble tetrapodal N, O ligands incorporating soft N-heterocycles for the selective complexation of Am(III) over Ln(III)

    Energy Technology Data Exchange (ETDEWEB)

    Heitzmann, M.; Gateau, Ch.; Delangle, P. [CEA Grenoble, Inac, Service de Chimie Inorganique et Biologique, UMR E 3 CEA UJF, FRE CNRS 3200, F-38054 Grenoble (France); Chareyre, L.; Miguirditchian, M.; Charbonnel, M.Ch. [CEA Marcoule, DEN, DRCP, SCPS, F-30207, Bagnols-sur-Ceze (France)

    2010-07-01

    A series of four water-soluble N, O-tetrapodal ligands derived from ethylenediamine, bearing hard acetate groups and soft N-heterocycles, either pyridine or pyrazine, was developed to study the impact of the softness of N-donors on the complexation properties with trivalent f ions. Two novel ligands of enhanced soft character, bearing three pyridines (L{sup 3py}) or three pyrazines (L{sup 3pz}), were synthesized and the related lanthanide complexes were studied in solution. The ligand containing three pyridyl-methyl moieties L{sup 3py} gives complexes with a coordination similar to EDTA, i.e. a hexa-dentate coordination mode as indicated by NMR and luminescence decays (q = 3) and stability constants in the range log {beta}{sub 110} = 6.99-9.3 (La-Lu). On the other hand, the softest molecule L{sup 3pz} forms much less stable complexes with log {beta}{sub 110} = 4.0-4.4 (La-Eu). The selective back-extraction of Am(III) from organic solutions containing 4f and 5f elements was tested with the four water-soluble complexing agents. The ligand L{sup 3pz} demonstrates poor stripping ability and selectivity. In contrast, the three ligands L{sup py}, L{sup pz} and L{sup 3py} give interesting back-extraction results with Eu/Am separation factors ranging from 36 to 46, which are significantly higher than with HEDTA. This exemplifies the role of the N-hetero-cycle softness in enhancing the separation between Am(III) and Eu(III). Interestingly, the pyrazine-based ligand, L{sup pz}, demonstrates the best stripping properties, with a distribution factor that approaches that of HEDTA in the same conditions (D{sub Am{approx}}0.3). This molecule is a good compromise between softness and hardness and forms complexes still stable at pH 3 due to its low basicity. (authors)

  20. En route to controlled catalytic CVD synthesis of densely packed and vertically aligned nitrogen-doped carbon nanotube arrays

    Directory of Open Access Journals (Sweden)

    Slawomir Boncel

    2014-03-01

    Full Text Available The catalytic chemical vapour deposition (c-CVD technique was applied in the synthesis of vertically aligned arrays of nitrogen-doped carbon nanotubes (N-CNTs. A mixture of toluene (main carbon source, pyrazine (1,4-diazine, nitrogen source and ferrocene (catalyst precursor was used as the injection feedstock. To optimize conditions for growing the most dense and aligned N-CNT arrays, we investigated the influence of key parameters, i.e., growth temperature (660, 760 and 860 °C, composition of the feedstock and time of growth, on morphology and properties of N-CNTs. The presence of nitrogen species in the hot zone of the quartz reactor decreased the growth rate of N-CNTs down to about one twentieth compared to the growth rate of multi-wall CNTs (MWCNTs. As revealed by electron microscopy studies (SEM, TEM, the individual N-CNTs (half as thick as MWCNTs grown under the optimal conditions were characterized by a superior straightness of the outer walls, which translated into a high alignment of dense nanotube arrays, i.e., 5 × 108 nanotubes per mm2 (100 times more than for MWCNTs grown in the absence of nitrogen precursor. In turn, the internal crystallographic order of the N-CNTs was found to be of a ‘bamboo’-like or ‘membrane’-like (multi-compartmental structure morphology. The nitrogen content in the nanotube products, which ranged from 0.0 to 3.0 wt %, was controlled through the concentration of pyrazine in the feedstock. Moreover, as revealed by Raman/FT-IR spectroscopy, the incorporation of nitrogen atoms into the nanotube walls was found to be proportional to the number of deviations from the sp2-hybridisation of graphene C-atoms. As studied by XRD, the temperature and the [pyrazine]/[ferrocene] ratio in the feedstock affected the composition of the catalyst particles, and hence changed the growth mechanism of individual N-CNTs into a ‘mixed base-and-tip’ (primarily of the base-type type as compared to the purely

  1. 同时蒸馏萃取燕麦炒米香味物质的气相色谱-质谱分析%Simultaneous Distillation and Extraction and GC-MS Analysis of Aroma Components from Fried Oat

    Institute of Scientific and Technical Information of China (English)

    任清; 黄明泉; 杨震安; 郭项雨

    2012-01-01

    Aroma components were extracted from fried oat by simultaneous distillation and extraction (SDE), and analyzed by gas chromatography-mass spectroscopy (GC-MS). A total of 86 components were separated. Of them, 58 were identified, accounting for 85.23% of total peak area. The major components were Z,Z-9,12-octadecadienoic acid (20.01%), E,E-2,4-decadienal (7.15%), hexadecanamide (5.30%), eicosane (4.38%), hexadecane (4.17%), ethyl acetate (3.52%), 2,6-dimethyl-pyrazine (3.03%), 3- ethyl-2,5-dimethyl-pyrazine (2.96%), hexanal (2.65%), 2-ethyl-5-methyl-pyrazine (2.64%) and 1-pentanol (2.11%).%采用同时蒸馏萃取法提取燕麦炒米香味物质,然后利用气相色谱一质谱技术对提取的燕麦炒米香味物质进行检测和成分分析。结果共分离出86种成分,鉴定出58种,占香味物质总峰面积的85.23%。主要成分有Z,Z-9,12-十八碳二烯酸(20.01%)、E,E-2,4-癸二烯醛(7.15%)、十六烷酰胺(5.30%)、二十烷(4.38%)、十六烷(4.17%)、乙酸LN(3.52%)、2,6.二甲基吡嗪(3.03%)、3-乙基-2,5-二甲基一吡嗪(2.96%)、己醛(2.65%)、2-乙基一5-甲基吡嗪(2.64%)、乙酸丁酯(2.39%)、1-戊醇(2.11%)

  2. A 3D complex containing novel 2D Cu{sup II}-azido layers: Structure, magnetic properties and effects of 'Non-innocent' reagent

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Xue-Miao; Guo, Qian [School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384 (China); Zhao, Jiong-Peng, E-mail: horryzhao@yahoo.com [School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384 (China); Liu, Fu-Chen, E-mail: fuchenliutj@yahoo.com [School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384 (China); Lanzhou Petrochemical College of Vocational Technology, Lanzhou 730060 (China)

    2012-12-15

    A novel copper-azido coordination polymer, [Cu{sub 2}(N{sub 3}){sub 3}(L)]{sub n} (1, HL=pyrazine-2-carboxylic acid), has been synthesized by hydrothermal reaction with 'Non-innocent' reagent in the aqueous solution. In the reaction system, Cu{sup II} ions are avoided to reduce to Cu{sup I} ions due to the existence of Nd{sup III}. It is found that the complex is a 3D structure based on two double EO azido bridged trimmers and octahedron Cu{sup II} ions, in which the azide ligands take on EO and {mu}{sub 1,1,3} mode to form Cu{sup II}-azido 2D layers, furthermore L ligands pillar 2D layers into an infinite 3D framework with the Schlaefli symbol of {l_brace}4;6{sup 2}{r_brace}4{l_brace}4{sup 2};6{sup 12};8{sup 10};10{sup 4}{r_brace}{l_brace}4{sup 2};6{sup 4}{r_brace}. Magnetic studies revealed that the interactions between the Cu{sup II} ions in the trimmer are ferromagnetic for the Cu-N-Cu angle nearly 98 Degree-Sign , while the interactions between the trimmer and octahedron Cu{sup II} ion are antiferromgantic and result in an antiferromagnetic state. - Graphical abstract: A 3D complex containing novel 2D Cu{sup II}-azido layers, [Cu{sub 2}(N{sub 3}){sub 3}(L)]{sub n} (HL=pyrazine-2-carboxylic acid), was synthesized by hydrothermal reaction and exhibit interesting structure and magnetic properties. Highlights: Black-Right-Pointing-Pointer 'Non-innocent' reagents plays a key role in the process of formation of this complex. Black-Right-Pointing-Pointer 2D layer is formed only by Cu{sup II} ions and azido ligands. Black-Right-Pointing-Pointer Pyrazine-2-carboxylate ligands reinforce 2D layers and pillar them into an infinite 3D framework. Black-Right-Pointing-Pointer Magnetic study indicates that alternating FM-AF coupling exists in the complex.

  3. Iron-promoted nucleophilic additions to diimine-type ligands: a synthetic and structural study.

    Science.gov (United States)

    Vallina, Ana Tesouro; Stoeckli-Evans, Helen; Neels, Antonia; Ensling, Jürgen; Decurtins, Silvio

    2003-05-19

    We report here three examples of the reactivity of protic nucleophiles with diimine-type ligands in the presence of Fe(II) salts. In the first case, the iron-promoted alcoholysis reaction of one nitrile group of the ligand 2,3-dicyano-5,6-bis(2-pyridyl)-pyrazine (L1) permitted the isolation of an stable E-imido-ester, [Fe(L1')(2)](CF(3)SO(3))(2) (1), which has been characterized by spectroscopic studies (IR, ES-MS, Mössbauer), elemental analysis, and crystallographically. Compound 1 consists of mononuclear octahedrally coordinated Fe(II) complexes where the Fe(II) ion is in its low-spin state. The iron-mediated nucleophilic attack of water to the asymmetric ligand 2,3-bis(2-pyridyl)pyrido[3,4-b]pyrazine (L2) has also been studied. In this context, the crystal structures of two hydration-oxidation Fe(III) products, [Fe(L2')(2)](ClO(4))(3).3CH(3)CN (2) and trans-[FeL2"Cl(2)] (3), are described. Compounds 2 and 3 are both mononuclear Fe(III) complexes where the metals occupy octahedral positions. In principle, L2 is expected to coordinate to metal ions through its bipyridine-type units to form a five-membered ring; however, this is not the case in compounds 2 and 3. In 2, the ligand coordinates through its pyridines and through the hydroxyl group attached to the pyrazine imino carbon after hydration, that is, in an N,O,N tridentate manner. In compound 3, the ligand has suffered further transformations leading to a very stable diamido complex. In this case, the metal ion achieves its octahedral geometry by means of two pyridines, two amido N atoms, and two axial chlorine atoms. Magnetic susceptibility measurements confirmed the spin state of these two Fe(III) species: compounds 2 and 3 are low-spin and high-spin, respectively.

  4. Organoleptic and chemical quality of farmed meagre (Argyrosomus regius) as affected by size.

    Science.gov (United States)

    Giogios, Ioannis; Grigorakis, Kriton; Kalogeropoulos, Nick

    2013-12-01

    Two fish groups differing in size (average weighing 830±220 and 1600±350 g, respectively) were evaluated for their sensory, somatometric and chemical quality characteristics. No differences were found in the yields and fillet proximate composition of the two groups. Although taste panels indicated high acceptability for both groups, the large fish received significantly better hedonic rates for their overall acceptance. Differences were also observed in the fatty acid profiles of the two groups with the large fish having significantly higher 18:2n-6 and total n-6 contents. Their volatile compounds also differed, with small fish containing higher total amount, as well as more total aldehydes, furans and pyrazines. All these findings indicate size-dependent quality alterations, but also sufficient quality for small fish to be commercialised. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. 1.1.3. Substitution on Re(IV complexes: a tool for the synthesis of novel mono- and polynuclear compounds

    Directory of Open Access Journals (Sweden)

    Carlos Kremer

    2014-04-01

    Full Text Available Rhenium(IV complexes are relatively scarce if compared with those of other oxidation states as Re(V or Re(VII. It is a 5d3 ion, and usually forms octahedral complexes which are reasonably stable against redox processes and inert to ligand substitution. This is the basis for the preparation of mononuclear species that can act as ligands towards other transition metal ions. For example, complexes containing dicarboxylic ligands, [ReX4(ox]2–and [ReX4(mal]2– (X = Cl, Br; ox = oxalato; mal = malonato, or N-donor ligands, [ReCl5(pyz]– (pyz = pyrazine have been used as building blocks to construct heteropolynuclear complexes. The different synthetic routes, as well as the designed structures, from discrete binuclear complexes to extended chain-like compounds, are reviewed in this contribution.

  6. The effect of pH on the formation of volatile compounds produced by heating a model system containing 5?-Imp and cysteine

    Directory of Open Access Journals (Sweden)

    Madruga Marta Suely

    1998-01-01

    Full Text Available The identification of volatile compounds formed from the reactions of Inosine-5?-Monophosphate (5?-IMP with Cysteine at three different pH (3.0; 4.5; 6.0 and 140 °C were performed using dynamic headspace analysis. The results gave over 90 volatile compounds, mainly heterocyclic compounds, including sulphur containing furans, thiophenes, thiazoles, furans, alkyl sulphides, bicyclic compounds and cyclic sulphides. The studies showed that sulphur-substituted furans, mercaptoketones and alkylfurans were formed mainly at acidic pH, while pyrazines were completely inhibited at high pH. These findings support an earleir observation that pH has a great influence on volatile compounds formed in Maillard type reactions.

  7. Realistic vs sudden turn-on of natural incoherent light: Coherences and dynamics in molecular excitation and internal conversion

    Energy Technology Data Exchange (ETDEWEB)

    Grinev, Timur; Brumer, Paul [Chemical Physics Theory Group, Department of Chemistry, and Center for Quantum Information and Quantum Control, University of Toronto, Toronto, Ontario M5S 3H6 (Canada)

    2015-12-28

    Molecular excitation with incoherent light is examined using realistic turn-on time scales, and results are compared to those obtained via commonly used sudden turn-on, or pulses. Two significant results are obtained. First, in contrast to prior studies involving sudden turn-on, realistic turn-on is shown to lead to stationary coherences for natural turn-on time scales. Second, the time to reach the final stationary mixed state, known to result from incoherent excitation, is shown to depend directly on the inverse of the molecular energy level spacings, in both sudden and realistic turn-on cases. The S{sub 0} → S{sub 2}/S{sub 1} internal conversion process in pyrazine is used as an example throughout. Implications for studies of natural light harvesting systems are noted.

  8. Volatile substances from male Anastrepha fraterculus wied. (Diptera: Tephritidae: identification and behavioural activity

    Directory of Open Access Journals (Sweden)

    Lima Ivanildo S.

    2001-01-01

    Full Text Available Volatile compounds produced by calling males of Anastrepha species have previously been reported from A. ludens and A. suspensa. Both species mate in the afternoon, release a similar range of compounds in different proportions, and only differ in the production of monoterpenes. When calling, male A. fraterculus releases two isomers of the sesquiterpene alpha-farnesene, three lactones (anastrephin, epianastrephin and (E,E-suspensolide, and two monoterpenes (limonene and (Z-beta-ocimene. The dimorphic male salivary glands produce and/or store the same isomers of alpha-farnesene and suspensolide, and four pyrazines. Two of these compounds have been previously reported from male A. ludens and A. suspensa. Salivary glands from virgin calling male A. fraterculus showed behavioural activity when bioassayed with virgin mature female flies, but immature females were not attracted.

  9. Biological Activity of Volatiles from Marine and Terrestrial Bacteria

    Directory of Open Access Journals (Sweden)

    Irene Wagner-Dobler

    2010-12-01

    Full Text Available The antiproliferative activity of 52 volatile compounds released from bacteria was investigated in agar diffusion assays against medically important microorganisms and mouse fibroblasts. Furthermore, the activity of these compounds to interfere with the quorum-sensing-systems was tested with two different reporter strains. While some of the compounds specific to certain bacteria showed some activity in the antiproliferative assay, the compounds common to many bacteria were mostly inactive. In contrast, some of these compounds were active in the quorum-sensing-tests. γ-Lactones showed a broad reactivity, while pyrazines seem to have only low intrinsic activity. A general discussion on the ecological importance of these findings is given.

  10. Photoconductive and nonlinear optical properties of composites based on metallophthalocyanines

    Science.gov (United States)

    Vannikov, A. V.; Grishina, A. D.; Gorbunova, Yu. G.; Tsivadze, A. Yu.

    2015-08-01

    The photoconductive, photorefractive and nonlinear optical properties of composites from polyvinylcarbazole or aromatic polyimide containing supramolecular ensembles of (tetra-15-crown-5) - phthalocyaninato gallium, indium, - phthalocyaninateacetato yttrium, - phthalocyaninato ruthenium with axially coordinated pyrazine molecules were investigated at 633, 1030 and 1064nmusing continuous and pulsed lasers. Supramolecular ensembles (SE) were prepared through dissolution of molecular metallophthalocyanines in tetrachloroethane (TCE) and subsequent treatment via three cycles of heating to 90∘C and slow cooling to room temperature. The zscan method in femtosecond and nanosecond regimeswas used for measuring nonlinear optical properties phthalocyaninato indium and yttrium in TCE solutions and polymer films. It was established that effect of heavy metallic atom is basic factor which determines the quantum yield, photorefractive amplification of laser object beam, dielectric susceptibility of third order and nonlinear optical properties of metallophthalocyanines.

  11. Novel Reaction of N,N'-Bisarylmethanediamines with Formaldehyde. Synthesis of Some New 1,3,5-Triaryl-1,3,5-hexahydrotriazines

    Directory of Open Access Journals (Sweden)

    Abolfazl Olyaei

    2006-07-01

    Full Text Available The acid-catalyzed cyclocondensation of N,N'-bisaryl (aryl = 2-pyrimidinyl, 2- pyrazinyl and 4-nitrophenyl methanediamines 5a-c with aqueous formaldehyde in refluxing acetonitrile leads to the formation of the corresponding 1,3,5-triaryl-1,3,5-hexa- hydrotriazines 6a-c. The stoichiometric reactions of 2-aminopyrimidine and 2-amino- pyrazine with aqueous formaldehyde in acetonitrile under reflux conditions also afforded 6a and 6b, respectively. Treatment of 2-aminopyrimidine with aqueous formaldehyde in a 3:2 ratio yielded N,N',N"-tris(2-pyrimidinyldimethylenetriamine (7a as a sole product, which upon subsequent reaction with formaldehyde also afforded 6a. The reaction of N,N'-biphenylmethanediamine with formaldehyde was also investigated.

  12. Synthesis of quinolino[2′,3′:8,7]cyclooct[]indole

    Indian Academy of Sciences (India)

    Leena Vairavelu; K J Rajendra Prasad

    2014-11-01

    A rapid and efficient synthetic route for the synthesis of 7,8,9,10-tetrahydroquinolino[2′,3′:8,7] cyclooct[]indole analogues has been developed by reaction of 1-oxo-1,2,3,4,5,6-hexahydrocyclooct[]indole with anthranilic acid and 3-amino pyrazine acid under POCl3 condition and the synthesis of 7,8,9,10-tetrahydroquinolino[2′,3′:8,7]cyclooct[]indole-6-carboxylic acid has been designed by reaction of 1-oxo-1,2,3,4,5,6-hexahydrocyclooct[]indole with isatin in the presence of NaOH via Pfitzinger reaction. These methods are more satisfactory in terms of the yield and simple one-pot operation. Structures of the products thus obtained were confirmed by spectral studies.

  13. Geosmin and Related Volatiles in Bioreactor-Cultured Streptomyces citreus CBS 109.60

    Science.gov (United States)

    Pollak, F. C.; Berger, R. G.

    1996-01-01

    Streptomyces citreus CBS 109.60 produced geosmin and a complex pattern of other volatile compounds during cultivation in a 2.5-liter laboratory bioreactor. Volatiles were isolated from disrupted cells, from the culture medium, and from the waste air of the bioreactor by adsorption on Lewatit OC 1064MD. Quantitative and qualitative analyses were carried out using capillary gas chromatography and coupled gas chromatography-mass spectroscopy. S. citreus produced 56 volatile compounds, which were mainly terpenoids but also included aliphatic ketones, alcohols, esters, pyrazines, furan(on)es, and aromatic types during the growth phase. The major components were geosmin and a germacradienol. A biosynthetic pathway for geosmin including eudesmanolides is proposed. PMID:16535293

  14. Three-dimensional hybrid networks based on aspartic acid

    Indian Academy of Sciences (India)

    Anupama Ghosh; R A Sanguramath

    2008-01-01

    Three-dimensional achiral coordination polymers of the general formula M2(D, L-NHCH (COO)CH2COO)2.C4H4N2 where M = Ni and Co and pyrazine acts as the linker molecule have been prepared under hydrothermal conditions starting with [M(L-NHCH(COO)CH2COO).3H2O] possessing a helical chain structure. A three-dimensional hybrid compound of the formula Pb2.5[N{CH(COO)CH2COO}22H2O] has also been prepared hydrothermally starting with aspartic acid and Pb(NO3)2. In this lead compound, where a secondary amine formed by the dimerisation of aspartic acid acts as the ligand, there is two-dimensional inorganic connectivity and one-dimensional organic connectivity.

  15. The Synthesis of 3,5-Dibromopyrazin-2-Amine%3,5-二溴-2-氨基吡嗪的合成

    Institute of Scientific and Technical Information of China (English)

    郑国祥; 邓斌

    2013-01-01

    以廉价易得的2-氰基吡嗪作为起始原料,经水解、重排、水解一锅法得到2-氨基吡嗪,再用NBS溴化得到3,5-二溴-2-氨基吡嗪。本方法反应时间短,条件温和,具有较高的应用价值。%2-Amino pyrazine was prepared via hydrolysis, rearrangement and hydrolysis of one pot by using 2-cyanopyrazine, which is an inexpensive and easily available raw material. Then 3,5-dibromopyrazin-2-amine was got via NBS bromination. This method had short reaction time, mild conditions and higher application value.

  16. Synthesis of Acenaphthyl and Phenanthrene Based Fused-Aromatic Thienopyrazine Co-Polymers for Photovoltaic and Thin Film Transistor Applications

    KAUST Repository

    Mondal, Rajib

    2009-08-11

    Dithiophene and fluorene co-polymers containing fused aromatic thieno[3,4-b]pyrazine moieties were synthesized for organic thin film transistor (OTFT) and organic photovoltaic (OPV) applications. Suzuki and Stille polycondensation reactions were used for the polymerization. The band gap (Eg) of the polymers was tuned in the range of 1.15-1.6 eV to match the solar spectrum. Density functional theory calculations were carried out to rationalize the low band gaps. These polymers showed field effect mobility (μ) as high as 0.2 cm2/(V.s) with an on/off ratio as high as 106 in OTFT devices. Interestingly, one polymer in this class also showed ambipolar charge transport. Power conversion efficiency (PCE) up to 1.3% was achieved in bulk heterojunction solar cells, indicating that these materials are promising for OPV applications. © 2009 American Chemical Society.

  17. Optical properties of molecules chemisorbed on the Ni (111) surface

    Energy Technology Data Exchange (ETDEWEB)

    Robota, H. J. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Whitmore, P. M. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Harris, C. B. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

    1982-02-15

    The adsorption of a variety of molecules on Ni(111) is studied by UV/visible spectroscopic ellipsometry. The spectra were analyzed within a simple dielectric model. The absorption spectra of annealed, thin, condensed layers of pyrazine, pyridine, and naphthalene on the Ni(111) surface resemble bulk crystal spectra, indicating minimal perturbations due to the metal substrate. Chemisorption of molecules on the Ni(111) surface produced enhanced absorption between 2800Å and 3100Å. The wide range of adsorbate properties and surface chemistry suggest a modification of the optical response of the metal upon chemisorption. Furthermore, this enhanced optical absorption is attributed to nonvertical interband transitions made possible by loss of translational invariance at the surface.

  18. Characterization of the key aroma compounds in beef extract using aroma extract dilution analysis.

    Science.gov (United States)

    Takakura, Yukiko; Sakamoto, Tomohiro; Hirai, Sachi; Masuzawa, Takuya; Wakabayashi, Hidehiko; Nishimura, Toshihide

    2014-05-01

    Aroma extract dilution analysis (AEDA) of an ether extract prepared from beef extract (BE) and subsequent identification experiments led to the determination of seven aroma-active compounds in the flavor dilution (FD) factor range of 32-128. Omission experiments to select the most aroma-active compounds from the seven aroma compounds suggested that 2,3,5-trimethyl pyrazine, 1-octen-3-ol, 3-methylbutanoic acid, and 4-hydroxy-2,5-dimethyl-3(2H)-furanone were the main active compounds contributing to the aroma of BE. Aroma recombination, addition, and omission experiments of the four aroma compounds in taste-reconstituted BE showed that each compound had an individual aroma profile. A comparison of the overall aroma between this recombination mixture and BE showed a high similarity, suggesting that the key aroma compounds had been identified successfully.

  19. Interaction between common antibiotics and a Shewanella strain isolated from an enhanced biological phosphorus removal activated sludge system.

    Science.gov (United States)

    Liu, Hang; Yang, Yongkui; Ge, Yanhui; Zhao, Lin; Long, Sha; Zhang, Ruochun

    2016-12-01

    With increasing production and consumption, more antibiotics are discharged into wastewater treatment plants and generally cannot be sufficiently removed. Because of the complexities of biological treatment processes, the fates of antibiotics and their effects on microorganisms, particularly those involved in the phosphorus removal system, are still unclear. Here, a Shewanella strain was isolated from an enhanced biological phosphorus removal (EBPR) system and was found to have the ability to remove phosphorus (P) and chemical oxygen demand (CODcr). Antibiotics affected the Shewanella strain through metabolism of the three main intracellular polymers, altering the ability of the strain to remove P and CODcr. These effects varied with the structure and concentration of the antibiotics. The Shewanella strain removed cefalexin and amoxicillin by degradation or adsorption, producing 2-hydroxy-3-phenyl pyrazine from cefalexin. This study enabled the recognition of the effect and removal of antibiotics during wastewater treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. Finite-size effects on the lattice dynamics in spin crossover nanomaterials. I. Nuclear inelastic scattering investigation

    Science.gov (United States)

    Mikolasek, Mirko; Félix, Gautier; Peng, Haonan; Rat, Sylvain; Terki, Férial; Chumakov, Aleksandr I.; Salmon, Lionel; Molnár, Gábor; Nicolazzi, William; Bousseksou, Azzedine

    2017-07-01

    We report the investigation of the size evolution of lattice dynamics in spin crossover coordination nanoparticles of [ Fe (pyrazine ) (Ni (CN) 4) ] through nuclear inelastic scattering (NIS) measurements. Vibrational properties in these bistable molecular materials are of paramount importance and NIS permits access to the partial vibrational density of states in both spin states [high spin (HS) and low spin (LS)] from which thermodynamical and mechanical properties can be extracted. We show that the size reduction leads to the presence of inactive metal centers with the coexistence of HS and LS vibrational modes. The confinement effect has only weak impact on the vibrational properties of nanoparticles, especially on the optical modes which remain almost unchanged. On the other hand, the acoustic modes are much more affected which results in the increase of the vibrational entropy and also the Debye sound velocity in the smallest particles (nanoparticles is also highlighted through the matrix dependence of the sound velocity.

  1. Effect of the third π ∗ resonance on the angular distributions for electron-pyrimidine scattering

    Science.gov (United States)

    Mašín, Zdeněk; Gorfinkiel, Jimena D.

    2016-07-01

    We present a detailed analysis of the effect of the well known third π∗ resonance on the angular behaviour of the elastic cross section in electron scattering from pyrimidine. This resonance, occurring approximately at 4.7 eV, is of mixed shape and core-excited character. Experimental and theoretical results show the presence of a peak/dip behaviour in this energy range, that is absent for other resonances. Our investigations show that the cause of the peak/dip is an interference of background p-wave to p-wave scattering amplitudes with the amplitudes for resonant scattering. The equivalent resonance in pyrazine shows the same behaviour and the effect is therefore likely to appear in other benzene-like molecules. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.

