Sample records for tandem oxidation coupling

  1. A Facile and Versatile Approach to Double N-Heterohelicenes: Tandem Oxidative C?N Couplings of N-Heteroacenes via Cruciform Dimers.

    PubMed

    Sakamaki, Daisuke; Kumano, Daisuke; Yashima, Eiji; Seki, Shu

    2015-04-27

    Novel double N-hetero[5]helicenes that are composed of two nitrogen-substituted heteropentacenes are synthesized by tandem oxidative C?N couplings via the cruciform heteropentacene dimers. The developed method is very facile and enables the synthesis of a double helicene in only two steps from commercially available naphthalene derivatives. These double N-hetero[5]helicenes have larger torsion angles in the fjord regions than typical [5]helicenes, and optical/electrochemical measurements revealed a significant increase in the electronic communication between the two heteropentacene moieties of the double helicenes compared with their cruciform dimers. The optical resolution of one of the double helicenes was successfully carried out, and their stability towards racemization was remarkably higher than those of typical [5]helicenes. The synthetic strategy proposed in this paper should be versatile and widely applicable to the preparation of double helicenes from other N-containing ?-conjugated planar molecules. PMID:25772706

  2. Rules of Stereoselectivity in Tandem Oxidative Polycyclization Reaction with Rhenium(VII) Oxides

    E-print Network

    Keinan, Ehud

    Rules of Stereoselectivity in Tandem Oxidative Polycyclization Reaction with Rhenium(VII) Oxides, Israel ReceiVed April 17, 1998 The tandem oxidative polycyclization reaction with rhenium- (VII) reagents

  3. Tandem Oxidative Cyclization with Rhenium Oxide. Total Synthesis of 17,18-bisepi-Goniocin

    E-print Network

    Keinan, Ehud

    Tandem Oxidative Cyclization with Rhenium Oxide. Total Synthesis of 17,18-bisepi-Goniocin Subhash C of a rhenium(VII) reagent to produce a single stereoisomer of a tris-THF product. Surprisingly, however

  4. Analysis of urinary 8-isoprostane as an oxidative stress biomarker by stable isotope dilution using automated online in-tube solid-phase microextraction coupled with liquid chromatography-tandem mass spectrometry.

    PubMed

    Mizuno, Keisuke; Kataoka, Hiroyuki

    2015-08-10

    We have developed a simple and sensitive method for the determination of the oxidative stress biomarker 8-isoprostane (8-IP) in human urine by automated online in-tube solid-phase microextraction (SPME) coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) using a Zorbax Eclipse XDB-8 column and 0.1% formic acid/methanol (25/75, v/v) as a mobile phase. Electrospray MS/MS for 8-IP was performed on an API 4000 triple quadruple mass spectrometer in negative ion mode. The optimum in-tube SPME conditions were 20 draw/eject cycles with a sample size of 40?L using a Carboxen 1006 PLOT capillary column for the extraction. The extracted compounds were easily desorbed from the capillary by passage of the mobile phase, and no carryover was observed. Total analysis time of this method including online extraction and analysis was about 30min for each sample. The in-tube SPME LC-MS/MS method showed good linearity in the concentration range of 20-1000pg/mL with a correlation coefficient r=0.9999 for 8-IP using a stable isotope-labeled internal standard, 8-IP-d4. The detection limit of 8-IP was 3.3pg/mL and the proposed method showed 42-fold higher sensitivity than the direct injection method. The intra-day and inter-day precisions (relative standard deviations) were below 5.0% and 8.5% (n=5), respectively. This method was applied successfully to the analysis of urine samples without pretreatment or interference peaks. The recovery rates of 8-IP spiked into urine samples were above 92%. This method is useful for assessing the effects of oxidative stress and antioxidant intake. PMID:25956225

  5. Simultaneous determination of the bilirubin oxidation end products Z-BOX A and Z-BOX B in human serum using liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Seidel, Raphael A; Kahnes, Marcel; Bauer, Michael; Pohnert, Georg

    2015-01-01

    Bilirubin oxidation end products (BOXes) appear upon endogenous heme degradation and can be found in the cerebrospinal fluid after hemorrhagic stroke. BOXes are assumed to contribute to delayed cerebral vasospasm and secondary loss of brain tissue. Here, we present a validated LC-ESI-MS/MS method for the sensitive determination of the regio-isomers Z-BOX A and Z-BOX B in human serum. We found that Z-BOX A and Z-BOX B appear in serum of healthy volunteers. The sample preparation includes the addition of 5-bromonicotinamide as internal standard and protein precipitation with acetonitrile. Baseline-separation was achieved on a C-18 column with a binary solvent gradient of formic acid in water/acetonitrile at 1 mL/min within a total analysis time of 17 min. Using single reaction monitoring in the positive ion mode, the linear working ranges were 2.74-163 pg/?L (Z-BOX A) and 2.12-162.4 pg/?L (Z-BOX B) with R(2)>0.995. Intra- and inter-day precisions were <10%. The inherent analyte concentrations of Z-BOX A (14.4 ± 5.1 nM) and Z-BOX B (10.9 ± 3.1 nM) in pooled human serum were determined by standard addition. The photolability of both analytes was demonstrated. This method enables to monitor Z-BOX A and Z-BOX B as a prerequisite to systematically study the biological significance of higher order metabolites of heme degradation. PMID:25463201

  6. Characterization of bisphenol A metabolites produced by Portulaca oleracea cv. by liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Watanabe, Ippei; Harada, Kazuo; Matsui, Takeshi; Miyasaka, Hitoshi; Okuhata, Hiroshi; Tanaka, Satoshi; Nakayama, Hideki; Kato, Ko; Bamba, Takeshi; Hirata, Kazumasa

    2012-01-01

    The garden plant portulaca (Portulaca oleracea cv.) efficiently removes bisphenol A (BPA), an endocrine-disrupting chemical, from a hydroponic solution, but the molecular mechanisms underlying BPA metabolism by portulaca remain unclear. In this study, BPA metabolites converted by portulaca were analyzed by liquid chromatography coupled with tandem mass spectrometry. We observed the hydroxylation of BPA and the oxidization of it to quinone. Polyphenol oxidases are likely to contribute to BPA degradation by portulaca. PMID:22738977

  7. Oxidation-induced conformational changes in calcineurin determined by covalent labeling and tandem mass spectrometry.

    PubMed

    Zhou, Xiao; Mester, Caitlin; Stemmer, Paul M; Reid, Gavin E

    2014-11-01

    The Ca(2+)/calmodulin activated phosphatase, calcineurin, is inactivated by H2O2 or superoxide-induced oxidation, both in vivo and in vitro. However, the potential for global and/or local conformation changes occurring within calcineurin as a function of oxidative modification, that may play a role in the inactivation process, has not been examined. Here, the susceptibility of calcineurin methionine residues toward H2O2-induced oxidation were determined using a multienzyme digestion strategy coupled with capillary HPLC-electrospray ionization mass spectrometry and tandem mass spectrometry analysis. Then, regions within the protein complex that underwent significant conformational perturbation upon oxidative modification were identified by monitoring changes in the modification rates of accessible lysine residues between native and oxidized forms of calcineurin, using an amine-specific covalent labeling reagent, S,S'-dimethylthiobutanoylhydroxysuccinimide ester (DMBNHS), and tandem mass spectrometry. Importantly, methionine residues found to be highly susceptible toward oxidation, and the lysine residues exhibiting large increases in accessibility upon oxidation, were all located in calcineurin functional domains involved in Ca(2+)/CaM binding regulated calcineurin stimulation. These findings therefore provide initial support for the novel mechanistic hypothesis that oxidation-induced global and/or local conformational changes within calcineurin contribute to inactivation via (i) impairing the interaction between calcineurin A and calcineurin B, (ii) altering the low-affinity Ca(2+) binding site in calcineurin B, (iii) inhibiting calmodulin binding to calcineurin A, and/or (iv) by altering the affinity between the calcineurin A autoinhibitory domain and the catalytic center. PMID:25286016

  8. Electrochromic devices embodying W oxide/Ni oxide tandem films

    SciTech Connect

    Azens, A.; Vaivars, G.; Veszelei, M.; Kullman, L.; Granqvist, C. G.

    2001-06-15

    Six-layer electrochromic devices of indium tin oxide (ITO)/NiO{sub x}H{sub y}/WO{sub 3}/ZrP-electrolyte/WO{sub 3}/ITO were made by reactive dc magnetron sputtering and lamination. The WO{sub 3} layer between the acidic ZrP-based electrolyte and the NiO{sub x}H{sub y} layer served as optically passive protective layer. The optical inactivity of the protective layer could be understood from arguments based on electron density of states. {copyright} 2001 American Institute of Physics.

  9. Tandem Dehydrogenation/Oxidation/Oxidative Cyclization Approach to Wrightiadione and Its Derivatives.

    PubMed

    Jeong, Yujeong; Moon, Youngtaek; Hong, Sungwoo

    2015-07-01

    Wrightiadione contains a unique tetracyclic isoflavone moiety and has been shown to exhibit a broad range of biological activities. An efficient and straightforward synthetic method for generating the molecular complexity of wrightiadione was developed through three-step tandem dehydrogenation/oxidation/oxidative cyclization reactions with a Pd/Cu catalytic system. This unprecedented one-pot route utilizes a broad range of substrates, providing a convenient and powerful synthetic tool for accessing naturally occurring tetracyclic isoflavone wrightiadione and its nitrogen-containing derivatives. PMID:26090926

  10. Perovskite catalysts for oxidative coupling

    DOEpatents

    Campbell, K.D.

    1991-06-25

    Perovskites of the structure A[sub 2]B[sub 2]C[sub 3]O[sub 10] are useful as catalysts for the oxidative coupling of lower alkane to heavier hydrocarbons. A is alkali metal; B is lanthanide or lanthanum, cerium, neodymium, samarium, praseodymium, gadolinium or dysprosium; and C is titanium.

  11. Equivalent circuit analysis of radiative coupling in monolithic tandem solar cells

    NASA Astrophysics Data System (ADS)

    Lan, Dongchen; Green, Martin A.

    2015-06-01

    As solar cell efficiency improves towards the Shockley-Queisser limit, so does the radiative efficiency of the cell. For tandem stacks of cells where energy conversion efficiency now exceeds 46%, radiative coupling between the cells is becoming increasingly important to consider in cell design, measurement, and performance prediction. We show how an equivalent circuit model can capture the complex radiative interactions between cells in such tandem stacks, allowing more insight into the impact on cell performance. The circuit's use is demonstrated by deriving results relevant to the critical step of eliminating coupling effects from measured cell spectral responses.

  12. Detailed balance analysis of area de-coupled double tandem photovoltaic modules

    NASA Astrophysics Data System (ADS)

    Strandberg, Rune

    2015-01-01

    This paper describes how layers of area de-coupled top and bottom cells in photovoltaic tandem modules can increase the efficiency of two-terminal tandem devices. The point of the area de-coupling is to allow the number of top cells to differ from the number of bottom cells. Within each of the layers, the cells can be horizontally series-connected and the layers can then be current- or voltage-matched with each other in a tandem module. Using detailed balance modeling, it is shown that two-terminal tandem modules of this type can achieve the same theoretical efficiency as stacks of independently operated cells, often referred to as four-terminal cells. Optimal ratios of the number of bottom cells to the number of top cells are calculated. Finally, it is shown that modules with a bottom layer consisting of 60 cells with a band gap of 1.11 eV, resembling standard silicon modules, offer sufficient resolution to optimize the number of top cells and achieve high efficiency over a large range of top cell band gaps. This result extends the list of materials that can be used as top cells in two-terminal tandem modules with silicon bottom cells.

  13. Oxidative catalysis using the stoichiometric oxidant as a reagent: an efficient strategy for single-electron-transfer-induced tandem anion-radical reactions.

    PubMed

    Kafka, František; Holan, Martin; Hidasová, Denisa; Pohl, Radek; Císa?ová, Ivana; Klepetá?ová, Blanka; Jahn, Ullrich

    2014-09-01

    Oxidative single-electron transfer-catalyzed tandem reactions consisting of a conjugate addition and a radical cyclization are reported, which incorporate the mandatory terminal oxidant as a functionality into the product. PMID:25070407

  14. Tandem oxidative processes catalyzed by polymer-incarcerated multimetallic nanoclusters with molecular oxygen.

    PubMed

    Miyamura, Hiroyuki; Kobayashi, Sh?

    2014-04-15

    Heterogeneous catalysis and one-pot tandem reactions are key for efficient and practical organic syntheses and for green and sustainable chemistry. Heterogeneous catalysts can be recovered and reused. These catalysts can be applied to efficient systems, such as continuous-flow systems. Tandem reactions often proceed via highly reactive but unstable intermediates. Tandem reactions do not require workup or much purification of the intermediate. This Account summarizes recent developments that we have made in the field of multifunctional heterogeneous metal nanocluster catalysts for use in tandem reactions based on aerobic oxidation reactions as key processes. We constructed our heterogeneous metal nanoclusters via two important procedures--microencapsulation and cross-linking--using polystyrene-based copolymers with cross-linking moieties. These frameworks can efficiently stabilize small metal nanoclusters to maintain high catalytic activity without aggregation and leaching of nanoclusters. Aggregation and leaching are prevented by weak but multiple interactions between metal nanocluster surfaces and benzene rings in the copolymer as well as by the physical envelopment of cross-linked polymer backbones. Small nanoclusters, including multimetallic alloy clusters (nanoalloys), can be "imprisoned" into these cross-linked polymer composites. The term we use for these processes is polymer incarceration. Direct oxidative esterifications were achieved with polymer-incarcerated (PI) Au nanocluster catalysts. Amides were synthesized from alcohols and amines under aerobic oxidative conditions with PI bimetallic nanocluster catalysts composed of Au and Fe-group metals that formed separated nanoclusters rather than alloys. Oxidative lactam formation from amino alcohols was also achieved. On the other hand, imines could be prepared selectively from alcohols and amines with PI Au-Pd bimetallic nanoclusters. We also achieved the integration of the aerobic oxidation of allylic alcohols and the following Michael reaction catalyzed by trimetallic PI catalysts containing Au-Pd alloy nanoclusters and tetraalkoxyborates as cross-linkers. All of these heterogeneous catalysts could be recovered by simple operations and reused without significant loss of activity or any leaching of metals. We have demonstrated that the polymer incarceration method enables the simultaneous immobilization of several metals, with which we can achieve one-pot tandem oxidative processes using molecular oxygen as an oxidant within the multifunctional heterogeneous catalysts. Suitable choices of metals and bimetallic structures are crucial for the reactivity and the selection of reaction pathways. PMID:24661043

  15. Facile synthesis of acridines via Pd(0)-diphosphine complex-catalyzed tandem coupling/cyclization protocol.

    PubMed

    Wang, Ting-Jun; Chen, Wen-Wen; Li, Yi; Xu, Ming-Hua

    2015-06-21

    A facile and efficient approach for the synthesis of a variety of acridines via the tandem coupling/cyclization of substituted 2-bromobenzaldehydes and anilines is described. The reaction can be accomplished with ease in the presence of a catalytic amount of Pd2(dba)3 and diphosphine ligand dppf, providing a broad range of substituted acridines in good to excellent yields (up to 99%). The Lewis acid, AlCl3, is required to promote the cyclization for less electron-rich anilines. PMID:25982344

  16. Coupled operation of the Oak Ridge isochronous cyclotron and the 25 MV tandem

    SciTech Connect

    Lord, R.S.; Ball, J.B.; Beckers, R.M.; Cleary, T.P.; Hudson, E.D.; Ludemann, C.A.; Martin, J.A.; Milner, W.T.; Mosko, S.W.; Ziegler, N.F.

    1981-01-01

    Coupled operation of the 25 MV tandem and the Oak Ridge Isochronous Cyclotron (ORIC) was achieved on January 27, 1981. A beam of 38 MeV /sup 16/O/sup 2 +/ was injected into ORIC, stripped to 8/sup +/ and accelerated to 324 MeV. Shortly afterwards, the energy was increased to the maximum design value of 25 MeV/amu (400 MeV). A spectrum taken of the scattering of this beam from a thin /sup 208/Pb target in the broad range spectrograh exhibited a resolution of 115 keV (FWHM). Performance of the system was in close agreement with that predicted from calculations.

  17. Tandem strip mill's multi-parameter coupling dynamic modeling based on the thickness control

    NASA Astrophysics Data System (ADS)

    Peng, Yan; Zhang, Yang; Sun, Jianliang; Zang, Yong

    2015-03-01

    The rolling process is determined by the interaction of a number of different movements, during which the relative movement occurs between the vibrating roll system and the rolled piece, and the roll system's vibration interacts with the strip's deformation and rigid movement. So many parameters being involved leads to a complex mechanism of this coupling effect. Through testing and analyzing the vibration signals of the mill in the rolling process, the rolling mill's coupled model is established with comprehensive consideration of the coupling interaction between the mill's vertical vibration, its torsional vibration and the working roll's horizontal vibration, and vibration characteristics of different forms of rolling mill's vibration are analyzed under the coupling effect. With comprehensive attention to the relationship between the roll system, the moving strip and the rolling parameters' dynamic properties, and also from the strip thickness control point of view, further research is done on the coupling mechanism between the roll system's movement and the moving strip's characteristics in the rolling process. As a result, the law of inertial coupling and the stiffness coupling effect caused by different forms of the roll system's vibration is determined and the existence of nonlinear characteristics caused by the elastic deformation of moving strip is also found. Furthermore, a multi-parameter coupling-dynamic model is established which takes the tandem strip mill as its research object by making a detailed kinematics analysis of the roll system and using the principle of virtual work. The coupling-dynamic model proposes the instruction to describe the roll system's movement, and analyzes its dynamic response and working stability, and provides a theoretical basis for the realization of the strip thickness' dynamic control.

  18. Oxidative coupling of methane in a solid oxide membrane reactor

    SciTech Connect

    Guo, X.M.; Hidajat, K.; Ching, C.B. [National Univ. of Singapore (Singapore). Dept. of Chemical Engineering; Chen, H.F. [Tianjin Univ. (China). Dept. of Chemical Engineering

    1997-09-01

    The oxidative coupling of methane (OCM) has been studied using the 1 wt% Sr/La{sub 2}O{sub 3}-Bi{sub 2}O{sub 3}-Ag-YSZ solid oxide membrane reactor. The effects of oxygen flux, temperature and feed concentration on the performance of oxidative coupling of methane reaction have been investigated. Two mathematical models based on well-mixed flow (CSTM) or plug flow (PFM) in the reactor have been developed to describe the behavior of the solid oxide membrane reactors. The simulation results show good agreement with experimental data. However, the simulation results of the CSTM fit experimental data much better than that of PFM over a broad range of experimental conditions. The simulation results also show it is very important to match reaction conditions and reactor parameters.

  19. Catalytic migratory oxidative coupling of nitrones.

    PubMed

    Hashizume, Shogo; Oisaki, Kounosuke; Kanai, Motomu

    2011-08-19

    A Cu(I)-catalyzed migratory oxidative coupling between nitrones and heterocycles or a methylamine is described. Selective C-C bond-formation proceeds through cleavage of two C(sp(3))-H bonds concomitant with C?N double bond-migration. The reaction provides an alternating nitrone moiety, allowing for further synthetically useful transformations. Radical clock studies suggest that the nucleophilic addition of nitrones to an oxidatively generated carbocation is a key step. PMID:21766802

  20. Controllable Tuning Plasmonic Coupling with Nanoscale Oxidation

    PubMed Central

    2015-01-01

    The nanoparticle on mirror (NPoM) construct is ideal for the strong coupling of localized plasmons because of its simple fabrication and the nanometer-scale gaps it offers. Both of these are much harder to control in nanoparticle dimers. Even so, realizing controllable gap sizes in a NPoM remains difficult and continuous tunability is limited. Here, we use reactive metals as the mirror so that the spacing layer of resulting metal oxide can be easily and controllably created with specific thicknesses resulting in continuous tuning of the plasmonic coupling. Using Al as a case study, we contrast different approaches for oxidation including electrochemical oxidation, thermal annealing, oxygen plasma treatments, and photo-oxidation by laser irradiation. The thickness of the oxidation layer is calibrated with depth-mode X-ray photoemission spectroscopy (XPS). These all consistently show that increasing the thickness of the oxidation layer blue-shifts the plasmonic resonance peak while the transverse mode remains constant, which is well matched by simulations. Our approach provides a facile and reproducible method for scalable, local and controllable fabrication of NPoMs with tailored plasmonic coupling, suited for many applications of sensing, photochemistry, photoemission, and photovoltaics. PMID:25978297

  1. Controllable Tuning Plasmonic Coupling with Nanoscale Oxidation.

    PubMed

    Ding, Tao; Sigle, Daniel; Zhang, Liwu; Mertens, Jan; de Nijs, Bart; Baumberg, Jeremy

    2015-06-23

    The nanoparticle on mirror (NPoM) construct is ideal for the strong coupling of localized plasmons because of its simple fabrication and the nanometer-scale gaps it offers. Both of these are much harder to control in nanoparticle dimers. Even so, realizing controllable gap sizes in a NPoM remains difficult and continuous tunability is limited. Here, we use reactive metals as the mirror so that the spacing layer of resulting metal oxide can be easily and controllably created with specific thicknesses resulting in continuous tuning of the plasmonic coupling. Using Al as a case study, we contrast different approaches for oxidation including electrochemical oxidation, thermal annealing, oxygen plasma treatments, and photo-oxidation by laser irradiation. The thickness of the oxidation layer is calibrated with depth-mode X-ray photoemission spectroscopy (XPS). These all consistently show that increasing the thickness of the oxidation layer blue-shifts the plasmonic resonance peak while the transverse mode remains constant, which is well matched by simulations. Our approach provides a facile and reproducible method for scalable, local and controllable fabrication of NPoMs with tailored plasmonic coupling, suited for many applications of sensing, photochemistry, photoemission, and photovoltaics. PMID:25978297

  2. Determination of endothelin-1 in rats using a high-performance liquid chromatography coupled to electrospray tandem mass spectrometry

    Microsoft Academic Search

    Maria Walczak; Andrzej Fedorowicz; Stefan Ch?opicki; Joanna Szymura-Oleksiak

    2010-01-01

    A sensitive and specific liquid chromatography tandem mass spectrometry method with electrospray ionization for the determination of endothelin-1 in rat plasma and lung effluents has been developed and validated. Detection was achieved by an Applied Biosystems MDS Sciex API 2000 triple quadrupole mass spectrometer coupled to an Agilent 1100 LC system. The limit of detection and the limit of the

  3. Benzene oxidation coupled to sulfate reduction

    USGS Publications Warehouse

    Lovley, D.R.; Coates, J.D.; Woodward, J.C.; Phillips, E.J.P.

    1995-01-01

    Highly reduced sediments from San Diego Bay, Calif., that were incubated under strictly anaerobic conditions metabolized benzene within 55 days when they were exposed initially to I ??M benzene. The rate of benzene metabolism increased as benzene was added back to the benzene-adapted sediments. When a [14C]benzene tracer was included with the benzene added to benzene-adapted sediments, 92% of the added radioactivity was recovered as 14CO2. Molybdate, an inhibitor of sulfate reduction, inhibited benzene uptake and production of 14CO2 from [14C]benzene. Benzene metabolism stopped when the sediments became sulfate depleted, and benzene uptake resumed when sulfate was added again. The stoichiometry of benzene uptake and sulfate reduction was consistent with the hypothesis that sulfate was the principal electron acceptor for benzene oxidation. Isotope trapping experiments performed with [14C]benzene revealed that there was no production of such potential extracellular intermediates of benzene oxidation as phenol, benzoate, p-hydroxybenzoate, cyclohexane, catechol, and acetate. The results demonstrate that benzene can be oxidized in the absence of O2, with sulfate serving as the electron acceptor, and suggest that some sulfate reducers are capable of completely oxidizing benzene to carbon dioxide without the production of extracellular intermediates. Although anaerobic benzene oxidation coupled to chelated Fe(III) has been documented previously, the study reported here provides the first example of a natural sediment compound that can serve as an electron acceptor for anaerobic benzene oxidation.

  4. Operational experience for coupled operation of the Holifield tandem electrostatic accelerator and isochronous cyclotron

    SciTech Connect

    Martin, J.A.; Dowling, D.T.; Haynes, D.L.; Hudson, E.D.; Jones, C.M.; Juras, R.C.; Lane, S.S.; Ludemann, C.A.; Meigs, M.J.; Milner, W.T.

    1986-10-01

    Coupled operation of the 25 MV tandem accelerator and the Oak Ridge Isochronous Cyclotron of the Holifield Heavy Ion Research Facility began in January 1981. Since that time the use of the cyclotron in this mode has become routine. Thirty-six different ion species in the range from /sup 9/Be to /sup 150/Nd have been accelerated; 106 separate beam setups have been provided. Since the beginning of coupled operation, significant improvement of cyclotron systems, and setup and operating techniques, have been made. The graphite electrostatic deflector septum formerly used for high-current light ion beams has been replaced by a thin molybdenum septum. Extraction system positioning mechanisms have been refined and recalibrated and more precise and reliable position readouts have been provided. The computer-based control system has been improved. The frequency range of the rf system has been increased to eliminate an energy dead-band. Cyclotron setup calculations have been improved and standardized methods have been developed to consistently achieve well-centered orbits, correct beam extraction system positions, and electrostatic and magnetic strengths. A totally new beam bunching system has been installed. The improvements in the phase-lock system of the beam buncher have been especially effective. A large number of obsolete and unreliable power supplies have been replaced. Beam extraction efficiency has been increased from approx.50% to approx.70%. Accuracy of obtaining the desired energy without fine tuning is now approx.1% compared to 2 to 3% in early coupled operation. Beam setup time (tuning) has been reduced by approx.20%. Unscheduled maintenance has been reduced by a factor of two.

  5. Oxidative coupling of methane over oxide-supported barium catalysts

    SciTech Connect

    Dissanayake, D.; Lunsford, J.H.; Rosynek, M.P. (Texas A M Univ., College Station, TX (United States))

    1993-09-01

    The effects of barium loading level and support basicity on the activity and C[sub 2+] selectivity for oxidative coupling of methane were examined for MgO-, CaO-, ZnO-, and Al[sub 2]O[sub 3]-supported Ba catalysts. The nature and distribution of catalyst surface species were characterized by XPS and ISS spectroscopic techniques, which indicated that there is no direct correlation between support basicity and oxidative coupling activity. However, catalysts containing sufficiently high Ba loadings are more easily poisoned by carbon dioxide than those with low Ba contents, due to increased stability of a BaCO[sub 3] phase. With supports of low basicity, or when the Ba is uniformly distributed on the catalyst support, the susceptibility to carbon dioxide poisoning is minimized. XPS characterization of the Ba/MgO catalysts confirmed that oxidative coupling activity is directly related to the capability of the catalyst to form surface O[sub 2][sup 2[minus

  6. Determination of fungicides in wine by mixed-mode solid phase extraction and liquid chromatography coupled to tandem mass spectrometry

    Microsoft Academic Search

    I. Carpinteiro; M. Ramil; I. Rodríguez; R. Cela

    A novel procedure for the determination of nine selected fungicides (metalaxyl-M, azoxystrobin, myclobutanil, flusilazole, penconazole, tebuconazole, propiconazole, diniconazole and difenoconazole) in wine samples is presented. Sample enrichment and purification is simultaneously performed using mixed-mode, anion exchange and reversed-phase, OASIS MAX solid-phase extraction (SPE) cartridges. Analytes were determined by liquid chromatography coupled to tandem mass spectrometry using atmospheric pressure electrospray ionization

  7. Multiresidue method for fast determination of pesticides in fruit juices by ultra performance liquid chromatography coupled to tandem mass spectrometry

    Microsoft Academic Search

    R. Romero-González; A. Garrido Frenich; J. L. Martínez Vidal

    2008-01-01

    A new analytical method for the simultaneous determination of 90 pesticides in fruit juices by ultra performance liquid chromatography coupled to tandem mass spectrometry (UPLC–MS\\/MS) has been developed and validated. Extraction was performed with acetonitrile, applying QuEChERS methodology, and the extracts were analyzed without any further clean-up step, providing better results than solid phase extraction (SPE) procedure. Before chromatographic step,

  8. Detection and identification of sulphonamide drugs in municipal waste water by liquid chromatography coupled with electrospray ionisation tandem mass spectrometry

    Microsoft Academic Search

    C. Hartig; T. Storm; M. Jekel

    1999-01-01

    High-performance liquid chromatography coupled with positive-ion electrospray ionisation tandem mass spectrometry was used for the determination and confirmation of 13 sulphonamide drugs in environmental water samples in the low ng\\/L-range. Enrichment with concentration factors of 130–670 was performed by solid phase extraction, achieving recoveries of 50 to 90%. After gradient elution HPLC, detection and quantification was performed using selected reaction

  9. A One-Pot Tandem Olefin Isomerization/Metathesis-Coupling (ISOMET) Reaction

    E-print Network

    Dobereiner, Graham E.

    A tandem catalytic reaction has been developed as part of a process to discover tungsten-based olefin metathesis catalysts that have a strong preference for terminal olefins over cis or trans internal isomers in olefin ...

  10. Measurement of trimethylamine-N-oxide by stable isotope dilution liquid chromatography tandem mass spectrometry

    PubMed Central

    Wang, Zeneng; Levison, Bruce S.; Hazen, Jennie E.; Donahue, Lillian; Li, Xin-Min; Hazen, Stanley L.

    2014-01-01

    Trimethylamine-N-oxide (TMAO) levels in blood predict future risk for major adverse cardiac events including myocardial infarction, stroke and death. Thus, the rapid determination of circulating TMAO concentration is of clinical interest. Here we report a method to measure TMAO in biological matrices by stable isotope dilution liquid chromatography tandem mass spectrometry (LC/MS/MS) with lower and upper limits of quantification of 0.05 and >200 µM, respectively. Spike and recovery studies demonstrate an accuracy at low (0.5 µM), mid (5 µM) and high (100 µM) levels of 98.2%, 97.3% and 101.6%, respectively. Additional assay performance metrics include intra-day and inter-day coefficients of variance of < 6.4% and < 9.9%, respectively, across the range of TMAO levels. Stability studies reveal TMAO in plasma is stable both during storage at ?80 °C for 5 years and to multiple freeze thaw cycles. Fasting plasma normal range studies among apparently healthy subjects (n=349) shows a range of 0.73 – 126 µM, median (interquartile range) levels of 3.45 (2.25–5.79) µM, and increasing values with age. The LC/MS/MS based assay reported should be of value for further studies evaluating TMAO as a risk marker and for examining the effect of dietary, pharmacologic and environmental factors on TMAO levels. PMID:24704102

  11. Oxidative Dehydrogenative Couplings of Pyrazol-5-amines Selectively Forming Azopyrroles

    PubMed Central

    2015-01-01

    New oxidative dehydrogenative couplings of pyrazol-5-amines for the selective synthesis of azopyrrole derivatives have been described. The former reaction simultaneously installs C–I and N–N bonds through iodination and oxidation, whereas the latter involved a copper-catalyzed oxidative coupling process. The resulting iodo-substituted azopyrroles were employed by treatment with various terminal alkynes through Sonogashira cross-coupling leading to new azo compounds. PMID:24731223

  12. Optimizing TiO2-based phosphopeptide enrichment for automated multidimensional liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Cantin, Greg T; Shock, Teresa R; Park, Sung Kyu; Madhani, Hiten D; Yates, John R

    2007-06-15

    An automated online multidimensional liquid chromatography system coupled to ESI-based tandem mass spectrometry was used to assess the effectiveness of TiO2 in the enrichment of phosphopeptides from tryptic digests of protein mixtures. By monitoring the enrichment of phosphopeptides, an optimized set of loading, wash, and elution conditions were realized for TiO2. A comparison of TiO2 with other resins used for phosphopeptide enrichment, Fe(III)-IMAC and ZrO2, was also carried out using tryptic digests of both simple and moderately complex protein mixtures; where TiO2 was shown to be superior in performance. PMID:17523591

  13. Optimizing TiO2-based phosphopeptide enrichment for automated multidimensional liquid chromatography coupled to tandem mass spectrometry

    PubMed Central

    Cantin, Greg T.; Shock, Teresa R.; Park, Sung Kyu; Madhani, Hiten D.; Yates, John R.

    2008-01-01

    An automated online multidimensional liquid chromatography system coupled to ESI-based tandem mass spectrometry was used to assess the effectiveness of TiO2 in the enrichment of phosphopeptides from tryptic digests of protein mixtures. By monitoring the enrichment of phosphopeptides, an optimized set of loading, wash, and elution conditions were realized for TiO2. A comparison of TiO2 with other resins used for phosphopeptide enrichment, Fe(III)-IMAC and ZrO2, was also carried out using tryptic digests of both simple and moderately complex protein mixtures; where TiO2 was shown to be superior in performance. PMID:17523591

  14. Trace Analysis of N -Nitrosamines in Water Using SolidPhase Microextraction Coupled with Gas Chromatograph–Tandem Mass Spectrometry

    Microsoft Academic Search

    Hsu-Wen Hung; Tsair-Fuh Lin; Chuen-Huey Chiu; Ya-Chi Chang; Tung-Ying Hsieh

    2010-01-01

    A method that utilizes solid-phase microextraction (SPME) coupled with gas chromatography (GC) and chemical ionization tandem\\u000a mass spectrometry (MS\\/MS) was developed for analyzing a group of emerging pollutants, N-nitrosamines, in water. The developed analytical method requires a water sample of less than 5 ml and only 1.5 h for complete\\u000a analysis. The method detection limits for N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine, and N-nitrosodi-n-propylamine were

  15. Defluorinated Sparfloxacin as a New Photoproduct Identified by Liquid Chromatography Coupled with UV Detection and Tandem Mass Spectrometry

    PubMed Central

    Engler, Michael; Rüsing, Guido; Sörgel, Fritz; Holzgrabe, Ulrike

    1998-01-01

    Photodegradation of sparfloxacin was observed by means of high-pressure liquid chromatography with UV detection and liquid chromatography coupled with UV detection and tandem mass spectrometry (LC-MS/MS). Three products were detected. Comparison with an independently synthesized derivative of sparfloxacin revealed the structure of one product which is believed to be 8-desfluorosparfloxacin. The second product is likely to be formed by the splitting off of a fluorine and a cyclopropyl ring. Thus, photodefluorination of quinolone antibacterial agents is found and proved for the first time by LC-MS/MS. PMID:9593143

  16. Protein Complexes Characterization in Arabidopsis thaliana by Tandem Affinity Purification Coupled

    E-print Network

    Hirt, Heribert

    in vivo protein complexes. Key words Arabidopsis thaliana, Protein complexes, Tandem affinity purification purification). The TAP method was initially developed to isolate and identify protein complexes in the yeast protocols allow the purification of better purified protein complexes compared to sin- gle-step procedures

  17. Determination of oxidized phosphatidylcholines by hydrophilic interaction liquid chromatography coupled to Fourier transform mass spectrometry.

    PubMed

    Sala, Pia; Pötz, Sandra; Brunner, Martina; Trötzmüller, Martin; Fauland, Alexander; Triebl, Alexander; Hartler, Jürgen; Lankmayr, Ernst; Köfeler, Harald C

    2015-01-01

    A novel liquid chromatography-mass spectrometry (LC-MS) approach for analysis of oxidized phosphatidylcholines by an Orbitrap Fourier Transform mass spectrometer in positive electrospray ionization (ESI) coupled to hydrophilic interaction liquid chromatography (HILIC) was developed. This method depends on three selectivity criteria for separation and identification: retention time, exact mass at a resolution of 100,000 and collision induced dissociation (CID) fragment spectra in a linear ion trap. The process of chromatography development showed the best separation properties with a silica-based Kinetex column. This type of chromatography was able to separate all major lipid classes expected in mammalian samples, yielding increased sensitivity of oxidized phosphatidylcholines over reversed phase chromatography. Identification of molecular species was achieved by exact mass on intact molecular ions and CID tandem mass spectra containing characteristic fragments. Due to a lack of commercially available standards, method development was performed with copper induced oxidation products of palmitoyl-arachidonoyl-phosphatidylcholine, which resulted in a plethora of lipid species oxidized at the arachidonoyl moiety. Validation of the method was done with copper oxidized human low-density lipoprotein (LDL) prepared by ultracentrifugation. In these LDL samples we could identify 46 oxidized molecular phosphatidylcholine species out of 99 possible candidates. PMID:25874761

  18. Determination of Oxidized Phosphatidylcholines by Hydrophilic Interaction Liquid Chromatography Coupled to Fourier Transform Mass Spectrometry

    PubMed Central

    Sala, Pia; Pötz, Sandra; Brunner, Martina; Trötzmüller, Martin; Fauland, Alexander; Triebl, Alexander; Hartler, Jürgen; Lankmayr, Ernst; Köfeler, Harald C.

    2015-01-01

    A novel liquid chromatography-mass spectrometry (LC-MS) approach for analysis of oxidized phosphatidylcholines by an Orbitrap Fourier Transform mass spectrometer in positive electrospray ionization (ESI) coupled to hydrophilic interaction liquid chromatography (HILIC) was developed. This method depends on three selectivity criteria for separation and identification: retention time, exact mass at a resolution of 100,000 and collision induced dissociation (CID) fragment spectra in a linear ion trap. The process of chromatography development showed the best separation properties with a silica-based Kinetex column. This type of chromatography was able to separate all major lipid classes expected in mammalian samples, yielding increased sensitivity of oxidized phosphatidylcholines over reversed phase chromatography. Identification of molecular species was achieved by exact mass on intact molecular ions and CID tandem mass spectra containing characteristic fragments. Due to a lack of commercially available standards, method development was performed with copper induced oxidation products of palmitoyl-arachidonoyl-phosphatidylcholine, which resulted in a plethora of lipid species oxidized at the arachidonoyl moiety. Validation of the method was done with copper oxidized human low-density lipoprotein (LDL) prepared by ultracentrifugation. In these LDL samples we could identify 46 oxidized molecular phosphatidylcholine species out of 99 possible candidates. PMID:25874761

  19. Magnetostructural and magnetodielectric coupling in spinel oxides

    NASA Astrophysics Data System (ADS)

    Kemei, Moureen Chemurgor

    Spinels oxides are of great interest functionally as multiferroic, battery, and magnetic materials as well as fundamentally because they exhibit novel spin, structural, and orbital ground states. Competing interactions are at the heart of novel functional behavior in spinels. Here, we explore the intricate landscape of spin, lattice, and orbital interactions in magnetic spinels by employing variable-temperature high-resolution synchrotron x-ray powder diffraction, total neutron scattering, magnetic susceptibility, dielectric, and heat capacity measurements. We show that the onset of long-range magnetic interactions often gives rise to lattice distortions. We present the complete crystallographic descriptions of the ground state structures of several spinels, thereby paving the way for accurate modeling and design of structure-property relationships in these materials. We also report the emergence of magnetodielectric coupling in the magnetostructural phases of some of the studied spinels. We begin by examining spin-lattice coupling in the Jahn-Teller active systems NiCr2O4 and CuCr2O4. Orbital ordering yields a cubic to tetragonal lattice distortion in these materials above their magnetic ordering temperatures, however, we find that magnetic ordering also drives structural distortions in these spinels through exchange striction. We provide the first orthorhombic structural descriptions of NiCr 2O4 and CuCr2O4. Our observation of strong spin-lattice coupling in NiCr2O4 and CuCr 2O4 inspired the study of magnetodielectric coupling in these spinels. Magnetocapacitance measurements of NiCr2O4 reveal multiferroic behavior and new magnetostructural distortions below the Neel temperature. This observation illustrates the sensitivity of dielectric measurements to magnetostructural transitions in spinel materials. Finally, in the examination of NiCr2O4 we show that magnetodielectric coupling is well described by Ginzburg-Landau theory. In addition to exchange striction, geometric frustration couples spin interactions to the lattice of the spinels MgCr2O4 and ZnCr2O4. Novel spin ground states that are important for memory and quantum computing applications are predicted to exist in these spinels. However, their structural and spin ground states are not well understood. We find that tetragonal and orthorhombic phases coexist in antiferromagnetic MgCr2O4 and ZnCr2O4. The structural deformations in these materials lift spin degeneracy by primarily distorting the pyrochlore Cr sublattice. In subsequent studies, we probe the effect of adding dilute spins on the non-magnetic cation sites of MgCr2O 4 and ZnCr2O4. Substitution of Co2+ cations in Zn1-xCoxCr2O4 completely suppress the spin-Jahn-Teller distortion of ZnCr2O4 while, Cu2+ substitutions in Mg1-xCuxCr 2O4 and Zn1-xCuxCr2O 4 induce Jahn-Teller distortions at temperatures above their magnetic ordering temperatures. The Jahn-Teller distortions of Mg1-xCu xCr2O4 and Zn1-xCuxCr 2O4 do not lift spin degeneracy, therefore magnetic ordering is still suppressed down to low temperatures. We show that only more than 20% magnetic A substituents can lift spin degeneracy in MgCr 2O4 and ZnCr2O4. We have also examined the magnetostructural phase transition of the spinel Mn3O4. We show that Mn3O4 undergoes a magnetostructural phase transition from tetragonal I4 1/amd symmetry to a phase coexistence regime consisting of tetragonal I41/amd and orthorhombic Fddd symmetries. Phase coexistence in Mn3O4 is mediated by strain due to a significant lattice mismatch between the low temperature orthorhombic phase and the high temperature tetragonal phase. We propose that strain could be used to control the structure and properties of Mn3O4. Our investigations of spin-driven lattice distortions in spinel oxides illustrate that structural phase coexistence is prevalent for spinels with Neel temperatures below 50 K.

  20. PhIO as a powerful cyclizing reagent: regiospecific [3+2]-tandem oxidative cyclization of imine toward cofacially self-aggregated low molecular mass organic materials.

    PubMed

    Pandit, Palash; Chatterjee, Nirbhik; Halder, Samiran; Hota, Sandip K; Patra, Amarendra; Maiti, Dilip K

    2009-03-20

    The powerful cyclization and tandem oxidation property of environmentally benign PhIO is developed for the first time, which leads to regiospecific [3+2]-tandem oxidative cyclization of imine at room temperature in rapid access to a new class of compounds, 1,2-functionalized 4,5-diarylimidazoles, in excellent yield with synthetic efficiency. Size, shape, and activity of the involved nanoreactors for the green approach built up from various surfactants are investigated. Spontaneous generation of low molecular mass self-aggregated organic materials, their cofacial one-dimensional packing, and interesting photophysical properties are reported. PMID:19284739

  1. Regiospecific synthesis of neuroprotective 1,4-benzoxazine derivatives through a tandem oxidation-Diels-Alder reaction.

    PubMed

    Nguyen, Khac Minh Huy; Schwendimann, Leslie; Gressens, Pierre; Largeron, Martine

    2015-03-28

    The tandem oxidation-inverse electron demand Diels-Alder reaction of o-aminophenol derivatives and enamines has been accomplished at room temperature using a stoichiometric amount of manganese dioxide as the oxidant to furnish highly substituted 1,4-benzoxazine cycloadducts with complete regiochemical control. Because of its efficiency in introducing diverse elements in both cycloaddition partners, this one-pot process should allow the assembly of libraries of biologically relevant 1,4-benzoxazine derivatives. In this respect, the 3,3-diphenyl-substituted-1,4-benzoxazine derivative 3n was found to be a potent neuroprotective agent in an animal model of excitotoxic lesions in newborn mice. PMID:25686764

  2. Upgrading light hydrocarbons via tandem catalysis: a dual homogeneous Ta/Ir system for alkane/alkene coupling.

    PubMed

    Leitch, David C; Lam, Yan Choi; Labinger, Jay A; Bercaw, John E

    2013-07-17

    Light alkanes and alkenes are abundant but are underutilized as energy carriers because of their high volatility and low energy density. A tandem catalytic approach for the coupling of alkanes and alkenes has been developed in order to upgrade these light hydrocarbons into heavier fuel molecules. This process involves alkane dehydrogenation by a pincer-ligated iridium complex and alkene dimerization by a Cp*TaCl2(alkene) catalyst. These two homogeneous catalysts operate with up to 60/30 cooperative turnovers (Ir/Ta) in the dimerization of 1-hexene/n-heptane, giving C13/C14 products in 40% yield. This dual system can also effect the catalytic dimerization of n-heptane (neohexene as the H2 acceptor) with cooperative turnover numbers of 22/3 (Ir/Ta). PMID:23799786

  3. High ethylene to ethane processes for oxidative coupling

    DOEpatents

    Chafin, R.B.; Warren, B.K.

    1991-12-17

    Oxidative coupling of lower alkane to higher hydrocarbon is conducted using a catalyst comprising barium and/or strontium component and a metal oxide combustion promoter in the presence of vapor phase halogen component. High ethylene to ethane mole ratios in the product can be obtained over extended operating periods.

  4. High ethylene to ethane processes for oxidative coupling

    DOEpatents

    Chafin, Richard B. (Hurricane, WV); Warren, Barbara K. (Charleston, WV)

    1991-01-01

    Oxidative coupling of lower alkane to higher hydrocarbon is conducted using catalyst comprising barium and/or strontium component and a metal oxide combustion promoter in the presence of vapor phase halogen component. High ethylene to ethane mole ratios in the product can be obtained over extended operating periods.

  5. Coupling Oxidative Signals to Protein Phosphorylation via Methionine Oxidation in Arabidopsis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The mechanisms involved in sensing oxidative signaling molecules such as H2O2 in plant and animal cells are not completely understood. In the present study, we tested the postulate that oxidation of methionine (Met) to Met sulfoxide (MetSO) can couple oxidative signals to changes in protein phosphor...

  6. Controllable Tuning Plasmonic Coupling with Nanoscale Oxidation

    E-print Network

    Ding, Tao; Sigle, Daniel; Zhang, Liwu; Mertens, Jan; de Nijs, Bart; Baumberg, Jeremy

    2015-05-15

    films were thermally oxidized in a tube furnace for 10 min under atmosphere at different annealing temperatures (450, 500, and 550 ?C). The Al films were electrochemically oxidized while monitoring dark field microscopy. The setup is 12... Silver Nanospheres near a Silver Surface. Nano Lett. 2011, 11, 91-95. (27) Parsons, R., Effect of an Oxygen Plasma on Uncoated Thin Aluminum Reflecting Films. Gulino, D. A., Ed. National Aeronautics and Space Administration, Washington, DC, 1987. (28...

  7. Simultaneous determination of nicotine and its nine metabolites in rat blood utilizing microdialysis coupled with UPLC-tandem mass spectrometry for pharmacokinetic application.

    PubMed

    Mao, Jian; Xu, Yan; Lu, Binbin; Liu, Junhui; Hong, Guangfeng; Zhang, Qidong; Sun, Shihao; Zhang, Jianxun

    2015-05-01

    To develop a simple and rapid method for the simultaneous determination of nicotine and its nine metabolites in rat blood, an in vivo microdialysis sampling technique coupled with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established for quantitation and characterization of the pharmacokinetics of nicotine and its metabolites. Microdialysis probes were inserted into the jugular vein of Sprague Dawley rats, and dialysates were collected after nicotine (0.5 mg/kg, i.p.) administration. Target analytes and corresponding deuterated internal standards were separated on a hydrophilic interaction liquid chromatography column (HILIC BEH 2.1.?×?150 mm, 1.7 ?m) and detected by UPLC-MS/MS under multiple reaction monitoring mode. The limits of quantification for nicotine and its nine metabolites ranged from 0.039 to 0.46 ng/mL. Intra- and inter-day precision and accuracy were well within the predefined limits of acceptability (<11 %). Pharmacokinetic results showed that the mean half-lives of nicotine, cotinine, nornicotine, norcotinine, nicotine-N'-oxide, cotinine-N'-oxide, trans-3'-hydroxy-cotinine, nicotine-N-glucuronide, cotinine-N-glucuronide, and trans-3'-hydroxy-cotinine-O-glucuronide in rat plasma were 63, 291, 175, 440, 251, 451, 322, 341, 488, and 516 min, respectively. The blood concentration-time profiles of nicotine and its nine metabolites indicate that nicotine is rapidly consumed after the administration and subsequently cotinine is generated as the main metabolite; meanwhile, cotinine and other eight minor metabolites exhibit longer retention times in rat body. PMID:25824453

  8. Simultaneous analysis of 28 urinary VOC metabolites using ultra high performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (UPLC-ESI/MSMS).

    PubMed

    Alwis, K Udeni; Blount, Benjamin C; Britt, April S; Patel, Dhrusti; Ashley, David L

    2012-10-31

    Volatile organic compounds (VOCs) are ubiquitous in the environment, originating from many different natural and anthropogenic sources, including tobacco smoke. Long-term exposure to certain VOCs may increase the risk for cancer, birth defects, and neurocognitive impairment. Therefore, VOC exposure is an area of significant public health concern. Urinary VOC metabolites are useful biomarkers for assessing VOC exposure because of non-invasiveness of sampling and longer physiological half-lives of urinary metabolites compared with VOCs in blood and breath. We developed a method using reversed-phase ultra high performance liquid chromatography (UPLC) coupled with electrospray ionization tandem mass spectrometry (ESI/MSMS) to simultaneously quantify 28 urinary VOC metabolites as biomarkers of exposure. We describe a method that monitors metabolites of acrolein, acrylamide, acrylonitrile, benzene, 1-bromopropane, 1,3-butadiene, carbon-disulfide, crotonaldehyde, cyanide, N,N-dimethylformamide, ethylbenzene, ethylene oxide, propylene oxide, styrene, tetrachloroethylene, toluene, trichloroethylene, vinyl chloride and xylene. The method is accurate (mean accuracy for spiked matrix ranged from 84 to 104%), sensitive (limit of detection ranged from 0.5 to 20 ng mL(-1)) and precise (the relative standard deviations ranged from 2.5 to 11%). We applied this method to urine samples collected from 1203 non-smokers and 347 smokers and demonstrated that smokers have significantly elevated levels of tobacco-related biomarkers compared to non-smokers. We found significant (p<0.0001) correlations between serum cotinine and most of the tobacco-related biomarkers measured. These findings confirm that this method can effectively quantify urinary VOC metabolites in a population exposed to volatile organics. PMID:23062436

  9. Analysis of tomato glycoalkaloids by liquid chromatography coupled with electrospray ionization tandem mass spectrometry.

    PubMed

    Cataldi, Tommaso R I; Lelario, Filomena; Bufo, Sabino A

    2005-01-01

    Steroidal glycoalkaloids (SGAs) extracted from tomato leaves and berries (Lycopersicon esculentum Mill.) were separated and identified using optimized reversed-phase liquid chromatography with electrospray ionization (ESI) and ion trap mass spectrometry (ITMS). The ESI source polarity and chromatographic conditions were evaluated. The ESI spectra contain valuable information, which includes the mass of SGAs, the mass of the aglycones, and several characteristic fragment ions. Cleavage at the interglycosidic bonds proximal to the aglycones is the most prominent process in the ESI process. A protonated molecule, [M+H]+, accompanied by a mixed adduct ion, [M+H+Na]2+, was observed for alpha-tomatine (i.e., m/z 1034.7 and 528.9) and dehydrotomatine (i.e., m/z 1032.6 and 527.9) in positive ion mode spectra. The structures of these tomato glycoalkaloids were confirmed using tandem mass spectrometry. The identification of a new alpha-tomatine isomer glycoalkaloid, named filotomatine (MW 1033), which shares a common tetrasaccharide structure (i.e., lycotretraose) with alpha-tomatine and dehydrotomatine, and soladulcidine as an aglycone, is described for the first time. It occurs in significant amounts in the extracts of wild tomato foliage. Multistage mass spectrometry both of the protonated molecules and of the doubly charged ions was used for detailed structural elucidation of SGAs. Key fragmentations and regularities in fragmentation pathways are described and the fragmentation mechanisms involved are proposed. PMID:16200652

  10. Dissipation and residues of clethodim and its oxidation metabolites in a rape-field ecosystem using QuEChERS and liquid chromatography/tandem mass spectrometry.

    PubMed

    You, Xiangwei; Liang, Lin; Liu, Fengmao

    2014-01-15

    A rapid, sensitive and selective method using Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) procedure for simultaneous determination of clethodim and its oxidation metabolites (clethodim sulfoxide and clethodim sulphone) in soil, rape plant and rape seed was developed using high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The limits of detection (LODs) of the proposed method ranged from 0.002mg/kg to 0.01mg/kg, and average recoveries were 78.7-104.2%. The trial results showed that clethodim dissipated so rapidly that few clethodim residues were detectable. Clethodim sulfoxide dissipated quickly in rape plant and soil with half-lives of 4.3 and 4.0days, respectively. Clethodim sulphone showed a tendency of rapid increase initially followed by a decrease in rape plant but could not be detected in soil. The terminal residues of clethodim in rape seedsat harvest time were below the maximum residue limit (MRL, 0.5mg/kg). PMID:24054227

  11. Nitric Oxide Enhances Charge-Coupled Device

    NASA Technical Reports Server (NTRS)

    Hecht, Michael H.; Poindexter, Edward H.

    1990-01-01

    Simple treatment increases and stabilizes quantum efficiency of charge-coupled-device photodetector illuminated on back surface at wavelengths less than 4,500 Angstrom. Must be biased in strong accumulation mode. Physical principle of enhancement explained more fully in "Metal Film Increases CCD Output" (NPO-16815). Useful for imaging at wavelengths from ultraviolet to blue; for example, in astronomical observations.

  12. Photoelectrochemical Behavior of Hierarchically Structured Si/WO3 Core-Shell Tandem Photoanodes

    E-print Network

    Braun, Paul

    Photoelectrochemical Behavior of Hierarchically Structured Si/WO3 Core-Shell Tandem Photoanodes-shell photoanodes exhibited en- hanced near-visible spectral response behavior, due to increased light absorption-oxide photoanodes coupled with Si photocathodes11,12 and composite metal-oxide photocatalysts,13 have mutually

  13. Oscillatory exchange coupling and positive magnetoresistance in epitaxial oxide heterostructures

    PubMed

    Nikolaev; Dobin; Krivorotov; Cooley; Bhattacharya; Kobrinskii; Glazman; Wentzovitch; Dahlberg; Goldman

    2000-10-23

    Oscillation in the exchange coupling between ferromagnetic La(2/3)Ba(1/3)MnO3 layers with paramagnetic LaNiO3 spacer layer thickness has been observed in epitaxial heterostructures of the two oxides. This behavior is explained within the RKKY model employing an ab initio calculated band structure of LaNiO3, taking into account strong electron scattering in the spacer. Antiferromagnetically coupled superlattices exhibit a positive current-in-plane magnetoresistance. PMID:11030992

  14. Determinations of airborne synthetic musks by polyurethane foam coupled with triple quadrupole gas chromatography tandem mass spectrometer.

    PubMed

    Wang, I-Ting Ivy; Cheng, Shu-Fang; Tsai, Shih-Wei

    2014-02-21

    Synthetic musk is widely used in various scented consumer products. However, the exposure via inhalation is often ignored due to pleasant smells. In addition, the information regarding the distribution of synthetic musk in air is limited. Hence, this research is aimed to develop a highly sensitive and widely applicable method for the determination of airborne synthetic musk. In this study, polyurethane foam (PUF) and filter were employed for active air sampling. Microwave assisted extraction (MAE) and nitrogen evaporator were performed for sample preparation. A gas chromatography coupled with triple quadrupole tandem mass spectrometer (GC/MS-MS) with specific multiple reaction monitoring (MRM) transition pairs was applied for sample analysis. Compared with using selected ion monitoring (SIM) mode traditionally, the sensitivities were improved in this study about an order at least. In terms of air concentration, as low as 0.48ngm(-3) can be determined when sampling at 3.5Lmin(-1) for 8h. The method established was further applied to the analysis of synthetic musk compounds in air samples collected in a cosmetics plant. The results showed that the airborne concentrations of gaseous polycyclic musk, gaseous nitro-musk, and particle-phase polycyclic musk were 6.4×10(2), 4.0×10(1) and 3.1×10(2)ngm(-3), respectively. Meanwhile, Cashmeran, Celstolide, Galaxolide, and Tonalide were found as the dominant musk compounds in the factory investigated. PMID:24480734

  15. Hydrophilic interaction liquid chromatography coupled with tandem mass spectrometry for acidic herbicides and metabolites analysis in fresh water.

    PubMed

    Fauvelle, Vincent; Mazzella, Nicolas; Morin, Soizic; Moreira, Sylvia; Delest, Brigitte; Budzinski, Hélène

    2015-03-01

    Theoretical papers and environmental applications of hydrophilic interaction liquid chromatography (HILIC) have been published for a wide range of analytes, but to our knowledge, no study focused on acidic herbicides (e.g., triketones, phenoxy acids, sulfonylurea, and acidic metabolites of chloroacetanilides). Matrix effects are the main obstacle to natural sample analysis by liquid chromatography coupled with tandem mass spectrometry (MS) via an electrospray ionization (ESI) interface. Therefore, we paid particular attention on limiting interference by (i) adapting the emerging HILIC technique, which is generally considered more sensitive than conventional reversed phase liquid chromatography and (ii) optimizing the solid phase extraction (SPE) step using a design of experiment. A rapid and reliable off line SPE-HILIC-ESI-MS/MS method was thus developed for the quantification of acidic herbicides in fresh water, with limits of quantifications (LOQs) ranging from 5 to 22 ng L(-1). Then, the analysis of freshwater samples highlighted the robustness of the method, and the importance of the chloroacetanilides metabolites among the studied analytes. PMID:24859693

  16. Quantitative determination of capecitabine and its six metabolites in human plasma using liquid chromatography coupled to electrospray tandem mass spectrometry.

    PubMed

    Deenen, Maarten J; Rosing, Hilde; Hillebrand, Michel J; Schellens, Jan H M; Beijnen, Jos H

    2013-01-15

    Capecitabine is the oral prodrug of the anticancer drug 5-fluorouracil (5-FU). The purpose of this study was to quantify capecitabine and its metabolites including 5'-deoxy-5-fluorocytidine (5'-dFCR), 5'-deoxy-5-fluorouridine (5'-dFUR), 5-FU, dihydro-5-fluorouracil (FUH(2)), ?-fluoro-ureidopropionic acid (FUPA) and fluoro-?-alanine (FBAL) in human plasma using liquid chromatography coupled to electrospray tandem mass spectrometry. To this end two individual assays were developed: one for the simultaneous quantification of capecitabine, 5'-dFCR and 5'-dFUR using reversed phase chromatography and gradient elution, and one assay for 5-FU, FUH(2), FUPA and FBAL using hydrophilic interaction chromatography and isocratic elution. Both assays were fully validated according to current FDA guidelines. Total run time for the capecitabine assay was 9.0min, and of the 5-FU assay 5.0min. Analyte extraction was performed by protein precipitation. Stable labeled isotopes for each of the analytes were used as internal standards. The linear ranges of the analytes were 50-6000ng/mL for the capecitabine assay and 50-5000ng/mL for the 5-FU assay. Validation results demonstrate that capecitabine and its metabolites can be rapidly, accurately, precisely and robustly quantified in human plasma with the presented methods. Both assays are currently in extensive use in support of pharmacokinetic studies in patients treated with capecitabine or 5-FU. PMID:23270936

  17. Strategies in protein sequencing and characterization: multi-enzyme digestion coupled with alternate CID/ETD tandem mass spectrometry.

    PubMed

    Nardiello, Donatella; Palermo, Carmen; Natale, Anna; Quinto, Maurizio; Centonze, Diego

    2015-01-01

    A strategy based on a simultaneous multi-enzyme digestion coupled with electron transfer dissociation (ETD) and collision-induced dissociation (CID) was developed for protein sequencing and characterization, as a valid alternative platform in ion-trap based proteomics. The effect of different proteolytic procedures using chymotrypsin, trypsin, a combination of both, and Lys-C, was carefully evaluated in terms of number of identified peptides, protein coverage, and score distribution. A systematic comparison between CID and ETD is shown for the analysis of peptides originating from the in-solution digestion of standard caseins. The best results were achieved with a trypsin/chymotrypsin mix combined with CID and ETD operating in alternating mode. A post-database search validation of MS/MS dataset was performed, then, the matched peptides were cross checked by the evaluation of ion scores, rank, number of experimental product ions, and their relative abundances in the MS/MS spectrum. By integrated CID/ETD experiments, high quality-spectra have been obtained, thus allowing a confirmation of spectral information and an increase of accuracy in peptide sequence assignments. Overlapping peptides, produced throughout the proteins, reduce the ambiguity in mapping modifications between natural variants and animal species, and allow the characterization of post translational modifications. The advantages of using the enzymatic mix trypsin/chymotrypsin were confirmed by the nanoLC and CID/ETD tandem mass spectrometry of goat milk proteins, previously separated by two-dimensional gel electrophoresis. PMID:25479873

  18. Determination of perfluorooctane sulfonate and perfluorooctanoic acid in food packaging using liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Poothong, Somrutai; Boontanon, Suwanna Kitpati; Boontanon, Narin

    2012-02-29

    This research aimed to monitor the amounts of PFOS and PFOA in food packaging and study the migration of PFOS and PFOA from food packaging, using a saliva simulant and pressurized liquid extraction (PLE) technique. Liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) was employed to determine residues of PFOS and PFOA by using a gradient reversed-phase method with ammonium acetate/acetonitrile buffer. A good linearity was established for PFOS and PFOA in a range of 0.05-10 ?gL(-1), with R2 ? 0.9998. Of the samples extracted by methanol, the highest concentration of PFOS was found in fast-food container samples, at a level of 92.48 ng dm(-2). For PFOA, the highest concentration in samples extracted by methanol was found in ice cream cup samples, at a level of 16.91 ng dm(-2). The amounts of PFOS and PFOA that migrated from food packaging samples through contact with saliva simulant were 4.80 and 4.55 ng dm(-2), respectively. Saliva simulant could leach PFOS and PFOA from the group of the thickest paper samples (?1 dm2 g(-1)) at levels of 7.01 and 6.41 ng dm(-2), respectively, indicating that paper with greater thickness and less area might release larger quantities of coated/added PFOS or PFOA. PMID:22265653

  19. Determination of salbutamol in human plasma and urine using liquid chromatography coupled to tandem mass spectrometry and its pharmacokinetic study.

    PubMed

    Zhang, Dujuan; Teng, Yanni; Chen, Keguang; Liu, Sha; Wei, Chunmin; Wang, Benjie; Yuan, Guiyan; Zhang, Rui; Liu, Xiaoyan; Guo, Ruichen

    2012-10-01

    A sensitive and selective liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was developed and validated for the determination of salbutamol in human plasma and urine, and successfully applied to the pharmacokinetic study of salbutamol in Chinese healthy volunteers after inhalation of salbutamol sulfate aerosol. Salbutamol and the internal standard (IS) acetaminophen in plasma and urine were extracted with ethyl acetate, separated on a C(18) reversed-phase column, eluted with mobile phase of acetonitrile-ammonium acetate (5?m m; 30:70, v/v), ionized by positive ion pneumatically assisted electrospray and detected in the multi-reaction monitoring mode using precursor???product ions of m/z 240.2???148.1 for salbutamol and 152???110 for the IS. The lower limits of quantitation of salbutamol in human plasma and urine by this method were 0.02 and 1?ng/mL, respectively. The specificity, matrix effect, recovery, sensitivity, linearity, accuracy, precision and several stabilities were validated for salbutamol in human plasma and urine. In conclusion, the validation results showed that this method is robust, specific and sensitive, and can successfully fulfill the requirement of clinical pharmacokinetic study of salbutamol in healthy Chinese volunteers. PMID:22213268

  20. Budesonide quantification by HPLC coupled to atmospheric pressure photoionization (APPI) tandem mass spectrometry. Application to a comparative systemic bioavailability of two budesonide formulations in healthy volunteers

    Microsoft Academic Search

    Ney Carter do Carmo Borges; Rafael Barrientos Astigarraga; Carlos Eduardo Sverdloff; Bruno Carter Borges; Thaís Rodrigues Paiva; Paulo Rebelo Galvinas; Ronilson Agnaldo Moreno

    2011-01-01

    In the present study, a novel, fast, sensitive and robust method to quantify budesonide in human plasma using 3-keto-desogestrel as the internal standard (IS) is described. The analyte and the IS were extracted from human plasma by liquid–liquid extraction (LLE) using ether. Extracted samples were analyzed by high performance liquid chromatography coupled to Atmospheric pressure photoionization tandem mass spectrometry (HPLC–APPI-MS\\/MS).

  1. High-performance liquid chromatography coupled with electrospray tandem mass spectrometry (LC\\/MS\\/MS) method for the simultaneous determination of diazepam, atropine and pralidoxime in human plasma

    Microsoft Academic Search

    Chadi Abbara; Isabelle Bardot; Annie Cailleux; Guy Lallement; Anne Le Bouil; Alain Turcant; Pascal Clair; Bertrand Diquet

    2008-01-01

    A high-performance liquid chromatography coupled with electrospray tandem mass spectrometry (LC\\/MS\\/MS) procedure for the simultaneous determination of diazepam from avizafone, atropine and pralidoxime in human plasma is described. Sample pretreatment consisted of protein precipitation from 100?l of plasma using acetonitrile containing the internal standard (diazepam D5). Chromatographic separation was performed on a X-Terra® MS C8 column (100mm×2.1mm, i.d. 3.5?m), with

  2. Copper-catalyzed, C-C coupling-based one-pot tandem reactions for the synthesis of benzofurans using o-iodophenols, acyl chlorides, and phosphorus ylides.

    PubMed

    Liu, Yunyun; Wang, Hang; Wan, Jie-Ping

    2014-11-01

    One-pot reactions involving acyl chlorides, phosphorus ylides, and o-iodophenols with copper catalysis have been established for the rapid synthesis of functionalized benzofurans. With all of these easily available and stable reactants, the construction of the target products has been accomplished via tandem transformations involving a key C-C coupling, leading to the formation of one C(sp(2))-C bond, one C(sp(2))-O bond, and one C ? C bond. PMID:25279735

  3. Determination of the change of flavonoid components as the defence materials of Citrus unshiu Marc. fruit peel against Penicillium digitatum by liquid chromatography coupled with tandem mass spectrometry

    Microsoft Academic Search

    Hae Gyeong Kim; Gon-Sup Kim; Jung Han Lee; Semin Park; Won Young Jeong; Yun-Hi Kim; Jae Hoon Kim; Soo Taek Kim; Young Ah Cho; Won Sup Lee; Soo Jung Lee; Jong Sung Jin; Sung Chul Shin

    2011-01-01

    A healthy fruit peel of Citrus unshiu Marc. and one infected by Penicillium digitatum were analysed for flavonoids via high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC–MS\\/MS) in the positive mode with selected ion monitoring (SIM). Among 16 flavonoid components characterised in C. unshiu Marc., four flavanones and nine flavones were identified for the first time. The identified compounds

  4. Residue determination of glyphosate, glufosinate and aminomethylphosphonic acid in water and soil samples by liquid chromatography coupled to electrospray tandem mass spectrometry

    Microsoft Academic Search

    María Ibáñez; Óscar J. Pozo; Juan V. Sancho; Francisco J. López; Félix Hernández

    2005-01-01

    This paper describes a method for the sensitive and selective determination of glyphosate, glufosinate and aminomethylphosphonic acid (AMPA) residues in water and soil samples. The method involves a derivatization step with 9-fluorenylmethylchloroformate (FMOC) in borate buffer and detection based on liquid chromatography coupled to electrospray tandem mass spectrometry (LC–ESI-MS\\/MS). In the case of water samples a volume of 10mL was

  5. COUPLING OF BIOTIC AND ABIOTIC ARSENITE OXIDATION IN SOIL

    E-print Network

    Sparks, Donald L.

    : __________________________________________________________ Blake C. Meyers, Ph.D. Chair of the Department of Plant & Soil Sciences ApprovedCOUPLING OF BIOTIC AND ABIOTIC ARSENITE OXIDATION IN SOIL by Laura Camille Jones A thesis submitted of Science in Plant & Soil Sciences Summer 2011 Copyright 2011 Laura Camille Jones All Rights Reserved #12

  6. Quantitative Analysis of amino acid oxidation markers by tandem mass spectrometry

    PubMed Central

    Vivekanandan-Giri, Anuradha; Byun, Jaeman; Pennathur, Subramaniam

    2011-01-01

    Oxidative stress plays a central role in the pathogenesis of diverse chronic inflammatory disorders including diabetic complications, cardiovascular disease, aging, neurodegenerative disease, autoimmune disorders and pulmonary fibrosis. Protein misfolding can lead to chronic endoplasmic reticulum (ER) stress which can exacerbate oxidative stress. This can trigger apoptotic cascades resulting in chronic inflammatory disorders. Despite intense interest in origins and magnitude of oxidative stress, ability to quantify oxidants has been limited because they are short-lived. We have developed quantitative mass spectrometry (MS) based analytical strategies to analyze stable end-products of protein oxidation. These molecules provide quantitative and mechanistic assessment of degree of oxidative stress in cell cultures, tissues and biofluids of animal models of disease and human samples. Our studies support the hypothesis that unique reactive intermediates generated in localized microenvironments of vulnerable tissues promote end-organ damage. The ability to quantify these changes and assess response to therapies will be pivotal in understanding disease mechanisms and monitoring efficacy of therapy. PMID:21329795

  7. Coupling of oxidative dehydrogenation and aromatization reactions of butane

    SciTech Connect

    Xu, Wen-Qing; Suib, S.L. (Univ. of Connecticut, Storrs, CT (United States))

    1994-01-01

    Coupling of oxidative dehydrogenation and aromatization of butane by using a dual function catalyst has led to a significant enhancement of the yields (from 25 to 40%) and selectivities to aromatics (from 39 to 64%). Butane is converted to aromatics by using either zinc-promoted [Ga]-ZSM-5 or zinc and gallium copromoted [Fe]-ZSM-5 zeolite as a catalyst. However, the formation of aromatics is severely limited by hydrocracking of butane to methane, ethane, and propane due to the hydrogen formed during aromatization reactions. On the other hand, the oxidative dehydrogenation of butane to butene over molybdate catalysts is found to be accompanied by a concurrent undesirable reaction, i.e., total oxidation. When two of these reactions (oxidative dehydrogenation and aromatization of butane) are coupled by using a dual function catalyst they have shown to complement each other. It is believed that the rate-limiting step for aromatization (butane to butene) is increased by adding an oxidative dehydrogenation catalyst (Ga-Zn-Mg-Mo-O). The formation of methane, ethane, and propane was suppressed due to the removal of hydrogen initially formed as water. Studies of ammonia TPD show that the acidities of [Fe]-ZSM-5 are greatly affected by the existence of metal oxides such as Ga[sub 2]O[sub 3], MgO, ZnO, and MoO[sub 3]. 40 refs., 9 figs., 1 tab.

  8. A novel one-pot method for the synthesis of substituted furopyridines: iodine-mediated oxidation of enaminones by tandem metal-free cyclization.

    PubMed

    Yan, Rulong; Li, Xiaoni; Yang, Xiaodong; Kang, Xing; Xiang, Likui; Huang, Guosheng

    2015-02-14

    A novel iodine-mediated oxidative tandem cyclization reaction of simple enaminones has been developed for the synthesis of substituted furopyridines through C-C/C-N/C-O bond formation in a one-pot procedure. Substituted furopyridines are obtained in moderate to good yield. In addition, I- and Br-substituted furopyridines have been successfully produced by the electrophilic substitution of N-iodo- or N-bromosuccinimide. PMID:25569222

  9. Simultaneous determination of 24 polycyclic aromatic hydrocarbons in edible oil by tandem solid-phase extraction and gas chromatography coupled/tandem mass spectrometry.

    PubMed

    Xu, Ting; Tang, Hua; Chen, Dazhou; Dong, Haifeng; Li, Lei

    2015-01-01

    An efficient and fast tandem SPE method followed by GC/MS/MS has been developed for the determination and the quantification of 24 polycyclic aromatic hydrocarbons (PAHs) in edible oil. This method includes the monitoring of 15 + 1 PAHs designated as a priority by the European Union in their 2005/108/EC recommendation and 16 PAHs listed by the U. S. Environmental Protection Agency. The sample preparation procedures were based on SPE in which PAH-dedicated cartridges with molecularly imprinted polymers and graphitized carbon black were used in series. The novel tandem SPE combination of selective extraction and purification of light and heavy PAHs provided highly purified analytes. Identification and quantification of 24 target PAHs were performed using GC/MS/MS with the isotope dilution approaches using D-labeled and (13)C-labeled PAHs. The advantages of GC/MS/MS as compared to other detection methods include high sensitivity, selectivity, and interpretation ability. The method showed satisfactory linearity (R(2) > 0.998) over the range assayed (0.5-200 ?g/kg); the LODs ranged from 0.03 to 0.6 ?g/kg, and LOQs from 0.1 to 2.0 ?g/kg. The recoveries using this method at three spiked concentration levels (2, 10, and 50 ?g/kg) ranged from 56.8 to 117.7%. The RSD was lower than 12.7% in all cases. The proposed analytical method has been successfully applied for the analysis of the 24 PAHs in edible oil. PMID:25905761

  10. Online deuterium hydrogen exchange and protein digestion coupled with ion mobility spectrometry and tandem mass spectrometry.

    PubMed

    Donohoe, Gregory C; Arndt, James R; Valentine, Stephen J

    2015-05-19

    Online deuterium hydrogen exchange (DHX) and pepsin digestion (PD) is demonstrated using drift tube ion mobility spectrometry (DTIMS) coupled with linear ion trap (LTQ) mass spectrometry (MS) with electron transfer dissociation (ETD) capabilities. DHX of deuterated ubiquitin, followed by subsequent quenching and digestion, is performed within ?60 s, yielding 100% peptide sequence coverage. The high reproducibility of the IMS separation allows spectral feature matching between two-dimensional IMS-MS datasets (undeuterated and deuterated) without the need for dataset alignment. Extracted ion drift time distributions (XIDTDs) of deuterated peptic peptides are mobility-matched to corresponding XIDTDs of undeuterated peptic peptides that were identified using collision-induced dissociation (CID). Matching XIDTDs allows a straightforward identification and deuterium retention evaluation for labeled peptides. Aside from the mobility separation, the ion trapping capabilities of the LTQ, combined with ETD, are demonstrated to provide single-residue resolution. Deuterium retention for the c- series ions across residues M(1)-L(15) and N(25)-R(42) are in good agreement with the known secondary structural elements within ubiquitin. PMID:25893550

  11. Proteomic Analysis of the Organ of Corti Using Nanoscale Liquid Chromatography Coupled with Tandem Mass Spectrometry

    PubMed Central

    Peng, Hong; Liu, Miao; Pecka, Jason; Beisel, Kirk W.; Ding, Shi-Jian

    2012-01-01

    The organ of Corti (OC) in the cochlea plays an essential role in auditory signal transduction in the inner ear. For its minute size and trace amount of proteins, the identification of the molecules in pathophysiologic processes in the bone-encapsulated OC requires both delicate separation and a highly sensitive analytical tool. Previously, we reported the development of a high resolution metal-free nanoscale liquid chromatography system for highly sensitive phosphoproteomic analysis. Here this system was coupled with a LTQ-Orbitrap XL mass spectrometer to investigate the OC proteome from normal hearing FVB/N male mice. A total of 628 proteins were identified from six replicates of single LC-MS/MS analysis, with a false discovery rate of 1% using the decoy database approach by the OMSSA search engine. This is currently the largest proteome dataset for the OC. A total of 11 proteins, including cochlin, myosin VI, and myosin IX, were identified that when defective are associated with hearing impairment or loss. This study demonstrated the effectiveness of our nanoLC-MS/MS platform for sensitive identification of hearing loss-associated proteins from minute amount of tissue samples. PMID:22942697

  12. Preparation of quinoxalines, dihydropyrazines, pyrazines and piperazines using tandem oxidation processes.

    PubMed

    Raw, Steven A; Wilfred, Cecilia D; Taylor, Richard J K

    2003-09-21

    Alpha-hydroxyketones undergo MnO2-mediated oxidation followed by in situ trapping with aromatic or aliphatic 1,2-diamines to give quinoxalines or dihydropyrazines, respectively, in a one pot procedure which avoids the need to isolate the highly reactive 1,2-dicarbonyl intermediates. Modifications of the procedure allow the formation of pyrazines and piperazines. PMID:14518877

  13. Rapid and sensitive hormonal profiling of complex plant samples by liquid chromatography coupled to electrospray ionization tandem mass spectrometry

    PubMed Central

    2011-01-01

    Background Plant hormones play a pivotal role in several physiological processes during a plant's life cycle, from germination to senescence, and the determination of endogenous concentrations of hormones is essential to elucidate the role of a particular hormone in any physiological process. Availability of a sensitive and rapid method to quantify multiple classes of hormones simultaneously will greatly facilitate the investigation of signaling networks in controlling specific developmental pathways and physiological responses. Due to the presence of hormones at very low concentrations in plant tissues (10-9 M to 10-6 M) and their different chemistries, the development of a high-throughput and comprehensive method for the determination of hormones is challenging. Results The present work reports a rapid, specific and sensitive method using ultrahigh-performance liquid chromatography coupled to electrospray ionization tandem spectrometry (UPLC/ESI-MS/MS) to analyze quantitatively the major hormones found in plant tissues within six minutes, including auxins, cytokinins, gibberellins, abscisic acid, 1-amino-cyclopropane-1-carboxyic acid (the ethylene precursor), jasmonic acid and salicylic acid. Sample preparation, extraction procedures and UPLC-MS/MS conditions were optimized for the determination of all plant hormones and are summarized in a schematic extraction diagram for the analysis of small amounts of plant material without time-consuming additional steps such as purification, sample drying or re-suspension. Conclusions This new method is applicable to the analysis of dynamic changes in endogenous concentrations of hormones to study plant developmental processes or plant responses to biotic and abiotic stresses in complex tissues. An example is shown in which a hormone profiling is obtained from leaves of plants exposed to salt stress in the aromatic plant, Rosmarinus officinalis. PMID:22098763

  14. Multiresidue determination of veterinary drugs in aquaculture fish samples by ultra high performance liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Lopes, Renata Pereira; Reyes, Rocío Cazorla; Romero-González, Roberto; Vidal, José Luis Martínez; Frenich, Antonia Garrido

    2012-05-01

    A simple, selective and fast multiresidue method was developed for the determination of 32 veterinary drug residues belonging to several families, in gilthead sea bream (Sparus aurata) by ultra high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). The extraction was based on modified QuEChERS (quick, easy, cheap, effective, rugged and safe) procedure, using as extraction solution a mixture of acetonitrile and methanol (75:25, v/v), and it reduces sample handling, increasing sample throughput in relation to current methodologies. The developed method was validated and mean recovery ranged from 69% to 125% (at 10, 25, 50 and 100 ?g/kg). Intra and interday precision, estimated as the same levels and expressed as relative standard deviation, RSD, were lower than 20% and 30%, respectively. Limits of detection (LODs) and quantification (LOQs) were lower than 7.5 and 25 ?g/kg, respectively, except for danofloxacin, oxytetracycline and tetracycline (LOD and LOQ of 15.0 and 50 ?g/kg, respectively). Decision limit (CC(?)) and detection capability (CC(?)) were also calculated and ranged from 16.7 ?g/kg (levamisole) to 605.0 (flumequine) ?g/kg and from 23.5 ?g/kg (levamisole) to 611.5 ?g/kg (flumequine), respectively. The expanded uncertainty, U, was also evaluated ant it was below 25% at 100 ?g/kg level, except for tetracycline (28%). Finally, the method was applied to ten samples obtained from local supermarkets in Almería (Spain) and traces of some compounds were detected. PMID:22465276

  15. Trace level liquid chromatography tandem mass spectrometry quantification of the mutagenic impurity 2-hydroxypyridine N-oxide as its dansyl derivative.

    PubMed

    Ding, Wei; Huang, Yande; Miller, Scott A; Bolgar, Mark S

    2015-03-20

    A derivatization LC-MS/MS method was developed and qualified for the trace level quantification of 2-hydroxypyridine N-oxide (HOPO). HOPO is a coupling reagent used in the syntheses of active pharmaceutical ingredients (APIs) to form amide bonds. HOPO was recently confirmed to generate a positive response in a GLP Ames bacterial-reverse-mutation test, classifying it as a mutagenic impurity and as such requiring its control in APIs to the threshold of toxicological concern (TTC). The derivatization reagent 5-dimethylamino-1-naphthalenesulfonyl chloride (dansyl chloride) was used in a basic solution to convert HOPO into the corresponding dansyl-derivative. The derivative was separated from different APIs and reagents by liquid chromatography. The detection of the HOPO dansyl-derivative was achieved by mass spectrometry in selected reaction monitoring (SRM) mode. The LC-MS/MS method had a reporting limit of 0.1ng/mL HOPO, which corresponds to 0.1ppm HOPO relative to an API at 1mg/mL, and a linearity range of 0.1-25ng/mL HOPO analyte. Recoveries of HOPO standards spiked into three different API matrices at 0.2, 1.2, and 20ppm levels were all within 90-100%. An SRM-based confirmatory methodology using the ratios of two fragment ions at three CID energies was developed to verify the identity of HOPO when present at ?0.6ppm. This identity confirmation can be employed to prevent potential false positive detection of mutagenic impurities at trace level. It can be broadly applicable for the confirmation of analytes when the analytes generate at least two major fragments in tandem mass spectrometry experiments. PMID:25683628

  16. Orthogonal tandem catalysis

    NASA Astrophysics Data System (ADS)

    Lohr, Tracy L.; Marks, Tobin J.

    2015-06-01

    Tandem catalysis is a growing field that is beginning to yield important scientific and technological advances toward new and more efficient catalytic processes. 'One-pot' tandem reactions, where multiple catalysts and reagents, combined in a single reaction vessel undergo a sequence of precisely staged catalytic steps, are highly attractive from the standpoint of reducing both waste and time. Orthogonal tandem catalysis is a subset of one-pot reactions in which more than one catalyst is used to promote two or more mechanistically distinct reaction steps. This Perspective summarizes and analyses some of the recent developments and successes in orthogonal tandem catalysis, with particular focus on recent strategies to address catalyst incompatibility. We also highlight the concept of thermodynamic leveraging by coupling multiple catalyst cycles to effect challenging transformations not observed in single-step processes, and to encourage application of this technique to energetically unfavourable or demanding reactions.

  17. Human G-protein-coupled inwardly rectifying potassium channel (GIRK1) gene (KCNJ3): Localization to chromosome 2 and identification of a simple tandem repeat polymorphism

    SciTech Connect

    Stoffel, M.; Powell, K.L.; Espinosa, R. III; Philipson, L.H.; Le Beau, M.M.; Bell, G.I. (Univ. of Chicago, IL (United States))

    1994-05-01

    The gene encoding the human G-protein-coupled inwardly rectifying potassium channel designated GIRK1 (gene symbol, KCNJ3) was mapped to chromosome 2 by analyzing its segregation in a panel of human-hamster somatic cell hybrids. This assignment was confirmed by fluorescence in situ hybridization to metaphase chromosomes, and the gene was further localized to band 2q24.1. A highly informative simple tandem repeat DNA polymorphism of the form (CA)[sub n] was identified and used to localize KCNJ3 within the genetic map of the long arm of chromosome 2. 8 refs., 1 fig., 2 tabs.

  18. Determination of perchlorate in river by ion-pair hollow-fiber liquid-phase microextraction coupled with electrospray ionization tandem mass spectrometry

    Microsoft Academic Search

    Hsin-Chang Chen; Wen-Tsen Chen; Wang-Hsien Ding

    2009-01-01

    This paper describes the analysis of perchlorate (ClO4?) in surface water samples by a rapid and reliable ion-pair hollow-fiber liquid-phase microextraction (HF-LPME) method coupled with flow-injection electrospray ionization tandem mass spectrometry (ESI-MS–MS) technique. The effects of the type and concentration of ion-pairing reagents, extraction time, temperature and pH value on the quantitative extraction of perchlorate by ion-pair HF-LPME were investigated

  19. OXIDATIVE COUPLING OF METHANE USING INORGANIC MEMBRANE REACTORS

    SciTech Connect

    Dr. Y.H. Ma; Dr. W.R. Moser; Dr. A.G. Dixon; Dr. A.M. Ramachandra; Dr. Y. Lu; C. Binkerd

    1998-04-01

    The objective of this research is to study the oxidative coupling of methane in catalytic inorganic membrane reactors. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and higher yields than in conventional non-porous, co-feed, fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gas phase reactions, which are believed to be a main route for the formation of CO{sub x} products. Such gas phase reactions are a cause of decreased selectivity in the oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Membrane reactor technology also offers the potential for modifying the membranes both to improve catalytic properties as well as to regulate the rate of the permeation/diffusion of reactants through the membrane to minimize by-product generation. Other benefits also exist with membrane reactors, such as the mitigation of thermal hot-spots for highly exothermic reactions such as the oxidative coupling of methane. The application of catalytically active inorganic membranes has potential for drastically increasing the yield of reactions which are currently limited by either thermodynamic equilibria, product inhibition, or kinetic selectivity.

  20. A novel method for the simultaneous analysis of seven biothiols in rice (Oryza sativa L.) using hydrophilic interaction chromatography coupled with electrospray tandem mass spectrometry.

    PubMed

    Cao, Zhao-Yun; Sun, Li-Hua; Mou, Ren-Xiang; Zhou, Rong; Zhu, Zhi-Wei; Chen, Ming-Xue

    2015-01-22

    Analysis of biothiols is still problematic, due to their high polarity, oxidation sensitivity and time-consuming sample preparation. In this paper, a direct, rapid and sensitive method was developed for simultaneous quantification of unbound cysteine (Cys), glutathione (GSH) and phytochelatins (PCs) in rice leaf, stem and root samples by hydrophilic interaction chromatography coupled with electrospray tandem mass spectrometry (HILIC-MS/MS). Homogenized samples were extracted with water containing 50mM dithiothreitol, without derivatization and further clean-up, and the extracts were injected directly onto an Xbridge Amide-HILIC column (3.5?m, 150mm×2.1mm i.d.). The best chromatographic separation and MS sensitivity was achieved using a linear gradient elution with 10mM aqueous ammonium formate and acetonitrile as the mobile phase. In MS/MS mode the detection limit (S/N?3) of seven biothiols was 3-105nM. Good linearities were observed (r>0.995) with linear dynamic range at least over three orders of magnitude. Recoveries for most analytes were within the range of 77-128%, with relative standard deviations less than 18.2%. The intra-day precision (n=7) was 6.1-11.7%, and the inter-day precision over 15 d (n=15) was 8.5-16.3% for all biothiols. The optimized HILIC-MS/MS method was applied to study the influence of different cadmium (Cd) concentrations (0, 1 and 50?M) on contents of Cys, GSH and PC2-6 in rice tissue. With increasing Cd concentrations in nutrient solutions, contents of PC2-4 in rice roots increased but contents of Cys and GSH decreased. Contents of PC2-4 in both rice leafs and stems increased markedly at high dose Cd (50?M) treatment compared with controls, compared with low Cd concentrations (1?M). However, both PC5 and PC6 were not detected throughout the stress experiment. PMID:25436484

  1. Tandem metal-coordination copolymerization and organocatalytic ring-opening polymerization via water to synthesize diblock copolymers of styrene oxide/CO2 and lactide.

    PubMed

    Wu, Guang-Peng; Darensbourg, Donald J; Lu, Xiao-Bing

    2012-10-24

    Selective transformation of carbon dioxide and epoxides into degradable polycarbonates (CO(2)-based copolymer) has been regarded as a most promising green polymerization process. Although tremendous progress has been made during the past decade, very few successful examples have been reported to synthesize well-defined block copolymers to expand the scope of these green copolymers. Herein, we report a tandem strategy combining two living polymerization techniques, salenCo(III)X-catalyzed styrene oxide SO/CO(2) copolymerization and ring-opening polymerization of lactide with DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), for the synthesis of poly(styrene carbonate-block-lactide) copolymers. The key to the success of this tandem strategy is the judicious choice of water as the chain transfer and/or chain terminator reagent, which is added at the end of the salenCo(III)X-catalyzed SO/CO(2) copolymerization to in situ generate hydroxyl groups at the end of the polymer chains. The resulting polycarbonates with -OH end groups can thus be directly used as macroinitiators to subsequently initiate ring-opening polymerization of lactide to synthesize the diblock copolymers. Because of the living polymerization nature of both steps in this tandem strategy, we have demonstrated that the diblock copolymers synthesized possess well-defined structures with narrow molecular weight distributions and controllable lengths of both styrene carbonate and lactide blocks. PMID:23016983

  2. Biomimetic oxidative coupling of sinapyl acetate by silver oxide: preferential formation of ?-O-4 type structures.

    PubMed

    Kishimoto, Takao; Takahashi, Nana; Hamada, Masahiro; Nakajima, Noriyuki

    2015-03-01

    Biomimetic oxidations of sinapyl alcohol and sinapyl acetate were carried out with Ag2O to better understand the high frequency of ?-O-4 structures in highly acylated natural lignins. The major products from the Ag2O oxidation of sinapyl alcohol were sinapyl aldehyde (14% yield), ?-O-4-coupled dimer (32% yield), and ?-?-coupled dimer (3% yield). In contrast, the Ag2O oxidation of sinapyl acetate produced ?-O-4-coupled dimer in 66% yield. Oligomeric products with predominantly ?-O-4 structures were also obtained in 18% yield. The yield of the ?-O-4-coupled products from sinapyl acetate was much higher than that from sinapyl alcohol. Computational calculations based on density functional theory showed that the negative charge at C? was significantly reduced by the ?-acetyl group. The computational calculations suggest that the Coulombic repulsion between C? and O4 in sinapyl acetate radicals was significantly reduced by the ?-acetyl group, contributing to the preferential formation of ?-O-4 structures from sinapyl acetate. PMID:25654327

  3. Coupling strengths and flux pinning in oxide superconductors

    SciTech Connect

    Lichti, R. L.; Chan, K. C. B.; Cooke, D. W.; Boekema, C.

    1989-06-05

    Muon spin relaxation measurements have been performed to obtain penetrationdepth versus temperature for several high-temperature oxide superconductors.Comparison with theoretical results based on the Eliashberg equations indicatesthat at 1 kOe the (/ital RE/)Ba/sub 2/Cu/sub 3/O/sub 7/ materials (data for /ital RE/=Gd,Er, and Eu) are in the very strong coupling, extremely dirty limit, while dataat 5 kOe for Bi/sub 2/CaSr/sub 2/Cu/sub 2/O/sub 8/ and Tl/sub 2/Ca/sub 2/Ba/sub 2/Cu/sub 3/O/sub 10/ follow thestrong coupling, clean limit curve.

  4. Tandem tracking

    USGS Multimedia Gallery

    Biologist Sabrina Davenport tandem tracks the Lower Missouri River during high water on June 2, 2011.  Two boats (note boat out window) tracking in tandem can detect fish effectively across a wider river and can turn to search behind wing dikes and sandbars where sturgeon can hide during h...

  5. Transition-metal-free tandem oxidative removal of benzylic methylene group by C-C and C-N bond cleavage followed by intramolecular new aryl C-N bond formation under radical conditions.

    PubMed

    Laha, Joydev K; Tummalapalli, K S Satyanarayana; Gupta, Ankur

    2014-09-01

    A novel tandem oxidative conversion of 10,11-dihydro-5H-dibenzo[b,e][1,4]diazepines to phenazines has been achieved under transition-metal-free, mild conditions using K2S2O8 or DDQ as the oxidizing agent. The transformation proceeds through oxidative removal of a benzylic methylene group by C-C and C-N bond cleavage followed by a new aryl C-N bond formation under radical conditions. PMID:25119523

  6. Tandem one-pot synthesis of polysubstituted NH-pyrroles involving the palladium-catalyzed intramolecular oxidative amination of the zinc bromide complex of ?-enamino esters.

    PubMed

    Kim, Ju Hyun; Choi, Suh Young; Bouffard, Jean; Lee, Sang-gi

    2014-10-01

    The Pd-catalyzed oxidative olefin amination of the zinc bromide complex intermediate, formed by the sequential reaction of nitriles with a Reformatsky reagent and 1-alkynes, affords pyrrole derivatives in good to excellent yields. This tandem protocol provides a simple, efficient, and atom- and pot-economical way to quickly build polysubstituted NH-pyrroles starting from readily available reagents in a regiocontrolled manner with a broad substrate scope and high functional group tolerance. In contrast, the Pd-catalyzed oxidative olefin amination of an isolated ?-vinyl-?-enamino ester did not proceed effectively, but the reaction efficiency can be restored by addition of n-BuZnBr or Zn(OAc)2, indicating the crucial role of the zinc complex in this transformation. The synthetic utility of this protocol is exemplified by the rapid synthesis of pyrrolophenanthrenes and pyranopyrrolones through selective Pd- and Cu-catalyzed C-C and C-O bond-forming reactions. PMID:25217006

  7. Forensic analysis of printing inks using tandem Laser Induced Breakdown Spectroscopy and Laser Ablation Inductively Coupled Plasma Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Subedi, Kiran; Trejos, Tatiana; Almirall, José

    2015-01-01

    Elemental analysis, using either LA-ICP-MS or LIBS, can be used for the chemical characterization of materials of forensic interest to discriminate between source materials originating from different sources and also for the association of materials known to originate from the same source. In this study, a tandem LIBS/LA-ICP-MS system that combines the benefits of both LIBS and LA-ICP-MS was evaluated for the characterization of samples of printing inks (toners, inkjets, intaglio and offset.). The performance of both laser sampling methods is presented. A subset of 9 black laser toners, 10 colored (CMYK) inkjet samples, 12 colored (CMYK) offset samples and 12 intaglio inks originating from different manufacturing sources were analyzed to evaluate the discrimination capability of the tandem method. These samples were selected because they presented a very similar elemental profile by LA-ICP-MS. Although typical discrimination between different ink sources is found to be > 99% for a variety of inks when only LA-ICP-MS was used for the analysis, additional discrimination was achieved by combining the elemental results from the LIBS analysis to the LA-ICP-MS analysis in the tandem technique, enhancing the overall discrimination capability of the individual laser ablation methods. The LIBS measurements of the Ca, Fe, K and Si signals, in particular, improved the discrimination for this specific set of different ink samples previously shown to exhibit very similar LA-ICP-MS elemental profiles. The combination of these two techniques in a single setup resulted in better discrimination of the printing inks with two distinct fingerprint spectra, providing information from atomic/ionic emissions and isotopic composition (m/z) for each ink sample.

  8. Calculation of the Lateral Stability of a Directly Coupled Tandem-Towed Fighter Airplane and Correlation with Experimental Data

    NASA Technical Reports Server (NTRS)

    Shanks, Robert E.

    1958-01-01

    A theoretical method is presented for predicting the dynamic lateral stability characteristics of an airplane towed in tandem by a much larger airplane. Values of period and time to damp to one-half amplitude and rolling motions calculated by an analog computer have been correlated with results of two experimental investigations conducted in the Langley free-flight tunnel which were part of a U.S. Air Force program (Project FICON) to develop a satisfactory arrangement by which a bomber could tow a parasite fighter. In general, the theoretical results agree with the experimental results.

  9. Liquid-phase microextraction of tributyltin and triphenyltin coupled with gas chromatography-tandem mass spectrometry. Comparison between 4-fluorophenyl and ethyl derivatizations.

    PubMed

    Shioji, Hirotaka; Tsunoi, Shinji; Harino, Hiroya; Tanaka, Minoru

    2004-09-01

    This paper describes the liquid-phase microextraction (LPME) of tributyltin (TBT) and triphenyltin coupled with gas chromatography-tandem mass spectrometry. The 4-fluorophenylation and ethylation reactions were used for the derivatization of the organotins. For the two derivatizations, the LPME parameters such as organic solvent, stirring rate, temperature, extraction time and the other additional conditions were examined. Using pure water, the calibration curves, method detection limits (MDLs) and reproducibilities (RSDs) of the two derivatizations were compared under the respective optimized procedures. The 4-fluorophenyl derivatization, which showed a lower MDL (0.36 ng/l) and better reproducibility (RSD = 11% at 10 ng/l) for TBT, was applied to the analysis of seawater. The TBT was detected in the range from 1.1 to 2.0 ng/l in the seawater samples collected in Osaka Bay. PMID:15453422

  10. Liquid chromatography–tandem mass spectrometry assay of reduced and oxidized glutathione and main precursors in mice liver

    Microsoft Academic Search

    Jérôme Bouligand; Alain Deroussent; Angelo Paci; Jackie Morizet; Gilles Vassal

    2006-01-01

    A liquid chromatography\\/tandem mass spectrometry assay of glutathione (GSH), glutathione disulfide (GSSG) and of precursors (?-glutamyl-cysteine, cysteinyl-glycine, cysteine, cystine, homocysteine and homocystine) was developed to study glutathione synthesis in mice liver. After iodoacetic acid derivatization, the analytes were analyzed using reversed-phase gradient HPLC and detected using multiple reaction monitoring. Linear calibrations were performed over the concentrations range of 100–10,000ng\\/mL for

  11. Measurement of chronic oxidative and inflammatory stress by quantification of isoketal/levuglandin gamma-ketoaldehyde protein adducts using liquid chromatography tandem mass spectrometry.

    PubMed

    Davies, Sean S; Amarnath, Venkataraman; Brame, Cynthia J; Boutaud, Olivier; Roberts, L Jackson

    2007-01-01

    Measurement of F(2)-isoprostanes (F(2)-IsoPs) has been independently verified as one of the most reliable approaches to assess oxidative stress in vivo. However, the rapid clearance of F(2)-IsoPs makes the timing of sample collection critical for short-lived oxidative insults. Isoketals (IsoKs) are gamma-ketoaldehydes formed via the IsoP pathway of lipid peroxidation that rapidly react with lysyl residues of proteins to form stable protein adducts. Oxidative stress can also activate cyclooxygenases to produce prostaglandin H(2), which can form two specific isomers of IsoK-levuglandin (LG) D(2) and E(2). Because adducted proteins are not rapidly cleared, IsoK/LG protein adduct levels can serve as a dosimeter of oxidative and inflammatory damage over prolonged periods of time as well as brief episodes of injury. Quantification of IsoK/LG protein adducts begins with liquid-phase extraction to separate proteins from lipid membranes, allowing measurement of both IsoK/LG protein adducts and F(2)-IsoP from the same sample if desired. IsoK/LG-lysyl-lactam adducts are measured by liquid chromatography tandem mass spectrometry after proteolytic digestion of extracted proteins, solid-phase extraction and preparative HPLC. PMID:17853863

  12. Separation of nucleobases, nucleosides, and nucleotides using two zwitterionic silica-based monolithic capillary columns coupled with tandem mass spectrometry.

    PubMed

    Moravcová, Dana; Haapala, Markus; Planeta, Josef; Hyötyläinen, Tuulia; Kostiainen, Risto; Wiedmer, Susanne K

    2014-12-19

    The capability of employing synthesized zwitterionic silica-based monolithic capillary columns (140 mm × 0.1mm) for separation of highly polar and hydrophilic nucleobases, nucleosides, and nucleotides in hydrophilic interaction chromatography is reported. The suitability of the columns for on-line conjunction with electrospray tandem mass spectrometry was explored. Our results show that the grafted layer of zwitterionic monomer ([2-(methacryloyloxy)ethyl]-dimethyl-(3-sulfopropyl)-ammonium hydroxide or 2-methacryloyloxyethyl phosphorylcholine) on the silica monolithic surface significantly improved the separation selectivity and reproducibility, as compared to the bare silica monolith. The stepwise elution from 90% to 70% of acetonitrile enabled separation of a complex sample mixture containing 21 compounds with a total analysis time less than 40 min. PMID:25465366

  13. Characterization of the chemical constituents in Da-Huang-Gan-Cao-Tang by liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry and liquid chromatography coupled with ion trap mass spectrometry.

    PubMed

    Wang, Shufang; Chen, Pinghong; Xu, Yimin; Li, Xiaodong; Fan, Xiaohui

    2014-07-01

    In this work, the chemical constituents in Da-Huang-Gan-Cao-Tang, a traditional Chinese formula, were studied by liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry and liquid chromatography coupled with ion trap mass spectrometry for the first time. Among the 146 compounds detected in Da-Huang-Gan-Cao-Tang, 104 compounds were identified unambiguously or tentatively based on their accurate molecular weight and multistage MS data, including one potential novel compound and two reported in Glycyrrhiza genus for the first time. The possible fragmentation pathways were proposed and fragmentation rules of the major types of compounds were concluded. This study provided an example to facilitate the tedious identification of chemical composition in traditional Chinese medicine, and maybe a promising reference approach to research the analogous formulae. PMID:24771648

  14. Profiling of oxidized phospholipids in lipoproteins from patients with coronary artery disease by hollow fiber flow field-flow fractionation and nanoflow liquid chromatography-tandem mass spectrometry.

    PubMed

    Lee, Ju Yong; Byeon, Seul Kee; Moon, Myeong Hee

    2015-01-20

    Oxidized phospholipids (Ox-PLs) are oxidatively modified PLs that are produced during the oxidation of lipoproteins; oxidation of low density lipoproteins especially is known to be associated with the development of coronary artery disease (CAD). In this study, different lipoprotein classes (high density, low density, and very low density lipoproteins) from pooled plasma of CAD patients and pooled plasma from healthy controls were size-sorted on a semipreparative scale by multiplexed hollow fiber flow field-flow fractionation (MxHF5), and Ox-PLs that were extracted from each lipoprotein fraction were quantified by nanoflow liquid chromatography-tandem mass spectrometry (nLC-ESI-MS/MS). The present study showed that oxidation of lipoproteins occurred throughout all classes of lipoproteins with more Ox-PLs identified from CAD patient lipoproteins: molecular structures of 283 unique PL species (including 123 Ox-PLs) from controls and 315 (including 169 Ox-PLs) from patients were identified by data-dependent collision-induced dissociation experiments. It was shown that oxidation of PLs occurred primarily with hydroxylation of PL; in particular, a saturated acyl chain such as 16:0, 18:0, or even 18:1 at the sn-1 location of the glycerol backbone along with sn-2 acyl chains with at least two double bonds were identified. The acyl chain combinations commonly found for hydroxylated Ox-PLs in the lipoproteins of CAD patients were 16:0/18:2, 16:0/20:4, 18:0/18:2, and 18:0/20:4. PMID:25494038

  15. Determination of irinotecan and its metabolite SN-38 in rabbit plasma and tumors using a validated method of tandem mass spectrometry coupled with liquid chromatography.

    PubMed

    Park, Dae J; Won, Jun H; Cho, A R; Yun, Hye J; Heo, Jeong H; Hwhang, Tae H; Lee, Dae H; Kim, Woo M

    2014-07-01

    New tandem mass spectrometric method coupled with liquid chromatography (LC-MS/MS) has been developed to determine the total concentration of camptothecin derivatives (irinotecan and SN-38) regardless of inter-conversion phenomenon between carboxylate and lactone forms. At first, all sample solutions were acidified for 1h in order to completely convert CPT derivatives into their lactone forms and then CPT derivatives were extracted with organic solution containing diethyl ether and ethyl acetate (2:1, v/v) just after alkalization in the range pH 8.0-8.5 in acid-treated solutions. Analytes were separated on a reverse phase C18 column (150×2.1mm) and eluted isocratically with a mobile phase which consisted of acetonitrile-methanol-buffer (0.1% formic acid, 5mM ammonium formate) (3:4:3, v/v). CPT derivatives were monitored by tandem mass spectrometry in electrospay-positive ionization and multiple reaction mode programmed to the following transitions (m/z): '587.6?167.2' of CPT-11, '393.6?349.3' of SN-38 and '349.4? 305.2' of CPT. The method was validated to have the proper linearity (r(2)>0.99) over the range of 5-1000ng/ml of CPT-11 and 1-250ng/ml of SN-38 with good accuracy (89.8-114.3%) and precision (less than 10%). In all stability tests, concentration of CPT-11 and SN-38 had been left in the acceptable range of 88.8-110.7% when sample solutions were acidified before determination of CPT derivatives. Newly developed LC-MS/MS method was suitable for the determination of CPT derivatives of both rabbit plasma and tumor tissues in the pharmacokinetic study. PMID:24927278

  16. Comparison of electrokinetics-based multidimensional separations coupled with electrospray ionization-tandem mass spectrometry for characterization of human salivary proteins.

    PubMed

    Fang, Xueping; Yang, Li; Wang, Weijie; Song, Tao; Lee, Cheng S; DeVoe, Don L; Balgley, Brian M

    2007-08-01

    The foundation for saliva-based diagnostics is the development of a complete catalog of secreted proteins detectable in saliva. Besides protein complexity, the greatest bioanalytical challenge facing comprehensive analysis of saliva samples is related to the large variation of protein relative abundances including the presence of high-abundance proteins such as amylases, mucins, proline-rich proteins (PRPs), and secretory IgA complex. Among a number of electrokinetic separation techniques, transient capillary isotachophoresis/capillary zone electrophoresis (CITP/CZE) specifically targets trace amounts of proteins and thus reduces the range of relative protein abundances for providing unparallel advantages toward the identification of low-abundance proteins. By employing a CITP/CZE-based multidimensional separation platform coupled with electrospray ionization-tandem mass spectrometry (ESI-tandem MS), a total of 6112 fully tryptic peptides are sequenced at a 1% false discovery rate (FDR), leading to the identification of 1479 distinct human SwissProt protein entries. By comparing with capillary isoelectric focusing (CIEF) as another electrokinetics-based stacking approach, CITP/CZE not only offers a broad field of application but also is less prone to protein/peptide precipitation during the analysis. The ultrahigh resolving power of CITP/CZE is evidenced by the large number of distinct peptide identifications measured from each CITP fraction together with the low peptide fraction overlapping among identified peptides. Furthermore, when evaluating the protein sequence coverage by the number of distinct peptides mapping to each protein identification, the CITP-based proteome technology similarly achieves the superior performance with 674 proteins (46%) having three or more distinct peptides, 288 (19%) having two distinct peptides, and 517 (35%) having a single distinct peptide. PMID:17614365

  17. Graphene oxide based in-tube solid-phase microextraction combined with liquid chromatography tandem mass spectrometry for the determination of triazine herbicides in water.

    PubMed

    Tan, Feng; Zhao, Cong; Li, Lianjun; Liu, Min; He, Xin; Gao, Jinsuo

    2015-07-01

    A novel in-tube solid-phase microextraction method based on a graphene oxide coated column was developed for the determination of triazines in waters. This column was prepared by the covalent modification of monolayer graphene oxide sheets onto the inner wall of a fused-silica capillary. Scanning electron microscopy showed that the thickness of the graphene oxide coating was ?30 nm, with a porous, wrinkled membrane-like structure. Its performance was evaluated through the extraction of triazines in water. Results showed that the coating was stable for at least 100 replicate extractions, and variety of multi-columns was less than 10%. Flow rate, loading volume, pH, and ionic strength of samples played an important effect on the extraction. The high extraction efficiency was mainly attributed to ?-? stacking and hydrogen bonding interactions. The in-tube solid-phase microextraction was used in the determination of triazines with liquid chromatography and tandem mass spectrometry, and the detection limits were 0.0005-0.005 ?g/L for five triazine compounds. Further, the method was applied to the analysis of triazine herbicides in real samples including tap water, sea water, and river water, and the recoveries were 82.8-112.0, 85.4-110.5, and 81.6-105.9%, respectively, with RSDs of 2.7-7.1%. PMID:25903447

  18. Magnetoelectric Coupling Effects in Multiferroic Complex Oxide Composite Structures

    NASA Astrophysics Data System (ADS)

    Liu, Ming; Hoffman, Jason; Wang, Jing; Zhang, Jinxing; Nelson-Cheeseman, Brittany; Bhattacharya, Anand

    2013-05-01

    A central goal of electronics based on correlated materials or `Mottronics' is the ability to switch between distinct collective states with a control voltage. Small changes in structure and charge density near a transition can tip the balance between competing phases, leading to dramatic changes in electronic and magnetic properties. In this work, we demonstrate that an electric field induced two-step ferroelastic switching pathway in (011) oriented 0.71Pb(Mg1/3Nb2/3)O3-0.29PbTiO3 (PMN-PT) substrates can be used to tune the Verwey metal-insulator transition in epitaxial Fe3O4 films in a stable and reversible manner. We also observe robust non-volatile resistance switching in Fe3O4 up to room temperature, driven by ferroelastic strain. These results provides a framework for realizing non-volatile and reversible tuning of order parameters coupled to lattice-strain in epitaxial oxide heterostructures over a broad range of temperatures, with potential device applications.

  19. [Determination of glufosinate residue in tea by liquid chromatography-tandem mass spectrometry coupled with precolumn derivatization].

    PubMed

    Lin, Yonghui; Liu, Zhengcai; Yang, Fang; Qiu, Yuanjin; Liu, Suzhen; Su, Zhijiao; Zhang, Qiong; Xue, Zhimin; Fang, Yu

    2012-12-01

    A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was established for the determination of glufosinate (GLUF) residue in tea. The GLUF was extracted with water for 30 min under ultrasonication, and cleaned-up using a C18 solid phase extraction cartridge, then derived using fluorenylmethylchloroformate (FMOC-Cl) in borate buffer for 2 h. The separation was performed on a Kinetex C18 column with the mobile phases of acetonitrile and 5 mmol/L ammonium acetate aqueous solution (containing 0.2% (v/v) formic acid) in a gradient elution mode. The identification and quantification of the GLUF were carried out by MS/MS in negative electrospray ionization (ESI(-)) and multiple reaction monitoring (MRM) mode, the quantification analysis was performed by external standard method. The calibration curve showed good linearity in the range of 2.5 - 50.0 microg/L with the correlation coefficient r2 > 0.999. The limit of quantification (LOQ) was 0.10 mg/kg. The average recoveries of GLUF spiked at 0.10, 0.50 and 1.00 mg/kg levels in tea were between 61.6% and 81.4%, and the relative standard deviations (RSDs) were between 3.2% and 8.4%. The method is simple, rapid, sensitive, accurate and suitable for the confirmation and quantification of GLUF in tea. PMID:23593883

  20. Determination of itopride in human plasma by liquid chromatography coupled to tandem mass spectrometric detection: application to a bioequivalence study.

    PubMed

    Lee, Heon-Woo; Seo, Ji-Hyung; Choi, Seung-Ki; Lee, Kyung-Tae

    2007-01-30

    A simple method using a one-step liquid-liquid extraction (LLE) with butyl acetate followed by high-performance liquid chromatography (HPLC) with positive ion electrospray ionization tandem mass spectrometric (ESI-MS/MS) detection was developed for the determination of itopride in human plasma, using sulpiride as an internal standard (IS). Acquisition was performed in multiple reaction monitoring (MRM) mode, by monitoring the transitions: m/z 359.5>166.1 for itopride and m/z 342.3>111.6 for IS, respectively. Analytes were chromatographed on an YMC C18 reverse-phase chromatographic column by isocratic elution with 1 mM ammonium acetate buffer-methanol (20: 80, v/v; pH 4.0 adjusted with acetic acid). Results were linear (r2=0.9999) over the studied range (0.5-1000 ng mL(-1)) with a total analysis time per run of 2 min for LC-MS/MS. The developed method was validated and successfully applied to bioequivalence studies of itopride hydrochloride in healthy male volunteers. PMID:17386535

  1. A quantitative assay for reductive metabolism of a pesticide in fish using electrochemistry coupled with liquid chromatography tandem mass spectrometry.

    PubMed

    Bussy, Ugo; Chung-Davidson, Yu-Wen; Li, Ke; Li, Weiming

    2015-04-01

    This is the first study to use electrochemistry to generate a nitro reduction metabolite as a standard for a liquid chromatography-mass spectrometry-based quantitative assay. This approach is further used to quantify 3-trifluoromethyl-4-nitrophenol (TFM) reductive metabolism. TFM is a widely used pesticide for the population control of sea lamprey (Petromyzon marinus), an invasive species of the Laurentian Great Lakes. Three animal models, sea lamprey, lake sturgeon (Acipenser fulvescens), and rainbow trout (Oncorhynchus mykiss), were selected to evaluate TFM reductive metabolism because they have been known to show differential susceptibilities to TFM toxicity. Amino-TFM (aTFM; 3-trifluoromethyl-4-aminophenol) was the only reductive metabolite identified through liquid chromatography-high-resolution mass spectrometry screening of liver extracts incubated with TFM and was targeted for electrochemical synthesis. After synthesis and purification, aTFM was used to develop a quantitative assay of the reductive metabolism of TFM through liquid chromatography and tandem mass spectrometry. The concentrations of aTFM were measured from TFM-treated cellular fractions, including cytosolic, nuclear, membrane, and mitochondrial protein extracts. Sea lamprey extracts produced the highest concentrations (500 ng/mL) of aTFM. In addition, sea lamprey and sturgeon cytosolic extracts showed concentrations of aTFM substantially higher than those of rainbow trout. However, other fractions of lake sturgeon extracts tend to show aTFM concentrations similar to those of rainbow trout but not with sea lamprey. These data suggest that the level of reductive metabolism of TFM may be associated with the sensitivities of the animals to this particular pesticide. PMID:25730707

  2. Rapid quantification of nebivolol in human plasma by liquid chromatography coupled with electrospray ionization tandem mass spectrometry.

    PubMed

    Ramakrishna, N V S; Vishwottam, K N; Koteshwara, M; Manoj, S; Santosh, M; Varma, D P

    2005-10-01

    A simple, sensitive and rapid liquid chromatographic/electrospray ionization tandem mass spectrometric method was developed and validated for the quantitation of nebivolol in human plasma. The method involved a simple single-step liquid-liquid extraction with diethyl ether/dichloromethane (70/30). The analyte was chromatographed on Waters symmetry C18 reversed-phase chromatographic column by isocratic elution with water:acetonitrile:formic acid (30:70:0.03, v/v) and analyzed by mass spectrometry in the multiple reaction monitoring mode. The precursor to product ion transitions of m/z 406.4-151.5 and m/z 409.1-228.1 were used to measure the analyte and the internal standard (I.S.), respectively. The chromatographic runtime was 2 min and the weighted (1/x2) calibration curves were linear over the range 50-10,000 pg/mL. The method was validated in terms of accuracy, precision, absolute recovery, freeze-thaw stability, bench-top stability and re-injection reproducibility. The limit of detection and lower limit of quantification in human plasma were 10 and 50 pg/mL, respectively. The within- and between-batch accuracy and precision were found to be well within acceptable limits (<10%). The analyte was stable after three freeze-thaw cycles (deviation <10%). The average absolute recoveries of nebivolol and tamsulosin, used as an internal standard, from spiked plasma samples were 73.4+/-3.7 and 72.1+/-2.0%, respectively. The assay method described here was applied to study the pharmacokinetics of nebivolol. PMID:16006083

  3. Membrane assisted solvent extraction coupled with liquid chromatography tandem mass spectrometry applied to the analysis of alkylphenols in water samples.

    PubMed

    Salgueiro-González, N; Turnes-Carou, I; Muniategui-Lorenzo, S; López-Mahía, P; Prada-Rodríguez, D

    2013-03-15

    This work describes the development and validation of a novel, simple, sensitive and environmental friendly analytical method for the determination of alkylphenols in different types of water samples. The methodology was based on a membrane assisted solvent extraction of only 15 mL of water sample with 500 ?L of hexane in combination with liquid chromatography-electrospray ionization tandem mass spectrometry in negative mode (LC-ESI-MS/MS). Acquisition was performed in the multiple reaction monitoring (MRM) mode recording two transitions for the identification of the target compounds. Quantitation is based on the use of deuterated labelled standards as surrogate standards. The figures of merit were satisfactory in all cases: absolute recoveries were close to 50% for most investigated compounds and relative recoveries varied between 81 and 108%. Repeatability and intermediate precision were <20% for all compounds. Uncertainty assessment of measurement was estimated on the basis of an in-house validation according to EURACHEM/CITAC guide. Quantitation limits of the method (MQL) were lower than 0.04 ?g L(-1) in all cases, which allow the achievement of the limits established by the Directive 2008/105/EC for surface and seawater samples and by the new proposal COM (2011) 876 final. The feasibility of the proposed method was demonstrated analyzing seawater, surface water and drinking water samples from different areas of A Coruña (Northwest of Spain). The analyses evidenced the presence of nonylphenol in seawater (MQL-0.13 ?g L(-1)) and surface water samples (0.12-0.19 ?g L(-1)). The highest concentration was observed in drinking water (0.25 ?g L(-1)). PMID:23394746

  4. Methyl Radicals in Oxidative Coupling of Methane Directly Confirmed by Synchrotron VUV Photoionization Mass Spectroscopy

    PubMed Central

    Luo, Liangfeng; Tang, Xiaofeng; Wang, Wendong; Wang, Yu; Sun, Shaobo; Qi, Fei; Huang, Weixin

    2013-01-01

    Gas-phase methyl radicals have been long proposed as the key intermediate in catalytic oxidative coupling of methane, but the direct experimental evidence still lacks. Here, employing synchrotron VUV photoionization mass spectroscopy, we have directly observed the formation of gas-phase methyl radicals during oxidative coupling of methane catalyzed by Li/MgO catalysts. The concentration of gas-phase methyl radicals correlates well with the yield of ethylene and ethane products. These results lead to an enhanced fundamental understanding of oxidative coupling of methane that will facilitate the exploration of new catalysts with improved performance. PMID:23567985

  5. MEASUREMENT OF NITRIC OXIDE PRODUCTION IN HUMANS USING 15N-ARGININE AND TANDEM LC/MS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Nitric oxide (NO) plays a critical role in several physiologic processes, including modulation of peripheral vascular resistance, gastrointestinal peristalsis, inflammation and neuronal function. NO is synthesized in tissues by three classes of nitric oxide synthases (NOS) and rapidly degraded to ni...

  6. Determination of Sudan dyes in chili pepper powder by online solid-phase extraction with a butyl methacrylate monolithic column coupled to liquid chromatography with tandem mass spectrometry.

    PubMed

    Liu, Yao; Wang, Man-Man; Ai, Lian-Feng; Zhang, Chang-Kun; Li, Xin; Wang, Xue-Sheng

    2014-07-01

    A poly(butyl methacrylate-co-ethylene dimethacrylate) monolithic column was fabricated and used as a novel sorbent for online solid-phase extraction coupled to liquid chromatography with tandem mass spectrometry for the simultaneous determination of Sudan I-IV in chili pepper powder. The prepared columns were characterized by scanning electron microscopy, nitrogen adsorption-desorption, and pressure drop measurements. Online solid-phase extraction was performed on the synthesized monolithic column using 10 mM ammonium acetate solution as the loading solution with the aid of an online cleanup chromatography system. The desorption of Sudan I-IV was achieved with acetonitrile as the eluting solution at the flow rate of 0.5 mL/min. The extracted analytes were subsequently eluted into a C18 analytical column for chromatographic separation using a mixture of 10% acetonitrile/90% formic acid (0.5%) solution as the mobile phase. Under the optimized conditions, the developed method had linear range of 1.0-50 ?g/kg, a detection limit of 0.3 ?g/kg, and a quantification limit of 1.0 ?g/kg for each analyte. The intraday and interday recoveries of Sudan I-IV in chili pepper powder samples ranged from 94.8 to 100.9% and 94.9 to 99.4%, respectively. The intraday and interday precision were between 3.37-7.01% and 5.01-7.68%, respectively. PMID:24723310

  7. Rapid and sensitive detection of auxins and flavonoids in plant samples by high-performance liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Liang, Yuan; Zhu, Xiaocui; Wu, Tongbo; Zhao, Meiping; Liu, Huwei

    2012-10-01

    Simultaneous determination of indole-3-acetic acid and methyl indole-3-acetic acid ester in small amounts of plant tissue is essential for elucidating their mutual transformation mechanism and the in vivo function of methyl indole-3-acetic acid ester. Rapid quantification of flavonoids in the same sample is important for clarifying their roles in the transport of auxins and other phytohormones. Herein, we describe a simple method for the simultaneous determination of indole-3-acetic acid and its methyl ester in the roots of the Arabidopsis thaliana seedlings and a protocol for the rapid extraction and quantification of quercetin and kaempferol in these seedlings. High-performance liquid chromatography coupled with electrospray ionization time-of-flight tandem mass spectrometry was used for the detection of all the compounds. Negative data for indole-3-acetic acid and positive data for methyl indole-3-acetic acid ester were collected in two successive files with a single injection of the extracted sample. Under optimized conditions, the limit of detection for the four compounds was 2 ng/mL for indole-3-acetic acid, 0.5 ng/mL for methyl indole-3-acetic acid ester, 5 ng/mL for quercetin, and 1 ng/mL for kaempferol, respectively. Because of the high sensitivity of the assay, only 2-10 mg of the plant material was required to obtain quantitative results. PMID:22815051

  8. A multi-residue method for determination of 70 organic micropollutants in surface waters by solid-phase extraction followed by gas chromatography coupled to tandem mass spectrometry.

    PubMed

    Terzopoulou, Evangelia; Voutsa, Dimitra; Kaklamanos, George

    2015-01-01

    A multi-residue method, based on gas chromatography coupled to tandem mass spectrometry (GC-MS/MS), has been developed for the determination of 70 organic micropollutants from various chemical classes (organochlorinated, organophosphorous, triazines, carbamate and urea, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, pharmaceuticals, phenols, etc.) in surface waters. A single-step SPE extraction using OASIS HLB cartridges was employed for the recovery of target micropollutants. The method has been validated according to monitoring performance criteria of the Water Framework Directive, taking into account the approved guidelines on quality assurance and quality control. The recoveries ranged from 60 to 110 %, the coefficient of variation from 0.84 to 27.4 %, and the uncertainty from 6 to 37 %. The LOD varied from 6.0 to 40 ng/L. The limits of quantification for the priority pollutants anthracene, alachlor, atrazine, benzo(a)pyrene, chlorfenvinphos, diuron, isoproturon, nonylphenol, simazine, and terbutryn fulfill the criterion of <30 % of the relevant environmental standards. The method was employed to investigate the water quality in the basin of a transboundary river, Strymonas, in NE Greece during three sampling campaigns conducted in the year 2013. Thirty-nine compounds were detected in the river water. Metolachlor, diuron, isoproturon, salicylic acid, chlorfenvinphos, 1,2-benzanthracene, pyrene, diflubenzuron, and carbaryl exhibited the highest detection frequencies. PMID:25109470

  9. Identification of metabolites of PSORALEAE FRUCTUS in rats by ultra performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry analysis.

    PubMed

    Wang, Pei-le; Yao, Zhi-Hong; Zhang, Feng-Xiang; Shen, Xiu-Yu; Dai, Yi; Qin, Ling; Yao, Xin-Sheng

    2015-08-10

    The fruit of Psoralea corylifolia (PSORALEAE FRUCTUS) is a traditional Chinese medicine (TCM), which has been used to prevent and treat vitiligo, psoriasis, and osteoporosis in China for thousands of years. Phytochemical investigation on PSORALEAE FRUCTUS, as well as some metabolism research focused on pharmacokinetics of several single compounds from this plant, has been reported. However, the effective material of PSORALEAE FRUCTUS is still unknown. In the present study, the metabolic fate of multiple components of PSORALEAE FRUCTUS in rats was investigated by ultra performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry (UPLC/Q-TOF-MS). Based on a three-step strategy, a total of 142 PSORALEAE FRUCTUS-related xenobiotics were identified or tentatively characterized in rat biofluids after oral administration of six representative single compounds and PSORALEAE FRUCTUS extract. All six different types of constituents of PSORALEAE FRUCTUS, including furocoumarin, coumestan, isoflavone, flavanone, chalcone and monoterpene phenol, could be absorbed into the circulation system. In addition, compared with the metabolism of six representative single compounds, different metabolic fate was observed after oral administration of PSORALEAE FRUCTUS extract, which indicated that the drug-drug interactions occurred when fed by multi-component herbal extract, and the investigations only focused on several main components were not sufficient to represent and reflect the overall efficacy of plants. The present study will be conducive to further pharmacological mechanism research on PSORALEAE FRUCTUS. PMID:25951619

  10. [Determination of deoxynivalenol in grain and its products by solid-phase extraction coupled with high performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Huang, Juan; Chen, Guosong; Zhang, Xiaoyan; Shen, Chongyu; Lü, Chen; Wu, Bin; Liu, Yan; Chen, Huilan; Ding, Tao

    2012-11-01

    A method was established for the determination of deoxynivalenol (vomitoxin) in grain and its products based on solid-phase extraction coupled with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The sample was firstly extracted by acetonitrile-water (84:16, v/v). The extract was then cleaned-up by an HLB solid phase extraction cartridge. The separation was carried out on a Phenomenex Kinetex C18 column (100 mm x4. 6 mm, 2.6 microm) with a gradient elution using 0.3% per hundred ammonia solution-acetonitrile as mobile phases. The analysis of deoxynivalenol was performed under electrospray negative ionization mode. The limit of detection (LOD, S/N= 3) and the limit of quantification (LOQ, S/N = 10) were 20 microg/kg and 50 microg/kg, respectively. A good linearity (r > 0.99) was achieved for the target compound over the range of 20-1000 pg/L. The recoveries at the three spiked levels (50, 100, 500 microg/kg) in the blank matrices such as flour, barley, soybean, rice, cornmeal, cassava and wheat, were varied from 75.6% to 111.0% with the relative standard deviations no more than 13. 0%. The method is accurate, efficient, sensitive and practical. The cost of pretreatment is obviously reduced by replacing immunoaffinity columns and Mycosep columns with HLB columns which have the same purification effect. PMID:23451526

  11. Multi-residue enantiomeric analysis of pharmaceuticals and their active metabolites in the Guadalquivir River basin (South Spain) by chiral liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    López-Serna, Rebeca; Kasprzyk-Hordern, Barbara; Petrovi?, Mira; Barceló, Damià

    2013-07-01

    This paper describes the development and application of a multi-residue chiral liquid chromatography coupled with tandem mass spectrometry method for simultaneous enantiomeric profiling of 18 chiral pharmaceuticals and their active metabolites (belonging to several therapeutic classes including analgesics, psychiatric drugs, antibiotics, cardiovascular drugs and ?-agonists) in surface water and wastewater. To the authors' knowledge, this is the first time an enantiomeric method including such a high number of pharmaceuticals and their metabolites has been reported. Some of the pharmaceuticals have never been studied before in environmental matrices. Among them are timolol, betaxolol, carazolol and clenbuterol. A monitoring programme of the Guadalquivir River basin (South Spain), including 24 sampling sites and five wastewater treatment plants along the basin, revealed that enantiomeric composition of studied pharmaceuticals is dependent on compound and sampling site. Several compounds such as ibuprofen, atenolol, sotalol and metoprolol were frequently found as racemic mixtures. On the other hand, fluoxetine, propranolol and albuterol were found to be enriched with one enantiomer. Such an outcome might be of significant environmental relevance as two enantiomers of the same chiral compound might reveal different ecotoxicity. For example, propranolol was enriched with S(-)-enantiomer, which is known to be more toxic to Pimephales promelas than R(+)-propranolol. Fluoxetine was found to be enriched with S(+)-enantiomer, which is more toxic to P. promelas than R(-)-fluoxetine. PMID:23579471

  12. [Analysis of aldicarb and its metabolites in ginger using ultra performance liquid chromatography-tandem mass spectrometry coupled with multiplug filtration clean up with multiwalled carbon nanotubes].

    PubMed

    Ma, Lili; Jia, Li; Zhou, Xinran; Liu, Yan; Fan, Xiaojing; Pan, Canping

    2014-06-01

    A simple and rapid pretreatment procedure was developed for the simultaneous determination of aldicarb and its metabolites, aldicarb sulfone and aldicarb sulfoxide in ginger. The samples were extracted with acetonitrile, and then cleaned up with multiplug filtration using multiwalled carbon nanotubes (MWCNTS). The eluate was dried with nitrogen gas at room temperature, and redissolved in an acetonitrile-water (5:95, v/v) mixture, then quantified by ultra performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (UPLC-ESI-MS/MS) operated in positive multiple reaction monitoring (MRM) mode. A linear relationship was achieved in the range of 0.5 -200 microg/L for the peak areas to the mass concentrations of the target compounds with the linear correlation coefficients (r2) higher than 0.99. The recoveries at three spiked levels of 2, 20 and 200 microg/kg were in the range from 71.4% to 89.8% with the relative standard deviations (RSDs, n = 6) from 0.7% to 13.2% under the selected conditions. The limits of quantification (LOQ, S/N = 10) of aldicarb, aldicarb sulfone, and aldicarb sulfoxide in ginger were 1.0, 2.0 and 1.0 microg/kg, respectively. The results demonstrate that the developed method is rapid, cost-effective, and can meet the requirements of the multiple pesticide residue analysis. The method is applicable to determine aldicarb and its metabolites in ginger. PMID:25269263

  13. High-performance liquid chromatography coupled with electrospray tandem mass spectrometry (LC/MS/MS) method for the simultaneous determination of diazepam, atropine and pralidoxime in human plasma.

    PubMed

    Abbara, Chadi; Bardot, Isabelle; Cailleux, Annie; Lallement, Guy; Le Bouil, Anne; Turcant, Alain; Clair, Pascal; Diquet, Bertrand

    2008-10-15

    A high-performance liquid chromatography coupled with electrospray tandem mass spectrometry (LC/MS/MS) procedure for the simultaneous determination of diazepam from avizafone, atropine and pralidoxime in human plasma is described. Sample pretreatment consisted of protein precipitation from 100microl of plasma using acetonitrile containing the internal standard (diazepam D5). Chromatographic separation was performed on a X-Terra MS C8 column (100mmx2.1mm, i.d. 3.5microm), with a quick stepwise gradient using a formate buffer (pH 3, 2mM) and acetonitrile at a flow rate of 0.2ml/min. The triple quadrupole mass spectrometer was operated in positive ion mode and multiple reaction monitoring was used for drug quantification. The method was validated over the concentration ranges of 1-500ng/ml for diazepam, 0.25-50ng/ml for atropine and 5-1000ng/ml for pralidoxime. The coefficients of variation were always <15% for both intra-day and inter-day precision for each analyte. Mean accuracies were also within +/-15%. This method has been successfully applied to a pharmacokinetic study of the three compounds after intramuscular injection of an avizafone-atropine-pralidoxime combination, in healthy subjects. PMID:18805073

  14. Antioxidant activity guided separation of major polyphenols of marjoram (Origanum majorana L.) using flash chromatography and their identification by liquid chromatography coupled with electrospray ionization tandem mass spectrometry†.