  2. Synthesis and Characterization of New Thienopyrazine-cored Dendrimer for Non-Doped Organic Red Light-Emitting Diodes

    Institute of Scientific and Technical Information of China (English)

    李青; 李久艳; 段永恒; 高占先; 刘迪

    2011-01-01

    A new thieno-[3,4-b]-pyrazine-cored dendrimer with polyphenyls dendrons (D2TP) was designed and synthesized for application as red emitter in non-doped organic light-emitting diodes (OLEDs). The bulky dendritic arms enable this molecule to possess significant molecular weight and good solubility in common organic solvents. As a result, D2TP is suitable for solution processing methods such as spin coating to make thin films and devices. In addition, these large dendrons provide site-isolation effect on the planar emissive core to prevent fluorescence quenching or intermolecular interaction. The photophysical and electrochemical properties of D2TP were investigated in its dilute solutions. D2TP was used as non-doped emitter to fabricate OLEDs by spin coating method and saturated red electroluminescence was obtained.

  3. Pollination by sexual deception-it takes chemistry to work.

    Science.gov (United States)

    Bohman, Björn; Flematti, Gavin R; Barrow, Russell A; Pichersky, Eran; Peakall, Rod

    2016-08-01

    Semiochemicals are of paramount importance in sexually deceptive plants. These plants sexually lure specific male insects as pollinators by chemical and physical mimicry of the female of the pollinator. The strategy has evolved repeatedly in orchids, with a wide diversity of insect groups exploited. Chemical communication systems confirmed by field bioassays include: alkenes and alkanes in bee pollinated Ophrys species, keto-acid and hydroxy-acids in scoliid wasp pollinated O. speculum, and cyclohexanediones and pyrazines in thynnine wasp pollinated Chiloglottis and Drakaea orchids, respectively. In Ophrys, stearoyl-acyl carrier protein desaturase (SAD) enzymes have been confirmed to control species level variation in alkene double bond position. The production of cyclohexanediones in Chiloglottis unexpectedly depends on UVB light, a phenomenon unknown for other plant specialised metabolites. Potential biosynthetic pathways for other systems are explored, and alternative approaches to further accelerate chemical discovery in sexually deceptive plants are proposed.

  4. The Theory of Surface Enhanced Hyper Raman Scattering

    CERN Document Server

    Chelibanov, V P

    2014-01-01

    The Dipole-Quadrupole theory of Surface Enhanced Hyper Raman Scattering (SEHRS), created by the authors is expounded in details. Peculiarities of the behavior of electromagnetic field on rough metal surfaces are considered. It is demonstrated that there is an enhancement of the dipole and quadrupole light-molecule interaction near the places with a large curvature. The expression for the SEHRS cross-section of symmetrical molecules, which consists of several contributions is obtained. Selection rules for the scattering contributions are obtained and a qualitative classification of the contributions after an enhancement degree is performed. Analysis of experimental spectra of pyrazine and phenazine, and also some another molecules is performed too. It is demonstrated a full coincidence of experimental regularities in these spectra with the theory suggested.

  5. (6-Acetyl-1,3,7-trimethyllumazine-κ3O4,N5,O6bis(triphenylphosphine-κPcopper(I hexafluoridophosphate

    Directory of Open Access Journals (Sweden)

    Francisco Hueso-Ureña

    2010-02-01

    Full Text Available The title compound, [Cu(C11H12N4O3(C18H15P2]PF6, is the third example reported in the literature of a five-coordinated CuIP2NO2 system. The metal is coordinated to both PPh3 molecules through the P atoms and to the pyrazine ring of the lumazine molecule through an N atom in a trigonal–planar arrangement; two additional coordinated O atoms, at Cu—O distances longer than 2.46 Å, complete the coordination. The coordination environment can be described as an intermediate square-pyramidal/trigonal–bipyramidal (SP/TBP polyhedron.

  6. 'Smoking' mephedrone: the identification of the pyrolysis products of 4-methylmethcathinone hydrochloride.

    Science.gov (United States)

    Kavanagh, Pierce; O'Brien, John; Power, John D; Talbot, Brian; McDermott, Seán D

    2013-05-01

    The ring-substituted cathinone - mephedrone - has gained popularity among recreational drug users over the past several years. It is generally consumed orally or by snorting but reports indicate that it is also ingested by vaporization/inhalation. This study examines the pyrolysis products produced by heating mephedrone under using simulated 'meth pipe' conditions. Thirteen pyrolysis products were identified, the major ones being iso-mephedrone, 4-methylpropiophenone, 4-methylphenylacetone, two pyrazine derivatives formed by dimerization of mephedrone, N-methylated mephedrone (N,N,4-trimethylcatinone), two hydroxylated oxidation products and a diketone. Other minor products formed were identified as 4-methylacetophenone, two α-chloro ketones and N-methylated iso-mephedrone.

  7. Synthesis and Characterization of Zinc β-Diketonate Complex Extended to the Macromolecular Polymers

    Directory of Open Access Journals (Sweden)

    Mohammed A. Al-Anber

    2014-01-01

    Full Text Available A mononuclear complex of [Zn(tta2(H2O2] (3 (tta = deprotonated of 1-thenoyl-4,4,4-trifluoro­acetone (1 has been prepared by the reaction of 1-thenoyl-4,4,4-trifluoro­acetone (H-tta: 1 with Zn(OAc2.4H2O (OAc = O2CMe in a 2:1 molar ratio. Complex 3 can be extended to form a coordination polymers of general formula [Zn(tta2(X]n (X = 4,4'-bipy (4, pz (5 by the reaction of zinc atom in 3 with s-donor ligand such as 4,4-bipyridine (4,4'-bipy and pyrazin (pz. The reaction completion was controlled via FTIR and elemental analysis.

  8. Realistic vs sudden turn-on of natural incoherent light: Coherences and dynamics in molecular excitation and internal conversion.

    Science.gov (United States)

    Grinev, Timur; Brumer, Paul

    2015-12-28

    Molecular excitation with incoherent light is examined using realistic turn-on time scales, and results are compared to those obtained via commonly used sudden turn-on, or pulses. Two significant results are obtained. First, in contrast to prior studies involving sudden turn-on, realistic turn-on is shown to lead to stationary coherences for natural turn-on time scales. Second, the time to reach the final stationary mixed state, known to result from incoherent excitation, is shown to depend directly on the inverse of the molecular energy level spacings, in both sudden and realistic turn-on cases. The S0 → S2/S1 internal conversion process in pyrazine is used as an example throughout. Implications for studies of natural light harvesting systems are noted.

  9. Evaluation of kinetic parameters and redox mechanism of quinoxaline at glassy carbon electrode

    Directory of Open Access Journals (Sweden)

    Aleksić Mara M.

    2014-01-01

    Full Text Available The electrochemical behavior of a biologically important heterocyclic compound quinoxaline (QUI was investigated by cyclic voltammetry (CV in solutions of differing pH, using a glassy carbon electrode (GCE. The reduction of QUI occurs as a quasi-reversible reaction in acid medium, reaching reversibility in alkaline solutions. The kinetic parameters of the electrode process such as αnα, diffusion coefficient (D and heterogeneous rate constant (ks, were evaluated and discussed. Redox mechanism of QUI was proposed on the basis of experimental results. Reduction process involves a transfer of two electrons and two protons at the pyrazine ring of QUI forming a dihydro-derivative. In acid solutions, the product of QUI reduction undergoes irreversible oxidation in a one-electron process. The electrode processes was found to be diffusion controlled. [Projekat Ministarstva nauke Republike Srbije, br. 172033

  10. Two-dimensional, phenanthroline-based, extended {pi}-conjugated molecules for single-molecule conduction

    Energy Technology Data Exchange (ETDEWEB)

    Wohlthat, Soeren; Reimers, Jeffrey R [School of Chemistry, The University of Sydney, Sydney, NSW 2006 (Australia); Pauly, Fabian [Institut fuer Theoretische Festkoerperphysik and DFG-Center for Functional Nanostructures, Universitaet Karlsruhe, 76128 Karlsruhe (Germany)], E-mail: reimers@chem.usyd.edu.au

    2008-07-23

    The conduction properties of phenanthroline-terminated, polycyclic extended {pi}-conjugated molecular wires are investigated using density functional theory (DFT) in combination with Green's function techniques and group theory. While these molecules could possibly be thought of as accessible graphene-like fragments, they are calculated to conduct poorly. The decay constant for their exponential decrease of conductance with length is in excess of 0.6 A{sup -1} for the addition of internal fused quinoxaline groups and in excess of 0.9 A{sup -1} for the addition of internal pyrazine-fused pyrene groups. Furthermore, while the bidentate phenanthroline connectors adhere strongly to gold, they are sometimes predicted to be less conductive than related monodentate connectors. Careful design is thus required for any graphene-like extended {pi}-system intended for single-molecule conduction applications.

  11. Quinoxaline, its derivatives and applications: A State of the Art review.

    Science.gov (United States)

    Pereira, Joana A; Pessoa, Ana M; Cordeiro, M Natália D S; Fernandes, Rúben; Prudêncio, Cristina; Noronha, João Paulo; Vieira, Mónica

    2015-06-01

    Quinoxaline derivatives are an important class of heterocycle compounds, where N replaces some carbon atoms in the ring of naphthalene. Its molecular formula is C8H6N2, formed by the fusion of two aromatic rings, benzene and pyrazine. It is rare in natural state, but their synthesis is easy to perform. In this review the State of the Art will be presented, which includes a summary of the progress made over the past years in the knowledge of the structure and mechanism of the quinoxaline and quinoxaline derivatives, associated medical and biomedical value as well as industrial value. Modifying quinoxaline structure it is possible to obtain a wide variety of biomedical applications, namely antimicrobial activities and chronic and metabolic diseases treatment.

  12. Optimization of a Series of Triazole Containing Mammalian Target of Rapamycin (mTOR) Kinase Inhibitors and the Discovery of CC-115.

    Science.gov (United States)

    Mortensen, Deborah S; Perrin-Ninkovic, Sophie M; Shevlin, Graziella; Elsner, Jan; Zhao, Jingjing; Whitefield, Brandon; Tehrani, Lida; Sapienza, John; Riggs, Jennifer R; Parnes, Jason S; Papa, Patrick; Packard, Garrick; Lee, Branden G S; Harris, Roy; Correa, Matthew; Bahmanyar, Sogole; Richardson, Samantha J; Peng, Sophie X; Leisten, Jim; Khambatta, Godrej; Hickman, Matt; Gamez, James C; Bisonette, René R; Apuy, Julius; Cathers, Brian E; Canan, Stacie S; Moghaddam, Mehran F; Raymon, Heather K; Worland, Peter; Narla, Rama Krishna; Fultz, Kimberly E; Sankar, Sabita

    2015-07-23

    We report here the synthesis and structure-activity relationship (SAR) of a novel series of triazole containing mammalian target of rapamycin (mTOR) kinase inhibitors. SAR studies examining the potency, selectivity, and PK parameters for a series of triazole containing 4,6- or 1,7-disubstituted-3,4-dihydropyrazino[2,3-b]pyrazine-2(1H)-ones resulted in the identification of triazole containing mTOR kinase inhibitors with improved PK properties. Potent compounds from this series were found to block both mTORC1(pS6) and mTORC2(pAktS473) signaling in PC-3 cancer cells, in vitro and in vivo. When assessed in efficacy models, analogs exhibited dose-dependent efficacy in tumor xenograft models. This work resulted in the selection of CC-115 for clinical development.

  13. A Chiral, Photoluminescent, and Spin-Canted {Cu(I)Re(IV)2}n Branched Chain.

    Science.gov (United States)

    Martínez-Lillo, José; Armentano, Donatella; Fortea-Pérez, Francisco R; Stiriba, Salah-Eddine; De Munno, Giovanni; Lloret, Francesc; Julve, Miguel; Faus, Juan

    2015-05-18

    A new heteroleptic 1D Cu(I)-Re(IV) coordination polymer of the formula {Cu(I)Re(IV)Cl4(μ-Cl)(μ-pyz)[Re(IV)Cl4(μ-bpym)]}n·nMeNO2 (1; pyz = pyrazine, bpym = 2,2'-bipyrimidine) has been prepared through the Cu(I)-mediated self-assembly of two different Re(IV) metalloligands, namely, [ReCl5(pyz)](-) and [ReCl4(bpym)]. 1 consists of chiral branched chains with an overall rack-type architecture displaying photoemission and magnetic ordering. These results constitute a first step toward making new multifunctional magnetic materials based on mixed 3d-5d molecular systems.

  14. Synthesis, Crystal Structure and Photoluminescent Property of Cadmium(II) Metal-organic Framework with Mixed Carboxylate and Bis(imidazole) Ligand

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Yong Hong [Huaibei Normal Univ., Huaibei (China); Tian, Yu Peng [Anhui Univ., Hefei (China)

    2013-09-15

    The rational design and appropriate use of the characteristic ligands is critical in the construction of the desired MOFs. Among various organic ligands, multidentate N- or O-donor ligands such as pyridine or pyrazine-carboxylic acids, have drawn extensive attention in the construction of coordination polymers owing to their versatile coordination modes and structural stability.7 For example, pyridine-2,6-, 2,5-, or 3,4-dicarboxylic and pyra-zile-2,3-dicarboxylic acids have been employed as successful multifunctional ligands, and a variety of MOFs with diverse topologies and interesting properties have been obtained. However, compared with other pyridine-dicarboxylic acids, pyridine-2,3-dicarboxylic acid (H{sub 2}PDA) is rarely employed as a linkage ligand.

  15. Effects of milk fat, cocoa butter, or selected fat replacers on flavor volatiles of chocolate ice cream.

    Science.gov (United States)

    Welty, W M; Marshall, R T; Grün, I U; Ellersieck, M R

    2001-01-01

    Selected volatile compounds of chocolate ice creams containing 0.6, 4.0, 6.0, or 9.0% milk fat or containing 2.5% milk fat, cocoa butter, or one of three fat replacers (Simplesse, Dairy Lo, or Oatrim) were analyzed by gas chromatography and gas chromatography-mass spectrometry using headspace solid-phase microextraction. The headspace concentration of most of the selected volatile compounds increased with decreasing milk fat concentration. Fat replacers generally increased the concentration of volatiles found in the headspace compared with milk fat or cocoa butter. Few differences in flavor volatiles were found between the ice cream containing milk fat and the ice cream containing cocoa butter. Among the selected volatiles, the concentration of 2,5-dimethyl-3(2-methyl propyl) pyrazine was the most highly correlated (negatively) with the concentration of milk fat, and it best discriminated among ice creams containing milk fat, cocoa butter, or one of the fat replacers.

  16. Trace and low concentration co2 removal methods and apparatus utilizing metal organic frameworks

    KAUST Repository

    Eddaoudi, Mohamed

    2016-03-10

    In general, this disclosure describes techniques for removing trace and low concentration CO2 from fluids using SIFSIX-n-M MOFs, wherein n is at least two and M is a metal. In some embodiments, the metal is zinc or copper. Embodiments include devices comprising SIFSIX-n-M MOFs for removing CO2 from fluids. In particular, embodiments relate to devices and methods utilizing SIFSIX-n-M MOFs for removing CO2 from fluids, wherein CO2 concentration is trace. Methods utilizing SIFSIX-n-M MOFs for removing CO2 from fluids can occur in confined spaces. SIFSIX-n-M MOFs can comprise bidentate organic ligands. In a specific embodiment, SIFSIX-n-M MOFs comprise pyrazine or dipryidilacetylene ligands.

  17. Alphabet-Inspired Design of (Hetero)Aromatic Push-Pull Chromophores.

    Science.gov (United States)

    Klikar, Milan; Solanke, Parmeshwar; Tydlitát, Jiří; Bureš, Filip

    2016-08-01

    Push-pull molecules represent a unique and fascinating class of organic π-conjugated materials. Herein, we provide a summary of their recent extraordinary design inspired by letters of the alphabet, especially focusing on H-, L-, T-, V-, X-, and Y-shaped molecules. Representative structures from each class were presented and their fundamental properties and prospective applications were discussed. In particular, emphasis is given to molecules recently prepared in our laboratory with T-, X-, and Y-shaped arrangements based on indan-1,3-dione, benzene, pyridine, pyrazine, imidazole, and triphenylamine. These push-pull molecules turned out to be very efficient charge-transfer chromophores with tunable properties suitable for second-order nonlinear optics, two-photon absorption, reversible pH-induced and photochromic switching, photocatalysis, and intercalation.

  18. trans-Dichloridotetrapyrazineruthenium(II dichloromethane disolvate

    Directory of Open Access Journals (Sweden)

    Vladimir N. Nesterov

    2012-09-01

    Full Text Available In the title compound, [RuCl2(C4H4N24]·2CH2Cl2, the RuII atom occupies a position of 222 symmetry and the C atom of the solvent molecule occupies a site with twofold symmetry. The RuII atom has a slightly distorted octahedral geometry. The pyrazine rings are propeller-like and rotated 45.1 (1° from the RuN4 plane. In the crystal, the complex and solvent molecules are bridged by weak C—H...N hydrogen bonds along the c axis. Weak intermolecular C—H...Cl contacts link the complexes in the ab plane, forming a network.

  19. Basis set generation for quantum dynamics simulations using simple trajectory-based methods.

    Science.gov (United States)

    Saller, Maximilian A C; Habershon, Scott

    2015-01-13

    Methods for solving the time-dependent Schrödinger equation generally employ either a global static basis set, which is fixed at the outset, or a dynamic basis set, which evolves according to classical-like or variational equations of motion; the former approach results in the well-known exponential scaling with system size, while the latter can suffer from challenging numerical problems, such as singular matrices, as well as violation of energy conservation. Here, we suggest a middle road: building a basis set using trajectories to place time-independent basis functions in the regions of phase space relevant to wave function propagation. This simple approach, which potentially circumvents many of the problems traditionally associated with global or dynamic basis sets, is successfully demonstrated for two challenging benchmark problems in quantum dynamics, namely, relaxation dynamics following photoexcitation in pyrazine, and the spin Boson model.

  20. Methodological CASPT2 study of the valence excited states of an iron-porphyrin complex.

    Science.gov (United States)

    Ben Amor, Nadia; Soupart, Adrien; Heitz, Marie-Catherine

    2017-02-01

    The singlet valence excited states of an iron-porphyrin-pyrazine-carbonyl complex are investigated up to the Soret band (about 3 eV) using multi-state complete active space with perturbation at the second order (MS-CASPT2). This complex is a model for the active site of carboxy-hemoglobin/myoglobin. The spectrum of the excited states is rather dense, comprising states of different nature: d→π* transitions, d→d states, π→π* excitations of the porphyrin, and doubly excited states involving simultaneous intra-porphyrin π→π* and d→d transitions. Specific features of the MS-CASPT2 method are investigated. The effect of varying the number of roots in the state average calculation is quantified as well as the consequence of targeted modifications of the active space. The effect of inclusion of standard ionization potential-electron affinity (IPEA) shift in the perturbation treatment is also investigated.

  1. Analysis of volatile components in a Chinese fish sauce,Fuzhou Yulu, by gas chromatography-mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    Yuan-fan YANG; Shen-ru CHEN; Hui NI; Xing-qian YE

    2008-01-01

    Volatile components of Fuzhou Yulu, a Chinese fish sauce, were analyzed by gas chromatography-mass spectrometry (GC-MS), and two pretreatment methods, i.e., purge and trap (P&T) GC-MS and ethyl acetate extraction followed by GC-MS, were compared. P&T-GC-MS method determined 12 components, including sulfur-containing constituents (such as dimethyl disulfide), nitrogen-containing constituents (such as pyrazine derivatives), aldehydes and ketones. Ethyl ace tate extraction fol-lowed by GC-MS method detected 10 components, which were mainly volatile organic acids (such as benzenepropanoic acid) and esters. Neither of the two methods detected alcohols or trimethylamine. This study offers an important reference to determine volatile flavor components of traditional fish sauce through modem analysis methods.

  2. Electrodynamical Forbiddance of Strong Quadrupole Light-Molecule Interaction in the Methane Molecule and its Manifestation in Surface Enhanced Hyper Raman Scattering Spectra

    CERN Document Server

    Chelibanov, V P

    2014-01-01

    It is demonstrated in the framework of the Dipole-Quadrupole theory, that strong quadrupole light-molecule interaction, which is responsible for the most enhancement of SEHRS in the methane molecule, which belongs to the symmetry group, experiences so-called electrodynamical forbiddance due to electrodynamical law, and does not influence on the formation of the SEHRS spectra. This forbiddance results in the fact that the lines, caused by the totally symmetric vibrations, transforming after the unit irreducible representation, which are observed in symmetrical molecules with another sufficiently high groups of the point symmetry, such as pyrazine and phenazine, with symmetry group, must be slight, or be absent at all. In this case in methane the most enhanced lines are those, caused by vibrations, transforming by the irreducible representation, or .

  3. Phthalocyanine and azaphthalocyanines containing eugenol: synthesis, DNA interaction and comparison of lipase inhibition properties

    Indian Academy of Sciences (India)

    GÜNAY KAYA KANTAR; ÖZLEM FAİZ; ONUR ŞAHİN; SELAMİ ŞAŞMAZ

    2017-08-01

    Novel eugenol-substituted zinc(II) azaphthalocyanines (ZnAzaPcs)were synthesised and their lipase inhibition and DNA binding properties compared with phthalocyanines (Pcs) containing eugenol. This is the first study on lipase inhibition and DNA binding of Pcs and AzaPcs containing a pharmacophore group, such as eugenol. The novel ZnAzaPcs were characterised using a combination of FT-IR, ¹HNMR, ¹³CNMR, UV–Vis, MS and elemental analysis. The crystal structures of two pyrazine compounds were also determined by the single crystal diffraction technique. This study showed that two phthalocyanines compounds (3a and 4a) could be potential lipase inhibitor agents due to greater hydrophobicity than other azaphtalocyanines. Compound 4a displayed lowest IC₅₀ value. Non-intercalative binding to DNA was identified only for compound 2a.

  4. Synthesis of RP 48497, an Impurity of Eszopiclone

    Directory of Open Access Journals (Sweden)

    Mao-Sheng Cheng

    2008-08-01

    Full Text Available Abstract: RP 48497 is a photodegradation product of eszopiclone, a non-benzodiazepine sedative-hypnotic used in the treatment of insomnia. We report herein the first synthesis of RP 48497 via reduction, chlorination, and recyclization of 6-(5-chloropyridin-2-yl-7-hydroxy-6,7-dihydropyrrolo[3,4-b]pyrazin-5-one (3, a key intermediate in the synthesis of eszopiclone. The structure of RP 48497 was confirmed by its 1H-NMR and MS data. The mechanism of the reduction step in the synthesis of RP 48497 was also studied and the key parameters were determined. These findings should be important for quality control purposes in the manufacture of eszopiclone.

  5. Unique microporous NbO-type CoII/ZnII MOFs from double helical chains: Sorption and luminescent properties

    Science.gov (United States)

    Dong, Wen-Wen; Xia, Liang; Peng, Zhen; Zhao, Jun; Wu, Ya-Pan; Zhang, Jian; Li, Dong-Sheng

    2016-06-01

    Under solvothermal conditions, the reactions of CoII/ZnII ions with bent ligand 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1,2,4-triazole (4-Hpzpt) afford two compounds {[M(4-pzpt)2] guest}n (guest=H2O, M=CoII (1), ZnII (2)). Both compounds are the thermally and hydrolytically robust 4-connected 3D NbO framework, which formed by double helical chains to give rise to 1D hollow nanochannel with uncoordinated nitrogens completely exposed on the pore surface. Compound 1 exhibits improved N2, CO2 and H2 uptake capacities, while compound 2 displays the strong luminescent emission with obvious red shift.

  6. Variation of volatile compounds among wheat varieties and landraces.

    Science.gov (United States)

    Starr, G; Petersen, M A; Jespersen, B M; Hansen, Å S

    2015-05-01

    Analysis of volatile compounds was performed on 81 wheat varieties and landraces, grown under controlled greenhouse conditions, in order to investigate the possibility of differentiating wheat varieties according to their volatile compound profiles. Volatile compounds from wheat samples were extracted by dynamic headspace extraction and analysed by gas chromatography-mass spectrometry. Seventy-two volatile compounds were identified in the wheat samples. Multivariate analysis of the data showed a large diversity in volatile profiles between samples. Differences occurred between samples from Austria compared to British, French and Danish varieties. Landraces were distinguishable from modern varieties and they were characterised by higher averaged peak areas for esters, alcohols, and some furans. Modern varieties were characterised by higher averaged peak areas for terpenes, pyrazines and straight-chained aldehydes. Differences in volatile profiles are demonstrated between wheat samples for the first time, based on variety. These results are significant to plant breeders and commercial users of wheat.

  7. Effect of cooking on aroma profile of red kidney beans (Phaseolus vulgaris) and correlation with sensory quality.

    Science.gov (United States)

    Mishra, Prashant K; Tripathi, Jyoti; Gupta, Sumit; Variyar, Prasad S

    2017-01-15

    Volatile aroma compounds of three varieties of red kidney beans (Phaseolus vulgaris) namely Kashmiri red, Sharmili and Chitra were extracted in raw state using solid-phase microextraction (SPME) and cooked state using simultaneous distillation extraction (SDE). During cooking a significant (p<0.05) reduction in the content of several aldehydes, alcohols and terpene hydrocarbons while an increase in content of various sulfurous compounds, terpene alcohols, ketones and pyrazines was noted. Descriptive sensory analysis showed that the maximum intensity of 'kidney bean', 'earthy' and 'smoky' odour was observed in Kashmiri red while Sharmili variety was characterised by 'sulfurous' odour. Correlation of volatile profile data with descriptive sensory analysis and odour activity values clearly established the role of compounds, such as methanethiol, diethyl sulfide, dimethyl disulfide, methional and dimethyl trisulfide, in contributing to 'cooked kidney bean' aroma, while dimethyl sulfoxide, dimethyl sulfone and ethyl methyl sulfone were responsible for 'sulfurous' aroma. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Modulation of coffee aroma via the fermentation of green coffee beans with Rhizopus oligosporus: II. Effects of different roast levels.

    Science.gov (United States)

    Lee, Liang Wei; Cheong, Mun Wai; Curran, Philip; Yu, Bin; Liu, Shao Quan

    2016-11-15

    This study aims to evaluate how changes of the volatile and non-volatile profiles of green coffees induced by Rhizopus oligosporus fermentation of green coffee beans (Part I) translated to changes in the volatile and aroma profiles of light, medium and dark roasted coffees and non-volatile profile of roasted coffee where fermentation effects were most distinctive (light roast). R. oligosporus fermentation resulted in 1.7-, 1.5- and 1.3-fold increases in pyrazine, 2-methylpyrazine and 2-ethylpyrazine levels in coffees of all roast degrees, respectively. This corresponded with the greater extent of amino acids degradation in light roasted fermented coffee. Ethyl palmitate was detected exclusively in medium and dark roasted fermented coffees. The sweet attribute of light and dark roasted coffees were increased following fermentation along with other aroma profile changes that were roast degree specific. This work aims to develop a direct but novel methodology for coffee aroma modulation through green coffee beans fermentation.

  9. Metabolites Produced by the Endophytic Fungus Aspergillus fumigatus from the Stem of Erythrophloeum fordii Oliv.

    Directory of Open Access Journals (Sweden)

    Yu-Sheng Shi

    2015-06-01

    Full Text Available A new diketopiperazine alkaloid named spirotryprostatin K (1, and five known alkaloids, spiro[5H,10H-dipyrrolo[1,2-a:1′,2′-d]pyrazine-2(3H,2′-[2H]-indole]-3′,5,10(1′H trione (2, 6-methoxyspirotryprostatin B (3, pseurotin A (4, N-β-acetyltryptamine (5, and lumichrome (6 were isolated from the endophytic fungus Aspergillus fumigatus. The structure and the absolute configuration of spirotryprostatin K were established by extensive spectroscopic analyses, acid hydrolysis and ECD calculations. Pseurotin A exhibited indirect anti-inflammatory activity by suppressing the lipopolysaccharide-induced proinflammatory factors in BV2 microglial cells, with an IC50 of 5.20 µM.