    PubMed

    Hossain, Mohammad B; Camphuis, Gabriel; Aguiló-Aguayo, Ingrid; Gangopadhyay, Nirupama; Rai, Dilip K

    2014-11-01

    Marjoram extracts have been separated into polar and nonpolar parts using liquid-liquid extraction. Both polar and nonpolar parts of the extracts were further fractionated by flash chromatography. The obtained fractions (90 polar and 45 nonpolar fractions) were investigated for their antioxidant activities by 2,2-diphenylpicrylhydrazyl and ferric ion reducing antioxidant power assays. A direct, positive, and linear relationship between antioxidant activity and total phenolic content of the fractions was observed. Based on antioxidant and total phenolic content data, the three fractions with the high antioxidant activities from polar and nonpolar part of the extract were analyzed for their constituent polyphenols by liquid chromatography coupled with electrospray ionization tandem mass spectrometry. Compounds were identified by matching the mass spectral data and retention time with those of authentic standards. Identification of the compounds for which there were no "in-house" standards available was carried out by accurate mass measurement of the precursor ions and product ions generated from collision-induced dissociation. Rosmarinic acid was found to be the strongest antioxidant polyphenol conferring the highest antioxidant activity to fractions 47 and 17 of polar and nonpolar part of the extract, respectively. The identification of the rosmarinic acid was further confirmed by (1) H NMR spectroscopy. PMID:25161079

  15. Structural Characterization of New Peptide Variants Produced by Cyanobacteria from the Brazilian Atlantic Coastal Forest Using Liquid Chromatography Coupled to Quadrupole Time-of-Flight Tandem Mass Spectrometry

    PubMed Central

    Sanz, Miriam; Andreote, Ana Paula Dini; Fiore, Marli Fatima; Dörr, Felipe Augusto; Pinto, Ernani

    2015-01-01

    Cyanobacteria from underexplored and extreme habitats are attracting increasing attention in the search for new bioactive substances. However, cyanobacterial communities from tropical and subtropical regions are still largely unknown, especially with respect to metabolite production. Among the structurally diverse secondary metabolites produced by these organisms, peptides are by far the most frequently described structures. In this work, liquid chromatography/electrospray ionization coupled to high resolution quadrupole time-of-flight tandem mass spectrometry with positive ion detection was applied to study the peptide profile of a group of cyanobacteria isolated from the Southeastern Brazilian coastal forest. A total of 38 peptides belonging to three different families (anabaenopeptins, aeruginosins, and cyanopeptolins) were detected in the extracts. Of the 38 peptides, 37 were detected here for the first time. New structural features were proposed based on mass accuracy data and isotopic patterns derived from full scan and MS/MS spectra. Interestingly, of the 40 surveyed strains only nine were confirmed to be peptide producers; all of these strains belonged to the order Nostocales (three Nostoc sp., two Desmonostoc sp. and four Brasilonema sp.). PMID:26096276

  16. Rapid analysis of trace organic compounds in water by automated online solid-phase extraction coupled to liquid chromatography-tandem mass spectrometry.

    PubMed

    Anumol, Tarun; Snyder, Shane A

    2015-01-01

    A fully automated online solid-phase extraction (SPE) with directly coupled liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for analysis of 34 trace organic compounds in diverse water matrices has been developed. The current method offers several advantages over traditional offline SPE methods including low sample volume (1.7 mL), decreased solvent use, higher throughput, and increased reproducibility. The method uses simultaneous positive and negative ESI for analysis of all compounds in one injection, which reduces cycle time (extraction+analysis) to <15 min. Method optimization included testing different online SPE cartridges, mobile phase compositions, and flow rates. The method detection limits (MDLs) ranged from 0.1 to 13.1 ng/L with 80% of the compounds having an MDL <5 ng/L. Matrix spike recoveries in three different water qualities were evaluated and ranged from 61.2% to145.1% with 95% of the recoveries ranging between 70-130%. As part of the method validation studies, linearity (0.9911-0.9998), intra-day variability (1.0-10.4%), inter-day variability (1.0-11.9%), and matrix effects were also assessed. The use of 26 isotopically-labeled standards increased the reliability of the method while retention time locking and use of two transitions for most compounds increased the specificity. The applicability of the method was tested on samples across treatment points from two wastewater plants, a septic tank, surface water and groundwater. PMID:25476282

  17. Headspace solid phase microextraction in-situ supercritical fluid extraction coupled to gas chromatography-tandem mass spectrometry for simultaneous determination of perfluorocarboxylic acids in sediments.

    PubMed

    Liu, Wen-Lin; Hwang, Bao-Huey; Li, Zu-Guang; Jen, Jen-Fon; Lee, Maw-Rong

    2011-10-28

    Headspace solid phase microextraction (HS-SPME) in-situ supercritical fluid extraction (SFE) was investigated for the determination of trace amounts of perfluorocarboxylic acids (PFCAs) in sediments. Quantitation was performed by using gas chromatography coupled to negative chemical ionization-tandem mass spectrometry (GC-NCI-MS/MS). The optimum conditions of HS-SPME following SFE were obtained using 500 ?L n-butanol as a derivatization reagent in supercritical carbon dioxide with static extraction for 10 min, then dynamic extraction for 20 min at 30 MPa and 70 °C and simultaneous collected with 100 ?m film thickness PDMS fiber. The linear range of proposed method was from 5 to 5000 ng g(-1), with limit of detection ranging from 0.39 to 0.54 ng g(-1) and limit of quantitation ranging from 1.30 to 1.80 ng g(-1). The developed method was successfully applied to analyze PFCAs in sediments from rivers and beach near industrial areas. The concentrations of PFCAs determined are from 282 to 4473 ng g(-1). PMID:21924729

  18. Structural Characterization of New Peptide Variants Produced by Cyanobacteria from the Brazilian Atlantic Coastal Forest Using Liquid Chromatography Coupled to Quadrupole Time-of-Flight Tandem Mass Spectrometry.

    PubMed

    Sanz, Miriam; Andreote, Ana Paula Dini; Fiore, Marli Fatima; Dörr, Felipe Augusto; Pinto, Ernani

    2015-01-01

    Cyanobacteria from underexplored and extreme habitats are attracting increasing attention in the search for new bioactive substances. However, cyanobacterial communities from tropical and subtropical regions are still largely unknown, especially with respect to metabolite production. Among the structurally diverse secondary metabolites produced by these organisms, peptides are by far the most frequently described structures. In this work, liquid chromatography/electrospray ionization coupled to high resolution quadrupole time-of-flight tandem mass spectrometry with positive ion detection was applied to study the peptide profile of a group of cyanobacteria isolated from the Southeastern Brazilian coastal forest. A total of 38 peptides belonging to three different families (anabaenopeptins, aeruginosins, and cyanopeptolins) were detected in the extracts. Of the 38 peptides, 37 were detected here for the first time. New structural features were proposed based on mass accuracy data and isotopic patterns derived from full scan and MS/MS spectra. Interestingly, of the 40 surveyed strains only nine were confirmed to be peptide producers; all of these strains belonged to the order Nostocales (three Nostoc sp., two Desmonostoc sp. and four Brasilonema sp.). PMID:26096276

  19. Multiresidue analysis of organic pollutants by in-tube solid phase microextraction coupled to ultra-high performance liquid chromatography-electrospray-tandem mass spectrometry.

    PubMed

    Masiá, A; Moliner-Martinez, Y; Muñoz-Ortuño, M; Pico, Y; Campíns-Falcó, P

    2013-09-01

    In this work, in-tube solid phase microextraction (IT-SPME) coupling with ultra-high-pressure liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) multiresidue analytical method has been proposed for the first time for on-line enrichment of 9 analytes included in Water Frame Directive 2000/60/EC (WFD). The device was equipped with a GC TRB-5 capillary column, used as pre-concentration loop, and two conventional six-port injection valves. Water sample and desorption solvent volumes were tested. The optimum conditions were 4mL of processed sample followed by elution with 40?L of methanol. The analytes were detected with a mass spectrometer after being ionized positively using an electrospray ionization (ESI) source. The method presents good linearity over the range assayed, 0.025-2.5?g/L for chlorpyriphos and 0.25-25?g/L for the other tested compounds and LODs between 0.025?g/L and 2.5?g/L. Enrichment factors ranged from 2.5 to 10. Intra and inter-day variation coefficients were <26 and 31.6% respectively. Once validated, the method was applied to several water samples from different sources demonstrating that it achieves the on-line enrichment of the analytes with the advantage of minimum sample manipulation, and the identification and quantification of some organic pollutants in water samples in the range of low parts-per-billion. The method provided similar analytical characteristics as those obtained in the established couple IT-SPME-Capillary Liquid Chromatography (CapLC). PMID:23910602

  20. Rapid screening of N-oxides of chemical warfare agents degradation products by ESI-tandem mass spectrometry.

    PubMed

    Sridhar, L; Karthikraj, R; Lakshmi, V V S; Raju, N Prasada; Prabhakar, S

    2014-08-01

    Rapid detection and identification of chemical warfare agents and related precursors/degradation products in various environmental matrices is of paramount importance for verification of standards set by the chemical weapons convention (CWC). Nitrogen mustards, N,N-dialkylaminoethyl-2-chlorides, N,N-dialkylaminoethanols, N-alkyldiethanolamines, and triethanolamine, which are listed CWC scheduled chemicals, are prone to undergo N-oxidation in environmental matrices or during decontamination process. Thus, screening of the oxidized products of these compounds is also an important task in the verification process because the presence of these products reveals alleged use of nitrogen mustards or precursors of VX compounds. The N-oxides of aminoethanols and aminoethylchlorides easily produce [M + H](+) ions under electrospray ionization conditions, and their collision-induced dissociation spectra include a specific neutral loss of 48 u (OH + CH2OH) and 66 u (OH + CH2Cl), respectively. Based on this specific fragmentation, a rapid screening method was developed for screening of the N-oxides by applying neutral loss scan technique. The method was validated and the applicability of the method was demonstrated by analyzing positive and negative samples. The method was useful in the detection of N-oxides of aminoethanols and aminoethylchlorides in environmental matrices at trace levels (LOD, up to 500 ppb), even in the presence of complex masking agents, without the use of time-consuming sample preparation methods and chromatographic steps. This method is advantageous for the off-site verification program and also for participation in official proficiency tests conducted by the Organization for the Prohibition of Chemical Weapons (OPCW), the Netherlands. The structure of N-oxides can be confirmed by the MS/MS experiments on the detected peaks. A liquid chromatography-mass spectrometry (LC-MS) method was developed for the separation of isomeric N-oxides of aminoethanols and aminoethylchlorides using a C18 Hilic column. Critical isomeric compounds can be confirmed by LC-MS/MS experiments, after detecting the N-oxides from the neutral loss scanning method. PMID:24553657

  1. A fully coupled model for water-gas-heat reactive transport with methane oxidation in landfill covers.

    PubMed

    Ng, C W W; Feng, S; Liu, H W

    2015-03-01

    Methane oxidation in landfill covers is a complex process involving water, gas and heat transfer as well as microbial oxidation. The coupled phenomena of microbial oxidation, water, gas, and heat transfer are not fully understood. In this study, a new model is developed that incorporates water-gas-heat coupled reactive transport in unsaturated soil with methane oxidation. Effects of microbial oxidation-generated water and heat are included. The model is calibrated using published data from a laboratory soil column test. Moreover, a series of parametric studies are carried out to investigate the influence of microbial oxidation-generated water and heat, initial water content on methane oxidation efficiency. Computed and measured results of gas concentration and methane oxidation rate are consistent. It is found that the coupling effects between water-gas-heat transfer and methane oxidation are significant. Ignoring microbial oxidation-generated water and heat can result in a significant difference in methane oxidation efficiency by 100%. PMID:25489976

  2. Tandem Mass Spectrometry in Physiology

    NSDL National Science Digital Library

    2007-12-01

    Tandem mass spectrometry coupled to liquid chromatography (LC-MS/MS) allows identification of proteins in a complex mixture without need for protein purification ("shotgun" proteomics). Recent progress in LC-MS/MS-based quantification, phosphoproteomic analysis, and targeted LC-MS/MS using multiple reaction monitoring (MRM) has made LC-MS/MS a powerful tool for the study of cell physiology.

  3. MEASUREMENT OF PYRETHROID RESIDUES IN ENVIRONMENTAL AND FOOD SAMPLES BY ENHANCED SOLVENT EXTRACTION/SUPERCRITICAL FLUID EXTRACTION COUPLED WITH GAS CHROMATOGRAPHY-TANDEM MASS SPECTROMETRY

    EPA Science Inventory

    The abstract summarizes pyrethorid methods development research. It provides a summary of sample preparation and analytical techniques such as supercritical fluid extraction, enhance solvent extraction, gas chromatography and tandem mass spectrometry....

  4. Determination of phosphoserine/threonine by nano ultra-performance liquid chromatography-tandem mass spectrometry coupled with microscale labeling.

    PubMed

    Chen, Rong-Chun; Chuang, Lea-Yea; Tseng, Wei-Lung; Tyan, Yu-Chang; Lu, Chi-Yu

    2013-12-15

    Protein phosphorylation is an important regulatory post-translational modification in many biochemical processes. The phosphopeptide analysis strategies developed in this study were all at microscale. After using a standard microwave oven to assist protein digestion, phosphoserine and phosphothreonine were tagged with chemical analogues, such as 2-mercaptoethanol and 3-mercapto-1-propanol, to enable simultaneously relative quantitation and identification. This method enabled the use of thio alcohols for direct labeling of phosphorylated sites (not labeled at the mercapto, amino, hydroxyl, or carboxyl groups) of phosphopeptides. Various digestion parameters (e.g., microwave power, reaction time, NH4HCO3 concentration) and derivatization efficiency parameters (e.g., reaction time, labeling tag concentration) were studied and optimized. In both control and experimental samples, microwave-assisted digestion coupled with relative quantitation using analogue tags enabled calculation of phosphopeptide ratios in the same sequence. A non-labeling method was also established for quantifying phosphopeptides in human plasma by using the abundant protein albumin as an internal control for normalizing relative quantities of phosphopeptides. Nano ultra-performance liquid chromatography (nanoUPLC) was combined with LTQ Orbitrap to enable simultaneous protein relative quantitation and identification. These strategies proved to be effective for quantifying phosphopeptides in biological samples. PMID:23994561

  5. Qualitative and quantitative analysis on chemical constituents from Curculigo orchioides using ultra high performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry.

    PubMed

    He, Yongjing; Dong, Xin; Jia, Xiaoxuan; Li, Mei; Yuan, Tingting; Xu, Hongtao; Qin, Luping; Han, Ting; Zhang, Qiaoyan

    2015-01-01

    A rapid ultra-high performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (UHPLC-ESI-Q-TOF/MS) method was developed for qualitative and quantitative determination of constituents in the rhizome of Curculigo orchioides. Qualitative analysis was performed on a Waters ACQUITY UHPLC @ HSS T3 column (1.8 ?m 100 × 2.1mm) using gradient elution with mobile phase of 0.1% formic acid and acetonitrile. Quantitative analysis was performed on an Agilent ZORBAX Eclipse plus C18 column (1.7 ?m 100 × 2.1mm) using gradient elution with mobile phase of 0.1% acetic acid and acetonitrile for at least 20 min. Quadrupole TOF/MS in either full scan mode or extracted ion mode was used for qualitative and quantitative analysis of the constituents. According to the mass spectrometric fragmentation mechanism and UHPLC-ESI-Q-TOF-MS data, chemical structures of 45 constituents in the rhizome of Curculigo orchioides, including 19 phenols and phenolic glycosides, 16 lignans and lignan glycosides, 8 triterpenoid saponins, one flavone and one sesquiterpene, were identified tentatively on-line without the time-consuming process of isolation. In addition, 8 phenolic glycosides including 5-hydroxymethylfurfural (HMF), 2-hydroxy-5-(2-hydroxyethyl) phenyl-?-D-glucopyranoside (HPG), anacardoside (ACD), orcinol glucoside (OGD), orcinol-1-O-?-D-apiofuranosyl-(1 ? 6)-?-D-glucopyranoside (OAG), 2,6-dimethoxybenzoic acid (DBA), curculigoside (CUR) and curculigine A (CCL) were quantitated in 11 collected samples and 10 commercial samples from different providers. The results show that UHPLC-ESI-Q-TOF-MS is a viable method for analysis and quality evaluation of the constituents from the rhizome of Curculigo orchioides. PMID:25305598

  6. Determination of chiral pharmaceuticals and illicit drugs in wastewater and sludge using microwave assisted extraction, solid-phase extraction and chiral liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Evans, Sian E; Davies, Paul; Lubben, Anneke; Kasprzyk-Hordern, Barbara

    2015-07-01

    This is the first study presenting a multi-residue method allowing for comprehensive analysis of several chiral pharmacologically active compounds (cPACs) including beta-blockers, antidepressants and amphetamines in wastewater and digested sludge at the enantiomeric level. Analysis of both the liquid and solid matrices within wastewater treatment is crucial to being able to carry out mass balance within these systems. The method developed comprises filtration, microwave assisted extraction and solid phase extraction followed by chiral liquid chromatography coupled with tandem mass spectrometry to analyse the enantiomers of 18 compounds within all three matrices. The method was successfully validated for 10 compounds within all three matrices (amphetamine, methamphetamine, MDMA, MDA, venlafaxine, desmethylvenlafaxine, citalopram, metoprolol, propranolol and sotalol), 7 compounds validated for the liquid matrices only (mirtazapine, salbutamol, fluoxetine, desmethylcitalopram, atenolol, ephedrine and pseudoephedrine) and 1 compound (alprenolol) passing the criteria for solid samples only. The method was then applied to wastewater samples; cPACs were found at concentration ranges in liquid matrices of: 1.7ngL(-1) (metoprolol) - 1321ngL(-1) (tramadol) in influent,

  7. Fully validated assay for the quantification of endogenous nucleoside mono- and triphosphates using online extraction coupled with liquid chromatography-tandem mass spectrometry.

    PubMed

    Machon, Christelle; Jordheim, Lars Petter; Puy, Jean-Yves; Lefebvre, Isabelle; Dumontet, Charles; Guitton, Jérôme

    2014-05-01

    An analytical method coupling online solid-phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed to quantify 16 endogenous nucleoside mono- and triphosphates in cellular samples. Separation was achieved on a porous graphitic carbon (PGC) column without ion-pairing agent in the mobile phase. Low levels of the ion-pairing agent diethylamine (DEA) added to the reconstitution solution were necessary to prevent peak tailing of nucleoside triphosphates. The mass spectrometer, a triple quadrupole with an electrospray ionisation source, was operated in positive mode. Two multiple reaction monitoring (MRM) segments were programmed, each an internal standard. Extraction and separation of nucleoside mono- and triphosphates were obtained within 20 min. The total duration of a single run was 37 min. Calibration curves, performed with labelled nucleotides added to the sample matrix, ranged from 0.29 to 18.8 pmol injected for deoxyribonucleotides and from 3.9 to 3,156 pmol for ribonucleotides. Accuracy did not deviate more than -14.6 and 10.2 % from nominal values for all compounds at all levels. CV results were all lower than 17.0 % for the LLOQ level and 14.6 % for the other levels. Quality control (QC) samples were also in agreement with acceptance criteria, except for the lower QC of GMP. Ion suppression, matrix effect, extraction recoveries and stability were assessed. After validation, the method was applied to the evaluation of the effects of gemcitabine and hydroxyurea on nucleotide pools in Messa cells. PMID:24633509

  8. Detection of seven pesticides in cucumbers using hollow fibre-based liquid-phase microextraction and ultra-high pressure liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Wang, Jianfeng; Du, Zhenxia; Yu, Wenlian; Qu, Shuping

    2012-07-20

    A liquid-phase microextraction (LPME) methodology based on the use of porous polyvinylidene fluoride (PVDF) hollow fibres was developed for extracting seven pesticides from cucumbers. The seven pesticides include propoxur, carbofuran, atrazine, cyanatryn, metolachlor, prometryn and tebuconazole. The PVDF hollow fibre provides higher extraction efficiency due to its higher porosity and better solvent compatibility. A new desorption methodology was developed since some pesticides were absorbed by the wall pore of the PVDF. Ultra-high pressure liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) was used for pesticide analysis. In order to obtain high recoveries and enrichment factors of the analytes, several parameters such as method of sealing, acceptor phase (organic solvents), stirring speed, extraction time, salting out effect, desorption mode and time were optimized. A fast, simple method for closing fibre ends was practiced by using mechanical crimping. Pesticides were extracted from the sample to the organic solvent and then desorbed in a mixture of methanol:water (1:1 v/v) prior to chromatographic analysis. Limits of detection (LOD) for the multi-reaction-monitoring (MRM) mode of the method varies from 0.01 to 0.31 ?g/kg with optimized sample preparation. Calibration curves are linear with R² ? 0.991. Enrichment factor of the hollow fibre LPME ranges from 100 to 147. Matrix effect has been considered and is in the range of 76-122%. The relative recoveries from cucumber samples are between 63% and 119% with the relative standard deviation (RSD, n=6) lower than 20%. PMID:22682952

  9. Profiling of phytohormones in rice under elevated cadmium concentration levels by magnetic solid-phase extraction coupled with liquid chromatography tandem mass spectrometry.

    PubMed

    Cai, Bao-Dong; Yin, Jia; Hao, Yan-Hong; Li, Yu-Nan; Yuan, Bi-Feng; Feng, Yu-Qi

    2015-08-01

    Phytohormones, a collection of signal small molecules with various structures, regulate a series of physiological processes of plants. For instance, they regulate the growth and development, response to biotic and abiotic stresses. Quantification of trace endogenous phytohormones is essential to elucidate their molecular mechanisms in response to stresses. However, the structural and chemical diversity of phytohormones make it difficult to purify and enrich multiple phytohormones in one-step. In the current study, a method was developed to comprehensively profile phytohormones, including 8 cytokinins (CKs), indole-3-acetic acid (IAA), abscisic acid (ABA), jasmonic acid (JA) and 10 gibberellins (GAs) by Fe3O4@TiO2-based magnetic solid-phase extraction coupled with ultra-performance liquid chromatography-electrospray tandem mass spectrometry (Fe3O4@TiO2-based MSPE-UPLC-MS/MS). In the proposed method, the phytohormones in the acetonitrile extract of plant tissues were captured and purified by one-step MSPE using Fe3O4@TiO2 as a sorbent prior to UPLC-MS/MS analysis. The sensitivity, accuracy and reproducibility of the proposed analytical method were demonstrated to satisfy the profiling of multiple phytohormones in plant tissue. We then further used the Fe3O4@TiO2-based MSPE-UPLC-MS/MS method to explore the change of phytohormones in rice under Cd stress. The results showed that CKs, IAA, ABA, JA and biological active GAs all increased under Cd stress, suggesting that these phytohormones may take part in response to Cd stress. The study may promote the further understanding of the physiological functions of phytohormones in response to Cd stress. PMID:26141271

  10. "Nanocrystal bilayer for tandem catalysis"

    SciTech Connect

    Yamada, Yusuke; Tsung, Chia Kuang; Huang, Wenyu; Huo, Ziyang; E.Habas, Susan E; Soejima, Tetsuro; Aliaga, Cesar E; Samorjai, Gabor A; Yang, Peidong

    2011-01-24

    Supported catalysts are widely used in industry and can be optimized by tuning the composition and interface of the metal nanoparticles and oxide supports. Rational design of metal-metal oxide interfaces in nanostructured catalysts is critical to achieve better reaction activities and selectivities. We introduce here a new class of nanocrystal tandem catalysts that have multiple metal-metal oxide interfaces for the catalysis of sequential reactions. We utilized a nanocrystal bilayer structure formed by assembling platinum and cerium oxide nanocube monolayers of less than 10 nm on a silica substrate. The two distinct metal-metal oxide interfaces, CeO2-Pt and Pt-SiO2, can be used to catalyse two distinct sequential reactions. The CeO2-Pt interface catalysed methanol decomposition to produce CO and H2, which were subsequently used for ethylene hydroformylation catalysed by the nearby Pt-SiO2 interface. Consequently, propanal was produced selectively from methanol and ethylene on the nanocrystal bilayer tandem catalyst. This new concept of nanocrystal tandem catalysis represents a powerful approach towards designing high-performance, multifunctional nanostructured catalysts

  11. Nanocrystal bilayer for tandem catalysis.

    PubMed

    Yamada, Yusuke; Tsung, Chia-Kuang; Huang, Wenyu; Huo, Ziyang; Habas, Susan E; Soejima, Tetsuro; Aliaga, Cesar E; Somorjai, Gabor A; Yang, Peidong

    2011-05-01

    Supported catalysts are widely used in industry and can be optimized by tuning the composition and interface of the metal nanoparticles and oxide supports. Rational design of metal-metal oxide interfaces in nanostructured catalysts is critical to achieve better reaction activities and selectivities. We introduce here a new class of nanocrystal tandem catalysts that have multiple metal-metal oxide interfaces for the catalysis of sequential reactions. We utilized a nanocrystal bilayer structure formed by assembling platinum and cerium oxide nanocube monolayers of less than 10 nm on a silica substrate. The two distinct metal-metal oxide interfaces, CeO(2)-Pt and Pt-SiO(2), can be used to catalyse two distinct sequential reactions. The CeO(2)-Pt interface catalysed methanol decomposition to produce CO and H(2), which were subsequently used for ethylene hydroformylation catalysed by the nearby Pt-SiO(2) interface. Consequently, propanal was produced selectively from methanol and ethylene on the nanocrystal bilayer tandem catalyst. This new concept of nanocrystal tandem catalysis represents a powerful approach towards designing high-performance, multifunctional nanostructured catalysts. PMID:21505495

  12. Nanocrystal bilayer for tandem catalysis

    NASA Astrophysics Data System (ADS)

    Yamada, Yusuke; Tsung, Chia-Kuang; Huang, Wenyu; Huo, Ziyang; Habas, Susan E.; Soejima, Tetsuro; Aliaga, Cesar E.; Somorjai, Gabor A.; Yang, Peidong

    2011-05-01

    Supported catalysts are widely used in industry and can be optimized by tuning the composition and interface of the metal nanoparticles and oxide supports. Rational design of metal-metal oxide interfaces in nanostructured catalysts is critical to achieve better reaction activities and selectivities. We introduce here a new class of nanocrystal tandem catalysts that have multiple metal-metal oxide interfaces for the catalysis of sequential reactions. We utilized a nanocrystal bilayer structure formed by assembling platinum and cerium oxide nanocube monolayers of less than 10 nm on a silica substrate. The two distinct metal-metal oxide interfaces, CeO2-Pt and Pt-SiO2, can be used to catalyse two distinct sequential reactions. The CeO2-Pt interface catalysed methanol decomposition to produce CO and H2, which were subsequently used for ethylene hydroformylation catalysed by the nearby Pt-SiO2 interface. Consequently, propanal was produced selectively from methanol and ethylene on the nanocrystal bilayer tandem catalyst. This new concept of nanocrystal tandem catalysis represents a powerful approach towards designing high-performance, multifunctional nanostructured catalysts.

  13. Amine-functional magnetic polymer modified graphene oxide as magnetic solid-phase extraction materials combined with liquid chromatography-tandem mass spectrometry for chlorophenols analysis in environmental water.

    PubMed

    Pan, Sheng-Dong; Zhou, Li-Xin; Zhao, Yong-Gang; Chen, Xiao-Hong; Shen, Hao-Yu; Cai, Mei-Qiang; Jin, Mi-Cong

    2014-10-01

    A novel planar-structure amine-functional magnetic polymer modified graphene oxide nanocomposite (NH2-MP@GO) was synthesized. The properties were characterized by transmission electron microscopy (TEM) and Fourier-transform infrared spectrometry (FTIR). The obtained adsorption results showed that the NH2-MP@GO had great adsorptive ability toward five chlorophenols (CPs), including 2-chlorophenol (2-CP), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP) and pentachlorophenol (PCP). Based on these, an effective magnetic solid-phase extraction (MSPE) procedure coupled with high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the preconcentration and determination of the five CPs in environmental water samples was developed. Various experimental parameters that could affect the extraction efficiencies had been investigated in detail. Under the optimum conditions, the enrichment factors of the method for the target CPs were found to be 1000. The proposed method was successfully applied for the analysis of environmental water samples with recoveries ranging from 86.4 to 99.8% with correlation coefficients (R) higher than 0.9994. Good linearities were obtained ranging from 10 to 500ng/L for 2-CP, 5 to 500ng/L for 2,4-DCP, 2 to 500ng/L for 2,4,6-TeCP and 2,3,4,6-TeCP, and 1 to 500ng/L for PCP, respectively. The limits of quantitation for the five CPs were 0.6-9.2ng/L. It was confirmed that the planar-structure NH2-MP@GO was a kind of highly effective MSPE materials used for the trace CPs analyses. PMID:25160956

  14. Reduced Coupling of Oxidative Phosphorylation In Vivo Precedes Electron Transport Chain Defects Due to Mild Oxidative Stress in Mice

    PubMed Central

    Siegel, Michael P.; Kruse, Shane E.; Knowels, Gary; Salmon, Adam; Beyer, Richard; Xie, Hui; Van Remmen, Holly; Smith, Steven R.; Marcinek, David J.

    2011-01-01

    Oxidative stress and mitochondrial function are at the core of many degenerative conditions. However, the interaction between oxidative stress and in vivo mitochondrial function is unclear. We used both pharmacological (2 week paraquat (PQ) treatment of wild type mice) and transgenic (mice lacking Cu, Zn-superoxide dismutase (SOD1?/?)) models to test the effect of oxidative stress on in vivo mitochondrial function in skeletal muscle. Magnetic resonance and optical spectroscopy were used to measure mitochondrial ATP and oxygen fluxes and cell energetic state. In both models of oxidative stress, coupling of oxidative phosphorylation was significantly lower (lower P/O) at rest in vivo in skeletal muscle and was dose-dependent in the PQ model. Despite this reduction in efficiency, in vivo mitochondrial phosphorylation capacity (ATPmax) was maintained in both models, and ex vivo mitochondrial respiration in permeabilized muscle fibers was unchanged following PQ treatment. In association with the reduced P/O, PQ treatment led to a dose-dependent reduction in PCr/ATP ratio and increased phosphorylation of AMPK. These results indicate that oxidative stress uncouples oxidative phosphorylation in vivo and results in energetic stress in the absence of defects in the mitochondrial electron transport chain. PMID:22132085

  15. Identification of Novel in vivo MAP Kinase Substrates in Arabidopsis thaliana Through Use of Tandem Metal Oxide Affinity Chromatography*

    PubMed Central

    Hoehenwarter, Wolfgang; Thomas, Martin; Nukarinen, Ella; Egelhofer, Volker; Röhrig, Horst; Weckwerth, Wolfram; Conrath, Uwe; Beckers, Gerold J. M.

    2013-01-01

    Mitogen-activated protein kinase (MPK) cascades are important for eukaryotic signal transduction. They convert extracellular stimuli (e.g. some hormones, growth factors, cytokines, microbe- or damage-associated molecular patterns) into intracellular responses while at the same time amplifying the transmitting signal. By doing so, they ensure proper performance, and eventually survival, of a given organism, for example in times of stress. MPK cascades function via reversible phosphorylation of cascade components MEKKs, MEKs, and MPKs. In plants the identity of most MPK substrates remained elusive until now. Here, we provide a robust and powerful approach to identify and quantify, with high selectivity, site-specific phosphorylation of MPK substrate candidates in the model plant Arabidopsis thaliana. Our approach represents a two-step chromatography combining phosphoprotein enrichment using Al(OH)3-based metal oxide affinity chromatography, tryptic digest of enriched phosphoproteins, and TiO2-based metal oxide affinity chromatography to enrich phosphopeptides from complex protein samples. When applied to transgenic conditional gain-of-function Arabidopsis plants supporting in planta activation of MPKs, the approach allows direct measurement and quantification ex vivo of site-specific phosphorylation of several reported and many yet unknown putative MPK substrates in just a single experiment. PMID:23172892

  16. Oxidative Coupling of Enolates, Enol Silanes and Enamines: Methods and Natural Product Synthesis

    PubMed Central

    Guo, Fenghai; Clift, Michael D.

    2013-01-01

    The oxidative coupling of enolates, enol silanes, and enamines provides a direct method for the construction of useful 1,4-dicarbonyl synthons. Despite being first reported in 1935, with subsequent important advances beginning in the 1970’s, the development of this powerful reaction into a reliable methodology was somewhat limited. In recent years, there have been a number of reports from several research groups demonstrating advances in several neglected areas of oxidative coupling. This microreview summarizes these new advances in methodology and provides an overview of recent natural product syntheses that showcase the power of these transformations. PMID:23471479

  17. Copper-mediated formally dehydrative biaryl coupling of azine N-oxides and oxazoles.

    PubMed

    Odani, Riko; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro

    2015-02-20

    A copper-mediated formally dehydrative biaryl coupling of azine N-oxides and oxazoles has been developed. The C-C bond-forming process proceeds, accompanied by the removal of the oxygen atom from the azine core, to directly afford the azine-oxazole biaryl linkage. Moreover, this system requires no noble transition metals such as palladium and rhodium, which are common promotors in the related dehydrogenative couplings with the azine N-oxide. Thus, the present protocol can provide a unique and less expensive approach to the azine-containing biheteroaryls of substantial interest in pharmaceutical and medicinal chemistry. PMID:25611158

  18. Enzymatic Processing of Fumiquinazoline F: A Tandem Oxidative-Acylation Strategy for the Generation of Multicyclic Scaffolds in Fungal Indole Alkaloid Biosynthesis†

    PubMed Central

    Ames, Brian D.; Liu, Xinyu; Walsh, Christopher T.

    2010-01-01

    Aspergillus fumigatus Af293 is a known producer of quinazoline natural products including the antitumor fumiquinazolines, of which the simplest member is fumiquinazoline F (FQF) with a 6-6-6 tricyclic core derived from anthranilic acid, tryptophan, and alanine. FQF is the proposed biological precursor to fumiquinazoline A (FQA) where the pendant indole side chain has been modified via oxidative coupling of an additional molecule of alanine, yielding a fused 6-5-5 imidazoindolone. We recently identified fungal anthranilate-activating non-ribosomal peptide synthetase (NRPS) domains through bioinformatics approaches. One domain previously identified is part of the trimodular NRPS Af12080, which we predict is responsible for FQF formation. We now show that two adjacent A. fumigatus ORFs, a monomodular NRPS Af12050 and a flavoprotein Af12060, are necessary and sufficient to convert FQF to FQA. Af12060 oxidizes the 2',3'-double bond of the indole side chain of FQF, and the three-domain NRPS Af12050 activates L-Ala as the adenylate, installs it as the pantetheinyl thioester on its carrier protein domain and acylates the oxidized indole for subsequent intramolecular cyclization to create the 6-5-5 imidazolindolone of FQA. This work provides experimental validation of the fumiquinazoline biosynthetic cluster of A. fumigatus A293, and describes an oxidative annulation biosynthetic strategy likely shared among several classes of polycyclic fungal alkaloids. PMID:20804163

  19. Oxidative Phosphorylation coupled with Aerobic and Anaerobic Respiration in a Bacterial Cell-free System

    Microsoft Academic Search

    Tomoko Ohnishi; Takeshi Mori

    1962-01-01

    IT has been presumed that in anaerobic respiration, such as nitrate1 or sulphate2 respiration, formation of some high-energy phosphate is coupled with the process in a similar way to oxidative phosphorylation in aerobic respiration. We have reported3 that, in the whole cell system of Pseudomonas denitrificans, radioactive inorganic phosphate (32Pi) is incorporated into labile organic phosphates coupled with the denitrification

  20. Coupling characteristics of thin-film metal-oxide-metal diodes at 10.6 microns

    NASA Technical Reports Server (NTRS)

    Wang, S. Y.; Gustafson, T. K.; Izawa, T.

    1975-01-01

    Direct detection experiments have demonstrated the coherent coupling of 10.6 micrometer radiation into photolithographically fabricated metal-oxide-metal tunnel junctions. A CO2 laser beam mechanically chopped at 1 KHz was focused at a variable angle of incidence with a power density of about 10 W/sq cm at the diodes. Diodes in which the junction resistance was much greater than the lead resistance displayed angular characteristics dominated by coherent antenna coupling.

  1. Hydrogen and formate oxidation coupled to dissimilatory reduction of iron or manganese by Alteromonas putrefaciens

    USGS Publications Warehouse

    Lovley, D.R.; Phillips, E.J.P.; Lonergan, D.J.

    1989-01-01

    The ability of Alteromonas putrefaciens to obtain energy for growth by coupling the oxidation of various electron donors to dissimilatory Fe(III) or Mn(IV) reduction was investigated. A. putrefaciens grew with hydrogen, formate, lactate, or pyruvate as the sole electron donor and Fe(III) as the sole electron acceptor. Lactate and pyruvate were oxidized to acetate, which was not metabolized further. With Fe(III) as the electron acceptor, A. putrefaciens had a high affinity for hydrogen and formate and metabolized hydrogen at partial pressures that were 25-fold lower than those of hydrogen that can be metabolized by pure cultures of sulfate reducers or methanogens. The electron donors for Fe(III) reduction also supported Mn(IV) reduction. The electron donors for Fe(III) and Mn(IV) reduction and the inability of A. putrefaciens to completely oxidize multicarbon substrates to carbon dioxide distinguish A. putrefaciens from GS-15, the only other organism that is known to obtain energy for growth by coupling the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV). The ability of A. putrefaciens to reduce large quantities of Fe(III) and to grow in a defined medium distinguishes it from a Pseudomonas sp., which is the only other known hydrogen-oxidizing, Fe(III)-reducing microorganism. Furthermore, A. putrefaciens is the first organism that is known to grow with hydrogen as the electron donor and Mn(IV) as the electron acceptor and is the first organism that is known to couple the oxidation of formate to the reduction of Fe(III) or Mn(IV). Thus, A. putrefaciens provides a much needed microbial model for key reactions in the oxidation of sediment organic matter coupled to Fe(III) and Mn(IV) reduction.

  2. Oxidation-induced biquadratic coupling in Co/Fe/MgO/Fe(001)

    NASA Astrophysics Data System (ADS)

    Chiang, Y. F.; Wong, Jared J. I.; Tan, X.; Li, Yan; Pi, K.; Wang, W. H.; Tom, H. W. K.; Kawakami, R. K.

    2009-05-01

    We investigate the interlayer exchange coupling in Co/Fe/MgO/Fe(001) via molecular-beam epitaxy synthesis and magneto-optic Kerr effect measurements across wedged samples. By independently varying the oxygen contents of the MgO film and the Fe/MgO interface, the biquadratic coupling is found to be correlated with the interfacial oxidation. Furthermore, the temperature dependence indicates that the biquadratic coupling originates from indirect exchange interactions with magnetic impurities in the MgO spacer.

  3. DMSO–PdI 2 as a powerful oxidizing couple of alkynes into benzils: one-pot synthesis of nitrogen-containing five- or six-membered heterocycles

    Microsoft Academic Search

    Céline Mousset; Olivier Provot; Abdallah Hamze; Jérôme Bignon; Jean-Daniel Brion; Mouâd Alami

    2008-01-01

    PdI2 in DMSO promoted the oxidation of functionalized diarylalkynes into benzil derivatives in excellent yields. This new oxidation reaction was achieved with short reaction times and low loading of palladium catalyst. This efficient catalytic process has been applied successfully to the one-pot construction of a series of nitrogen-containing heterocycles of biological interest according to a tandem oxidation–nitrogen nucleophiles condensation–cyclization.

  4. Tandem Mirror Reactor Systems Code (Version I)

    SciTech Connect

    Reid, R.L.; Finn, P.A.; Gohar, M.Y.; Barrett, R.J.; Gorker, G.E.; Spampinaton, P.T.; Bulmer, R.H.; Dorn, D.W.; Perkins, L.J.; Ghose, S.

    1985-09-01

    A computer code was developed to model a Tandem Mirror Reactor. Ths is the first Tandem Mirror Reactor model to couple, in detail, the highly linked physics, magnetics, and neutronic analysis into a single code. This report describes the code architecture, provides a summary description of the modules comprising the code, and includes an example execution of the Tandem Mirror Reactor Systems Code. Results from this code for two sensitivity studies are also included. These studies are: (1) to determine the impact of center cell plasma radius, length, and ion temperature on reactor cost and performance at constant fusion power; and (2) to determine the impact of reactor power level on cost.

  5. Production of N2 through Anaerobic Ammonium Oxidation Coupled to Nitrate Reduction in Marine Sediments

    Microsoft Academic Search

    Bo Thamdrup; Tage Dalsgaard

    2002-01-01

    In the global nitrogen cycle, bacterial denitrification is recognized as the only quantitatively important process that converts fixed nitrogen to atmospheric nitrogen gas, N2, thereby influencing many aspects of ecosystem function and global biogeochemistry. However, we have found that a process novel to the marine nitrogen cycle, anaerobic oxidation of ammonium coupled to nitrate reduction, contributes substantially to N2 production

  6. Nitrogen loss from soil through anaerobic ammonium oxidation coupled to iron reduction

    NASA Astrophysics Data System (ADS)

    Yang, Wendy H.; Weber, Karrie A.; Silver, Whendee L.

    2012-08-01

    The oxidation of ammonium is a key step in the nitrogen cycle, regulating the production of nitrate, nitrous oxide and dinitrogen. In marine and freshwater ecosystems, anaerobic ammonium oxidation coupled to nitrite reduction, termed anammox, accounts for up to 67% of dinitrogen production. Dinitrogen production through anaerobic ammonium oxidation has not been observed in terrestrial ecosystems, but the anaerobic oxidation of ammonium to nitrite has been observed in wetland soils under iron-reducing conditions. Here, we incubate tropical upland soil slurries with isotopically labelled ammonium and iron(III) to assess the potential for anaerobic ammonium oxidation coupled to iron(III) reduction, otherwise known as Feammox, in these soils. We show that Feammox can produce dinitrogen, nitrite or nitrate in tropical upland soils. Direct dinitrogen production was the dominant Feammox pathway, short-circuiting the nitrogen cycle and resulting in ecosystem nitrogen losses. Rates were comparable to aerobic nitrification and to denitrification, the latter being the only other process known to produce dinitrogen in terrestrial ecosystems. We suggest that Feammox could fuel nitrogen losses in ecosystems rich in poorly crystalline iron minerals, with low or fluctuating redox conditions.

  7. Identification of oxidative coupling products of xylenols arising from laboratory-scale phytoremediation.

    PubMed

    Poerschmann, J; Schultze-Nobre, L; Ebert, R U; Górecki, T

    2015-01-01

    Oxidative coupling reactions take place during the passage of xylenols through a laboratory-scale helophyte-based constructed wetland system. Typical coupling product groups including tetramethyl-[1,1'-biphenyl] diols and tetramethyl diphenylether monools as stable organic intermediates could be identified by a combination of pre-chromatographic derivatization and GC/MS analysis. Structural assignment of individual analytes was performed by an increment system developed by Zenkevich to pre-calculate retention sequences. The most abundant analyte turned out to be 3,3',5,5'-tetramethyl-[1,1'-biphenyl]-4,4'-diol, which can be formed by a combination of radicals based on 2,6-xylenol or by an attack of a 2,6-xylenol-based radical on 2,6-xylenol. Organic intermediates originating from oxidative coupling could also be identified in anaerobic constructed wetland systems. This finding suggested the presence of (at least partly) oxic conditions in the rhizosphere. PMID:24992220

  8. TANDEM: matching proteins with tandem mass spectra

    Microsoft Academic Search

    Robertson Craig; Ronald C. Beavis

    2004-01-01

    ABSTRACT Summary: Tandem mass spectra obtained from fragmenting peptide ions contain some peptide sequence specific information, but often there is not enough information to completely sequence the original peptide. Several proprietary software applications have been developed to attempt to match the spectra with a list of protein sequencesthat may contain the sequence of the peptide. The application TANDEM was writtento

  9. Simultaneous speciation of selenium and sulfur species in selenized odorless garlic (Allium sativum L. Shiro) and shallot (Allium ascalonicum) by HPLC-inductively coupled plasma-(octopole reaction system)-mass spectrometry and electrospray ionization-tandem mass spectrometry.

    PubMed

    Ogra, Yasumitsu; Ishiwata, Kazuya; Iwashita, Yuji; Suzuki, Kazuo T

    2005-11-01

    The simultaneous speciation of selenium and sulfur in selenized odorless garlic (Allium sativum L. Shiro) and a weakly odorous Allium plant, shallot (Allium ascalonicum), was performed by means of a hyphenated technique, a HPLC coupled with an inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) equipped with an octopole reaction system (ORS). The aqueous extracts of them contained the common seleno compound that was identified as gamma-glutamylmethylselenocysteine by an electrospray ionization-tandem mass spectrometry (ESI-MS/MS). Normal garlic contains alliin as the major sulfur-containing compound, which is the biological precursor of the garlic odorant, allicin. Alliin, however, was not detected in the extracts of the selenized odorless garlic. At least, four unidentified sulfur-containing compounds were detected in odorless garlic and shallot. Moreover, these Allium plants showed chemopreventive effects against human leukemia cells. PMID:16233877

  10. Predicting gold-mediated catalytic oxidative-coupling reactions from single crystal studies.

    PubMed

    Xu, Bingjun; Madix, Robert J; Friend, Cynthia M

    2014-03-18

    Though metallic gold is chemically inert under ambient conditions, its surface is extremely reactive and selective for many key oxidative chemical transformations when activated by atomic oxygen. A molecular-level understanding of the mechanism of these processes could allow researchers to design "green" catalytic processes mediated by gold-based materials. This Account focuses on the mechanistic framework for oxidative-coupling reactions established by fundamental studies on oxygen-activated Au(111) and the application of these principles to steady-state catalytic conditions. We also discuss the importance of the paradigms discovered both for predicting new oxidative-coupling reactions and for understanding existing literature. The mechanistic framework for the oxidative coupling of alcohols on gold surfaces predicts that new oxidative-coupling reactions should occur between amines and aldehydes and amines and alcohols as well as through alcohol carbonylation. Adsorbed atomic oxygen on the gold surface facilitates the activation of the substrates, and nucleophilic attack and ?-H elimination are the two fundamental reactions that propagate the versatile chemistry that ensues. In the self-coupling of primary alcohols, adsorbed atomic oxygen first activates the O-H bond in the hydroxyl group at ?150 K, which forms the corresponding adsorbed alkoxy groups. The rate-limiting step of the self-coupling reaction is the ?-H elimination reaction of alkoxy groups to form the corresponding aldehydes and occurs with an activation barrier of approximately 12 kcal/mol. The remaining alkoxy groups nucleophilically attack the electron-deficient aldehyde carbonyl carbon to yield the adsorbed "hemiacetal". This intermediate undergoes facile ?-H elimination to produce the final coupling products, esters with twice the number of carbon atoms as the starting alcohols. This mechanistic insight suggests that cross-coupling occurs between alcohols and aldehydes, based on the logic that the nucleophilic reaction should be independent of the origin of the aldehydes, whether formed in situ or introduced externally. As a further example, adsorbed amides, formed from deprotonation of amines by atomic oxygen, can also attack aldehydes nucleophilically to yield the corresponding amides. Our mechanistic framework can also explain more elaborate gold-mediated chemistry, such as a unique carbonylation reaction via two subsequent nucleophilic attacks. These model studies on well-defined Au(111) at low pressure predict steady-state catalytic behavior on nanoporous gold under practical conditions. The fundamental principles of this research can also explain many other oxygen-assisted gold-mediated reactions observed under ambient conditions. PMID:24387694

  11. Analysis of phenolic compounds by high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry in senescent and water-stressed tobacco

    Microsoft Academic Search

    Laura Torras-Claveria; Olga Jáuregui; Carles Codina; Antonio F. Tiburcio; Jaume Bastida; Francesc Viladomat

    Evaluation of a significant part of the phenylpropanoid pathway metabolites is facilitated by the fast high-performance liquid chromatography with electrospray ionization tandem mass spectrometry (LC–MS\\/MS) analytical method. The technology described was applied in tobacco plants (Nicotiana tabacum L. cv. Wisconsin) to identify 20 phenolic compounds and to detect differences in phenylpropanoid profiles in two types of experiments. In the first

  12. Specific method for determination of gefitinib in human plasma, mouse plasma and tissues using high performance liquid chromatography coupled to tandem mass spectrometry

    Microsoft Academic Search

    Ming Zhao; Carol Hartke; Antonio Jimeno; Jing Li; Ping He; Yelena Zabelina; Manuel Hidalgo; Sharyn D. Baker

    2005-01-01

    A rapid, sensitive and specific method was developed and validated using liquid chromatography–tandem mass spectrometry (LC\\/MS\\/MS) for determination of gefitinib in human plasma and mouse plasma and tissue. Sample preparation involved a single protein precipitation step by the addition of 0.1mL of plasma or a 200mg\\/mL tissue homogenate diluted 1\\/10 in human plasma with 0.3mL acetonitrile. Separation of the compounds

  13. Simultaneous determination of didanosine and its amino acid prodrug, valdidanosine by hydrophilic interaction chromatography coupled with electrospray ionization tandem mass spectrometry: Application to a pharmacokinetic study in rats

    Microsoft Academic Search

    Zhongtian Yan; Jin Sun; Jinling Wang; Youjun Xu; Yannan Chang; Ping Meng; Meng Zhu; Qiang Fu; Yongbing Sun; Zhonggui He

    2010-01-01

    A rapid, sensitive and selective ultra-performance liquid chromatography–tandem mass spectrometry (UPLC–MS\\/MS) method with hydrophilic interaction chromatography has been developed and validated for the simultaneous determination of didanosine and valdidanosine (L-valine amino acid ester prodrug of didanosine) in rat plasma. Solid-phase extraction (SPE) column was employed to extract the analytes from rat plasma, with high extraction recovery (>85%) for both didanosine

  14. Mismatched wear couple zirconium oxide and aluminum oxide in total hip arthroplasty

    Microsoft Academic Search

    Michael Morlock; Roman Nassutt; Rolf Janssen; Gerd Willmann; Matthias Honl

    2001-01-01

    A patient complained about a squeaking noise in his total hip arthroplasty. Clinical evaluation revealed good function, and there were no signs of loosening on the radiograph. Physiotherapy did not alter this phenomenon, and ultimately a revision was performed 42 months after the first surgery. The analysis of the retrievals revealed that a zirconium oxide ceramic head had been paired

  15. Increased levels of hydrogen peroxide and nitric oxide in male partners of infertile couples.

    PubMed

    Kullisaar, T; Türk, S; Kilk, K; Ausmees, K; Punab, M; Mändar, R

    2013-11-01

    We investigated the prevalence of oxidative stress in male partners of infertile couples displaying different inflammation patterns in their genital tract and/or oligospermia. The levels of acknowledged oxidative stress markers (8-isoprostanes [8-EPI], diene conjugates, reactive oxygen species-total antioxidant capacity [ROS-TAC] score) were elevated in both leukocytospermic men and subjects whose inflammation was limited only to expressed prostatic secretion and/or post-massage urine. Oligospermic men with severe inflammation were different from oligospermic men who had no inflammation at all - the former had elevated 8-EPI, diene conjugates and ROS-TAC score when compared to the latter indicating that inflammation has substantially more significant impact on oxidative stress markers than oligospermia status. At the same time nitric oxide (NO) and hydrogen peroxide (H2 O2 ) levels were significantly increased not only in the men with severe inflammation but also in men with borderline inflammation in their genital tact and in men having non-inflammatory oligospermia. NO, H2 O2 and 8-EPI were negatively correlated with per cent of normal sperms, and NO and H2 O2 showed negative correlation also with sperm count. We can conclude that in men presenting with couple infertility the acknowledged oxidative stress markers are substantially associated with markers of inflammation in genital tract while NO and H2 O2 display high levels also in patients with mild inflammation and non-inflammatory oligospermia. PMID:24106058

  16. Bimolecular Coupling Reactions through Oxidatively Generated Aromatic Cations: Scope and Stereocontrol.

    PubMed

    Cui, Yubo; Villafane, Louis A; Clausen, Dane J; Floreancig, Paul E

    2013-09-01

    Chromenes, isochromenes, and benzoxathioles react with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone to form stable aromatic cations that react with a range of nucleophiles. These oxidative fragment coupling reactions provide rapid access to structurally diverse heterocycles. Conducting the reactions in the presence of a chiral Brønsted acid results in the formation of an asymmetric ion pair that can provide enantiomerically enriched products in a rare example of a stereoselective process resulting from the generation of a chiral electrophile through oxidative carbon-hydrogen bond cleavage. PMID:23913987

  17. Bimolecular Coupling Reactions through Oxidatively Generated Aromatic Cations: Scope and Stereocontrol

    PubMed Central

    Cui, Yubo; Villafane, Louis A.; Clausen, Dane J.

    2013-01-01

    Chromenes, isochromenes, and benzoxathioles react with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone to form stable aromatic cations that react with a range of nucleophiles. These oxidative fragment coupling reactions provide rapid access to structurally diverse heterocycles. Conducting the reactions in the presence of a chiral Brønsted acid results in the formation of an asymmetric ion pair that can provide enantiomerically enriched products in a rare example of a stereoselective process resulting from the generation of a chiral electrophile through oxidative carbon–hydrogen bond cleavage. PMID:23913987

  18. Immobilization of laccase for oxidative coupling of trans-resveratrol and its derivatives.

    PubMed

    Zhang, Hong; Xun, Erna; Wang, Jiaxin; Chen, Ge; Cheng, Tiexin; Wang, Zhi; Ji, Tengfei; Wang, Lei

    2012-01-01

    Trametes Villosa Laccase (TVL) was immobilized through physical adsorption on SBA-15 mesoporous silica and the immobilized TVL was used in the oxidative coupling of trans-resveratrol. Higher loading and activity of the immobilized enzyme on SBA-15 were obtained when compared with the free enzyme. The effects of reaction conditions, such as buffer type, pH, temperature and substrate concentration were investigated, and the optimum conditions were screened and resulted in enzyme activity of up to 10.3 ?mol/g·h. Furthermore, the oxidative couplings of the derivatives of trans-resveratrol were also catalyzed by immobilized TVL. The immobilized TVL was recyclable and could maintain 78% of its initial activity after reusing it four times. PMID:22754345

  19. Immobilization of Laccase for Oxidative Coupling of Trans-Resveratrol and Its Derivatives

    PubMed Central

    Zhang, Hong; Xun, Erna; Wang, Jiaxin; Chen, Ge; Cheng, Tiexin; Wang, Zhi; Ji, Tengfei; Wang, Lei

    2012-01-01

    Trametes villosa Laccase (TVL) was immobilized through physical adsorption on SBA-15 mesoporous silica and the immobilized TVL was used in the oxidative coupling of trans-resveratrol. Higher loading and activity of the immobilized enzyme on SBA-15 were obtained when compared with the free enzyme. The effects of reaction conditions, such as buffer type, pH, temperature and substrate concentration were investigated, and the optimum conditions were screened and resulted in enzyme activity of up to 10.3 ?mol/g·h. Furthermore, the oxidative couplings of the derivatives of trans-resveratrol were also catalyzed by immobilized TVL. The immobilized TVL was recyclable and could maintain 78% of its initial activity after reusing it four times. PMID:22754345

  20. Development of Oxidative Coupling Strategies for Site-Selective Protein Modification.

    PubMed

    ElSohly, Adel M; Francis, Matthew B

    2015-07-21

    As the need to prepare ever more complex but well-defined materials has increased, a similar need for reliable synthetic strategies to access them has arisen. Accordingly, recent years have seen a steep increase in the development of reactions that can proceed under mild conditions, in aqueous environments, and with low concentrations of reactants. To enable the preparation of well-defined biomolecular materials with novel functional properties, our laboratory has a continuing interest in developing new bioconjugation reactions. A particular area of focus has been the development of oxidative reactions to perform rapid site- and chemoselective couplings of electron rich aromatic species with both unnatural and canonical amino acid residues. This Account details the evolution of oxidative coupling reactions in our laboratory, from initial concepts to highly efficient reactions, focusing on the practical aspects of performing and developing reactions of this type. We begin by discussing our rationale for choosing an oxidative coupling approach to bioconjugation, highlighting many of the benefits that such strategies provide. In addition, we discuss the general workflow we have adopted to discover protein modification reactions directly in aqueous media with biologically relevant substrates. We then review our early explorations of periodate-mediated oxidative couplings between primary anilines and p-phenylenediamine substrates, highlighting the most important lessons that were garnered from these studies. Key mechanistic insights allowed us to develop second-generation reactions between anilines and anisidine derivatives. In addition, we summarize the methods we have used for the introduction of aniline groups onto protein substrates for modification. The development of an efficient and chemoselective coupling of anisidine derivatives with tyrosine residues in the presence of ceric ammonium nitrate is next described. Here, our logic and workflow are used to highlight the challenges and opportunities associated with the optimization of site-selective chemistries that target native amino acids. We close by discussing the most recent reports from our laboratory that have capitalized on the unique reactivity of o-iminoquinone derivatives. We discuss the various oxidants and conditions that can be used to generate these reactive intermediates from appropriate precursors, as well as the product distributions that result. We also describe our work to determine the nature of iminoquinone reactivity with proteins and peptides bearing free N-terminal amino groups. Through this discussion, we hope to facilitate the use of oxidative approaches to protein bioconjugation, as well as inspire the discovery of new reactions for the site-selective modification of biomolecular targets. PMID:26057118

  1. A Critical Assessment of Li\\/MgO-Based Catalysts for the Oxidative Coupling of Methane

    Microsoft Academic Search

    Sebastian Arndt; Guillaume Laugel; Sergey Levchenko; Raimund Horn; Manfred Baerns; Matthias Scheffler; Robert Schlögl; Reinhard Schomäcker

    2011-01-01

    Li\\/MgO is one of the most frequently investigated catalysts for the oxidative coupling of methane. Besides catalytic testing, it is also a suitable system to perform surface science experiments and quantum chemical calculations, which is not possible for many other active catalysts. However, the real structure of Li\\/MgO, the nature of the active center and the structure - activity relationship

  2. Intramolecular oxidative coupling: I2/TBHP/NaN3-mediated synthesis of benzofuran derivatives.

    PubMed

    Xu, Wengang; Li, Qingcui; Cao, Chuanpeng; Zhang, Fanglin; Zheng, Hua

    2015-05-27

    A novel intramolecular oxidative coupling reaction has been established to prepare benzofuran derivatives via direct C(sp(2))-H functionalization for the formation of C-O bond. This transformation is mediated by I2/TBHP/NaN3 under metal-free conditions and a catalytic amount of NaN3 plays a crucial role in the reaction. Furthermore, the reaction tolerates a broad substrate scope with average to excellent yields. PMID:25946684

  3. Intramolecular anodic olefin coupling reactions: using competition studies to probe the mechanism of oxidative cyclization reactions.

    PubMed

    Xu, Hai-Chao; Moeller, Kevin D

    2010-04-16

    A competition experiment was designed so that the relative rates of anodic cyclization reactions under various electrolysis conditions can be determined. Reactions with ketene dithioacetal and enol ether-based substrates that use lithium methoxide as a base were shown to proceed through radical cation intermediates that were trapped by a sulfonamide anion. Results for the oxidative coupling of a vinyl sulfide with a sulfonamide anion using the same conditions were consistent with the reaction proceeding through a nitrogen-radical. PMID:20302359

  4. Anaerobic Oxidation of Methane Coupled to Nitrite Reduction by Halophilic Marine NC10 Bacteria.

    PubMed

    He, Zhanfei; Geng, Sha; Cai, Chaoyang; Liu, Shuai; Liu, Yan; Pan, Yawei; Lou, Liping; Zheng, Ping; Xu, Xinhua; Hu, Baolan

    2015-08-15

    Anaerobic oxidation of methane (AOM) coupled to nitrite reduction is a novel AOM process that is mediated by denitrifying methanotrophs. To date, enrichments of these denitrifying methanotrophs have been confined to freshwater systems; however, the recent findings of 16S rRNA and pmoA gene sequences in marine sediments suggest a possible occurrence of AOM coupled to nitrite reduction in marine systems. In this research, a marine denitrifying methanotrophic culture was obtained after 20 months of enrichment. Activity testing and quantitative PCR (qPCR) analysis were then conducted and showed that the methane oxidation activity and the number of NC10 bacteria increased correlatively during the enrichment period. 16S rRNA gene sequencing indicated that only bacteria in group A of the NC10 phylum were enriched and responsible for the resulting methane oxidation activity, although a diverse community of NC10 bacteria was harbored in the inoculum. Fluorescence in situ hybridization showed that NC10 bacteria were dominant in the enrichment culture after 20 months. The effect of salinity on the marine denitrifying methanotrophic culture was investigated, and the apparent optimal salinity was 20.5‰, which suggested that halophilic bacterial AOM coupled to nitrite reduction was obtained. Moreover, the apparent substrate affinity coefficients of the halophilic denitrifying methanotrophs were determined to be 9.8 ± 2.2 ?M for methane and 8.7 ± 1.5 ?M for nitrite. PMID:26048927

  5. A high-performance liquid chromatography-tandem mass spectrometry method coupled with protein precipitation for determination of granisetron in human plasma and its application to a comparative pharmacokinetic study.

    PubMed

    Zhou, Ying; Jiang, Ji; Hu, Pei; Wang, Hongyun

    2014-12-01

    A rapid, simple and validated method based on liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) has been developed for the determination of granisetron in human plasma. Plasma samples were pre-purified by protein precipitation procedure. The chromatographic separation was achieved with Synergi Polar-RP (75?×?2 mm, 4 µm) column using a mixture of 5 mm pH4.0 ammonium formate and methanol (300:316, v/v) under isocratic conditions at a flow rate of 0.3 mL/min. The detection was performed on a triple quadrupole tandem mass spectrometer in multiple reaction monitoring mode using positive electrospray ionization. The analysis time was about 2.5 min. The method was fully validated over the concentration range 0.1-10 ng/mL. The lower limit of quantification was 0.1 ng/mL. Inter- and intra-batch precision was <6.1% and the accuracy was within 95.6-100.0%. The mean extraction recovery was 96.3%. Selectivity, matrix effect and stability were also validated. The method was applied to the comparative pharmacokinetic study of granisetron in Chinese healthy subjects. PMID:24811001

  6. In situ high temperature oxidation analysis of Zircaloy-4 using acoustic emission coupled with thermogravimetry

    NASA Astrophysics Data System (ADS)

    Omar, Al Haj; Véronique, Peres; Eric, Serris; François, Grosjean; Jean, Kittel; François, Ropital; Michel, Cournil

    2015-06-01

    Zircaloy-4 oxidation behavior at high temperature (900 °C), which can be reached in case of severe accidental situations in nuclear pressurised water reactor, was studied using acoustic emission analysis coupled with thermogravimetry. Two different atmospheres were used to study the oxidation of Zircaloy-4: (a) helium and pure oxygen, (b) helium and oxygen combined with slight addition of air. The experiments with 20% of oxygen confirm the dependence on oxygen anions diffusion in the oxide scale. Under a mixture of oxygen and air in helium, an acceleration of the corrosion was observed due to the detrimental effect of nitrogen. The kinetic rate increased significantly after a kinetic transition (breakaway). This acceleration was accompanied by an acoustic emission activity. Most of the acoustic emission bursts were recorded after the kinetic transition (post-transition) or during the cooling of the sample. The characteristic features of the acoustic emission signals appear to be correlated with the different populations of cracks and their occurrence in the ZrO2 layer or in the ?-Zr(O) layer. Acoustic events were recorded during the isothermal dwell time at high temperature under air. They were associated with large cracks in the zirconia porous layer. Acoustic events were also recorded during cooling after oxidation tests both under air or oxygen. For the latter, cracks were observed in the oxygen enriched zirconium metal phase and not in the dense zirconia layer after 5 h of oxidation.

  7. Diagnostic ion filtering strategy for chemical characterization of Guge Fengtong Tablet with high-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry.

    PubMed

    Zeng, Su-Ling; Liu, Xin-Guang; Lai, Chang-Jiang-Sheng; Liu, E-Hu; Li, Ping

    2015-05-01

    The present study was designed to characterize the chemical constituents of Guge Fengtong Tablet (GGFTT). Based on the chromatographic retention behavior, fragmentation pathways of chemical components and the published literatures, a diagnostic ion filtering strategy with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (HPLC-ESI-Q-TOF/MS) was established to identify the multiple bioactive constituents of GGFTT. The rapid identification of forty-seven components, including 18 phenolic acids, 8 saponins, 14 gingerol-related compounds, and 7 diarylhepatonoids, was accomplished using this newly developed method. The coupling of HPLC-ESI-Q-TOF/MS with the diagnostic ion filtering strategy was useful and efficient for the in-depth structural elucidation of chemical compounds of GGFTT. PMID:25986289

  8. Skeletal diverse synthesis of N-fused polycyclic heterocycles via the sequence of Ugi-type MCR and CuI-catalyzed coupling/tandem Pictet-Spengler reaction.

    PubMed

    Tyagi, Vikas; Khan, Shahnawaz; Bajpai, Vikas; Gauniyal, Harsh M; Kumar, Brijesh; Chauhan, Prem M S

    2012-02-01

    Several diversity-oriented syntheses of N-fused polycyclic heterocycles have been demonstrated but most of them are based on point diversity within the same library and usually involve time-consuming sequential multistep syntheses, which also suffer from low yields and/or poor precursor scopes. We have developed a new strategy for the syntheses of skeletal diverse N-fused polycyclic compounds via an Ugi-type MCR followed by a CuI-catalyzed coupling reaction or tandem Pictet-Spengler reaction. This two-step sequence provides eight distinct skeleton of fused {6-5-5-6}, {5-5-5-6}, {6-5-6-6}, and {5-5-6-6} ring systems that have applications in medicinal chemistry and chemical genetics too. PMID:22272987

  9. Electric-induced oxide breakdown of a charge-coupled device under femtosecond laser irradiation.

    PubMed

    Gao, Liuzheng; Zhu, Zhiwu; Shao, Zhengzheng; Cheng, Xiang'ai; Chang, Shengli

    2013-11-01

    A femtosecond laser provides an ideal source to investigate the laser-induced damage of a charge-coupled device (CCD) owing to its thermal-free and localized damage properties. For conventional damage mechanisms in the nanosecond laser regime, a leakage current and degradation of a point spread function or modulation transfer function of the CCD are caused by the thermal damages to the oxide and adjacent electrodes. However, the damage mechanisms are quite different for a femtosecond laser. In this paper, an area CCD was subjected to Ti: sapphire laser irradiation at 800 nm by 100 fs single pulses. Electric-induced oxide breakdown is considered to be the primary mechanism to cause a leakage current, and the injured oxide is between the gate and source in the metal-oxide semiconductor field-effect transistor (MOSFET) structure for one CCD pixel. Optical microscopy and scanning electron microscopy are used to investigate the damaged areas and the results show that the electrodes and the oxide underneath are not directly affected by the femtosecond laser, which helps to get rid of the conventional damage mechanisms. For the primary damage mechanism, direct damage by hot carriers, anode hole injection, and an enlarged electric field in the insulating layer are three possible ways to cause oxide breakdown. The leakage current is proved by the decrease of the resistance of electrodes to the substrate. The output saturated images and the dynamics of an area CCD indicate that the leakage current is from an electrode to a light sensing area (or gate to source for a MOSFET), which proves the oxide breakdown mechanism. PMID:24216654

  10. Different Sources of Nitric Oxide Mediate Neurovascular Coupling in the Lateral Geniculate Nucleus of the Cat

    PubMed Central

    de Labra, Carmen; Rivadulla, Casto; Espinosa, Nelson; Dasilva, Miguel; Cao, Ricardo; Cudeiro, Javier

    2009-01-01

    Understanding the link between neuronal responses (NRs) and metabolic signals is fundamental to our knowledge of brain function and it is a milestone in our efforts to interpret data from modern non invasive optical techniques such as fMRI, which are based on the close coupling between metabolic demand of active neurons and local changes in blood flow. The challenge is to unravel the link. Here we show, using spectrophotometry to record oxyhaemoglobin and methemoglobin (surrogate markers of cerebral flow and nitric oxide levels respectively) together with extracellular neuronal recordings in vivo and applying a multiple polynomial regression model, that the markers are able to predict up about 80% of variability in NR. Furthermore, we show that the coupling between blood flow and neuronal activity is heavily influenced by nitric oxide (NO). While NRs show the typical saturating response, blood flow shows a linear behaviour during contrast-response curves, with nitric oxide from different sources acting differently for low and high intensity. PMID:19826613

  11. Quantitative determination of plant phenolics in Urtica dioica extracts by high-performance liquid chromatography coupled with tandem mass spectrometric detection.

    PubMed

    Or?i?, Dejan; Franciškovi?, Marina; Bekvalac, Kristina; Svir?ev, Emilija; Beara, Ivana; Lesjak, Marija; Mimica-Duki?, Neda

    2014-01-15

    A method for quantification of 45 plant phenolics (including benzoic acids, cinnamic acids, flavonoid aglycones, C- and O-glycosides, coumarins, and lignans) in plant extracts was developed, based on reversed phase HPLC separation of extract components, followed by tandem mass spectrometric detection. The phenolic profile of 80% MeOH extracts of the stinging nettle (Urtica dioica L.) herb, root, stem, leaf and inflorescence was obtained by using this method. Twenty-one of the investigated compounds were present at levels above the reliable quantification limit, with 5-O-caffeoylquinic acid, rutin and isoquercitrin as the most abundant. The inflorescence extracts were by far the richest in phenolics, with the investigated compounds amounting 2.5-5.1% by weight. As opposed to this, the root extracts were poor in phenolics, with only several acids and derivatives being present in significant amounts. The results obtained by the developed method represent the most detailed U. dioica chemical profile so far. PMID:24054211

  12. Multianalysis of 35 mycotoxins in traditional Chinese medicines by ultra-high-performance liquid chromatography-tandem mass spectrometry coupled with accelerated solvent extraction.

    PubMed

    Han, Zheng; Ren, Yiping; Zhu, Junfeng; Cai, Zengxuan; Chen, Yong; Luan, Lianjun; Wu, Yongjiang

    2012-08-22

    A generic procedure, which involved accelerated solvent extraction and homemade cleanup cartridges, has been developed for the extraction and purification of 35 mycotoxins in various traditional Chinese medicine (TCM) matrixes, i.e., rhizomes and roots, seeds, flowers, and grasses and leaves, for subsequent analysis by ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). All target analytes could be simultaneously quantitated in less than 17 min per run, showing narrow symmetrical peaks. The developed method was also successfully applied in routine monitoring programs, which implied a significant reduction of both effort and time, to investigate the contamination of TCMs. Among 60 commercial TCMs analyzed, 50 were positive. The achieved data underpin the practical application of the UHPLC-MS/MS method as a valuable tool for the trace analysis of multiple mycotoxins in TCMs. PMID:22823451

  13. Pharmacokinetic profile and metabolite identification of yuanhuapine, a bioactive component in Daphne genkwa by ultra-high performance liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Chen, Yanyan; Guo, Jianming; Tang, Yuping; Wu, Liang; Tao, Weiwei; Qian, Yefei; Duan, Jin-Ao

    2015-08-10

    Daphne genkwa Sieb. et Zucc. (Thymelaeaceae) is mainly used for the treatment of edema, asthma, and cancer in China and Korea for centuries. The major bioactive components in D. genkwa are daphnane-type diterpenoids, which showed pharmacological activities such as antileukemic, antifertility and skin irritants. In this study, the pharmacokinetics and metabolism profile of yuanhuapine, an effective and toxic diterpenoid, was investigated in rats. The plasma exposure of yuanhuapine was determined by ultra-performance liquid chromatography tandem triple-quadrupole mass spectrometry (UPLC-TQ-MS), and the pharmacokinetic parameters were calculated using the DAS 2.0 pharmacokinetic program. The metabolites were identified through ultra-performance liquid chromatography tandem quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF/MS) and a Metabolynx™ (v4.1) program. After oral administration (5mg/kg), yuanhuapine was slowly absorbed and reached a maximum concentration of 579.20±212.85ng/mL at 7.33±1.03h, it also eliminated slowly. As the cumulative excretion of yuanhuapine in urine and feces were only 0.7% and 3.3%, we supposed that biotransformation in vivo was of significant importance to this component. Not only the prototype but also twelve metabolites were found and tentatively identified in rat urine after oral administration of yuanhuapine. The metabolic pathway mainly involves hydroxylation, methylation, glucuronidation and cysteine conjugation during the phase I and phase II biotransformation pathway. All the information gained here was useful in understanding the pharmacological actions and toxic properties of yuanhuapine, and providing a meaningful basis for clinical application of such a bioactive compound of herbal medicines. PMID:25956226

  14. Assessment of the stoichiometry and efficiency of CO2 fixation coupled to reduced sulfur oxidation

    PubMed Central

    Klatt, Judith M.; Polerecky, Lubos

    2015-01-01

    Chemolithoautotrophic sulfur oxidizing bacteria (SOB) couple the oxidation of reduced sulfur compounds to the production of biomass. Their role in the cycling of carbon, sulfur, oxygen, and nitrogen is, however, difficult to quantify due to the complexity of sulfur oxidation pathways. We describe a generic theoretical framework for linking the stoichiometry and energy conservation efficiency of autotrophic sulfur oxidation while accounting for the partitioning of the reduced sulfur pool between the energy generating and energy conserving steps as well as between the main possible products (sulfate vs. zero-valent sulfur). Using this framework, we show that the energy conservation efficiency varies widely among SOB with no apparent relationship to their phylogeny. Aerobic SOB equipped with reverse dissimilatory sulfite reductase tend to have higher efficiency than those relying on the complete Sox pathway, whereas for anaerobic SOB the presence of membrane-bound, as opposed to periplasmic, nitrate reductase systems appears to be linked to higher efficiency. We employ the framework to also show how limited rate measurements can be used to estimate the primary productivity of SOB without the knowledge of the sulfate-to-zero-valent-sulfur production ratio. Finally, we discuss how the framework can help researchers gain new insights into the activity of SOB and their niches.

  15. Tandem hydrofoil system

    Microsoft Academic Search

    Konstantin I. Matveev; Ivan Ivanovich Matveev

    2001-01-01

    A tandem hydrofoil system enables an improvement in the lift-drag ratio of a high-speed ship. The conditions for favorable application of this type of foil structure are determined. The data on hydrofoil boats using a tandem system are presented. The problem of the stability of the vertical plane motion of a hydrofoil with bow and stern foils is considered. The

  16. High rates of anaerobic oxidation of methane, ethane and propane coupled to thiosulphate reduction.

    PubMed

    Suarez-Zuluaga, Diego A; Weijma, Jan; Timmers, Peer H A; Buisman, Cees J N

    2015-03-01

    Anaerobic methane oxidation coupled to sulphate reduction and the use of ethane and propane as electron donors by sulphate-reducing bacteria represent new opportunities for the treatment of streams contaminated with sulphur oxyanions. However, growth of microbial sulphate-reducing populations with methane, propane or butane is extremely slow, which hampers research and development of bioprocesses based on these conversions. Thermodynamic calculations indicate that the growth rate with possible alternative terminal electron acceptors such as thiosulphate and elemental sulphur may be higher, which would facilitate future research. Here, we investigate the use of these electron acceptors for oxidation of methane, ethane and propane, with marine sediment as inoculum. Mixed marine sediments originating from Aarhus Bay (Denmark) and Eckernförde Bay (Germany) were cultivated anaerobically at a pH between 7.2 and 7.8 and a temperature of 15 °C in the presence of methane, ethane and propane and various sulphur electron acceptors. The sulphide production rates in the conditions with methane, ethane and propane with sulphate were respectively 2.3, 2.2 and 1.8 ?mol S L(-1) day(-1). For sulphur, no reduction was demonstrated. For thiosulphate, the sulphide production rates were up to 50 times higher compared to those of sulphate, with 86.2, 90.7 and 108.1 ?mol S L(-1) day(-1) for methane, ethane and propane respectively. This sulphide production was partly due to disproportionation, 50 % for ethane but only 7 and 14 % for methane and propane respectively. The oxidation of the alkanes in the presence of thiosulphate was confirmed by carbon dioxide production. This is, to our knowledge, the first report of thiosulphate use as electron acceptor with ethane and propane as electron donors. Additionally, these results indicate that thiosulphate is a promising electron acceptor to increase start-up rates for sulphate-reducing bioprocesses coupled to short-chain alkane oxidation. PMID:25256585

  17. Using Tandem Mass Spectrometry to Quantify Site?Specific Chlorination and Nitration of Proteins: Model System Studies with High?Density Lipoprotein Oxidized by Myeloperoxidase

    Microsoft Academic Search

    Baohai Shao; Jay W. Heinecke

    2008-01-01

    Protein oxidation is implicated in atherogenesis and other inflammatory conditions. Measuring levels of chlorinated and nitrated proteins in biological matrices serves as a quantitative index of oxidative stress in vivo. One potential mechanism for oxidative stress involves myeloperoxidase, a heme protein expressed by neutrophils, monocytes, and some populations of macrophages. The enzyme uses hydrogen peroxide to generate an array of

  18. Pinball liquid phase from Hund's coupling in frustrated transition-metal oxides

    NASA Astrophysics Data System (ADS)

    Ralko, Arnaud; Merino, Jaime; Fratini, Simone

    2015-04-01

    The interplay of nonlocal Coulomb repulsion and Hund's coupling in the d -orbital manifold in frustrated triangular lattices is analyzed by a multiband extended Hubbard model. We find a rich phase diagram with several competing phases, including a robust pinball liquid phase, which is an unconventional metal characterized by threefold charge order, bad metallic behavior, and the emergence of high-spin local moments. Our results naturally explain the anomalous charge-ordered metallic state observed in the triangular layered compound AgNiO2. The potential relevance to other triangular transition-metal oxides is discussed.

  19. Oxidative coupling of methane in a mixed-conducting perovskite membrane reactor

    Microsoft Academic Search

    J. E. ten Elshof; H. J. M. Bouwmeester; H. Verweij

    1995-01-01

    Ionic-electronic mixed-conducting perovskite-type oxide La0.6Sr0.4Co0.8Fe0.2O3 was applied as a dense membrane for oxygen supply in a reactor for methane coupling. The oxygen permeation properties were studied in the pO2-range of 10?3?1 bar at 1073–1273 K, using helium as a sweeping gas at the permeate side of the membrane. The oxygen semi-permeability has a value close to 1 mmol m?2 s?1

  20. Extremely strong organic-metal oxide electronic coupling caused by nucleophilic addition reaction.

    PubMed

    Fujisawa, Jun-Ichi; Hanaya, Minoru

    2015-07-01

    Electronic interactions between organic materials and inorganic semiconductors play important roles in various electronic and optoelectronic functions and also provide new functions such as optical interfacial charge-transfer (ICT) transitions having the following features. ICT transitions enable the capture of lower-energy photons than HOMO-LUMO gaps or band gaps and allow one-step charge separation without loss of energy. The hybrid material generated by the nucleophilic addition reaction between TiO2 and TCNQ exclusively exhibits strong ICT transitions. In this study, we report that strong organic-metal oxide electronic coupling is caused by the nucleophilic addition reaction, which enhances the ICT transitions. The electronic coupling between TiO2 and TCNQ occurs according to a two-step mechanism. First, the lowest unoccupied molecular orbital (LUMO (?*)) of TCNQ is elevated by the nucleophilic attack of a deprotonated hydroxy group on TiO2 to TCNQ and the electron distribution is moved toward TiO2. By this elevation and redistribution, the LUMO (?*) strongly interacts with the d(t2g) orbitals of a surface Ti atom. From avoided-crossing behavior with a large splitting energy of ca. 0.95 eV, the coupling energy was estimated to be as much as 0.5 eV in the mono-Ti model complex. This strong d-?* electronic coupling leads to strong coupling between complete ICT excited states and partial ICT excited states with a large splitting energy of ca. 0.92 eV, which considerably increases the probabilities of ICT transition. This study clarified the mechanisms of the strong organic-inorganic electronic coupling and the enhancement of ICT absorption in the TiO2-TCNQ hybrid material. PMID:26041649

  1. Anaerobic methane oxidation coupled to denitrification is the dominant methane sink in a deep lake

    PubMed Central

    Deutzmann, Joerg S.; Stief, Peter; Brandes, Josephin; Schink, Bernhard

    2014-01-01

    Anaerobic methane oxidation coupled to denitrification, also known as “nitrate/nitrite-dependent anaerobic methane oxidation” (n-damo), was discovered in 2006. Since then, only a few studies have identified this process and the associated microorganisms in natural environments. In aquatic sediments, the close proximity of oxygen- and nitrate-consumption zones can mask n-damo as aerobic methane oxidation. We therefore investigated the vertical distribution and the abundance of denitrifying methanotrophs related to Candidatus Methylomirabilis oxyfera with cultivation-independent molecular techniques in the sediments of Lake Constance. Additionally, the vertical distribution of methane oxidation and nitrate consumption zones was inferred from high-resolution microsensor profiles in undisturbed sediment cores. M. oxyfera-like bacteria were virtually absent at shallow-water sites (littoral sediment) and were very abundant at deep-water sites (profundal sediment). In profundal sediment, the vertical distribution of M. oxyfera-like bacteria showed a distinct peak in anoxic layers that coincided with the zone of methane oxidation and nitrate consumption, a strong indication for n-damo carried out by M. oxyfera-like bacteria. Both potential n-damo rates calculated from cell densities (660–4,890 µmol CH4?m?2?d?1) and actual rates calculated from microsensor profiles (31–437 µmol CH4?m?2?d?1) were sufficiently high to prevent methane release from profundal sediment solely by this process. Additionally, when nitrate was added to sediment cores exposed to anoxic conditions, the n-damo zone reestablished well below the sediment surface, completely preventing methane release from the sediment. We conclude that the previously overlooked n-damo process can be the major methane sink in stable freshwater environments if nitrate is available in anoxic zones. PMID:25472842

  2. Analysis of phenolic compounds by high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry in senescent and water-stressed tobacco.

    PubMed

    Torras-Claveria, Laura; Jáuregui, Olga; Codina, Carles; Tiburcio, Antonio F; Bastida, Jaume; Viladomat, Francesc

    2012-01-01

    Evaluation of a significant part of the phenylpropanoid pathway metabolites is facilitated by the fast high-performance liquid chromatography with electrospray ionization tandem mass spectrometry (LC-MS/MS) analytical method. The technology described was applied in tobacco plants (Nicotiana tabacum L. cv. Wisconsin) to identify 20 phenolic compounds and to detect differences in phenylpropanoid profiles in two types of experiments. In the first one, senescent and non-senescent parts of flowering plants were compared, while in the second, watered plants were compared with water-stressed young plants. The 20 identified phenolic compounds were: seven hydroxycinnamoylquinic acids, seven hydroxycinnamic acid glucosides, one salicylic acid glucoside, two conjugated flavonols with disaccharides, and three hydroxycinnamic acid amides (HCAA) of putrescine. In general, the levels of phenylpropanoid compounds increased under water stress or senescent conditions, with the exception of HCAA, which decreased in senescent samples, and 4-O-p-coumaroylquinic acid and trihydroxycinamic acid-O-glucoside, which did not change in both experiments. The main product in all the samples was 5-O-caffeoylquinic acid (neochlorogenic acid). Another compound, kaempferol-7-O-neohesperidoside, was tentatively identified for the first time in tobacco plants. This method, which can be applied in other plant species, allows a simple and efficient comparative study of metabolite profile variations (qualitative and quantitative) in response to different physiological and/or environmental plant situations. PMID:22118617

  3. A validated assay for the simultaneous quantification of six tyrosine kinase inhibitors and two active metabolites in human serum using liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    van Erp, Nielka P; de Wit, Djoeke; Guchelaar, Henk-Jan; Gelderblom, Hans; Hessing, Trees J; Hartigh, Jan den

    2013-10-15

    A sensitive, sophisticated and practical bioanalytical assay for the simultaneous determination of six tyrosine kinase inhibitors (imatinib, sunitinib, nilotinib, dasatinib, pazopanib, regorafenib) and two active metabolites (N-desmethyl imatinib and N-desethyl sunitinib) was developed and validated. For the quantitative assay, a mixture of three stable isotopes as internal standards was added to human serum, standards and controls. Thereafter, samples were pre-treated using protein precipitation with methanol. The supernatant was diluted with water and injected into an ultra pressure liquid chromatographic system with an Acquity TQ tandem mass spectrometry detector. The compounds were separated on an Acquity BEH C18 analytical column (100mm×2.1mm ID, 1.7?m particle size) and eluted with a linear gradient system. The ions were detected in the multiple reaction monitoring mode. The lower limit of quantification and the linearity of all compounds generously met with the concentrations that are to be expected in clinical practice. The developed bioanalytical assay can be used for guiding TKI therapy in daily clinical practice as well as for investigator-initiated research. PMID:24013127

  4. [Determination of seven pesticide residues in bamboo shoots by high performance liquid chromatography-tandem mass spectrometry coupled with solid-phase extraction].

    PubMed

    Ding, Ming; Zhong, Donglian; Tang, Fubin; Fang, Wei

    2013-02-01

    A simple and efficient method based on solid-phase extraction (SPE) and high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was developed for the determination of butylene fipronil, chlorpyrifos, chlorantraniliprole, fipronil, imidacloprid, indoxacarb and phoxim residues in bamboo shoots. The sample was extracted with acetonitrile and purified by a primary secondary amine (PSA) solid-phase extraction cartridge. The detection of targets was performed by HPLC-MS/MS with multiple reaction monitoring (MRM) mode. All the seven pesticides were completely separated in 15 min with an excellent linear relationship. The limits of detection and the limits of quantification for the seven pesticides were 0.02-0.5 microg/kg and 0.08-1.5 microg/kg, respectively. The recoveries of the seven pesticides spiked in a bamboo shoot sample at the levels of 4, 8, 32 microg/kg were in the range from 76.0% to 102.6% (the RSD < or = 11.0%, n = 3). The method was successfully applied to the real bamboo shoot samples. The method has high accuracy and sensitivity, and is simple and quick. It can meet the requirement of the simultaneous determination of the seven pesticides in bamboo shoots. PMID:23697174

  5. A simple sample preparation approach based on hydrophilic solid-phase extraction coupled with liquid chromatography-tandem mass spectrometry for determination of endogenous cytokinins.

    PubMed

    Cai, Bao-Dong; Zhu, Jiu-Xia; Shi, Zhi-Guo; Yuan, Bi-Feng; Feng, Yu-Qi

    2013-12-30

    Cytokinins (CKs), a vital family of phytohormones, play important roles in the regulation of shoot and root development. However, the quantification of CKs in plant samples is frequently affected by the complex plant matrix. In the current study, we developed a simple, rapid and efficient hydrophilic interaction chromatography-solid phase extraction (HILIC-SPE) method for CKs purification. CKs were extracted by acetonitrile (ACN) followed by HILIC-SPE (silica as sorbents) purification. The extraction solution of plant samples could be directly applied to HILIC-SPE without solvent evaporation step, which simplified the analysis process. Moreover, with HILIC chromatographic retention mechanism, the hydrophobic co-extracted impurities were efficiently removed. Subsequently, CKs were separated by RPLC, orthogonal to the HILIC pretreatment process, and detected by tandem mass spectrometry. The method exhibits high specificity and recovery yield (>77.0%). Good linearities were obtained for all eight CKs ranging from 0.002 to 100ngmL(-1) with correlation coefficients (r) higher than 0.9927. The limits of detection (LODs, signal/noise=5) for the CKs were between 1.0 and 12.4pgmL(-1). Reproducibility of the method was evaluated by intra-day and inter-day measurements and the results showed that relative standard deviations (RSDs) were less than 10.5%. Employing this method, we successfully quantified six CKs in 20mg Oryza sativa leaves and the method was also successfully applied to Brassica napus (flower and leaves). PMID:24212141

  6. Multi-analyte high performance liquid chromatography coupled to high resolution tandem mass spectrometry method for control of pesticide residues, mycotoxins, and pyrrolizidine alkaloids.

    PubMed

    Dzuman, Zbynek; Zachariasova, Milena; Veprikova, Zdenka; Godula, Michal; Hajslova, Jana

    2015-03-10

    A new reliable and highly sensitive method based on high performance liquid chromatographic (HPLC) separation and high resolution tandem mass spectrometric detection (HRMS/MS) has been developed and validated for determination of 323 pesticide residues, 55 mycotoxins, and 11 plant toxins represented by pyrrolizidine alkaloids. The method was validated for three matrices, leek, wheat, and tea differing in nature/amount of co-extracts that may cause various matrix effects. For target analytes isolation, optimized QuEChERS-based (quick, easy, cheap, effective, rugged, and safe) extraction procedure was employed. Spectral HRMS/MS library has been established providing an entire spectrum of fragment ions for each analyte, which allows unbiased identification and confirmation of target compounds. The limits of quantification (LOQs) of target analytes were below 10 ?g kg(-1) for 82%, 81%, and 61% for matrices leek, wheat, and tea, respectively. Recoveries were in the acceptable range (70-120%) according to SANCO/12571/2013 for most of target analytes, except for highly polar 'masked' mycotoxin deoxynivalenol-3-glucoside with recoveries 35%, 47%, and 42% for matrices leek, wheat, and tea, respectively. The linearities of calibration curves expressed as coefficients of determination were in the range of 0.9661-1.000, and repeatabilities expressed as relative standard deviations (RSDs) at LOQs lied in the range of 0.25-13.51%. The trueness of the method was verified using several certified reference materials (CRMs) and proficiency test samples. PMID:25732310

  7. Rapid analysis of three ?-agonist residues in food of animal origin by automated on-line solid-phase extraction coupled to liquid chromatography and tandem mass spectrometry.

    PubMed

    Mi, Jiebo; Li, Shujing; Xu, Hong; Liang, Wei; Sun, Tao

    2014-09-01

    An automated online solid-phase extraction with liquid chromatography and tandem mass spectrometry method was developed and validated for the detection of clenbuterol, salbutamol, and ractopamine in food of animal origin. The samples from the food matrix were pretreated with an online solid-phase extraction cartridge by Oasis MCX for <5 min after acid hydrolysis for 30 min. The peak focusing mode was used to elute the target compounds directly onto a C18 column. Chromatographic separation was achieved under gradient conditions using a mobile phase composed of acetonitrile/0.1% formic acid in aqueous solution. Each analyte was detected in two multiple reaction monitoring transitions via an electrospray ionization source in a positive mode. The relative standard deviations ranged from 2.6 to 10.5%, and recovery was between 76.7 and 107.2% at all quality control levels. The limits of quantification of three ?-agonists were in the range of 0.024-0.29 ?g/kg in pork, sausage, and milk powder, respectively. This newly developed method offers high sensitivity and minimum sample pretreatment for the high-throughput analysis of ?-agonist residues. PMID:24916570

  8. Liquid chromatography coupled with tandem mass spectrometry to characterise trace levels of cyanobacteria and dinoflagellate toxins in suspended solids and sediments.

    PubMed

    Rivetti, Claudia; Gómez-Canela, Cristian; Lacorte, Silvia; Barata, Carlos

    2015-02-01

    Microcystins, anatoxins and okadaic acid are toxins produced by freshwater cyanobacteria and marine dinoflagellates. These toxins have been the responsible for the illness and death of biota and humans. To determine their presence in water during blooms, sensitive analytical methods are needed. In this study, we have developed a new liquid chromatography tandem mass spectrometry (LC-MS/MS) method for fast multiresidue determination of five toxins in suspended material and sediment samples. For each target compound, two selected reaction monitoring (SRM) transitions were optimised. Chromatographic conditions were optimised considering that the compounds analysed had different chemical structure and chromatographic behaviour. Using a Luna C18 column and specific SRM transitions, five phytotoxins were resolved. Method detection limits (MDL) for anatoxin-a, microcystins RR, LR and YR and okadaic acid were 7.1, 3.3, 81.7, 102.8 and 28.8 ng g(-1) dry weight in sediment, respectively. The developed analytical method was successfully applied to analyse the presence of toxins in suspended solids and sediment from Ebro River (NE Spain) and Ebro delta-associated lagoons. Anatoxin-a was detected downstream of the Riba-Roja reservoir with levels ranging from 20 to 1120 ng g(-1) dry weight of suspended solids. Okadaic acid was only detected in three samples collected in the Alfacs Bay (Ebro delta, Spain) affected by Dinophysis blooms in 2012. PMID:25619981

  9. Ubiquitous long-range antiferromagnetic coupling across the interface between superconducting and ferromagnetic oxides.

    PubMed

    De Luca, G M; Ghiringhelli, G; Perroni, C A; Cataudella, V; Chiarella, F; Cantoni, C; Lupini, A R; Brookes, N B; Huijben, M; Koster, G; Rijnders, G; Salluzzo, M

    2014-01-01

    The so-called proximity effect is the manifestation, across an interface, of the systematic competition between magnetic order and superconductivity. This phenomenon has been well documented and understood for conventional superconductors coupled with metallic ferromagnets; however it is still less known for oxide materials, where much higher critical temperatures are offered by copper oxide-based superconductors. Here we show that, even in the absence of direct Cu-O-Mn covalent bonding, the interfacial CuO2 planes of superconducting La(1.85)Sr(0.15)CuO(4) thin films develop weak ferromagnetism associated to the charge transfer of spin-polarised electrons from the La(0.66)Sr(0.33)MnO(3) ferromagnet. Theoretical modelling confirms that this effect is general to all cuprate/manganite heterostructures and the presence of direct bonding only affects the strength of the coupling. The Dzyaloshinskii-Moriya interaction, also at the origin of the weak ferromagnetism of bulk cuprates, propagates the magnetisation from the interface CuO2 planes into the superconductor, eventually depressing its critical temperature. PMID:25418631

  10. Microwaves and their coupling to advanced oxidation processes: enhanced performance in pollutants degradation.

    PubMed

    Nascimento, Ulisses M; Azevedo, Eduardo B

    2013-01-01

    This review assesses microwaves (MW) coupled to advanced oxidation processes (AOPs) for pollutants degradation, as well as the basic theory and mechanisms of MW dielectric heating. We addressed the following couplings: MW/H2O2, MW/UV/H2O2, MW/Fenton, MW/US, and MW/UV/TiO2, as well as few studies that tested alternative oxidants and catalysts. Microwave Discharge Electrodeless Lamps (MDELs) are being extensively used with great advantages over ballasts. In their degradation studies, researchers generally employed domestic ovens with minor adaptations. Non-thermal effects and synergies between UV and MW radiation play an important role in the processes. Published papers so far report degradation enhancements between 30 and 1,300%. Unfortunately, how microwaves enhance pollutants is still obscure and real wastewaters scarcely studied. Based on the results surveyed in the literature, MW/AOPs are promising alternatives for treating/remediating environmental pollutants, whenever one considers high degradation yields, short reaction times, and small costs. PMID:23573926

  11. Coupling anammox and advanced oxidation-based technologies for mature landfill leachate treatment.

    PubMed

    Anfruns, A; Gabarró, J; Gonzalez-Olmos, R; Puig, S; Balaguer, M D; Colprim, J

    2013-08-15

    The aim of this study was to evaluate the suitability to couple anammox process with advanced oxidation processes (AOPs) to treat mature landfill leachate with high nitrogen and non-biodegradable organic matter concentrations (2309±96 mg N-TN L(-1) and 6200±566 mg COD L(-1)). The combination of a partial nitiration-anammox system coupled with two AOP-based technologies (coagulation/flocculation+ozonation and photo-Fenton) was assessed in terms of nitrogen and carbon removal. Total nitrogen removal efficiency within a range of 87-89% was obtained with both configurations without the need of any external carbon source. The COD removal efficiencies attained were 91% with coagulation/flocculation+ozonation and 98% with photo-Fenton. Applying the biological treatment prior to advanced oxidation processes-based technologies reduced the quantity of needed reagents giving attaining higher removal efficiencies. From a basic economical point of view and taking into account the results of this study, the combination of partial nitritation-anammox system with photo-Fenton treatment was more favorable than with coagulation/flocculation+ozonation treatment. PMID:23692680

  12. An inorganic geochemical argument for coupled anaerobic oxidation of methane and iron reduction in marine sediments.

    PubMed

    Riedinger, N; Formolo, M J; Lyons, T W; Henkel, S; Beck, A; Kasten, S

    2014-03-01

    Here, we present results from sediments collected in the Argentine Basin, a non-steady state depositional marine system characterized by abundant oxidized iron within methane-rich layers due to sediment reworking followed by rapid deposition. Our comprehensive inorganic data set shows that iron reduction in these sulfate and sulfide-depleted sediments is best explained by a microbially mediated process-implicating anaerobic oxidation of methane coupled to iron reduction (Fe-AOM) as the most likely major mechanism. Although important in many modern marine environments, iron-driven AOM may not consume similar amounts of methane compared with sulfate-dependent AOM. Nevertheless, it may have broad impact on the deep biosphere and dominate both iron and methane cycling in sulfate-lean marine settings. Fe-AOM might have been particularly relevant in the Archean ocean, >2.5 billion years ago, known for its production and accumulation of iron oxides (in iron formations) in a biosphere likely replete with methane but low in sulfate. Methane at that time was a critical greenhouse gas capable of sustaining a habitable climate under relatively low solar luminosity, and relationships to iron cycling may have impacted if not dominated methane loss from the biosphere. PMID:24460948

  13. Interaction between Nitric Oxide Synthase Inhibitor Induced Oscillations and the Activation Flow Coupling Response

    PubMed Central

    Ances, Beau M.; Greenberg, Joel. H.; Detre, John A.

    2009-01-01

    The role of nitric oxide (NO) in the activation-flow coupling (AFC) response to periodic electrical forepaw stimulation was investigated using signal averaged laser Doppler (LD) flowmetry. LD measures of calculated cerebral blood flow (CBF) were obtained both prior and after intra-peritoneal administration of the non-selective nitric oxide synthase (NOS) inhibitor, NG-nitro-L-arginine (L-NNA) (40 mg/kg). Characteristic baseline low frequency vasomotion oscillations (0.17 Hz) were observed after L-NNA administration. These LDCBF oscillations were synchronous within but not between hemispheres. L-NNA reduced the magnitude of the AFC response (p< 0.05) for longer stimuli (1 minute) with longer inter-stimulus intervals (2 minutes). In contrast, the magnitude of the AFC response for short duration stimuli (4 seconds) with short inter-stimulus intervals (20 seconds) was augmented (p < 0.05) after L-NNA. An interaction occurred between L-NNA induced vasomotion oscillations and the AFC response with the greatest increase occurring at the stimulus harmonic closest to the oscillatory frequency. Nitric oxide may therefore modulate the effects of other vasodilators involved in vasomotion oscillations and the AFC response. PMID:19900416

  14. Determination of Phenolic Acids and Flavonoids in Taraxacum formosanum Kitam by Liquid Chromatography-Tandem Mass Spectrometry Coupled with a Post-Column Derivatization Technique

    PubMed Central

    Chen, Hung-Ju; Inbaraj, Baskaran Stephen; Chen, Bing-Huei

    2012-01-01

    A liquid chromatography-tandem mass spectrometry method (LC-MS/MS) was developed for the determination of phenolic acids and flavonoids in a medicinal Chinese herb Taraxacum formosanum Kitam. Initially, both phenolic acids and flavonoids were extracted with 50% ethanol in a water-bath at 60 °C for 3 h and eventually separated into acidic fraction and neutral fraction by using a C18 cartridge. A total of 29 compounds were separated within 68 min by employing a Gemini C18 column and a gradient solvent system of 0.1% formic acid and acetonitrile at a flow rate of 1.0 mL/min. Based on the retention behavior as well as absorption and mass spectra, 19 phenolic acids and 10 flavonoids were identified and quantified in T. formosanum, with the former ranging from 14.1 ?g/g to 10,870.4 ?g/g, and the latter from 9.9 ?g/g to 325.8 ?g/g. For further identification of flavonoids, a post-column derivatization method involving shift reagents such as sodium acetate or aluminum chloride was used and the absorption spectral characteristics without or with shift reagents were compared. An internal standard syringic acid was used for quantitation of phenolic acids, whereas (±) naringenin was found suitable for quantitation of flavonoids. The developed LC-MS/MS method showed high reproducibility, as evident from the relative standard deviation (RSD) values for intra-day and inter-day variability being 1.0–6.8% and 2.0–7.7% for phenolic acids and 3.7–7.4% and 1.5–8.1% for flavonoids, respectively, and thus may be applied for simultaneous determination of phenolic acids and flavonoids in Chinese herb and nutraceuticals. PMID:22312251

  15. Simultaneous determination of 15 top-prescribed pharmaceuticals and their metabolites in influent wastewater by reversed-phase liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Tarcomnicu, Isabela; van Nuijs, Alexander L N; Simons, Ward; Bervoets, Lieven; Blust, Ronny; Jorens, Philippe G; Neels, Hugo; Covaci, Adrian

    2011-01-15

    A fast and sensitive high performance reversed-phase liquid chromatography-tandem mass spectrometry method was developed and validated for the analysis of 15 prescription pharmaceuticals and four of their metabolites in influent wastewater. The selected pharmaceuticals belonged to various classes, such as angiotensin converting enzyme inhibitors, angiotensin receptor antagonists, calcium antagonists, ?-blockers, antidepressants, analgetics, anticonvulsants, platelet antiaggregants, and cholesterol lowering agents. They were selected from the list of top-sold prescription pharmaceuticals in Belgium. The chromatographic separation was optimized in order to achieve suitable retention times, good resolution for analytes susceptible of mass spectrometric cross-talk and high sensitivity in one single run. All compounds eluted within 9 min on a Phenomenex Kinetex C18 column, based on a newly developed technology that allows a very narrow distribution of the core-shell particles, providing high separation efficiency. Sample preparation was executed with solid-phase extraction on Oasis MCX cartridges. The method was validated by assessing specificity, selectivity, lower limit of quantification (LLOQ), linearity, accuracy, precision, extraction recovery, and matrix effects following Food and Drug Administration guidelines. The method LLOQs ranged from 0.5 to 25 ng/L. Calibration curves and LLOQs were designed to provide a good analytical performance at concentrations expected in real influent wastewater samples for each target compound. Eight deuterated analogues were used as internal standards for quantification. The method was applied to influent wastewater samples collected from 17 different wastewater treatment plants throughout Belgium. Most of the analytes were measured in the samples at concentrations above LLOQ. Seven of the compounds were for the first time reported in influent wastewater. The newly developed analytical method is currently used to assess relationships between sales figures of pharmaceuticals and their corresponding concentrations in influent wastewater. PMID:21147322

  16. Enantioselective determination of 3-n-butylphthalide (NBP) in human plasma by liquid chromatography on a teicoplanin-based chiral column coupled with tandem mass spectrometry.

    PubMed

    Diao, Xingxing; Ma, Zhiyu; Lei, Peng; Zhong, Dafang; Zhang, Yifan; Chen, Xiaoyan

    2013-11-15

    A novel and sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed and validated to determine the exposure of 3-n-butylphthalide (NBP) enantiomers in human plasma. The NBP enantiomers were extracted from human plasma using methyl tert-butyl ether. The baseline separation of R-(+)-NBP and S-(-)-NBP was achieved within 11.0min using a teicoplanin-based Astec Chirobiotic T column (250mm×4.6mm i.d., 5?m) under isocratic conditions at a flow rate of 0.6mL/min. The selection of the chiral stationary phase and the effect of the mobile phase composition on the resolution of the enantiomers were discussed. The selectivity, linearity, precision, accuracy, matrix effect, recovery, and stability were evaluated under optimized conditions. The LC-MS/MS method using 200?L of human plasma was linear over the concentration range of 5.00-400ng/mL for each enantiomer. The lower limit of quantification (LLOQ) for both enantiomers was 5.00ng/mL. The intra- and inter-assay precision values of the replicated quality control samples were within 8.0% for each enantiomer. The mean accuracy values for the quality control samples were within ±6.1% of the nominal values for R-(+)-NBP and S-(-)-NBP. No chiral inversion was observed during sample storage, preparation, and analysis. The method proved suitable for enantioselective pharmacokinetic studies of NBP after an oral administration of a therapeutic dose of racemic NBP. PMID:24103433

  17. Simultaneous targeted analysis of five active compounds in licorice by ultra-fast liquid chromatography coupled to hybrid linear-ion trap tandem mass spectrometry.

    PubMed

    Kong, Weijun; Wen, Jing; Yang, Yinhui; Qiu, Feng; Sheng, Ping; Yang, Meihua

    2014-04-21

    An ultra-fast liquid chromatography with electrospray ionization tandem mass spectrometry (UFLC-ESI-MS/MS) method was developed for targeted analysis of 5 active compounds in licorice for the first time. The sample preparation procedure, chromatographic and mass spectrographic conditions were optimized. By using a Kinetex C18 100A column, the five compounds were separated within 8.0 min by gradient elution using methanol containing 0.1% acetic acid and 0.1% aqueous acetic acid. The precursor and product ions of the analytes were monitored on a hybrid quadrupole/linear ion trap mass spectrometer equipped with a turbo ion spray interface in negative ionization mode (ESI(-)) and were simultaneously characterized and quantified based on the multiple reaction monitoring-information-dependent acquisition-enhanced product ion (MRM-IDA-EPI) mode. All standard calibration curves expressed satisfactory linearity (r ? 0.9954) within a relatively wide range. The precision was evaluated by intra- and inter-day tests, which revealed relative standard deviation (RSD) values within the ranges of 1.15-4.56% and 0.81-3.95%, respectively. The recovery assays for the quantified compounds were between 97.33 and 100.4% with RSD values less than 4.27%. The proposed method was demonstrated to be simple, rapid, specific and reliable and was successfully applied for identification and quantification of 5 active compounds in 10 batches of licorice. The results showed that the contents of the 5 compounds in licorice from different sources were widely varied. PMID:24551874

  18. Citrinin Determination in Red Fermented Rice Products by Optimized Extraction Method Coupled to Liquid Chromatography Tandem Mass Spectrometry (LC-MS/MS).

    PubMed

    Ji, Xiaofeng; Xu, Junfeng; Wang, Xiaofu; Qi, Peipei; Wei, Wei; Chen, Xiaoyun; Li, Rui; Zhou, Yu

    2015-06-01

    A rapid and sensitive method was developed and validated for citrinin determination in red fermented rice products by liquid chromatography tandem mass spectrometry (LC-MS/MS) under the selected reaction monitoring mode. Sample preparation was especially focused, and the quantitative methods of LC-MS/MS and high-performance liquid chromatography with fluorescence detection (HPLC-FLD) were compared. In red fermented rice samples, the limit of detection was 1.0 ?g/kg for LC-MS/MS compared to 250 ?g/kg for HPLC-FLD, the limit of quantification was 3.0 ?g/kg for LC-MS/MS compared to 825 ?g/kg for HPLC-FLD. High correlation coefficient was obtained (R(2) = 0.999) within the linear range (0.1 to 100 ?g/L) in the MS method. The recoveries ranging from 80.9% to 106.5% were obtained in different spiking concentrations. The average intra- and inter-day accuracy ranged from 75.4% to 103.1%, and the intra- and inter-day precisions were from 3.3% to 7.9%. The developed method was applied to 12 commercial red fermented rice products, and citrinin was found in 10 samples ranging from 0.14 to 44.24 mg/kg. Compared to traditional qualitative and quantitative methods, the newly developed LC-MS/MS method for citrinin determination includes the merits of using a small amount of extraction solvent, simple preparation steps, and high sensitivity. PMID:25943499

  19. Weathering of the Rio Blanco quartz diorite, Luquillo Mountains, Puerto Rico: Coupling oxidation, dissolution, and fracturing

    USGS Publications Warehouse

    Buss, H.L.; Sak, P.B.; Webb, S.M.; Brantley, S.L.

    2008-01-01

    In the mountainous Rio Icacos watershed in northeastern Puerto Rico, quartz diorite bedrock weathers spheroidally, producing a 0.2-2 m thick zone of partially weathered rock layers (???2.5 cm thickness each) called rindlets, which form concentric layers around corestones. Spheroidal fracturing has been modeled to occur when a weathering reaction with a positive ??V of reaction builds up elastic strain energy. The rates of spheroidal fracturing and saprolite formation are therefore controlled by the rate of the weathering reaction. Chemical, petrographic, and spectroscopic evidence demonstrates that biotite oxidation is the most likely fracture-inducing reaction. This reaction occurs with an expansion in d (0 0 1) from 10.0 to 10.5 A??, forming 'altered biotite'. Progressive biotite oxidation across the rindlet zone was inferred from thin sections and gradients in K and Fe(II). Using the gradient in Fe(II) and constraints based on cosmogenic age dates, we calculated a biotite oxidation reaction rate of 8.2 ?? 10-14 mol biotite m-2 s-1. Biotite oxidation was documented within the bedrock corestone by synchrotron X-ray microprobe fluorescence imaging and XANES. X-ray microprobe images of Fe(II) and Fe(III) at 2 ??m resolution revealed that oxidized zones within individual biotite crystals are the first evidence of alteration of the otherwise unaltered corestone. Fluids entering along fractures lead to the dissolution of plagioclase within the rindlet zone. Within 7 cm surrounding the rindlet-saprolite interface, hornblende dissolves to completion at a rate of 6.3 ?? 10-13 mol hornblende m-2 s-1: the fastest reported rate of hornblende weathering in the field. This rate is consistent with laboratory-derived hornblende dissolution rates. By revealing the coupling of these mineral weathering reactions to fracturing and porosity formation we are able to describe the process by which the quartz diorite bedrock disaggregates and forms saprolite. In the corestone, biotite oxidation induces spheroidal fracturing, facilitating the influx of fluids that react with other minerals, dissolving plagioclase and chlorite, creating additional porosity, and eventually dissolving hornblende and precipitating secondary minerals. The thickness of the resultant saprolite is maintained at steady state by a positive feedback between the denudation rate and the weathering advance rate driven by the concentration of pore water O2 at the bedrock-saprolite interface. ?? 2008 Elsevier Ltd. All rights reserved.

  20. Diagnosing tandem cells

    SciTech Connect

    Hou, J.; Fonash, S.J. [Pennsylvania State Univ., University Park, PA (United States). Electronic Materials and Processing Research Laboratory; Ghosh, M.; Xi, J.; Liu, T.; Kampas, F. [Advanced Photovoltaic Systems Inc., San Bruno, CA (United States)

    1994-12-31

    In this paper the authors report three new diagnostic techniques for identifying problem areas in tandem cells. These techniques can be easily extended to diagnosing triple junction cells. They applied these techniques to diagnose an a-Si:H based tandem cell having an extraordinarily low Voc. As they demonstrated, the assessments of the problem in this cell produced by each of the diagnostic approaches agree well with each other.

  1. Graphene oxide based in-tube solid-phase microextraction combined with liquid chromatography tandem mass spectrometry for the determination of triazine herbicides in water.

    PubMed

    Tan, Feng; Zhao, Cong; Li, Lianjun; Liu, Min; He, Xin; Gao, Jinsuo

    2015-07-01

    J. Sep. Sci. 2015, 38, 2312-2319. DOI: 10.1002/jssc.201500070 Monolayer graphene oxide sheets were covalently modified onto the inner wall of a fusedsilica capillary to prepare a graphene oxide coating with 30 nm thickness and porous wrinkled-membrane-like structure, which was used as an extraction column for in-tube solid phase microextraction. The coating showed enough stability and high extraction efficiency to triazine compounds due to ?-? stacking and hydrogen bonding interactions between graphene oxide and triazine molecules. The proposed in-tube solid phase microextraction method was applied to simultaneous analysis of trace triazine herbicides in environmental samples, with good recoveries and repeatability. PMID:26148733

  2. Facile Cu(I)-catalyzed oxidative coupling of anilines to azo compounds and hydrazines with diaziridinone under mild conditions.

    PubMed

    Zhu, Yingguang; Shi, Yian

    2013-04-19

    A mild and highly efficient Cu(I)-catalyzed oxidative coupling of anilines is described. Various primary and secondary anilines can be efficiently coupled under mild conditions to the corresponding azo compounds and hydrazines in high yields. This method provides a direct and practical access to these compounds and is also amenable to gram scale with no special precautions to exclude air or moisture. PMID:23545123

  3. A Facile Cu(I)-Catalyzed Oxidative Coupling of Anilines to Azo Compounds and Hydrazines with Diaziridinone under Mild Conditions

    PubMed Central

    Zhu, Yingguang; Shi, Yian

    2013-01-01

    A mild and highly efficient Cu(I)-catalyzed oxidative coupling of anilines is described. Various primary and secondary anilines can be efficiently coupled under mild conditions to the corresponding azo compounds and hydrazines in high yields. This method provides a direct and practical access to these compounds, and is also amenable to gram scale with no special precautions to exclude air or moisture. PMID:23545123

  4. Measurement of chronic oxidative and inflammatory stress by quantification of isoketal\\/levuglandin ?-ketoaldehyde protein adducts using liquid chromatography tandem mass spectrometry

    Microsoft Academic Search

    Sean S Davies; Venkataraman Amarnath; Cynthia J Brame; Olivier Boutaud; L Jackson Roberts

    2007-01-01

    Measurement of F2-isoprostanes (F2-IsoPs) has been independently verified as one of the most reliable approaches to assess oxidative stress in vivo. However, the rapid clearance of F2-IsoPs makes the timing of sample collection critical for short-lived oxidative insults. Isoketals (IsoKs) are ?-ketoaldehydes formed via the IsoP pathway of lipid peroxidation that rapidly react with lysyl residues of proteins to form

  5. Comparison of the Determination of Eight Cholesterol Oxides in Dry–Cured Shoulder by GC–FID, GC–MS, and GC Tandem Mass Spectrometry

    Microsoft Academic Search

    Maria Clariana; Isabel Díaz; Carmen Sárraga; Jose A. García-Regueiro

    The analysis of eight cholesterol oxidation products: 7?–hydroxycholesterol, 7?–hydroxycholesterol, ?–epoxycholesterol, ?–epoxycholesterol,\\u000a 20?–hydroxycholesterol, cholestanetriol, 25–hydroxycholesterol, and 7–ketocholesterol in dry–cured shoulder was carried out.\\u000a The extraction of lipids was performed by using the Bligh and Dyer method (1959). Interferences were removed by solid-phase extraction (SPE) in two steps with silica and aminipropylsilica SPE columns.\\u000a The separation of the eight cholesterol oxidation products

  6. Nitrate reduction coupled with pyrite oxidation in the surface sediments of a sulfide-rich ecosystem

    NASA Astrophysics Data System (ADS)

    Hayakawa, Atsushi; Hatakeyama, Mizuho; Asano, Ryoki; Ishikawa, Yuichi; Hidaka, Shin

    2013-06-01

    studies of denitrification have focused on organic carbon as an electron donor, but reduced sulfur can also support denitrification. Few studies have reported nitrate (NO3-) reduction coupled with pyrite oxidation and its stoichiometry in surface sediments, especially without experimental pyrite addition. In this study, we evaluated NO3- reduction coupled with sulfur oxidation by long-term incubation of surface sediments from a sulfide-rich ecosystem in Akita Prefecture, Japan. The surface sediments were sampled from a mud pool and a riverbed. Fresh sediments and water were incubated under anoxic conditions (and one oxic condition) at 20°C. NO3- addition increased the SO42- concentration and decreased the NO3- concentration. SO42- production (?SO42-) was strongly and linearly correlated with NO3- consumption (?NO3-) during the incubation period (R2 = 0.983, P < 0.01, and n = 8), and the slope of the regression (?NO3-/?SO42-) and the stoichiometry indicated sulfur-driven NO3- reduction by indigenous autotrophic denitrifying bacteria. Framboidal pyrite and marcasite (both FeS2) were present in the sediments and functioned as the electron donors for autotrophic denitrification. Both ?NO3- and ?SO42- were higher in the riverbed sediment than in the mud pool sediment, likely because of the higher amount of easily oxidizable S (pyrite) in the riverbed sediment. Consistently low ammonium (NH4+) concentrations indicated that NO3- reduction by dissimilatory NO3- reduction to NH4+ was small but could not be disregarded. Our results demonstrate that sulfide-rich ecosystems with easily oxidizable metal-bound sulfides such as FeS2 near the ground surface may act as denitrification hot spots.

  7. Ionic liquid-based one-step micellar extraction of multiclass polar compounds from hawthorn fruits by ultrahigh-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry.

    PubMed

    Hu, Shuai-Shuai; Yi, Ling; Li, Xing-Ying; Cao, Jun; Ye, Li-Hong; Cao, Wan; Da, Jian-Hua; Dai, Han-Bin; Liu, Xiao-Juan

    2014-06-11

    An ionic liquid (IL)-based one-step micellar extraction procedure was developed for the extraction of multiclass polar analytes (protocatechuic acid, chlorogenic acid, epicatechin, hyperoside, isoquercitrin, quercetin) from hawthorn fruits and their determination using ultrahigh-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry (UHPLC-Q-TOF/MS). Compared to conventional organic solvent extractions, this newly proposed method was much easier, more sensitive, environmentally friendly, and effective as well. Several important parameters influencing the micellar extraction efficiency are discussed, such as selection of ILs, surfactant concentration, and extraction time. Under the optimal conditions, good linearity was achieved for each analyte with correlation coefficients (r(2)) ranging from 0.9934 to 0.9999, and the recovery values ranged from 89.3 to 106% with relative standard deviations lower than 5.5%. Results suggest that the IL-based one-step micellar extraction could be an alternative and promising means in future food analysis. PMID:24845828

  8. Liquid chromatography coupled with ultraviolet absorbance detection, electrospray ionization, collision-induced dissociation and tandem mass spectrometry on a triple quadrupole for the on-line characterization of polyphenols and methylxanthines in green coffee beans.

    PubMed

    Alonso-Salces, Rosa Maria; Guillou, Claude; Berrueta, Luis A

    2009-02-01

    Liquid chromatography coupled with a photodiode array detector, electrospray ionization, collision-induced dissociation and tandem mass spectrometry (LC-DAD/ESI-CID-MS/MS) on a triple quadrupole (QqQ) has been used to detect and characterize polyphenols and methylxanthines in green coffee beans: three phenolic acids (caffeic acid, ferulic acid and dimethoxycinnamic acid), three isomeric caffeoylquinic acids (M(r) 354), three feruloylquinic acids (M(r) 368), one p-coumaroylquinic acid (M(r) 338), three dicaffeoylquinic acids (M(r) 516), three feruloyl-caffeoylquinic acids (M(r) 530), four p-coumaroyl-caffeoylquinic acids (M(r) 500), three diferuloylquinic acids (M(r) 544), six dimethoxycinnamoyl-caffeoylquinic acids (M(r) 544), three dimethoxycinnamoyl-feruloylquinic acids (M(r) 558), six cinnamoyl-amino acid conjugates, three cinnamoyl glycosides, and three methylxanthines (caffeine, theobromine and theophylline). Dimethoxycinnamic acid, three isomers of dimethoxycinnamoyl-caffeoylquinic acids and another three of dimethoxycinnamoyl-feruloylquinic acids, as well as the three cinnamoyl glycosides, had not previously been reported in coffee beans. Structures have been assigned on the basis of the complementary information obtained from UV-visible spectra, relative hydrophobicity, scan mode MS spectra, and fragmentation patterns in MS(2) spectra (both in the positive and negative ion modes) obtained using a QqQ at different collision energies. A structure diagnosis scheme is provided for the identification of different isomers of polyphenols and methylxanthines. PMID:19127547

  9. Potential of methyl fluoride as a universal reaction gas to overcome spectral interference in the determination of ultratrace concentrations of metals in biofluids using inductively coupled plasma-tandem mass spectrometry.

    PubMed

    Bolea-Fernandez, Eduardo; Balcaen, Lieve; Resano, Martín; Vanhaecke, Frank

    2014-08-01

    Methyl fluoride (a mixture of 10% CH3F and 90% of He) was evaluated as a reaction gas in inductively coupled plasma-tandem mass spectrometry (ICPMS/MS) in the context of the determination of ultratrace concentrations of medically relevant metals (Al, Co, Cr, Mn, Ni, Ti, and V) in blood serum and urine. Via product ion scanning, whereby only ions of the mass-to-charge ratio of the target nuclide were admitted into the octopole reaction cell, the various reaction product ions formed for each of the target elements were identified at different CH3F gas flow rates. Limits of detection (LODs) and of quantification (LOQs) and linearity of the calibration curve were documented under (i) optimized ICPMS/MS conditions for single-element monitoring and (ii) compromise conditions, allowing for multielement determination. Even under compromise settings, instrumental LODs were below 10 ng/L for all target elements, while the use of CH3F provided interference-free conditions for their determination in the biofluids of interest. Quantitative data obtained for Seronorm blood serum and urine reference materials were in excellent agreement with the corresponding reference values and/or results obtained using double-focusing sector-field ICPMS (for those elements for which no certified values were available or that were affected during reconstitution), proving the potential of this reaction gas for multielement ultratrace analysis via ICPMS/MS. PMID:25062450

  10. Selectively Adsorptive Extraction of Phenylarsonic Acids in Chicken Tissue by Carboxymethyl ?-Cyclodextrin Immobilized Fe3O4 Magnetic Nanoparticles Followed Ultra Performance Liquid Chromatography Coupled Tandem Mass Spectrometry Detection

    PubMed Central

    Jia, Jing; Zhang, Wei; Wang, Jing; Wang, Peilong; Zhu, Ruohua

    2014-01-01

    Carboxymethyl ?-cyclodextrin immobilized Fe3O4 magnetic nanoparticles (CM-?-CD-Fe3O4) were synthesized for the selectively adsorptive extraction of five phenylarsonic acids including p-amino phenylarsonic acid, p-nitro phenylarsonic acid, p-hydroxy phenylarsonic acid, p-acylamino phenylarsonic acid and p-hydroxy-3-nitro phenylarsonic acid in chicken tissue. Using ultra performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS), a highly sensitive analytical method was proposed for the determination of five phenylarsonic acids. It was shown that CM-?-CD-Fe3O4 could extract the five phenylarsonic acids in complex chicken tissue samples with high extraction efficiency. Under the optimal conditions, a high enrichment factor, ranging from 349 to 606 fold, was obtained. The limits of detection (LODs) (at a signal-to-noise ratio of 3) were in the range of 0.05–0.11 µg/kg for the five phenylarsonic acids. The proposed method was applied for the determination of five target phenylarsonic acids in chicken muscle and liver samples. Recoveries for the spiked samples with 0.2 µg/kg, 2.0 µg/kg and 20 µg/kg of each phenylarsonic acids were in the range of 77.2%–110.2%, with a relative standard deviation (RSD) of less than 12.5%. PMID:25215503

  11. Determination of ochratoxin A and T-2 toxin in alcoholic beverages by hollow fiber liquid phase microextraction and ultra high-pressure liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Romero-González, R; Frenich, A Garrido; Vidal, J L Martínez; Aguilera-Luiz, M M

    2010-06-30

    A new method for the determination of ochratoxin A and T-2 toxin in alcoholic beverages (wine and beer) by hollow fiber liquid microextraction was optimized. The extraction step was followed by ultra high-pressure liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). The extraction procedure was based on the extraction of mycotoxins from the sample to the organic solvent (1-octanol) immobilized in the fiber, and afterwards, they were desorbed in a mixture of acetonitrile/water (80:20, v/v) at pH 7 prior to chromatographic determination. Different variables affecting the extraction process such as organic solvent, salt content, extraction time and desorption solution were studied. The developed method was validated in wine and beer, using white wine and alcoholic beer as representative matrices for both types of samples. Relative recoveries higher than 70% were obtained for the selected mycotoxins. Good linearity (R(2)>0.993) was obtained and quantification limits (0.02-0.09 microg L(-1)) below European regulatory levels were achieved. Repeatability, expressed as relative standard deviation, was always lower than 12%, whereas interday precision was lower than 21%. The proposed method was applied to the analysis of several types of wines and beers and ochratoxin A was detected in a rosé wine at 1.1 microg L(-1). PMID:20685453

  12. Chemical Profiling of Re-Du-Ning Injection by Ultra-Performance Liquid Chromatography Coupled with Electrospray Ionization Tandem Quadrupole Time-of-Flight Mass Spectrometry through the Screening of Diagnostic Ions in MSE Mode

    PubMed Central

    Wang, Zhenzhong; Geng, Jianliang; Dai, Yi; Xiao, Wei; Yao, Xinsheng

    2015-01-01

    The broad applications and mechanism explorations of traditional Chinese medicine prescriptions (TCMPs) require a clear understanding of TCMP chemical constituents. In the present study, we describe an efficient and universally applicable analytical approach based on ultra-performance liquid chromatography coupled to electrospray ionization tandem quadrupole time-of-flight mass spectrometry (UPLC-ESI-Q/TOF-MS) with the MSE (E denotes collision energy) data acquisition mode, which allowed the rapid separation and reliable determination of TCMP chemical constituents. By monitoring diagnostic ions in the high energy function of MSE, target peaks of analogous compounds in TCMPs could be rapidly screened and identified. “Re-Du-Ning” injection (RDN), a eutherapeutic traditional Chinese medicine injection (TCMI) that has been widely used to reduce fever caused by viral infections in clinical practice, was studied as an example. In total, 90 compounds, including five new iridoids and one new sesquiterpene, were identified or tentatively characterized by accurate mass measurements within 5 ppm error. This analysis was accompanied by MS fragmentation and reference standard comparison analyses. Furthermore, the herbal sources of these compounds were unambiguously confirmed by comparing the extracted ion chromatograms (EICs) of RDN and ingredient herbal extracts. Our work provides a certain foundation for further studies of RDN. Moreover, the analytical approach developed herein has proven to be generally applicable for profiling the chemical constituents in TCMPs and other complicated mixtures. PMID:25875968

  13. Noninvasive measurement of aristolochic acid-DNA adducts in urine samples from aristolochic acid-treated rats by liquid chromatography coupled tandem mass spectrometry: evidence for DNA repair by nucleotide-excision repair mechanisms.

    PubMed

    Leung, Elvis M K; Chan, Wan

    2014-01-01

    Nephrotoxic aristolochic acids (AAs) form covalently bonded DNA adducts upon metabolic activation. In this work, a non-invasive approach to detect AAs exposure by quantifying urinary excreted DNA-AA adducts is presented. The developed method entails solid-phase extraction (SPE) enrichment of the urine-excreted DNA-AAs adducts, addition of internal standard, and quantification by liquid chromatography coupled tandem mass spectrometric (LC-MS/MS) analysis. Quantitative analysis revealed 7-(deoxyadenosine-N(6)-yl)-aristolactam II and 7-(deoxyguanosine-N(2)-yl)-aristolactam I that were previously detected as major DNA-AA adducts in different organs of AA-dosed rats, were detected as the major urine excreted adducts. Lower levels of 7-(deoxyadenosine-N(6)-yl)-aristolactam I and 7-(deoxyguanosine-N(2)-yl)-aristolactam II were also detected in the collected urine samples. The identities of the detected urinary DNA-AA adducts were confirmed by comparing chromatographic retention time with synthetic standards, by high-accuracy MS, and MS/MS analyses. LC-MS/MS analysis of the urine samples collected from the AAs-dosed rats demonstrated a time-dependent decrease in the urinary adduct levels, indicating the urinary DNA-AA adduct levels were reflective of the tissue adduct levels. It is expected that the developed approach of detecting urinary DNA-AA adducts will facilitate further carcinogenesis investigations of AAs. PMID:25847264

  14. Nitrogen loss through anaerobic ammonium oxidation coupled to iron reduction from paddy soils in a chronosequence.

    PubMed

    Ding, Long-Jun; An, Xin-Li; Li, Shun; Zhang, Gan-Lin; Zhu, Yong-Guan

    2014-09-16

    Anaerobic ammonium oxidation coupled to iron(III) reduction (termed Feammox) with dinitrogen, nitrite, or nitrate as the end-product is a recently discovered process of nitrogen cycling. However, Feammox has not been described in paddy soils, which are rich in iron(III) oxides and subjected to intensive nitrogen fertilization. Here, evidence for Feammox in a paddy soil chronosequence with a gradient of microbially reducible iron(III) levels was obtained in Southern China using (15)N-labeled ammonium-based isotopic tracing and acetylene inhibition techniques. Our study demonstrated the occurrence of Feammox in the chronosequence, and direct dinitrogen production was shown to be the dominant Feammox pathway. Within the chronosequence, three paddy soils with higher microbially reducible iron(III) levels had higher Feammox rates (ranged from 0.17 to 0.59 mg N kg(-1) d(-1)) compared to an uncultivated soil (0.04 mg N kg(-1) d(-1)). It is estimated that a loss of 7.8-61 kg N ha(-1) year(-1) is associated with Feammox in the examined paddy soils. Overall, we discover that rice cultivation could enrich microbially reducible iron(III), accelerate Feammox reaction and thus fuel nitrogen loss from soils, and suggest that Feammox could be a potentially important pathway for nitrogen loss in paddy soils. PMID:25158120

  15. Oxidative coupling of CH{sub 4} over molybdates: Catalyst performance and characterization

    SciTech Connect

    Kiwi, J.; Thampi, K.R.; Graetzel, M. [Institut de chimie physique, Lausanne (Switzerland)] [and others

    1992-02-06

    The effect oxidative coupling of methane, a variety of molybdates were used as catalysts with sustained activity for more than 280 h. The reaction was studied by cofeeding methane and oxygen at atmospheric pressure, through continuous conventional flow reactors containing the catalyst. The effects of operating conditions were studied and the optimum reactor temperature to achieve high yields of ethane and ethylene was ca. 700-780 {degrees}C, depending on the reactor dimensions. The influence of reactor dimensions on the distribution of products is also reported. Molybdate catalysts are active and yet resistant to deactivation and sintering. Selectivities X(C{sub 2})% up to 20.0 and 7.0% were observed, respectively. The reactor feed had a CH{sub 4} to O{sub 2} ratio of ca. 1.1. The authors results present the effects of varying several operating conditions and the significant gas-phase products observed were H{sub 2}, C{sub 2}H{sub 4}, C{sub 2}H{sub 6}, C{sub 3}H{sub 6}, H{sub 2}O, and traces of HCHO and CH{sub 3}OH. C{sub 2}H{sub 2} formation was not observed. The main oxidation products were CO{sub 2} and CO. Structural characterization of the molybdates was carried out by elemental analysis, infrared spectroscopy (IR), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). 46 refs., 8 figs., 2 tabs.

  16. Coupling osmium complexes to epoxy-functionalised polymers to provide mediated enzyme electrodes for glucose oxidation.

    PubMed

    Ó Conghaile, Peter; Pöller, Sascha; MacAodha, Domhnall; Schuhmann, Wolfgang; Leech, Dónal

    2013-05-15

    Newly synthesised osmium complex-modified redox polymers were tested for potential application as mediators in glucose oxidising enzyme electrodes for application to biosensors or biofuel cells. Coupling of osmium complexes containing amine functional groups to epoxy-functionalised polymers of variable composition provides a range of redox polymers with variation possible in redox potential and physicochemical properties. Properties of the redox polymers as mediators for glucose oxidation were investigated by co-immobilisation onto graphite with glucose oxidase or FAD-dependent glucose dehydrogenase using a range of crosslinkers and in the presence and absence of multiwalled carbon nanotubes. Electrodes prepared by immobilising [P20-Os(2,2'-bipyridine)2(4-aminomethylpyridine)Cl].PF6, carbon nanotubes and glucose oxidase exhibit glucose oxidation current densities as high as 560?Acm(-2) for PBS containing 100mM glucose at 0.45V vs. Ag/AgCl. Films prepared by crosslinking [P20-Os(4,4'-dimethoxy-2,2'-bipyridine)2(4-aminomethylpyridine)Cl].PF6, an FAD-dependent glucose dehydrogenase, and carbon nanotubes achieve current densities of 215?Acm(-2) in 5mM glucose at 0.2V vs. Ag/AgCl, showing some promise for application to glucose oxidising biosensors or biofuel cells. PMID:23274194

  17. An oxidative coupling product of luteolin with cysteine ester and its enhanced inhibitory activity for xanthine oxidase.