  10. Electronic structures of ruthenium complexes encircling non-innocent ligand assembly

    Indian Academy of Sciences (India)

    Amit Das; Dipanwita Das; Tanaya Kundu; Goutam Kumar Lahiri

    2012-11-01

    Electronic structural forms of selected mononuclear and dinuclear ruthenium complexes encompassing redox non-innocent terminal as well as bridging ligands have been addressed. The sensitive valence and spin situations of the complexes have been established in the native and accessible redox states via detailed analysis of their crystal structures, electrochemistry, UV/VIS/NIR spectroelectrochemistry, EPR signatures at the paramagnetic states and DFT calculations. Mononuclear complexes exhibit significant variations in valence and spin distribution processes based on the simple modification of the non-innocent ligand frameworks as well as electronic nature of the co-ligands, -donating or -accepting. Dinuclear complexes with modified pyrazine, -quinone and azo-derived redox-active bridging ligands show complex features including redoxinduced electron-transfer (RIET), remote metal to metal spin-interaction in a three-spin metal-bridge-metal arrangement as well as electron-transfer driven chemical transformation (EC).

  11. Analysis of the SEHR Spectra of Symmetrical Molecules on the Base of the Dipole-Quadrupole Theory

    CERN Document Server

    Polubotko, A M

    2011-01-01

    The paper analyses the SEHR spectra of symmetrical molecules on the base of the dipole-quadrupole SEHRS theory. Existence of the bands, caused by vibrations transforming after the unitary irreducible representations of corresponding symmetry groups is demonstrated. As it follows from the theoretical group analysis, these bands are forbidden in phenazine, pyrazine and in usual HRS in molecules with and higher symmetry groups. Their appearance strongly confirms the dipole-quadrupole SEHRS theory, which is able to explain other features of the SEHR spectra of these molecules also. Investigation of the SEHR spectra of pyridine and crystal violet demonstrates that they can be explained by this theory too. Thus examination of these spectra strongly confirms the dipole-quadrupole SEHRS theory, which succeeded in explanation of the SERS phenomenon. All these results point out the existence of the strong quadrupole light-molecule interaction, which is the reason of surface-enhanced optical processes.

  12. Manifestation of the strong quadrupole light-molecule interaction in the SEHR spectra of symmetrical molecules

    CERN Document Server

    Polubotko, A M

    2009-01-01

    The paper demonstrates possibility of giant enhancement of Surface Enhanced Hyper Raman Scattering on the base of qualitative consideration of electromagnetic field near some models of rough metal surfaces and of some features of the dipole and quadrupole light-molecule interaction, such as it was made in the dipole-quadrupole SERS theory. Consideration of symmetrical molecules permits to obtain selection rules for their SEHR spectra and establish such regularity as appearance of the bands, caused by the totally symmetric vibrations, transforming after the unitary irreducible representation in molecules with C2h,D and higher symmetry groups, which are forbidden in usual HRS spectra. Analysis of literature data on trans-1,2-bis (4-pyridyle) ethylene and pyridine molecules demonstrates that their SEHR spectra can be explained by the SEHRS dipole-quadrupole theory, while analysis of the SEHR spectrum of pyrazine reveals appearance of the strong forbidden bands, caused by vibrations transforming after the unitary...

  13. Investigation of the effect of pore size on gas uptake in two metal-organic frameworks.

    Science.gov (United States)

    Wang, Rongming; Meng, Qingguo; Zhang, Liangliang; Wang, Haifeng; Dai, Fangna; Guo, Wenyue; Zhao, Lianming; Sun, Daofeng

    2014-05-18

    Two porous metal–organic frameworks (1 and 2) with a fsc topology based on mixed ligands have been assembled and characterized. The different pillared ligands (pyrazine for 1 and 4,4′-bipyridine for 2) significantly influence the pore size of the frameworks. Gas uptake measurements reveal that complex 1 possesses higher H2, CO2, and CH4 uptake capacities than 2, although the surface area of 1 is lower than that of complex 2. These results further experimentally prove that the pore size plays an important role in gas uptake in porous MOFs, and the slit pore with a size of ~6 Å exhibits stronger interactions with gas molecules.

  14. Quantum symmetry and photoreactivity of azabenzenes

    Energy Technology Data Exchange (ETDEWEB)

    Chesko, James David Mark [Univ. of California, Berkeley, CA (United States)

    1995-06-01

    The fundamental processes associated with a photochemical reaction are described with reference to experimental properties of azabenzenes. Consideration of both excitation and relaxation processes led to presentation of the symmetry propagator, a unifying principle which maps system fluctuations (perturbations acting on an initial state) with dissipations (transitions to different states), thus directing the energy flow along competing reactive and nonreactive pathways. A coherent picture of relaxation processes including chemical reactions was constructed with the aid of spectroscopic data. Pyrazine (1,4 diazine) possesses vibronically active modes which provide an efficient mechanism for internal conversion to the first excited singlet state, where other promoting modes of the correct symmetry induce both intersystem crossing to the triplet manifold, isomerization through diaza-benzvalene, and chemical reactions through cycloreversion of dewar pyrazine to yield HCN plus an azete. At higher energies simple H atom loss and internal conversion become more predominant, leading to ring opening followed by elimination of methylene nitrile and ground state reaction products. Efficiency of chemical transformations as dissipation mechanisms versus competing fluorescence, phosphorescence and radiationless relaxation was mapped from near ultraviolet to far ultraviolet by photodissociation quantum yields into reaction channels characterized by molecular beam photofragment translational spectroscopy. A reaction path model for azabenzene photochemistry was presented and tested against experiment. Presence of undiscovered channels in other azabenzene systems was predicted and verified. The dominant process, HCN elimination, was resolved into three distinct channels. Both molecular and atomic hydrogen elimination was observed, the former with significant vibrational excitation. Small yields of isomerization products, acetylene and N2, were also observed.

  15. Using design of experiments to optimize derivatization with methyl chloroformate for quantitative analysis of the aqueous phase from hydrothermal liquefaction of biomass.

    Science.gov (United States)

    Madsen, René Bjerregaard; Jensen, Mads Mørk; Mørup, Anders Juul; Houlberg, Kasper; Christensen, Per Sigaard; Klemmer, Maika; Becker, Jacob; Iversen, Bo Brummerstedt; Glasius, Marianne

    2016-03-01

    Hydrothermal liquefaction is a promising technique for the production of bio-oil. The process produces an oil phase, a gas phase, a solid residue, and an aqueous phase. Gas chromatography coupled with mass spectrometry is used to analyze the complex aqueous phase. Especially small organic acids and nitrogen-containing compounds are of interest. The efficient derivatization reagent methyl chloroformate was used to make analysis of the complex aqueous phase from hydrothermal liquefaction of dried distillers grains with solubles possible. A circumscribed central composite design was used to optimize the responses of both derivatized and nonderivatized analytes, which included small organic acids, pyrazines, phenol, and cyclic ketones. Response surface methodology was used to visualize significant factors and identify optimized derivatization conditions (volumes of methyl chloroformate, NaOH solution, methanol, and pyridine). Twenty-nine analytes of small organic acids, pyrazines, phenol, and cyclic ketones were quantified. An additional three analytes were pseudoquantified with use of standards with similar mass spectra. Calibration curves with high correlation coefficients were obtained, in most cases R (2)  > 0.991. Method validation was evaluated with repeatability, and spike recoveries of all 29 analytes were obtained. The 32 analytes were quantified in samples from the commissioning of a continuous flow reactor and in samples from recirculation experiments involving the aqueous phase. The results indicated when the steady-state condition of the flow reactor was obtained and the effects of recirculation. The validated method will be especially useful for investigations of the effect of small organic acids on the hydrothermal liquefaction process.

  16. Flavor Characteristics of Hanwoo Beef in Comparison with Other Korean Foods

    Directory of Open Access Journals (Sweden)

    Hoa Van Ba

    2012-03-01

    Full Text Available The present study identified volatile flavor components of Hanwoo longissimus muscle and other Korean foods (Doenjang, Chungukjang, sesame oil and their traits were compared in relation with flavor precursors that include fatty acids and protein degradation products. Hanwoo longissimus muscle was purchased from a commercial abattoir while the other foods were sampled from three separate households. The results showed totals of 68 (9.94 μg/g, 60 (15.75 μg/g, 49 (107.61 μg/ml and 50 (7.20 μg/g volatile components for Doenjang, Chungukjang, sesame oil and Hanwoo beef longissimus, respectively (p<0.05. Aldehydes were the most predominant components in beef, but alcohols, acids and esters, and pyrazines are probably the major contributors to the flavor characteristics of other foods. SDS-PAGE revealed that beef longissimus muscle and Doenjang showed higher protein degradation than other foods which could be likely related to chiller ageing and ripening process. The total polyunsaturated fatty acids were approximately 50, 60, 41 and 5% for Doenjang, Chungukjang, sesame oil and beef longissimus muscle, respectively. Based on the mechanism(s of generation of the volatile compounds and the chemical composition of each food sample, differences and traits of volatile flavor components among the four food types are likely due to fatty acid profiles, proteolytic activity and processing conditions. Aroma intense compounds like pyrazines and sulfur-containing compounds were limited in cooked beef in the current experimental condition (i.e., relatively low heating temperature. This suggests that higher heating temperature as in the case of roasting is needed for the generation of high aroma notes in meat. Furthermore, proteolytic activity and stability of fatty acids during ageing have a great influence on the generation of flavor components in cooked beef.

  17. An NMR Study of the Bortezomib Degradation under Clinical Use Conditions

    Directory of Open Access Journals (Sweden)

    Adele Bolognese

    2009-01-01

    Full Text Available The (R-3-methyl-1-((S-3-phenyl-2-(pyrazine-2-carboxamidopropanamidobutyl-boronic acid, bortezomib (BTZ, which binds the 20S proteasome subunit and causes a large inhibition of its activity, is a peptidomimetic boronic drug mainly used for the treatment of multiple myeloma. Commercial BTZ, stabilized as mannitol derivative, has been investigated under the common conditions of the clinical use because it is suspected to be easily degradable in the region of its boronic moiety. Commercial BTZ samples, reconstituted according to the reported commercial instructions and stored at 4∘C, were analyzed by high-field nuclear magnetic resonance spectroscopy in comparison with identical samples bubbled with air and argon, respectively. All the samples remained unchanged for a week. After a month, the air filled samples showed the presence of two main degradation products (6% of starting material, the N-(1-(1-hydroxy-3-methylbutylamino-1-oxo-3-phenylpropan-2-yl pyrazine-2-carboxamide (BTZ1; 5%, determined from NMR integration and the (S-N-(1-(3-methylbutanamido-1-oxo-3-phenylpropan-2-ylpyrazine-2-carboxamide (BTZ2; 1%, determined from NMR integration, identified on the basis of their chemical and spectroscopic properties. The BTZ1 and BTZ2 finding suggests that, under the common condition of use and at 4∘C, commercial BTZ-mannitol is stable for a week, and that, in time, it undergoes slow oxidative deboronation which partially inactivates the product. Low temperature and scarce contact with air decrease the degradation process.

  18. [μ-2,3,5,6-Tetrakis(2-pyridylpyrazine-κ6N6,N1,N2:N3,N4,N5]bis[diaqua(dihydrogen m-phenylenediphosphonato-κOnickel(II] dihydrate

    Directory of Open Access Journals (Sweden)

    Paul DeBurgomaster

    2010-11-01

    Full Text Available The title compound [Ni2(C6H6O6P22(C24H16N6(H2O4]·2H2O or [Ni2(tpyprz(1,3-HO3PC6H4PO3H2(H2O4]·2H2O [tpyprz = tetrakis(2-pyridylpyrazine, C24H16N6] is a binuclear complex with a crystallographic inversion center located at the center of the pyrazine ring. The equivalent nickel(II sites exhibit a distorted {NiO3N3} octahedral coordination, with the three nitrogen donors of each terminus of the tpyprz ligand in a meridional orientation. An aqua ligand occupies the position trans to the pyrazine nitrogen donor, while the second aqua ligand is trans to the oxygen donor of the dihydrogen-1,3-phenyldiphosphonate ligand. The Ni—O and Ni—N bond lengths fall in the range 2.011 (3 to 2.089 (3 Å. The protonation sites on the organophosphonate ligand are evident in the significantly longer P—O bonds compared to the unprotonated sites. In the crystal structure, the complex molecules and the solvent water molecules are linked into a three-dimensional hydrogen-bonded framework through O—H...O interactions between the aqua ligands, the protonated organophosphonate oxygen atoms and the water molecules of crystallization. Intramolecular π-stacking between the phenyl group of the phosphonate ligand and a pyridyl group of the tpyprz ligand, at a distance of 3.244 (5 Å between ring centroids, is also observed.

  19. Effect of ascorbic acid on the properties of ammonia caramel colorant additives and acrylamide formation.

    Science.gov (United States)

    Chen, Hongxing; Gu, Zhengbiao

    2014-09-01

    Ammonia caramels are among the most widely used colorant additives in the food industry. They are commonly prepared through the Maillard reaction and caramelization of mixtures of reducing sugars with ammonia or ammonium salts. Antioxidants are known to inhibit acrylamide formation during the Maillard reaction, and they may affect the properties of the ammonia caramel products. Thus, the objective of this study was to investigate the effect of the antioxidant ascorbic acid on the properties of ammonia caramel. A mixture of glucose and ammonia was allowed to react at 120 °C for 60 min in the presence of ascorbic acid at final concentrations of 0 to 0.08 M. The ammonia caramels obtained from these reactions were all positively charged. As the concentration of ascorbic acid increased, the color intensity of the ammonia caramel showed a decreasing trend, while the intensity of the fluorescence and total amount of pyrazines in the volatiles showed a tendency to increase. The addition of ascorbic acid did not result in obvious changes in the UV-visible spectra of the ammonia caramels and the types of pyrazines in the volatiles were also unchanged. It is noteworthy that the addition of 0.02 to 0.08 M ascorbic acid did reduce the formation of the by-product acrylamide, a harmful substance in food. When the concentration of ascorbic acid added reached 0.04 M, the content of acrylamide in the ammonia caramel was 20.53 μg/L, which was approximately 44% lower than that without ascorbic acid. As a result, ascorbic acid can be considered to improve the quality and safety of ammonia caramels.

  20. Effects of dicarbonyl trapping agents, antioxidants, and reducing agents on the formation of furan and other volatile components in canned-coffee model systems.

    Science.gov (United States)

    Zheng, Li Wei; Chung, Hyun; Kim, Young-Suk

    2015-09-01

    The formation of furan and certain volatiles related to furan formation mechanisms was studied using gas chromatography-mass spectrometry combined with solid-phase micro extraction after adding dicarbonyl trapping agents [epicatechin (EC), epigallocatechin gallate (EGCG), and catechin], water-soluble antioxidants (Trolox, caffeic acid, ferulic acid, and chlorogenic acid), fat-soluble antioxidants (α-tocopherol, BHT, and β-carotene), and reducing agents (glutathione and sodium sulfite) to canned-coffee model systems (CMS). The level of furan formation decreased significantly following the addition of EC (by 65.3%), EGCG (by 60.0%), and catechin (by 44.7%). In addition, the formation of Maillard reaction products, including furan derivatives (furfural and 5-methylfurfural), Strecker aldehyde (2-methylbutanal), pyrazines (2,6-dimethylpyrazine), and lipid oxidation products (including hexanal and 2-pentylfuran) was suppressed when any of the dicarbonyl trapping agents was added. Among the water-soluble antioxidants studied, chlorogenic acid most significantly decreased the furan level, by 67.0%, followed by ferulic acid (57.6%), Trolox (50.1%), and caffeic acid (48.2%) in the CMS. Chlorogenic acid also reduced the formation of furfural and lipid oxidation products. However, the addition of caffeic acid, ferulic acid, and chlorogenic acid decreased the generation of key coffee aroma components, such as Strecker aldehydes (2-methylpropanal and 2-methylbutanal), 5-methylfurfural, and pyrazines (2,6-dimethylpyrazine and 2-ethyl-5-methylpyrazine). Among the fat-soluble antioxidants, BHT and α-tocopherol decreased the furan level by 49.3% and 39.3%, respectively, while β-carotene increased the furan level by 34.8%. The addition of sodium sulfite and glutathione to CMS also led to considerable reductions in furan, of 64.1% and 44.9%, respectively. Copyright © 2015 Elsevier Ltd. All rights reserved.

  1. MPX-004 and MPX-007: New Pharmacological Tools to Study the Physiology of NMDA Receptors Containing the GluN2A Subunit.

    Science.gov (United States)

    Volkmann, Robert A; Fanger, Christopher M; Anderson, David R; Sirivolu, Venkata Ramana; Paschetto, Kathy; Gordon, Earl; Virginio, Caterina; Gleyzes, Melanie; Buisson, Bruno; Steidl, Esther; Mierau, Susanna B; Fagiolini, Michela; Menniti, Frank S

    2016-01-01

    GluN2A is the most abundant of the GluN2 NMDA receptor subunits in the mammalian CNS. Physiological and genetic evidence implicate GluN2A-containing receptors in susceptibility to autism, schizophrenia, childhood epilepsy and neurodevelopmental disorders such as Rett Syndrome. However, GluN2A-selective pharmacological probes to explore the therapeutic potential of targeting these receptors have been lacking. Here we disclose a novel series of pyrazine-containing GluN2A antagonists exemplified by MPX-004 (5-(((3-chloro-4-fluorophenyl)sulfonamido)methyl)-N-((2-methylthiazol-5-yl)methyl)pyrazine-2-carboxamide) and MPX-007 (5-(((3-fluoro-4-fluorophenyl)sulfonamido)methyl)-N-((2-methylthiazol-5-yl)methyl)methylpyrazine-2-carboxamide). MPX-004 and MPX-007 inhibit GluN2A-containing NMDA receptors expressed in HEK cells with IC50s of 79 nM and 27 nM, respectively. In contrast, at concentrations that completely inhibited GluN2A activity these compounds have no inhibitory effect on GluN2B or GluN2D receptor-mediated responses in similar HEK cell-based assays. Potency and selectivity were confirmed in electrophysiology assays in Xenopus oocytes expressing GluN2A-D receptor subtypes. Maximal concentrations of MPX-004 and MPX-007 inhibited ~30% of the whole-cell current in rat pyramidal neurons in primary culture and MPX-004 inhibited ~60% of the total NMDA receptor-mediated EPSP in rat hippocampal slices. GluN2A-selectivity at native receptors was confirmed by the finding that MPX-004 had no inhibitory effect on NMDA receptor mediated synaptic currents in cortical slices from GRIN2A knock out mice. Thus, MPX-004 and MPX-007 offer highly selective pharmacological tools to probe GluN2A physiology and involvement in neuropsychiatric and developmental disorders.

  2. The Molecular Identification and Flavor Compounds Preliminary Analysis of a Thermophilic Monascus Strain%一株嗜热红曲霉的分子鉴定及其风味物质初步分析

    Institute of Scientific and Technical Information of China (English)

    周健; 姚霞; 崔小亮; 方春玉; 王洋

    2016-01-01

    To identify the thermophilic monascus strain screened from Luzhou-flavor Daqu by molecular method combining with its morphological,physiological characteristics,and construct phylogenetic tree.And then take the monascus strain to do liquid-state and solid-state fermentation respectively.Use headspace solid-phase micro extraction and gas chromatography-mass spectrometry (HS-SPME-GC-MS)to analyze the flavor substances of thermophilic monascus strain's metabolism products.The result shows that the monascus strain is Monascus fuliginosus mutant strain.There are 11 kinds of flavor substances in liquid-state fermentation,including alcohol,pyrazine,alkane. There are 19 kinds of flavor substances in solid-state fermentation,including alcohol,pyrazine, alkane,ester,aldehyde.%对浓香型大曲中筛选的一株嗜热红曲霉 MH-WLY 提取 DNA,并构建系统发育树,结合它的形态、生理特征对其进行鉴定;再将这株红曲霉分别进行液态发酵和固态发酵,利用顶空固相微萃取-气相色谱-质谱联用(HS-SPME-GC-MS)分析其代谢的风味物质。结果认定这株红曲霉为烟色红曲霉(Monascus fuliginosus )突变株;液态发酵的主要风味物质有11种,分为醇、吡嗪、烷烃3大类,固态发酵的主要风味物质有19种,包含醇、吡嗪、烷烃、酯、醛5大类。

  3. Chemical characterization & bioactivity of diketopiperazine derivatives from the mangrove derived Pseudonocardia endophytica

    Directory of Open Access Journals (Sweden)

    Usha Kiranmayi Mangamuri

    2016-06-01

    Full Text Available Sediment samples from the mangrove ecosystem of Nizampatnam have been analyzed for actinomycetes as an elite source to screen for the formulation and production of antimicrobial and cytotoxic compounds. The actinomycetes strain VUK-10 has an interesting bioactivity profile and was isolated during our systematic study of mangrove actinomycetes. It was identified as Pseudonocardia endophytica with the aid of polyphasic taxonomy. The ethyl acetate extract of the actinobacterial culture filtrate has been purified by gel-filtration and silica gel column chromatographic purifications led to the isolation of two diketopiperazine compounds, (3S,8aS-3-isobutylhexahydropyrrolo[1,2-a]pyrazine-1,4-dione (1 and (3R,8aS-3-isobutylhexahydropyrrolo[1,2-a]pyrazine-1,4-dione (2. The compounds listed, alluring cytotoxic activity against MDA-MB-231, HeLa, MCF-7 and OAW-42 cancer cell lines and also exhibited antimicrobial activities against gram-positive, gram-negative bacteria and fungi. Compound 1 recorded significant antibacterial activity against Xanthomonas campestris and Escherichia coli (8 μg/ml and compound 2 presented highest activity against Bacillus subtilis (4 μg/ml. Compounds 1 and 2 were active against pathogenic fungi to plants and human beings. The activity was compared with griseofulvin and amphotericin-B, which are standard fungicides. The activity of 16 μg/ml by compound 1 was recorded against Epidermophyton floccosum; an anthropophilic dermatophyte responsible for tinea pedis, tinea cruris and tinea corporis. To the best of our knowledge this is the first narration on the isolation of supra said compounds from the genus Pseudonocardia.

  4. Volatile Flavor Compounds of Chestnuts and Puffed Chestnut Products%板栗及其膨化制品的挥发性香气成分分析

    Institute of Scientific and Technical Information of China (English)

    王文艳; 刘凌; 吴娜; 张晓磊

    2012-01-01

    采用顶空固相微萃取结合气相色谱-质谱联用技术对生板栗粉、煮板栗和3种膨化板栗制品的挥发性香气成分进行分离鉴定。共鉴定出68种挥发性物质,初步认定吡嗪类物质中的甲基吡嗪、2,3-二甲基吡嗪、2.乙基-6-甲基吡嗪、2,6-二-甲基吡嗪;呋喃类物质中的2-戊基呋喃、γ-丁内酯、2-糠醇、2,5-二氢-3,5-二甲基-2-呋喃酮和1-辛内酯及芳香族类物质中的苯甲醛是板栗的特征风味物质。煮制可提升板栗的香气。膨化板栗片的膨化加工方式对其香气成分影响显著,挤压膨化板栗片的香气物质组成和煮板栗比较相似,微波膨化板栗片中易产生具有枯焦气息的2,4-二叔丁基苯酚,油炸膨化板栗片的挥发性成分最复杂,醛类物质较多。%The volatile flavor compounds of chestnut powder, boiled chestnut and three puffed chestnut products were determined by HS-SPME-GC/MS. Sixty eight kinds of volatile flavor compounds were identified. Four kinds of pyrazine (methylpyrazine, 2,3-dimethyl pyrazine, 2-ethyl-6-methyl pyrazine, 2,6 - dimethyl pyrazine) , five kinds of furans (2-pentyl furan, γ-Butyrolactone, 2-furfuryl alcohol, 2,5-dihydro-3,5-dimethyl-2-furanone, 2 ( 3 H )-Fura-none, 5-butyldihydro-) as well as one kind of aromatic substances ( Benzaldehyde ) were initially identified as impor-tant aroma impact compounds. Chestnut aroma enhanced after cooking. Different puffing significantly influence aroma compositions of puffed chestnuts crisps. The aroma substance composition of extruded chestnut crisps and boiled chestnut are quite similar. A lot of 2,4-di-tert-butylphenol, which has paste flavor was generated in microwave puffing chestnut crisps. Volatile components of fried puffed chestnut crisps were the most complex which contained more alde-hydes substances.

  5. Determining the exchange parameters of spin-1 metal-organic molecular magnets in pulsed magnetic fields

    Energy Technology Data Exchange (ETDEWEB)

    Mcdonald, Ross D [Los Alamos National Laboratory; Singleton, John [Los Alamos National Laboratory; Lancaster, Tom [OXFORD UNIV.; Goddard, Paul [OXFORD UNIV.; Manson, Jamie [EASTERN WASHINGTON UNIV.

    2011-01-14

    We nave measured the high-field magnetization of a number of Ni-based metal-organic molecular magnets. These materials are self-assembly coordination polymers formed from transition metal ions and organic ligands. The chemistry of the compounds is versatile allowing many structures with different magnetic properties to be formed. These studies follow on from previous measurements of the Cu-based analogues in which we showed it was possible to extract the exchange parameters of low-dimensional magnets using pulsed magnetic fields. In our recent experiments we have investigated the compound (Ni(HF{sub 2})(pyz){sub 2})PF{sub 6}, where pyz = pyrazine, and the Ni-ions are linked in a quasi-two-dimensional (Q2D) square lattice via the pyrazine molecules, with the layers held together by HF{sub 2} ligands. We also investigated Ni(NCS){sub 2}(pyzdo){sub 2}, where pyzdo = pyrazine dioxide. The samples are grown at Eastern Washington University using techniques described elsewhere. Measurements are performed at the pulsed magnetic field laboratory in Los Alamos. The magnetization of powdered samples is determined using a compensated coil magnetometer in a 65 T short pulse magnet. Temperatures as low as 500 mK are achievable using a {sup 3}He cryostat. The main figure shows the magnetization of the spin-1 [Ni(HF{sub 2})(pyz){sub 2}]PF{sub 6} compound at 1.43 K. The magnetization rises slowly at first, achieving a rounded saturation whose midpoint is around 19 T. A small anomaly is also seen in the susceptibility at low fields ({approx}3 T), which might be attributed to a spin-flop transition. In contrast, the spin-1/2 [Cu(HF{sub 2})(pyz){sub 2}]PF{sub 6} measured previously has a saturation magnetization of 35.5 T and a strongly concave form of M(B) below this field. This latter compound was shown to be a good example of a Q2D Heisenberg antiferromagnet with the strong exchange coupling (J{sub 2D} = 12.4 K, J{sub {perpendicular}}/J{sub 2D} {approx} 10{sup -2}) directed along

  6. 固相微萃取-气质联用技术测定5种食用植物油挥发性成分%Detection of volatile components in 5 edible vegetable oils by solid phase micro-extraction-gas chromatography-mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    高蓓; 章晴; 杨悠悠; 杨永坛

    2015-01-01

    Objective To identify and classify the volatile components in 5 kinds of edible vegetable oils (soybean oil, sesame oil, peanut oil, olive oil, and grape seed oil) by gas chromatography-mass spectrometry (GC-MS) technology.MethodsThe solid phase micro-extraction (SPME) technology had been used to extract volatile components in those edible vegetable oils, and the volatile components in 5 kinds of edible vegetable oils were determined by gas chromatography-mass spectrometry (GC-MS).ResultsThe total of 101 volatile compounds were detected in 5 edible vegetable oils, with soybean oil 11, peanut oil 28, sesame oil 65, olive oil 25, and grape seed oil 5, respectively. The volatile compounds were mainly aldehydes, ester, alcohols, heterocyclic, phenols and acids. The major components were pentanal, hexanal and hexanoic acid in soybean oil, hexanal, 2,5-dimethyl pyrazine and benzofuran, 2,3-dihydro- in peanut oil,2-furancarboxaldehyde, 5-methyl-, 2-formylpyrrole,2-furanmethanol, phenol, 2-methoxy-, pyrazine, methyl-,and pyrazine, 2-ethyl-6-methyl- in sesame oil,3-hexen-1-ol, (Z)- and 4-hexen-1-ol, acetate in olive oil, and hexanal in grape seed oil. ConclusionThe volatile composition and content are greatly different in 5 edible vegetable oils, which can provide reference to the adulteration of edible vegetable oil.%目的:采用气相色谱-质谱(GC-MS)对大豆油、芝麻油、花生油、橄榄油、葡萄籽油5种食用植物油中挥发性成分进行分析。方法采用顶空固相微萃取(HS-SPME)技术对5种食用植物油中的挥发性成分进行萃取,并结合气相色谱-质谱(GC-MS)技术对挥发性成分进行测定。结果5种食用植物油中共检测出101种挥发性化合物,其中大豆油11种、花生油28种、芝麻油65种、橄榄油25种、葡萄籽油5种。主要包括醛类、酯类、醇类、杂环类、酚类、酸类等10类物质。大豆油中主要的挥发性成分有戊醛、已醛和己酸,花生油中主要

  7. Comparison of polarizable continuum model and quantum mechanics/molecular mechanics solute electronic polarization: study of the optical and magnetic properties of diazines in water.