    PubMed

    Masuda, Toshiya; Nojima, Shoko; Miura, Yukari; Honda, Sari; Masuda, Akiko

    2015-08-15

    Oxidative coupling reactions of several flavonoids with a cysteine ester (a radicalic and nucleophilic biochemical) were carried out and the abilities of the coupling products against xanthine oxidase (XO) were screened. One of the products, derived from luteolin, showed a notable inhibitory effect. A potent XO inhibitory compound was isolated from the complex mixture of the product of the coupling of luteolin and cysteine ethyl ester, and its structure was determined by NMR and MS analysis. The compound has a unique 1,4-thiazine ring unit on the luteolin B-ring and is inhibited XO 4.5 times more strongly than it did luteolin. PMID:26096677

  18. Tandem Air Propellers - II

    NASA Technical Reports Server (NTRS)

    Lesley, E. P.

    1939-01-01

    Tests of three-blade, adjustable-pitch counterrotating tandem model propellers, adjusted to absorb equal power at maximum efficiency of the combination, were made at Stanford University. The aerodynamic characteristics, for blade-angle settings of 15, 25, 35, 45, 55, and 65 degrees at 0.75R of the forward propeller and for diameters spacings of 8-1/2, 15 and 30% were compared with those of three-blade and six-blade propellers of the same blade form. It was found that, in order to realize the condition of equal power at maximum efficiency, the blade angles for the rear propeller must be generally less than for the forward propeller, the difference increasing the blade angle. The tests showed that, at maximum efficiency, the tandem propellers absorb about double the power of three-blade propellers and about 8% more power than six-blade propellers having the pitch of the forward propeller of the tandem combination. The maximum efficiency of the tandem propellers was found to be from 2-15% greater than for six-blade propellers, the difference varying directly with blade angle. It was also found that the maximum efficiency of the tandem propellers was greater than that of a three-blade propeller for blade angles at 0.75R of 25 degrees or more. The difference in maximum efficiency again varied directly with blade angle, being about 9% for 65 degrees at 0.75R.

  19. Determination of cadmium by inductively coupled plasma mass spectrometry-reduction of molybdenum oxide interferences by addition of acetonitrile

    Microsoft Academic Search

    D Karunasagar; J Arunachalam

    2001-01-01

    The determination of cadmium at trace and ultra trace levels is important due to its toxicity. Inductively coupled plasma mass spectrometry (ICP-MS) is a highly sensitive and rapid technique suitable for the analysis of cadmium. But when a quadrupole analyzer is used isobaric interferences due to oxide ions of molybdenum can pose a problem and lead to erroneous results. A

  20. Bimetallic zinc complex--active species in coupling of terminal alkynes with aldehydes via nucleophilic addition/Oppenauer oxidation.

    PubMed

    Yuan, Jiwen; Wang, Jing; Zhang, Guanghui; Liu, Chao; Qi, Xiaotian; Lan, Yu; Miller, Jeffrey T; Kropf, A Jeremy; Bunel, Emilio E; Lei, Aiwen

    2015-01-11

    A mechanistic study on the zinc-promoted coupling between aldehydes and terminal alkynes via nucleophilic addition/Oppenauer oxidation using operando IR, XANES/EXAFS techniques and DFT calculations was demonstrated. It was determined that a bimetallic zinc complex was the active species. PMID:25413491

  1. Regulating proton-coupled electron transfer for efficient water splitting by manganese oxides at neutral pH

    PubMed Central

    Yamaguchi, Akira; Inuzuka, Riko; Takashima, Toshihiro; Hayashi, Toru; Hashimoto, Kazuhito; Nakamura, Ryuhei

    2014-01-01

    Manganese oxides have been extensively investigated as model systems for the oxygen-evolving complex of photosystem II. However, most bioinspired catalysts are inefficient at neutral pH and functional similarity to the oxygen-evolving complex has been rarely achieved with manganese. Here we report the regulation of proton-coupled electron transfer involved in water oxidation by manganese oxides. Pyridine and its derivatives, which have pKa values intermediate to the water ligand bound to manganese(II) and manganese(III), are used as proton-coupled electron transfer induction reagents. The induction of concerted proton-coupled electron transfer is demonstrated by the detection of deuterium kinetic isotope effects and compliance of the reactions with the libido rule. Although proton-coupled electron transfer regulation is essential for the facial redox change of manganese in photosystem II, most manganese oxides impair these regulatory mechanisms. Thus, the present findings may provide a new design rationale for functional analogues of the oxygen-evolving complex for efficient water splitting at neutral pH. PMID:24977746

  2. Regulating proton-coupled electron transfer for efficient water splitting by manganese oxides at neutral pH

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Akira; Inuzuka, Riko; Takashima, Toshihiro; Hayashi, Toru; Hashimoto, Kazuhito; Nakamura, Ryuhei

    2014-06-01

    Manganese oxides have been extensively investigated as model systems for the oxygen-evolving complex of photosystem II. However, most bioinspired catalysts are inefficient at neutral pH and functional similarity to the oxygen-evolving complex has been rarely achieved with manganese. Here we report the regulation of proton-coupled electron transfer involved in water oxidation by manganese oxides. Pyridine and its derivatives, which have pKa values intermediate to the water ligand bound to manganese(II) and manganese(III), are used as proton-coupled electron transfer induction reagents. The induction of concerted proton-coupled electron transfer is demonstrated by the detection of deuterium kinetic isotope effects and compliance of the reactions with the libido rule. Although proton-coupled electron transfer regulation is essential for the facial redox change of manganese in photosystem II, most manganese oxides impair these regulatory mechanisms. Thus, the present findings may provide a new design rationale for functional analogues of the oxygen-evolving complex for efficient water splitting at neutral pH.

  3. Iodine-mediated oxidative annulation for one-pot synthesis of pyrazines and quinoxalines using a multipathway coupled domino strategy.

    PubMed

    Viswanadham, K K Durga Rao; Prathap Reddy, Muktapuram; Sathyanarayana, Pochampalli; Ravi, Owk; Kant, Ruchir; Bathula, Surendar Reddy

    2014-11-14

    An efficient iodine-mediated oxidative annulation of aryl acetylenes-arylethenes-aromatic ketones with 1,2-diamines for the synthesis of pyrazines and regioselective synthesis of quinoxalines is presented. A multipathway coupled domino approach has been developed for the one-pot synthesis of 1,4-diazines with high functional group compatibility. PMID:25238170

  4. Kinetic Effects Of Increased Proton Transfer Distance On Proton-Coupled Oxidations Of Phenol-Amines

    PubMed Central

    Rhile, Ian J.

    2011-01-01

    To test the effect of varying the proton donor-acceptor distance in proton-coupled electron transfer (PCET) reactions, the oxidation of a bicyclic amino-indanol (2) is compared with that of a closely related phenol with an ortho CPh2NH2 substituent (1). Spectroscopic, structural, thermochemical and computational studies show that the two amino-phenols are very similar, except that the O?N distance (dON) is >0.1 Å longer in 2 than in 1. The difference in dON is 0.13 ± 0.03 Å from X-ray crystallography and 0.165 Å from DFT calculations. Oxidations of these phenols by outer-sphere oxidants yield distonic radical cations •OAr–NH3+ by concerted proton-electron transfer (CPET). Simple tunneling and classical kinetic models both predict that the longer donor-acceptor distance in 2 should lead to slower reactions, by ca. two orders of magnitude, as well as larger H/D kinetic isotope effects (KIEs). However, kinetic studies show that the compound with the longer proton-transfer distance, 2, exhibits smaller KIEs and has rate constants that are quite close to those of 1. For example, the oxidation of 2 by the triarylamminium radical cation N(C6H4OMe)3•+ (3a+) occurs at (1.4 ± 0.1) × 104 M-1 s-1, only a factor of two slower than the closely related reaction of 1 with N(C6H4OMe)2(C6H4Br)•+ (3b+). This difference in rate constants is well accounted for by the slightly different free energies of reaction: ?G°(2 + 3a+) = +0.078 V vs. ?G°(1 + 3b+) = +0.04 V. The two phenol-amines do display some subtle kinetic differences: for instance, compound 2 has a shallower dependence of CPET rate constants on driving force (Brønsted ?, ?ln(k)/?ln(Keq)). These results show that the simple tunneling model is not a good predictor of the effect of proton donor-acceptor distance on concerted-electron transfer reactions involving strongly hydrogen-bonded systems. Computational analysis of the observed similarity of the two phenols emphasizes the importance of the highly anharmonic O?H?N potential energy surface and the influence of proton vibrational excited states. PMID:21919508

  5. The mechanism for proton-coupled electron transfer from tyrosine in a model complex and comparisons with Y(Z) oxidation in photosystem II.

    PubMed Central

    Sjödin, Martin; Styring, Stenbjörn; Akermark, Björn; Sun, Licheng; Hammarström, Leif

    2002-01-01

    In the water-oxidizing reactions of photosystem II (PSII), a tyrosine residue plays a key part as an intermediate electron-transfer reactant between the primary donor chlorophylls (the pigment P(680)) and the water-oxidizing Mn cluster. The tyrosine is deprotonated upon oxidation, and the coupling between the proton reaction and electron transfer is of great mechanistic importance for the understanding of the water-oxidation mechanism. Within a programme on artificial photosynthesis, we have made and studied the proton-coupled tyrosine oxidation in a model system and been able to draw mechanistic conclusions that we use to interpret the analogous reactions in PSII. PMID:12437887

  6. Insights into proton-coupled electron transfer mechanisms of electrocatalytic H2 oxidation and production

    PubMed Central

    Horvath, Samantha; Fernandez, Laura E.; Soudackov, Alexander V.; Hammes-Schiffer, Sharon

    2012-01-01

    The design of molecular electrocatalysts for H2 oxidation and production is important for the development of alternative renewable energy sources that are abundant, inexpensive, and environmentally benign. Recently, nickel-based molecular electrocatalysts with pendant amines that act as proton relays for the nickel center were shown to effectively catalyze H2 oxidation and production. We developed a quantum mechanical approach for studying proton-coupled electron transfer processes in these types of molecular electrocatalysts. This theoretical approach is applied to a nickel-based catalyst in which phosphorous atoms are directly bonded to the nickel center, and nitrogen atoms of the ligand rings act as proton relays. The catalytic step of interest involves electron transfer between the nickel complex and the electrode as well as intramolecular proton transfer between the nickel and nitrogen atoms. This process can occur sequentially, with either the electron or proton transferring first, or concertedly, with the electron and proton transferring simultaneously without a stable intermediate. The electrochemical rate constants are calculated as functions of overpotential for the concerted electron-proton transfer reaction and the two electron transfer reactions in the sequential mechanisms. Our calculations illustrate that the concerted electron-proton transfer standard rate constant will increase as the equilibrium distance between the nickel and nitrogen atoms decreases and as the pendant amines become more flexible to facilitate the contraction of this distance with a lower energy penalty. This approach identifies the favored mechanisms under various experimental conditions and provides insight into the impact of substituents on the nitrogen and phosphorous atoms. PMID:22529352

  7. Insights into proton-coupled electron transfer mechanisms of electrocatalytic H2 oxidation and production

    SciTech Connect

    Horvath, Samantha; Fernandez, Laura; Soudackov, Alexander V.; Hammes-Schiffer, Sharon

    2012-09-25

    The design of molecular electrocatalysts for H2 oxidation and production is important for the development of alternative renewable energy sources that are abundant, inexpensive, and environmentally benign. Recently nickel-based molecular electrocatalysts with pendant amines that act as proton relays for the nickel center were shown to effectively catalyze H2 oxidation and production. We developed a quantum mechanical approach for studying proton-coupled electron transfer processes in these types of molecular electrocatalysts. This theoretical approach is applied to a nickel-based catalyst in which phosphorous atoms are directly bonded to the nickel center and nitrogen atoms of the ligand rings act as proton relays. The cataly c step of interest involves electron transfer between the nickel complex and the electrode as well as intramolecular proton transfer between the nickel and nitrogen atoms. This process can occur sequentially, with either the electron or proton transferring first, or concertedly, with the electron and proton transferring simultaneously without a stable intermediate. The heterogeneous rate constants are calculated as functions of overpotential for the concerted electron-proton transfer reaction and the two electron transfer reactions in the sequential mechanisms. Our calculations illustrate that the concerted electron-proton transfer standard rate constant will increase as the equilibrium distance between the nickel and nitrogen atoms decreases and as the nitrogen atoms become more mobile to facilitate the contraction of this distance. This approach assists in the identification of the favored mechanisms under various experimental conditions and provides insight into the qualitative impact of substituents on the nitrogen and phosphorous atoms. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under FWP 56073.

  8. Sexual intercourse with leukocytospermic men may be a possible booster of oxidative stress in female partners of infertile couples.

    PubMed

    Mändar, R; Kullisaar, T; Borovkova, N; Punab, M

    2013-05-01

    Human semen has undoubtedly significant influence on the organism of the female counterpart. At the same time there are no studies in English literature investigating the influence of sexual intercourse on oxidative stress level in women's organism. Seventeen infertile couples where male partners were with (n = 5) or without (n = 12) leukocytospermia were enrolled in the study. Systemic oxidative stress levels were measured, whereby twice in female partners - before and 8-12 h after sexual intercourse. The men with leukocytospermia were characterized by oxidative stress that was substantially transferred to their partners during sexual intercourse as revealed by increase in 8-isoprostanes level (median 32.7 vs. 70.4 ng/mmol creatinine, p = 0.006). Sexual intercourse with male partner having leukocytospermia increases the oxidative stress level in the women's organism that may interfere with fertilization. PMID:23316004

  9. Manifold, bus support and coupling arrangement for solid oxide fuel cells

    Microsoft Academic Search

    1989-01-01

    This patent describes a modular solid oxide fuel cell arrangement. It comprises: a solid oxide fuel cell having an anode, a cathode and a solid electrolyte therebetween and responsive to an oxidant and a fuel gas provided thereto for converting chemical energy of the fuel gas to DC electrical energy; structural means disposed about the solid oxide fuel cell and

  10. Metal-Free Intermolecular Oxidative C-N Bond Formation via Tandem C-H and N-H Bond Functionalization

    PubMed Central

    Kantak, Abhishek A.; Potavathri, Shathaverdhan; Barham, Rose A.; Romano, Kaitlyn M.

    2011-01-01

    The development of a novel intermolecular oxidative amination reaction, a synthetic transformation that involves the simultaneous functionalization of both an N-H and C-H bond, is described. The process, which is mediated by an I(III) oxidant and contains no metal catalysts, provides a rapid and green method for synthesizing protected anilines from simple arenes and phthalimide. Mechanistic investigations indicate that the reaction proceeds via nucleophilic attack of the phthalimide on an aromatic radical cation, as opposed to the electrophilic aromatic amination that has been reported for other I(III) amination reactions. The application of this new reaction to the synthesis of a variety of substituted aniline derivatives is demonstrated. PMID:22010982

  11. Oxidative reactions of 6-pentyl indolo[3,2-b]carbazole: formation of novel C-C and C-N coupled dimers.

    PubMed

    Gu, Rong; Van Hecke, Kristof; Van Meervelt, Luc; Toppet, Suzanne; Dehaen, Wim

    2006-10-21

    The oxidative coupling reactions of 6-pentyl-5,11-dihydroindolo[3,2-b]carbazole have been studied and as a result, a number of novel dimers of the indolo[3,2-b]carbazole derivative have been prepared, forming C-C coupled compound when treated with FeCl(3) x 6H(2)O or C-N coupled compounds and when oxidized with air or Pd(OAc)(2), respectively. PMID:17024285

  12. Matrix effect during the membrane-assisted solvent extraction coupled to liquid chromatography tandem mass spectrometry for the determination of a variety of endocrine disrupting compounds in wastewater.

    PubMed

    Iparraguirre, A; Navarro, P; Rodil, R; Prieto, A; Olivares, M; Etxebarria, N; Zuloaga, O

    2014-08-22

    Membrane-assisted solvent extraction (MASE) coupled to liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) was studied for the determination of a variety of emerging and priority compounds in wastewater. Among the target analytes studied certain hormones (estrone (E1), 17?-estradiol (E2), androsterone (ADT), 17?-ethynyl estradiol (EE2), diethylstilbestrol (DES), equilin (EQ), testosterone (TT), mestranol (MeEE2), 19-norethisterone (NT), progesterone (PG) and equilenin (EQN)), alkylphenols (APs) (4-tert-octylphenol (4tOP), nonylphenol technical mixture (NPs) and 4n-octylphenol (4nOP)) and BPA were included. The work was primarily focused in the LC-MS/MS detection step, both in terms of variable optimization and with respect to the matrix effect study. Both, electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) were assessed both in the negative and positive mode, including the optimization of MS/MS operating conditions. The best results were obtained, in most of the cases, for ESI using 0.05% ammonium hydroxide as buffer solution in the mobile phase, composed with methanol and water. Under optimum detection conditions, matrix effect during the detection step was thoroughly studied. Dilution, correction with deuterated analogues and clean-up of the extracts were evaluated for matrix effect correction. Clean-up with Florisil together with correction with deuterated analogues provided the most satisfactory results, with apparent recoveries in the 57-136% range and method detection limits in the low ngL(-1) level for most of the analytes. For further validation of the method, two separated extraction procedures, the above mentioned MASE, and conventional solid phase extraction (SPE) were compared during the analysis of real samples and comparable results were successfully obtained for E1, E2, EE2, DES, NT, TT, EQ, PG, BPA, ADT, 4nOP, 4tOP, NPs and EQN. PMID:25001332

  13. On-line solid-phase extraction coupled to ultra-performance liquid chromatography with tandem mass spectrometry detection for the determination of benzotriazole UV stabilizers in coastal marine and wastewater samples.

    PubMed

    Montesdeoca-Esponda, Sarah; Sosa-Ferrera, Zoraida; Santana-Rodríguez, José Juan

    2012-05-01

    Benzotriazoles are a group of UV absorbing compounds considered emerging contaminants that are used in different personal care products, and therefore, it is of high interest to develop sensitive and fast methods for investigating their presence in the environment. In this work, we present the development and application of a novel method based on on-line solid-phase extraction coupled to ultra-performance liquid chromatography with tandem mass spectrometry detection (SPE-UPLC-MS/MS) for the determination of seven benzotriazole UV stabilizers (BUVSs) in coastal marine and wastewater samples. This process is compared with a conventional off-line SPE procedure followed by UPLC-MS/MS. The parameters affecting the performance of the sample preparation and determination processes were evaluated. The results indicate that the on-line procedure provides for better sensitivity and reproducibility and is faster and easier than the off-line procedure. The detection limits and quantification limits achieved were in the range of 0.6-4.1 ng?L(-1) and 2.1-14 ng?L(-1) and relative standard deviation between 6.2 and 10%. The developed method was applied to coastal marine and wastewater samples from Gran Canaria Island (Spain). All of the BUVSs studied were detected in the samples from wastewater treatment plants and two were found in the seawater samples (UV P in the range of 2.8-4.4 ng?L(-1) and UV 360 between 3.6 and 5.2 ng?L(-1)). PMID:22411539

  14. Simultaneous determination of chlorpyrifos and 3,5,6-trichloro-2-pyridinol in duck muscle by modified QuEChERS coupled to gas chromatography tandem mass spectrometry (GC-MS/MS).

    PubMed

    Li, Rui; He, Liang; Zhou, Ting; Ji, Xiaofeng; Qian, Mingrong; Zhou, Yu; Wang, Qiang

    2014-05-01

    A rapid, specific, and sensitive method based on modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) coupled to gas chromatography tandem mass spectrometry (GC-MS/MS) was developed and validated for simultaneous determination of chlorpyrifos (CP) and its metabolite 3,5,6-trichloro-2-pyridinol (TCP) in duck muscle. The residues of CP and TCP were extracted by acidified acetonitrile. The fat layer of the extract was removed under -20 °C, then the organic layer was evaporated. The analytes were derivatized by N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA) and cleaned up by a mixture of 150 mg MgSO4, 25 mg graphitized carbon black (GCB), and 50 mg N-propylethylenediamine (PSA) to remove interference. The final extract was analyzed by GC-MS/MS. Recovery values at the spiking concentrations ranged from 86.2 to 92.3 % for CP and from 74.8 to 81.8 % for TCP, with relative standard deviations (RSDs) lower than 9.5 and 12.3, respectively. The correlation coefficients of CP (from 2 to 2,000 ?g/kg) and TCP (from 1 to 1,000 ?g/kg) were equal to or higher than 0.998. The limits of detection (LODs) were 0.3 and 0.15 ?g/kg, and the limits of quantification (LOQs) were 1.0 and 0.5 ?g/kg for CP and TCP in duck muscle, respectively. The average intra- and inter-day accuracy ranged from 84.6 to 91.2 % for CP and 75.6 to 82.3 % for TCP, and the intra- and inter-day precisions were from 5.8 to 8.2 % for CP and 6.5 to 11.9 % for TCP. Furthermore, the CP and TCP residues in duck muscle samples were detected for dietary risk assessment using the validated method. PMID:24691719

  15. Multiresidue analysis of 88 polar organic micropollutants in ground, surface and wastewater using online mixed-bed multilayer solid-phase extraction coupled to high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Huntscha, Sebastian; Singer, Heinz P; McArdell, Christa S; Frank, Carolin E; Hollender, Juliane

    2012-12-14

    An automated multiresidue method consisting of an online solid-phase extraction step coupled to a high performance liquid chromatography-tandem mass spectrometer (online-SPE-HPLC-MS/MS method) was developed for the determination of 88 polar organic micropollutants with a broad range of physicochemical properties (logD(OW) (pH 7): -4.2 to 4.2). Based on theoretical considerations, a single mixed-bed multilayer cartridge containing four different extraction materials was composed for the automated enrichment of water samples. This allowed the simultaneous analysis of pesticides, biocides, pharmaceuticals, corrosion inhibitors, many of their transformation products, and the artificial sweetener sucralose in three matrices groundwater, surface water, and wastewater. Limits of quantification (LOQs) were in the environmentally relevant concentration range of 0.1-87 ng/L for groundwater and surface water, and 1.5-206 ng/L for wastewater. The majority of the compounds could be quantified below 10 ng/L in groundwater (82%) and surface water (80%) and below 100 ng/L in wastewater (80%). Relative recoveries were largely between 80 and 120%. Intraday and inter-day precision, expressed as relative standard deviation, were generally better than 10% and 20%, respectively. 50 isotope labeled internal standards were used for quantification and accordingly, relative recoveries as well as intraday and inter-day precision were better for compounds with corresponding internal standard. The applicability of this method was shown during a sampling campaign at a riverbank filtration site for drinking water production with travel times of up to 5 days. 36 substances of all compound classes investigated could be found in concentrations between 0.1 and 600 ng/L. The results revealed the persistence of carbamazepine and sucralose in the groundwater aquifer as well as degradation of the metamizole metabolite 4-acetamidoantipyrine. PMID:23137864

  16. Tandem resonator reflectance modulator

    Microsoft Academic Search

    I. J. Fritz; J. R. Wendt

    1994-01-01

    A wide band optical modulator is grown on a substrate as tandem Fabry-Perot resonators including three mirrors spaced by two cavities. The absorption of one cavity is changed relative to the absorption of the other cavity by an applied electric field, to cause a change in total reflected light, as light reflecting from the outer mirrors is in phase and

  17. Tandem mirror fusion research

    SciTech Connect

    Baldwin, D.E.

    1983-12-02

    The tandem mirror program has evolved considerably in the last decade. Of significance is the viable reactor concept embodied in the MARS design. An aggressive experimental program, culminating in the operation of MFTF-B in late 1986, will provide a firm basis for refining the MARS design as necessary for constructing a reactor prototype in the 1990s.

  18. Solar-to-Chemical Energy Conversion with Photoelectrochemical Tandem Cells.

    PubMed

    Sivula, Kevin

    2013-01-01

    Efficiently and inexpensively converting solar energy into chemical fuels is an important goal towards a sustainable energy economy. An integrated tandem cell approach could reasonably convert over 20% of the sun's energy directly into chemical fuels like H2 via water splitting. Many different systems have been investigated using various combinations of photovoltaic cells and photoelectrodes, but in order to be economically competitive with the production of H2 from fossil fuels, a practical water splitting tandem cell must optimize cost, longevity and performance. In this short review, the practical aspects of solar fuel production are considered from the perspective of a semiconductor-based tandem cell and the latest advances with a very promising technology - metal oxide photoelectrochemical tandem cells - are presented. PMID:23574955

  19. Catalytic oxidative coupling of methane over Li/MgO using N2O as an oxidant 

    E-print Network

    Yamamoto, Hiroshi

    1992-01-01

    Pa. 49 14. The selectivity of CO~ over Li/MgO with respect to variation of CH while keeping N 0 at 60 kPa. 15. The rate of CH~ consumption over I. i/MgO with respect to variation of CH while keeping N~O at 60 k.../MgO with respect to temperature using O~ as an oxidant. . 59 20 The selectivity for CO over Li/MgO with respect to temperature using O~ as an oxidant. . 60 21 The conversion of CH~ over Li/MgO with respect to temperature using N~O as an oxidant. 62 22...

  20. Kraft lignin chain extension chemistry via propargylation, oxidative coupling, and Claisen rearrangement.

    PubMed

    Sen, Sanghamitra; Sadeghifar, Hasan; Argyropoulos, Dimitris S

    2013-10-14

    Despite its aromatic and polymeric nature, the heterogeneous, stochastic, and reactive characteristics of softwood kraft lignin seriously limit its potential for thermoplastic applications. Our continuing efforts toward creating thermoplastic lignin polymers are now focused at exploring propargylation derivatization chemistry and its potential as a versatile novel route for the eventual utilization of technical lignins with a significant amount of molecular control. To do this, we initially report the systematic propargylation of softwood kraft lignin. The synthesized derivatives were extensively characterized with thermal methods (DSC, TGA), (1)H, (13)C, and quantitative (31)P NMR and IR spectroscopies. Further on, we explore the versatile nature of the lignin pendant propargyl groups by demonstrating two distinct chain extension chemistries; the solution-based, copper-mediated, oxidative coupling and the thermally induced, solid-state, Claissen rearrangement polymerization chemistries. Overall, we show that it is possible to modulate the reactivity of softwood kraft lignin via a combination of methylation and chain extension providing a rational means for the creation of higher molecular weight polymers with the potential for thermoplastic materials and carbon fibers with the desired control of structure-property relations. PMID:23962343

  1. R&D issues in scale-up and manufacturing of amorphous silicon tandem modules

    NASA Astrophysics Data System (ADS)

    Arya, R. R.; Carlson, D. E.; Chen, L. F.; Ganguly, G.; He, M.; Lin, G.; Middya, R.; Wood, G.; Newton, J.; Bennett, M.; Jackson, F.; Willing, F.

    1999-03-01

    R & D on amorphous silicon based tandem junction devices has improved the throughtput, the material utilization, and the performance of devices on commercial tin oxide coated glass. The tandem junction technology has been scaled-up to produce 8.6 Ft2 monolithically integrated modules in manufacturing at the TF1 plant. Optimization of performance and stability of these modules is ongoing.

  2. Liquid-phase polymer-based retention and coupled electrocatalytic oxidation to remove Arsenic in the presence of competitive species

    Microsoft Academic Search

    María del Carmen Aguirre; Bernabé L. Rivas; Carlos Peña; Luis Basaez

    The goal was to remove arsenate species in the presence of competitive anions by coupling of liquid-phase polymer-based retention,\\u000a LPR, a procedure based on the selective As(V) adsorption properties of cationic water-soluble polymers, with an electro-catalytic\\u000a oxidation process (EO) of As(III) into its more easily removable As(V). The electro-catalytic oxidation of As(III) to As(V)\\u000a was performed with an organic supporting

  3. Measurement of the surface charge accumulation using anodic aluminum oxide(AAO) structure in an inductively coupled plasma

    NASA Astrophysics Data System (ADS)

    Park, Ji-Hwan; Oh, Seung-Ju; Lee, Hyo-Chang; Kim, Yu-Sin; Kim, Young-Cheol; Kim, June Young; Ha, Chang-Seoung; Kwon, Soon-Ho; Lee, Jung-Joong; Chung, Chin-Wook

    2014-10-01

    As the critical dimension of the nano-device shrinks, an undesired etch profile occurs during plasma etch process. One of the reasons is the local electric field due to the surface charge accumulation. To demonstrate the surface charge accumulation, an anodic aluminum oxide (AAO) membrane which has high aspect ratio is used. The potential difference between top electrode and bottom electrode in an anodic aluminum oxide contact structure is measured during inductively coupled plasma exposure. The voltage difference is changed with external discharge conditions, such as gas pressure, input power, and gas species and the result is analyzed with the measured plasma parameters.

  4. Rapid liquid chromatography-tandem mass spectrometry analysis of 4-hydroxynonenal for the assessment of oxidative degradation and safety of vegetable oils.

    PubMed

    Gabbanini, Simone; Matera, Riccardo; Valvassori, Alice; Valgimigli, Luca

    2015-04-15

    A novel method for the UHPLC-MS/MS analysis of (E)-4-hydroxynonenal (4-HNE) is described. The method is based on derivatization of 4-HNE with pentafluorophenylhydrazine (1) or 4-trifluoromethylphenylhydrazine (2) in acetonitrile in the presence of trifluoroacetic acid as catalyst at room temperature and allows complete analysis of one sample of vegetable oil in only 21 min, including sample preparation and chromatography. The method involving hydrazine 1, implemented in an ion trap instrument with analysis of the transition m/z 337?154 showed LOD=10.9 nM, average accuracy of 101% and precision ranging 2.5-4.0% RSD intra-day (2.7-4.1% RSD inter-day), with 4-HNE standard solutions. Average recovery from lipid matrices was 96.3% from vaseline oil, 91.3% from sweet almond oil and 105.3% from olive oil. The method was tested on the assessment of safety and oxidative degradation of seven samples of dietary oil (soybean, mixed seeds, corn, peanut, sunflower, olive) and six cosmetic-grade oils (avocado, blackcurrant, apricot kernel, echium, sesame, wheat germ) and effectively detected increased 4-HNE levels in response to chemical (Fenton reaction), photochemical, or thermal stress and aging, aimed at mimicking typical oxidation associated with storage or industrial processing. The method is a convenient, cost-effective and reliable tool to assess quality and safety of vegetable oils. PMID:25818139

  5. Acetate Oxidation Coupled to Fe(III) Reduction in Hyperthermophilic Microorganisms

    Microsoft Academic Search

    JASON M. TOR; KAZEM KASHEFI; DEREK R. LOVLEY

    2001-01-01

    No hyperthermophilic microorganisms have previously been shown to anaerobically oxidize acetate, the key extracellular intermediate in the anaerobic oxidation of organic matter. Here we report that two hyperther- mophiles, Ferroglobus placidus and \\

  6. Recruitment of the adaptor protein Nck to PECAM-1 couples oxidant stress to canonical NF-?B signaling and inflammation

    PubMed Central

    Chen, Jie; Leskov, Igor L.; Yurdagul, Arif; Thiel, Bonnie; Kevil, Christopher G.; Stokes, Karen Y.; Orr, A. Wayne

    2015-01-01

    Oxidant stress drives nuclear factor ?B (NF-?B) activation and NF-?B-dependent proinflammatory gene expression in endothelial cells during several pathological conditions, including ischemia/reperfusion injury. We showed that the Nck family of adaptor proteins linked tyrosine kinase signaling to oxidant stress-induced activation of NF-?B through the classic I?B kinase (IKK)-dependent pathway. Depletion of Nck prevented oxidant stress induced by exogenous peroxide or hypoxia/reoxygenation injury from triggering the activation of NF-?B in endothelial cells, increases in the abundance of the pro-inflammatory molecules ICAM-1 (intracellular adhesion molecule 1) and VCAM-1 (vascular cell adhesion molecule 1), and leukocyte recruitment. Nck depletion also attenuated endothelial cell expression of genes encoding proinflammatory factors, but not those encoding antioxidants. We further showed that Nck promoted oxidant stress-induced activation of NF-?B by coupling the tyrosine phosphorylation of platelet-endothelial cell adhesion molecule-1 (PECAM-1) to the activation of p21 activated kinase, which mediates oxidant stress-induced NF-?B signaling. Consistent with this model, treatment of mice subjected to ischemia/reperfusion injury in the cremaster muscle with a Nck inhibitory peptide inhibited leukocyte adhesion and emigration and the accompanying vascular leak. Together, these data identify Nck as an important mediator of oxidant stress-induced inflammation and a potential therapeutic target for ischemia/reperfusion injury. PMID:25714462

  7. Biological Oxidation of Fe(II) in Reduced Nontronite Coupled with Nitrate Reduction by Pseudogulbenkiania sp. Strain 2002

    SciTech Connect

    Zhao, Linduo; Dong, Hailiang; Kukkadapu, Ravi K.; Agrawal, A.; Liu, Deng; Zhang, Jing; Edelmann, Richard E.

    2013-10-15

    Nitrate contamination in soils, sediments, and water bodies is a significant issue. Although much is known about nitrate degradation in these environments, especially via microbial pathways, a complete understanding of all degradation processes, especially in clay mineral-rich soils, is still lacking. The objective of this study was to study the potential of removing nitrate contaminant using structural Fe(II) in clay mineral nontronite. Specifically, the coupled processes of microbial oxidation of Fe(II) in microbially reduced nontronite (NAu-2) and nitrate reduction by Pseudogulbenkiania species strain 2002 was investigated. Bio-oxidation experiments were conducted in bicarbonate-buffered medium under both growth and nongrowth conditions. The extents of Fe(II) oxidation and nitrate reduction were measured by wet chemical methods. X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), and 57Fe-Mössbauer spectroscopy were used to observe mineralogical changes associated with Fe(III) reduction and Fe(II) oxidation in nontronite. The bio-oxidation extent under growth and nongrowth conditions reached 93% and 57%, respectively. Over the same time period, nitrate was completely reduced under both conditions to nitrogen gas (N2), via an intermediate product nitrite. Magnetite was a mineral product of nitrate-dependent Fe(II) oxidation, as evidenced by XRD data and TEM diffraction patterns. The results of this study highlight the importance of iron-bearing clay minerals in the global nitrogen cycle with potential applications in nitrate removal in soils.

  8. Real-time Measurement of Secondary Organic Aerosols From The Photo-oxidation of Toluene Using Atmospheric Pressure Chemical Ionisation Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Collin, F.; Arias, M. C.; Merritt, J. V.; Hastie, D. R.

    A system has been developed to study the chemical composition of secondary or- ganic aerosol (SOA) from the photo-oxidation of hydrocarbons using real-time atmo- spheric pressure chemical ionisation triple quadrupole mass spectrometry (APCI/MS- MS) analysis. To complement existing work with a smog chamber, a two-litre dynamic reaction cell has been built. This has a residence time of around two minutes (instead of several hours for smog chamber experiments), thus permitting on-line analysis. Sample gases are introduced into the air stream and irradiated by a 1000 W xenon arc lamp. Af- ter dilution, some of the mixture from the reaction cell is introduced in the MS ion source via a heated probe, with the particle number density being determined by a condensation nucleus counter on the remainder. The focus so far has been on SOA from the photo-oxidation of toluene by HO radicals in presence of NO, with the HO radicals being generated by the photolysis of Isopy- lNitrite (IPN). Prior to performing analyses on the SOA, target compounds (detected in the particulate phase in other studies) were selected and three ions designated to make a fingerprint for each compound. Finally, by using either a denuder, a granu- lar bed diffusion battery or a filter, both gas and particulate phases have been studied independently and compared. Preliminary results show that a number of target compounds, such as methylglyoxylic acid, benzaldehyde or cresol, have been detected in both gas and particulate phases. Most of these compounds appear to be present mainly in the gas phase. An exhaustive identification of organic compounds is a part of the on-going work.

  9. Indium-catalyzed oxidative cross-dehydrogenative coupling of chromenes with 1,3-dicarbonyls and aryl rings.

    PubMed

    Li, Fanmei; Meng, Zhilin; Hua, Jing; Li, Wei; Lou, Hongxiang; Liu, Lei

    2015-05-28

    An effective indium-catalyzed oxidative cross-dehydrogenative coupling of electronically varied chromenes with 1,3-dicarbonyl compounds and aryl rings has been established. Both the C-H alkylation and arylation proceed smoothly at room temperature to afford diverse ?-substituted chromene compounds in up to 91% yields. Besides these two types of C-H components, simple ketones like cyclohexanones also prove to be well tolerated. PMID:25897807

  10. Self-assembly of a superparamagnetic raspberry-like silica/iron oxide nanocomposite using epoxy-amine coupling chemistry.

    PubMed

    Cano, Manuel; de la Cueva-Méndez, Guillermo

    2015-02-28

    The fabrication of colloidal nanocomposites would benefit from controlled hetero-assembly of ready-made particles through covalent bonding. Here we used epoxy-amine coupling chemistry to promote the self-assembly of superparamagnetic raspberry-like nanocomposites. This adaptable method induced the covalent attachment of iron oxide nanoparticles sparsely coated with amine groups onto epoxylated silica cores in the absence of other reactants. PMID:25635377

  11. Copper-mediated cross-coupling-cyclization-oxidation: a one-pot reaction to construct polysubstituted pyrroles.

    PubMed

    Liu, Pei; Liu, Jin-ling; Wang, Heng-shan; Pan, Ying-ming; Liang, Hong; Chen, Zhen-Feng

    2014-05-14

    A novel and efficient procedure for the synthesis of polysubstituted pyrroles has been developed in this work. The polysubsituted pyrroles were synthesized directly from terminal alkenes, amines and ?-keto esters through cross-coupling-cyclization-oxidation in the presence of a catalytic amount of cuprous chloride. This method provides a one-pot synthesis route from terminal alkenes to polysubstituted pyrroles for the first time and opens a new area in cuprous catalysis. PMID:24481463

  12. Control of sulfidogenesis through bio-oxidation of H2S coupled to (per)chlorate reduction.

    PubMed

    Gregoire, Patrick; Engelbrektson, Anna; Hubbard, Christopher G; Metlagel, Zoltan; Csencsits, Roseann; Auer, Manfred; Conrad, Mark E; Thieme, Jürgen; Northrup, Paul; Coates, John D

    2014-12-01

    We investigated H2S attenuation by dissimilatory perchlorate-reducing bacteria (DPRB). All DPRB tested oxidized H2S coupled to (per)chlorate reduction without sustaining growth. H2S was preferentially utilized over organic electron donors resulting in an enriched (34S)-elemental sulfur product. Electron microscopy revealed elemental sulfur production in the cytoplasm and on the cell surface of the DPRB Azospira suillum. Based on our results, we propose a novel hybrid enzymatic-abiotic mechanism for H2S oxidation similar to that recently proposed for nitrate-dependent Fe(II) oxidation. The results of this study have implications for the control of biosouring and biocorrosion in a range of industrial environments. PMID:25756108

  13. Iron-Catalyzed Oxidative C-H/C-H Cross-Coupling between Electron-Rich Arenes and Alkenes.

    PubMed

    Ma, Yiyang; Zhang, Dongchao; Yan, Zhiyuan; Wang, Mengfan; Bian, Changliang; Gao, Xinlong; Bunel, Emilio E; Lei, Aiwen

    2015-05-01

    A novel oxidative C-H/C-H cross-coupling reaction between electron-rich arenes and alkenes is established utilizing FeCl3 as the catalyst and DDQ as the oxidant. Interestingly, direct arylation products are obtained with diaryl-ethylenes and double arylation products are obtained with styrene derivatives, which show high chemoselectivity and good substrate scope. A radical trapping experiment and EPR (electron paramagnetic resonance) experiments indicate that this reaction proceeds through a radical pathway in which DDQ plays a key role in the aryl radical formation. XAFS (X-ray absorption fine structure) experiments reveal that the oxidation state of the iron catalyst does not change during the reaction, suggesting that FeCl3 might be used as a Lewis acid. Finally, a detailed mechanism is proposed for this transformation. PMID:25860622

  14. Advancing tandem solar cells by spectrally selective multilayer intermediate reflectors.

    PubMed

    Hoffmann, Andre; Paetzold, Ulrich W; Zhang, Chao; Merdzhanova, Tsvetelina; Lambertz, Andreas; Ulbrich, Carolin; Bittkau, Karsten; Rau, Uwe

    2014-08-25

    Thin-film silicon tandem solar cells are composed of an amorphous silicon top cell and a microcrystalline silicon bottom cell, stacked and connected in series. In order to match the photocurrents of the top cell and the bottom cell, a proper photon management is required. Up to date, single-layer intermediate reflectors of limited spectral selectivity are applied to match the photocurrents of the top and the bottom cell. In this paper, we design and prototype multilayer intermediate reflectors based on aluminum doped zinc oxide and doped microcrystalline silicon oxide with a spectrally selective reflectance allowing for improved current matching and an overall increase of the charge carrier generation. The intermediate reflectors are successfully integrated into state-of-the-art tandem solar cells resulting in an increase of overall short-circuit current density by 0.7 mA/cm(2) in comparison to a tandem solar cell with the standard single-layer intermediate reflector. PMID:25322181

  15. Tandem resonator reflectance modulator

    DOEpatents

    Fritz, Ian J. (Albuquerque, NM); Wendt, Joel R. (Albuquerque, NM)

    1994-01-01

    A wide band optical modulator is grown on a substrate as tandem Fabry-Perot resonators including three mirrors spaced by two cavities. The absorption of one cavity is changed relative to the absorption of the other cavity by an applied electric field, to cause a change in total reflected light, as light reflecting from the outer mirrors is in phase and light reflecting from the inner mirror is out of phase with light from the outer mirrors.

  16. Tandem resonator reflectance modulator

    DOEpatents

    Fritz, I.J.; Wendt, J.R.

    1994-09-06

    A wide band optical modulator is grown on a substrate as tandem Fabry-Perot resonators including three mirrors spaced by two cavities. The absorption of one cavity is changed relative to the absorption of the other cavity by an applied electric field, to cause a change in total reflected light, as light reflecting from the outer mirrors is in phase and light reflecting from the inner mirror is out of phase with light from the outer mirrors. 8 figs.

  17. Studies of nitrile oxide cycloadditions, and the phenolic oxidative coupling of vanillin aldoxime by Geobacillus sp. DDS012 from Italian rye grass silage.

    PubMed

    Kelly, David R; Baker, Simon C; King, David S; de Silva, Deepa S; Lord, Gwyn; Taylor, Jason P

    2008-02-21

    During studies directed towards the discovery of nitrile hydrolysing enzymes from thermophiles, vanillin aldoxime was incubated with the thermophilic organism, Geobacillus sp. DDS012 isolated from Italian rye grass (Lolium multiflorum) silage. The predominant product was a dihydro-dimer, which could only be characterised by LC-MS. This was initially imagined to be the product of cycloaddition of vanillin aldoxime with the corresponding nitrile oxide, but preparation of the supposed adduct and model studies excluded this possibility. The rate constant for the second order dimerisation of 4-O-acetyl vanillin nitrile oxide was measured (1.21 x 10(-4) M(-1) s(-1), 0.413 M, 25 degrees C) and the (13)C-NMR signal for the nitrile oxide carbon was observed (delta(C) 34.4, br. t (1)J(13)C,(14)N circa 50 Hz). Treatment of vanillin aldoxime with potassium persulfate and iron sulfate gave material with the same LC-MS properties as the natural product, which is therefore identified as 5,5'-dehydro-di-(vanillin aldoxime) 1d formed by phenolic oxidative coupling. PMID:18264580

  18. Indium-zinc-oxide electric-double-layer thin-film transistors gated by silane coupling agents 3-triethoxysilylpropylamine–graphene oxide solid electrolyte

    NASA Astrophysics Data System (ADS)

    Guo, Liqiang; Huang, Yukai; Shi, Yangyang; Cheng, Guanggui; Ding, Jianning

    2015-07-01

    Silane coupling agents 3-triethoxysilylpropyla-mine-graphene oxide (KH550-GO) solid electrolyte are prepared by spin coating process. A high proton conductivity of ~1.2???×???10?3 Scm?1 is obtained at room temperature. A strong electric-double-layer (EDL) effect is observed due to the accumulation of protons at KH550-GO/IZO interface. Indium-Zinc-Oxide thin film transistors gated by KH550-GO solid electrolyte are self-assembled on ITO glass substrates. Good electrical performances are obtained, such as a low subthreshold swing of ~140?mV/dec., a high current on/off ratio of ~2.9???×???107 and a high field-effect mobility of ~13.2?cm2 V?1 S?1, respectively.

  19. High throughput sample preparation in combination with gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-MS/MS): a smart procedure for (ultra)trace analysis of brominated flame retardants in fish.

    PubMed

    Kalachova, Kamila; Cajka, Tomas; Sandy, Chris; Hajslova, Jana; Pulkrabova, Jana

    2013-02-15

    In this study, gas chromatography (GC) coupled to triple quadrupole tandem mass spectrometry (MS/MS) operated in electron ionisation mode (EI) has been shown to be an effective tool for the (ultra)trace analysis of several representative brominated flame retardants (BFRs) including polybrominated diphenyl ethers (PBDEs), pentabromotoluene (PBT), pentabromoethylbenzene (PBEB), etc. in complex food and environmental matrices. Using this type of instrumentation, improved selectivity and sensitivity of the instrumental analysis was achieved. In addition to GC-MS/MS (EI), a GC-MS method employing QqQ as a single quadrupole in negative chemical ionisation (NCI) mode was also developed, as this technique might be preferred for those compounds where EI did not provide suitable (intensive enough) mass transitions (e.g., decabromodiphenyl ethane). Following the development of the GC-MS/MS method, a substantial simplification of the sample preparation method was achieved by employing an ethyl acetate QuEChERS-based extraction followed by silica minicolumn clean-up. Using this novel approach, six samples may be prepared in approx. one hour, thus significant time savings were achieved compared to routinely used methods. In addition, the method employs the reduced amounts of organic solvent and other chemicals. Under the optimised conditions, recoveries of all target analytes using both GC-MS/MS (EI) and GC-MS (NCI) were within the range of 70-119% and repeatabilities of the analytical procedure were ? 16% at all three spiking levels (0.1, 1 and 5 ?g kg(-1)). Regarding quantification limits (LOQs), as expected, a single quadruple operated in NCI provided significantly lower LOQs compared to EI. However, using the triple quadrupole mass analyser, comparable LOQs were achieved for both methods (0.005-1 ?g kg(-1) and 0.005-0.1 ?g kg(-1) for GC-MS/MS (EI) and GC-MS (NCI), respectively). Moreover, when highly selective mass transitions in GC-MS/MS (EI) were used for identification and quantification, a significant decrease of problematic interferences was observed compared to NCI where most of the compounds were quantified according to the less selective m/z 79 corresponding to a bromine atom. PMID:23597996

  20. The SUMO E3-ligase PIAS1 couples reactive oxygen species-dependent JNK activation to oxidative cell death

    PubMed Central

    Leitao, Beatriz B.; Jones, Marius C.; Brosens, Jan J.

    2011-01-01

    Human endometrial stromal cells (HESCs) exposed to reactive oxygen species (ROS) mount a hypersumoylation response in a c-Jun N-terminal kinase (JNK)-dependent manner. The mechanism that couples JNK signaling to the small ubiquitin-related modifier (SUMO) pathway and its functional consequences are not understood. We show that ROS-dependent JNK activation converges on the SUMO pathway via PIAS1 (protein inhibitor of activated STAT1). Unexpectedly, PIAS1 knockdown not only prevented ROS-dependent hypersumoylation but also enhanced JNK signaling in HESCs. Conversely, PIAS overexpression increased sumoylation of various substrates, including c-Jun, yet inhibited basal and ROS-dependent JNK activity independently of its SUMO ligase function. Expression profiling demonstrated that PIAS1 knockdown enhances and profoundly modifies the transcriptional response to oxidative stress signals. Using a cutoff of 2-fold change or more, a total of 250 ROS-sensitive genes were identified, 97 of which were not dependent on PIAS1. PIAS1 knockdown abolished the regulation of 43 genes but also sensitized 110 other genes to ROS. Importantly, PIAS1 silencing was obligatory for the induction of several cellular defense genes in response to oxidative stress. In agreement, PIAS1 knockdown attenuated ROS-dependent caspase-3/7 activation and subsequent apoptosis. Thus, PIAS1 determines the level of JNK activity in HESCs, couples ROS signaling to the SUMO pathway, and promotes oxidative cell death.—Leitao, B. B., Jones, M. C., Brosens, J. J. The SUMO E3-ligase PIAS1 couples reactive oxygen species-dependent JNK activation to oxidative cell death. PMID:21676946

  1. Oxidative coupling of the pyrogallol Bring with a galloyl group during enzymatic oxidation of epigallocatechin 3- O-gallate

    Microsoft Academic Search

    Yan Li; Takashi Tanaka; Isao Kouno

    2007-01-01

    In order to clarify the mechanism for formation of catechin oligomers during the fermentation stage of black tea manufacture, epigallocatechin-3-O-gallate, the most abundant tea flavanol in fresh tea leaves, was enzymatically oxidized and the resulting unstable quinone metabolites were converted to phenazine derivatives by treatment with o-phenylenediamine. In addition to formation of monomeric and dimeric derivatives, four trimeric derivatives were

  2. CO2-promoted oxidative cross-coupling reaction for C-S bond formation via masked strategy in an odourless way.

    PubMed

    Qiao, Zongjun; Ge, Nanyang; Jiang, Xuefeng

    2015-06-11

    Cu-catalyzed direct oxidative cross-coupling between boronic acids and masked sulfides delivering thioethers was described, in which the SO3(-), as a mask, has shown a distinctive effect on the oxidative cross-coupling condition. Disulfide could be suppressed efficiently via masked strategy under CO2 atmosphere. A broad scope of aromatics and scalable processes indicates its practicality, which could be further applied to drug late-stage modification and unsymmetrical dibenzothiophenes (DBTs) synthesis. PMID:26022891

  3. Phenol wastewater remediation: advanced oxidation processes coupled to a biological treatment

    Microsoft Academic Search

    A. Rubalcaba; M. E. Suárez-Ojeda; F. Stüber; A. Fortuny; C. Bengoa; I. Metcalfe; J. Carrera; A. Fabregat

    2007-01-01

    Nowadays, there are increasingly stringent regulations requiring more and more treatment of industrial effluents to generate product waters which could be easily reused or disposed of to the environment without any harmful effects. Therefore, different advanced oxidation processes were investigated as suitable precursors for the biological treatment of industrial effluents containing phenol. Wet air oxidation and Fenton process were tested

  4. Peroxidase-Catalyzed Oxidative Coupling of Phenols in the Presence of Geosorbents

    SciTech Connect

    Huang, Qingguo; Weber, Walter J., Jr.

    2003-03-26

    This study focuses on elucidation of the reaction behaviors of peroxidase-mediated phenol coupling in the presence of soil/sediment materials. Our goal is a mechanistic understanding of the influences of geosorbent materials on enzymatic coupling reactions in general and the development of methods for predicting such influences. Extensive experimental investigations of coupling reactions were performed under strategically selected conditions in systems containing model geosorbents having different properties and chemical characteristics. The geosorbents tested were found to influence peroxidase-mediated phenol coupling through one or both of two principal mechanisms; i.e., (1) mitigation of enzyme inactivation and/or (2) participation in cross-coupling reactions. Such influences were found to correlate with the chemical characteristics of the sorbent materials and to be simulated well by a modeling approach designed in this paper. The results of the study have important implications for potential engineering implementation and enhancement of enzymatic coupling reactions in soil/subsurface remediation practice.

  5. Monolithic tandem solar cell

    DOEpatents

    Wanlass, Mark W. (Golden, CO)

    1994-01-01

    A single-crystal, monolithic, tandem, photovoltaic solar cell is described which includes (a) an InP substrate having upper and lower surfaces, (b) a first photoactive subcell on the upper surface of the InP substrate, (c) a second photoactive subcell on the first subcell; and (d) an optically transparent prismatic cover layer over the second subcell. The first photoactive subcell is GaInAsP of defined composition. The second subcell is InP. The two subcells are lattice matched.

  6. Monolithic tandem solar cell

    DOEpatents

    Wanlass, Mark W. (Golden, CO)

    1991-01-01

    A single-crystal, monolithic, tandem, photovoltaic solar cell is described which includes (a) an InP substrate having upper and lower surfaces, (b) a first photoactive subcell on the upper surface of the InP substrate, and (c) a second photoactive subcell on the first subcell. The first photoactive subcell is GaInAsP of defined composition. The second subcell is InP. The two subcells are lattice matched. The solar cell can be provided as a two-terminal device or a three-terminal device.

  7. Synfuels from fusion: producing hydrogen with the Tandem Mirror Reactor and thermochemical cycles

    SciTech Connect

    Werner, R.W.; Ribe, F.L.

    1981-01-21

    This volume contains the following sections: (1) the Tandem Mirror fusion driver, (2) the Cauldron blanket module, (3) the flowing microsphere, (4) coupling the reactor to the process, (5) the thermochemical cycles, and (6) chemical reactors and process units. (MOW)

  8. Iodine(III)-mediated oxidative cross-coupling of enamines and propargylamines under metal-free conditions: an alternative way to prepare highly substituted 3-pyrrolines.

    PubMed

    Zheng, Chen; Wang, Yu; Fan, Renhua

    2015-02-20

    A PhIO/Bu4NI-mediated oxidative cross-coupling reaction between enamines and propargylamines under metal-free conditions has been developed. Bu4NI works as an activator of PhIO. The resulting coupling products are ready to undergo copper(II)-mediated electrophilic cyclization to form highly substituted 3-pyrrolines. PMID:25658698

  9. The Efficacy of Oxidative Coupling for Promoting In-Situ Immobilization of Hydroxylated Aromatics in Contaminated Soil and Sediments Systems - Final Report

    SciTech Connect

    Weber Jr., W. J.

    2000-10-01

    The study clearly shows that the structure and composition of the organic matter of soils and sediments are essential considerations for the selection of materials for engineered applications of oxidative coupling processes. A rate model was developed to facilitate quantitative evaluation and mechanistic interpretation of these fairly complex coupling processes.

  10. Photoelectrocatalytic/photoelectro-Fenton coupling system using a nanostructured photoanode for the oxidation of a textile dye: Kinetics study and oxidation pathway.

    PubMed

    Almeida, Lucio C; Silva, Bianca F; Zanoni, Maria V B

    2015-10-01

    In this study, a coupled photoelectrocatalytic/photoelectro-Fenton reactor was designed to enhance the degradation efficiency of organic pollutants and tested using the azo dye Orange G as a model compound. Pt-decorated TiO2 nanotubes were used as a photoanode with an air-diffusion polytetrafluoroethylene cathode for H2O2 generation. The sum of individual effects of coupling the photoelectrocatalytic and photoelectro-Fenton processes was evaluated as a function of the decolorization and mineralization of Orange G solutions. The dye solutions were only completely decolorized in more acidic conditions (pH 3.0). The mineralization of the Orange G solutions increased in the sequence photoelectrocatalyticcoupled photoelectrocatalytic/photoelectro-Fenton due to the gradual increase in the production of OH radicals. Total organic carbon reductions of 80% for photoelectrocatalysis, 87% for electro-Fenton and 97% for the coupled processes were obtained when using an applied electric charge per unit volume of electrolyzed solution of 200mAhL(-1). The Orange G decays for all treatments followed pseudo-first-order kinetics, suggesting the attack of a constant concentration of OH radicals. Aromatics such as naphthalenic and benzenic compounds were formed as by-products and were identified using LC-MS/MS analysis. In addition, the generated aliphatic acids were identified using ion-exclusion high-performance liquid chromatography. The final by-products of oxalic and formic acid were identified as ultimate by-products and formed Fe(III) complexes that were rapidly mineralized to CO2 by UV-Vis irradiation. Then, according to the identified oxidation by-products, a plausible pathway was proposed for the degradation of Orange G dye by the coupled process. PMID:25935699

  11. Alkyne hydroacylation: switching regioselectivity by tandem ruthenium catalysis.

    PubMed

    Chen, Qing-An; Cruz, Faben A; Dong, Vy M

    2015-03-11

    By using tandem Ru-catalysis, internal alkynes can be coupled with aldehydes for the synthesis of ?,?-unsaturated ketones. The catalyst promotes alkyne transformations with high regioselectivity, with examples that include the differentiation of a methyl vs ethyl substituent on the alkyne. Mechanistic studies suggest that the regioselectivity results from a selective allene formation that is governed by allylic strain. PMID:25608143

  12. Tandem constructs: preventing the rise of superweeds.

    PubMed

    Gressel, J

    1999-09-01

    Transgenic crops may interbreed with nearby weeds, increasing their competitiveness, and may themselves become a 'volunteer' weed in the following crop. The desired transgene can be coupled in tandem with genes that would render hybrid offspring or volunteer weeds less able to compete with crops, weeds and wild species. Genes that prevent seed shatter or secondary dormancy, or that dwarf the recipient could all be useful for mitigation and may have value to the crop. Many such genes have been isolated in the past few years. PMID:10461182

  13. Carbon-coated magnetic palladium: applications in partial oxidation of alcohols and coupling reactions.

    EPA Science Inventory

    Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; catalyst can be used for oxidation of alcohols, amination reaction and arylation of aryl halides (cross coupli...

  14. Steady-state properties of coupled systems in mitochondrial oxidative phosphorylation.

    PubMed Central

    Hill, T L

    1980-01-01

    At steady state there is effective coupling among various otherwise independent membrane and internal mitochondrial systems that share the same substrates or ligands (e.g., H+, Ca2+, Pi, ADP, ATP). The number of different systems, coupled through shared substrates or ligands, is no doubt very large. But, just as an infinite series can be approximated by a finite number of terms, here the number of systems included in the analysis can be limited, as an approximation. In two previous papers, the basic but oversimplified set of four tightly coupled systems was studied. These are: respiratory chain; reverse ATPase; proton-phosphate cotransport; and ADP-ATP exchange. Essentially as illustrations of the methodology required for a more realistic analysis, two much more complicated examples are formulated here: eight tightly coupled systems, and the original four systems but with the tight coupling relaxed in two of these four. PMID:6248859

  15. Synthesis of highly functionalized 9,10-phenanthrenequinones by oxidative coupling using MoCl5.

    PubMed

    Trosien, Simon; Waldvogel, Siegfried R

    2012-06-15

    The strong oxidative power of molybdenum pentachloride gives rise to an efficient oxidative C-C bond formation of benzil derivatives to the corresponding 9,10-phenanthrenequinones. A highly complementary method to previous approaches was developed. The required derivatives are accessible in a modular fashion and in excellent yields. By this approach the orchid-derived natural product cypripediquinone A was synthesized for the first time. PMID:22655861

  16. Study on anaerobic ammonium oxidation process coupled with denitrification microbial fuel cells (MFCs) and its microbial community analysis.

    PubMed

    Li, Chao; Ren, Hongqiang; Xu, Ming; Cao, Jiashun

    2014-11-01

    Denitrifying MFC was successfully coupled with anaerobic ammonium oxidation process in this study. With the help of cathode electrons, the stoichiometry relationship ?(-)NH3-N:?(-)NO2(-)-N:?(+)NO3(-)-N was approximate 1:1.37:0.03 during the stable operation, which demonstrated its further nitrite and nitrate reduction. According to microbial community analysis, Candidatus Brocadia sinica was the main anammox community, and Rhodopseudomonas palustris with electrochemical driven denitrifying ability, especially enriched in biofilm. Higher abundance of nirK genes in biofilm (compare to the control) and invariable amx genes in suspended sludge were responsible for its better nitrogen removal. The sludge and biofilm performed their own duties on anammox and denitrification, respectively, according to genes quantification. Under the totally autotrophic system, electron donors were "concentrated supplied" and easy to control, which avoided the suppression of anammox growth, making this autotrophic coupling process appears to be more promising. PMID:25459866

  17. A metalloenzyme-like catalytic system for the chemoselective oxidative cross-coupling of primary amines to imines under ambient conditions.

    PubMed

    Largeron, Martine; Fleury, Maurice-Bernard

    2015-02-23

    The direct oxidative cross-coupling of primary amines is a challenging transformation as homocoupling is usually preferred. We report herein the chemoselective preparation of cross-coupled imines through the synergistic combination of low loadings of Cu(II) metal-catalyst and o-iminoquinone organocatalyst under ambient conditions. This homogeneous cooperative catalytic system has been inspired by the reaction of copper amine oxidases, a family of metalloenzymes with quinone organic cofactors that mediate the selective oxidation of primary amines to aldehydes. After optimization, the desired cross-coupled imines are obtained in high yields with broad substrate scope through a transamination process that leads to the homocoupled imine intermediate, followed by dynamic transimination. The ability to carry out the reactions at room temperature and with ambient air, rather than molecular oxygen as the oxidant, and equimolar amounts of each coupling partner is particularly attractive from an environmentally viewpoint. PMID:25643811

  18. Nitrogen isotope fractionation during archaeal ammonia oxidation: Coupled estimates from isotopic measurements of ammonium and nitrite

    NASA Astrophysics Data System (ADS)

    Mooshammer, Maria; Stieglmeier, Michaela; Bayer, Barbara; Jochum, Lara; Melcher, Michael; Wanek, Wolfgang

    2014-05-01

    Ammonia-oxidizing archaea (AOA) are ubiquitous in marine and terrestrial environments and knowledge about the nitrogen (N) isotope effect associated with their ammonia oxidation activity will allow a better understanding of natural abundance isotope ratios, and therefore N transformation processes, in the environment. Here we examine the kinetic isotope effect for ammonia oxidation in a pure soil AOA culture (Ca. Nitrososphaera viennensis) and a marine AOA enrichment culture. We estimated the isotope effect from both isotopic signatures of ammonium and nitrite over the course of ammonia oxidation. Estimates of the isotope effect based on the change in the isotopic signature of ammonium give valuable insight, because these estimates are not subject to the same concerns (e.g., accumulation of an intermediate) as estimates based on isotopic measurements of nitrite. Our results show that both the pure soil AOA culture and a marine AOA enrichment culture have similar but substantial isotope effect during ammonia consumption (31-34 per mill; based on ammonium) and nitrite production (43-45 per mill; based on nitrite). The 15N fractionation factors of both cultures tested fell in the upper range of the reported isotope effects for archaeal and bacterial ammonia oxidation (10-41 per mill) or were even higher than those. The isotope fractionation for nitrite production was significantly larger than for ammonium consumption, indicating that (1) some intermediate (e.g., hydroxylamine) of ammonia oxidation accumulates, allowing for a second 15N fractionation step to be expressed, (2) a fraction of ammonia oxidized is lost via gaseous N forms (e.g., NO or N2O), which is 15N-enriched or (3) a fraction of ammonium is assimilated into AOA biomass, biomass becoming 15N-enriched. The significance of these mechanisms will be explored in more detail for the soil AOA culture, based on isotope modeling and isotopic measurements of biomass and N2O.

  19. Galvanizing couplings in an ammoniate electrolyte with a high zinc oxide content

    Microsoft Academic Search

    Ao V. Kireeva; R. M. Barabash; T. A. Zasukhina

    1977-01-01

    Production of gas and water pipes 75.5 mm in diameter has been introduced at our plant. Galvanized couplings 2.5 in. in diameter are needed to join the pipes..at a number of plants, couplings are galvanized by the hot-dipping or electrochemical methods in stationary baths and on automated lines, ks a rule, galvanizing in stationary baths employs a sulfuric acid electrolyte

  20. Simulation of a catalytic membrane reactor for oxidative coupling of methane

    SciTech Connect

    Cheng, S.; Shuai, X. [Univ. of British Columbia, Vancouver, British Columbia (Canada). Dept. of Chemical Engineering] [Univ. of British Columbia, Vancouver, British Columbia (Canada). Dept. of Chemical Engineering

    1995-06-01

    There is considerable interest in direct and indirect conversion of methane to more valuable products such as basic feedstock and liquid fuel. However, total oxidation of methane leading to useless carbon dioxide and water is thermodynamically favored over the formation of ethane and ethylene, and in addition the desired C{sub 2} products tend to undergo further oxidation. Considerable efforts screening a large number of mainly metal oxide-based catalysts have been made to obtain a suitable one active and especially selective toward the desired C{sub 2} products, and the C{sub 2} yield of up to 30% has been reported. There are few studies regarding the potential advantages of using membrane reactors in the conversion of methane. The authors report here a simulation study showing that using a catalytic membrane reactor would greatly improve the selectivity and yield to C{sub 2} compounds, compared with the conventional cofeed operation.

  1. Fueling of tandem mirror reactors

    SciTech Connect

    Gorker, G.E.; Logan, B.G.

    1985-01-01

    This paper summarizes the fueling requirements for experimental and demonstration tandem mirror reactors (TMRs), reviews the status of conventional pellet injectors, and identifies some candidate accelerators that may be needed for fueling tandem mirror reactors. Characteristics and limitations of three types of accelerators are described; neutral beam injectors, electromagnetic rail guns, and laser beam drivers. Based on these characteristics and limitations, a computer module was developed for the Tandem Mirror Reactor Systems Code (TMRSC) to select the pellet injector/accelerator combination which most nearly satisfies the fueling requirements for a given machine design.