    Science.gov (United States)

    Manzoni, Vinícius; Lyra, Marcelo L; Coutinho, Kaline; Canuto, Sylvio

    2011-10-14

    A combination of the polarizable continuum model (PCM) and the hybrid quantum mechanics/molecular mechanics (QM/MM) methodology, PCM-MM/QM, is used to include the solute electronic polarization and then study the solvent effects on the low-lying n→π(∗) excitation energy and the (15)N nuclear magnetic shielding of pyrazine and pyridazine in aqueous environment. The results obtained with PCM-MM/QM are compared with two other procedures, i.e., the conventional PCM and the iterative and sequential QM/MM (I-QM/MM). The QM calculations are made using density functional theory in the three procedures. For the excitation energies, the time-dependent B3LYP/6-311+G(d) model is used. For the magnetic shielding, the B3LYP/aug-pcS2(N)/pcS2(C,O,H) is used with the gauge-including atomic orbitals. In both cases, i.e., PCM-MM/QM and I-QM/MM, that use a discrete model of the solvent, the solute is surrounded by a first shell of explicit water molecules embedded by an electrostatic field of point charges for the outer shells. The best results are obtained including 28 explicit water molecules for the spectral calculations and 9 explicit water molecules for the magnetic shielding. Using the PCM-MM/QM methodology the results for the n→π(∗) excitation energies of pyridazine and pyrazine are 32,070 ± 80 cm(-1) and 32,675 ± 60 cm(-1), respectively, in good agreement with the corresponding I-MM/QM results of 32,540 ± 80 cm(-1) and 32,710 ± 60 cm(-1) and the experimental results of 33,450-33,580 cm(-1) and 32,700-33,300 cm(-1). For the (15)N magnetic shielding, the corresponding numbers for the gas-water shifts obtained with PCM-MM/QM are 47.4 ± 1.3 ppm for pyridazine and 19.7 ± 1.1 ppm for pyrazine, compared with the I-QM/MM values of 53.4 ± 1.3 ppm and 19.5 ± 1.2 ppm and the experimental results of 42-54 ppm and 17-22 ppm, respectively. The agreement between the two procedures is found to be very good and both are in agreement with the experimental values. PCM

  8. Photoinduced mixed valency in zinc porphyrin dimer of triruthenium cluster dyads.

    Science.gov (United States)

    Henderson, Jane; Kubiak, Clifford P

    2014-10-20

    The preparation, electrochemistry, and spectroscopic characterization of three new species, (ZnTPPpy)Ru3O(OAc)6(CO)-pz-Ru3O(OAc)6(CO)L, where ZnTPPpy = zinc(II) 5-(4-pyridyl)-10,15,20-triphenylporphyin, L = pyridyl ligand, and pz = pyrazine, are reported. These porphyrin-coordinated Ru3O–BL–Ru3O (BL = bridging ligand) dyads are capable of undergoing intramolecular electron transfer from the photoexcited Zn porphyrin to Ru3O donor–bridge–acceptor dimer systems. Seven reversible redox processes are observed in the cyclic voltammograms of the newly synthesized dyads, showing no significant electrochemical interaction between the redox active porphyrin and the pyrazine-bridged ruthenium dimer of Ru3O trimers. From the electrochemical behavior of the dyads, large comproportionation constants (Kc = 6.0 × 10(7) for L = dmap) were calculated from the reduction potentials of the Ru(III)Ru(III)Ru(II) clusters, indicating a stable mixed-valence state. Electronic absorption spectra of the singly reduced mixed-valence species show two intervalence charge transfer (IVCT) bands assigned within the Brunschwig–Creutz–Sutin semiclassical three-state model as metal-to-bridge and metal-to-metal in character. The progression from most to least delocalized mixed-valence dimer ions, as determined by the divergence of the IVCT bands and in agreement with electrochemical data, follows the order of L = 4-dimethylaminopyridine (dmap) > pyridine (py) > 4-cyanopyridine (cpy). These systems show dynamic coalescence of the infrared spectra in the ν(CO) region of the singly reduced state. This sets the time scale of electron exchange at dimer is predicted to be thermodynamically favorable, with ΔGFET(0) ranging from −0.54 eV for L = dmap to −0.62 eV for L = cpy. Observation of IVCT band growth under continual photolysis (λexc = 568 nm) confirms a phototriggered intramolecular electron transfer process resulting in a strongly coupled singly reduced mixed-valence species.

  9. Optimization of Preparation of Coffee Flavor by Thermal Reaction%咖啡香精的热反应制备工艺优化

    Institute of Scientific and Technical Information of China (English)

    朱新鹏; 姚敏

    2011-01-01

    In this study,orthogonal array design was employed to optimize thermal reaction conditions for the preparation of coffee flavor.This was followed by reaction product analysis by gas chromatography-mass spectrometry(GC-MS).When the reaction system was composed of 5 g of amino acids,4 g of reducing sugar,100 g of propylene glycol,10 g of 95% ethanol and 40 g of deionized water at pH 6-8,the optimal reaction conditions were glucose/fructose ratio of 1: 1.5,arginine/lysine ratio of 2.5: 1,reaction temperature of 115 ℃,and reaction time of 4.5 h.The reaction resulted in the generation of 25 volatile flavor compounds such as furfuryl alcohol,maltol,dimethyl pyrazine,acetyl pyrrole and mercaptans.Moreover,pyrazine,pyrrodine,furan,phenol and their substitutes were the major volatile flavor compounds.%通过正交试验确定热反应制备咖啡香精的工艺条件,并用气相色谱-质谱联用(gas chromatography-massspectrometry,GC-MS)对产物进行分析。结果表明,在氨基酸总添加量5g、还原糖总添加量4g、丙二醇100g、95%乙醇10g、去离子水40g、pH6~8时,优化的工艺条件是葡萄糖和果糖配比1:1.5、精氨酸和赖氨酸配比2.5:1、反应温度115℃、反应时间4.5h,此条件下所得咖啡香精的颜色和香气最好。样品经正己烷萃取、GC-MS分析,共检测出糠醇、麦芽酚、二甲基吡嗪、乙酰基吡咯、硫醇等25种挥发性风味物质,主要为吡嗪、吡咯、呋喃、酚等及其取代物。

  10. Computational Studies of CO 2 Sorption and Separation in an Ultramicroporous Metal–Organic Material

    KAUST Repository

    Forrest, Katherine A.

    2013-08-29

    Grand canonical Monte Carlo (GCMC) simulations of CO2 sorption and separation were performed in [Zn(pyz)2SiF6], a metal-organic material (MOM) consisting of a square grid of Zn2+ ions coordinated to pyrazine (pyz) linkers and pillars of SiF6 2- ions. This MOM was recently shown to have an unprecedented selectivity for CO2 over N2, CH4, and H 2 under industrially relevant conditions. The simulated CO 2 sorption isotherms and calculated isosteric heat of adsorption, Qst, values were in excellent agreement with the experimental data for all the state points considered. CO2 saturation in [Zn(pyz) 2SiF6] was achieved at near-ambient temperatures and pressures lower than 1.0 atm. Moreover, the sorbed CO2 molecules were representative of a liquid/fluid under such conditions as confirmed through calculating the isothermal compressibility, βT, values. The simulated CO2 uptakes within CO2/N2 (10:90), CO2/CH4 (50:50), and CO2/H2 (30:70) mixture compositions, characteristic of flue gas, biogas, and syngas, respectively, were comparable to those that were produced in the single-component CO2 sorption simulations. The modeled structure at saturation revealed a loading of 1 CO2 molecule per unit cell. The favored CO2 sorption site was identified as the attraction of the carbon atoms of CO2 molecules to four equatorial fluorine atoms of SiF6 2- anions simultaneously, resulting in CO2 molecules localized at the center of the channel. Furthermore, experimental studies have shown that [Zn(pyz)2SiF6] sorbed minimal amounts of CO2 and N2 at their respective liquid temperatures. Analysis of the crystal structure at 100 K revealed that the unit cell undergoes a slight contraction in all dimensions and contains pyrazine rings that are mildly slanted with an angle of 13.9. Additionally, molecular dynamics (MD) simulations revealed that the sorbate molecules are anchored to the framework at low temperatures, which inhibits diffusion. Thus, it is hypothesized that the sorbed molecules

  11. 花生油香气特征在其属性识别中的初步应用%Primary application of aromatic characteristic in peanut oil discrimination

    Institute of Scientific and Technical Information of China (English)

    李苑雯; 陈素娟; 柏文良; 熊岑; 郑彦婕

    2013-01-01

    A fast analysis method of aroma compounds in peanut oil using optimized headspace solid-phase microextraction conditions combined with GC/MS was established.74compounds were identified,including Pyrazine,Furans,Pyrroles,Pyridines,Aldehydes,Ketones,Alcohols,Acids in main component of peanut oil aroma.There were 19 Pyrazine compounds and 7 Furan compounds considered the main contributors of peanut oil flavor.Pure peanut oils and other vegetable oils with 116 aroma compounds calculated by internal standard were analyzed through principal component analysis (PCA),and the result showed those 116 compound can help in identifying peanut oil and others.%采用HS-SPME-GC/MS技术,通过优化SPME萃取涂层与萃取条件建立了花生油中香气成分的快速检测方法,共鉴定出71种化合物为花生油主要的香气组分,包括吡嗪、呋喃、吡咯、吡啶、醛、酮、醇、酸等化合物.吡嗪类化合物共19种,约占主要组分数的30%,另外呋喃类化合物7种,约占主要组分数的10%,以上2类化合物是花生油香气的主要贡献者.采用内标法计算116种化合物的相对比例,并利用主成分分析法,对17个纯花生油和16个其他植物油进行分类,结果表明116种香气组分能够很好地将花生油或其他植物油分成2大类.

  12. Design and Synthesis of Organic Dyes Based on Acenaphthopyrazine for Dye-sensitized Solar Cells%用于染料敏化太阳能电池的苊并吡嗪类染料的合成

    Institute of Scientific and Technical Information of China (English)

    杨翠翠; 孔志霞; 崔京南

    2011-01-01

    Three acenaphthopyrazine derivatives were designed and synthesized, during the process of which pyrazine groups were used as the electron acceptor connected by carboxyl acids to aromatic groups used as electron donor, applied in the production of dye-sensitized solar cells(DSSC). A higher total solar energy conversion efficiency ( r)) of 3. 06 % was obtained for the 3-( diphenylamino) acenaphtho[ 1,2] pyrazine-8-carboxylic acid( Va) .compared with the conventional N719 dye,whose efficiency is 7. 05% under the same conditions. The range of absorption of the dye Va is concentrated within 400 to 500 nm and the voltage of LUMO is - 1. 10 eV, which indicate that the process of electrons being injected into CB of TiO2 to form the excited dyes is theoretically feasible in thermodynamics. The data of Ehom 1. 31eV,more positive than I~/I3~ redox couple 0.4 eV,also indicate that the oxidized dyes could be reduced effectively by electrolyte and then regenerated.%以吡嗪环作为吸电子基团,单羧基为连接基团,选用不同的芳环供电基团设计合成了3个苊并吡嗪类染料敏化太阳能电池(DSSC)染料.其中,以二苯胺为供电基的染料Va性能最好,主要吸光范围是400-500 nm,ELOMO为-1.10 eV,远负于TiO2的导带能级-0.5 eV,说明染料的激发态电子注入到纳米TiO2的导带在热力学上是可行的;EHOMO为1.31 eV,远正于I-/I3-的氧化还原电位0.4 eV,说明处于氧化态的染料分子从氧化还原电对得到电子再生.光电转换效率最高为3.06%,达到经典染料N719效率的43%.

  13. In vitro antitumor activity and targeted sites of two novel platinum-based (Ⅱ) complexes on SW620 colon cancer cell line%新型铂(Ⅱ)类配合物对大肠癌SW620细胞株的体外抑癌作用及药物作用靶点研究

    Institute of Scientific and Technical Information of China (English)

    Rui Li; Baolin Liu; Hongzhuan Yin; Feng Xu; Qi Su

    2011-01-01

    Objective:The aim of our study was to evaluate the in vitro antitumor activity of two novel platinum-based (Ⅱ) complexes (2.3-pyridinedicarboxylic acid dehydrate platinum and 2.3-pyrazinedicarboxylic acid dehydrate platinum),which were concurrently provided with hydrophilic carboxyl group and lipophilic pyrazinyl or pyridyl group,on SW620 colorectal cancer cell line and the impact of the two compounds on the cell cycle and apoptosis of the cells when compared with the oxaliplatin,desiring the new ligand combined with hydrophilic and lipophilic properties would facilitate the transportation and transmembrane of the drugs,showing a better antitumor activity.Methods:After SW620 cells were treated with different doses of the three platinum-based agents for 24,48 and 72 h,the cell proliferation inhibition rate was determined using methyl thiazolyl tetrazolium (MTT) assay; the morphology of cells were evaluated under inverted microscope; the changes in cell cycle were determined using flow cytometry; the percent apoptosis was measured using Annexin V/PI double staining and the micromorphology of the cells after drug exposure was evaluated using scanning electron microscopy.Results:The evaluation on the proliferation inhibition rate revealed that the three platinum-based agents inhibited the SW620 cells in a time- and dosedependent manner and showed different strengths as pyridine > pyrazine > Oxa.Under optical microscope,the morphological changes such as cell shrinkage,round cells and dead cells were frequently observed after drug exposure.Cell cycle determination showed that all of the three agents could function to block the cells converting from phase S to phase G2M.Apoptosis evaluation revealed that the three agents promoted the apoptosis of SW620 cells in a time- and dose-dependent manner and showed different strengths as pyridine > pyrazine > Oxa.Typical early and late apoptotic morphological changes could be detected during electron microscopy.Conclusion:The two

  14. Reactions of Dinuclear Platinum(II) Complexes with Peptides.

    Science.gov (United States)

    Rajković, Snežana; Živković, Marija D; Djuran, Miloš I

    2016-01-01

    The present review article highlights recent findings in the reactions between different dinuclear Pt(II) complexes with peptides containing cysteine, methionine and histidine residues. The reactions of {trans-[Pt(NH3)2Cl]2(μ-X)}(2+) and {trans-[Pt(NH3)2(H2O)]2(μ-X)}(4+) type complexes with different bridging ligands (X) (X = pyrazine, 4,4'-bipyridyl and 1,2-bis(4-pyridyl)ethane) with the tripeptide glutathione proceeded in two steps. In the first step, one water or chlorido ligand of the dinuclear Pt(II) complex was substituted by the sulfhydryl group of GSH, while in the second step, the remaining water or chlorido ligand from the dinuclear Pt(II)-peptide complex was replaced by the second molecule of glutathione, finally leading to the formation of the {trans-[Pt(NH3)2(GS)]2(μ-X)}(2+) complex. It was shown that the bridging ligand had an important influence on the reactivity of these complexes with glutathione. No hydrolytic cleavage of any amide bond was observed in the reactions between these complexes and glutathione. However, in reactions performed in acidic media (2.0 complexes with the general formulae {[Pt(L)(H2O)]2(μ-diazine)}(4+) (L is different bidentate coordinated diamine ligands and diazine is a pyrazine- or pyridazine-bridging ligand) and Nacetylated peptides containing L-methionine and L-histidine amino acids in the side chains (Ac-L-Met-Gly, Ac-L-His-Gly and Ac-L-Met-Gly-L-His-GlyNH2), regioselective cleavage of these peptides occurred. The mechanism of these hydrolytic reactions was discussed in relation to the structure of the diazine-bridged Pt(II) complex and the investigated peptides. A systematic summary of these results could contribute to the future design of new dinuclear Pt(II) complexes as potential reagents for regioselective cleavage of peptides and proteins.

  15. Transferable potentials for phase equilibria. 9. Explicit hydrogen description of benzene and five-membered and six-membered heterocyclic aromatic compounds.

    Science.gov (United States)

    Rai, Neeraj; Siepmann, J Ilja

    2007-09-13

    The explicit hydrogen version of the transferable potentials for phase equilibria (TraPPE-EH) force field is extended to benzene, pyridine, pyrimidine, pyrazine, pyridazine, thiophene, furan, pyrrole, thiazole, oxazole, isoxazole, imidazole, and pyrazole. While the Lennard-Jones parameters for carbon, hydrogen (two types), nitrogen (two types), oxygen, and sulfur are transferable for all 13 compounds, the partial charges are specific for each compound. The benzene dimer energies for sandwich, T-shape, and parallel-displaced configurations obtained for the TraPPE-EH force field compare favorably with high-level electronic structure calculations. Gibbs ensemble Monte Carlo simulations were carried out to compute the single-component vapor-liquid equilibria for benzene, pyridine, three diazenes, and eight five-membered heterocycles. The agreement with experimental data is excellent with the liquid densities and vapor pressures reproduced within 1 and 5%, respectively. The critical temperatures and normal boiling points are predicted with mean deviations of 0.8 and 1.6%, respectively.

  16. High-intensity ultrasound production of Maillard reaction flavor compounds in a cysteine-xylose model system.

    Science.gov (United States)

    Ong, Olivia X H; Seow, Yi-Xin; Ong, Peter K C; Zhou, Weibiao

    2015-09-01

    Application of high intensity ultrasound has shown potential in the production of Maillard reaction odor-active flavor compounds in model systems. The impact of initial pH, sonication duration, and ultrasound intensity on the production of Maillard reaction products (MRPs) by ultrasound processing in a cysteine-xylose model system were evaluated using Response Surface Methodology (RSM) with a modified mathematical model. Generation of selected MRPs, 2-methylthiophene and tetramethyl pyrazine, was optimal at an initial pH of 6.00, accompanied with 78.1 min of processing at an ultrasound intensity of 19.8 W cm(-2). However, identification of volatiles using gas chromatography-mass spectrometry (GC/MS) revealed that ultrasound-assisted Maillard reactions generated fewer sulfur-containing volatile flavor compounds as compared to conventional heat treatment of the model system. Likely reasons for this difference in flavor profile include the expulsion of H2S due to ultrasonic degassing and inefficient transmission of ultrasonic energy. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. N,S,O-Heterocycles in Aged Champagne Reserve Wines and Correlation with Free Amino Acid Concentrations.

    Science.gov (United States)

    Le Menn, Nicolas; Marchand, Stephanie; de Revel, Gilles; Demarville, Dominique; Laborde, Delphine; Marchal, Richard

    2017-03-22

    Champagne regulations allow winegrowers to stock still wines to compensate for quality shifts in vintages, mainly due to climate variations. According to their technical requirements and house style, Champagne producers use these stored wines in their blends to enhance complexity. The presence of lees and aging at low pH (2.95-3.15), as in Champagne wines, lead to several modifications in wine composition. These conditions, combined with extended aging, result in the required environment for the Maillard chemical reaction, involving aromatic molecules, including sulfur, oxygen, and nitrogen heterocycles (such as thiazole, furan, and pyrazine derivatives), which may have a sensory impact on wine. Some aromatic heterocycles in 50 monovarietal wines aged from 1 to 27 years provided by Veuve Clicquot Ponsardin Champagne house were determined by the SPME-GC-MS method. The most interesting result highlighted a strong correlation between certain heterocycle concentrations and wine age. The second revealed a correlation between heterocyclic compound and free amino acid concentrations measured in the wines, suggesting that these compounds are potential aromatic precursors when wine is aged on lees and, thus, potential key compounds in the bouquet of aged Champagnes. The principal outcome of these assays was to reveal, for the first time, that aromatic heterocycle concentrations in Champagne base wines are correlated with wine age.

  18. Exploiting Natural Products to Build Metalla-Assemblies: The Anticancer Activity of Embelin-Derived Rh(III and Ir(III Metalla-Rectangles

    Directory of Open Access Journals (Sweden)

    Gajendra Gupta

    2014-05-01

    Full Text Available Six new pentamethylcyclopentadienyl Rh(III and Ir(III metalla-rectangles ([3](CF3SO34–[8](CF3SO34 have been prepared by a self-assembly strategy using the embelin-derived metalla-clips (η5-C5Me52M2(μ4-C6HRO4-κOCl2 (M = Rh, 1; M = Ir, 2; R = (CH210CH3 and the linear ditopic ligands, pyrazine, 4,4'-bipyridine and 1,2-bis (4-pyridylethylene. These new metalla-rectangles have been obtained in high yield and isolated as their triflate salts. The complexes have been fully characterized by standard spectroscopic techniques and the antiproliferative activity of these tetranuclear complexes was evaluated in vitro on cancerous (DU-145, A-549, HeLa and noncancerous (HEK-293 cell lines. The biological study has showed a better activity for the rhodium derivatives over the iridium analogs and for all complexes a very good selectivity for cancerous over noncancerous cells. The presence of lipophilic side chains coupled with the positive charge of the tetranuclear complexes suggested a cytotoxic activity involving the mitochondrial machinery, as demonstrated by multiple biological experiments.

  19. Synthetic strategy and antiviral evaluation of diamide containing heterocycles targeting dengue and yellow fever virus.

    Science.gov (United States)

    Saudi, Milind; Zmurko, Joanna; Kaptein, Suzanne; Rozenski, Jef; Gadakh, Bharat; Chaltin, Patrick; Marchand, Arnaud; Neyts, Johan; Van Aerschot, Arthur

    2016-10-04

    High-throughput screening of a subset of the CD3 chemical library (Centre for Drug Design and Discovery; KU Leuven) provided us with a lead compound 1, displaying low micromolar potency against dengue virus and yellow fever virus. Within a project aimed at discovering new inhibitors of flaviviruses, substitution of its central imidazole ring led to synthesis of variably substituted pyrazine dicarboxylamides and phthalic diamides, which were evaluated in cell-based assays for cytotoxicity and antiviral activity against the dengue virus (DENV) and yellow fever virus (YFV). Fourteen compounds inhibited DENV replication (EC50 ranging between 0.5 and 3.4 μM), with compounds 6b and 6d being the most potent inhibitors (EC50 0.5 μM) with selectivity indices (SI) > 235. Compound 7a likewise exhibited anti-DENV activity with an EC50 of 0.5 μM and an SI of >235. In addition, good antiviral activity of seven compounds in the series was also noted against the YFV with EC50 values ranging between 0.4 and 3.3 μM, with compound 6n being the most potent for this series with an EC50 0.4 μM and a selectivity index of >34. Finally, reversal of one of the central amide bonds as in series 13 proved deleterious to the inhibitory activity.

  20. Synthesis, Antimycobacterial, Antifungal and Photosynthesis-Inhibiting Activity of Chlorinated N-phenylpyrazine-2-carboxamides †

    Directory of Open Access Journals (Sweden)

    Katarina Kralova

    2010-11-01

    Full Text Available A series of sixteen pyrazinamide analogues with the -CONH- linker connecting the pyrazine and benzene rings was synthesized by the condensation of chlorides of substituted pyrazinecarboxylic acids with ring-substituted (chlorine anilines. The prepared compounds were characterized and evaluated for their antimycobacterial and antifungal activity, and for their ability to inhibit photosynthetic electron transport (PET. 6-Chloro-N-(4-chlorophenylpyrazine-2-carboxamide manifested the highest activity against Mycobacterium tuberculosis strain H37Rv (65% inhibition at 6.25 μg/mL. The highest antifungal effect against Trichophyton mentagrophytes, the most susceptible fungal strain tested, was found for 6-chloro-5-tert-butyl-N-(3,4-dichlorophenylpyrazine-2-carboxamide (MIC = 62.5 μmol/L. 6-Chloro-5-tert-butyl-N-(4-chlorophenylpyrazine-2-carboxamide showed the highest PET inhibition in spinach chloroplasts (Spinacia oleracea L. chloroplasts (IC50 = 43.0 μmol/L. For all the compounds, the relationships between the lipophilicity and the chemical structure of the studied compounds as well as their structure-activity relationships are discussed.

  1. Study on superoxide and hydroxyl radicals generated in indirect electrochemical oxidation by chemiluminescence and UV-visible spectra

    Institute of Scientific and Technical Information of China (English)

    Zhang Botao; Zhao Lixia; Lin Jinming

    2008-01-01

    The generation and transformation of radicals on the cathode of indirect electrochemical oxidation were studied by chemiluminescence (CL) and UV-visible spectra in the reactor with a salt bridge that connected the separated chambers. The CL intensity of 4 × 10-9 mol/L luminol on the cathode with bubbling oxygen was about seven times that of the intensity without it, which was because of the generation of reactive oxygen species (ROS). The existence of ROS, especially the generation of the superoxide radical, could be affirmed by the fact that the CL intensity of 4 × 10--9 mol/L 2-methyl-6-(4-methoxyphenyl)-3,7-dihydroimidazo[1,2-a]pyrazin-3-one with bubbling oxygen was about four times that of the intensity without it. However, there was no chemiluminescence on the anode under the same condition. The change in the UV-visible spectra of nitro blue tetrazolium and N,N-dimethyl-4-nitrosoaniline at the cathode chamber affirmed the transformation from oxygen to superoxide and hydroxyl radicals. The mechanism of the superoxide and hydroxyl radical generation and transformation on the cathode was discussed with the help of the experimental results and relative references.

  2. A Comparative Analysis of the Influence of Human Salivary Enzymes on Odorant Concentration in Three Palm Wines

    Directory of Open Access Journals (Sweden)

    Ola Lasekan

    2013-09-01

    Full Text Available The influence of human salivary enzymes on palm wines’ odorant concentrations were investigated by the application of aroma extracts dilution analysis (AEDA and by the calculation of odour activity values (OAVs, respectively. The odorants were quantified by means of stable isotope dilution assays (SIDA, and the degradation profiles of odorants by human saliva were also studied. Results revealed 46 odour-active compounds in the flavour dilution (FD factor range of 4-256, and all were subsequently identified. Of the 46 odorants, 41 were identified in the Elaeis guineensis wine, 36 in Raphia hookeri wine and 29 in Borassus flabellifer wine. Among the odorants, the highest FD-factors were obtained from acetoin, 2-acetyl-1-pyrroline and 3-isobutyl-2-methoxypyrazine. Among the 13 potent odorants identified, five aroma compounds are reported here as important contributors to palm wine aroma, namely 3-isobutyl-2-methoxy-pyrazine, acetoin, 2-acetyl-1-pyrroline, 3-methylbutylacetate and ethyl hexanoate. Meanwhile, salivary enzymic degradation of odorants was more pronounced among the aldehydes, esters and thiols.

  3. Formation of flavor components by the reaction of amino acid and carbonyl compounds in mild conditions.

    Science.gov (United States)

    Pripis-Nicolau, L; de Revel, G; Bertrand, A; Maujean, A

    2000-09-01

    This work describe products of reactions between four alpha-dicarbonyl compounds (diacetyl, pentan-2,3-dione, glyoxal, and methylglyoxal) or two alpha-hydroxy ketones, (acetoine and acetol) and amino acids present in wines. The results shows the formation of odorous products or strong-smelling additives resulting from the Maillard and Strecker reaction in a primarily aqueous medium, at low temperature and low pH ( approximately pH 3.5) of the wine. GC/FID, GC/FPD, GC/NPD and GC/MS techniques were used. The olfactive characteristics of the products are described. In the presence of sulfur amino acids and in particular cysteine, many products were formed with a heterocycle production such as pyrazines and methylpyrazines, methylthiazoles, acetylthiazoles, acetylthiazolines, acetylthiazolidines, trimethyloxazole, and dimethylethyloxazoles. These various compounds present odors of sulfur, cornlike, pungent, nut, popcorn, roasted hazelnut, toasted, roasted, and ripe fruits. The chemical conditions of the model reactions are specified. The influence of temperature and pH on the reactions in the presence of cysteine were also studied.

  4. Effect of pretreatment with dehulling and microwaving on the flavor characteristics of cold-pressed rapeseed oil by GC-MS-PCA and electronic nose discrimination.

    Science.gov (United States)

    Zhou, Qi; Yang, Mei; Huang, Fenghong; Zheng, Chang; Deng, Qianchun

    2013-07-01

    Raw and dehulled rapeseeds were treated with microwave energy (800 W) from 1 to 8 min with 1-min intervals at a frequency of 2450 MHz to investigate the influence of microwaving and dehulling pretreatment on the flavor characteristics of rapeseed oil extracted by pressing. Headspace solid phase microextraction was used to isolate the volatile compounds of rapeseed oil, which were then identified by gas chromatography-mass spectrometry analysis. The results indicated that microwave and dehulling pretreatment of rapeseed can significantly influence the kinds and content of volatile compounds. The key flavor compounds in rapeseed oil were oxidized volatiles, heterocyclic compounds, and degradation products of glucosinolates. A pungent compound, 4-isothiocyanato-1-butene, was reduced by 97% in rapeseed treated for 3 min with microwaves energy when compared to the rapeseed oil without any treatment. The pyrazine compounds in the oil appeared after 6 min of microwave pretreatment and give a pleasant roasting flavor when compared to crude oils. Principal component analysis was able to differentiate between oils obtained using 4 pretreatment processes based on volatile compounds and electronic nose. The results showed that dehulling pretreatment could improve the flavor, yet microwaving had a greater effect on the flavor of rapeseed oils.

  5. Penicillium commune metabolic profile as a promising source of antipathogenic natural products.

    Science.gov (United States)

    Diblasi, Lorena; Arrighi, Federico; Silva, Julio; Bardón, Alicia; Cartagena, Elena

    2015-01-01

    Penicillium is an important genus of ascomycetous fungi in the environment and in food and drug production. This paper aims to investigate statins and antipathogenic natural products from a Penicillium commune environmental isolate. Fractions (F1, F2, F3 and F4) were obtained from an ethyl acetate extract. Direct insertion probe/electron ionisation/ion trap detection mass spectrometry (MS and MS/MS) identified lovastatin (1) in F1, while GC-MS showed that 3-isobutylhexahydropyrrolo[1,2-a]pyrazine-1,4-dione (2) was the main constituent of F2 (49.34%). F4 presented 3 (16.38%) as an analogue of 2 and their known structures were similar to that of an autoinducer-signal. F1 produced a significant decrease in the Pseudomonas aeruginosa biofilms, which is the main cause of bacterial pathogenicity. F2 and F4 were effective against Staphylococcus aureus biofilms, but when F2 was associated with oxacillin, it showed an important activity against both bacteria. These novel results suggest that P. commune INTA1 is a new source of promising antipathogenic products.

  6. Synthesis, crystal structures, and thermal and spectroscopic properties of two Cd(II) metal-organic frameworks with a versatile ligand

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jia-Ming; He, Kun-Huan; Shi, Zhong-Feng [Qinzhou Univ. (China). Guangxi Colleges and Univs. Key Lab. of Beibu Gulf Oil and Natural Gas Resource Effective Utilization; Gao, Hui-Yuan; Jiang, Yi-Min [Guangxi Normal Univ., Guilin (China). Key Lab. for the Chemistry and Molecular Engineering of Medicinal Resources

    2016-11-01

    Two new metal-organic frameworks, namely, [Cd(L)(H{sub 2}O)]{sub n} (1) and {[Cd_0_._5(L)(4,4"'-bipy)_0_._5][Cd_0_._5(H_2O)(4,4"'-bipy)_0_._5].H_2O}{sub n} (2), where H{sub 2}L = N-pyrazinesulfonyl-glycine and 4,4{sup '}-bipy = 4,4{sup '}-bipyridine, have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental, thermogravimetric, and photoluminescent analysis. X-ray diffraction crystallographic analyses indicate that 1 displays a distorted octahedral metal coordination in a 3-connected (4, 8{sup 2}) topology, while the molecular structure of 2 has a 4-connected (4, 4) topology with two perfectly octahedrally coordinated Cd centers. The L{sup 2-} ligand serves as a N,N,O-tridentate, μ{sub 2}-pyrazine-bridging, and μ{sub 2}-carboxylate-bridging ligand in 1, and as a N,O-bidentate and μ{sub 2}-carboxylate-bridging ligand in 2. In the crystal, a 3D supramolecular architecture is formed by O-H..O hydrogen bond interactions in 1, but through O-H..O as well as π..π stacking in 2. The two compounds show intense fluorescence in the solid state at room temperature.

  7. Continuous One-Step Synthesis of Porous M-XF6 -Based Metal-Organic and Hydrogen-Bonded Frameworks.

    Science.gov (United States)

    Guillerm, Vincent; Garzón-Tovar, Luis; Yazdi, Amirali; Imaz, Inhar; Juanhuix, Jordi; Maspoch, Daniel

    2017-05-17

    Metal-organic frameworks (MOFs) built up from connecting M-XF6 pillars through N-donor ligands are among the most attractive adsorbents and separating agents for CO2 and hydrocarbons today. The continuous, one-step spray-drying synthesis of several members of this isoreticular MOF family varying the anionic pillar (XF6 =[SiF6 ](2-) and [TiF6 ](2-) ), the N-donor organic ligand (pyrazine and 4,4'-bipyridine) and the metal ion (M=Co, Cu and Zn) is demonstrated here. This synthetic method allows them to be obtained in the form of spherical superstructures assembled from nanosized crystals. As confirmed by CO2 and N2 sorption studies, most of the M-XF6 -based MOFs synthesised through spray-drying can be considered "ready-to-use" sorbents as they do not need additional purification and time consuming solvent exchange steps to show comparable porosity and sorption properties with the bulk/single-crystal analogues. Stability tests of nanosized M-SiF6 -based MOFs confirm their low stability in most solvents, including water and DMF, highlighting the importance of protecting them once synthesised. Finally, for the first time it was shown that the spray-drying method can also be used to assemble hydrogen-bonded open networks, as evidenced by the synthesis of MPM-1-TIFSIX. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Design, synthesis, and biological activities of novel hexahydropyrazino[1,2-a]indole derivatives as potent inhibitors of apoptosis (IAP) proteins antagonists with improved membrane permeability across MDR1 expressing cells.

    Science.gov (United States)

    Shiokawa, Zenyu; Hashimoto, Kentaro; Saito, Bunnai; Oguro, Yuya; Sumi, Hiroyuki; Yabuki, Masato; Yoshimatsu, Mie; Kosugi, Yohei; Debori, Yasuyuki; Morishita, Nao; Dougan, Douglas R; Snell, Gyorgy P; Yoshida, Sei; Ishikawa, Tomoyasu

    2013-12-15

    We previously reported octahydropyrrolo[1,2-a]pyrazine derivative 2 (T-3256336) as a potent antagonist for inhibitors of apoptosis (IAP) proteins. Because compound 2 was susceptible to MDR1 mediated efflux, we developed another scaffold, hexahydropyrazino[1,2-a]indole, using structure-based drug design. The fused benzene ring of this scaffold was aimed at increasing the lipophilicity and decreasing the basicity of the scaffold to improve the membrane permeability across MDR1 expressing cells. We established a chiral pool synthetic route to yield the desired tricyclic chiral isomers. Chemical modification of the core scaffold led to a representative compound 50, which showed strong inhibition of IAP binding (X chromosome-linked IAP [XIAP]: IC50 23 nM and cellular IAP [cIAP]: IC50 1.1 nM) and cell growth inhibition (MDA-MB-231 cells: GI50 2.8 nM) with high permeability and low potential of MDR1 substrate.

  9. Honeydew volatile emission acts as a kairomonal message for the Asian lady beetle Harmonia axyridis (Coleoptera:Coccinellidae)

    Institute of Scientific and Technical Information of China (English)

    Pascal D. Leroy; Eric Haubruge; Stéphanie Heuskin; Ahmed Sabri; Fran(c)ois J. Verheggen; Julien Farmakidis; Georges Lognay; Philippe Thonart; Jean-Paul Wathelet; Yves Brostaux

    2012-01-01

    The Asian lady beetle Harmonia axyridis Pallas is considered as an invasive species in most territories where it has been introduced.Because aphid honeydew acts as an attractant for many aphid predators and parasitoids,the objectives of this work were to collect and identify the volatile compounds released from the aphid excretory product to evaluate how these semiochemicals could affect the H.axyridis foraging behavior.Twelve volatile chemicals were identified from the Megoura viciae Buckton honeydew including four alcohols,three ketones,three aldehydes,a pyrazine and a monoterpene.The volatiles 3-methyl-1-butanol and 3-methyl-butanal were highlighted as the two most abundant semiochemicals released from the M.viciae honeydew.Vicia faba L.plants treated with crude honeydew attracted more than 80% of the tested individuals with 40% of attracted beetles located on the plant.Four volatile compounds (3-hydroxy-2-butanone,3-methyl-butanal,3-methyl-1-butanol and limonene) were also highlighted to attract more than 75% of the coccinellids toward the odor source and to locate about 35% of them on the plants.Limonene was the most efficient attractant since 89% of the H.axyridis responded to this odor.The use of the identified semiochemicals as well as the composition of an artificial honeydew could certainly be helpful to control the dispersal of the Asian lady beetle H.axyridis.

  10. Interdisciplinary investigation on ancient Ephedra twigs from Gumugou Cemetery (3800 B.P.) in Xinjiang region, northwest China.

    Science.gov (United States)

    Xie, Mingsi; Yang, Yimin; Wang, Binghua; Wang, Changsui

    2013-07-01

    In the dry northern temperate regions of the northern hemisphere, the genus Ephedra comprises a series of native shrub species with a cumulative application history reaching back well over 2,000 years for the treatment of asthma, cold, fever, as well as many respiratory system diseases, especially in China. There are ethnological and philological evidences of Ephedra worship and utilization in many Eurasia Steppe cultures. However, no scientifically verifiable, ancient physical proof has yet been provided for any species in this genus. This study reports the palaeobotanical finding of Ephedra twigs discovered from burials of the Gumugou archaeological site, and ancient community graveyard, dated around 3800 BP, in Lop Nor region of northwestern China. The macro-remains were first examined by scanning electron microscope (SEM) and then by gas chromatography-mass spectrometry (GC-MS) for traits of residual biomarkers under the reference of modern Ephedra samples. The GC-MS result of chemical analysis presents the existence of Ephedra-featured compounds, several of which, including benzaldehyde, tetramethyl-pyrazine, and phenmetrazine, are found in the chromatograph of both the ancient and modern sample. These results confirm that the discovered plant remains are Ephedra twigs. Although there is no direct archaeological evidence for the indication of medicinal use of this Ephedra, the unified burial deposit in which the Ephedra was discovered is a strong indication of the religious and medicinal awareness of the human inhabitants of Gumugou towards this plant.

  11. C2H2 adsorption in three isostructural metal-organic frameworks: boosting C2H2 uptake by rational arrangement of nitrogen sites.

    Science.gov (United States)

    Song, Chengling; Jiao, Jingjing; Lin, Qiyi; Liu, Huimin; He, Yabing

    2016-03-21

    Replacing the benzene spacer in the organic linker 5,5'-(benzene-1,4-diyl)diisophthalate with the nitrogen containing heterocyclic rings, namely, pyrazine, pyridazine, and pyrimidine results in three organic linkers, which were reacted with copper ions under solvothermal conditions to form three isostructural metal-organic frameworks (ZJNU-46, ZJNU-47 and ZJNU-48) exhibiting exceptionally high sorption capacities with regard to acetylene due to the simultaneous immobilization of open metal sites and Lewis basic nitrogen sites in the frameworks. At 1 atm and 295 K, the gravimetric C2H2 adsorption uptakes reach 187, 213 and 193 cm(3) (STP) g(-1) for these three compounds. The gravimetric C2H2 adsorption amount of ZJNU-47a is the second highest reported for MOF materials. Notably, despite their same porosities, and densities of open metal sites and uncoordinated nitrogen sites, distinctly different C2H2 adsorption capacities were observed for these three compounds, which we think are mainly associated with the difference in the relative position of nitrogen atoms leading to different binding affinities of the frameworks towards C2H2 guest molecules, and thus different C2H2 adsorptions. This work demonstrates that the rational arrangement of open nitrogen sites will favorably improve the C2H2 uptake and thus provides useful information for future design of porous MOFs with high acetylene storage capacities.

  12. Exploratory and discriminative studies of commercial processed Brazilian coffees with different degrees of roasting and decaffeinated

    Directory of Open Access Journals (Sweden)

    Juliano Souza Ribeiro

    2013-09-01

    Full Text Available The fingerprints of the volatile compounds of 21 commercial Brazilian coffee samples submitted to different industrial processing i.e. decaffeinated or different roasting degrees (traditional and dark were studied. The volatiles were collected by headspace solid phase microextraction (HS-SPME and analyzed by GC-FID and GC-MS. The chromatographic data matrices (fingerprints obtained were explored by the principal component analysis (PCA and partial least squares - discriminative analysis (PLS-DA. Initially the chromatographic profiles were aligned by the algorithm correlation optimized warping (COW. The PCA showed the discrimination of the decaffeinated coffees from the others with both the SPME fibres used. This separation probably occurred due to the loss of some volatile precursors during the decaffeination process, such as sucrose. For both the fibres tested, PDMS/DVB and CX / PDMS SPME, the PLS-DA models correctly classified 100% of the samples according to their roasting degree: (medium and dark, the main differences being the concentrations of some of the volatile compounds such as 2-methyl furan, 2-methylbutanal, 2,3-pentanedione, pyrazine, 2-carboxyaldehyde pyrrole, furfural and 2-furanmethanol.

  13. Synthesis, structural, conformational and pharmacological study of some amides derived from 3 -methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-amine

    Science.gov (United States)

    Iriepa, I.; Bellanato, J.; Gálvez, E.; Gil-Alberdi, B.

    2010-07-01

    Some mono-substituted amides ( 2- 5) derived from 3-methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-amine were synthesized and studied by IR, 1H and 13C NMR spectroscopy. The crystal structure of 3-methyl-2,4-diphenyl-9α-(3,5-dichlorobenzamido)-3-azabicyclo[3.3.1]nonane ( 3) was determined by X-ray diffraction. NMR data showed that all compounds adopt in CDCl 3 a preferred flattened chair-chair conformation with the N-CH 3 group in equatorial disposition. X-ray data agreed with this conformation in the case of compound 3. IR data revealed that compounds 2 and 3 present a C dbnd O⋯HN intermolecular bond in the solid state. This conclusion was also confirmed by X-ray data of compound 3. In the case of compound 5, IR results suggested intermolecular NH⋯N-heterocyclic bonding. On the contrary, in the pyrazine derivative ( 4), IR, 1H and 13C NMR data showed the presence of an intramolecular NH⋯N1″-heterocyclic hydrogen bond in the solid state and solution. Moreover, NMR and IR data showed a preferred trans disposition for the NH-C dbnd O group. NMR also revealed free rotation of the -NH-CO-R group around C9-NH bond. Pharmacological assays on mice were drawn to evaluate analgesic activity.

  14. Activation and silencing of secondary metabolites in Streptomyces albus and Streptomyces lividans after transformation with cosmids containing the thienamycin gene cluster from Streptomyces cattleya.

    Science.gov (United States)

    Braña, Alfredo F; Rodríguez, Miriam; Pahari, Pallab; Rohr, Jurgen; García, Luis A; Blanco, Gloria

    2014-05-01

    Activation and silencing of antibiotic production was achieved in Streptomyces albus J1074 and Streptomyces lividans TK21 after introduction of genes within the thienamycin cluster from S. cattleya. Dramatic phenotypic and metabolic changes, involving activation of multiple silent secondary metabolites and silencing of others normally produced, were found in recombinant strains harbouring the thienamycin cluster in comparison to the parental strains. In S. albus, ultra-performance liquid chromatography purification and NMR structural elucidation revealed the identity of four structurally related activated compounds: the antibiotics paulomycins A, B and the paulomenols A and B. Four volatile compounds whose biosynthesis was switched off were identified by gas chromatography-mass spectrometry analyses and databases comparison as pyrazines; including tetramethylpyrazine, a compound with important clinical applications to our knowledge never reported to be produced by Streptomyces. In addition, this work revealed the potential of S. albus to produce many others secondary metabolites normally obtained from plants, including compounds of medical relevance as dihydro-β-agarofuran and of interest in perfume industry as β-patchoulene, suggesting that it might be an alternative model for their industrial production. In S. lividans, actinorhodins production was strongly activated in the recombinant strains whereas undecylprodigiosins were significantly reduced. Activation of cryptic metabolites in Streptomyces species might represent an alternative approach for pharmaceutical drug discovery.

  15. 脱氧果糖嗪%Deoxyfructosazines

    Institute of Scientific and Technical Information of China (English)

    黎艳玲; 杨华武; 陈雄; 赵瑜

    2006-01-01

      脱氧果糖嗪既是一种重要的香料潜香物,又有较强的生理活性和药用价值,特别在预防和治疗Ⅱ型糖尿病及其并发症方面有较好疗效。本文对其存在形式以及分离提取、合成方法、反应机理、衍生化研究及其作为香料和药物方面的应用加以概述。%  Deoxyfructosazines, as a kind of important potential precursors of flavor-related tobacco smoke pyrazines, have some physiological and pharmaceutical activities, especially on treatment and prevention of diabetes (typeⅡ) or complications of diabetes (typeⅡ). In this paper, the progress of studies on natural existence and isolation, extraction of deoxyfructosazines, synthesis, reacting mechanism, derivatization, and application as flavors and medicament were described.

  16. Isotypic one-dimensional coordination polymers: catena-poly[[dichloridocadmium]-μ-5,6-bis(pyridin-2-ylpyrazine-2,3-dicarboxylato-κ2N5:N6] and catena-poly[[dichloridomercury(II]-μ-5,6-bis(pyridin-2-ylpyrazine-2,3-dicarboxylato-κ2N5:N6

    Directory of Open Access Journals (Sweden)

    Montserrat Alfonso

    2016-08-01

    Full Text Available The isotypic title one-dimensional coordination polymers, [CdCl2(C18H14N4O4]n, (I, and [HgCl2(C18H14N4O4]n, (II, are, respectively, the cadmium(II and mercury(II complexes of the dimethyl ester of 5,6-bis(pyridin-2-ylpyrazine-2,3-dicarboxylic acid. In both compounds, the metal ions are located on a twofold rotation axis and a second such axis bisects the Car—Car bonds of the pyrazine ring. The metal ions are bridged by binding to the N atoms of the two pyridine rings and have an MN2Cl2 bisphenoidal coordination geometry. The metal–Npyrazine distances are much longer than the metal–Npyridine distances; the difference is 0.389 (2 Å for the Cd—N bonds but only 0.286 (5 Å for the Hg—N bond lengths. In the crystals of both compounds, the polymer chains are linked via pairs of C—H...Cl hydrogen bonds, forming corrugated slabs parallel to the ac plane.

  17. T-705 (favipiravir) inhibition of arenavirus replication in cell culture.

    Science.gov (United States)

    Mendenhall, Michelle; Russell, Andrew; Juelich, Terry; Messina, Emily L; Smee, Donald F; Freiberg, Alexander N; Holbrook, Michael R; Furuta, Yousuke; de la Torre, Juan-Carlos; Nunberg, Jack H; Gowen, Brian B

    2011-02-01

    A number of New World arenaviruses (Junín [JUNV], Machupo [MACV], and Guanarito [GTOV] viruses) can cause human disease ranging from mild febrile illness to a severe and often fatal hemorrhagic fever syndrome. These highly pathogenic viruses and the Old World Lassa fever virus pose a significant threat to public health and national security. The only licensed antiviral agent with activity against these viruses, ribavirin, has had mixed success in treating severe arenaviral disease and is associated with significant toxicities. A novel pyrazine derivative currently in clinical trials for the treatment of influenza virus infections, T-705 (favipiravir), has demonstrated broad-spectrum activity against a number of RNA viruses, including arenaviruses. T-705 has also been shown to be effective against Pichinde arenavirus infection in a hamster model. Here, we demonstrate the robust antiviral activity of T-705 against authentic highly pathogenic arenaviruses in cell culture. We show that T-705 disrupts an early or intermediate stage in viral replication, distinct from absorption or release, and that its antiviral activity in cell culture is reversed by the addition of purine bases and nucleosides, but not with pyrimidines. Specific inhibition of viral replication/transcription by T-705 was demonstrated using a lymphocytic choriomeningitis arenavirus replicon system. Our findings indicate that T-705 acts to inhibit arenavirus replication/transcription and may directly target the viral RNA-dependent RNA polymerase.

  18. Monitoring of Yeast Communities and Volatile Flavor Changes During Traditional Korean Soy Sauce Fermentation.

    Science.gov (United States)

    Song, Young-Ran; Jeong, Do-Youn; Baik, Sang-Ho

    2015-09-01

    Flavor development in soy sauce is significantly related to the diversity of yeast species. Due to its unique fermentation with meju, the process of making Korean soy sauce gives rise to a specific yeast community and, therefore, flavor profile; however, no detailed analysis of the identifying these structure has been performed. Changes in yeast community structure during Korean soy sauce fermentation were examined using both culture-dependent and culture-independent methods with simultaneous analysis of the changes in volatile compounds by GC-MS analysis. During fermentation, Candida, Pichia, and Rhodotorula sp. were the dominant species, whereas Debaryomyces, Torulaspora, and Zygosaccharomyces sp. were detected only at the early stage. In addition, Cryptococcus, Microbotryum, Tetrapisispora, and Wickerhamomyces were detected as minor strains. Among the 62 compounds identified in this study, alcohols, ketones, and pyrazines were present as the major groups during the initial stages, whereas the abundance of acids with aldehydes increased as the fermentation progressed. Finally, the impacts of 10 different yeast strains found to participate in fermentation on the formation of volatile compounds were evaluated under soy-based conditions. It was revealed that specific species produced different profiles of volatile compounds, some of which were significant flavor contributors, especially volatile alcohols, aldehydes, esters, and ketones.

  19. Cyanide- and phenoxo-bridged heterobimetallic Fe(III)-Mn(III) complexes: Synthesis, crystal structures and magnetic properties

    Indian Academy of Sciences (India)

    Daopeng Zhang; Ping Wang; Kexun Chen; Xia Chen

    2014-11-01

    By employing two -tricyanidoiron(III) precursors [Ph4P][FeIII(pcq)(CN)3] and [Ph4P][FeIII (pzq)(CN)3] as building blocks and a salen-tpye Schiff-basemanganese (III) compound as assembling segment, two tetranuclear cyanide- and phenoxo- bridged heterobimetallic Fe(III)-Mn(III) complexes {[Mn(saltmen)] [Fe(pcq)(CN)3]}2·2CH3OH (1) and {[Mn(saltmen)] [Fe(pzq)(CN)3]}2·2CH3OH (2) (pcq = 8-(pyridine-2-carboxamido, pzq = 8-(pyrazine-2-carboxamido, saltmen2− = N,N′-(1,1,2,2-tetramethylethylene)bis(salicylideneaminato) dianion) have been synthesized and characterized by elemental analysis, IR spectroscopy and X-ray structure determination. Single x-ray analysis reveals their isostructural cyanide-bridged Fe(III)-Mn(III) binuclear structure. The binuclear entity is self-complementary through phenoxo oxygen from the neighbouring complex, giving cyanide- and phenoxo- bridged tetranuclear structure. Furthermore, under the help of the intermolecular - interaction, these two complexes can be constructed into 1D infinite chain supramolecular structure. Investigation over magnetic susceptibilities reveals the overall ferromagnetic coupling between the adjacent Fe(III) and Mn(III) ions bridged by cyanide group with = 5.34 cm-1 and 5.55 cm-1 for complexes 1 and 2, respectively.

  20. Structural and Magnetic Properties of Copper(II) Coordination Polymers Containing Fluoride-Based Anions and Ancillary Organic Ligands

    Science.gov (United States)

    Conner, M.; McConnell, A.; Schlueter, J.; Manson, J.

    2006-02-01

    The fluoride (F-) and bifluoride (HF 2 - ) anions have been little used in the self-assembly of molecular and polymeric magnets. We have recently synthesized several new compounds, namely CuF2(3-OHpy)4 (OHpy = hydroxypyridine) (1), Cu(SiF6)(2,6-me2pyz)4 (me2pyz = dimethylpyrazine) (2), CuF2(H2O)2(pyz) (pyz = pyrazine) (3) and [Cu(HF2)(pyz)2]BF4 (4). Compound 1 contains coordinate covalent and hydrogen bonding interactions that link the Cu(II) ions into 3D networks while 2 features square-pyramidal Cu(II) ions that are weakly bridged by SiF 6 2- anions into 1D chains. Preliminary structural data indicate that compound 3 contains 1D Cu-pyz-Cu chains while 4 contains two dimensional [Cu(pyz)2]2+ layers, which held together via HF 2 - anions so as to form an unprecedented 3D network. The magnetic properties of each are briefly described herein.

  1. Gas Chromatographic-Selected Ion Monitoring-Mass Spectrometric Determination of Cigarette Mainstream Smoke Components with Sensory Attributes

    Directory of Open Access Journals (Sweden)

    Coleman WM

    2014-12-01

    Full Text Available A new method has been developed that detects significant quantitative differences in the amounts of pyrazines, pyridines, furfurals, carboxylic acids, b-damascenone, sclareolide, and megastigmatrienones in the mainstream smoke of a series of five commercial cigarettes. This new quantitative method is based on the gas chromatographic-selected ion monitoring-mass spectrometric (GC-SIM-MS determination of the selected smoke constituents. The accuracy and precision of the approach were well within acceptable parameters with the majority of cases relative standard deviation (RSD values consistently around 5%. Sample preparation was simple requiring only the dissolution of the trapped particulate material in a known volume of methanol followed by injection of this clear dark colored solution into the gas chromatograph. This approach represents an advance in the technology in terms of higher sample throughput and less sample workup. Certain products demonstrated consistent trends in concentration of specific chemical classes. The mainstream smoke from a University of Kentucky reference cigarette, 2R4F, was included for reference purposes. These results are applicable in the overall evaluation of the components responsible for the taste associated with cigarette products.