  2. A new optically pumped tandem magnetometer: principles and experiences

    NASA Astrophysics Data System (ADS)

    Pulz, E.; Jäckel, K.-H.; Linthe, H.-J.

    1999-11-01

    In this paper we describe a new design for an optically pumped tandem magnetometer situated at the GeoForschungsZentrum Potsdam. A tandem magnetometer combines the fast response of a self-oscillating vapour magnetometer with the accuracy of a narrow line Mz-type magnetometer. A newly patented method of coupling the two sensors avoids any stray magnetic fields and so allows a compact design of the instrument itself, as well as facilitating its operation in close proximity to other magnetometers. A prototype Cs-K tandem magnetometer for use in magnetic observatories is described. We then show typical results of a long-term comparison with both a second type of optically pumped magnetometer and an Overhauser proton magnetometer. Finally, a resuméis given of four years of continuous operation of this new type of magnetometer with respect to the data quality produced and its operational reliability.

  3. Electro-mechanical coupling of semiconductor film grown on stainless steel by oxidation

    E-print Network

    Volinsky, Alex A.

    of oxidation films must be considered as additional stress corrosion cracking mechanisms. VC 2013 AIP to stress corrosion cracking (SCC) is poor, especially in chloride-containing environments.4 The SCC G. Wang,1 L. Q. Guo,1 L. J. Qiao,1,a) and Alex A. Volinsky1,2 1 Corrosion and Protection Center, Key

  4. Coupling of transcriptional response to oxidative stress and secondary metabolism regulation in filamentous fungi.

    PubMed

    Montibus, Mathilde; Pinson-Gadais, Laëtitia; Richard-Forget, Florence; Barreau, Christian; Ponts, Nadia

    2015-08-01

    To survive sudden and potentially lethal changes in their environment, filamentous fungi must sense and respond to a vast array of stresses, including oxidative stresses. The generation of reactive oxygen species, or ROS, is an inevitable aspect of existence under aerobic conditions. In addition, in the case of fungi with pathogenic lifestyles, ROS are produced by the infected hosts and serve as defense weapons via direct toxicity, as well as effectors in fungal cell death mechanisms. Filamentous fungi have thus developed complex and sophisticated responses to evade oxidative killing. Several steps are determinant in these responses, including the activation of transcriptional regulators involved in the control of the antioxidant machinery. Gathering and integrating the most recent advances in knowledge of oxidative stress responses in fungi are the main objectives of this review. Most of the knowledge coming from two models, the yeast Saccharomyces cerevisiae and fungi of the genus Aspergillus, is summarized. Nonetheless, recent information on various other fungi is delivered when available. Finally, special attention is given on the potential link between the functional interaction between oxidative stress and secondary metabolism that has been suggested in recent reports, including the production of mycotoxins. PMID:24041414

  5. Enantioselective synthesis of arylglycine derivatives by direct C-H oxidative cross-coupling.

    PubMed

    Wei, Xiao-Hong; Wang, Gang-Wei; Yang, Shang-Dong

    2015-01-18

    A new method for the synthesis of chiral ?-amino acid derivatives by enantioselective C-H arylation of N-aryl glycine esters with aryl boric acids in the presence of a chiral Pd(II)-catalyst has been developed. This work successfully integrates the direct C-H oxidation with asymmetric arylation and exhibits excellent enantioselectivity. PMID:25348347

  6. Limestone Corrosion by Neutrophilic Sulfur-Oxidizing Bacteria: A Coupled Microbe-Mineral System

    Microsoft Academic Search

    Elspeth S. Steinhauer; Christopher R. Omelon; Philip C. Bennett

    2010-01-01

    Subsurface karst aquifers receiving sulfidic water can host complex chemolithotrophic microbial communities that are capable of dissolving limestone, forming new karstic habitat. Neutrophilic sulfur-oxidizing bacteria use reduced sulfur compounds as energy rich substrate, potentially producing sulfuric acid as a geochemically reactive byproduct. The physicochemical relationship between a biofilm forming on a limestone surface and the extent of microbial influence on

  7. Access to cinnamyl derivatives from arenes and allyl esters by a biomimetic aerobic oxidative dehydrogenative coupling.

    PubMed

    Gigant, Nicolas; Bäckvall, Jan-E

    2014-03-21

    An efficient biomimetic aerobic oxidative dehydrogenative alkenylation of arenes with allyl esters is presented. The reaction proceeds under an ambient pressure of oxygen with relatively low catalyst loading of palladium acetate, employing catalytic amounts of electron-transfer mediators (ETMs). This study represents a new environmentally friendly method for the synthesis of cinnamyl derivatives. PMID:24606049

  8. A computational study on enzymatically driven oxidative coupling of chlorophenols: an indirect dehalogenation reaction.

    PubMed

    Szatkowski, Lukasz; Dybala-Defratyka, Agnieszka

    2013-04-01

    Density functional theory calculations have been used to describe the mechanism of the dimerization reaction catalyzed by peroxidases and predict whether it could be accompanied by chlorine isotopic fractionation when various chlorophenols are used as their substrates. Since free radicals formed during the catalytic cycle of peroxidases can undergo coupling reactions (either radical-radical or radical-molecule) that can lead to dimers and also polymers formation four different pathways have been considered: radical-anion, radical-cation, radical-radical (singlet state) and radical-radical (triplet state). The following substrates have been investigated: 2-chlorophenol, 4-chlorophenol, 2,4,6-trichlorophenol and 4-chloro-2,6-dimethylphenol. Based on the obtained energetic profiles radical-cation and radical-radical (singlet) coupling seem to be the most probable. Radical-anion coupling although energetically more expensive should not be disregarded taking into account the excess of the anionic form of the substrate being provided in the course of enzymatic reaction. Upon dimer formation halogen is released during radical-anion and radical-radical triplet coupling. However only the latter pathway exhibits chlorine isotopic fractionation. Radical-cation and radical-radical singlet couplings are two-step reactions where the second step comprises intramolecular chlorine transfer accompanied by large chlorine isotope effect. PMID:23273327

  9. Pd loaded amphiphilic COF as catalyst for multi-fold Heck reactions, C-C couplings and CO oxidation.

    PubMed

    Mullangi, Dinesh; Nandi, Shyamapada; Shalini, Sorout; Sreedhala, Sheshadri; Vinod, Chathakudath P; Vaidhyanathan, Ramanathan

    2015-01-01

    COFs represent a class of polymers with designable crystalline structures capable of interacting with active metal nanoparticles to form excellent heterogeneous catalysts. Many valuable ligands/monomers employed in making coordination/organic polymers are prepared via Heck and C-C couplings. Here, we report an amphiphilic triazine COF and the facile single-step loading of Pd(0) nanoparticles into it. An 18-20% nano-Pd loading gives highly active composite working in open air at low concentrations (Conc. Pd(0) <0.05?mol%, average TON 1500) catalyzing simultaneous multiple site Heck couplings and C-C couplings using 'non-boronic acid' substrates, and exhibits good recyclability with no sign of catalyst leaching. As an oxidation catalyst, it shows 100% conversion of CO to CO2 at 150?°C with no loss of activity with time and between cycles. Both vapor sorptions and contact angle measurements confirm the amphiphilic character of the COF. DFT-TB studies showed the presence of Pd-triazine and Pd-Schiff bond interactions as being favorable. PMID:26057044

  10. An inorganic approach to wet-chemical fabrication of 3rd generation tandem cells

    Microsoft Academic Search

    Meng Tao

    2006-01-01

    The article consists of a Powerpoint presentation on wet chemical fabrication for 3rd generation solar cell. The paper concludes that semiconducting metal oxides for 3rd generation solar cells; all wet-chemical fabrication process; multijunction tandem cells; Deposition of mixed-valence metal oxides for suitable band gaps; doping to control conduction type and conductivity in metal oxides; mixed-valence metal oxides and electrochemical deposition

  11. Cross-over from antiferromagnetic to ferromagnetic interface exchange coupling in epitaxial ferromagnetic oxides

    NASA Astrophysics Data System (ADS)

    Singamaneni, Srinivasa Rao; Prater, John T.; Narayan, Jay

    2015-03-01

    Interface magnetism in La0.7Sr0.3MnO3/SrRuO3 (LSMO/SRO) bilayer (BL) has been the subject of great interest in the recent past owing to interesting physics and potential applications. Through a novel approach, LSMO (131nm)/SRO (45nm) and LSMO (33nm)/SRO (45nm) bilayers have been epitaxially integrated with Si (100). Notably, in the former sample, positive exchange bias is observed -indication of antiferromagnetic exchange coupling and is found to be absent in the later. Interestingly, in the former sample, the cross-over from antiferromagnetic to ferromagnetic interface exchange coupling is noticed by varying the cooling field. We have verified that the coupling is of magnetic origin, not due to electrostatic interaction by inserting a thin (~ 10nm) SrTiO3 layer between LSMO and SRO. We believe that the formation of interface domain walls and strong interplay among Zeeman, anisotropy and exchange energies could play a dominant role. Our results would have important implications for the physics of magnetic exchange coupled systems.

  12. Proton-coupled electron transfer and multielectron oxidations in complexes of ruthenium and osmium

    Microsoft Academic Search

    Dovletoglou

    1992-01-01

    This doctoral research concerns the mechanism of proton-coupled electron transfer over an extended pH range. These processes between ruthenium and osmium complexes and hydroquinones have been studied using spectrophotometric methods and cyclic voltammetry. Elucidation of the mechanistic details has been attempted by using isotopic labelling, kinetic analysis, and numerical simulation of complex kinetic schemes. The coordination and redox chemistry of

  13. Regioselective decarboxylative cross-coupling of carboxy isoquinoline N-oxides.

    PubMed

    Rouchet, Jean-Baptiste E Y; Schneider, Cédric; Fruit, Corinne; Hoarau, Christophe

    2015-06-01

    A straightforward method for direct decarboxylative arylation of 1- and 3-carboxy isoquinaldic acid N-oxides with aryl iodides is reported. The reaction proceeded selectively at the carboxy function site to exclusively give the corresponding C-1 or C-3 arylated product. This methodology tolerates various aryl iodides substituted by electronically different groups. Combined with subsequent Reissert-Henze chlorination and SNAr amination, the decarboxylative arylation provides an efficient access to 1,3-functionalized isoquinoline-based antitumor agent. PMID:25938169

  14. Room Temperature Oxidation of Secondary Alcohols by Bromate-Bromide Couple in Acidic Water

    Microsoft Academic Search

    Sanna Pääkkönen; Jouni Pursiainen; Marja Lajunen

    2011-01-01

    The use of environmentally benign reactions is currently an important aspect in the field of synthetic chemistry. Here we report a high yield method to oxidize aliphatic or aromatic secondary alcohols into corresponding ketones by using nonhazardous and inexpensive BrOH reagent at room temperature in water. BrOH reagent was derived from NaBr and NaBrO3 in aqueous acid. Based on presented

  15. Room-Temperature Oxidation of Secondary Alcohols by Bromate–Bromide Coupling in Acidic Water

    Microsoft Academic Search

    Sanna Pääkkönen; Jouni Pursiainen; Marja Lajunen

    2012-01-01

    The use of environmentally benign reactions is currently an important topic in the field of synthetic chemistry. Here we report a high-yielding method to oxidize aliphatic or aromatic secondary alcohols into corresponding ketones using nonhazardous and inexpensive BrOH reagent at room temperature in water. BrOH reagent was derived from NaBr and NaBrO3 in aqueous acid. Based on the presented results,

  16. Overview of the Applications of Tandem Mass Spectrometry (MS\\/MS) in Food Analysis of Nutritionally Harmful Compounds

    Microsoft Academic Search

    Stamatia I. Kotretsou; Aglaia Koutsodimou

    2006-01-01

    Tandem mass spectrometry (MS\\/MS) has proved to be a useful and a time saving analytical tool, with many applications of direct detection of target molecules in food samples. When coupled with chromatographic techniques, it combines the separation capabilities of chromatography and the power of MS\\/MS as an identification and confirmation method. This article reviews the use of tandem mass spectrometry

  17. 76 FR 40935 - Vertical Tandem Lifts in Marine Terminals; Extension of the Office of Management and Budget's...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-07-12

    ...OSHA-2011-0066] Vertical Tandem Lifts in Marine Terminals; Extension of the Office of Management...Vertical Tandem Lifts (VTLs) in Marine Terminals (29 CFR part 1917). The collection...transporting vertically coupled containers in a terminal. DATES: Comments must be...

  18. Oxidative coupling of methane over (Na 2WO 4+Mn or Ce)\\/SiO 2 catalysts: In situ measurement of electrical conductivity

    Microsoft Academic Search

    Zeinab Gholipour; Azim Malekzadeh; Reza Hatami; Yadollah Mortazavi; Abasali Khodadadi

    2010-01-01

    The effects of manganese oxide or ceria promoters on the performance of Na2WO4\\/SiO2 catalysts for oxidative coupling of methane (OCM) are reported. The OCM reaction was performed in a continuous-flow microreactor at 800 °C, atmospheric pressure and under GHSV = 13200 ml·gCat?1·h?1. Catalysts were characterized by in situ conductivity measurement, FT-IR spectroscopy, XRD, SEM and temperature programmed reduction analysis. Manganese

  19. Direct determination of trace elements in niobium, tantalum and their oxides by inductively coupled plasma atomic emission spectrometry after microwave dissolution

    Microsoft Academic Search

    O. N. Grebneva; I. V. Kubrakova; T. F. Kudinova; N. M. Kuz'min

    1997-01-01

    Analytical schemes for the determination of trace elements in high-purity niobium, tantalum and their oxides are proposed. The schemes are based on microwave dissolution of the metals and oxides followed by inductively coupled plasma atomic emission spectrometry (ICP-AES) determination of impurities in the solutions. The possibilities of interelement and off-peak background corrections in ICP-AES analysis are discussed. The accuracy of

  20. CHARACTERIZATION OF DOXYLAMINE AND PYRILAMINE METABOLITES VIA THERMOSPRAY/MASS SPECTROMETRY AND TANDEM MASS SPECTROMETRY

    EPA Science Inventory

    Analysis of doxylamine N-oxide and pyrilamine N-oxide as synthetic standards and biologically derived metabolites by thermospray mass spectrometry (TSP/MS) provided (M + H)+ ions for each metabolite. TSP/tandem mass spectrometry (TSP/MS/MS) of the (M + H)+ ions provided fragment ...

  1. Tandem pump assembly

    SciTech Connect

    Dzioba, D.L.

    1986-05-06

    In combination, an engine having an oil pan containing oil at a certain level, a tandem pump arrangement is described mounted in the oil pan, the pump arrangement comprising an oil pump for delivering the oil under pressure to lubricate the engine and a vacuum pump for establishing a vacuum, the oil pump having two meshing gears of different pitch diameter adapted to produce oil pumping action by their meshing engagement upon drive to the one gear having the larger pitch diameter and the drive thereby of the other gear having the smaller pitch diameter at a higher speed, drive means for connecting the engine to drive the one gear. The vacuum pump has an input connected to be driven by the other gear whereby the vacuum pump is driven through the the oil pump at increased speed with an overdrive ratio determined by the ratio of the pitch diameters of the gears, the vacuum pump being lubricated by the oil in the oil pan and having an exhaust line exiting in the oil pan above the oil level so as to ensure return of such oil to the oil pan.

  2. Hydrophobic monolayered nanoflakes of tungsten oxide: coupled exfoliation and fracture in a nonpolar organic medium.

    PubMed

    Honda, Masashi; Oaki, Yuya; Imai, Hiroaki

    2015-06-01

    Coupled exfoliation and fracture induced formation of hydrophobic monolayered nanoflakes in a nonpolar organic medium. The hydrophobic monolayered nanoflakes 5-20 nm in lateral size consisted of a tungstate layer with surface modification by stearylammonium ions (C18H37NH3)0.397 H0.603Cs3W11O35·xH2O (x < 0.625). PMID:26009313

  3. Ultra high performance liquid chromatography with photodiode array detector and quadrupole time-of-flight tandem mass spectrometry coupled with discriminant analysis to evaluate Angelicae pubescentis radix from different regions.

    PubMed

    Ge, Ai-Hua; Ma, Wen-Fang; Wang, Chun-Peng; Li, Jin; He, Jun; Liu, Er-Wei; Adelakum, Tiwalade Adegoke; Zhang, Bo-Li; Gao, Xiumei; Chang, Yan-Xu

    2014-09-01

    A rapid and effective method was developed for the qualitative and quantitative analysis of the major chemical constituents in Angelicae pubescentis radix by ultra high performance liquid chromatography with photodiode array detection and quadrupole time-of-flight tandem mass spectrometry. The chromatographic separation was achieved on an ACQUITY UHPLC BEH C18 column (2.1 × 100 mm, 1.7 ?m). Nine phenolic acids, 30 coumarins, bisabolangelone, and adenosine were identified by quadrupole time-of-flight tandem mass spectrometry. All calibration curves exhibited good linearity (r > 0.9996) within the linear ranges. The relative standard deviation calculated for intraday and interday precision, stability, and accuracy were <5%. The mean recovery ranged from 95.8 to 106%. The overall limits of detection and quantification were 0.025-0.160 and 0.100-0.560 ?g/mL, respectively. Discriminant analysis was investigated as a method for evaluating the quality of the samples with 100% correction in their classification. The results demonstrated that the developed method could successfully be used to differentiate samples from different regions and could be a helpful tool for detection and confirmation of the quality of traditional Chinese medicines. PMID:25044521

  4. Doped Mott Insulators in (111) Bilayers of Perovskite Transition-Metal Oxides with a Strong Spin-Orbit Coupling

    SciTech Connect

    Okamoto, Satoshi [ORNL

    2013-01-01

    The electronic properties of Mott insulators realized in (111) bilayers of perovskite transition-metal oxides are studied. The low-energy effective Hamiltonians for such Mott insulators are derived in the presence of a strong spin-orbit coupling. These models are characterized by the antiferromagnetic Heisenberg interaction and the anisotropic interaction whose form depends on the $d$ orbital occupancy. From exact diagonalization analyses on finite clusters, the ground state phase diagrams are derived, including a Kitaev spin liquid phase in a narrow parameter regime for $t_{2g}$ systems. Slave-boson mean-field analyses indicate the possibility of novel superconducting states induced by carrier doping into the Mott-insulating parent systems, suggesting the present model systems as unique playgrounds for studying correlation-induced novel phenomena. Possible experimental realizations are also discussed.

  5. Glutamate Utilization Couples Oxidative Stress Defense and the Tricarboxylic Acid Cycle in Francisella Phagosomal Escape

    PubMed Central

    Ramond, Elodie; Gesbert, Gael; Rigard, Mélanie; Dairou, Julien; Dupuis, Marion; Dubail, Iharilalao; Meibom, Karin; Henry, Thomas; Barel, Monique; Charbit, Alain

    2014-01-01

    Intracellular bacterial pathogens have developed a variety of strategies to avoid degradation by the host innate immune defense mechanisms triggered upon phagocytocis. Upon infection of mammalian host cells, the intracellular pathogen Francisella replicates exclusively in the cytosolic compartment. Hence, its ability to escape rapidly from the phagosomal compartment is critical for its pathogenicity. Here, we show for the first time that a glutamate transporter of Francisella (here designated GadC) is critical for oxidative stress defense in the phagosome, thus impairing intra-macrophage multiplication and virulence in the mouse model. The gadC mutant failed to efficiently neutralize the production of reactive oxygen species. Remarkably, virulence of the gadC mutant was partially restored in mice defective in NADPH oxidase activity. The data presented highlight links between glutamate uptake, oxidative stress defense, the tricarboxylic acid cycle and phagosomal escape. This is the first report establishing the role of an amino acid transporter in the early stage of the Francisella intracellular lifecycle. PMID:24453979

  6. One-electron oxidation of DNA: reaction at thymine.

    PubMed

    Joseph, Joshy; Schuster, Gary B

    2010-11-14

    The feature article is a review of the reaction of thymine in the one-electron oxidation of duplex DNA. Oxidation of DNA causes chemical reactions that result in remote damage (mutation) to a nucleobase. Normally this reaction occurs at guanine, but in oligonucleotides that lack guanines, or when the DNA contains a thymine-thymine mispair, reaction occurs primarily at thymine notwithstanding its high oxidation potential. Selective substitution of uracil for thymine in TT sequences indicates the operation of a tandem reaction mechanism at adjacent thymines. Analysis of the reaction products suggests that proton-coupled electron transfer generates the 5-thymidyl methyl radical, which is trapped by molecular oxygen to give eventually 5-formyl-2'-deoxyuridine and 5-(hydroxymethyl)-2'-deoxyuridine. In a second process, water adds to the 5,6-double bond of the oxidized thymine giving eventually the cis- and trans-diastereomers of 5,6-dihydroxy-5,6-dihydrothymidine. PMID:20830420

  7. Oxidative Reactivity and Cytotoxic Properties of a Platinum(II) Complex Prepared by Outer-Sphere Amide Bond Coupling

    PubMed Central

    Wilson, Justin J.; Lippard, Stephen J.

    2012-01-01

    Benzyl amine was coupled to the dangling carboxylic acid groups of the platinum(II) complex [Pt(edda)Cl2], where edda = ethylenediamine-N,N’-diacetic acid, to give the diamidetethered complex [Pt(L)Cl2] (1), where L = ethylenediamine-N,N’-bis(N-benzylacetamide). Complex 1 was oxidized with both PhICl2 and Br2. Oxidation with PhICl2 cleanly afforded the tetrachloride complex, [Pt(L)Cl4] (2), whereas oxidation with Br2 gave rise to several mixed halide complexes of the general formula, [Pt(L)ClxBr4-x], where x = 1, 2, or 3. Complexes 1 and 2 were fully characterized by 1H, 13C, and 195Pt NMR spectroscopy, as well as by ESI-MS. These compounds exist as a mixture of diastereomers that arise from the chirality of the two coordinated nitrogen atoms. Crystal structures of 1, 2, and [Pt(L)ClxBry] (3) are reported. Although refined as the tetrabromide complex [Pt(L)Br4], the crystal structure of 3 is a mixture of species with site-occupancy disorder of chloride and bromide ligands. DFT calculations indicate that the two sets of diastereomers of 1 and 2 are effectively thermoneutral, a conclusion that is also supported by the observation of both members of each pair by NMR spectroscopy. The cytotoxicity of 1 and 2 was measured by the MTT assay in HeLa cells and compared to that of cisplatin. Both exhibit IC50 values close to 50 ?M and are therefore substantially less toxic than cisplatin, for which the IC50 is 1 ?M. PMID:24489429

  8. Nitric oxide mediates metabolic coupling of omentum-derived adipose stroma to ovarian and endometrial cancer cells.

    PubMed

    Salimian Rizi, Bahar; Caneba, Christine; Nowicka, Aleksandra; Nabiyar, Ahmad W; Liu, Xinran; Chen, Kevin; Klopp, Ann; Nagrath, Deepak

    2015-01-15

    Omental adipose stromal cells (O-ASC) are a multipotent population of mesenchymal stem cells contained in the omentum tissue that promote endometrial and ovarian tumor proliferation, migration, and drug resistance. The mechanistic underpinnings of O-ASCs' role in tumor progression and growth are unclear. Here, we propose a novel nitric oxide (NO)-mediated metabolic coupling between O-ASCs and gynecologic cancer cells in which O-ASCs support NO homeostasis in malignant cells. NO is synthesized endogenously by the conversion of l-arginine into citrulline through nitric oxide synthase (NOS). Through arginine depletion in the media using l-arginase and NOS inhibition in cancer cells using N(G)-nitro-l-arginine methyl ester (l-NAME), we demonstrate that patient-derived O-ASCs increase NO levels in ovarian and endometrial cancer cells and promote proliferation in these cells. O-ASCs and cancer cell cocultures revealed that cancer cells use O-ASC-secreted arginine and in turn secrete citrulline in the microenvironment. Interestingly, citrulline increased adipogenesis potential of the O-ASCs. Furthermore, we found that O-ASCs increased NO synthesis in cancer cells, leading to decrease in mitochondrial respiration in these cells. Our findings suggest that O-ASCs upregulate glycolysis and reduce oxidative stress in cancer cells by increasing NO levels through paracrine metabolite secretion. Significantly, we found that O-ASC-mediated chemoresistance in cancer cells can be deregulated by altering NO homeostasis. A combined approach of targeting secreted arginine through l-arginase, along with targeting microenvironment-secreted factors using l-NAME, may be a viable therapeutic approach for targeting ovarian and endometrial cancers. PMID:25425006

  9. Proton-coupled electron transfer and multielectron oxidations in complexes of ruthenium and osmium

    SciTech Connect

    Dovletoglou, A.

    1992-01-01

    This doctoral research concerns the mechanism of proton-coupled electron transfer over an extended pH range. These processes between ruthenium and osmium complexes and hydroquinones have been studied using spectrophotometric methods and cyclic voltammetry. Elucidation of the mechanistic details has been attempted by using isotopic labelling, kinetic analysis, and numerical simulation of complex kinetic schemes. The coordination and redox chemistry of polypyridyl-acetylacetonato and -oxalato complexes of ruthenium and the role of ancillary ligands in defining the properties of Ru[sup IV]O complexes were explored. These studies represent the first attempt to probe possible 2e[sup [minus

  10. Monomolecular layers and thin films of silane coupling agents by vapor-phase adsorption on oxidized aluminum

    SciTech Connect

    Kurth, D.G.; Bein, T. [Purdue Univ., West Lafayette, IN (United States)

    1992-08-06

    Thin films of tetraethoxysilane [TEOS], (3-bromopropyl)trimethoxysilane [BPS], trimethoxyvinylsilane [VS], and 3-(trimethoxysilyl) propyl methacrylate [TPM] on oxidized aluminum surfaces have been investigated by reflection-absorption FTIR spectroscopy, ellipsometry, contact angle, and quartz crystal microbalance (QCM) measurements. Gravimetric measurements with the QCM can reveal quantitative aspects of adsorption and film formation, even for films as thin as monolayers. Adsorption of these silane coupling agents from solution typically produces multilayer films. Vapor-phase adsorption of TEOS and TPM at room temperature results in monomolecular layers. The coupling agents VS and BPS require additional heating after the vapor-phase adsorption to initiate the hydrolysis and condensation reactions necessary for the surface attachment, which produces one to three layers. For vapor adsorbed films a packing density of 4-7 molecules/nm{sup 2} was found. The data strongly suggest that the organic moieties in several of these films have a preferential orientation on the surface; they can be viewed as two-dimensional, oligomeric siloxane networks with oriented organic chains. Subsequent heating of TPM films results in structural rearrangements; heating of TEOS results in complete condensation to SiO{sub 2} films. 43 refs., 6 figs., 4 tabs.

  11. Strongly coupled Pd nanotetrahedron/tungsten oxide nanosheet hybrids with enhanced catalytic activity and stability as oxygen reduction electrocatalysts.

    PubMed

    Lu, Yizhong; Jiang, Yuanyuan; Gao, Xiaohui; Wang, Xiaodan; Chen, Wei

    2014-08-20

    The design and synthesis of highly active oxygen reduction reaction (ORR) catalysts with strong durability at low cost is extremely desirable but still remains a significant challenge. Here we develop an efficient strategy that utilizes organopalladium(I) complexes containing palladium-palladium bonds as precursors for the synthesis of strongly coupled Pd tetrahedron-tungsten oxide nanosheet hybrids (Pd/W18O49) to improve the electrocatalytic activity and stability of Pd nanocrystals. The hybrid materials are synthesized by direct nucleation, growth, and anchoring of Pd tetrahedral nanocrystals on the in situ-synthesized W18O49 nanosheets. Compared to supportless Pd nanocrystals and W18O49, their hybrids exhibited not only surprisingly high activity but also superior stability to Pt for the ORR in alkaline solutions. X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, and electrochemical analyses indicated that the enhanced electrocatalytic activity and durability are associated with the increased number and improved catalytic activity of active sites, which is induced by the strong interaction between the Pd tetrahedrons and W18O49 nanosheet supports. The present study provides a novel strategy for synthesizing hybrid catalysts with strong chemical attachment and electrical coupling between nanocatalysts and supports. The strategy is expected to open up exciting opportunities for developing a novel class of metal-support hybrid nanoelectrocatalysts with improved ORR activity and durability for both fuel cells and metal-air batteries. PMID:25054583

  12. Tandem Cylinder Noise Predictions

    NASA Technical Reports Server (NTRS)

    Lockhard, David P.; Khorrami, Mehdi R.; CHoudhari, Meelan M.; Hutcheson, Florence V.; Brooks, Thomas F.; Stead, Daniel J.

    2007-01-01

    In an effort to better understand landing-gear noise sources, we have been examining a simplified configuration that still maintains some of the salient features of landing-gear flow fields. In particular, tandem cylinders have been studied because they model a variety of component level interactions. The present effort is directed at the case of two identical cylinders spatially separated in the streamwise direction by 3.7 diameters. Experimental measurements from the Basic Aerodynamic Research Tunnel (BART) and Quiet Flow Facility (QFF) at NASA Langley Research Center (LaRC) have provided steady surface pressures, detailed off-surface measurements of the flow field using Particle Image Velocimetry (PIV), hot-wire measurements in the wake of the rear cylinder, unsteady surface pressure data, and the radiated noise. The experiments were conducted at a Reynolds number of 166 105 based on the cylinder diameter. A trip was used on the upstream cylinder to insure a fully turbulent shedding process and simulate the effects of a high Reynolds number flow. The parallel computational effort uses the three-dimensional Navier-Stokes solver CFL3D with a hybrid, zonal turbulence model that turns off the turbulence production term everywhere except in a narrow ring surrounding solid surfaces. The current calculations further explore the influence of the grid resolution and spanwise extent on the flow and associated radiated noise. Extensive comparisons with the experimental data are used to assess the ability of the computations to simulate the details of the flow. The results show that the pressure fluctuations on the upstream cylinder, caused by vortex shedding, are smaller than those generated on the downstream cylinder by wake interaction. Consequently, the downstream cylinder dominates the noise radiation, producing an overall directivity pattern that is similar to that of an isolated cylinder. Only calculations based on the full length of the model span were able to capture the complete decay in the spanwise correlation, thereby producing reasonable noise radiation levels.

  13. Proton conducting sodium alginate electrolyte laterally coupled low-voltage oxide-based transistors

    NASA Astrophysics Data System (ADS)

    Liu, Yang Hui; Qiang Zhu, Li; Shi, Yi; Wan, Qing

    2014-03-01

    Solution-processed sodium alginate electrolyte film shows a high proton conductivity of ˜5.5 × 10-3 S/cm and a high lateral electric-double-layer (EDL) capacitance of ˜2.0 ?F/cm2 at room temperature with a relative humidity of 57%. Low-voltage in-plane-gate indium-zinc-oxide-based EDL transistors laterally gated by sodium alginate electrolytes are fabricated on glass substrates. The field-effect mobility, current ON/OFF ratio, and subthreshold swing of such EDL transistors are estimated to be 4.2 cm2 V-1 s-1, 2.8 × 106, and 130 mV/decade, respectively. At last, a low-voltage driven resistor-load inverter is also demonstrated. Such in-plane-gate EDL transistors have potential applications in portable electronics and low-cost biosensors.

  14. Manifold, bus support and coupling arrangement for solid oxide fuel cells

    DOEpatents

    Parry, G.W.

    1988-04-21

    Individual, tubular solid oxide fuel cells (SOFCs) are assembled into bundles called a module within a housing, with a plurality of modules arranged end-to-end in a linear, stacked configuration called a string. A common set of piping comprised of a suitable high temperature resistant material (1) provides fuel and air to each module housing, (2) serves as electrically conducting buses, and (3) provides structural support for a string of SOFC modules. Ceramic collars are used to connect fuel and air inlet piping to each of the electrodes in an SOFC module and provide (1) electrical insulation for the current carrying bus bars and gas manifolds, (2) damping for the fuel and air inlet piping, and (3) proper spacing between the fuel and air inlet piping to prevent contact between these tubes and possible damage to the SOFC. 11 figs.

  15. Proton conducting sodium alginate electrolyte laterally coupled low-voltage oxide-based transistors

    SciTech Connect

    Liu, Yang Hui; Wan, Qing, E-mail: wanqing@nju.edu.cn [Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201 (China); School of Electronic Science and Engineering, Nanjing University, Nanjing 210093 (China); Qiang Zhu, Li, E-mail: lqzhu@nimte.ac.cn [Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201 (China); Shi, Yi [School of Electronic Science and Engineering, Nanjing University, Nanjing 210093 (China)

    2014-03-31

    Solution-processed sodium alginate electrolyte film shows a high proton conductivity of ?5.5?×?10{sup ?3} S/cm and a high lateral electric-double-layer (EDL) capacitance of ?2.0??F/cm{sup 2} at room temperature with a relative humidity of 57%. Low-voltage in-plane-gate indium-zinc-oxide-based EDL transistors laterally gated by sodium alginate electrolytes are fabricated on glass substrates. The field-effect mobility, current ON/OFF ratio, and subthreshold swing of such EDL transistors are estimated to be 4.2 cm{sup 2} V{sup ?1} s{sup ?1}, 2.8?×?10{sup 6}, and 130?mV/decade, respectively. At last, a low-voltage driven resistor-load inverter is also demonstrated. Such in-plane-gate EDL transistors have potential applications in portable electronics and low-cost biosensors.

  16. Opiate, cannabinoid, and eicosanoid signaling converges on common intracellular pathways nitric oxide coupling.

    PubMed

    Fimiani, C; Liberty, T; Aquirre, A J; Amin, I; Ali, N; Stefano, G B

    1999-01-01

    Scientific fields as they emerge initially appear to be unrelated to other projects even if they are in a similar area of interest. This is especially true in the case of opiate, cannabinoid, and eicosanoid signaling processes. In this limited speculative review, we attempt to examine aspects of their intracellular cascading signaling systems for their commonalities. We find intracellular calcium mobilization, nuclear factor kappa B involvement, adenylate cyclase activity, and, finally, constitutive nitric oxide release to be converging points for these signaling processes, occurring by separate and distinct receptor-mediated effector systems. Phosphokinase C, mitogen activated protein kinase, and cytosolic phospholipase A2 also represent points of common impact. In this regard, aspirin also appears to be involved in an aspect of this signaling convergence. We conclude that many of the physiological observations regarding the actions of these signaling molecules, for example, immunosuppression, neurotransmission, vasodilation, cellular adherence, and cytotoxicity, can now be understood by considering their converging biochemical cascades. PMID:10367294

  17. Manifold, bus support and coupling arrangement for solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Parry, Gareth W.

    1988-04-01

    Individual, tubular solid oxide fuel cells (SOFCs) are assembled into bundles called a module within a housing, with a plurality of modules arranged end-to-end in a linear, stacked configuration called a string. A common set of piping comprised of a suitable high temperature resistant material: (1) provides fuel and air to each module housing, (2) serves as electrically conducting buses, and (3) provides structural support for a string of SOFC modules. Ceramic collars are used to connect fuel and air inlet piping to each of the electrodes in an SOFC module and provide: (1) electrical insulation for the current carrying bus bars and gas manifolds, (2) damping for the fuel and air inlet piping, and (3) proper spacing between the fuel and air inlet piping to prevent contact between these tubes and possible damage to the SOFC.

  18. Isolation and Characterization of Microbes Mediating Thermodynamically Favorable Coupling of Anaerobic Oxidation of Methane and Metal Reduction

    NASA Astrophysics Data System (ADS)

    Glass, J. B.; Reed, B. C.; Sarode, N. D.; Kretz, C. B.; Bray, M. S.; DiChristina, T. J.; Stewart, F. J.; Fowle, D. A.; Crowe, S.

    2014-12-01

    Methane is the third most reduced environmentally relevant electron donor for microbial metabolisms after organic carbon and hydrogen. In anoxic ecosystems, the major sink for methane is anaerobic oxidation of methane (AOM) mediated by syntrophic microbial consortia that couple AOM to reduction of an oxidized electron acceptor to yield free energy. In marine sediments, AOM is generally coupled to reduction of sulfate despite an extremely small amount of free energy yield because sulfate is the most abundant electron acceptor in seawater. While AOM coupled to Fe(III) and Mn(IV) reduction (Fe- and Mn-AOM) is 10-30x more thermodynamically favorable than sulfate-AOM, and geochemical data suggests that it occurs in diverse environments, the microorganisms mediating Fe- and Mn-AOM remain unknown. Lake Matano, Indonesia is an ideal ecosystem to enrich for Fe- and Mn-AOM microbes because its anoxic ferruginous deep waters and sediments contain abundant Fe(III), Mn(IV) and methane, and extremely low sulfate and nitrate. Our research aims to isolate and characterize the microbes mediating Fe- and Mn-AOM from three layers of Lake Matano sediments through serial enrichment cultures in minimal media lacking nitrate and sulfate. 16S rRNA amplicon sequencing of sediment inoculum revealed the presence of the Fe(III)-reducing bacterium Geobacter (5-10% total microbial community in shallow sediment and 35-60% in deeper sediment) as well as 1-2% Euryarchaeota implicated in methane cycling, including ANME-1 and 2d and Methanosarcinales. After 90 days of primary enrichment, all three sediment layers showed high levels of Fe(III) reduction (60-90 ?M Fe(II) d-1) in the presence of methane compared to no methane and heat-killed controls. Treatments with added Fe(III) as goethite contained higher abundances of Geobacter than the inoculum (60-80% in all layers), suggesting that Geobacter may be mediating Fe(III) reduction in these enrichments. Quantification of AOM rates is underway, and will be used to estimate the plausibility of metal-AOM as a thermodynamically favorable methane sink in anoxic ecosystems of both the modern and ancient Earth.

  19. Frontispiece: a visible light photocatalytic cross-dehydrogenative coupling/dehydrogenation/6?-cyclization/oxidation cascade: synthesis of 12-nitroindoloisoquinolines from 2-aryltetrahydroisoquinolines.

    PubMed

    Rusch, Fabian; Unkel, Lisa-Natascha; Alpers, Dirk; Hoffmann, Frank; Brasholz, Malte

    2015-06-01

    Cross-Dehydrogenative Coupling The photocatalytic C1-functionalization of 2-aryltetrahydroisoquinolines by cross-dehydrogenative coupling with nitroalkanes is a well-established method for the preparation of 1-nitroalkyl-2-aryl-tetrahydroisoquinolines. In their Communication on page?8336?ff., M. Brasholz et al. describe that these primary coupling products readily undergo a subsequent oxidative cascade cyclization to furnish 12-nitroindolo[2,1-a]isoquinoline derivatives. Key to this hitherto unreported one-pot transformation is the presence of a base, such as K3 PO4 and aminoanthraquinones emerged as the ideal organic photocatalysts. PMID:26014505

  20. Ruthenium-catalyzed oxidative coupling of 2-aryl-4-quinazolinones with olefins: synthesis of pyrrolo[2,1-b]quinazolin-9(1H)-one motifs.

    PubMed

    Zheng, Yong; Song, Wei-Bin; Zhang, Shu-Wei; Xuan, Li-Jiang

    2015-06-21

    A ruthenium-catalyzed oxidative coupling of 2-aryl-quinazolinones with olefins via C-H bond activation followed by an intramolecular aza-Michael reaction is described. This strategy allows the direct and efficient construction of pyrrolo[2,1-b]quinazolin-9(1H)-one scaffolds. PMID:25996242

  1. Oxidative cross-coupling of pyridine N-oxides and ethers between C(sp(2))-H/C(sp(3))-H bonds under transition-metal-free conditions.

    PubMed

    Sun, Wei; Xie, Zuguang; Liu, Jie; Wang, Lei

    2015-04-21

    A novel and efficient method based on the cross-coupling reactions of pyridine N-oxides with ethers between C(sp(2))-H/C(sp(3))-H bonds in the presence of TBHP was developed. The strategy provides an alternative approach to the pyridine moiety under transition-metal-free conditions. PMID:25785666

  2. Automatic Quality Assessment of Peptide Tandem Mass Spectra

    Microsoft Academic Search

    Marshall W. Bern; David Goldberg; W. Hayes Mcdonald; John R. Yates III

    2004-01-01

    Motivation: A powerful proteomics methodology couples high-performance liquid chromatography (HPLC) with tandem mass spectrometry and database-search software, such as SEQUEST. Such a set-up, however, produces a large num- ber of spectra, many of which are of too poor quality to be useful. Hence a filter that eliminates poor spectra before the database search can significantly improve throughput and robustness. Moreover,

  3. Manifold, bus support and coupling arrangement for solid oxide fuel cells

    DOEpatents

    Parry, Gareth W. (East Windsor, CT)

    1989-01-01

    Individual, tubular solid oxide fuel cells (SOFCs) are assembled into bundles called a module within a housing, with a plurality of modules arranged end-to-end in a linear, stacked configuration called a string. A common set of piping comprised of a suitable high temperture resistant material (1) provides fuel and air to each module housing, (2) serves as electrically conducting buses, and (3) provides structural support for a string of SOFC modules. The piping thus forms a manfold for directing fuel and air to each module in a string and makes electrical contact with the module's anode and cathode to conduct the DC power generated by the SOFC. The piping also provides structureal support for each individual module and maintains each string of modules as a structurally integral unit for ensuring high strength in a large 3-dimensional array of SOFC modules. Ceramic collars are used to connect fuel and air inlet piping to each of the electrodes in an SOFC module and provide (1) electrical insulation for the current carrying bus bars and gas manifolds, (2) damping for the fuel and air inlet piping, and (3) proper spacing between the fuel and air inlet piping to prevent contact between these tubes and possible damage to the SOFC.

  4. DNA Damage by Ionizing Radiation: Tandem Double Lesions by Charged Particles

    NASA Technical Reports Server (NTRS)

    Huo, Winifred M.; Chaban, Galina M.; Wang, Dunyou; Dateo, Christopher E.

    2005-01-01

    Oxidative damages by ionizing radiation are the source of radiation-induced carcinogenesis, damage to the central nervous system, lowering of the immune response, as well as other radiation-induced damages to human health. Monte Carlo track simulations and kinetic modeling of radiation damages to the DNA employ available molecular and cellular data to simulate the biological effect of high and low LET radiation io the DNA. While the simulations predict single and double strand breaks and base damages, so far all complex lesions are the result of stochastic coincidence from independent processes. Tandem double lesions have not yet been taken into account. Unlike the standard double lesions that are produced by two separate attacks by charged particles or radicals, tandem double lesions are produced by one single attack. The standard double lesions dominate at the high dosage regime. On the other hand, tandem double lesions do not depend on stochastic coincidences and become important at the low dosage regime of particular interest to NASA. Tandem double lesions by hydroxyl radical attack of guanine in isolated DNA have been reported at a dosage of radiation as low as 10 Gy. The formation of two tandem base lesions was found to be linear with the applied doses, a characteristic of tandem lesions. However, tandem double lesions from attack by a charged particle have not been reported.

  5. Coupled cycles of dissolved oxygen and nitrous oxide in rivers along a trophic gradient in southern Ontario, Canada.

    PubMed

    Rosamond, Madeline S; Thuss, Simon J; Schiff, Sherry L; Elgood, Richard J

    2011-01-01

    Diel (24-h) cycling of dissolved O2 (DO) in rivers is well documented, but evidence for coupled diel changes in DO and nitrogen cycling has only been demonstrated in hypereutrophic systems where DO approaches zero at night. Here, we show diel changes in N2O and DO concentration at several sites across a trophic gradient. Nitrous oxide concentration increased at night at all but one site in spring and summer, even when gas exchange was rapid and minimum water column DO was well above hypoxic conditions. Diel N2O curves were not mirror images of DO curves and were not symmetrical about the mean. Although inter- and intrasite variation was high, N2O peaked around the time of lowest DO at most of the sites. These results suggest that N2O must be measured several times per diel period to characterize curve shape and timing. Nitrous oxide concentration was not significantly correlated with NO3- concentration, contrary to studies in agricultural streams and to the current United Nations Intergovernmental Panel for Climate Change protocols for N2O emission estimation. The strong negative correlation between N2O concentration and daily minimum DO concentration suggested that N2O production was limited by DO. This is consistent with N2O produced by nitrite reduction. The ubiquity of diel N2O cycling suggests that most DO and N2O sampling strategies used in rivers are insufficient to capture natural variability. Ecosystem-level effects of microbial processes, such as denitrification, are sensitive to small changes in redox conditions in the water column even in low-nutrient oxic rivers, suggesting diel cycling of redox-sensitive compounds may exist in many aquatic systems. PMID:21488515

  6. New Effective Material Couple--Oxide Ceramic and Carbon Nanotube-- Developed for Aerospace Microsystem and Micromachine Technologies

    NASA Technical Reports Server (NTRS)

    Miyoshi, Kazuhisa; VanderWal, Randall L.; Tomasek, Aaron J.; Sayir, Ali; Farmer, Serene C.

    2004-01-01

    The prime driving force for using microsystem and micromachine technologies in transport vehicles, such as spacecraft, aircraft, and automobiles, is to reduce the weight, power consumption, and volume of components and systems to lower costs and increase affordability and reliability. However, a number of specific issues need to be addressed with respect to using microsystems and micromachines in aerospace applications--such as the lack of understanding of material characteristics; methods for producing and testing the materials in small batches; the limited proven durability and lifetime of current microcomponents, packaging, and interconnections; a cultural change with respect to system designs; and the use of embedded software, which will require new product assurance guidelines. In regards to material characteristics, there are significant adhesion, friction, and wear issues in using microdevices. Because these issues are directly related to surface phenomena, they cannot be scaled down linearly and they become increasingly important as the devices become smaller. When microsystems have contacting surfaces in relative motion, the adhesion and friction affect performance, energy consumption, wear damage, maintenance, lifetime and catastrophic failure, and reliability. Ceramics, for the most part, do not have inherently good friction and wear properties. For example, coefficients of friction in excess of 0.7 have been reported for ceramics and ceramic composite materials. Under Alternate Fuels Foundation Technologies funding, two-phase oxide ceramics developed for superior high-temperature wear resistance in NASA's High Operating Temperature Propulsion Components (HOTPC) project and new two-layered carbon nanotube (CNT) coatings (CNT topcoat/iron bondcoat/quartz substrate) developed in NASA's Revolutionary Aeropropulsion Concepts (RAC) project have been chosen as a materials couple for aerospace applications, including micromachines, in the nanotechnology lubrication task because of their potential for superior friction and wearf properties in air and in an ultrahigh vacuum, spacelike environment. At the NASA Glenn Research Center, two-phase oxide ceramic eutectics, Al2O3/ZrO2(Y2O3), were directionally solidified using the laser-float-zone process, and carbon nanotubes were synthesized within a high-temperature tube furnace at 800 C. Physical vapor deposition was used to coat all quartz substrates with 5-nm-thick iron as catalyst and bondcoat, which formed iron islands resembling droplets and serving as catalyst particles on the quartz. A series of scanning electron micrographs showing multiwalled carbon nanotubes directionally grown as aligned "nanograss" on quartz is presented. Unidirectional sliding friction eperiments were conducted at Glenn with the two-layered CNT coatings in contact with the two-phase Al2O3/ZrO2(Y2O3) eutectics in air and in ultrachigh vacuum. The main criteria for judging the performance of the materials couple for solid lubrication and antistick applications in a space environment were the coefficient of friction and the wear resistance (reciprocal of wear rate), which had to be less than 0.2 and greater than 10(exp 5) N(raised dot)/cubic millimetes, respectively, in ultrahigh vacuum. In air, the coefficient of friction for the CNT coatings in contact with Al2O3/ZrO2 (Y2O3) eutectics was 0.04, one-fourth of that for quartz. In an ultrahigh vacuum, the coefficient of friction for CNT coatings in contact with Al2O3/ZrO2 (Y2O3) was one-third of that for quartz. The two-phase Al2O3/ZrO2 (Y2O3) eutectic coupled with the two-layered CNT coating met the coefficient of friction and wear resistance criteria both in air and in an ultrahigh vacuum, spacelike environment. This material's couple can dramatically improve the stiction (or adhesion), friction, and wear resistance of the contacting surfaces, which are major issues for microdevices and micromachines.

  7. Assessing the kinetics of high temperature oxidation of Inconel 617 in a dedicated HTR impure helium facility coupling thermogravimetry and gas phase chromatography

    NASA Astrophysics Data System (ADS)

    Chapovaloff, J.; Rouillard, F.; Combrade, P.; Pijolat, M.; Wolski, K.

    2013-10-01

    A new facility coupling thermogravimetric analysis (TGA) with gas phase chromatography (GPC) has been developed. This facility is dedicated for studying high temperature oxidation of Inconel 617 in impure helium environment containing H2O, H2 and CO at very low partial pressures (in the Pa range), which is representative of the high temperature reactor (HTR) concept developed within the Generation IV Forum. Simultaneous acquisition of mass gain and gas composition has allowed the influence of carbon monoxide and water vapour on the kinetics of oxidation to be studied. GPC measurements of gas consumption have allowed the plotting of individual mass gain curves for oxidation by H2O and CO. During isothermal exposure at 1123 K for 20 h, the oxidation was mainly due to water vapour with a minor contribution of carbon monoxide during the first hours. The contribution of water vapour to the oxidation kinetics was extracted. It was shown to obey a complete parabolic law and to be limited by an interfacial reaction during the first few hours of oxidation and to be controlled by a mixed interfacial and diffusion process, diffusion becoming the rate-determining step for long term oxidation. There was very good agreement between GPC measurements and the experimental TGA results.

  8. Exergy & Economic Analysis of Catalytic Coal Gasifiers Coupled with Solid Oxide Fuel Cells

    SciTech Connect

    Siefert, Nicholas; Litster, Shawn

    2012-01-01

    The National Energy Technology Laboratory (NETL) has undertaken a review of coal gasification technologies that integrate with solid oxide fuel cells (SOFC) to achieve system efficiencies near 60% while capturing and sequestering >90% of the carbon dioxide. One way to achieve an overall system efficiency of greater than 60% is in a power plant in which a catalytic coal gasifier produces a syngas with a methane composition of roughly 25% on a dry volume basis and this is sent to a SOFC, with CO{sub 2} capture occurring either before or after the SOFC. Integration of a catalytic gasifier with a SOFC, as opposed to a conventional entrained flow gasifier, is improved due to (a) decreased exergy destruction inside a catalytic, steam-coal gasifier producing a high-methane content syngas, and (b) decreased exergy destruction in the SOFC due to the ability to operate at lower air stoichiometric flow ratios. For example, thermal management of the SOFC is greatly improved due to the steam-methane reforming in the anode of the fuel cell. This paper has two main goals. First, we converted the levelized cost of electricity (LCOE) estimates of various research groups into an average internal rate of return on investment (IRR) in order to make comparisons between their results, and to underscore the increased rate of return on investment for advanced integrated gasification fuel cell systems with carbon capture & sequestration (IGFC-CCS) compared with conventional integrated gasification combined cycle (IGCC-CCS) systems and pulverized coal combustion (PCC-CCS) systems. Using capital, labor, and fuel costs from previous researchers and using an average price of baseload electricity generation of $61.50 / MW-hr, we calculated inflation-adjusted IRR values of up to 13%/yr for catalytic gasification with pressurized fuel cell and carbon dioxide capture and storage (CCS), whereas we calculate an IRR of ?4%/yr and ?2%/yr for new, conventional IGCC-CCS and PCC-CCS, respectively. If the carbon dioxide is used for enhanced oil recovery rather than for saline aquifer storage, then the IRR values improve to 16%/yr, 10%/yr, and 8%/yr, respectively. For comparison, the IRR of a new conventional IGCC or PCC power plant without CO{sub 2} capture are estimated to be 11%/yr and 15.0%/yr, respectively. Second, we conducted an exergy analysis of two different configurations in which syngas from a catalytic gasifier fuels a SOFC. In the first case, the CO{sub 2} is captured before the SOFC, and the anode tail gas is sent back to the catalytic gasifier. In the second case, the anode tail gas is oxy-combusted using oxygen ion ceramic membranes and then CO{sub 2} is captured for sequestration. In both cases, we find that the system efficiency is greater than 60%. These values compare well with previous system analysis. In future work, we plan to calculate the IRR of these two cases and compare with previous economic analyses conducted at NETL.

  9. Solid-phase extraction coupled with ultra high performance liquid chromatography and electrospray tandem mass spectrometry for the highly sensitive determination of five iodinated X-ray contrast media in environmental water samples.

    PubMed

    Li, Xia; Hu, Junjian; Yin, Daqiang; Hu, Xialin

    2015-06-01

    A highly sensitive method based on solid-phase extraction and ultra high performance liquid chromatography with electrospray tandem mass spectrometry has been developed for simultaneous determination of five iodinated X-ray contrast media in environmental water samples. Various solid-phase extraction cartridges have been evaluated and a combination of LiChrolute EN and ENVI-Carb solid phase extraction cartridges was selected for sample enrichment. The method was comprehensively validated on ground water, tap water, surface water, drinking water, and waste water by the conventional procedures: linearity, method detection limits, accuracy and precision, matrix effects. Good linearity (R(2) > 0.999), low detection limits (0.4-8.1 ng/L), satisfactory recoveries (55.1-109.5%) and precision (0.8-10.0% for intra-day precisions and 0.6-16.5% for inter-day precisions) were obtained for all the target compounds. Iopamidol, iohexol, and diatrizoate in some matrices were affected by matrix effects, which were slightly eased by using the isotope-labeled internal standard. The developed method was successfully applied for real samples collected in Shanghai, China, with detected concentrations up to 2200 ± 200 and 9000 ± 1000 ng/L for iohexol and iopamidol, respectively. PMID:25832295

  10. An analysis method for simultaneous screening of deoxyribonucleic acid-binding active compounds and investigating their mechanisms by ultra-fast liquid chromatography tandem mass spectrometry coupled with fluorescence detection technology.

    PubMed

    Zhang, Cangman; Ren, Biao; Lin, Zongtao; Tong, Lingkun; Wang, Hong; Chen, Shizhong

    2015-02-13

    DNA has been known as the cellular target for many cytotoxic anticancer agents over the years. Discovering DNA-binding compounds has become an active research area, while various DNA-binding mechanisms make the drug discovery even more difficult. In this article, we present a novel analysis method to rapidly identify specific DNA-binding compounds from Pyrrosia lingua (Thunb.) using DNA-dual-fluorescent probes, ethidium bromide and Hoechst 33258, with the technology of ultra-fast liquid chromatography-diode array detector-tandem mass spectrometry and dual-wavelength fluorescence detector (UFLC-DAD-MS(n)-DFLD). Sixty-two compounds were identified, of which 22 were found to be active in DNA-binding. After investigation of their dose-response behaviors and structure-activity relationships, chlorogenic acids and flavonoid glycosides were found to be DNA-binders via both minor groove-binding and intercalation modes. The precision, reproducibility and stability of this method were validated by vitexin. The established system was sensitive, precise, and reliable to be used for both screening of DNA-binding compounds and investigating of their mechanisms. PMID:25616969

  11. Oxidative and stepwise grafting of dopamine inner-sphere redox couple onto electrode material: electron transfer activation of dopamine.

    PubMed

    Ghilane, Jalal; Hauquier, Fanny; Lacroix, Jean-Christophe

    2013-12-01

    The immobilization of dopamine, a neurotransmitter, onto macroelectrode and microelectrode surfaces has been performed following two strategies. The first consists of a one-step grafting based on electrochemical oxidation of an amino group in acidic media. The second is a stepwise process starting with electrochemical grafting of diazonium, leading to the attachment of aryl layer bearing an acidic headgroup, followed by chemical coupling leading to immobilized dopamine molecules onto the electrode surface. Electrochemical, infrared (IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS) analyses evidence that both methods are suitable for the immobilization of dopamine onto millimetric and micronic electrodes. The electrochemical responses of modified electrodes demonstrate that the electroactivity of the attached dopamine layer appears unaffected by the nature of the spacer, alkyl or aryl layers, suggesting that the communication, through tunneling, between the attached dopamine and the electrode is possible. More interestingly, the dopamine-modified electrode exhibits electron transfer activation toward dopamine in solution. As a result, not only does the dopamine modified electrode yield a fast electron transfer with lower ?E(p) (30 mV) than the majority of pretreatment procedures but also the ?E(p) is as small as that observed for more complex surface treatments. PMID:24171668

  12. Magnetization States of All-Oxide Spin Valves Controlled by Charge-orbital Ordering of Coupled Ferromagnets

    PubMed Central

    Wu, Han-Chun; Mryasov, Oleg N.; Abid, Mohamed; Radican, Kevin; Shvets, Igor V.

    2013-01-01

    Charge-orbital ordering is commonly present in complex transition metal oxides and offers interesting opportunities for novel electronic devices. In this work, we demonstrate for the first time that the magnetization states of the spin valve can be directly manipulated by charge-orbital ordering. We investigate the interlayer exchange coupling (IEC) between two epitaxial magnetite layers separated by a nonmagnetic epitaxial MgO dielectric. We find that the state of the charge-orbital ordering in magnetite defines the strength, and even the sign of the IEC. First-principles calculations further show that the charge-orbital ordering modifies the spin polarized electronic states at the Fe3O4/MgO interfaces and results in a sufficiently large phase shift of wave function which are responsible for the observed IEC sign change across Verwey temperature. Our findings may open new interesting avenues for the electric field control of the magnetization states of spin valves via charge-orbital ordering driven IEC sign change. PMID:23665858

  13. A novel use of oxidative coupling reactions for determination of some statins (cholesterol-lowering drugs) in pharmaceutical formulations

    NASA Astrophysics Data System (ADS)

    Ashour, Safwan; Bahbouh, Mahmoud; Khateeb, Mouhammed

    2011-03-01

    New, accurate and reliable spectrophotometric methods for the assay of three statin drugs, atorvastatin calcium (AVS), fluvastatin sodium (FVS) and pravastatin sodium (PVS) in pure form and pharmaceutical formulations have been described. All methods involve the oxidative coupling reaction of AVS, FVS and PVS with 3-methyl-2-benzothiazolinone hydrazone hydrochloride monohydrate (MBTH) in the presence of Ce(IV) in an acidic medium to form colored products with ?max at 566, 615 and 664 nm, respectively. Beer's law was obeyed in the ranges of 2.0-20.0, 4.9-35.4 and 7.0-30.0 ?g mL -1 for AVS-MBTH, FVS-MBTH and PVS-MBTH, respectively. Molar absorptivities for the above three methods were found to be 3.24 × 10 4, 1.05 × 10 4 and 0.68 × 10 4 L mol -1 cm -1, respectively. Statistical treatment of the experimental results indicates that the methods are precise and accurate. The proposed methods have been applied to the determination of the components in commercial forms with no interference from the excipients. A comparative study between the suggested procedures and the official methods for these compounds in the commercial forms showed no significant difference between the two methods.

  14. X-ray absorption spectroscopy studies of spin-orbit coupling in 5d transition metal oxides.

    PubMed

    Cho, Deok-Yong; Park, Junghwan; Yu, Jaejun; Park, Je-Geun

    2012-02-01

    In order to examine the effects of strong valence band spin-orbit coupling (SOC) in 5d transition metal oxides (TMOs), we have investigated the L(2) and L(3) edge white-line intensities of the x-ray absorption spectra of several 5d TMOs. The white-line intensities at both edges are found to decrease monotonously with increasing 5d electron occupancy, while their ratio showed anomalous behavior for late 5d TMOs (IrO(2), PtO(2), and Au(2)O(3)), deviating significantly from the theoretical value of 2 expected for the case of weak SOC. This observation serves as a clear experimental indication of strong SOC effects in 5d TMOs. We also discussed how the 5d TMOs can have charge transfer effects different from their counterpart 5d elemental metals by making comparative studies. Our works demonstrate the importance of j quantum states due to strong SOC in the 5d system. PMID:22227572

  15. Aerobic methane oxidation coupled to denitrification in a membrane biofilm reactor: treatment performance and the effect of oxygen ventilation.

    PubMed

    Sun, Fei-yun; Dong, Wen-yi; Shao, Ming-fei; Lv, Xiao-mei; Li, Ji; Peng, Liang-yu; Wang, Hong-jie

    2013-10-01

    Aerobic methane-oxidation coupled to denitrification (AME-D) process was successfully achieved in a membrane biofilm reactor (MBfR). PVDF membrane was employed to supply the methane and oxygen for biofilm, which was coexistence of methanotrophs and denitrifier. With a feeding NO3(-)-N of 30 mg/L, up to 97% nitrate could be removed stably. The oxygen ventilation modes impacted the denitrification performance remarkably, resulting in different nitrate removal efficiencies and biofilm microorganism distribution. The biofilm sludge showed a high resistance to the DO inhibition, mainly due to the co-existing methanotroph being capable of utilizing oxygen perferentially within biofilm, and create an anoxic micro-environment. The denitrification of both nitrate and nitrite by biofilm sludge conformed to the Monod equation, and the maximum specific nitrate utilization rate (k) ranged from 1.55 to 1.78 NO3(-)-N/g VSS-d. The research findings should be significant to understand the considerable potential of MBfR as a bioprocess for denitrification. PMID:23582221

  16. Tunable electrochemical pH modulation in a microchannel monitored via the proton-coupled electro-oxidation of hydroquinone.

    PubMed

    Contento, Nicholas M; Bohn, Paul W

    2014-07-01

    Electrochemistry is a promising tool for microfluidic systems because it is relatively inexpensive, structures are simple to fabricate, and it is straight-forward to interface electronically. While most widely used in microfluidics for chemical detection or as the transduction mechanism for molecular probes, electrochemical methods can also be used to efficiently alter the chemical composition of small (typically <100 nl) microfluidic volumes in a manner that improves or enables subsequent measurements and sample processing steps. Here, solvent (H2O) electrolysis is performed quantitatively at a microchannel Pt band electrode to increase microchannel pH. The change in microchannel pH is simultaneously tracked at a downstream electrode by monitoring changes in the i-V characteristics of the proton-coupled electro-oxidation of hydroquinone, thus providing real-time measurement of the protonated forms of hydroquinone from which the pH can be determined in a straightforward manner. Relative peak heights for protonated and deprotonated hydroquinone forms are in good agreement with expected pH changes by measured electrolysis rates, demonstrating that solvent electrolysis can be used to provide tunable, quantitative pH control within a microchannel. PMID:25379105

  17. Oxidative coupling of tyrosine and ferulic acid residues: Intra- and extra-protoplasmic occurrence, predominance of trimers and larger products, and possible role in inter-polymeric cross-linking

    Microsoft Academic Search

    Stephen C. Fry

    2004-01-01

    I discuss the range of oxidative phenolic coupling products formed from the tyrosine residues of cell wall glycoproteins and from the feruloyl residues of wall polysaccharides possibly by the action of peroxidases and\\/or laccases. In the cases of both tyrosine- and ferulate-coupling, the coupling products are not confined to dimers but include trimers and probably higher oligomers, which are sometimes

  18. Simultaneous speciation of selenium and sulfur species in selenized odorless garlic ( Allium sativum L. Shiro) and shallot ( Allium ascalonicum) by HPLC–inductively coupled plasma-(octopole reaction system)-mass spectrometry and electrospray ionization-tandem mass spectrometry

    Microsoft Academic Search

    Yasumitsu Ogra; Kazuya Ishiwata; Yuji Iwashita; Kazuo T. Suzuki

    2005-01-01

    The simultaneous speciation of selenium and sulfur in selenized odorless garlic (Allium sativum L. Shiro) and a weakly odorous Allium plant, shallot (Allium ascalonicum), was performed by means of a hyphenated technique, a HPLC coupled with an inductively coupled plasma-mass spectrometry (HPLC–ICP-MS) equipped with an octopole reaction system (ORS). The aqueous extracts of them contained the common seleno compound that

  19. Insights into the effects of surface properties of oxides on the catalytic activity of Pd for C-C coupling reactions

    NASA Astrophysics Data System (ADS)

    Zhang, Sai; Li, Jing; Gao, Wei; Qu, Yongquan

    2015-02-01

    Understanding the interaction between Pd nanocatalysts and metal oxide supports for heterogeneous C-C coupling reactions is still ambiguous since many factors influence the catalytic behavior of Pd nanocatalysts. Herein, three porous nanorods of CeO2 with controllable surface properties were employed as supports for Pd nanocatalysts with similar dispersion, which avoided the impact of other factors including surface area, morphology and accessible active sites. It provides an ideal approach to probe synergetic catalytic behavior of metal nanoparticles on supports. The results obtained by studying three C-C coupling reactions (Ullman, Suzuki and Heck) indicate a strong correlation between the surface properties of supports and the catalytic activity of Pd nanocatalysts: supports with a strong basicity and a high concentration of oxygen vacancies result in a rich electron density of Pd and accelerate the first step of oxidative addition reaction for C-C coupling. The infrared spectroscopic study on ?[CO] of CO-treated catalysts and XPS analysis of the Pd(3d) core level provide strong evidence supporting the interaction of Pd/supports for C-C coupling reactions.Understanding the interaction between Pd nanocatalysts and metal oxide supports for heterogeneous C-C coupling reactions is still ambiguous since many factors influence the catalytic behavior of Pd nanocatalysts. Herein, three porous nanorods of CeO2 with controllable surface properties were employed as supports for Pd nanocatalysts with similar dispersion, which avoided the impact of other factors including surface area, morphology and accessible active sites. It provides an ideal approach to probe synergetic catalytic behavior of metal nanoparticles on supports. The results obtained by studying three C-C coupling reactions (Ullman, Suzuki and Heck) indicate a strong correlation between the surface properties of supports and the catalytic activity of Pd nanocatalysts: supports with a strong basicity and a high concentration of oxygen vacancies result in a rich electron density of Pd and accelerate the first step of oxidative addition reaction for C-C coupling. The infrared spectroscopic study on ?[CO] of CO-treated catalysts and XPS analysis of the Pd(3d) core level provide strong evidence supporting the interaction of Pd/supports for C-C coupling reactions. Electronic supplementary information (ESI) available: More characterization of catalysts; calculations of jo and TOF. See DOI: 10.1039/c4nr06482h

  20. CuBr catalyzed aerobic oxidative coupling of 2-aminopyridines with cinnamaldehydes: direct access to 3-formyl-2-phenyl-imidazo[1,2-a]pyridines.