  2. Brazilian roasted coffee oil obtained by mechanical expelling: compositional analysis by GC-MS Óleo de café torrado brasileiro obtido por prensagem dos grãos: análise da composição por GC-MS

    Directory of Open Access Journals (Sweden)

    Alessandra L. de Oliveira

    2005-12-01

    Full Text Available A preliminary analysis by GC-MS comparing the mass spectrum of the compounds with the Wiley 275 L mass spectral data base was used to identify the fatty acids and mainly, some volatile compounds responsible for the flavor of the roasted coffee oil. The oil was obtained by mechanical expelling of Brazilian beans (Coffea arabica roasted at 238ºC for 10 minutes. Different sample preparation methodologies such as headspace, adsorbent suction trapping and esterification were used. It was possible to identify pyrazines, pyridines, furan derivatives and other compounds not reported in the literature.Análise preliminar utilizando GC-MS através da comparação dos espectros de massas dos compostos com aqueles da base de dados Wiley 275 L foi feita para identificar ácidos graxos e principalmente componentes voláteis responsáveis pelo aroma e odor do óleo de café torrado. O óleo foi obtido por prensagem dos grãos de café brasileiro (Coffea arabica, torrado a 238ºC por 10 min. Diferentes metodologias de preparo de amostra como "headspace", adsorção por sucção em armadilha com polímero e esterificação foram usadas. Foi possível identificar pirazinas, piridinas, derivados de furanos e outros componentes ainda não apresentados na literatura.

  3. Unique microporous NbO-type Co{sup II}/Zn{sup II} MOFs from double helical chains: Sorption and luminescent properties

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Wen-Wen; Xia, Liang; Peng, Zhen; Zhao, Jun; Wu, Ya-Pan [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key laboratory of inorganic nonmetallic crystalline and energy conversion materials, China Three Gorges University, Yichang 443002 (China); Zhang, Jian [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fujian, Fuzhou 350002 (China); Li, Dong-Sheng, E-mail: lidongsheng1@126.com [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key laboratory of inorganic nonmetallic crystalline and energy conversion materials, China Three Gorges University, Yichang 443002 (China)

    2016-06-15

    Under solvothermal conditions, the reactions of Co{sup II}/Zn{sup II} ions with bent ligand 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1,2,4-triazole (4-Hpzpt) afford two compounds {[M(4-pzpt)_2] guest}{sub n} (guest=H{sub 2}O, M=Co{sup II} (1), Zn{sup II} (2)). Both compounds are the thermally and hydrolytically robust 4-connected 3D NbO framework, which formed by double helical chains to give rise to 1D hollow nanochannel with uncoordinated nitrogens completely exposed on the pore surface. Compound 1 exhibits improved N{sub 2}, CO{sub 2} and H{sub 2} uptake capacities, while compound 2 displays the strong luminescent emission with obvious red shift. - Graphical abstract: Two 2-fold interpenetrated NbO-type MOFs with 1D nanochannel were synthesized. Compound 1 exhibits improved N{sub 2}, CO{sub 2} and H{sub 2} uptake capacities, while compound 2 displays the strong fluorescent emission with obvious red shift. Display Omitted.

  4. The chemistry of antipredator defense by secondary compounds in neotropical lepidoptera: facts, perspectives and caveats

    Directory of Open Access Journals (Sweden)

    Trigo José R.

    2000-01-01

    Full Text Available Chemical defense against predation in butterflies and moths has been studied since nineteenth century. A classical example is that of the larvae of the monarch butterfly Danaus plexippus, which feed on leaves of Asclepias curassavica (Asclepiadaceae, sequestering cardenolides. The adults are protected against predation by birds. Several other substances may be involved in chemical defense, such as iridoid glycosides, cyanogenic glycosides, glucosinolates, pyrrolizidine and tropane alkaloids, aristolochic acids, glycosidase inhibitors and pyrazines. The acquisition of these substances by lepidopterans can be due to sequestration from larval or adult host plants or de novo biosynthesis. Many Lepidoptera are known to be unpalatable, including the butterflies Troidini (Papilionidae, Pierinae (Pieridae, Eurytelinae, Melitaeinae, Danainae, Ithomiinae, Heliconiinae and Acraeinae (Nymphalidae, and Arctiidae moths, but knowledge of the chemical substances responsible for property is often scarce. This review discusses mainly three topics: field and laboratory observations on rejection of butterflies and moths by predators, correlation between unpalatability and chemicals found in these insects, and bioassays that test the activity of these chemicals against predators. Perspectives and future directions are suggested for this subject.

  5. Hemolysin, Protease, and EPS Producing Pathogenic Aeromonas hydrophila Strain An4 Shows Antibacterial Activity against Marine Bacterial Fish Pathogens

    Directory of Open Access Journals (Sweden)

    Anju Pandey

    2010-01-01

    Full Text Available A pathogenic Aeromonas hydrophila strain An4 was isolated from marine catfish and characterized with reference to its proteolytic and hemolytic activity along with SDS-PAGE profile (sodium dodecyl sulphate-Polyacrylamide gel electrophoresis of ECPs (extracellular proteins showing hemolysin (approximately 50 kDa. Agar well diffusion assay using crude cell extract of the bacterial isolate clearly demonstrated antibacterial activity against indicator pathogenic bacteria, Staphylococcus arlettae strain An1, Acinetobacter sp. strain An2, Vibrio parahaemolyticus strain An3, and Alteromonas aurentia SE3 showing inhibitory zone >10 mm well comparable to common antibiotics. Further GC-MS analysis of crude cell extract revealed several metabolites, namely, phenolics, pyrrolo-pyrazines, pyrrolo-pyridine, and butylated hydroxytoluene (well-known antimicrobials. Characterization of EPS using FTIR indicated presence of several protein-related amine and amide groups along with peaks corresponding to carboxylic and phenyl rings which may be attributed to its virulent and antibacterial properties, respectively. Besides hemolysin, EPS, and protease, Aeromonas hydrophila strain An4 also produced several antibacterial metabolites.

  6. Experimental and molecular modeling studies of the interaction of the polypyridyl Fe(II) and Fe(III) complexes with DNA and BSA.

    Science.gov (United States)

    Behnamfar, Mohammad Taghi; Hadadzadeh, Hassan; Simpson, Jim; Darabi, Farivash; Shahpiri, Azar; Khayamian, Taghi; Ebrahimi, Malihe; Amiri Rudbari, Hadi; Salimi, Mona

    2015-01-01

    Two mononuclear iron complexes, [Fe(tppz)₂](PF₆)₂·H₂O (1) and Fe(tppz)Cl₃·2CHCl₃ (2) where tppz is (2,3,5,6-tetra(2-pyridyl)pyrazine), have been synthesized and characterized by elemental analysis, spectroscopic methods (UV-Vis and IR) and single crystal X-ray structure analysis. The interaction of (1) as the nitrate salt ([Fe(tppz)₂](NO₃)₂) with calf-thymus DNA (CT-DNA) has been monitored by UV-Vis spectroscopy, competitive fluorescence titration, circular dichroism (CD), voltammetric techniques, viscosity measurement, and gel electrophoresis. Gel electrophoresis of DNA with [Fe(tppz)₂](NO₃)₂ demonstrated that the complex also has the ability to cleave supercoiled plasmid DNA. The results have indicated that the complex binds to CT-DNA by three binding modes, viz., electrostatic, groove and partial insertion of the pyridyl rings between the base stacks of double-stranded DNA. Molecular docking of [Fe(tppz)₂](NO₃)₂ with the DNA sequence d(ACCGACGTCGGT)₂ suggests the complex fits into the major groove. The water-insoluble complex (2) can catalyze the cleavage of BSA at 40 °C. There are no reports of the catalytic effect of polypyridyl metal complexes on the BSA cleavage. Molecular docking of (2) with BSA suggests that, when the chloro ligands in the axial positions are replaced by water molecules, the BSA can interact with the Fe(III) complex more easily.

  7. Fused aromatic thienopyrazines: structure, properties and function

    KAUST Repository

    Mondal, Rajib

    2010-01-01

    Recent development of a fused aromatic thieno[3.4-b]pyrazine system and their application in optoelectronic devices are reviewed. Introduction of a fused aromatic unit followed by side chain engineering, dramatically enhanced the charge carrier mobility in thin film transistor devices and mobilities up to 0.2 cm2/Vs were achieved. The optoelectronic properties of these fused aromatic thienopyrazine polymers (Eg = 1.3 to 1.6 eV, HOMO = -4.9 to -5.2 V) were tuned by introduction of various fused aromatic rings within thienopyrazine. By balancing the fundamental properties of these polymers, both high charge carrier mobilities and moderate PCEs in solar cells were achieved. Further, effects of copolymerizing units are discussed. Low band gap semiconducting polymer (Eg ∼ 1 eV) with high field effect mobility (0.044 cm2/Vs) was obtained using cyclopentadithiophene as copolymerizing unit. Finally, a molecular design approach to enhance the absorption coefficients is discussed, which resulted in improved power conversion efficiency in bulk heterojunction solar cells. © 2010 The Royal Society of Chemistry.

  8. Determination of roasted pistachio (Pistacia vera L.) key odorants by headspace solid-phase microextraction and gas chromatography-olfactometry.

    Science.gov (United States)

    Aceña, Laura; Vera, Luciano; Guasch, Josep; Busto, Olga; Mestres, Montserrat

    2011-03-23

    Key odorants in roasted pistachio nuts have been determined for the first time. Two different pistachio varieties (Fandooghi and Kerman) have been analyzed by means of headspace solid-phase microextraction (HS-SPME) and gas chromatography-olfactometry (GCO). The aroma extract dilution analyses (AEDA) applied have revealed 46 and 41 odor-active regions with a flavor dilution (FD) factor≥64 for the Fandooghi and the Kerman varieties, respectively, and 39 of them were related to precisely identified compounds. These included esters, pyrazines, aldehydes, acids, furans, and phenols. The results show that the Fandooghi variety presents, not only more odor-active regions but also higher FD factors than the Kerman variety that can lead to the conclusion that the first variety has a richer aromatic profile than the second one. The descriptive sensory analysis (DSA) showed that the roasted, chocolate/coffee, and nutty attributes were rated significantly higher in the Fandooghi variety, whereas the green attribute was significantly higher in the Kerman one.

  9. Quinoxaline ozonation in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Andreozzi, R.; Caprio, V.; D' Amore, M.G.; Insola, A. (Universita di Napoli (Italy))

    The oxidation of quinoxaline by ozone in aqueous solution is investigated. The chemical and kinetic evolution of the oxidation process at varying pH are followed by means of semi-batch and batch ozonation experiments. Results indicate that quinoxaline ozonation can develop according to both radical and ionic mechanisms whose relative occurrence can be varied by means of addition to the reacting system of radical scavengers or ozone decomposition promoters. It is shown that each mechanism involves an initial attack of ozone to both the homocyclic and heterocyclic rings of quinoxaline. Pyrazinedicarboxylic acid is formed as a stable final product in ionic ozonation, whereas it appears as an intermediate still reactive towards ozone in radical ozonation. Despite this, the radical ozonation of quinoxaline appears to be more selective than ionic ozonation with respect to production of pyrazinedicarboxylic acid. Reaction schemes are proposed to account for the observed kinetic behaviors and product formations. Oxidation experiments have also been extended to pyrazine, and its sensitivity to only radical ozonation is shown.

  10. Treatment Efficiency by means of a Nonthermal Plasma Combined with Heterogeneous Catalysis of Odoriferous Volatile Organic Compounds Emissions from the Thermal Drying of Landfill Leachates

    Directory of Open Access Journals (Sweden)

    Daniel Almarcha

    2014-01-01

    Full Text Available The objective of the present work was to assess the odoriferous volatile organic compounds depuration efficiency of an experimental nonthermal plasma coupled to a catalytic system used for odor abatement of real emissions from a leachate thermal drying plant installed in an urban solid waste landfill. VOC screening was performed by means of HRGC-MS analysis of samples taken at the inlet and at the outlet of the nonthermal plasma system. Odor concentration by means of dynamic olfactometry, total organic carbon, mercaptans, NH3, and H2S were also determined in order to assess the performance of the system throughout several days. Three plasma frequencies (100, 150, and 200 Hz and two catalyst temperatures (150°C and 50°C were also tested. Under conditions of maximum capacity of the treatment system, the results show VOC depuration efficiencies around 69%, with average depuration efficiencies between 44 and 95% depending on the chemical family of the substance. Compounds belonging to the following families have been detected in the samples: organic acids, alcohols, ketones, aldehydes, pyrazines, and reduced sulphur compounds, among others. Average total organic carbon removal efficiency was 88%, while NH3 and H2S removal efficiencies were 88% and 87%, respectively, and odor concentration abatement was 78%.

  11. Discovery of 4-(phenyl)thio-1H-pyrazole derivatives as agonists of GPR109A, a high affinity niacin receptor.

    Science.gov (United States)

    Kim, Hyeon Young; Jadhav, Vithal B; Jeong, Dae Young; Park, Woo Kyu; Song, Jong-Hwan; Lee, Sunkyung; Cho, Heeyeong

    2015-06-01

    Even though nicotinic acid (niacin) appears to have beneficial effects on human lipid profiles, niacin-induced cutaneous vasodilatation called flushing limits its remedy to patient. GPR109A is activated by niacin and mediates the anti-lipolytic effects. Based on the hypothesis that β-arrestin signaling mediates niacin-induced flushing, but not its anti-lipolytic effect, we tried to find GPR109A agonists which selectively elicit Gi-protein-biased signaling devoid of β-arrestin internalization using a β-lactamase assay. We identified a 4-(phenyl)thio-1H-pyrazole as a novel scaffold for GPR109A agonist in a high throughput screen, which has no carboxylic acid moiety known to be important for binding. While 1-nicotinoyl derivatives (5a-g, 6a-e) induced β-arrestin recruitment, 1-(pyrazin-2-oyl) derivatives were found to play as G-protein-biased agonists without GPR109A receptor internalization. The activity of compound 5a (EC50 = 45 nM) was similar to niacin (EC50 = 52 nM) and MK-6892 (EC50 = 74 nM) on calcium mobilization assay, but its activity at 10 μM on β-arrestin recruitment were around two and five times weaker than niacin and MK-6892, respectively. The development of G-protein biased GPR109A ligands over β-arrestin pathway is attainable and might be important in differentiation of pharmacological efficacy.

  12. Electrochemistry of surface wired cytochrome c and bioelectrocatalytic sensing of superoxide

    Indian Academy of Sciences (India)

    Susmita Behera; Ramendra Sundar Dey; Manas Kumar Rana; C Retna Raj

    2013-03-01

    Electrochemistry of cytochrome c (Cyt-c) wired on an electrode modified with the self-assemblies of 4,4'-dithio-dibutyric acid (DTB) and 2-pyrazineethane thiol (PET) by covalent and electrostatic binding and the amperometric sensing of superoxide (O$^{−}_{2}$) are described. Cyt-c wired on the mixed self-assembly of DTB and PET displays well-defined voltammetric response at 0.025V with a peak-to-peak separation ( ) of 5mV. Pyrazine unit in the mixed self-assembly promotes the electron transfer in the redox reaction of surface wired Cyt-c. Cyt-c wired on the mixed self-assembly has been used for the amperometric sensing of superoxide. The enzymatically generated superoxide has been successfully detected using the Cyt-c wired electrode. High sensitivity and fast response for superoxide have been achieved. Uric acid does not interfere in the amperometric measurement of superoxide. The interference due to H2O2 has been eliminated by using enzyme catalase.

  13. Selective Binding, Self-Assembly and Nanopatterning of the Creutz-Taube Ion on Surfaces

    Directory of Open Access Journals (Sweden)

    Qingling Hang

    2009-02-01

    Full Text Available The surface attachment properties of the Creutz-Taube ion, i.e., [(NH35Ru(pyrazineRu(NH35]5+, on both hydrophilic and hydrophobic types of surfaces were investigated using X-ray photoelectron spectroscopy (XPS. The results indicated that the Creutz-Taube ions only bound to hydrophilic surfaces, such as SiO2 and –OH terminated organic SAMs on gold substrates. No attachment of the ions on hydrophobic surfaces such as –CH3 terminated organic SAMs and poly(methylmethacrylate (PMMA thin films covered gold or SiO2 substrates was observed. Further ellipsometric, atomic force microscopy (AFM and time-dependent XPS studies suggested that the attached cations could form an inorganic analog of the self-assembled monolayer on SiO2 substrate with a “lying-down” orientation. The strong electrostatic interaction between the highly charged cations and the anionic SiO2 surface was believed to account for these observations. Based on its selective binding property, patterning of wide (~200 nm and narrow (~35 nm lines of the Creutz-Taube ions on SiO2 surface were demonstrated through PMMA electron resist masks written by electron beam lithography (EBL.

  14. Reversible structural transformations in a Co(II)-based 2D dynamic metal-organic framework showing selective solvent uptake

    Indian Academy of Sciences (India)

    Sanjog S Nagarkar; Sujit K Ghosh

    2015-04-01

    A Co(II)-based two-dimensional (2D) metal-organic framework (MOF) [Co(pca)(bdc)0.5(H2O)2] (1) {pca = pyrazine carboxylic acid, and bdc = 1,4-benzene dicarboxylic acid} was synthesized solvothermally. The compound loses the coordinated lattice water molecules on heating which is accompanied by solidstate structural transformation to yield dehydrated phase [Co(pca)(bdc)0.5] (1′). The hydrated structure can be regained by exposing 1′ to water vapour (1′′). These reversible solid-state structural transformations are accompanied by a visible colour change in the material. The dehydrated compound also shows highly selective water uptake over other solvents like MeOH, EtOH, THF. This selective water uptake can be ascribed to the high affinity of polar water molecule towards the open metal site created on heating. The present report provides important insights into the reversible structural transformations observed due to variable coordination number of the central metal ion and transformability of the framework. The selective water uptake over alcohols along with visible colour change demonstrates the potential of the present compound in bio-alcohol purification.

  15. Thiophene-rich fused-aromatic thienopyrazine acceptor for donor–acceptor low band-gap polymers for OTFT and polymer solar cell applications

    KAUST Repository

    Mondal, Rajib

    2010-01-01

    Thiophene enriched fused-aromatic thieno[3,4-b]pyrazine systems were designed and employed to produce low band gap polymers (Eg = 1.0-1.4 eV) when copolymerized with fluorene and cyclopentadithiophene. The copolymers are mainly investigated for organic thin film transistor and organic photovoltaic applications. Molecular packing in the thin films of these polymers was investigated using Grazing incidence X-ray Scattering. Although both fluorene and cyclopentadithiophene polymers follow similar face to face π-π stacking, the latter polymers show much smaller lamellar d-spacings due to side-chain interdigitation between the lamellae. This lead to the higher charge carrier mobilities in cyclopentadithiophene polymers (up to 0.044 cm2/V.s) compared to fluorene polymers (up to 8.1 × 10-3 cm2/V.s). Power conversion efficiency of 1.4% was achieved using fluorene copolymer in solar cells with a fullerene derivative as an acceptor. Although the cyclopentadithiophene polymers show lower band gaps with higher absorption coefficients compared to fluorene copolymers, but the power conversion efficiencies in solar cells of these polymers are low due to their low ionization potentials. © The Royal Society of Chemistry 2010.

  16. Volatile organic emissions from the distillation and pyrolysis of vegetation

    Directory of Open Access Journals (Sweden)

    J. P. Greenberg

    2006-01-01

    Full Text Available Leaf and woody plant tissue (Pinus ponderosa, Eucalyptus saligna, Quercus gambelli, Saccharum officinarum and Oriza sativa were heated from 30 to 300°C and volatile organic compound (VOC emissions were identified and quantified. Major VOC emissions were mostly oxygenated and included acetic acid, furylaldehyde, acetol, pyrazine, terpenes, 2,3-butadione, phenol and methanol, as well as smaller emissions of furan, acetone, acetaldehyde, acetonitrile and benzaldehyde. Total VOC emissions from distillation and pyrolysis were on the order of 10 gC/kgC dry weight of vegetation, as much as 33% and 44% of CO2 emissions (gC(VOC/gC(CO2 measured during the same experiments, in air and nitrogen atmospheres, respectively. The emissions are similar in identity and quantity to those from smoldering combustion of woody tissue and of different character than those evolved during flaming combustion. VOC emissions from the distillation of pools and endothermic pyrolysis under low turbulence conditions may produce flammable concentrations near leaves and may facilitate the propagation of wildfires. VOC emissions from charcoal production are also related to distillation and pyrolysis; the emissions of the highly reactive VOCs from production are as large as the carbon monoxide emissions.

  17. Electroantennogram and behavioral responses of the imported fire ant, Solenopsis invicta Buren, to an alarm pheromone component and its analogues.

    Science.gov (United States)

    Guan, Di; Lu, Yong-Yue; Liao, Xiao-Lan; Wang, Lei; Chen, Li

    2014-12-10

    A characteristic behavior in ants is to move rapidly to emission sources of alarm pheromones. The addition of ant alarm pheromones to bait is expected to enhance its attractiveness. To search for candidate compounds for bait enhancement in fire ant control, 13 related alkylpyrazine analogues in addition to synthetic alarm pheromone component were evaluated for electroantennogram (EAG) and behavioral activities in Solenopsis invicta. Most compounds elicited dose-dependent EAG and behavioral responses. There exists a correlation between the EAG and behavioral responses. Among the 14 tested alkylpyrazines, three compounds, 2-ethyl-3,6(5)-dimethyl pyrazine (1), 2,3,5-trimethylpyrazine (7), and 2,3-diethyl-5-methylpyrazine (12), elicited significant alarm responses at a dose range of 0.1-1000 ng. Further bait discovery bioassay with the three most active alkylpyrazines demonstrated that food bait accompanied by sample-treated filter paper disk attracted significantly more fire ant workers in the first 15 min period. EAG and behavioral bioassays with pure pheromone isomers accumulated by semi-preparative high-performance liquid chromatography demonstrated that 2-ethyl-3,6-dimethylpyrazine was significantly more active than 2-ethyl-3,5-dimethylpyrazine.

  18. Effects of RPR 118723, a novel antagonist at the glycine site of the NMDA receptor, in vitro.

    Science.gov (United States)

    Boireau, A; Monterrat, C; Bordier, F; Meunier, M; Imperato, A

    2000-08-04

    RPR 118723 ((8-chloro-5-methyl-2,3-dioxo-1,4-dihydro-5H-indeno[1, 2-b]pyrazin-5-yl) acetic acid) was previously reported to exhibit potent affinity for the glycine site of the N-methyl-D-aspartate (NMDA) receptor-channel complex in the nanomolar range (K(i)=3.1+/-0. 8 nM). We now report on the effects of RPR 118723 in two functional tests reflecting the interaction between the glycine site and the NMDA receptor. First, RPR 118723 potently inhibited [3H]N-[1-(2-thienyl)cyclohexyl]-3,4-piperidine ([3H]TCP) binding in the presence of NMDA (IC(50)=3.5+/-0.4 nM). Second, RPR 118723 antagonized the NMDA-induced increase in [3H]dopamine release in mouse striatal slices (IC(50)=8.0+/-1.1 nM). In both experimental models, an excess of glycine reversed the effect of RPR 118723. These results show that RPR 118723 interferes functionally in the nanomolar range with the glycine site coupled to the NMDA receptor in vitro. The blockade of the glycine site with RPR 118723 may be useful for the therapy of the disorders linked to excessive NMDA stimulation.

  19. Theoretical Design of High-spin Organic Molecules with-·N-N-as a Spin-containing Fragment and Heterocycles as an End Group

    Institute of Scientific and Technical Information of China (English)

    CHU De-Qing; WANG Li-Min; ZHANG Jing-Ping; WANG Rong-Shun

    2006-01-01

    Novel stable high spin molecules possessing three different arranged fashions are designed with -·N-N< as a spin-containing (SC) fragment, various aromatic, such as benzene (1), pyridine (2), pyridazine (3), pyrimidine (4),pyrazine (5), triazine (6) as end groups (EG) and phenyl as a ferromagnetic coupling (FC) unit. The effects of a different end groups on the spin multiplicities of the ground states and their stabilities were investigated by means of AM1-CI approach. It has been found that the spin densities on the two atoms of the SC fragment are different from delocalization resulting in the specific stability of -·N-N<. In these molecules, the stabilities of the triplet states decrease when the distance between the atoms of central SC (-N-) increases. The orders of the stability of triplet states for 1an, 1bn, 1cn [They are isomers in which SC is connected with FC in different way (1an, NiNNN1; 1bn,N1N NiN; 1cn, NN1N1N) and six heterocycles are EG] show that the tability of triplet states with heterocycles as end groups is higher than that with phenyl as end groups, and in the order: triazine (EG)>pyrimidine, pyrazine>pyridine, pyridazine.

  20. Theoretical Design of High-spin Organic Molecules with Heterocycles as Ferromagnetic Coupling Units

    Institute of Scientific and Technical Information of China (English)

    WANG Li-min; ZHANG Jing-ping; WANG Rong-shun

    2003-01-01

    Novel stable high spin molecules possessing three different arranged fashions are designed with -*N-N< as a spin-containing(SC) fragment, phenylene as an end group and various aromatic molecules, such as benzene(1), 2,6-pyridine(2), 3,5-pyridine(3), pyridazine(4), 4,6-pyrimidine(5), 2,6-pyrimidine(6), pyrazine(7) and triazine(8), as a ferromagnetic coupling(FC) unit. The effects of the different coupling units on the spin multiplicities of the ground states and their stabilities were investigated by means of AM1-CI approach. It has been found that the spin densities on the two atoms of the SC fragment are different from delocalization results in the specific stability of -*N-N<. In these molecules, the stabilities of the triplet states decrease when the distance between the atoms of central SC(-N-) increases. It is shown that the heterocycles as the coupling units have influence on the stabilities of the high-spin ground states. That the heteroatom lying in m-phenyl can improve ferromagnetic coupling, while the heteroatom lying in o-phenyl or p-phenyl is not in favor of the ferromagnetic coupling.

  1. Growth media affect the volatilome and antimicrobial activity against Phytophthora infestans in four Lysobacter type strains.

    Science.gov (United States)

    Lazazzara, Valentina; Perazzolli, Michele; Pertot, Ilaria; Biasioli, Franco; Puopolo, Gerardo; Cappellin, Luca

    2017-08-01

    Bacterial volatile organic compounds (VOCs) play important ecological roles in soil microbial interactions. Lysobacter spp. are key determinants of soil suppressiveness against phytopathogens and the production of non-volatile antimicrobial metabolites has been extensively characterised. However, the chemical composition and antagonistic properties of the Lysobacter volatilome have been poorly investigated. In this work, VOC emission profiles of four Lysobacter type strains grown on a sugar-rich and a protein-rich medium were analysed using solid-phase microextraction gas chromatography-mass spectrometry and proton transfer reaction-time of flight-mass spectrometry. Lysobacter antibioticus, L. capsici, L. enzymogenes and L. gummosus type strains were recognised according to their volatilome assessed using both headspace mass spectrometry methods Moreover, the chemical profiles and functional properties of the Lysobacter volatilome differed according to the growth medium, and a protein-rich substrate maximised the toxic effect of the four Lysobacter type strains against Phytophthora infestans. Antagonistic (pyrazines, pyrrole and decanal) and non-antagonistic (delta-hexalactone and ethanol) VOCs against Ph. infestans or putative plant growth stimulator compounds (acetoin and indole) were mainly emitted by Lysobacter type strains grown on protein- and sugar-rich media respectively. Thus nutrient availability under soil conditions could affect the aggressiveness of Lysobacter spp. and possibly optimise interactions of these bacterial species with the other soil inhabitants. Copyright © 2017 Elsevier GmbH. All rights reserved.