    PubMed

    Bharate, Jaideep B; Abbat, Sheenu; Bharatam, Prasad V; Vishwakarma, Ram A; Bharate, Sandip B

    2015-07-28

    Copper bromide catalyzed aerobic oxidative coupling of 2-aminopyridines with cinnamaldehydes directly led to the formation of 3-formyl-2-phenyl-imidazo[1,2-a]pyridines. The quantum chemical calculations were performed to trace the reaction mechanism and get insights into the possible reaction pathway. 2-Aminopyridines on coupling with cinnamaldehyde generate (E)-3-phenyl-3-(pyridin-2-ylamino)acrylaldehyde IV as a key intermediate, which undergoes C-N bond formation reaction to produce 3-formyl-2-phenyl-imidazo[1,2-a]pyridines. PMID:26103156

  1. Axisymmetric Tandem Mirrors: Stabilization and Confinement Studies

    SciTech Connect

    Post, R.F.; Fowler, T.K.; Bulmer, R.; Byers, J.; Hua, D.; Tung, L. [Lawrence Livermore National Laboratory (United States)

    2005-01-15

    The 'Kinetic Stabilizer' has been proposed as a means of MHD stabilizing an axisymmetric tandem mirror system. The K-S concept is based on theoretical studies by Ryutov, confirmed experimentally in the Gas Dynamic Trap experiment in Novosibirsk. In the K-S beams of ions are directed into the end of an 'expander' region outside the outer mirror of a tandem mirror. These ions, slowed, stagnated, and reflected as they move up the magnetic gradient, produce a low-density stabilizing plasma.At the Lawrence Livermore National Laboratory we have been conducting theoretical and computational studies of the K-S Tandem Mirror. These studies have employed a low-beta code written especially to analyze the beam injection/stabilization process,and a new code SYMTRAN (by Hua and Fowler)that solves the coupled radial and axial particle and energy transport in a K-S T-M. Also, a 'legacy' MHD stability code, FLORA, has been upgraded and employed to benchmark the injection/stabilization code and to extend its results to high beta values.The FLORA code studies so far have confirmed the effectiveness of the K-S in stabilizing high-beta (40%) plasmas with stabilizer plasmas the peak pressures of which are several orders of magnitude smaller than those of the confined plasma.Also the SYMTRAN code has shown D-T plasma ignition from alpha particle energy deposition in T-M regimes with strong end plugging.Our studies have confirmed the viability of the K-S T-M concept with respect to MHD stability and radial and axial confinement. We are continuing these studies in order to optimize the parameters and to examine means for the stabilization of possible residual instability modes, such as drift modes and 'trapped-particle' modes. These modes may in principle be controlled by tailoring the stabilizer plasma distribution and/or the radial potential distribution.In the paper the results to date of our studies are summarized and projected to scope out possible fusion-power versions of the K-S T-M.

  2. Separation and quantification of four isomers of indole-3-acetyl-myo-inositol in plant tissues using high-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry.

    PubMed

    Wu, Tongbo; Liang, Yuan; Zhu, Xiaocui; Zhao, Meiping; Liu, Huwei

    2014-05-01

    Indole-3-acetyl-myo-inositol (IAInos) is one of the most important auxin conjugates for storage and transportation of auxin. The information of its composition, distribution, and metabolism is particularly desired for elucidating the related signal transduction pathways of the plant hormones. However, separation and quantification of the four individual IAInos isomers in plant tissues have not been reported so far. In this work, we first synthesized and isolated four IAInos isomers using semi-preparative high-performance liquid chromatography (HPLC). The IAInos isomer structures were characterized using liquid chromatography-electrospray ionization quadrupole time-of-flight tandem mass spectrometry (LC-QTOF/MS) and nuclear magnetic resonance spectroscopy (NMR). Using these pure compounds as internal or external standards, an efficient LC-MS method was developed for simultaneous detection of indole-3-acetic acid, methyl indole-3-acetic acid ester, and the four IAInos isomers in plant tissue samples. The linear working range and lower limit of detection for the four IAInos isomers are 10-2,000 ng mL(-1) and 5.0 ng mL(-1), respectively. The stabilities and interconversion pathways of IAInos isomers were studied using our synthetic isomers. It was found that two IAInos isomers existed in Zea mays kernels, while all of the four IAInos isomers were present in the roots of Arabidopsis thaliana. The content of IAInos in A. thaliana roots was much lower than in the Z. mays kernels. The methodology in this article provides useful techniques and methods for systematic study on the phytophysiology and phytochemistry of IAA conjugates and other related plant hormones. PMID:24633567

  3. Simultaneous determination of N7-alkylguanines in DNA by isotope-dilution LC-tandem MS coupled with automated solid-phase extraction and its application to a small fish model.

    PubMed

    Chao, Mu-Rong; Wang, Chien-Jen; Yen, Cheng-Chieh; Yang, Hsi-Hsien; Lu, Yao-Cheng; Chang, Louis W; Hu, Chiung-Wen

    2007-03-15

    In the present study, we report the development of a sensitive and selective assay based on LC (liquid chromatography)-MS/MS (tandem MS) to simultaneously measure N7-MeG (N7-methylguanine) and N7-EtG (N7-ethylguanine) in DNA hydrolysates. With the use of isotope internal standards (15N5-N7-MeG and 15N5-N7-EtG) and on-line SPE (solid-phase extraction), the detection limit of this method was estimated as 0.42 fmol and 0.17 fmol for N7-MeG and N7-EtG respectively. The high sensitivity achieved here makes this method applicable to small experimental animals. This method was applied to measure N7-alkylguanines in liver DNA from mosquito fish (Gambusia affinis) that were exposed to NDMA (N-nitrosodimethylamine) and NDEA (N-nitrosodiethylamine) alone or their combination over a wide range of concentrations (1-100 mg/l). Results showed that the background level of N7-MeG in liver of control fish was 7.89+/-1.38 mmol/mol of guanine, while N7-EtG was detectable in most of the control fish with a range of 0.05-0.19 mmol/mol of guanine. N7-MeG and N7-EtG were significantly induced by NDMA and NDEA respectively, at a concentration as low as 1 mg/l and increased in a dose-dependent manner. Taken together, this LC-MS/MS assay provides the sensitivity and high throughput required to evaluate the extent of alkylated DNA lesions in small animal models of cancer induced by alkylating agents. PMID:17134374

  4. Simultaneous determination of N7-alkylguanines in DNA by isotope-dilution LC-tandem MS coupled with automated solid-phase extraction and its application to a small fish model

    PubMed Central

    Chao, Mu-Rong; Wang, Chien-Jen; Yen, Cheng-Chieh; Yang, Hsi-Hsien; Lu, Yao-Cheng; Chang, Louis W.; Hu, Chiung-Wen

    2006-01-01

    In the present study, we report the development of a sensitive and selective assay based on LC (liquid chromatography)–MS/MS (tandem MS) to simultaneously measure N7-MeG (N7-methylguanine) and N7-EtG (N7-ethylguanine) in DNA hydrolysates. With the use of isotope internal standards (15N5-N7-MeG and 15N5-N7-EtG) and on-line SPE (solid-phase extraction), the detection limit of this method was estimated as 0.42 fmol and 0.17 fmol for N7-MeG and N7-EtG respectively. The high sensitivity achieved here makes this method applicable to small experimental animals. This method was applied to measure N7-alkylguanines in liver DNA from mosquito fish (Gambusia affinis) that were exposed to NDMA (N-nitrosodimethylamine) and NDEA (N-nitrosodiethylamine) alone or their combination over a wide range of concentrations (1–100 mg/l). Results showed that the background level of N7-MeG in liver of control fish was 7.89±1.38 ?mol/mol of guanine, while N7-EtG was detectable in most of the control fish with a range of 0.05–0.19 ?mol/mol of guanine. N7-MeG and N7-EtG were significantly induced by NDMA and NDEA respectively, at a concentration as low as 1 mg/l and increased in a dose-dependent manner. Taken together, this LC-MS/MS assay provides the sensitivity and high throughput required to evaluate the extent of alkylated DNA lesions in small animal models of cancer induced by alkylating agents. PMID:17134374

  5. Magnetic order and interfacial coupling in oxide thin films and heterostructures probed with soft x-ray dichroism

    SciTech Connect

    Arenholz, Elke; van der Laan, G.

    2009-02-01

    The combination of novel magnetic properties induced by reduced dimensionality and strong magnetic interactions across interfaces leads to intriguing new properties in magnetic hetero- and nanostructures not observed in the constituent materials in bulk form. It is the careful optimization of the characteristics of the individual layers as well as the magnetic coupling across the interface that allows us to control the magnetic properties and tailor them for devices, e.g., in information storage and processing technology. Soft x-ray magnetic spectroscopies can make unique contributions to improving our understanding of complex magnetic nanostructures since these techniques provide elemental, valence- and site-symmetry specific information with high sensitivity and tunable probing depth. X-ray magnetic circular dichroism (XMCD) is sensitive to (unidirectional) ferromagnetic order, while x-ray magnetic linear dichroism (XMLD) can also detect (uniaxial) antiferromagnetic order. A crystalline electric field with cubic symmetry induces only a weak angular dependence in XMCD spectra [1] but can cause a very pronounced anisotropy in XMLD spectra [2]. Furthermore, non-magnetic sites with a distorted local cubic symmetry can give rise to an x-ray linear dichroism (XLD). In this presentation, we discuss how to distinguish between the individual contributions to soft x-ray dichroism spectra in order to extract the wealth of information about magnetic thin films, interfaces and hetero- and nanostructures contained in the data [3, 4, 5] We determined the magnetic structure of La{sub 0.7}Sr{sub 0.3}MnO{sub 3} (LSMO)/La{sub 0.7}Sr{sub 0.3}FeO{sub 3} (LSFO) superlattices with 6 unit cell thick sublayers using soft x-ray magnetic dichroism [5]. Circular dichroism was employed to study the characteristics of the ferromagnetic LSMO layer indicating a reduced magnetic ordering temperature of 200 K compared to the bulk value of 360 K. Linear dichroism is used to analyze the antiferromagnetic order in the LSFO layers which persists up to the bulk Neel temperature near 400 K. Our experiments clearly show that when the magnetization of the LSMO layer is aligned with a magnetic field, a torque is created on the Fe moments in the LSFO layer through exchange coupling at the interface realigning the Fe moments as well. Through comparison with theoretical calculations we are able to show that independent of the LSMO magnetization direction in the sample surface plane, the Fe moments are always oriented perpendicular to the Mn moments. This perpendicular alignment is due to the frustrated exchange coupling at the interface and the weak anisotropy in the thin LSFO layer. Revisiting previous XMLD studies of the Co/NiO(001) interface taking the impact of the crystal electric field on the XMLD into account for the first time, we show that NiO(001) exhibits a crystallographic and magnetic domain structure near the surface that is identical to that of the bulk. Upon Co deposition perpendicular coupling of Co and Ni moments is observed [2, 3] that persists even in the presence of uncompensated interface moments. We also measured the asphericity and the energy splitting of the 4f states in EuO thin films [4] - a material with fascinating properties and of technological importance for spintronics applications - using XMLD. Our measurements, which are confirmed by multiplet calculations, show that there is significant 4f anisotropy. This suggests that pinning of the f states by the local environment becomes feasible and can be tuned by external conditions, chemical doping, and strain for use in device applications. Moreover, we will discuss the impact of epitaxial strain on the magnetic properties and XMLD spectra of complex oxide thin films.

  6. Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane

    SciTech Connect

    Heinemann, H.; Somorjai, G.A.; Perry, D.L.

    1992-03-01

    Work will continue on the oxidative coupling reaction of methane over ternary oxide catalysts to produce C{sub 2}, C{sub 3} and C{sub 4} hydrocarbons and particularly olefins with high selectivity. The work which has shown that close to 100% selectivity can be obtained has received wide attention and has resulted in collaborative efforts with industry (CRADA) towards the development of a commercial process. An immediate purpose of additional work is to increase the conversion without diminishing the extremely high selectivity of the reaction and also to permit operation at higher space velocity to reduce equipment size. The mechanism of this reaction is not understood and much additional work is needed to explain the role of carbon formation and of water as intermediates in the reaction and to investigate whether carbon oxides are intermediates. It has been found that oxides other than calcium-nickel-potassium oxides can be useful catalysts for this reaction in the presence of steam and at relatively low temperatures and long contact times. Better definition of the class of binary metal oxides is required and better catalyst characterization is needed to ensure reproducibility of catalyst preparation and operational results. Pretreatment of the catalyst should be shortened and higher space velocities must be obtained. Close collaboration with Orion ACT is required to advance the project toward the pilot plant stage. In the area of coal and char catalytic steam gasification, the large volume of data obtained at atmospheric pressure will be extended to operations at higher pressures.

  7. Effect of acidic pretreatment combined with a silane coupling agent on bonding durability to silicon oxide ceramic.

    PubMed

    Foxton, Richard M; Nakajima, Masatoshi; Tagami, Junji; Miura, Hiroyuki

    2005-04-01

    This study examined the effect of different acidic treatments and the role of a phosphate monomer in a silane coupling agent on the durability of the dual-cure resin cement/silicon oxide bond. Ceramic blocks (Vita Celay Blanks) were cut into multiple 3 mm-thick slices and polished using 600 grit SiC paper. Two pairs were left untreated [controls (CTRL)], two pairs were treated with 40% phosphoric acid and rinsed with water for 30 s (PA), and another two pairs treated with 20% hydrofluoric acid followed by 30 s water rinsing (HF). Half the specimens were silanated with Tokuso Ceramics Primer (TCP) (Tokuyama) and the other half with TCP formulated without phosphate monomer (TCP-NoPM). All the pairs were bonded with Bistite II dual-cure resin cement (Tokuyama) and light cured. After 24 h water storage at 37 degrees C, 0.7 mm-thick slabs were serially sectioned. Immediately, after 6 months and after 1 year of water storage, two slabs were randomly selected from each subgroup, and sliced into beams (6 x 0.7 x 0.7 mm) for the microtensile bond strength (muTBS) test. The muTBS data were statistically analyzed using multiple Wilcoxon Signed Rank tests (p < 0.05). Failure modes were determined using a confocal laser-scanning microscope. Ceramic surface morphology after the different acidic treatments was examined using an SEM. After 1 day, in the case of silane treatment with TCP, there were no significant differences in muTBS between the control and acid-treated groups (p > 0.05), whereas with TCP-NoPM, the muTBS of the control was significantly lower than the acid-treated groups (p < 0.05). All the TCP and acid-treated TCP-NoPM groups exhibited significant reductions in muTBS after 6 months (p < 0.05). After 1 year, the muTBS of the acid-treated TCP groups were not significantly different from the control TCP group (p > 0.05). There was also no significant difference between the HF-treated TCP and TCP-NoPM groups (p > 0.05) after 1 year, all exhibiting greater than 10 MPa tensile bond strength. It is suggested that acidic pretreatment of the ceramic surface does not improve the durability of the dual-cure resin cement/silicon oxide ceramic bond when an acidic phosphate monomer is present as an activator in a ceramic primer. PMID:15625674

  8. Denitrification-Coupled Iron(II) Oxidation: A Key Process Regulating the Fate and Transport of Nitrate, Phosphate, and Arsenic in a Wastewater-Contaminated Aquifer

    NASA Astrophysics Data System (ADS)

    Smith, R. L.; Kent, D. B.; Repert, D. A.; Hart, C. P.

    2007-12-01

    Denitrification in the subsurface is often viewed as a heterotrophic process. However, some denitrifiers can also utilize inorganic electron donors. In particular, Fe(II), which is common in many aquifers, could be an important reductant for contaminant nitrate. Anoxic iron oxidation would have additional consequences, including decreased mobility for species like arsenic and phosphate, which bind strongly to hydrous Fe(III) oxide. A study was conducted in a wastewater contaminant plume on Cape Cod to assess the potential for denitrification- coupled Fe(II) oxidation. Previous changes in wastewater disposal upgradient of the study area had resulted in nitrate being transported into a portion of the anoxic zone of the plume and decreased concentrations of Fe(II), phosphate, and arsenic. A series of anoxic tracers (groundwater + nitrate + bromide) were injected into the unaffected, Fe(II)-containing zone under natural gradient conditions. Denitrification was stimulated within 1 m of transport (4 days) for both low and high (100 & 1000 ?M) nitrate additions, initially producing stiochiometric quantities of nitrous oxide (>300 ?M N) and trace amounts of nitrite. Subsequent injections at the same site reduced nitrate even more rapidly and produced less nitrous oxide, especially over longer transport distances. Fe(II) and nitrate concentrations decreased together and this was accompanied by an increase in colloidal Fe(III) and decreases in pH, total arsenic, and phosphate concentrations. All plume constituents returned to background levels several weeks after the tracer tests were completed. Groundwater microorganisms collected on filters during the tracer test rapidly and immediately reduced nitrite and oxidized Fe(II) in 3-hr laboratory incubations. Several pure cultures of Fe(II)-oxidizing denitrifying bacteria were isolated from core material and subsequently characterized. All of the isolates were mixotrophic, simultaneously oxidizing organic carbon and Fe(II). These results demonstrate that denitrification-coupled Fe(II) oxidation can readily occur within anoxic groundwater; that it could be key to controlling iron speciation in certain situations and that the outcome of the process can impact the mobility of other chemical species that are not directly involved in the oxidation-reduction reaction.

  9. Thermal stability of TiAlN/TiAlON/Si{sub 3}N{sub 4} tandem absorbers prepared by reactive direct current magnetron sputtering

    SciTech Connect

    Barshilia, Harish C.; Selvakumar, N.; Rajam, K. S. [Surface Engineering Division, National Aerospace Laboratories, Post Bag No. 1779, Bangalore 560 017 (India)

    2007-03-15

    Spectrally selective TiAlN/TiAlON/Si{sub 3}N{sub 4} tandem absorber was deposited on copper, stainless steel, and Nimonic substrates using a reactive direct current magnetron sputtering system. The absorptance and the emittance of the tandem absorbers were characterized using solar spectrum reflectometer and emissometer. The surface morphology of the tandem absorbers was studied using atomic force microscopy. The compositions and the thicknesses of the individual component layers have been optimized in such a way to achieve high absorptance (0.958) and low emittance (0.07 at 82 deg. C). In order to study the thermal stability of the tandem absorbers, they were subjected to heat treatment (in air and vacuum) at different temperatures and durations. The structural changes as a result of heating of the tandem absorbers were studied using micro-Raman spectroscopy. The tandem absorbers deposited on copper substrates exhibited high solar selectivity in the order of 9-10 even after heat treatment in air up to 600 deg. C for 2 h. These tandem absorbers also exhibited very high thermal stability (525 deg. C) in air for longer durations (50 h). The onset of oxidation for the tandem stack deposited on silicon substrates was 900 deg. C, indicating a very high oxidation resistance. The results of the present study indicate the importance of TiAlN/TiAlON/Si{sub 3}N{sub 4} tandem absorber for high temperature solar selective applications.

  10. Analysis of oxidation byproducts of dyfonate in various oxidant systems using high performance liquid chromatography coupled with quadrupole ion trap mass spectrometry

    Microsoft Academic Search

    Tongwen Wang; Evelyn Chamberlain; Honglan Shi; Craig D. Adams; Yinfa Ma

    2010-01-01

    Dyfonate is a dithiophosphonate pesticide used to control lepidopterous insects in corn, potatoes, and peanuts. It may be transferred to the surface water and underground water system and can be degraded by free chlorine and other oxidants, which are used by water treatment plants during the disinfection process, to produce oxidation byproducts. These byproducts may be more toxic than their

  11. Chemically induced ferromagnetic spin coupling: Electronic and geometric structures of chromium-oxide cluster anions, Cr2On (n=1-3), studied by photoelectron spectroscopy

    Microsoft Academic Search

    Kensuke Tono; Akira Terasaki; Toshiaki Ohta; Tamotsu Kondow

    2003-01-01

    Dichromium oxide cluster anions, Cr2On- (n=1-3), were found to possess highly spin-polarized electronic structures, which were revealed by the measurements of photoelectron spectra and the analyses by the density-functional calculations. Their spin magnetic moments were as large as 9, 9, and 7 muB for n=1, 2, and 3, respectively, due to a ferromagnetic coupling between local spins on the chromium

  12. Copper(II)-catalysed oxidative coupling reaction of 3-hydroxyacetanilide with 3-methyl-2-benzothiazolinone hydrazone for the spectrophotometric determination of traces of copper(II)

    Microsoft Academic Search

    M. S. Hemantha Kumar; P. Nagaraja; H. S. Yathirajan

    2003-01-01

    A spectrophotometric method is developed for the determination of traces of copper(II), based on the catalytic oxidative coupling reaction of 3-hydroxyacetanilide with 3-methyl-2-benzothiazolinone hydrazone in the presence of ammonia and hydrochloric acid. Beer's law is obeyed in the copper(II) concentration range of 0.008-0.16 wg mLу, and the molar absorptivity at 530 nm is 2.5쎹 L molу cmу. The Sandell's sensitivity

  13. Tandem electrostatic accelerators for BNCT

    SciTech Connect

    Ma, J.C. [Yanch and W.B. Howard Massachusetts Inst. of Technology, Cambridge, MA (United States)

    1994-12-31

    The development of boron neutron capture therapy (BNCT) into a viable therapeutic modality will depend, in part, on the availability of suitable neutron sources compatible with installation in a hospital environment. Low-energy accelerator-based intense neutron sources, using electrostatic or radio frequency quadrupole proton accelerators have been suggested for this purpose and are underdevelopment at several laboratories. New advances in tandem electrostatic accelerator technology now allow acceleration of the multi-milliampere proton beams required to produce therapeutic neutron fluxes for BNCT. The relatively compact size, low weight and high power efficiency of these machines make them particularly attractive for installation in a clinical or research facility. The authors will describe the limitations on ion beam current and available neutron flux from tandem accelerators relative to the requirements for BNCT research and therapy. Preliminary designs and shielding requirements for a tandern accelerator-based BNCT research facility will also be presented.

  14. Photo-induced water oxidation at the aqueous GaN (101?0) interface: Deprotonation kinetics of the first proton-coupled electron-transfer step

    DOE PAGESBeta

    Ertem, Mehmed Z. [Brookhaven National Lab. (BNL), Upton, NY (United States); Yale Univ., New Haven, CT (United States); Kharche, Neerav [Brookhaven National Lab. (BNL), Upton, NY (United States); Batista, Victor S. [Yale Univ., New Haven, CT (United States); Hybertsen, Mark S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Tully, John C. [Yale Univ., New Haven, CT (United States); Muckerman, James T. [Brookhaven National Lab. (BNL), Upton, NY (United States)

    2015-04-03

    Photoeclectrochemical water splitting plays a key role in a promising path to the carbon-neutral generation of solar fuels. Wurzite GaN and its alloys (e.g., GaN/ZnO and InGaN) are demonstrated photocatalysts for water oxidation, and they can drive the overall water splitting reaction when coupled with co-catalysts for proton reduction. In the present work, we investigate the water oxidation mechanism on the prototypical GaN (101?0) surface using a combined ab initio molecular dynamics and molecular cluster model approach taking into account the role of water dissociation and hydrogen bonding within the first solvation shell of the hydroxylated surface. The investigation of free-energy changes for the four proton-coupled electron-transfer (PCET) steps of the water oxidation mechanism shows that the first PCET step for the conversion of –Ga-OH to –Ga-O?? requires the highest energy input. We further examine the sequential PCETs, with the proton transfer (PT) following the electron transfer (ET), and find that photo-generated holes localize on surface –NH sites is thermodynamically more favorable than –OH sites. However, proton transfer from –OH sites with subsequent localization of holes on oxygen atoms is kinetically favored owing to hydrogen bonding interactions at the GaN (101?0)–water interface. We find that the deprotonation of surface –OH sites is the limiting factor for the generation of reactive oxyl radical ion intermediates and consequently for water oxidation.

  15. Novel biomarkers of protein oxidation sites and degrees using horse cytochrome c as the target by mass spectrometry.

    PubMed

    Zong, Wansong; Liu, Rutao; Guo, Changying; Sun, Feng

    2011-05-01

    Biomarkers held both incredible application and significant challenge in probing the oxidation mechanisms of proteins under oxidative stress. Here, mass spectrometry (MS) coupled with liquid chromatography (LC) was applied to establish a new pipeline to probe the oxidation sites and degrees of horse cytochrome c (HCC) with its oxidative products serving as the biomarkers. Samples of native and UV/H(2)O(2) oxidized HCCs were digested by trypsin and subjected to biomarker discovery using LC/MS and tandem mass spectrometry (MS/MS). Experiment results proved that the main oxidation sites were located at Cys(14), Cys(17), Met(65) and Met(80) residues in peptides C(14)AQC(heme)HTVEK(22), C(14)AQCHTVEK(22), E(60)ETLMEYLENPKK(73), M(80)IFAGIK(86) and M(80)IFAGIKK(87). Quantitative analysis on the oxidized peptides showed the oxidation degrees of target sites had positive correlations with extended oxidation dose and controlled by residues types and their accessibility to solvent molecules. Being able to provide plentiful information for the oxidation sites and oxidation degrees, the identified oxidized products were feasibility biomarkers for HCC oxidation, compared with the conventional protein carbonyl assay. PMID:21377407

  16. Abrupt reoxygenation following hypoxia reduces electrical coupling between endothelial cells of wild-type but not connexin40 null mice in oxidant- and PKA-dependent manner.

    PubMed

    Bolon, Michael L; Ouellette, Yves; Li, Fuyan; Tyml, Karel

    2005-10-01

    Although electrical coupling along the arteriolar endothelium is central in arteriolar conducted response and in control of vascular resistance, little is known about the pathophysiological effect of hypoxia and reoxygenation (H/R) on this coupling. We examined this effect in a monolayer of cultured microvascular endothelial cells (ECs) derived from wild-type (WT) or connexin (Cx)40-/- mice (Cx40 is a key gap junction protein in ECs). To assess electrical coupling, we used a current injection technique and Bessel function model to compute the monolayer intercellular resistance. Hypoxia (0.1% O2, 1 h) followed by abrupt reoxygenation (5-90 min) reduced coupling (i.e., increased resistance) in WT but not in Cx40-/- monolayer. H/R increased superoxide production and reduced protein kinase A (PKA) activity in both monolayers. Activation of PKA by 8-bromo-cAMP prevented the reduction in coupling. Preloading of the WT monolayer with the antioxidant ascorbate prevented reductions in both PKA activity and cell coupling. Inhibition of PKA with 6-22 amide during normoxia mimicked the reduction in coupling. Finally, hypoxia followed by slow reoxygenation caused no change in superoxide level, PKA activity, or coupling. Using intravital microscopy, we assessed the physiological relevance of these findings in terms of KCl-induced conducted vasoconstriction in arterioles of WT mouse cremaster muscle in vivo. Ischemia (1 h) followed by abrupt reperfusion (15-30 min) reduced conduction. 8-bromo-cAMP prevented this reduction, while 6-22 amide mimicked this reduction in control nonischemic arterioles. We propose that abrupt reoxygenation reduces interendothelial electrical coupling via oxidant- and PKA-dependent signaling that targets Cx40. We suggest that this mechanism contributes to compromised arteriolar function after H/R. PMID:16037099

  17. Reversed-phase chiral liquid chromatography on polysaccharide-based stationary phase coupled with tandem mass spectrometry for simultaneous determination of four stereoisomers of MK-0974 in human plasma.

    PubMed

    Xu, Yang; Musson, Donald G

    2008-10-01

    MK-0974 (1a), N-[(3R,6S)-6-(2,3-difluorophenyl)-2-oxo-1-(2,2,2-trifuoroethyl)azepan-3-yl]-4-(2-oxo-2,3-dihydro-1H-imidazo-[4,5-B] pyridine-1-yl)piperidine-1-carboxamide, is a novel calcitonin gene-related peptide (CGRP) receptor antagonist with two chiral centers. Direct separation of its four stereoisomers (1a-d) was achieved using a cellulose chiral stationary phase, a Chiralcel OJ-RH column (150 mm x 4.6 mm), under reversed-phase condition, following the extraction of 0.2 mL plasma on Oasis muElution HLB 96-well solid-phase-extraction (SPE) plate. The tandem mass spectrometric detection was conducted in the positive-ion mode with a turbo-ion-spray (TIS) interface using multiple-reaction-monitoring on a Sciex API3000. Addition of ammonium trifluoroacetate to low-organic mobile phase improved detection sensitivity by more than 30-fold. The simultaneous quantification of the four stereoisomers in human plasma was validated over the ranges of 0.5-5000 nM for 1a and 0.5-500 nM for its three isomers (1b-d). Intraday validation, conducted with five lots of human control plasma, resulted in <12.4% (% coefficient of variation, CV) precision and 96.3-105.4% accuracy for all four stereoisomers. Further evaluation indicated that the assay was specific, the samples were stable after three freeze/thaw cycles, the recovery was reasonable (above 65%) and no matrix effect was observed for all four isomers. Investigation on the chiral integrity of 1a indicated that the diastereomer 1c, inversion at azepinone-3 carbon, was the only isomer observed in the post-dose clinical samples and accounted for 2.4-5.2% of MK-0974 exposure in the circulatory system. The possibility of inversion during blood collection, plasma storage and sample preparation was ruled out, while inversion was observed in the clinical formulation accounting for approximately 0.12% of 1a in a 100-mg capsule. PMID:18799366

  18. The construction of tandem dye-sensitized solar cells from chemically-derived nanoporous photoelectrodes

    NASA Astrophysics Data System (ADS)

    Choi, Hongsik; Hwang, Taehyun; Lee, Sangheon; Nam, Seunghoon; Kang, Joonhyeon; Lee, Byungho; Park, Byungwoo

    2015-01-01

    A tandem dye-sensitized solar cell (tandem-DSSC) was synthesized on the basis of thin-film semiconductor electrodes. The nanoporous p-type NiO films were successfully obtained by simultaneous deposition of Al and Ni, followed by selective etching of Al and oxidation. Likewise, the n-type photoanode was made where Ag was etched in nitric acid after the initial formation of Ag/TiO2 nanocomposites. Such dye-sensitized photoelectrodes were combined to construct a tandem solar cell which exhibited an enhanced open-circuit voltage. Also, the tandem devices were subjected to various light fluxes to correlate the experimental cell parameters (open-circuit voltage, short-circuit current, fill factor, recombination shunt resistance, etc.) with the ideal one-diode model. Interestingly, impedance spectra of the tandem cell was well matched with the parameters from each of the n-type or p-type DSSC, indicative of successfully-designed tandem structure.

  19. Hybrid tandem photovoltaic devices with a transparent conductive interconnecting recombination layer

    SciTech Connect

    Kim, Taehee; Choi, Jin Young; Jeon, Jun Hong; Kim, Youn-Su; Kim, Bong-Soo; Lee, Doh-Kwon; Kim, Honggon; Han, Seunghee [Solar Cell Research Center, Korea Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul 136-791 (Korea, Republic of)] [Solar Cell Research Center, Korea Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul 136-791 (Korea, Republic of); Kim, Kyungkon, E-mail: kimkk@ewha.ac.kr [Solar Cell Research Center, Korea Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul 136-791 (Korea, Republic of) [Solar Cell Research Center, Korea Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul 136-791 (Korea, Republic of); Department of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750 (Korea, Republic of)

    2012-10-15

    Highlights: ? This work enhanced power conversion efficiency of the hybrid tandem solar cell from 1.0% to 2.6%. ? The interfacial series resistance of the tandem solar cell was eliminated by inserting ITO layer. ? This work shows the feasibility of the highly efficient hybrid tandem solar cells. -- Abstract: We demonstrate hybrid tandem photovoltaic devices with a transparent conductive interconnecting recombination layer. The series-connected hybrid tandem photovoltaic devices were developed by combining hydrogenated amorphous silicon (a-Si:H) and polymer-based organic photovoltaics (OPVs). In order to enhance the interfacial connection between the subcells, we employed highly transparent and conductive indium tin oxide (ITO) thin layer. By using the ITO interconnecting layer, the power conversion efficiency of the hybrid tandem solar cell was enhanced from 1.0% (V{sub OC} = 1.041 V, J{sub SC} = 2.97 mA/cm{sup 2}, FF = 32.3%) to 2.6% (V{sub OC} = 1.336 V, J{sub SC} = 4.65 mA/cm{sup 2}, FF = 41.98%) due to the eliminated interfacial series resistance.

  20. Unexpected weak magnetic exchange coupling between haem and non-haem iron in the catalytic site of nitric oxide reductase (NorBC) from Paracoccus denitrificans1.

    PubMed

    Van Wonderen, Jessica H; Oganesyan, Vasily S; Watmough, Nicholas J; Richardson, David J; Thomson, Andrew J; Cheesman, Myles R

    2013-05-01

    Bacterial NOR (nitric oxide reductase) is a major source of the powerful greenhouse gas N2O. NorBC from Paracoccus denitrificans is a heterodimeric multi-haem transmembrane complex. The active site, in NorB, comprises high-spin haem b3 in close proximity with non-haem iron, FeB. In oxidized NorBC, the active site is EPR-silent owing to exchange coupling between FeIII haem b3 and FeBIII (both S=5/2). On the basis of resonance Raman studies [Moënne-Loccoz, Richter, Huang, Wasser, Ghiladi, Karlin and de Vries (2000) J. Am. Chem. Soc. 122, 9344-9345], it has been assumed that the coupling is mediated by an oxo-bridge and subsequent studies have been interpreted on the basis of this model. In the present study we report a VFVT (variable-field variable-temperature) MCD (magnetic circular dichroism) study that determines an isotropic value of J=-1.7 cm-1 for the coupling. This is two orders of magnitude smaller than that encountered for oxo-bridged diferric systems, thus ruling out this configuration. Instead, it is proposed that weak coupling is mediated by a conserved glutamate residue. PMID:23421449

  1. Short Tandem Repeat DNA Internet Database

    National Institute of Standards and Technology Data Gateway

    SRD 130 Short Tandem Repeat DNA Internet Database (Web, free access)   Short Tandem Repeat DNA Internet Database is intended to benefit research and application of short tandem repeat DNA markers for human identity testing. Facts and sequence information on each STR system, population data, commonly used multiplex STR systems, PCR primers and conditions, and a review of various technologies for analysis of STR alleles have been included.

  2. Efficient Tandem Polymer Solar Cells Fabricated by All-Solution Processing

    Microsoft Academic Search

    Jin Young Kim; Kwanghee Lee; Nelson E. Coates; Daniel Moses; Thuc-Quyen Nguyen; Mark Dante; Alan J. Heeger

    2007-01-01

    Tandem solar cells, in which two solar cells with different absorption characteristics are linked to use a wider range of the solar spectrum, were fabricated with each layer processed from solution with the use of bulk heterojunction materials comprising semiconducting polymers and fullerene derivatives. A transparent titanium oxide (TiOx) layer separates and connects the front cell and the back cell.

  3. Biological oxidation of Mn(II) coupled with nitrification for removal and recovery of minor metals by downflow hanging sponge reactor.

    PubMed

    Cao, Linh Thi Thuy; Kodera, Hiroya; Abe, Kenichi; Imachi, Hiroyuki; Aoi, Yoshiteru; Kindaichi, Tomonori; Ozaki, Tomonori; Ohashi, Akiyoshi

    2015-01-01

    Biogenic manganese oxides (bio-MnO?) have been shown to absorb minor metals. Bioreactor cultivation of heterotrophic manganese oxidizing bacteria (MnOB), which produce bio-MnO? via oxidation of Mn (II), can be expected to be involved in a promising system for removal and recovery of minor metals from wastewater. However, MnOB enrichment in wastewater treatment is difficult. This study investigated whether MnOB can be cultivated when coupled with nitrification in a system in which soluble microbial products (SMP) from nitrifiers are provided to MnOB as a substrate. A downflow hanging sponge (DHS) reactor was applied for MnOB cultivation with ammonium (NH??) and Mn (II) continuously supplied. During long-term operation, Mn (II) oxidation was successfully established at a rate of 48 g Mn m?³ d?¹ and bio-MnO? that formed on the sponges were recovered from the bottom of the reactor. The results also revealed that Ni and Co added to the influent were simultaneously removed. Microbial 16S rRNA gene clone analysis identified nitrifiers supporting MnOB growth and showed that only one clone of Bacillus subtilis, which was affiliated with a known MnOB cluster, was present, suggesting the existence of other novel bacteria with the ability to oxidize Mn (II). PMID:25462760

  4. 47 CFR 69.129 - Signalling for tandem switching.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ...2010-10-01 false Signalling for tandem switching. 69.129 Section 69...Charges § 69.129 Signalling for tandem switching. A charge that is expressed...company for provision of signalling for tandem switching. [59 FR 32930, June...

  5. Improved monolithic tandem solar cell

    SciTech Connect

    Wanlass, M.W.

    1991-04-23

    A single-crystal, monolithic, tandem, photovoltaic solar cell is described which includes (a) an InP substrate having upper and lower surfaces, (b) a first photoactive subcell on the upper surf ace of the InP substrate, (c) a second photoactive subcell on the first subcell; and (d) an optically transparent prismatic cover layer over the second subcell. The first photoactive subcell is GaInAsP of defined composition. The second subcell is InP. The two subcells are lattice matched.

  6. Sensitive, Preclinical Detection of Prions in Brain by nanospray liquid chromatography/tandem mass spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    More sensitive detection of prions in brain is important because it would allow early detection of disease in young animals and assure a safer food supply. We quantitated the amount of proteinase K-resistant prion protein (PrP 27-30) by use of nano-scale liquid chromatography coupled to a tandem ma...

  7. 10 K Ring Electrode Trap—Tandem Mass Spectrometer for Infrared Spectroscopy of Mass Selected Ions

    Microsoft Academic Search

    Daniel J. Goebbert; Gerard Meijer; Knut R. Asmis

    2009-01-01

    A novel instrumental setup for measuring infrared photodissociation spectra of buffer gas cooled, mass-selected ions is described and tested. It combines a cryogenically cooled, linear radio frequency ion trap with a tandem mass spectrometer, optimally coupling continuous ion sources to pulsed laser experiments. The use of six independently adjustable DC potentials superimposed over the trapping radio frequency field provides control

  8. 10 K Ring Electrode Trap-Tandem Mass Spectrometer for Infrared Spectroscopy of Mass Selected Ions

    Microsoft Academic Search

    Daniel J. Goebbert; Gerard Meijer; Knut R. Asmis

    2009-01-01

    A novel instrumental setup for measuring infrared photodissociation spectra of buffer gas cooled, mass-selected ions is described and tested. It combines a cryogenically cooled, linear radio frequency ion trap with a tandem mass spectrometer, optimally coupling continuous ion sources to pulsed laser experiments. The use of six independently adjustable DC potentials superimposed over the trapping radio frequency field provides control

  9. Argonne Tandem-Linac Accelerator System

    NASA Astrophysics Data System (ADS)

    Bollinger, L. M.

    1983-03-01

    Design considerations and operational experience for the existing heavy-ion accelerator consisting of a tandem injecting into a superconducting linac are summarized, with emphasis on the general features of the system. This introduction provides the basis for a discussion of the objectives and design of ATLAS, a larger tandem-linac system being formed by expanding the existing superconducting linac.

  10. 33 CFR 401.41 - Tandem lockage.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...Navigable Waters 3 2010-07-01 2010-07-01 false Tandem lockage. 401.41 Section 401.41 Navigation and Navigable...REGULATIONS AND RULES Regulations Seaway Navigation § 401.41 Tandem lockage. Where two or more vessels are being locked...

  11. Tandem Z-Selective Cross-Metathesis/Dihydroxylation: Synthesis of anti-1,2-Diols.

    PubMed

    Dornan, Peter K; Wickens, Zachary K; Grubbs, Robert H

    2015-06-01

    A stereoselective synthesis of anti-1,2-diols has been developed using a multitasking Ru catalyst in an assisted tandem catalysis protocol. A cyclometalated Ru complex catalyzes first a Z-selective cross-metathesis of two terminal olefins, followed by a stereospecific dihydroxylation. Both steps are catalyzed by Ru, as the Ru complex is converted to a dihydroxylation catalyst upon addition of NaIO4 . A variety of olefins were transformed into valuable, highly functionalized, and stereodefined molecules. Mechanistic experiments were performed to probe the nature of the oxidation step and catalyst inhibition pathways. These experiments point the way to more broadly applicable tandem catalytic transformations. PMID:25914354

  12. Organic Dye-Sensitized Tandem Photoelectrochemical Cell for Light Driven Total Water Splitting.

    PubMed

    Li, Fusheng; Fan, Ke; Xu, Bo; Gabrielsson, Erik; Daniel, Quentin; Li, Lin; Sun, Licheng

    2015-07-22

    Light driven water splitting was achieved by a tandem dye-sensitized photoelectrochemical cell with two photoactive electrodes. The photoanode is constituted by an organic dye L0 as photosensitizer and a molecular complex Ru1 as water oxidation catalyst on meso-porous TiO2, while the photocathode is constructed with an organic dye P1 as photoabsorber and a molecular complex Co1 as hydrogen generation catalyst on nanostructured NiO. By combining the photocathode and the photoanode, this tandem DS-PEC cell can split water by visible light under neutral pH conditions without applying any bias. PMID:26132113

  13. Software dependability in the Tandem GUARDIAN system

    NASA Technical Reports Server (NTRS)

    Lee, Inhwan; Iyer, Ravishankar K.

    1995-01-01

    Based on extensive field failure data for Tandem's GUARDIAN operating system this paper discusses evaluation of the dependability of operational software. Software faults considered are major defects that result in processor failures and invoke backup processes to take over. The paper categorizes the underlying causes of software failures and evaluates the effectiveness of the process pair technique in tolerating software faults. A model to describe the impact of software faults on the reliability of an overall system is proposed. The model is used to evaluate the significance of key factors that determine software dependability and to identify areas for improvement. An analysis of the data shows that about 77% of processor failures that are initially considered due to software are confirmed as software problems. The analysis shows that the use of process pairs to provide checkpointing and restart (originally intended for tolerating hardware faults) allows the system to tolerate about 75% of reported software faults that result in processor failures. The loose coupling between processors, which results in the backup execution (the processor state and the sequence of events) being different from the original execution, is a major reason for the measured software fault tolerance. Over two-thirds (72%) of measured software failures are recurrences of previously reported faults. Modeling, based on the data, shows that, in addition to reducing the number of software faults, software dependability can be enhanced by reducing the recurrence rate.

  14. Surface electrochemistry of CO2 reduction and CO oxidation on Sm-doped CeO(2-x): coupling between Ce(3+) and carbonate adsorbates.

    PubMed

    Feng, Zhuoluo A; Machala, Michael L; Chueh, William C

    2015-05-14

    The efficient electro-reduction of CO2 to chemical fuels and the electro-oxidation of hydrocarbons for generating electricity are critical toward a carbon-neutral energy cycle. The simplest reactions involving carbon species in solid-oxide fuel cells and electrolyzer cells are CO oxidation and CO2 reduction, respectively. In catalyzing these reactions, doped ceria exhibits a mixed valence of Ce(3+) and Ce(4+), and has been employed as a highly active and coking-resistant electrode. Here we report an operando investigation of the surface reaction mechanism on a ceria-based electrochemical cell using ambient pressure X-ray photoelectron spectroscopy. We show that the reaction proceeds via a stable carbonate intermediate, the coverage of which is coupled to the surface Ce(3+) concentration. Under CO oxidation polarization, both the carbonate and surface Ce(3+) concentration decrease with overpotential. Under CO2 reduction polarization, on the other hand, the carbonate coverage saturates whereas the surface Ce(3+) concentration increases with overpotential. The evolution of these reaction intermediates was analyzed using a simplified two-electron reaction scheme. We propose that the strong adsorbate-adsorbate interaction explains the coverage-dependent reaction mechanism. These new insights into the surface electrochemistry of ceria shed light on the optimization strategies for better fuel cell electrocatalysts. PMID:25891363

  15. Polyethylene glycol/graphene oxide coated solid-phase microextraction fiber for analysis of phenols and phthalate esters coupled with gas chromatography.

    PubMed

    Hou, Xiudan; Yu, Hui; Guo, Yong; Liang, Xiaojing; Wang, Shuai; Wang, Licheng; Liu, Xia

    2015-08-01

    A new polyethylene glycol/graphene oxide composite material bonded on the surface of a stainless-steel wire was used for solid-phase microextraction. The layer-by-layer structure increased the adsorption sites of the novel fiber, which could facilitate the extraction of trace compounds. The polyethylene glycol/graphene oxide was characterized by Fourier transform infrared spectroscopy and elemental analysis, which verified that polyethylene glycol was successfully grafted onto the surface of graphene oxide. The performance of the polyethylene glycol/graphene oxide coated fiber was investigated for phenols and phthalate esters coupled with gas chromatography with flame ionization detection under the optimal extraction and desorption conditions, and the proposed method exhibited an excellent extraction capacity and high thermal stability. Wide linear ranges were obtained for the analytes with good correlation coefficients in the range of 0.9966-0.9994, and the detection limits of model compounds ranged from 0.003 to 0.025 ?g/L. Furthermore, the as-prepared fiber was used to determine the model compounds in the water and soil samples and satisfactory results were obtained. PMID:26012698

  16. Simulation and optimization of ammonia removal at low temperature for a double channel oxidation ditch based on fully coupled activated sludge model (FCASM): a full-scale study.

    PubMed

    Yang, Min; Sun, Peide; Wang, Ruyi; Han, Jingyi; Wang, Jianqiao; Song, Yingqi; Cai, Jing; Tang, Xiudi

    2013-09-01

    An optimal operating condition for ammonia removal at low temperature, based on fully coupled activated sludge model (FCASM), was determined in a full-scale oxidation ditch process wastewater treatment plant (WWTP). The FCASM-based mechanisms model was calibrated and validated with the data measured on site. Several important kinetic parameters of the modified model were tested through respirometry experiment. Validated model was used to evaluate the relationship between ammonia removal and operating parameters, such as temperature (T), dissolved oxygen (DO), solid retention time (SRT) and hydraulic retention time of oxidation ditch (HRT). The simulated results showed that low temperature have a negative effect on the ammonia removal. Through orthogonal simulation tests of the last three factors and combination with the analysis of variance, the optimal operating mode acquired of DO, SRT, HRT for the WWTP at low temperature were 3.5 mg L(-1), 15 d and 14 h, respectively. PMID:23831896

  17. Photo-induced water oxidation at the aqueous GaN (101?0) interface: Deprotonation kinetics of the first proton-coupled electron-transfer step

    DOE PAGESBeta

    Ertem, Mehmed Z.; Kharche, Neerav; Batista, Victor S.; Hybertsen, Mark S.; Tully, John C.; Muckerman, James T.

    2015-04-03

    Photoeclectrochemical water splitting plays a key role in a promising path to the carbon-neutral generation of solar fuels. Wurzite GaN and its alloys (e.g., GaN/ZnO and InGaN) are demonstrated photocatalysts for water oxidation, and they can drive the overall water splitting reaction when coupled with co-catalysts for proton reduction. In the present work, we investigate the water oxidation mechanism on the prototypical GaN (101?0) surface using a combined ab initio molecular dynamics and molecular cluster model approach taking into account the role of water dissociation and hydrogen bonding within the first solvation shell of the hydroxylated surface. The investigation ofmore »free-energy changes for the four proton-coupled electron-transfer (PCET) steps of the water oxidation mechanism shows that the first PCET step for the conversion of –Ga-OH to –Ga-O?? requires the highest energy input. We further examine the sequential PCETs, with the proton transfer (PT) following the electron transfer (ET), and find that photo-generated holes localize on surface –NH sites is thermodynamically more favorable than –OH sites. However, proton transfer from –OH sites with subsequent localization of holes on oxygen atoms is kinetically favored owing to hydrogen bonding interactions at the GaN (101?0)–water interface. We find that the deprotonation of surface –OH sites is the limiting factor for the generation of reactive oxyl radical ion intermediates and consequently for water oxidation.« less

  18. A liquid chromatography/atmospheric pressure ionization tandem mass spectrometry quantitation method for nevirapine and its two oxidative metabolites, 2-hydroxynevirapine and nevirapine 4-carboxylic acid, and pharmacokinetics in baboons.

    PubMed

    Liu, Zhongfa; Fan-Havard, Patty; Xie, Zhiliang; Ren, Chen; Chan, Kenneth K

    2007-01-01

    A rapid highly sensitive and specific electrospray ionization (ESI) liquid chromatography/tandem mass spectrometry (LC/MS/MS) method for quantification of nevirapine (NVP) and its two metabolites, 2-hydroxynevirapine (2-OHNVP) and nevirapine 4-carboxylic acid (4-CANVP), in baboon serum was developed and validated. Nevirapine, 2-OHNVP, 4-CANVP, and the internal standard, hesperetin, were extracted from baboon serum with ethyl acetate. Components in the extract were separated on a 50 x 2.1 mm Aquasil C(18) 5 microm stainless steel column by isocratic elution with 40% acetonitrile/0.1% formic acid at a flow rate of 0.2 mL/min. The liquid flow was passed through a pre-source splitter and 5% of the eluant was introduced into the atmospheric pressure ionization (API) source. The components were analyzed in the multiple-reaction monitoring (MRM) mode as the precursor/product ion pair of m/z 267.2/226.2 for NVP, 283.0/161.2 for 2-OHNVP, 297.2/279.2 for 4-CANVP, and 303.2/177.2 for hesperetin. Linear calibration curves were obtained in the range of 1-1000 ng/mL for NVP and 2-OHNVP and 5-1000 ng/mL for 4-CANVP, using 0.2 mL baboon serum, respectively. The within-day and between-day precisions were <10% for NVP and 2-OHNVP, and <11.5% for 4-CANVP. Due to the similar structures and fragmentation patterns of 2-OHNVP and 3-OHNVP, it is not expected that the LC/MS/MS can differentiate 2-OHNVP and 3-OHNVP and they were assayed as a composite. The method was applied to a single-dose escalation study of NVP in non-pregnant baboons (Papio anubis) to characterize the pharmacokinetics of NVP, 2-OHNVP plus 3-OHNVP, and 4-CANVP, and to determine the appropriate dose necessary to achieve comparable peak serum concentration of NVP as reported in healthy human adults. PMID:17654464

  19. Electrostatic super coupling in copper sulphide (Cu2S)-reduced graphene oxide composite and their enhanced optical characteristics

    NASA Astrophysics Data System (ADS)

    Kamalanathan, M.; Gopalakrishnan, R.

    2015-06-01

    The composite of reduced graphene oxide-Cu2S was synthesized by facile and cost effective one-step hydrothermal process. Powder XRD reveals the formation of Reduced Graphene Oxide (RGO) and Cu2S composite nanostructures. Average crystallite size of 16.5 nm was estimated for composite material from XRD measurement. Raman and FTIR analysis confirm the formation of graphene oxide and reduced graphene oxide-Cu2S composites. Origin of strong electrostatic interaction between Cu2S and RGO was also inferred from FTIR and Raman investigations. UV absorption spectral analysis illustrates the wide optical absorption region of the prepared composite material. The band gap of the composite was also calculated using the absorbance spectra. The obtained band gap of the composite was 1.64 eV which was much lower expected for copper sulphide particles in nano regime.

  20. A visible light photocatalytic cross-dehydrogenative coupling/dehydrogenation/6?-cyclization/oxidation cascade: synthesis of 12-nitroindoloisoquinolines from 2-aryltetrahydroisoquinolines.

    PubMed

    Rusch, Fabian; Unkel, Lisa-Natascha; Alpers, Dirk; Hoffmann, Frank; Brasholz, Malte

    2015-06-01

    A visible light-induced photocatalytic dehydrogenation/6?-cyclization/oxidation cascade converts 1-(nitromethyl)-2-aryl-1,2,3,4-tetrahydroisoquinolines into novel 12-nitro-substituted tetracyclic indolo[2,1-a]isoquinoline derivatives. Various photocatalysts promote the reaction in the presence of air and a base, the most efficient being 1-aminoanthraquinone in combination with K3 PO4 . Further, the 12-nitroindoloisoquinoline products can be accessed directly from C1-unfunctionalized 2-aryl-1,2,3,4-tetrahydroisoquinolines by extending the one-pot protocol with a foregoing photocatalytic cross-dehydrogenative coupling reaction, resulting in a quadruple cascade transformation. PMID:25917406

  1. Exchange bias and antiferromagnetic interfacial exchange coupling in the mixed-spin oxide Li{sub 2/7}Ni{sub 5/7}O

    SciTech Connect

    Shi, C. X.; Ren, W. J., E-mail: wjren@imr.ac.cn; Liu, W.; Zhang, Z. D. [Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016 (China)

    2014-01-28

    We present a detailed study on magnetic properties of mixed spin oxide Li{sub 2/7}Ni{sub 5/7}O, where small ferromagnetic (FM) clusters (with averaged diameter of ?18?Å) immersed with an antiferromagnetic (AFM) host. The exchange bias (EB) with shifts of the hysteresis loop along both the field and magnetization axes is found, which is due to the interfacial interaction between the FM clusters and the AFM host. An AFM interfacial exchange coupling is deduced from the exchange interactions between Ni ions. The type and strength of this interfacial exchange interaction are discussed in terms of the EB at low temperature.

  2. Detection of glucose via enzyme-coupling reaction based on a DT-diaphorase fluorescence probe.

    PubMed

    Gao, Xinghui; Li, Xiaohua; Wan, Qiongqiong; Li, Zhao; Ma, Huimin

    2014-03-01

    Enzyme-coupling reactions play an important role in the assay of analytes. In this manuscript, we developed a new fluorescent probe for the detection of glucose through the enzyme-coupling reaction of DT-diaphorase (DTD). The probe was synthesized through a mild and simple synthetic procedure, and showed good fluorescence response to DTD. The reactions for the detection of glucose proceed as follows: glucose dehydrogenase oxidizes glucose to gluconolactone with NAD(+) as the electron acceptor to yield NADH, and NADH can be utilized by DTD to further react with the probe releasing resorufin. As a result of these tandem reactions, fluorescence off-on response will occur. The method showed high selectivity for glucose with a detection limit of 0.2 µM, which may provide a potential way for fluorescence detection of glucose through enzyme-coupling reactions. Furthermore, the applicability of the method has been demonstrated by detecting glucose in human urine samples. PMID:24468396

  3. Clinical Quantitation of Prostate-specific Antigen Biomarker in the Low Nanogram/Milliliter Range by Conventional Bore Liquid Chromatography-Tandem Mass Spectrometry (Multiple Reaction Monitoring) Coupling and Correlation with ELISA Tests

    PubMed Central

    Fortin, Tanguy; Salvador, Arnaud; Charrier, Jean Philippe; Lenz, Cristof; Lacoux, Xavier; Morla, Aymeric; Choquet-Kastylevsky, Geneviève; Lemoine, Jérôme

    2009-01-01

    Proteomics discovery leads to a list of potential protein biomarkers that have to be subsequently verified and validated with a statistically viable number of patients. Although the most sensitive, the development of an ELISA test is time-consuming when antibodies are not available and need to be conceived. Mass spectrometry analysis driven in quantitative multiple reaction monitoring mode is now appearing as a promising alternative to quantify proteins in biological fluids. However, all the studies published to date describe limits of quantitation in the low ?g/ml range when no immunoenrichment of the target protein is applied, whereas the concentration of known clinical biomarkers is usually in the ng/ml range. Using prostate-specific antigen as a model biomarker, we now provide proof of principle that mass spectrometry enables protein quantitation in a concentration range of clinical interest without immunoenrichment. We have developed and optimized a robust sample processing method combining albumin depletion, trypsin digestion, and solid phase extraction of the proteotypic peptides starting from only 100 ?l of serum. For analysis, mass spectrometry was coupled to a conventional liquid chromatography system using a 2-mm-internal diameter reverse phase column. This mass spectrometry-based strategy was applied to the quantitation of prostate-specific antigen in sera of patients with either benign prostate hyperplasia or prostate cancer. The quantitation was performed against an external calibration curve by interpolation, and results showed good correlation with existing ELISA tests applied to the same samples. This strategy might now be implemented in any clinical laboratory or certified company for further evaluation of any putative biomarker in the low ng/ml range of serum or plasma. PMID:19068476

  4. Sensitive determination of isoprostanes in exhaled breath condensate samples with use of liquid chromatography-tandem mass spectrometry.

    PubMed

    Janicka, Monika; Kubica, Pawe?; Kot-Wasik, Agata; Kot, Jacek; Namie?nik, Jacek

    2012-04-15

    Oxidative stress is the hallmark of various inflammatory lung diseases. Increased concentrations of reactive oxygen species in the lungs are reflected by elevated concentrations of oxidative stress markers in the breath, airways, lung tissue and blood. The aim of this work was to develop a method for the fast measurement of F2-isoprostanes in exhaled breath condensate (EBC) samples using equipment which is nowadays available and routinely exploited in analytical laboratories, liquid chromatography coupled with tandem mass spectrometry. Because of the limited volume of an EBC sample and the very low concentrations of biomarkers, we chose lyophilization as the preconcentration technique. The diastereoisomers determined show similar fragmentation patterns, which is why complete chromatographic separation with excellent peak shapes was essential for accurate quantitation. Isoprostanes were separated using a narrow-bore Agilent Extend C-18 column in isocratic elution mode using acetonitrile/methanol and water with the addition of 0.01%(v/v) formic acid. The limits of determination and quantitation for the determination of four isoprostanes in samples of EBC ranged from 1 to 3 pg/ml. The recoveries of all isoprostanes ranged from 96.7 to 101.7, with a relative standard deviation of <7%. The stability of the isoprostanes at different temperatures was measured as well. PMID:22445305

  5. Pulsating Tandem Microbubble for Localized and Directional Single Cell Membrane Poration

    PubMed Central

    Sankin, G.N.; Yuan, F.; Zhong, P.

    2013-01-01

    The interaction of laser-generated tandem microbubble (maximum diameter about 50 ?m) with single (rat mammary carcinoma) cells is investigated in a 25-?m liquid layer. Anti-phase and coupled oscillation of the tandem microbubble leads to the formation of alternating, directional microjets (with max. microstreaming velocity of 10 m/s) and vortices (max. vorticity of 350,000 s?1) in opposite directions. Localized and directional membrane poration (200 nm to 2 ?m in pore size) can be produced by the tandem microbubble in an orientation and proximity dependent manner, which is absence from a single oscillating microbubble of comparable size and at the same stand-off distance. PMID:20868077

  6. Subsurface Uranium Fate and Transport: Integrated Experiments and Modeling of Coupled Biogeochemical Mechanisms of Nanocrystalline Uraninite Oxidation by Fe(III)-(hydr)oxides - Project Final Report

    SciTech Connect

    Peyton, Brent M. [Montana State University; Timothy, Ginn R. [University of California Davis; Sani, Rajesh K. [South Dakota School of Mines and Technology

    2013-08-14

    Subsurface bacteria including sulfate reducing bacteria (SRB) reduce soluble U(VI) to insoluble U(IV) with subsequent precipitation of UO2. We have shown that SRB reduce U(VI) to nanometer-sized UO2 particles (1-5 nm) which are both intra- and extracellular, with UO2 inside the cell likely physically shielded from subsequent oxidation processes. We evaluated the UO2 nanoparticles produced by Desulfovibrio desulfuricans G20 under growth and non-growth conditions in the presence of lactate or pyruvate and sulfate, thiosulfate, or fumarate, using ultrafiltration and HR-TEM. Results showed that a significant mass fraction of bioreduced U (35-60%) existed as a mobile phase when the initial concentration of U(VI) was 160 µM. Further experiments with different initial U(VI) concentrations (25 - 900 ?M) in MTM with PIPES or bicarbonate buffers indicated that aggregation of uraninite depended on the initial concentrations of U(VI) and type of buffer. It is known that under some conditions SRB-mediated UO2 nanocrystals can be reoxidized (and thus remobilized) by Fe(III)-(hydr)oxides, common constituents of soils and sediments. To elucidate the mechanism of UO2 reoxidation by Fe(III) (hydr)oxides, we studied the impact of Fe and U chelating compounds (citrate, NTA, and EDTA) on reoxidation rates. Experiments were conducted in anaerobic batch systems in PIPES buffer. Results showed EDTA significantly accelerated UO2 reoxidation with an initial rate of 9.5?M day-1 for ferrihydrite. In all cases, bicarbonate increased the rate and extent of UO2 reoxidation with ferrihydrite. The highest rate of UO2 reoxidation occurred when the chelator promoted UO2 and Fe(III) (hydr)oxide dissolution as demonstrated with EDTA. When UO2 dissolution did not occur, UO2 reoxidation likely proceeded through an aqueous Fe(III) intermediate as observed for both NTA and citrate. To complement to these laboratory studies, we collected U-bearing samples from a surface seep at the Rifle field site and have measured elevated U concentrations in oxic iron-rich sediments. To translate experimental results into numerical analysis of U fate and transport, a reaction network was developed based on Sani et al. (2004) to simulate U(VI) bioreduction with concomitant UO2 reoxidation in the presence of hematite or ferrihydrite. The reduction phase considers SRB reduction (using lactate) with the reductive dissolution of Fe(III) solids, which is set to be microbially mediated as well as abiotically driven by sulfide. Model results show the oxidation of HS– by Fe(III) directly competes with UO2 reoxidation as Fe(III) oxidizes HS– preferentially over UO2. The majority of Fe reduction is predicted to be abiotic, with ferrihydrite becoming fully consumed by reaction with sulfide. Predicted total dissolved carbonate concentrations from the degradation of lactate are elevated (log(pCO2) ~ –1) and, in the hematite system, yield close to two orders-of-magnitude higher U(VI) concentrations than under initial carbonate concentrations of 3 mM. Modeling of U(VI) bioreduction with concomitant reoxidation of UO2 in the presence of ferrihydrite was also extended to a two-dimensional field-scale groundwater flow and biogeochemically reactive transport model for the South Oyster site in eastern Virginia. This model was developed to simulate the field-scale immobilization and subsequent reoxidation of U by a biologically mediated reaction network.

  7. Total microcystins analysis in water using laser diode thermal desorption-atmospheric pressure chemical ionization-tandem mass spectrometry.

    PubMed

    Roy-Lachapelle, Audrey; Fayad, Paul B; Sinotte, Marc; Deblois, Christian; Sauvé, Sébastien

    2014-04-11

    A new approach for the analysis of the cyanobacterial microcystins (MCs) in environmental water matrices has been developed. It offers a cost efficient alternative method for the fast quantification of total MCs using mass spectrometry. This approach permits the quantification of total MCs concentrations without requiring any derivatization or the use of a suite of MCs standards. The oxidation product 2-methyl-3-methoxy-4-phenylbutyric acid (MMPB) was formed through a Lemieux oxidation and represented the total concentration of free and bound MCs in water samples. MMPB was analyzed using laser diode thermal desorption-atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS). LDTD is a robust and reliable sample introduction method with ultra-fast analysis time (<15 s sample(-1)). Several oxidation and LDTD parameters were optimized to improve recoveries and signal intensity. MCs oxidation recovery yield was 103%, showing a complete reaction. Internal calibration with standard addition was achieved with the use of 4-phenylbutyric acid (4-PB) as internal standard and showed good linearity (R(2)>0.999). Limits of detection and quantification were 0.2 and 0.9 ?g L(-1), respectively. These values are comparable with the WHO (World Health Organization) guideline of 1 ?g L(-1) for total microcystin-LR congener in drinking water. Accuracy and interday/intraday variation coefficients were below 15%. Matrix effect was determined with a recovery of 91%, showing no significant signal suppression. This work demonstrates the use of the LDTD-APCI-MS/MS interface for the screening, detection and quantification of total MCs in complex environmental matrices. PMID:24745740

  8. Coupled Fe(II)-Fe(III) electron and atom exchange as a mechanism for Fe isotope fractionation during dissimilatory iron oxide reduction.

    PubMed

    Crosby, Heidi A; Johnson, Clark M; Roden, Eric E; Beard, Brian L

    2005-09-01

    Microbial dissimilatory iron reduction (DIR) is an important pathway for carbon oxidation in anoxic sediments, and iron isotopes may distinguish between iron produced by DIR and other sources of aqueous Fe(II). Previous studies have shown that aqueous Fe(II) produced during the earliest stages of DIR has delta56Fe values that are 0.5-2.0%o lowerthan the initial Fe(III) substrate. The new experiments reported here suggest that this fractionation is controlled by coupled electron and Fe atom exchange between Fe(II) and Fe(III) at iron oxide surfaces. In hematite and goethite reduction experiments with Geobacter sulfurreducens, the 56Fe/54Fe isotopic fractionation between aqueous Fe(II) and the outermost layers of Fe(III) on the oxide surface is approximately -3%o and can be explained by equilibrium Fe isotope partitioning between reactive Fe(II) and Fe(III) pools that coexist during DIR. The results indicate that sorption of Fe(II) to Fe(III) substrates cannot account for production of low-delta56Fe values for aqueous Fe(II) during DIR. PMID:16190229

  9. Weak coupling between sulfate reduction and the anaerobic oxidation of methane in methane-rich seafloor sediments during ex situ incubation

    NASA Astrophysics Data System (ADS)

    Bowles, Marshall W.; Samarkin, Vladimir A.; Bowles, Kathy M.; Joye, Samantha B.