  2. Volatile compounds of some popular Mediterranean seafood species

    Directory of Open Access Journals (Sweden)

    I. GIOGIOS

    2013-06-01

    Full Text Available The volatile compounds of highly commercialised fresh Mediterranean seafood species, including seven fish (sand-smelt Atherina boyeri, picarel Spicara smaris, hake Merluccius merluccius, pilchard Sardina pilchardus, bogue Boobps boops, anchovy Engraulis encrasicolus and striped-mullet Mullus barbatus, squid (Loligo vulgaris, shrimp (Parapenaeus longirostris and mussel (Mytilus galloprovincialis, were evaluated by simultaneous steam distillation-extraction and subsequent GC-MS analysis. A total of 298 volatile compounds were detected. The mussels contained the highest total concentration of volatile compounds, while pilchard among fish species contained the highest number and concentrations of volatile compounds. Individual patterns of volatile compounds have been distinguished. The fish species when compared to the shellfish species studied, contained 6 to 30 times more 1-penten-3-ol, higher quantities of 2-ethylfuran, and 2,3-pentanedione, which was absent from the shellfish species. Pilchard is characterized by a high concentration of alcohols, shrimps by the high presence of amines and S-compounds, while mussels by high amounts of aldehydes, furans, and N-containing compounds (pyridine, pyrazines and pyrrols. The fatty acid-originating carbonyl compounds in fish seem to be related to the species’ fat content.

  3. Interactions between odorant functional group and hydrocarbon structure influence activity in glomerular response modules in the rat olfactory bulb.

    Science.gov (United States)

    Johnson, Brett A; Farahbod, Haleh; Leon, Michael

    2005-03-07

    To investigate the effect of odorant hydrocarbon structure on spatial representations in the olfactory bulb systematically, we exposed rats to odorant chemicals possessing one of four different oxygen-containing functional groups on one of five different hydrocarbon backbones. We also used several hydrocarbon odorants lacking other functional groups. Hydrocarbon structural categories included straight-chained, branched, double-bonded, alicyclic, and aromatic features. Activity throughout the entire glomerular layer was measured as uptake of [(14)C]2-deoxyglucose and was mapped into anatomically standardized data matrices for statistical comparisons across different animals. Patterns evoked by straight-chained aliphatic odorants confirmed an association of activity in particular glomerular response modules with particular functional groups. However, the amount of activity in these same modules also was affected significantly by differences in hydrocarbon structure. Thus, the molecular features recognized by receptors projecting to these response modules appear to involve both functional group and hydrocarbon structural elements. In addition, particular benzyl and cyclohexyl odorants evoked activity in dorsal modules previously associated with the ketone functional group, which represents an exception to the rule of one feature per response module that had emerged from our previous studies. These dorsal modules also responded to nitrogen-containing aromatic compounds involving pyridine and pyrazine rings. The unexpected overlap in modular responses to ketones and odorants seemingly unrelated to ketones may reflect some covert shared molecular feature, the existence of odorant sensory neurons with multiple specificities, or a mosaic of sensory neuron projections to these particular modules.

  4. Capsicum--production, technology, chemistry, and quality. Part III. Chemistry of the color, aroma, and pungency stimuli.

    Science.gov (United States)

    Govindarajan, V S

    1986-01-01

    The spice capsicum, the fruits of the genus Capsicum (Family Solanaceae), is a very popular food additive in many parts of the world, valued for the important sensory attributes of color, pungency, and aroma. A large number of varieties are widely cultivated and traded. The characteristic carotenoids of the bright red paprika and cayenne-type chillies, the high character impact aroma stimuli, the methoxy pyrazine of green bell capsicum, the esters of ripe tabasco and the highly potent pungency stimuli, and the capsaicinoids of African and other Asian varieties of chillies, have been of great interest to chemists and biochemists. Research workers in other disciplines such as genetics and breeding, agriculture, and technology have been interested in this spice to develop new varieties with combinations of different optimal levels of the stimuli for the sensory attributes and to maximize production of storable products for specific end uses. Physiologists have been intensely studying the action of the highly potent pungency stimuli and social psychologists the curious aspect of growing acceptance and preference for the initially unacceptable pungency sensation. In the sequential review of all these aspects of the fruit spice Capsicum, the earlier two parts covered history, botany, cultivation and primary processing, and processed products, standards, world production, and trade. In Part III, the chemistry, the compositional variations, synthesis and biosynthesis of the functional components, the carotenoids, the volatiles, and the capsaicinoids are comprehensively reviewed.

  5. Synthesis and application of novel ion-imprinted polymer coated magnetic multi-walled carbon nanotubes for selective solid phase extraction of lead(II) ions.

    Science.gov (United States)

    Fayazi, Maryam; Taher, Mohammad Ali; Afzali, Daryoush; Mostafavi, Ali; Ghanei-Motlagh, Masoud

    2016-03-01

    In this study, novel magnetic ion-imprinted polymer (MIIP) nanoparticles were utilized for the sensitive and selective detection of Pb(II) ions by graphite furnace atomic absorption spectrometry (GFAAS). The Pb(II)-imprinted polymer was synthesized by using 4-vinylpyridine (4VP) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as the cross-linker, 2,3,5,6-tetra(2-pyridyl) pyrazine (TPPZ) as the chelating agent and magnetic multi-walled carbon nanotubes (MMWCNTs) as the carrier. The synthesized MIIP materials were characterized by field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and vibrating sample magnetometer (VSM). Various analytical parameters such as extraction and desorption time, eluent type and concentration, pH and sample volume were systematically examined. The selectivity of MIIP sorbent for Pb(II) ions in the presence of some cations was also evaluated. The limit of detection (LOD, 3S(b)) and the relative standard deviation (RSD, n=8, c=25 ng L(-1)) were found to be 2.4 ng L(-1) and 5.6%, respectively. The maximum sorption capacity of the MIIP for Pb(II) was found to be 48.1 mg g(-1). Finally, the proposed analytical procedure was successfully applied to monitoring lead in human hair and water samples with satisfactory results for the spiked samples.

  6. Synthesis of new heterocyclic lupeol derivatives as nitric oxide and pro-inflammatory cytokine inhibitors.

    Science.gov (United States)

    Bhandari, Pamita; Patel, Neeraj Kumar; Bhutani, Kamlesh Kumar

    2014-08-01

    A series of heterocyclic derivatives including indoles, pyrazines along with oximes and esters were synthesized from lupeol and evaluated for anti-inflammatory activity through inhibition of lipopolysaccharide (LPS) induced nitric oxide (NO) production in RAW 264.7 and J774A.1 cells. All the synthesized molecules of lupeol were found to be more active in inhibiting NO production with an IC50 of 18.4-48.7 μM in both the cell lines when compared to the specific nitric oxide synthase (NOS) inhibitor, L-NAME (IC50=69.21 and 73.18 μM on RAW 264.7 and J774A.1 cells, respectively). The halogen substitution at phenyl ring of indole moiety leads to potent inhibition of NO production with half maximal concentration ranging from 18.4 to 41.7 μM. Furthermore, alkyl (11, 12) and p-bromo/iodo (15, 16) substituted compounds at a concentration of 20 μg/mL exhibited mild inhibition (29-42%) of LPS-induced tumor necrosis factor alpha (TNF-α) and weak inhibition (10-22%) towards interleukin 1-beta (IL-1β) production in both the cell lines. All the derivatives were found to be non-cytotoxic when tested at their IC50 (μM). These findings suggest that the derivatives of lupeol could be a lead to potent inhibitors of NO.

  7. Metal Dependence of Signal Transmission through MolecularQuantum-Dot Cellular Automata (QCA: A Theoretical Studyon Fe, Ru, and Os Mixed-Valence Complexes

    Directory of Open Access Journals (Sweden)

    Ken Tokunaga

    2010-08-01

    Full Text Available Dynamic behavior of signal transmission through metal complexes [L5M-BL-ML5]5+ (M=Fe, Ru, Os, BL=pyrazine (py, 4,4’-bipyridine (bpy, L=NH3, which are simplified models of the molecular quantum-dot cellular automata (molecular QCA, is discussed from the viewpoint of one-electron theory, density functional theory. It is found that for py complexes, the signal transmission time (tst is Fe(0.6 fs < Os(0.7 fs < Ru(1.1 fs and the signal amplitude (A is Fe(0.05 e < Os(0.06 e < Ru(0.10 e. For bpy complexes, tst and A are Fe(1.4 fs < Os(1.7 fs < Ru(2.5 fs and Os(0.11 e < Ru(0.12 e

  8. Spin-flop transition accompanied with changing the type of magnetic ordering

    Science.gov (United States)

    Syromyatnikov, A. V.

    2017-03-01

    We discuss theoretically rather rear example of spin-flop transition which is accompanied with changing the type of magnetic ordering and which seemingly has not been addressed yet. We demonstrate that changing the type of magnetic ordering can manifest itself in antiferromagnetic (AF) resonance experiments as an apparent peculiar switching of the anisotropy at the transition from the easy-axis type to the easy-plane one. We argue that this kind of spin-flop transition is observed recently by Povarov et al. (2013) [12] in Cu(pz)2(ClO4)2 (where pz denotes pyrazine), one of the best realizations of spin-1/2 Heisenberg AFs on square lattice having a very small anisotropy. We show that the magnetic ordering changes at the spin-flop transition in this material in the direction perpendicular to AF square planes. We examine the microscopic mechanism of such behavior in Cu(pz)2(ClO4)2 and find that dipolar forces and extremely small exchange coupling between spins from neighboring planes are responsible for it.

  9. Angular Dependence of Ionization by Circularly Polarized Light Calculated with Time-Dependent Configuration Interaction with an Absorbing Potential.

    Science.gov (United States)

    Hoerner, Paul; Schlegel, H Bernhard

    2017-02-16

    The angular dependence of ionization by linear and circularly polarized light has been examined for N2, NH3, H2O, CO2, CH2O, pyrazine, methyloxirane, and vinyloxirane. Time-dependent configuration interaction with single excitations and a complex absorbing potential was used to simulate ionization by a seven cycle 800 nm cosine squared pulse with intensities ranging from 0.56 × 10(14) to 5.05 × 10(14) W cm(-2). The shapes of the ionization yield for linearly polarized light can be understood primarily in terms of the nodal structure of the highest occupied orbitals. Depending on the orbital energies, ionization from lower-lying orbitals may also make significant contributions to the shapes. The shapes of the ionization yield for circularly polarized light can be readily explained in terms of the shapes for linearly polarized light. Averaging the results for linear polarization over orientations perpendicular to the direction of propagation yields shapes that are in very good agreement with direct calculations of the ionization yield by circularly polarized light.

  10. Quality and flavour stability of coffee substitute prepared by extrusion of wheat germ and chicory roots.

    Science.gov (United States)

    Fadel, H H M; Abdel Mageed, M A; Lotfy, S N

    2008-02-01

    A mixture of roasted chicory roots and wheat germ (1:1 w/w) was subjected to extrusion processing for preparation of coffee substitute. Comparative studies concerning sensory characteristics and headspace volatiles were carried out between genuine coffee and a freshly prepared coffee substitute. The sensory evaluation revealed similarities between the two samples. The comparative odour profile analysis showed that the sweetish/caramel-like note scored higher in our coffee substitute sample than in real coffee, whereas the other odour quality attributes showed an opposite trend. The high quality of the fresh coffee substitute was correlated to the presence of volatiles that are responsible for the fresh coffee aroma, such as: 2-methylbutanal, 3-methylbutanal, 2-methylfuran and 2,3-butanedione in high concentration. Storage of coffee substitute samples revealed a noticeable decrease in concentration of the Strecker aldehydes and diketones and a remarkable increase in phenolic compounds, whereas pyrazine and furan derivatives showed no linear changes during storage. The ratio of 2,3-butanedione/2-methylfuran (B/M) was used as an indicator for aging of coffee substitute samples. The variation in this ratio (B/M) during storage for 6 months was consistent with that of the odour profile analysis.

  11. Theoretical Study on the Structures and Properties of Hydrogen Bonding Complexes between Diazines and Water

    Institute of Scientific and Technical Information of China (English)

    LI, Quan; HUANG, Fang-Qian; HU, Jing-Dan; ZHAO, Ke-Qing

    2006-01-01

    Density functional theory B3LYP method and second-order Moller-Plesset perturbation theory MP2 method were employed to obtain the optimized geometries of the ground state and interaction energy for diazines and water complexes. The results show that the ground state complexes have strong hydrogen bonding interaction with -20.99,- 16.73 and - 15.31 kJ/mol after basis set superposition error and zero-point vibration energy correction for pyridazine-water, pyrimidine-water and pyrazine-water, respectively, and large red-shift for the symmetric H-O stretching vibration frequencies due to the formation of N…H-O hydrogen bond in the diazine-water complexes.The NBO analysis indicates that intermolecular charge transfer are 0.0316, 0.0255 and 0.0265 e respectively. In addition, the first singlet (n,π*) vertical excitation energy of the monomer and the hydrogen bonding complexes between diazines and water was investigated by time-dependent density functional theory.

  12. Frog volatile compounds: application of in vivo SPME for the characterization of the odorous secretions from two species of Hypsiboas treefrogs.

    Science.gov (United States)

    Brunetti, Andrés E; Merib, Josias; Carasek, Eduardo; Caramão, Elina B; Barbará, Janaina; Zini, Claudia A; Faivovich, Julián

    2015-04-01

    A novel in vivo design was used in combination with solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) to characterize the volatile compounds from the skin secretion of two species of tree frogs. Conventional SPME-GC/MS also was used for the analysis of volatiles present in skin samples and for the analysis of volatiles present in the diet and terraria. In total, 40 and 37 compounds were identified in the secretion of Hypsiboas pulchellus and H. riojanus, respectively, of which, 35 were common to both species. Aliphatic aldehydes, a low molecular weight alkadiene, an aromatic alcohol, and other aromatics, ketones, a methoxy pyrazine, sulfur containing compounds, and hemiterpenes are reported here for the first time in anurans. Most of the aliphatic compounds seem to be biosynthesized by the frogs following different metabolic pathways, whereas aromatics and monoterpenes are most likely sequestered from environmental sources. The characteristic smell of the secretion of H. pulchellus described by herpetologists as skunk-like or herbaceous is explained by a complex blend of different odoriferous components. The possible role of the volatiles found in H. pulchellus and H. riojanus is discussed in the context of previous hypotheses about the biological function of volatile secretions in frogs (e.g., sex pheromones, defense secretions against predators, mosquito repellents).

  13. Mutagenic and physiological responses in the juveniles of African catfish, Clarias gariepinus (Burchell 1822) following short term exposure to praziquantel.

    Science.gov (United States)

    Nwani, Christopher Dididgwu; Nnaji, Macniel Chijioke; Oluah, Stanley Ndubuisi; Echi, Paul Chinedu; Nwamba, Helen Ogochukwu; Ikwuagwu, Ogbonnaya Egbe; Ajima, Malachy Nwigwe Okechukwu

    2014-08-01

    Praziquantel (PZQ) is an acylated quinoline-pyrazine originally developed for veterinary application but now one of the most used anti-helminthic drugs for treatment of certain trematodes and cestodes in both human and other animals. The present study investigated the mutagenic and physiological responses in the juveniles of African catfish, Clarias gariepinus following short term exposure to praziquantel. Based on the 53.52 mg/l 96 h LC50 of PZQ obtained, two sublethal concentrations of 5.35 and 10.70 mg/l of the drug were selected and fish were exposed to these concentrations and control for 15 days. Micronuclei induction in the peripheral blood of PZQ-exposed fish was highest on day 10 but the fish morphological parameters were not affected. The packed cell volume (PCV) was significantly reduced (p0.05) from the control. Alanine aminotransferase (ALT), aspartate aminotransferase (AST) and glucose levels significantly increased while protein reduced (p<0.05) throughout the exposure period but a mixed trend was observed in the leukocyte differentials. PZQ should be used with caution as sublethal exposure elicited micronucleus induction and alterations of hematological and biochemical parameters in the fish.

  14. Ladderlike oligomers; intramolecular hydrogen bonding, push-pull character, and electron affinity.

    Science.gov (United States)

    Pieterse, K; Vekemans, J A; Kooijman, H; Spek, A L; Meijer, E W

    2000-12-15

    Symmetrical 2,5-bis(2-aminophenyl)pyrazines have been synthesized by application of the Stille coupling strategy. These cotrimers feature three important properties, namely strong intramolecular hydrogen bonding, push-pull character, and high electron affinity. The presence of intramolecular hydrogen bonds has been confirmed by 1H NMR, IR spectroscopy, and single-crystal X-ray diffraction. The hydrogen bond strength can be increased by substituting the amino groups with stronger electron-withdrawing functionalities. Despite the anticipated enhanced pi-conjugation through planarization, a hypsochromic shift was observed in the UV/Vis spectra, explained by a decrease in push-pull character. The electron affinity of the cotrimers was deduced from the first reduction potentials measured by cyclic voltammetry and is related to the electron-withdrawing character of the amino substituents. The results obtained have been compared with those of the corresponding 4-aminophenyl analogues and show that intramolecular hydrogen bonds can be used to design polymers with enhanced pi conjugation as well as a high electron affinity.

  15. Supramolecular architectures constructed using angular bipyridyl ligands

    CERN Document Server

    Barnett, S A

    2003-01-01

    This work details the synthesis and characterization of a series of coordination frameworks that are formed using bidentate angular N-donor ligands. Pyrimidine was reacted with metal(ll) nitrate salts. Reactions using Cd(NO sub 3) sub 2 receive particular focus and the analogous reactions using the linear ligand, pyrazine, were studied for comparison. In all cases, two-dimensional coordination networks were prepared. Structural diversity is observed for the Cd(ll) centres including metal-nitrate bridging. In contrast, first row transition metal nitrates form isostructural one-dimensional chains with only the bridging N-donor ligands generating polymeric propagation. The angular ligand, 2,4-bis(4-pyridyl)-1,3,5-triazine (dpt), was reacted with Cd(NO sub 3) sub 2 and Zn(NO sub 3) sub 2. Whereas Zn(NO sub 3) sub 2 compounds exhibit solvent mediated polymorphism, a range of structures were obtained for the reactions with Cd(NO sub 3) sub 2 , including the first example of a doubly parallel interpenetrated 4.8 sup...

  16. Search for greener Li-ion batteries: an alternative offered by organic electroactive materials

    Science.gov (United States)

    Geng, Joaquin; Renault, Stéven; Poizot, Philippe; Dolhem, Franck

    2011-06-01

    The threats of climate change and the issues of secure energy supply are among the fundamental challenges of the 21stcentury that push humanity to adopt a sustainable development and to favour the use of renewable sources of energy. In addition to their historical use, LIBs seem on the road to power the next "Zero Emission" vehicles or could be used to assist the integration of renewable energy sources both on- and off-the-grid. Consequently, production of LIBs is expected to keep on growing. However LIBs are nearly exclusively based on inorganic compounds, non-renewable and energy-greedy materials. Thus in parallel with regular research on inorganic-based LIBs, we have recently proposed to probe an alternative pathway by searching for redox-active organic materials, easier to discard while possibly derived from biomass resources. As solid-state electrochemistry of organics is not that well documented, our current approach consists in a global survey of selected organic structures in order to grasp relevant parameters that affect the redox potential, the stability upon cycling and so on. In this report, we extend our current database of redox-active organic structures by evaluating vs. Li bulky pyrazine-based structures and dilithium polyporate as a supplementary specimen of p-benzoquinone derivatives.

  17. Bioactive Metabolites Produced by Pseudonocardia endophytica VUK-10 from Mangrove Sediments: Isolation, Chemical Structure Determination and Bioactivity.

    Science.gov (United States)

    Mangamuri, Usha Kiranmayi; Vijayalakshmi, Muvva; Poda, Sudhakar; Manavathi, Bramanandam; Bhujangarao, Ch; Venkateswarlu, Y

    2015-05-01

    Chemical investigation of the actinobacterial isolate Pseudonocardia endophytica VUK-10 has led to the segregation of two known bioactive compounds, namely 4-(2-acetamidoethyl) phenyl acetate and 4-((1, 4-dioxooctahydropyrrolo [1, 2-a] pyrazin-3-yl) methyl) phenyl acetate. The strain was isolated from a sediment sample of the Nizampatnam mangrove ecosystem, south coastal Andhra Pradesh, India. The chemical structure of the active compounds was established on the basis of spectroscopic analysis, including (1)H NMR and (13)C NMR spectroscopies, FTIR, and EIMS. The antimicrobial and cytotoxic activities of the bioactive compounds produced by the strain were tested against opportunistic and pathogenic bacteria and fungi and on MDA-MB-231, OAW, HeLa, and MCF-7 cell lines. The compounds exhibited antimicrobial activities against gram-positive and gram-negative bacteria and fungi and also showed potent cytotoxic activity against MDA-MB-231, OAW, HeLa, and MCF-7 cell lines. This is the first example for this class of bioactive compounds isolated from Pseudonocardia of mangrove origin.

  18. Thioetherification of chloroheteroarenes: a binuclear catalyst promotes wide scope and high functional-group tolerance.

    Science.gov (United States)

    Platon, Mélanie; Wijaya, Novi; Rampazzi, Vincent; Cui, Luchao; Rousselin, Yoann; Saeys, Mark; Hierso, Jean-Cyrille

    2014-09-22

    A constrained binuclear palladium catalyst system affords selective thioetherification of a wide range of functionalized arenethiols with chloroheteroaromatic partners with the highest turnover numbers (TONs) reported to date and tolerates a large variety of reactive functions. The scope of this system includes the coupling of thiophenols with six- and five-membered 2-chloroheteroarenes (i.e., functionalized pyridine, pyrazine, quinoline, pyrimidine, furane, and thiazole) and 3-bromoheteroarenes (i.e., pyridine and furane). Electron-rich congested thiophenols and fluorinated thiophenols are also suitable partners. The coupling of unprotected amino-2-chloropyridines with thiophenol and the successful employment of synthetically valuable chlorothiophenols are described with the same catalyst system. DFT studies attribute the high performance of this binuclear palladium catalyst to the decreased stability of thiolate-containing resting states. Palladium loading was as low as 0.2 mol %, which is important for industrial application and is a step forward in solving catalyst activation/deactivation problems. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Low bandgap polymers synthesized by FeCl{sub 3} oxidative polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Cai, Tianqi [Materials and Surface Chemistry/Polymer Technology, Chalmers University of Technology, SE-412 96 Goeteborg (Sweden); School of Materials Science and Engineering, East China University of Science and Technology, Meilong Road 130, 200237 Shanghai (China); Zhou, Yi; Zhang, Fengling; Inganaes, Olle [Biomolecular and Organic Electronics, IFM, and Centre of Organic Electronics, Linkoeping University, SE-581 83 Linkoeping (Sweden); Wang, Ergang; Hellstroem, Stefan [Materials and Surface Chemistry/Polymer Technology, Chalmers University of Technology, SE-412 96 Goeteborg (Sweden); Xu, Shiai [School of Materials Science and Engineering, East China University of Science and Technology, Meilong Road 130, 200237 Shanghai (China); Andersson, Mats R. [Materials and Surface Chemistry/Polymer Technology, Chalmers University of Technology, SE-412 96 Goeteborg (Sweden); Biomolecular and Organic Electronics, IFM, and Centre of Organic Electronics, Linkoeping University, SE-581 83 Linkoeping (Sweden)

    2010-07-15

    Four low bandgap polymers, combining an alkyl thiophene donor with benzo[c][1,2,5]thiadiazole, 2,3-diphenylquinoxaline, 2,3-diphenylthieno[3,4-b]pyrazine and 6,7-diphenyl-[1,2,5]thiadiazolo[3,4-g]quinoxaline acceptors in a donor-acceptor-donor architecture, were synthesized via FeCl{sub 3} oxidative polymerization. The molecular weights of the polymers were improved by introducing o-dichlorobenzene (ODCB) as the reaction solvent instead of the commonly used solvent, chloroform. The photophysical, electrochemical and photovoltaic properties of the resulting polymers were investigated and compared. The optical bandgaps of the polymers vary between 1.0 and 1.9 eV, which is promising for solar cells. The devices spin-coated from an ODCB solution of P1DB:[70]PCBM showed a power conversion efficiency of 1.08% with an open-circuit voltage of 0.91 V and a short-circuit current density of 3.36 mA cm{sup -2} under irradiation from an AM1.5G solar simulator (100 mW cm{sup -2}). (author)

  20. Metallo-porphyrazines with eight [5-thiopentyl 3,4,5-tris(benzyloxy)benzoate] groups: Synthesis, characterization, aggregation, and solubility behavior

    Science.gov (United States)

    Gonca, Ergün

    2017-02-01

    Metal-free and metallo-porphyrazines having eight 5-hydroxypentylthio units at the peripheral positions have been prepared from 2,3-bis(5-hydroxypentylthio)maleonitrile. By the esterification reaction of magnesium hydroxy-porphyrazine with 3,4,5-tris(benzyloxy)benzoic acid in dicyclohexylcarbodiimide and toluene-p-sulfonic acid, the reactivity of the hydroxypentyl units was indicated. On the other hand, iron porphyrazine derivatives with eight [5-thiopentyl 3,4,5-tris(benzyloxy)benzoate] groups attached to the periphery positions were synthesized. By the reaction of metal-free porphyrazine with iron (II) acetate and further processing with HCl solution, FePzCl was obtained. Finally, by reacting FePzCl with pyridine or pyrazine, [FePz(py)2] and [FePz(pyz)]n complexes were prepared, respectively. The characterizations of target complexes were carried out by utilizing different spectroscopic methods such as FT-IR, UV-vis, mass, 1H NMR, and 13C NMR together with elemental analysis.

  1. Simulation study on the effects of chemical structure and molecular size on the acceptor strength in poly(3-hexylthiophene)-based copolymer with alternating donor and acceptor for photovoltaic applications

    Science.gov (United States)

    Rassamesard, Areefen; Pengpan, Teparksorn

    2017-02-01

    This research assessed the effects of various chemical structures and molecular sizes on the simulated geometric parameters, electron structures, and spectroscopic properties of single-chain complex alternating donor-acceptor (D-A) monomers and copolymers that are intended for use as photoactive layer in a polymer solar cell by using Kohn-Sham density functional theory with B3LYP exchange-correlation functional. The 3-hexylthiophene (3HT) was selected for electron donor, while eight chemicals, namely thiazole (Z), thiadiazole (D), thienopyrazine (TP), thienothiadiazole (TD), benzothiadiazole (BT), thiadiazolothieno-pyrazine (TPD), oxadiazole (OXD) and 5-diphenyl-1,2,4-triazole (TAZ), were employed as electron acceptor functional groups. The torsional angle, bridge bond length, intramolecular charge transfer, energy levels, and molecular orbitals were analyzed. The simulation results reveal that the geometry and electron structure of donor-acceptor monomer and copolymer are significantly impacted by heterocyclic rings, heteroatoms, fused rings, degree of steric hindrance and coplanarity of the acceptor molecular structure. Planar conformation was obtained from the D copolymer, and a pseudo-planar structure with the TD copolymer. The TAZ acceptor exhibited strong steric hindrance due to its bulky structure and non-planarity of its structure. An analysis of the electron structures indicated that the degree of intramolecular electron-withdrawing capability had the rank order TAZ  group provides a compromise in the characteristics of a donor-acceptor copolymer, useful in a polymeric candidate material for the photoactive layer in a polymer solar cell.

  2. Electrogenerated chemiluminescent behavior of MCLA at an indium-tin-oxide electrode

    Energy Technology Data Exchange (ETDEWEB)

    Chen Zhihuang [MOE Key Laboratory of Analysis and Detection Technology for Food Safety, and Department of Chemistry, Fuzhou University, Fuzhou, Fujian 350002 (China); Wang Jian [MOE Key Laboratory of Analysis and Detection Technology for Food Safety, and Department of Chemistry, Fuzhou University, Fuzhou, Fujian 350002 (China); Lin Zhengyu [MOE Key Laboratory of Analysis and Detection Technology for Food Safety, and Department of Chemistry, Fuzhou University, Fuzhou, Fujian 350002 (China); Chen Guonan [MOE Key Laboratory of Analysis and Detection Technology for Food Safety, and Department of Chemistry, Fuzhou University, Fuzhou, Fujian 350002 (China)]. E-mail: gnchen@fzu.edu.cn

    2006-08-15

    In this paper, the electrogenerated chemiluminescence (ECL) behavior of 6-(4-methoxyphenyl)-2-methylimidazo[1,2-a]pyrazin-3(7H)-one (MCLA) at an indium-tin-oxide (ITO) electrode in phosphate buffer solution has been investigated when linear sweep voltammetry was applied. The optimum chemical conditions and electrochemical parameters for this ECL system have been investigated in detail. Under the optimum conditions, it was found that the ECL intensity was linear with the concentration of MCLA in the range of 6.0 x 10{sup -7} to 1.0 x 10{sup -5} mol/L, and its detection limit for MCLA was 2.0 x 10{sup -7} mol/L. The possible mechanism for ECL of MCLA at the ITO electrode was also discussion. Furthermore, it was found that some sophora flavescens, such as matrine and oxymatrine, might enhance the ECL intensity of MCLA. Therefore, it is possible to develop a new ECL method for determination of matrine and oxymatrine.

  3. Investigating the Variation of Volatile Compound Composition in Maotai-Flavoured Liquor During Its Multiple Fermentation Steps Using Statistical Methods

    Directory of Open Access Journals (Sweden)

    Zheng-Yun Wu

    2016-01-01

    Full Text Available The use of multiple fermentations is one of the most specific characteristics of Maotai-flavoured liquor production. In this research, the variation of volatile composition of Maotai-flavoured liquor during its multiple fermentations is investigated using statistical approaches. Cluster analysis shows that the obtained samples are grouped mainly according to the fermentation steps rather than the distillery they originate from, and the samples from the first two fermentation steps show the greatest difference, suggesting that multiple fermentation and distillation steps result in the end in similar volatile composition of the liquor. Back-propagation neural network (BNN models were developed that satisfactorily predict the number of fermentation steps and the organoleptic evaluation scores of liquor samples from their volatile compositions. Mean impact value (MIV analysis shows that ethyl lactate, furfural and some high-boiling-point acids play important roles, while pyrazine contributes much less to the improvement of the flavour and taste of Maotai-flavoured liquor during its production. This study contributes to further understanding of the mechanisms of Maotai-flavoured liquor production.

  4. Volatile composition of Catharanthus roseus (L.) G. Don using solid-phase microextraction and gas chromatography/mass spectrometry.

    Science.gov (United States)

    De Pinho, P Guedes; Gonçalves, Rui F; Valentão, Patrícia; Pereira, David M; Seabra, Rosa M; Andrade, Paula B; Sottomayor, Mariana

    2009-04-05

    A total of 88 volatile and semi-volatile components were formally or tentatively identified in flowers, leaves and stems of Catharanthus roseus (L.) G. Don (cv. Little Bright Eye), by headspace solid-phase microextraction (HS-SPME) and by dichloromethane extraction, combined with gas chromatography-mass spectrometry (GC-MS). These include some diterpenic compounds (manool and manoyl oxides), a sesquiterpen (alpha-bisabolol), and some pyridine, pyrazine, indol and carotenoid derivatives. Applying multivariate analysis (principal component analysis and agglomerative hierarchic cluster analysis) to the HS-SPME-GC-MS data, it was possible to characterize each part of the vegetal material using a relative small number of compounds. Hence, flowers were richer in terpenic molecules (including limonene), alpha-bisabolol, methyljasmonate, cis-jasmone, 2-phenylethanol, phenylacetaldehyde, trans-2-octenal, benzylic alcohol and 2-isobutyl-3-methoxypyrazine. Leaves can be characterized by the methyl and propyl esters of fatty acids, mono- and disaturated, trans-phytol, carotenoid derivative compounds, hydrofarnesylacetone, methylanthranilate, manool and epi-manool oxide, while stems have high levels of volatile aldehydes, such as hexanal, octanal, cis-2-nonenal, cis-2-decenal, cis, trans-2,6-nonadienal, trans, trans-2,4-decadienal and cis, trans-2,4-decadienal. Dichloromethane extraction allowed also the identification of some alkaloid-like compounds that were not detected by HS-SPME.

  5. Theoretical modeling of spin crossover in metal-organic frameworks: [Fe(pz)2Pt(CN)4] as a case study.

    Science.gov (United States)

    Cirera, Jordi; Babin, Volodymyr; Paesani, Francesco

    2014-10-20

    Metal-organic frameworks (MOFs) with spin-crossover behavior are promising materials for applications in memory storage and sensing devices. A key parameter that characterizes these materials is the transition temperature T1/2, defined as the temperature with equal populations of low-spin and high-spin species. In this study, we describe the development, implementation, and application of a novel hybrid Monte Carlo/molecular dynamics method that builds upon the Ligand Field Molecular Mechanics approach and enables the modeling of spin-crossover properties in bulk materials. The new methodology is applied to the study of a spin-crossover MOF with molecular formula [Fe(pz)2Pt(CN)4] (pz = pyrazine). The total magnetic moment of the material is determined as a function of the temperature from direct calculations of the relative equilibrium populations of both low-spin and high-spin states of each Fe(II) center of the framework. The T1/2 value, calculated from the temperature dependence of the magnetization curve, is in good agreement with the available experimental data. A comparison between the spin-crossover behavior of the isolated secondary building block of the framework and the bulk material is presented, which reveals the origin of the different spin-crossover properties of the isolated molecular system and corresponding MOF structure.

  6. Yeasts are essential for cocoa bean fermentation.

    Science.gov (United States)

    Ho, Van Thi Thuy; Zhao, Jian; Fleet, Graham

    2014-03-17

    Cocoa beans (Theobroma cacao) are the major raw material for chocolate production and fermentation of the beans is essential for the development of chocolate flavor precursors. In this study, a novel approach was used to determine the role of yeasts in cocoa fermentation and their contribution to chocolate quality. Cocoa bean fermentations were conducted with the addition of 200ppm Natamycin to inhibit the growth of yeasts, and the resultant microbial ecology and metabolism, bean chemistry and chocolate quality were compared with those of normal (control) fermentations. The yeasts Hanseniaspora guilliermondii, Pichia kudriavzevii and Kluyveromyces marxianus, the lactic acid bacteria Lactobacillus plantarum and Lactobacillus fermentum and the acetic acid bacteria Acetobacter pasteurianus and Gluconobacter frateurii were the major species found in the control fermentation. In fermentations with the presence of Natamycin, the same bacterial species grew but yeast growth was inhibited. Physical and chemical analyses showed that beans fermented without yeasts had increased shell content, lower production of ethanol, higher alcohols and esters throughout fermentation and lesser presence of pyrazines in the roasted product. Quality tests revealed that beans fermented without yeasts were purplish-violet in color and not fully brown, and chocolate prepared from these beans tasted more acid and lacked characteristic chocolate flavor. Beans fermented with yeast growth were fully brown in color and gave chocolate with typical characters which were clearly preferred by sensory panels. Our findings demonstrate that yeast growth and activity were essential for cocoa bean fermentation and the development of chocolate characteristics.

  7. Small-Molecule Inhibition and Activation-Loop Trans-Phosphorylation of the IGF1 Receptor

    Energy Technology Data Exchange (ETDEWEB)

    Wu,J.; Li, W.; Craddock, B.; Foreman, K.; Mulvihill, M.; Ji, Q.; Miller, W.; Hubbard, S.

    2008-01-01

    The insulin-like growth factor-1 receptor (IGF1R) is a receptor tyrosine kinase (RTK) that has a critical role in mitogenic signalling during embryogenesis and an antiapoptotic role in the survival and progression of many human tumours. Here, we present the crystal structure of the tyrosine kinase domain of IGF1R (IGF1RK), in its unphosphorylated state, in complex with a novel compound, cis-3-[3-(4-methyl-piperazin-l-yl)-cyclobutyl]-1-(2-phenyl-quinolin-7-yl)-imidazo[1, 5-a]pyrazin-8-ylamine (PQIP), which we show is a potent inhibitor of both the unphosphorylated (basal) and phosphorylated (activated) states of the kinase. PQIP interacts with residues in the ATP-binding pocket and in the activation loop, which confers specificity for IGF1RK and the highly related insulin receptor (IR) kinase. In this crystal structure, the IGF1RK active site is occupied by Tyr1135 from the activation loop of an symmetry (two-fold)-related molecule. This dimeric arrangement affords, for the first time, a visualization of the initial trans-phosphorylation event in the activation loop of an RTK, and provides a molecular rationale for a naturally occurring mutation in the activation loop of the IR that causes type II diabetes mellitus.

  8. Fecal volatile components elicit aggregation in the oriental migratory locust, Locusta migratoria manilensis (Orthoptera: Acrididae)

    Institute of Scientific and Technical Information of China (English)

    Wang-Peng Shi; Hong-Li Sun; Nyndat Edward; Yu-Hua Yan

    2011-01-01

    The aggregation components from fecal volatiles of the oriental migratory locust, Locusta migratoria manilensis were identified with gas chromatographic/electroantennographic detector (GC-EAD), GC-MS (mass spectrometry) analyses and behavioral bioassays. Both last instar nymphs and adults of the oriental migratory locust have similar aggregation pheromones in their volatiles. A total of 11 electrophysioiogically active compounds, namely, hexanal, cyclohexanol, heptanal, phenol, 2,5-dimethylpyrazine, benzyl alcohol, benzaldehyde, guaiacol, nonanal, 2,6,6-trimethyl-2-cyclohexene1,4-dione and decyl aldehyde were identified in the fecal volatiles of 2-day-old immature adult male locusts. Only hexanal, nonanal, benzaldehyde, cyclohexanol and 2,5-dimethylpyrazine elicited significant aggregation responses in immature 2-day-old adult males.However, adult males had significantly lower behavioral responses to synthetics of five single compounds than the blend of cyclohexanol, 2,5-dimethyl-pyrazine, benzaldehyde,nonanal, hexanal in ratios of 100 : 100 : 2 : 60 : 30 in the range of 30-60 μg/mL. We propose that it is the blend of these five compounds that plays a key role in eliciting and sustaining aggregation in gregarious oriental migratory locusts. These results also showed that the aggregation pheromones of the oriental migratory locust are significantly different from those found in the desert locust.

  9. Volatile components of the frying process

    Directory of Open Access Journals (Sweden)

    Nawar, W. W.

    1998-08-01

    Full Text Available In the course of deep fat frying, food contacts oil at about 180 °C and is partially exposed to air for various periods of time. Thus frying, more than any other standard food process or handling method, has the greatest potential for causing chemical changes in fat, and sizeable amounts of this fat are carried with the food (5-40% fat by weight is absorbed. During frying, oxidative reactions involving the formation and decomposition of hydroperoxides lead to such compounds as saturated and unsaturated aldehydes, ketones, hydrocarbons, lactones, alcohols, acids and esters. Sulfur compounds and pyrazine derivatives may develop in the food itself or from the interactions between the food and oil. Food absorbs varying amounts of oil during deep-fat frying (potato chips have a final fat content of about 35%. The food itself can release some of its endogenous lipids (e.g., fat from chicken into the frying fat and consequently the oxidative stability of the new mixture may be different from that of the original frying fat. The changes that occur in the oil and food during frying should not be automatically construed as undesirable or harmful. In fact, some of these changes are necessary to provide the sensory qualities typical of fried food. On the other hand, extensive decomposition, resulting from lack of adequate control of the frying operation, can be a potential source of damage not only to sensory quality of the fried food but also to nutritional value.

  10. Volatile compounds of some popular Mediterranean seafood species

    Directory of Open Access Journals (Sweden)

    I. GIOGIOS

    2013-07-01

    Full Text Available The volatile compounds of highly commercialised fresh Mediterranean seafood species, including seven fish (sand-smelt Atherina boyeri, picarel Spicara smaris, hake Merluccius merluccius, pilchard Sardina pilchardus, bogue Boobps boops, anchovy Engraulis encrasicolus and striped-mullet Mullus barbatus, squid (Loligo vulgaris, shrimp (Parapenaeus longirostris and mussel (Mytilus galloprovincialis, were evaluated by simultaneous steam distillation-extraction and subsequent GC-MS analysis. A total of 298 volatile compounds were detected. The mussels contained the highest total concentration of volatile compounds, while pilchard among fish species contained the highest number and concentrations of volatile compounds. Individual patterns of volatile compounds have been distinguished. The fish species when compared to the shellfish species studied, contained 6 to 30 times more 1-penten-3-ol, higher quantities of 2-ethylfuran, and 2,3-pentanedione, which was absent from the shellfish species. Pilchard is characterized by a high concentration of alcohols, shrimps by the high presence of amines and S-compounds, while mussels by high amounts of aldehydes, furans, and N-containing compounds (pyridine, pyrazines and pyrrols. The fatty acid-originating carbonyl compounds in fish seem to be related to the species’ fat content.

  11. Design of a flexible organometallic tecton: host-guest chemistry with picric acid and self-assembly of platinum macrocycles.

    Science.gov (United States)

    Jana, Achintya; Bhowmick, Sourav; Kaur, Supreet; Kashyap, Hemant K; Das, Neeladri

    2017-02-14

    The synthesis and characterization of a new pyrazine-based "flexible" and ditopic platinum(ii) organometallic molecule (3) is being reported. Flexibility in this molecule is due to the presence of ether functional groups that bridge the rigid core and periphery. Due to the presence of square planar Pt(ii) centers at the two ends, the molecule's potential to act as an acceptor building block in the construction of metallamacrocycles was tested. Upon reaction of 3 with various dicarboxylates in a 1 : 1 stoichiometric ratio, [2 + 2] self-assembled neutral metallacycles (M1-M3) were obtained in high yields. M1-M3 were characterized using multinuclear NMR, high resolution mass spectrometry and elemental analyses. The shape and dimensions of these supramolecular structures were also confirmed by optimizing the geometry using the density functional theory (DFT) approach. Computational studies suggest that M1-M3 are nanoscalar macrocyles. Furthermore, using isothermal titration calorimetry (ITC), it was shown that 3 can bind with picric acid (PA) to yield a 3·(PA)2 host-guest complex. The magnitude of the binding constant indicates that 3 has significant affinity for PA.

  12. Thermochemistry of Alane Complexes for Hydrogen Storage: A Theoretical and Experimental Comparison

    CERN Document Server

    Wong, Bryan M; Nielsen, Ida M B; Graetz, Jason; Allendorf, Mark D; 10.1021/jp112258s

    2011-01-01

    Knowledge of the relative stabilities of alane (AlH3) complexes with electron donors is essential for identifying hydrogen storage materials for vehicular applications that can be regenerated by off-board methods; however, almost no thermodynamic data are available to make this assessment. To fill this gap, we employed the G4(MP2) method to determine heats of formation, entropies, and Gibbs free energies of formation for thirty-eight alane complexes with NH3-nRn (R = Me, Et; n = 0-3), pyridine, pyrazine, triethylenediamine (TEDA), quinuclidine, OH2-nRn (R = Me, Et; n = 0-2), dioxane, and tetrahydrofuran (THF). Monomer, bis, and selected dimer complex geometries were considered. Using these data, we computed the thermodynamics of the key formation and dehydrogenation reactions that would occur during hydrogen delivery and alane regeneration, from which trends in complex stability were identified. These predictions were tested by synthesizing six amine-alane complexes involving trimethylamine, triethylamine, di...

  13. Variation in the chemical composition of cone volatiles within the African cycad genus Encephalartos.

    Science.gov (United States)

    Suinyuy, Terence N; Donaldson, John S; Johnson, Steven D

    2013-01-01

    Volatiles play a key role in attraction of pollinators to cycad cones, but the extent to which volatile chemistry varies among cycad species is still poorly documented. Volatile composition of male and female cones of nineteen African cycad species (Encephalartos; Zamiaceae) was analysed using headspace technique and gas chromatography-mass spectrometry (GC-MS). A total of 152 compounds were identified among the species included in this study, the most common of which were monoterpenes, nitrogen-containing compounds and unsaturated hydrocarbons. Male and female cones emitted similar volatile compounds which varied in relative amounts with two unsaturated hydrocarbons (3E)-1,3-octadiene and (3E,5Z)-1,3,5-octatriene present in the volatile profile of most species. In a multivariate analysis of volatile profiles using non-metric multidimensional scaling (NMDS), a number of species clusters were identified according to shared emission of unsaturated hydrocarbons, pyrazines, benzenoids, aldehydes, alkanes and terpenoids. In comparison, terpenoids are common in Zamia and dominant in Macrozamia species (both in the family Zamiaceae) while benzenoids, esters, and alcohols are dominant in Cycas (Cycadaceae) and in Stangeria (Stangeriaceae). It is likely that volatile variation among Encephalartos species reflects both phylogeny and adaptations to specific beetle pollinators.

  14. Linear hexanuclear nickel complexes with rich electrochemical features and facility to reduction

    Science.gov (United States)

    Wang, Wen-Zhen; Zhao, Dan; Zhao, Meng-Jiao; Li, Haoyong; Liu, Shuang; Ismayilov, Rayyat H.; Lee, Gene-Hsiang; Peng, Shie-Ming

    2017-02-01

    Two novel linear hexanuclear nickel complexes [Ni6(μ6-dpznda)4Cl2](PF6)2(1) and [Ni6(μ6-dpznda)4(NCS)2](PF6)2(2) (H2dpznda = N2,N7-di(pyrazin-2-yl)-1,8-naphthyridine-2,7-diamine) were synthesized and structurally characterized. Both the two complexes consist of a linear metal chain and four supporting ligands which are helically wrapped around the metal core. The single crystal X-ray structural analysis showed that the complex 1 belonged to rhombohedral system, space group R-3 with a = b = 34.2051(8), c = 20.7751(5) Å, V = 21050.2(9) Å3 and Z = 9. Direct-current magnetic susceptibility measurements showed weak antiferromagnetic interactions with coupling parameters of g = 2.04 and J = -8.27 cm-1 for 1 and g = 2.02 and J = -12.62 cm-1 for 2, respectively (Ĥ = -JŜ1Ŝ2, S1 = S2 = 1). The decrease of magnetic moments at low temperature was partly attributed to ZFS. The electrochemical study on complex 1 shows rich features and facility to reduction in its cyclic voltammogram by displaying four reversible redox couples at E1/2 = +0.01, -0.29, -0.64 and -0.73 V (vs. Ag/AgCl).

  15. Antimicrobial activities of secondary metabolites and phylogenetic study of sponge endosymbiotic bacteria, Bacillus sp. at Agatti Island, Lakshadweep Archipelago

    Directory of Open Access Journals (Sweden)

    Gopi Mohan

    2016-09-01

    Full Text Available Twenty-one species of sponges were recorded under the class of Demospongiae and Calcareous sponges of which 19 species were new to Agatti reef. A total of 113 Sponge endosymbiotic bacterial strains were isolated from twenty-one species of sponges and screened for antimicrobial activity. Five bacterial strains of sponge endosymbiotic bacteria (SEB namely SEB32, SEB33, SEB36, SEB43 and SEB51 showed antimicrobial activity against virulent marine fish pathogens such as Vibrio alginolyticus, Vibrio vulnificus, Vibrio parahaemolyticus, Aeromonas salmonicida, Flavobacterium sp., Edwardsiella sp., Proteus mirabilis and Citrobacter brackii. The secondary metabolites produced by SEB32 from sponge Dysidea fragilis (Montagu, 1818 [48] was selected with broad range of antibacterial activity and subjected for production, characterization by series of chromatography techniques and spectroscopic methods. Based on the results of FT-IR and mass spectrometry, the active molecule was tentatively predicted as “Pyrrol” and the structure is Pyrrolo[1,2-a]pyrazine-1,4-dione, hexahydro- with molecular formula of C7H10N2O2. The LC50 of active molecule was 31 μg/ml and molecular weight of the metabolites was 154. The potential strain SEB32 was identified by gene sequence (GenBank Accession number JX985748 and identified as Bacillus sp. from GenBank database.

  16. EXPERIMENTAL AND COMPUTATIONAL STUDIES OF THE FORMATION MECHANISM OF PROTONATED INTERSTELLAR DIAZINES

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhe-Chen; Cole, Callie A.; Bierbaum, Veronica M. [Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309 (United States); Snow, Theodore P., E-mail: zhwa4666@colorado.edu [Department of Astrophysical and Planetary Sciences, University of Colorado, Boulder, CO 80309 (United States)

    2015-01-10

    Studies of interstellar chemistry have grown in number and complexity by both observations and laboratory measurements, and nitrogen-containing aromatics have been implicated as important interstellar molecules. In this paper, the gas-phase collision induced dissociation (CID) processes of protonated pyridazine (1,2-diazine), pyrimidine (1,3-diazine), and pyrazine (1,4-diazine) cations (C{sub 4}H{sub 5}N{sub 2} {sup +}) are investigated in detail both experimentally and theoretically. The major neutral loss for all three CID processes is HCN, leading to the formation of C{sub 3}H{sub 4}N{sup +} isomers; our density functional theory (DFT) calculations support and elucidate our experimental results. The formation of C{sub 3}H{sub 4}N{sup +} isomers from the reaction of abundant interstellar acrylonitrile (CH{sub 2}CHCN) and H{sup +}is also studied employing DFT calculations. Our results lead to a novel mechanism for interstellar protonated diazine formation from the consecutive reactions of CH{sub 2}CHCN+ H{sup +} + HCN. Moreover, our results motivate the continuing search for interstellar C{sub 3}H{sub 4}N{sup +} isomers as well as polycyclic aromatic N-containing hydrocarbons (PANHs)

  17. Theoretical assessment of the elastic constants and hydrogen storage capacity of some metal-organic framework materials

    Science.gov (United States)

    Samanta, Amit; Furuta, Terumi; Li, Ju

    2006-08-01

    Metal-organic frameworks (MOFs) are promising materials for applications such as separation, catalysis, and gas storage. A key indicator of their structural stability is the shear modulus. By density functional theory calculations in a 106-atom supercell, under the local density approximation, we find c11=29.2GPa and c12=13.1GPa for Zn-based MOF 5. However, we find c44 of MOF-5 to be exceedingly small, only 1.4GPa at T =0K. The binding energy Eads of a single hydrogen molecule in MOF-5 is evaluated using the same setup. We find it to be -0.069to-0.086eV/H2 near the benzene linker and -0.106to-0.160eV/H2 near the Zn4O tetrahedra. Substitutions of chlorine and hydroxyl in the benzene linker have negligible effect on the physisorption energies. Pentacoordinated copper (and aluminum) in a framework structure similar to MOF-2 gives Eads≈-0.291eV/H2 (and -0.230eV/H2), and substitution of nitrogen in benzene (pyrazine) further enhances Eads near the organic linker to -0.16eV/H2, according to density functional theory with local density approximation.

  18. In situ hydrothermal syntheses, structures and photoluminescent properties of four novel metal-organic frameworks constructed by lanthanide (Ln=Ce(III), Pr(III), Eu(III)) and Cu(I) metals with flexible dicarboxylate acids and piperazine-based ligands

    Energy Technology Data Exchange (ETDEWEB)

    Ay, Burak; Karaca, Serkan [Department of Chemistry, Arts and Science Faculty, Çukurova University, 01330 Adana (Turkey); Yildiz, Emel, E-mail: eeyildiz@cu.edu.tr [Department of Chemistry, Arts and Science Faculty, Çukurova University, 01330 Adana (Turkey); Lopez, Valerie [Department of Chemistry, Syracuse University, Syracuse, NY 13244 (United States); Nanao, Max H. [European Molecular Biology Laboratory, Grenoble Outstation, 71 Avenue des Martyrs, CS 90181, 38042 Grenoble Cedex 9 (France); University Grenoble Alpes-Centre National de la Recherche Scientifique-EMBL Unit of Virus Host-Cell Interactions, 71 Avenue des Martyrs, CS 90181, 38042 Grenoble Cedex 9 (France); Zubieta, Jon [Department of Chemistry, Syracuse University, Syracuse, NY 13244 (United States); Université Grenoble Alpes Laboratoire de Physiologie Cellulaire & Végétale, Institut de Recherches en Technologies et Sciences pour le Vivant, 17 rue des Martyrs, 38054 Grenoble cedex 9 (France)

    2016-01-15

    Four novel metal-organic frameworks,[Cu{sub 2}Cl{sub 2}(pyrz)]{sub n} (1) and (H{sub 2}pip){sub n}[Ln{sub 2}(pydc){sub 4}(H{sub 2}O){sub 2}]{sub n} (Ln=Ce (2), Pr (3) and Eu (4), H{sub 2}pzdc=2,3-pyrazinedicarboxylic acid, pyrz=pyrazine, H{sub 2}pydc=2,6-pyridinedicarboxylic acid, H{sub 2}pip=piperazine) have been synthesized under hydrothermal conditions and characterized by the elemental analysis, ICP, Far IR (FIR), FT-IR spectra, TGA, single crystal X-ray diffraction analysis and powder X-ray diffraction (PXRD). Compound 1 is two-dimensional containing Cl-Cu-Cl sites, while the lanthanide complexes contain one-dimensional infinite Ln–O-Ln chains. All the complexes show high thermal stability. The complexes 1–3 exhibit luminescence emission bands at 584, 598 and 614 nm at room temperature when excited at 300 nm. Complex 4 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature. - Graphical abstract: Four novel metal-organic frameworks have been synthesized under hydrothermal conditions. Thermal and luminescent properties of the compounds have been investigated.

  19. Colorimetric and luminescent bifunctional iridium(III) complexes for the sensitive recognition of cyanide ions

    Science.gov (United States)

    Chen, Xiudan; Wang, Huili; Li, Jing; Hu, Wenqin; Li, Mei-Jin

    2017-02-01

    Two new cyclometalated iridium(III) complexes [(ppy)2Irppz]Cl (1) and [(ppy)2Irbppz]Cl (2) (where ppy = 2-phenylpyridine, ppz = 4,7-phenanthrolino-5,6:5,6-pyrazine, bppz = 2.3-di-2-pyridylpyrazine), were designed and synthesized. The structure of [(ppy)2Irppz]Cl was determined by single crystal X-ray diffraction. Their photophysical properties were also studied. This kind of complexes could coordinate with Cu2 +, the photoluminescence (PL) of the complex was quenched, and the color changed from orange-red to green. The forming M-Cu (M: complexes 1 and 2) ensemble could be further utilized as a colorimetric and emission "turn-on" bifunctional detection for CN-, especially for complex 1-Cu2 + showed a high sensitivity toward CN- with a limit of diction is 97 nM. Importantly, this kind of iridium(III) complexes shows a unique recognition of cyanide ions over other anions which makes it an eligible sensing probe for cyanide ions.

  20. Changes in Levels of Amino Acids and Basic Components in Burley Tobacco Produced by Roasting

    Directory of Open Access Journals (Sweden)

    Li P

    2014-12-01

    Full Text Available Three burley tobacco samples from three different areas in China and Brazil were roasted under three processing conditions. The amino acids and basic components of the burley tobacco samples were determined before and after roasting. Routine tobacco variables (reducing sugars, total water-soluble sugars, total nitrogen, total alkaloids, total volatile bases, and pH were determined according to the Chinese National Standard Methods (CNSM. Free amino acids were determined by high performance liquid chromatography (HPLC. The basic compounds were isolated by use of simultaneous distillation and extraction (SDE equipment. Their levels were determined qualitatively and quantitatively on a a gas chromatograph (GC equipped with a nitrogen-phosphorus detector (NPD and b by gas chromatography mass spectrometry (GC-MS. The results indicated that the chemical changes occurring during roasting have a significant impact on burley tobacco quality. Roasting decreased the tobacco pH value and the levels of total nitrogen, reducing sugars, free amino acids, and other nitrogenous substances, such as amines and alkaloids. The latter are usually related to the irritancy and sharp taste of burley tobacco smoke. In contrast, the levels of pyrazines, important contributors to the characteristic burley flavor, increased.