    2011-01-01

    We investigated coupling between sulfate reduction (SR) and anaerobic oxidation of methane (AOM) by quantifying pore water geochemical profiles, determining rates of microbial processes, and examining microbial community structure at two sites within Mississippi Canyon lease block 118 (MC118) in the Northern Gulf of Mexico. Sediments from the northwest seep contained high concentrations of methane while sediments from the southwest seep contained methane, gaseous n-alkanes and liquid hydrocarbons and had abundant surficial accumulations of gas hydrate. Volumetric (21.5 ?mol cm -3 day -1) and integrated (1429 mmol m -2 day -1) rates of SR at MC118 in ex situ incubations are the highest reported thus far for seafloor environments. AOM rates were small in comparison, with volumetric rates ranging from 0.1 to 12.6 nmol cm -3 day -1. Diffusion cannot adequately supply the sulfate required to support these high SR rates so additional mechanisms, possibly biological sulfide oxidation and/or downward advection, play important roles in supplying sulfate at these sites. The microbial communities at MC118 included sulfate-reducing bacteria phylogenetically associated with Desulfobacterium anilini, which is capable of complex hydrocarbon degradation. Despite low AOM rates, the majority of archaea identified were phylogenetically related to previously described methane oxidizing archaea. To evaluate whether weak coupling between SR and AOM occurs in habitats lacking the complex hydrocarbon milieu present at MC118, we compiled available SR and AOM rates and found that the global median ratio of SR to AOM was 10.7:1 rather than the expected 1:1. The global median integrated AOM rate was used to refine global estimates for AOM rates at cold seeps; these new estimates are only 5% of the previous estimate.

  10. Performance of a solid oxide fuel cell CHP system coupled with a hot water storage tank for

    E-print Network

    Berning, Torsten

    a solid oxide fuel cell (SOFC) system for cogeneration of heat and power integrated with a stratified heat and returning the coldest fluid back to SOFC heat recovery heat-exchanger. A model of the SOFC system gradients over the tank height. The results of the numerical simulation are used to size the SOFC system

  11. In vitro demonstration of anaerobic oxidation of methane coupled to sulphate reduction in sediment from a marine gas hydrate area

    Microsoft Academic Search

    Katja Nauhaus; Antje Boetius; Martin Kruger; Friedrich Widdel

    2002-01-01

    Summary Anaerobic oxidation of methane (AOM) and sulphate reduction were examined in sediment samples from a marine gas hydrate area (Hydrate Ridge, NE Pacific). The sediment contained high numbers of microbial consortia consisting of organisms that affi- liate with methanogenic archaea and with sulphate- reducing bacteria. Sediment samples incubated under strictly anoxic conditions in defined mineral medium (salinity as in

  12. High performance liquid chromatography coupled with post-column electrochemical oxidation for the detection of PSP toxins.

    PubMed

    Boyer, G L; Goddard, G D

    1999-01-01

    High Performance Liquid Chromatography (HPLC) is an important tool for the study of PSP toxins. It provides an alternative to bioassays and gives the concentration of individual toxin isomers. The current HPLC protocol uses a post-column chemical reaction system (PCRS) to oxidize the saxitoxin ring system to form a fluorescent chromophore. This oxidation is sensitive to changes in the flow rate, temperature, pH and age of the reagents. We have previously shown that this oxidation can be accomplished using electrochemical techniques. Termed the electrochemical oxidation system (ECOS), this approach provides a simpler alternative to the traditional PCRS-based HPLC system. A detailed description of the construction and maintenance of an HPLC-ECOS system for the analysis of PSP toxins is presented. Comparisons of the mouse bioassay, HPLC-PCRS and HPLC-ECOS system are presented for three different sample matrices: toxic dinoflagellates (Alexandrium tamarense), geoduck (Panopea generosa) and scallops (Placopectin magellanicus). In all three cases, the correlation of the HPLC-ECOS system to the mouse bioassay is similar to that obtained using the HPLC-PCRS system for the analysis of PSP toxins. PMID:11122529

  13. THE EFICACY OF OXIDATIVE COUPLING FOR PROMOTING IN-SITU IMMOBILIZATION OF HYDROXYLATED AROMATICS IN CONTAMINATED SOIL AND SEDIMENTS SYSTEMS

    EPA Science Inventory

    An urgent science need for DOE is to obtain a better understanding of processes controlling the fate and transport of contaminants in subsurface environments in order to improve conceptual modeling capabilities and current remediation technologies. Our research on the oxidative c...

  14. Ultrasensitive diagnosis for an anthrax-protective antigen based on a polyvalent directed peptide polymer coupled to zinc oxide nanorods.

    PubMed

    Park, Hye-Yeon; Gedi, Vinayakumar; Kim, Joungmok; Park, Hae-Chul; Han, Sung-Hwan; Yoon, Moon-Young

    2011-12-01

    A flexible poly-D-lysine polymer conjugated with different target-binding peptides is demonstrated with an ultralow concentration detection limit compared to those of other conventional detection systems. This polyvalent directed peptide polymer (PDPP) exhibits increased binding affinity and detects anthrax protective antigen at low levels using a well-known zinc oxide nanorod detection system. PMID:21997757

  15. A decoupled observer for tandem systems

    E-print Network

    Earhart, Robert Jenkins

    1971-01-01

    A DECOUPLED OBSERVER FOR TANDEM SYSTEMS A Thesis by Robert Jenkins Earhart Submitted to the Graduate College of Texas AGM University in partial fulfillment of the requirement for the degree of MASTER OF SCIENCE August 1971 Major Subject...: Electrical Engineering A DECOUPLED OBSERVER FOR TANDEM SYSTEMS A Thesis by Robert Jenkins Earhart Approved as to style and content by: ( airman of Comms tee) He of D tment) Member) Member) Member) (Member) Member August 1971 ABSTRACT A Decoupled...

  16. Microstability of the TMX tandem mirror experiments

    Microsoft Academic Search

    T. A. Casper; L. V. Berzins

    1987-01-01

    In the tandem mirror device, an efficient source of warm ions, the central cell, is available for stabilization of ion loss-cone instabilities. These instabilities previously limited ion confinement in single-cell mirror experiments. In the simple tandem mirror device, TMX, the drift cyclotron loss-cone (DCLC) mode was stabilized by plasma flow from the central cell into the end cell. However, to

  17. Enhancing light out-coupling of organic light-emitting devices using indium tin oxide-free low-index transparent electrodes

    SciTech Connect

    Huang, Yi-Hsiang; Lu, Chun-Yang; Tsai, Shang-Ta; Tsai, Yu-Tang; Chen, Chien-Yu; Tsai, Wei-Lung; Lin, Chun-Yu; Chang, Hong-Wei; Lee, Wei-Kai; Jiao, Min; Wu, Chung-Chih, E-mail: wucc@ntu.edu.tw [Department of Electrical Engineering, Graduate Institute of Photonics and Optoelectronics, Graduate Institute of Electronics Engineering, and Innovative Photonics Advanced Research Center (i-PARC), National Taiwan University, Taipei 10617, Taiwan (China)

    2014-05-05

    With its increasing and sufficient conductivity, the conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has been capable of replacing the widely used but less cost-effective indium tin oxides (ITOs) as alternative transparent electrodes for organic light-emitting devices (OLEDs). Intriguingly, PEDOT:PSS also possesses an optical refractive index significantly lower than those of ITO and typical organic layers in OLEDs and well matching those of typical OLED substrates. Optical simulation reveals that by replacing ITO with such a low-index transparent electrode, the guided modes trapped within the organic/ITO layers in conventional OLEDs can be substantially suppressed, leading to more light coupled into the substrate than the conventional ITO device. By applying light out-coupling structures onto outer surfaces of substrates to effectively extract radiation into substrates, OLEDs using such low-index transparent electrodes achieve enhanced optical out-coupling and external quantum efficiencies in comparison with conventional OLEDs using ITO.

  18. Magnetic phase coupled to an electric memory state in d0 oxide ZrO2 films

    Microsoft Academic Search

    Y. Jo; I. R. Hwang; B. H. Park; K. J. Lee; S. I. Lee; M. H. Jung

    2009-01-01

    It is quite interesting to develop a multifunctional device using a single material with a simple structure. One of the possible candidates could be multiferroics, which are both ferroelectric and magnetic. By taking advantage of the strong spin-charge coupling, the electric field can control the magnetic polarization and the magnetic field can control the electric polarization. However, these multiferroics are

  19. Coupled Monte Carlo-Energy Relaxation Analysis of Hot Carrier Light Emission in Metal Oxide Semiconductor Field Effect Transistors's

    Microsoft Academic Search

    Hiroyuki Kurino; Hiroyuki Kiba; Hiroki Mori; Shin Yokoyama; Ken Yamaguchi; Mitsumasa Koyanagi

    1991-01-01

    A new two-dimensional device simulator to analyze hot carrier photon emission has been developed. A new calculation algorithm of coupled Monte Carlo energy relaxation analysis is employed to obtain the carrier temperature distribution and the carrier energy distribution function at a fast computation turn around time. The relation between the hot carrier energy and the photon emission characteristics is easily

  20. Palladium/zirconium oxide nanocomposite as a highly recyclable catalyst for C-C coupling reactions in water.

    PubMed

    Monopoli, Antonio; Nacci, Angelo; Calò, Vincenzo; Ciminale, Francesco; Cotugno, Pietro; Mangone, Annarosa; Giannossa, Lorena Carla; Azzone, Pietro; Cioffi, Nicola

    2010-07-01

    Palladium nanoparticles have been electrochemically supported on zirconium oxide nanostructured powders and all the nanomaterials have been characterized by several analytical techniques. The Pd/ZrO(2) nanocatalyst is demonstrated to be a very efficient catalyst in Heck, Ullmann, and Suzuki reactions of aryl halides in water. The catalyst efficiency is attributed to the stabilization of Pd nanophases provided by tetra(alkyl)- ammonium hydroxide, which behaves both as base and PTC (phase transfer catalyst) agent. PMID:20657374

  1. Oxidative chemistry of the natural antioxidant hydroxytyrosol: hydrogen peroxide-dependent hydroxylation and hydroxyquinone\\/ o-quinone coupling pathways

    Microsoft Academic Search

    Maria De Lucia; Lucia Panzella; Alessandro Pezzella; Alessandra Napolitano; Marco d'Ischia

    2006-01-01

    Oxidation of the natural antioxidant hydroxytyrosol (1) with peroxidase\\/H2O2 in phosphate buffer at pH 7.4 led to the formation of two main ethyl acetate-extractable products. These could be isolated by preparative TLC after reduction and acetylation, and were identified as the tetraacetyl derivative of 2-(2,4,5-trihydroxyphenyl)ethanol (3) and the heptaacetyl derivative of the pentahydroxybiphenyl 4 by 2D NMR and MS analysis.

  2. Fast Photochemical Oxidation of Proteins Coupled to Multidimensional Protein Identification Technology (MudPIT): Expanding Footprinting Strategies to Complex Systems

    NASA Astrophysics Data System (ADS)

    Rinas, Aimee; Jones, Lisa M.

    2015-04-01

    Peptides containing the oxidation products of hydroxyl radical-mediated protein footprinting experiments are typically much less abundant than their unoxidized counterparts. This is inherent to the design of the experiment as excessive oxidation may lead to undesired conformational changes or unfolding of the protein, skewing the results. Thus, as the complexity of the systems studied using this method expands, the detection and identification of these oxidized species can be increasingly difficult with the limitations of data-dependent acquisition (DDA) and one-dimensional chromatography. Here we report the application of multidimensional protein identification technology (MudPIT) in combination with hydroxyl radical footprinting as a method to increase the identification of quantifiable peptides in these experiments. Using this method led to a 37% increase in unique peptide identifications as well as a 70% increase in protein group identifications over one-dimensional data-dependent acquisition on the same samples. Furthermore, we demonstrate the combination of these methods as a means to investigate megadalton complexes.

  3. Quantitation of carbon in oil shale process wastewaters: coulometry coupled with ultraviolet-peroxydisulfate and high-temperature oxidation

    SciTech Connect

    Langlois, G.W.; Jones, B.M.; Sakaji, R.H.; Daughton, C.G.

    1984-07-01

    Wastewaters from the production of synfuels, in particular oil shale retort waters, present several major problems to various instrument configurations designed for carbon analysis. A carbon analyzer was fabricated from commercially available oxidation and detection units. Carbon oxidation occurred in an ultraviolet (UV) photochemical reactor using acid peroxydisulfate; quantitation of the evolved carbon dioxide was accomplished with an automatic coulometric titrator. This new design eliminated the problems of (1) instrument downtime caused by fouling of high-temperature combustion catalysts and corrosion of furnace combustion tubes, (2) limited linear dynamic range and upper detection limit (namely, infrared detection), and (3) frequent detector calibration (namely, infrared and flame ionization detection). The UV-persulfate/coulometric titration carbon analyzer was compared statistically with a high-temperature combustion system that is suitable for use with an ASTM method on the basis of (1) the accuracy and precision of recovery of total dissolved carbon (TDC) and dissolved organic carbon (DOC) for nitrogen heterocycles, which were of primary interest because of their preponderance in oil shale process waters and their reported resistance to certain oxidation methods, and (2) the precision of TDC and DOC determinations for nine oil shale process wastewaters. Several qualitative considerations are discussed for both analyzers, including ease of operation, instrument downtime, and maintenance costs. 35 references, 7 figures, 5 tables.

  4. A novel tandem sequence to pyrrole syntheses by 5-endo-dig cyclization of 1,3-enynes with amines.

    PubMed

    Bharathiraja, Ganesan; Sakthivel, Sekarpandi; Sengoden, Mani; Punniyamurthy, Tharmalingam

    2013-10-01

    The synthesis of pentasubstituted pyrroles has been described using molecular iodine from 1,3-enynes and amines via a sequential tandem aza-Michael addition, iodocyclization, and oxidative aromatization. The protocol is simple and efficient to afford the target products at ambient conditions. PMID:24032607

  5. Iron-facilitated oxidative radical decarboxylative cross-coupling between ?-oxocarboxylic acids and acrylic acids: an approach to ?,?-unsaturated carbonyls.

    PubMed

    Jiang, Qing; Jia, Jing; Xu, Bin; Zhao, An; Guo, Can-Cheng

    2015-04-01

    The first Fe-facilitated decarboxylative cross-coupling reaction between ?-oxocarboxylic acids and acrylic acids in aqueous solution has been developed. This transformation is characterized by its wide substrate scope and good functional group compatibility utilizing inexpensive and easily accessible reagents, thus providing an efficient and expeditious approach to an important class of ?,?-unsaturated carbonyls frequently found in bioactive compounds. The synthetic potential of the coupled products is also demonstrated in subsequent functionalization reactions. Preliminary mechanism studies suggest that a free radical pathway is involved in this process: the generation of an acyl radical from ?-oxocarboxylic acid via the excision of carbon dioxide followed by the addition of an acyl radical to the ?-position of the double bond in acrylic acid then delivers the ?,?-unsaturated carbonyl adduct through the extrusion of another carbon dioxide. PMID:25757053

  6. A peroxynitrite complex of copper: formation from a copper–nitrosyl complex, transformation to nitrite and exogenous phenol oxidative coupling or nitration

    PubMed Central

    Park, Ga Young; Deepalatha, Subramanian; Puiu, Simona C.; Lee, Dong-Heon; Mondal, Biplab; Sarjeant, Amy A. Narducci; del Rio, Diego; Pau, Monita Y. M.; Solomon, Edward I.; Karlin, Kenneth D.

    2010-01-01

    Reaction of nitrogen monoxide with a copper(I) complex possessing a tridentate alkylamine ligand gives a Cu(I)–(·NO) adduct, which when exposed to dioxygen generates a peroxynitrite (O=NOO?)–Cu(II) species. This undergoes thermal transformation to produce a copper(II) nitrito (NO2?) complex and 0.5 mol equiv O2. In the presence of a substituted phenol, the peroxynitrite complex effects oxidative coupling, whereas addition of chloride ion to dissociate the peroxynitrite moiety instead leads to phenol ortho nitration. Discussions include the structures (including electronic description) of the copper–nitrosyl and copper–peroxynitrite complexes and the formation of the latter, based on density functional theory calculations and accompanying spectroscopic data. PMID:19662443

  7. Base-catalyzed halogen dance reaction and oxidative coupling sequence as a convenient method for the preparation of dihalo-bisheteroarenes.

    PubMed

    Getmanenko, Yulia A; Tongwa, Paul; Timofeeva, Tatiana V; Marder, Seth R

    2010-05-01

    A one-pot preparation of the 2,2'-dibromo-1,1'-bisheteroarenes 3a-d from bromo-heteroarenes utilizing the sequence of the base-catalyzed halogen dance (BCHD) reaction and CuCl(2)-promoted oxidative coupling of the in situ formed alpha-lithio-beta-halo-heteroarenes 2a-d provides a convenient access to precursors for the preparation of tricyclic heteroaromatic cores. The structures of 3a,b,d, 6, and 9 were confirmed by single-crystal X-ray analysis, and dibromides 3a and 3b were used for the preparation of dithieno-[2,3-b:3',2'-d]-pyrrole 10a and its selenophene analogue 10b, respectively. PMID:20377230

  8. The use of a gas chromatograph coupled to a metal oxide sensor for rapid assessment of stool samples from irritable bowel syndrome and inflammatory bowel disease patients.

    PubMed

    Shepherd, S F; McGuire, N D; de Lacy Costello, B P J; Ewen, R J; Jayasena, D H; Vaughan, K; Ahmed, I; Probert, C S; Ratcliffe, N M

    2014-06-01

    There is much clinical interest in the development of a low-cost and reliable test for diagnosing inflammatory bowel disease (IBD) and irritable bowel syndrome (IBS), two very distinct diseases that can present with similar symptoms. The assessment of stool samples for the diagnosis of gastro-intestinal diseases is in principle an ideal non-invasive testing method. This paper presents an approach to stool analysis using headspace gas chromatography and a single metal oxide sensor coupled to artificial neural network software. Currently, the system is able to distinguish samples from patients with IBS from patients with IBD with a sensitivity and specificity of 76% and 88% respectively, with an overall mean predictive accuracy of 76%. PMID:24674940

  9. Synfuels from fusion: using the tandem mirror reactor and a thermochemical cycle to produce hydrogen

    SciTech Connect

    Werner, R.W. (ed.)

    1982-11-01

    This study is concerned with the following area: (1) the tandem mirror reactor and its physics; (2) energy balance; (3) the lithium oxide canister blanket system; (4) high-temperature blanket; (5) energy transport system-reactor to process; (6) thermochemical hydrogen processes; (7) interfacing the GA cycle; (8) matching power and temperature demands; (9) preliminary cost estimates; (10) synfuels beyond hydrogen; and (11) thermodynamics of the H/sub 2/SO/sub 4/-H/sub 2/O system. (MOW)

  10. Acrolein coupling on reduced TiO 2(1 1 0): The effect of surface oxidation and the role of subsurface defects

    NASA Astrophysics Data System (ADS)

    Benz, Lauren; Haubrich, Jan; Quiller, Ryan G.; Friend, Cynthia M.

    2009-04-01

    Reactions of acrolein, water, and oxygen with the vacuum-reduced surface of TiO 2(1 1 0) are reported in a temperature programmed reaction study of the interaction of an aldehydic pollutant with a reducible metal oxide. A total of 25% of the acrolein that binds to the surface is converted to products. Notably, carbon-carbon coupling occurs with 86% selectivity for formation of C 6 products: C 6H 8, identified as 1,3-cyclohexadiene, in a peak at 500 K and benzene immediately thereafter at 530 K. Acrolein is evolved from the surface in three peaks: a peak independent of coverage at 495 K, attributed to decomposition of an intermediate that is partly converted to C 6H 8; a coverage-dependent peak that shifts from 370 K (low coverage) to 260 K (high coverage), which is attributed to adsorption at 5-fold coordinated Ti sites; and a multilayer state at 160 K. Water and acrolein compete for 5-fold coordinated titanium sites when dosed sequentially. The addition of water also opens a new reaction pathway, leading to the hydrogenation of acrolein to form propanal. Water has no effect on the yield of 1,3-cyclohexadiene. Exposure of the surface to oxygen prior to acrolein dosing quenches the evolution of acrolein at 495 K and concurrently eliminates the coupling. From these results, we propose that reduced subsurface defects such as titanium ion interstitials play a role in the reactions observed here. The notion that subsurface defects may contribute to the reactivity of organic molecules over reducible oxide substrates may prove to be general.

  11. Endothelial Nitric-oxide Synthase (eNOS) Is Activated through G-protein-coupled Receptor Kinase-interacting Protein 1 (GIT1) Tyrosine Phosphorylation and Src Protein*

    PubMed Central

    Liu, Songling; Premont, Richard T.; Rockey, Don C.

    2014-01-01

    Nitric oxide (NO) is a critical regulator of vascular tone and plays an especially prominent role in liver by controlling portal blood flow and pressure within liver sinusoids. Synthesis of NO in sinusoidal endothelial cells by endothelial nitric-oxide synthase (eNOS) is regulated in response to activation of endothelial cells by vasoactive signals such as endothelins. The endothelin B (ETB) receptor is a G-protein-coupled receptor, but the mechanisms by which it regulates eNOS activity in sinusoidal endothelial cells are not well understood. In this study, we built on two previous strands of work, the first showing that G-protein ?? subunits mediated activation of phosphatidylinositol 3-kinase and Akt to regulate eNOS and the second showing that eNOS directly bound to the G-protein-coupled receptor kinase-interacting protein 1 (GIT1) scaffold protein, and this association stimulated NO production. Here we investigated the mechanisms by which the GIT1-eNOS complex is formed and regulated. GIT1 was phosphorylated on tyrosine by Src, and Y293F and Y554F mutations reduced GIT1 phosphorylation as well as the ability of GIT1 to bind to and activate eNOS. Akt phosphorylation activated eNOS (at Ser1177), and Akt also regulated the ability of Src to phosphorylate GIT1 as well as GIT1-eNOS association. These pathways were activated by endothelin-1 through the ETB receptor; inhibiting receptor-activated G-protein ?? subunits blocked activation of Akt, GIT1 tyrosine phosphorylation, and ET-1-stimulated GIT1-eNOS association but did not affect Src activation. These data suggest a model in which Src and Akt cooperate to regulate association of eNOS with the GIT1 scaffold to facilitate NO production. PMID:24764294

  12. Numerical simulation of in-situ chemical oxidation (ISCO) and biodegradation of petroleum hydrocarbons using a coupled model for bio-geochemical reactive transport

    NASA Astrophysics Data System (ADS)

    Marin, I. S.; Molson, J. W.

    2013-05-01

    Petroleum hydrocarbons (PHCs) are a major source of groundwater contamination, being a worldwide and well-known problem. Formed by a complex mixture of hundreds of organic compounds (including BTEX - benzene, toluene, ethylbenzene and xylenes), many of which are toxic and persistent in the subsurface and are capable of creating a serious risk to human health. Several remediation technologies can be used to clean-up PHC contamination. In-situ chemical oxidation (ISCO) and intrinsic bioremediation (IBR) are two promising techniques that can be applied in this case. However, the interaction of these processes with the background aquifer geochemistry and the design of an efficient treatment presents a challenge. Here we show the development and application of BIONAPL/Phreeqc, a modeling tool capable of simulating groundwater flow, contaminant transport with coupled biological and geochemical processes in porous or fractured porous media. BIONAPL/Phreeqc is based on the well-tested BIONAPL/3D model, using a powerful finite element simulation engine, capable of simulating non-aqueous phase liquid (NAPL) dissolution, density-dependent advective-dispersive transport, and solving the geochemical and kinetic processes with the library Phreeqc. To validate the model, we compared BIONAPL/Phreeqc with results from the literature for different biodegradation processes and different geometries, with good agreement. We then used the model to simulate the behavior of sodium persulfate (NaS2O8) as an oxidant for BTEX degradation, coupled with sequential biodegradation in a 2D case and to evaluate the effect of inorganic geochemistry reactions. The results show the advantages of a treatment train remediation scheme based on ISCO and IBR. The numerical performance and stability of the integrated BIONAPL/Phreeqc model was also verified.

  13. Structural changes coupled to two-electron-transfer reactions: Oxidation mechanism of pseudo-triple-decker complexes of Co and Rh

    SciTech Connect

    Edwin, J.; Geiger, W.E. (Univ. of Vermont, Burlington (USA))

    1990-09-26

    A series of four pseudo-triple-decker complexes ({eta}{sup 5}-C{sub 5}R{sub 5}){sub 2}M{sub 2}({mu}-C{sub 8}H{sub 8}), M = Co or Rh, R = H or Me, undergoes a chemically reversible two-electron oxidation. The neutral complexes have the two metals on either side of a tub-shaped cyclooctatetraene bridging ligand, whereas the dications have a twisted bridging C{sub 8} ring which has two planar C{sub 4} fragments. The two dicobalt complexes Cp{sub 2}Co{sub 2}({mu}-C{sub 8}H{sub 8}), 1, and Cp{sup *}{sub 2}Co{sub 2}({mu}-C{sub 8}H{sub 8}), 2, display quasi-reversible couples with E{degree} = +0.10 V vs SCE, k{sub s} > 2 {times} 10{sup {minus}2} cm/s and E{degree} = {minus}0.22 V, k{sub s} = 4.6 {times} 10{sup {minus}3} cm/s, respectively, in CH{sub 2}Cl{sub 2}. This conclusion is based on data from cyclic voltammetry, controlled potential coulometry, dc polarography, and rotating ring-disc voltammetry experiments. Similar experiments on the dirhodium complex 3, Cp{sub 2}Rh{sub 2}({mu}-C{sub 8}H{sub 8}), show more complex voltammetric behavior. The oxidation wave for 3/3{sup 2+} is over 500 mV positive of the reduction wave for 3{sup 2+}/3, with CV peak potentials of ca. +0.43 V for the former and {minus}0.11 V for the latter. This couple is described by a square scheme in which the electron-transfer reactions are experimentally separable from the tub {rightleftharpoons} twist isomerizations.

  14. Delivery of tobramycin coupled to iron oxide nanoparticles across the biofilm of mucoidal Pseudonomas aeruginosa and investigation of its efficacy

    NASA Astrophysics Data System (ADS)

    Armijo, Leisha M.; Kopciuch, Michael; Olszá½¹wka, Zuzia; Wawrzyniec, Stephen J.; Rivera, Antonio C.; Plumley, John B.; Cook, Nathaniel C.; Brandt, Yekaterina I.; Huber, Dale L.; Smolyakov, Gennady A.; Adolphi, Natalie L.; Smyth, Hugh D. C.; Osi?ski, Marek

    2014-03-01

    Pseudomonas aeruginosa bacterium is a deadly pathogen, leading to respiratory failure in cystic fibrosis and nosocomial pneumonia, and responsible for high mortality rates in these diseases. P. aeruginosa has inherent as well as acquired resistance to many drug classes. In this paper, we investigate the effectiveness of two classes; aminoglycoside (tobramycin) and fluoroquinolone (ciprofloxacin) administered alone, as well as conjugated to iron oxide (magnetite) nanoparticles. P. aeruginosa possesses the ability to quickly alter its genetics to impart resistance to the presence of new, unrecognized treatments. As a response to this impending public health threat, we have synthesized and characterized magnetite nanoparticles capped with biodegradable short-chain carboxylic acid derivatives conjugated to common antibiotic drugs. The functionalized nanoparticles may carry the drug past the mucus and biofilm layers to target the bacterial colonies via magnetic gradient-guided transport. Additionally, the magnetic ferrofluid may be used under application of an oscillating magnetic field to raise the local temperature, causing biofilm disruption, slowed growth, and mechanical disruption. These abilities of the ferrofluid would also treat multi-drug resistant strains, which appear to be increasing in many nosocomial as well as acquired opportunistic infections. In this in vitro model, we show that the iron oxide alone can also inhibit bacterial growth and biofilm formation.

  15. Aerobic oxidation of methanol to formic acid on Au8-: benchmark analysis based on completely renormalized coupled-cluster and density functional theory calculations.

    PubMed

    Hansen, Jared A; Ehara, Masahiro; Piecuch, Piotr

    2013-10-10

    The left-eigenstate completely renormalized coupled-cluster (CC) method with singles, doubles, and noniterative triples [CR-CC(2,3)] and a few representative density functional theory (DFT) approaches have been applied to methanol oxidation to formic acid on a Au8(-) cluster, which is a model for aerobic oxidations on gold nanoparticles. It is demonstrated that CR-CC(2,3) supports the previous exothermic reaction mechanism, placing the initial rate-determining transition state, which corresponds to hydrogen transfer from the methoxy species to the molecular oxygen, at about 20 kcal/mol above the reactants, less than 40 kcal/mol above the O2 and CH3O(-) species coadsorbed on Au8(-), and considerably above the remaining two transition states along the reaction pathway. The DFT calculations using the previously exploited M06 hybrid functional show reasonable agreement with CR-CC(2,3), but B3LYP offers additional improvements in the description of the relevant activation energies. Pure functionals, including M06-L, BP86, and TPSS, do not work well, significantly underestimating the activation barriers, but dispersion corrections, as in B97-D, bring the results closer to the M06 accuracy level. PMID:23962375

  16. Ant search strategies after interrupted tandem runs.

    PubMed

    Franks, Nigel R; Richardson, Thomas O; Keir, Samantha; Inge, Stephen J; Bartumeus, Frederic; Sendova-Franks, Ana B

    2010-05-01

    Tandem runs are a form of recruitment in ants. During a tandem run, a single leader teaches one follower the route to important resources such as sources of food or better nest sites. In the present study, we investigate what tandem leaders and followers do, in the context of nest emigration, if their partner goes missing. Our experiments involved removing either leaders or followers at set points during tandem runs. Former leaders first stand still and wait for their missing follower but then most often proceed alone to the new nest site. By contrast, former followers often first engage in a Brownian search, for almost exactly the time that their former leader should have waited for them, and then former followers switch to a superdiffusive search. In this way, former followers first search their immediate neighbourhood for their lost leader before becoming ever more wide ranging so that in the absence of their former leader they can often find the new nest, re-encounter the old one or meet a new leader. We also show that followers gain useful information even from incomplete tandem runs. These observations point to the important principle that sophisticated communication behaviours may have evolved as anytime algorithms, i.e. procedures that are beneficial even if they do not run to completion. PMID:20435821

  17. Analysis of caged xanthones from the resin of Garcinia hanburyi using ultra-performance liquid chromatography\\/electrospray ionization quadrupole time-of-flight tandem mass spectrometry

    Microsoft Academic Search

    Yan Zhou; Xin Liu; Jing Yang; Quan-Bin Han; Jing-Zheng Song; Song-Lin Li; Chun-Feng Qiao; Li-Sheng Ding; Hong-Xi Xu

    2008-01-01

    On-line ultra high-performance liquid chromatography (UHPLC) coupled with electrospray quadrupole time-of-flight tandem mass spectrometry (ESI–QTOF–MS\\/MS\\/MS) has been developed for the analysis of a series of caged xanthones in the resin of Garcinia hanburyi. The fragmentation of protonated molecular ions for 12 known cadged xanthones was carried out using low-energy collision-induced electrospray ionization tandem mass spectrometry. It was found that Retro-Diels-Alder

  18. Graphene oxide liquid crystals as a versatile and tunable alignment medium for the measurement of residual dipolar couplings in organic solvents.

    PubMed

    Lei, Xinxiang; Xu, Zhen; Sun, Han; Wang, Shun; Griesinger, Christian; Peng, Li; Gao, Chao; Tan, Ren X

    2014-08-13

    Residual dipolar couplings (RDCs) have proven to be an invaluable anisotropic NMR parameter for the structural elucidation of complex biopolymers and organic molecules. However, a remaining bottleneck limiting its wider use by organic and natural product chemists is the lack of a range of easily applicable aligning media for diverse organic solvents. In this study, graphene oxide (GO) liquid crystals (LCs) were developed to induce partial orientation of organic molecules to allow RDC measurements. These LCs were determined to be maintainable at very low concentrations (as low as 1 mg/mL, corresponding to quadrupolar (2)H splittings ranging from 2.8 to 30 Hz and maximum (13)C-(1)H dipolar couplings of 20 Hz for camphor in a CH3COCH3/water system) and to be remarkably stable and broadly compatible with aqueous and organic solvents such as dimethyl sulfoxide, CH3COCH3, and CH3CN. Moreover, compared with those for other alignment media, very clean and high-quality NMR spectra were acquired with the GO molecules in solution because of their rigidity and high molecular weight. The developed medium offers a versatile and robust method for RDC measurements that may routinize the RDC-based structure determination of organic molecules. PMID:25075756

  19. Functional coupling of a Ca2+/calmodulin-dependent nitric oxide synthase and a soluble guanylyl cyclase in vertebrate photoreceptor cells.

    PubMed Central

    Koch, K W; Lambrecht, H G; Haberecht, M; Redburn, D; Schmidt, H H

    1994-01-01

    Electrophysiological recordings on retinal rod cells, horizontal cells and on-bipolar cells indicate that exogenous nitric oxide (NO) has neuromodulatory effects in the vertebrate retina. We report here endogenous NO formation in mammalian photoreceptor cells. Photoreceptor NO synthase resembled the neuronal NOS type I from mammalian brain. NOS activity utilized the substrate L-arginine (Km = 4 microM) and the cofactors NADPH, FAD, FMN and tetrahydrobiopterin. The activity showed a complete dependence on the free calcium concentration ([Ca2+]) and was mediated by calmodulin. NO synthase activity was sufficient to activate an endogenous soluble guanylyl cyclase that copurified in photoreceptor preparations. This functional coupling was strictly controlled by the free [Ca2+] (EC50 = 0.84 microM). Activation of the soluble guanylyl cyclase by endogenous NO was up to 100% of the maximal activation of this enzyme observed with the exogenous NO donor compound sodium nitroprusside. This NO/cGMP pathway was predominantly localized in inner and not in outer segments of photoreceptors. Immunocytochemically, we localized NO synthase type I mainly in the ellipsoid region of the inner segments and a soluble guanylyl cyclase in cell bodies of cone photoreceptor cells. We conclude that in photoreceptors endogenous NO is functionally coupled to a soluble guanylyl cyclase and suggest that it has a neuromodulatory role in visual transduction and in synaptic transmission in the outer retina. Images PMID:7519146

  20. Nogo-A couples with Apg-1 through interaction and co-ordinate expression under hypoxic and oxidative stress

    PubMed Central

    Kern, Florian; Stanika, Ruslan I.; Sarg, Bettina; Offterdinger, Martin; Hess, Daniel; Obermair, Gerald J.; Lindner, Herbert; Bandtlow, Christine E.; Hengst, Ludger; Schweigreiter, Rüdiger

    2013-01-01

    Nogo-A is the largest isoform of the Nogo/RTN4 (reticulon 4) proteins and has been characterized as a major myelin-associated inhibitor of regenerative nerve growth in the adult CNS (central nervous system). Apart from the myelin sheath, Nogo-A is expressed at high levels in principal neurons of the CNS. The specificity of Nogo-A resides in its central domain, NiG. We identified Apg-1, a member of the stress-induced Hsp110 (heat-shock protein of 110 kDa) family, as a novel interactor of NiG/Nogo-A. The interaction is selective because Apg-1 interacts with Nogo-A/RTN4-A, but not with RTN1-A, the closest paralogue of Nogo-A. Conversely, Nogo-A binds to Apg-1, but not to Apg-2 or Hsp105, two other members of the Hsp110 family. We characterized the Nogo-A–Apg-1 interaction by affinity precipitation, co-immunoprecipitation and proximity ligation assay, using primary hippocampal neurons derived from Nogo-deficient mice. Under conditions of hypoxic and oxidative stress we found that Nogo-A and Apg-1 were tightly co-regulated in hippocampal neurons. Although both proteins were up-regulated under hypoxic conditions, their expression levels were reduced upon the addition of hydrogen peroxide. Taken together, we suggest that Nogo-A is closely involved in the neuronal response to hypoxic and oxidative stress, an observation that may be of relevance not only in stroke-induced ischaemia, but also in neuroblastoma formation. PMID:23909438

  1. 14 CFR 105.45 - Use of tandem parachute systems.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ...part. (3) The tandem parachute system contains an operational automatic...manufacturer of that tandem parachute system. The device must— (i) Have...is equipped with a single-point release system. (6) The reserve...

  2. 14 CFR 105.45 - Use of tandem parachute systems.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ...part. (3) The tandem parachute system contains an operational automatic...manufacturer of that tandem parachute system. The device must— (i) Have...is equipped with a single-point release system. (6) The reserve...

  3. 14 CFR 105.45 - Use of tandem parachute systems.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ...part. (3) The tandem parachute system contains an operational automatic...manufacturer of that tandem parachute system. The device must— (i) Have...is equipped with a single-point release system. (6) The reserve...

  4. 14 CFR 105.45 - Use of tandem parachute systems.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ...part. (3) The tandem parachute system contains an operational automatic...manufacturer of that tandem parachute system. The device must— (i) Have...is equipped with a single-point release system. (6) The reserve...

  5. heritability. The overdue promise of short tandem repeat variation for

    E-print Network

    Queitsch, Christine

    heritability. The overdue promise of short tandem repeat variation for Maximilian Press, Keisha D variation for heritability.1 2 Maximilian O. Press, Keisha D. Carlson, Christine Queitsch3 Keywords: short tandem repeats, microsatellites, heritability, epistasis,9 sequencing technologies.10

  6. Organic Tandem Solar Cells: Design and Formation

    NASA Astrophysics Data System (ADS)

    Chen, Chun-Chao

    In the past decade, research on organic solar cells has gone through an important development stage leading to major enhancements in power conversion efficiency, from 4% to 9% in single-junction devices. During this period, there are many novel processing techniques and device designs that have been proposed and adapted in organic solar-cell devices. One well-known device architecture that helps maximize the solar cell efficiency is the multi-junction tandem solar-cell design. Given this design, multiple photoactive absorbers as subcells are stacked in a monolithic fashion and assembled via series connection into one complete device, known as the tandem solar cell. Since multiple absorbers with different optical energy bandgaps are being applied in one tandem solar-cell device, the corresponding solar cell efficiency is maximized through expanded absorption spectrum and reduced carrier thermalization loss. In Chapter 3, the architecture of solution-processible, visibly transparent solar cells is introduced. Unlike conventional organic solar-cell devices with opaque electrodes (such as silver, aluminum, gold and etc.), the semi-transparent solar cells rely on highly transparent electrodes and visibly transparent photoactive absorbers. Given these two criteria, we first demonstrated the visibly transparent single-junction solar cells via the polymer absorber with near-infrared absorption and the top electrode based on solution-processible silver nanowire conductor. The highest visible transparency (400 ˜ 700 nm) of 65% was achieved for the complete device structure. More importantly, power conversion efficiency of 4% was also demonstrated. In Chapter 4, we stacked two semi-transparent photoactive absorbers in the tandem architecture in order to realize the semi-transparent tandem solar cells. A noticeable performance improvement from 4% to 7% was observed. More importantly, we modified the interconnecting layers with the incorporation of a thin conjugated polyelectrolyte layer functioning as the surface dipole formation layer to provide better electrical contact with the photoactive layer. Due to the effectiveness of the conjugated polyelectrolyte layer, performance improvement was also observed. Furthermore, other issues regarding the semi-transparent tandem solar cells (e.g., photocurrent matching, exterior color tuning, and transparency tuning) are all explored to optimize best performance. In Chapter 5 and 6, the architectures of double- and triple-junction tandem solar cells are explored. Theoretically, triple-junction tandem solar cells with three photoactive absorbers with cascaded energy bandgaps have the potential to achieve higher performance, in comparison with double-junction tandem solar cells. Such expectations can be ascribed to the minimized carrier thermalization loss and further improved light absorption. However, the design of triple-junction solar cells often involves sophisticated multiple layer deposition as well as substantial optimization. Therefore, there is a lack of successful demonstrations of triple-junction solar cells outperforming the double-junction counterparts. To solve the incompatible issues related to the layer deposition in the fabrication, we proposed a novel architecture of inverted-structure tandem solar cells with newly designed interconnecting layers. Our design of interconnecting layers does not only focus on maintaining the orthogonal solution processing advantages, but also provides an excellent compatibility in the energy level alignment to allow different absorber materials to be used. Furthermore, we also explored the light management inside the double- and triple-junction tandem solar cells. The study of light management was carried out through optical simulation method based transfer matrix formalism. The intention is to obtain a balanced photocurrent output from each subcells inside the tandem solar cell, thus the minimal recombination loss at the contact of interconnecting layers and the optimal efficiency can be expected. With help from simulations, we were able to ca

  7. Microwave-Assisted Copper-Catalyzed Four-Component Tandem Synthesis of 3-N-Sulfonylamidine Coumarins.

    PubMed

    Murugavel, Govindarasu; Punniyamurthy, Tharmalingam

    2015-06-19

    Microwave-assisted copper-catalyzed four-component tandem synthesis of 3-N-sulfonylamidine coumarins has been accomplished by the coupling of salicylaldehydes, propiolates, sulfonyl azides, and secondary amines. This one-pot protocol affords an effective route for the construction of functionalized coumarin structural frameworks in a single operation with moderate to high yields. PMID:26024048

  8. Quantification of iodide and sodium-iodide symporter inhibitors in human urine using ion chromatography tandem mass spectrometry

    Microsoft Academic Search

    Liza Valentín-Blasini; Benjamin C. Blount; Amy Delinsky

    2007-01-01

    We developed a sensitive and selective method for quantifying nitrate, thiocyanate, perchlorate and iodide in human urine using ion chromatography coupled with electrospray ionization tandem mass spectrometry. Analysis of proficiency testing materials and spiked urine indicates that the method is precise (coefficients of variation 99% of urine samples tested. Measurement of these four toxicologically-related analytes in one assay will provide

  9. Photoelectric properties of a-Si/mesoporous ZnO tandem solar cells

    NASA Astrophysics Data System (ADS)

    Wu, Guizhi; Shen, Yue; Cheng, Wanxi; Gu, Feng; Zhang, Jiancheng; Wang, Linjun

    2011-02-01

    Mesoporous nanocrystalline ZnO applied to a-Si/mesoporous tandem solar cell was synthesized through the hydrothermal method. The structures and morphologies were characterized by X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and Brunauer-Emmett-Teller (BET) analysis based on the nitrogen adsorption isotherm. The test results indicated that the samples had an average pore size of 17 nm and the BET specific surface area was approximately 37.5 m2/g. The transparent a-Si film on fluorine-tin-oxide (FTO) coated glass was obtained by chemical treatment and was used to structure a-Si/mesoporous ZnO tandem solar cell. Under AM 1.5 irradiation, the a- Si/mesoporous tandem solar cell had an open circuit voltage (Voc) of 560 mV, a short circuit current (Jsc) of 3.61 mA/cm2 and a conversion efficiency of 0.28%. The conversion efficiency of tandem solar cell was improved obviously than that of the transparent a-Si film, which had lost special solar cell properties in chemical processing.

  10. Measuring Parathyroid Hormone (PTH) in Patients with Oxidative Stress – Do We Need a Fourth Generation Parathyroid Hormone Assay?

    PubMed Central

    Stoeva, Stanka; Reichetzeder, Christoph; Grön, Hans Jürgen; Lieker, Ina; Khadzhynov, Dmytro; Slowinski, Torsten; Roth, Heinz Jürgen

    2012-01-01

    Oxidation of PTH at methionine residues results in loss of biological activity. PTH may be oxidized in patients with renal disease. The aim of this study was to develop an assay considering oxidation of PTH. Oxidized hPTH was analyzed by high resolution nano-liquid chromatography coupled to ESI-FTT tandem mass spectrometry (nanoLC-ESI-FT-MS/MS) directly and after proteolytic cleavage. The oxidized hPTH(1–84) sample shows TIC-peaks at 18–20 min and several mass peaks due to mass shifts caused by oxidations. No significant signal for oxidized hPTH(1–84) species after removal of oxidized PTH molecules by a specific column with monoclonal antibodies (MAB) raised against the oxidized hPTH was detectable. By using this column in samples from 18 patients on dialysis we could demonstrate that measured PTH concentrations were substantially lower when considering oxidized forms of PTH. The relationship between PTH concentrations determined directly and those concentrations measured after removal of the oxidized PTH forms varies substantially. In some patients only 7% of traditionally measured PTH was free of oxidation, whereas in other patients 34% of the traditionally measured PTH was real intact PTH. In conclusion, a huge but not constant proportion of PTH molecules are oxidized in patients requiring dialysis. Since oxidized PTH is biologically inactive, the currently used methods to detect PTH in daily clinical practice may not adequately reflect PTH-related bone and cardiovascular abnormalities in patients on dialysis. PMID:22792251

  11. Efficient photoinduced charge accumulation in reduced graphene oxide coupled with titania nanosheets to show highly enhanced and persistent conductance.

    PubMed

    Cai, Xingke; Sakai, Nobuyuki; Ozawa, Tadashi C; Funatsu, Asami; Ma, Renzhi; Ebina, Yasuo; Sasaki, Takayoshi

    2015-06-01

    Tuning of the electrical properties of graphene via photoexcitation of a heteroassembled material has started to attract attention for electronic and optoelectronic applications. Actually photoinduced carrier doping from the hexagonal boron nitride (h-BN) substrate greatly modulated the transport property of the top layer graphene, showing promising potential for this approach. However, for practical applications, the large scale production of this two-dimensional heterostructure is needed. Here, a superlattice film constructed from reduced graphene oxide (rGO) and photoactive titania nanosheets (Ti0.87O2(0.52-)) was employed as a channel to construct a field effect transistor (FET) device, and its UV light response on the electrical transport property was examined. The UV light illumination induced significant improvement of the electrical conductance by ?7 times on the basis of simultaneous enhancements of the electron carrier concentration and its mobility in rGO. Furthermore, the polarity of the FET response changed from ambipolar to n-type unipolar. Such modulated properties persisted in vacuum even after the UV light was turned off. These interesting behaviors may be explained in terms of photomodulation effects from Ti0.87O2(0.52-) nanosheets. The photoexcited electrons in Ti0.87O2(0.52-) are injected into rGO to increase the electron carrier concentration as high as 7.6 × 10(13) cm(-2). On the other hand, the holes are likely trapped in the Ti0.87O2(0.52-) nanosheets. These photocarriers undergo reduction and oxidation of oxygen and water molecules adsorbed in the film, respectively, which act as carrier scattering centers, contributing to the enhancement of the carrier mobility. Since the film likely contains more water molecules than oxygen, upon extinction of UV light, a major portion of electrons (?80% of the concentration at the UV off) survives in rGO, showing the highly enhanced conductance for days. This surpassing photomodulated FET response and its persistency observed in the present superlattice system of rGO/Ti0.87O2(0.52-) are noteworthy compared with previous studies such as the device with a heteroassembly of graphene/h-BN. PMID:25945510

  12. White-emissive tandem-type hybrid organic/polymer diodes with (0.33, 0.33) chromaticity coordinates.

    PubMed

    Guo, Tzung-Fang; Wen, Ten-Chin; Huang, Yi-Shun; Lin, Ming-Wei; Tsou, Chuan-Cheng; Chung, Chia-Tin

    2009-11-01

    This study reports fabrication of white-emissive, tandem-type, hybrid organic/polymer light-emitting diodes (O/PLED). The tandem devices are made by stacking a blue-emissive OLED on a yellow-emissive phenyl-substituted poly(para-phenylene vinylene) copolymer-based PLED and applying an organic oxide/Al/molybdenum oxide (MoO(3)) complex structure as a connecting structure or charge-generation layer (CGL). The organic oxide/Al/MoO(3) CGL functions as an effective junction interface for the transport and injection of opposite charge carriers through the stacked configuration. The electroluminescence (EL) spectra of the tandem-type devices can be tuned by varying the intensity of the emission in each emissive component to yield the visible-range spectra from 400 to 750 nm, with Commission Internationale de l'Eclairage chromaticity coordinates of (0.33, 0.33) and a high color rendering capacity as used for illumination. The EL spectra also exhibit good color stability under various bias conditions. The tandem-type device of emission with chromaticity coordinates, (0.30, 0.31), has maximum brightness and luminous efficiency over 25,000 cd/m(2) and approximately 4.2 cd/A, respectively. PMID:19997359

  13. Tandem mass spectrometry in the clinical chemistry laboratory

    Microsoft Academic Search

    Kent C. Dooley

    2003-01-01

    Tandem mass spectrometry is becoming an increasingly important analytical technology in the clinical laboratory environment. Applications in toxicology and therapeutic drug monitoring have opened the door for tandem mass spectrometry and now we are seeing a vast array of new applications being developed. It has been the combination of tandem mass spectrometry with sample introduction techniques employing atomospheric pressure ionization

  14. Tandem repeats finder: a program to analyze DNA sequences

    Microsoft Academic Search

    Gary Benson

    1999-01-01

    A tandem repeat in DNA is two or more contiguous, approximate copies of a pattern of nucleotides. Tandem repeats have been shown to cause human disease, may play a variety of regulatory and evolutionary roles and are important laboratory and analytic tools. Extensive knowledge about pattern size, copy number, mutational history, etc. for tandem repeats has been limited by the

  15. Techniques for detecting approximate tandem repeats in DNA

    Microsoft Academic Search

    Thao T. Tran; Vincent A. Emanuele; G. Tong Zhou II

    2004-01-01

    The detection of tandem repeats is important in biology and medicine as it can be used for phylogenetic studies and disease diagnosis. The paper proposes two techniques for detecting approximate tandem repeats (ATRs) in DNA sequences. First, an evolutionary force heuristic is proposed to merge interspersed perfect tandem repeat sequences into an ATR structure. Next., a more general method is

  16. 14 CFR 105.45 - Use of tandem parachute systems.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ...2010-01-01 2010-01-01 false Use of tandem parachute systems. 105.45 Section...Equipment and Packing § 105.45 Use of tandem parachute systems. (a) No person may conduct a parachute operation using a tandem parachute system, and no pilot in...

  17. Strongly coupled metal oxide nanorod arrays with graphene nanoribbons and nanosheets enable novel solid-state hybrid cells

    NASA Astrophysics Data System (ADS)

    Xiao, Junwu; Xi, Jiangbo; Xu, Yangyang; Yang, Shihe; Jin, Yunxia; Xiao, Fei; Wang, Shuai

    2015-06-01

    Electrochemical capacitors and rechargeable batteries are still limited in applications by the low energy and power densities they can deliver, respectively, holding back their deployment in electric vehicles. Here we develop a type of solid-state hybrid cells (SHCs) composed of graphene nanoribbons and nanosheets-coated metal oxide nanorod arrays ((MOx/GNR)@GNS). GNR and GNS are deposited on the surface of MOx nanorod arrays to improve the electron transport characteristic, and thus enhance the energy storage performance. The (MOx/GNR)@GNS-based SHCs can achieve a maximum volumetric energy density of 0.9 mWh cm-3, and still retain 0.4 mWh cm-3 even at 0.1 W cm-3. The energy storage performance is much better than the electrochemical capacitors reported previously, and can even rival the commercial Li thin-film battery but with a significantly higher power density, lower cost and higher safety. Also demonstrated is the good long-term cycle life with only ?17% loss after 2500 cycles. These salient features make the (MOx/GNR)@GNS composites-based SHCs a strong contender for electrochemical energy storage.

  18. Coupling digestion in a pilot-scale UASB reactor and electrochemical oxidation over BDD anode to treat diluted cheese whey.

    PubMed

    Katsoni, Alphathanasia; Mantzavinos, Dionissios; Diamadopoulos, Evan

    2014-11-01

    The efficiency of the anaerobic treatment of cheese whey (CW) at mesophilic conditions was investigated. In addition, the applicability of electrochemical oxidation as an advanced post-treatment for the complete removal of chemical oxygen demand (COD) from the anaerobically treated cheese whey was evaluated. The diluted cheese whey, having a pH of 6.5 and a total COD of 6 g/L, was first treated in a 600-L, pilot-scale up-flow anaerobic sludge blanket (UASB) reactor. The UASB process, which was operated for 87 days at mesophilic conditions (32?±?2 °C) at a hydraulic retention time (HRT) of 3 days, led to a COD removal efficiency between 66 and 97 %, while the particulate matter of the wastewater was effectively removed by entrapment in the sludge blanket of the reactor. When the anaerobic reactor effluent was post-treated over a boron-doped diamond (BDD) anode at 9 and 18 A and in the presence of NaCl as the supporting electrolyte, complete removal of COD was attained after 3-4 h of reaction. During electrochemical experiments, three groups of organochlorinated compounds, namely trihalomethanes (THMs), haloacetonitriles (HANs), and haloketons (HKs), as well as 1,2-dichloroethane (DCA) and chloropicrin were identified as by-products of the process; these, alongside free chlorine, are thought to increase the matrix ecotoxicity to Artemia salina. PMID:24793070

  19. Inductively coupled plasma torch efficiency at atmospheric pressure for organo-chlorine liquid waste removal: chloroform destruction in oxidative conditions.

    PubMed

    Kamgang-Youbi, Georges; Poizot, Karine; Lemont, Florent

    2013-01-15

    The performance of a plasma reactor for the degradation of chlorinated hydrocarbon waste is reported. Chloroform was used as a target for a recently patented destruction process based using an inductive plasma torch. Liquid waste was directly injected axially into the argon plasma with a supplied power of ~4kW in the presence of oxygen as oxidant and carrier gas. Decomposition was performed at CHCl(3) feed rates up to 400 g h(-1) with different oxygen/waste molar ratios, chloroform destruction was obtained with at least 99% efficiency and the energy efficiency reached 100 g kWh(-1). The conversion end products were identified and assayed by online FTIR spectroscopy (CO(2), HCl and H(2)O) and redox titration (Cl(2)). Considering phosgene as representative of toxic compounds, only very small quantities of toxics were released (<1 g h(-1)) even with high waste feed rates. The experimental results were very close to the equilibrium composition predicted by thermodynamic calculations. At the bottom of the reactor, the chlorinated acids were successfully trapped in a scrubber and transformed into mineral salts, hence, only CO(2) and H(2)O have been found in the final off-gases composition. PMID:23246953

  20. Identification of Glioblastoma Phosphotyrosine-Containing Proteins with Two-Dimensional Western Blotting and Tandem Mass Spectrometry

    PubMed Central

    Guo, Tianyao; Wang, Xiaowei; Li, Maoyu; Yang, Haiyan; Li, Ling; Peng, Fang

    2015-01-01

    To investigate the presence of, and the potential biological roles of, protein tyrosine phosphorylation in the glioblastoma pathogenesis, two-dimensional gel electrophoresis- (2DGE-) based Western blotting coupled with liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) analysis was used to detect and identify the phosphotyrosine immunoreaction-positive proteins in a glioblastoma tissue. MS/MS and Mascot analyses were used to determine the phosphotyrosine sites of each phosphopeptide. Protein domain and motif analysis and systems pathway analysis were used to determine the protein domains/motifs that contained phosphotyrosine residue and signal pathway networks to clarify the potential biological functions of protein tyrosine phosphorylation. A total of 24 phosphotyrosine-containing proteins were identified. Each phosphotyrosine-containing protein contained at least one tyrosine kinase phosphorylation motif and a certain structural and functional domains. Those phosphotyrosine-containing proteins were involved in the multiple signal pathway systems such as oxidative stress, stress response, and cell migration. Those data show 2DGE-based Western blotting, MS/MS, and bioinformatics are a set of effective approaches to detect and identify glioblastoma tyrosine-phosphorylated proteome and to effectively rationalize the biological roles of tyrosine phosphorylation in the glioblastoma biological systems. It provides novel insights regarding tyrosine phosphorylation and its potential role in the molecular mechanism of a glioblastoma.

  1. Base excision repair of oxidative DNA damage coupled with removal of a CAG repeat hairpin attenuates trinucleotide repeat expansion

    PubMed Central

    Xu, Meng; Lai, Yanhao; Torner, Justin; Zhang, Yanbin; Zhang, Zunzhen; Liu, Yuan

    2014-01-01

    Trinucleotide repeat (TNR) expansion is responsible for numerous human neurodegenerative diseases. However, the underlying mechanisms remain unclear. Recent studies have shown that DNA base excision repair (BER) can mediate TNR expansion and deletion by removing base lesions in different locations of a TNR tract, indicating that BER can promote or prevent TNR expansion in a damage location–dependent manner. In this study, we provide the first evidence that the repair of a DNA base lesion located in the loop region of a CAG repeat hairpin can remove the hairpin, attenuating repeat expansion. We found that an 8-oxoguanine located in the loop region of CAG hairpins of varying sizes was removed by OGG1 leaving an abasic site that was subsequently 5?-incised by AP endonuclease 1, introducing a single-strand breakage in the hairpin loop. This converted the hairpin into a double-flap intermediate with a 5?- and 3?-flap that was cleaved by flap endonuclease 1 and a 3?-5? endonuclease Mus81/Eme1, resulting in complete or partial removal of the CAG hairpin. This further resulted in prevention and attenuation of repeat expansion. Our results demonstrate that TNR expansion can be prevented via BER in hairpin loops that is coupled with the removal of TNR hairpins. PMID:24423876

  2. Emerging concepts in bioenergetics and cancer research: metabolic flexibility, coupling, symbiosis, switch, oxidative tumors, metabolic remodeling, signaling and bioenergetic therapy.

    PubMed

    Obre, Emilie; Rossignol, Rodrigue

    2015-02-01

    The field of energy metabolism dramatically progressed in the last decade, owing to a large number of cancer studies, as well as fundamental investigations on related transcriptional networks and cellular interactions with the microenvironment. The concept of metabolic flexibility was clarified in studies showing the ability of cancer cells to remodel the biochemical pathways of energy transduction and linked anabolism in response to glucose, glutamine or oxygen deprivation. A clearer understanding of the large-scale bioenergetic impact of C-MYC, MYCN, KRAS and P53 was obtained, along with its modification during the course of tumor development. The metabolic dialog between different types of cancer cells, but also with the stroma, also complexified the understanding of bioenergetics and raised the concepts of metabolic symbiosis and reverse Warburg effect. Signaling studies revealed the role of respiratory chain-derived reactive oxygen species for metabolic remodeling and metastasis development. The discovery of oxidative tumors in human and mice models related to chemoresistance also changed the prevalent view of dysfunctional mitochondria in cancer cells. Likewise, the influence of energy metabolism-derived oncometabolites emerged as a new means of tumor genetic regulation. The knowledge obtained on the multi-site regulation of energy metabolism in tumors was translated to cancer preclinical studies, supported by genetic proof of concept studies targeting LDHA, HK2, PGAM1, or ACLY. Here, we review those different facets of metabolic remodeling in cancer, from its diversity in physiology and pathology, to the search of the genetic determinants, the microenvironmental regulators and pharmacological modulators. PMID:25542180

  3. Coupled modeling of gas hydrate formation and anaerobic methane oxidation in near-surface sediments at Hydrate Ridge

    NASA Astrophysics Data System (ADS)

    Haeckel, M.; Rickert, D.; Suess, E.

    2001-12-01

    A comprehensive one-dimensional transport-reaction model (C. CANDI) was modified to investigate the formation of near-surface methane gas hydrates through ascending methane-bearing fluids at the sea floor of the southern summit of Hydrate Ridge, Cascadia Margin. A considerable salinity increase was observed 120 cm below the sediment-surface. A hydrate layer was almost unaffected from sampling and the adjacent sediment visually dry and fragmented. The piece of hydrate was removed immediately from the sediment before dissociation could commence. Samples separated in that way showed chloride concentrations up to 800 mM, a salt-enrichment of about 1.5 times the seawater salinity. Corresponding ? 18O and ? D profiles indicate that chloride anomalies certainly originated from hydrate formation. The enhanced diagenetic model C.CANDI was applied to pore water chloride and sulfate profiles using steady state as well as non-steady state approaches to simulate the response of gas hydrate formation to varying fluid-flow rates and time. Upward fluid flow rates of 20 cm/yr, as determined by the model, are sufficient to account for the pore water sulfate profiles that arise from methane oxidation. The potential maximum concentration of dissolved methane in interstitial water in the presence of gas hydrate is given by thermodynamic considerations. The general trend of the measured chloride concentrations can be described by a source function for hydrate that produces significant quantities of gas hydrate at 120 cm sediment depth, the lower model boundary. Integrated hydrate formation rates of 102-103 mol m-2 h-1 were determined by the non-steady state modeling approach. These rates are about 10 times smaller than values reported from hydrate formation from water solution in the laboratory and several orders of magnitude larger than values calculated for Blake Ridge sediments (ODP 997).

  4. Stable Isotope Systematics of Abiotic Nitrite Reduction Coupled with Anaerobic Iron Oxidation: The Role of Reduced Clays and Fe-bearing Minerals

    NASA Astrophysics Data System (ADS)

    Grabb, K. C.; Buchwald, C.; Hansel, C. M.; Wankel, S. D.

    2014-12-01

    Under anaerobic conditions, it is widely assumed that nitrate (NO3-) and nitrite (NO2-) reduction is primarily the result of microbial respiration. However, it has also been shown that abiotic reduction of nitrate and nitrite by reduced iron (Fe(II)), whether mineral-bound or surface-associated, may also occur under certain environmentally relevant conditions. With a range of experimental conditions, we investigated the nitrogen and oxygen stable isotope systematics of abiotic nitrite reduction by Fe(II) in an effort to characterize biotic and abiotic processes in the environment. While homogenous reactions between NO2- and Fe(II) in artificial seawater showed little reduction, heterogeneous reactions involving Fe-containing minerals showed considerable nitrite loss. Specifically, rapid nitrite reduction was observed in experiments that included reduced clays (illite, Na-montmorillonite, and nontronite) and those that exhibited iron oxide formation (ferrihydrite, magnetite and/or green rust). While these iron oxides and clay minerals offer both a source of reduced iron in the mineral matrix as well as a surface for Fe(II) activation, control experiments with corundum as a non-Fe containing mineral surface showed little NO2- loss, implicating a more dominant role of structural Fe in the clays during nitrite reduction. The isotope effects for 15N and 18O (15? and 18?) ranged from 5 to 14‰ for 15? and 5 to 17‰ for 18? and were typically coupled such that 15? ~ 18?. Reactions below pH 7 were slower and the 18? was affected by oxygen atom exchange with water. Although little data exist for comparison with the dual isotopes of microbial NO2- reduction, these data serve as a benchmark for evaluating the role of abiotic processes in N reduction, particularly in sediment systems low in organic carbon and high in iron.

  5. Technology for large tandem mirror experiments

    SciTech Connect

    Thomassen, K.I.

    1980-09-04

    Construction of a large tandem mirror (MFTF-B) will soon begin at Lawrence Livermore National Laboratory (LLNL). Designed to reach break-even plasma conditions, the facility will significantly advance the physics and technology of magnetic-mirror-based fusion reactors. This paper describes the objectives and the design of the facility.

  6. Short tandem repeat polymorphism evolution in humans

    Microsoft Academic Search

    F Calafell; A Shuster; WC Speed; JR Kidd; KK Kidd

    1998-01-01

    Forty-five dinucleotide short tandem repeat polymorphisms were typed in ten large samples of a globally distributed set of populations. Although these markers had been selected for high heterozygosity in European populations, we found them to be sufficiently informative for linkage analysis in non-Europeans. Heterozygosity, mean number of alleles, and mean number of private alleles followed a common trend: they were

  7. Swept Inducer Blades With Tandem Radial Slots

    NASA Technical Reports Server (NTRS)

    Meng, Sen Y.

    1995-01-01

    Slanted radial slots at tandem positions along approximate streamlines incorporated into swept inducer blades in turbopump, according to proposal. With suitable design, slots suppress low-frequency oscillations induced by cavitation, without causing excessive loss of inducer head. Slots cut into solid blades by wire electrical-discharge machining.

  8. Palladium-phosphorus/sulfur nanoparticles (NPs) decorated on graphene oxide: synthesis using the same precursor for NPs and catalytic applications in Suzuki-Miyaura coupling.

    PubMed

    Joshi, Hemant; Sharma, Kamal Nayan; Sharma, Alpesh K; Singh, Ajai Kumar

    2014-05-01

    PdP2 and Pd4S nanoparticles (NPs) (size: ?2-6 and 9-15 nm respectively) have been prepared for the first time from a single source precursor complex [Pd(L)Cl2] (1) by its one pot thermolysis at 200 °C in TOP and OA/ODE (1?:?1) respectively. These NPs were stirred with graphene oxide (GO) at room temperature to prepare NP composites, GO-PdP2 and GO-Pd4S. The GO-PdP2 NPs have been synthesized for the first time. The thioether ligand L prepared by reaction of 1,3-dibromo-2-propanol with the in situ generated PhSNa reacts with [PdCl2(CH3CN)2] in CH3CN at 70 °C resulting in 1. The L and 1 have been characterized by (1)H and (13)C{(1)H} NMR and HR-MS. The single crystal structure of 1 determined by X-ray diffraction reveals nearly square planar geometry around the Pd metal centre. The catalytic activities of two palladium nano-phases having phosphorus and sulphur respectively as a co-constituent for Suzuki-Miyaura coupling have been found to be exceptionally different, as PdP2 nanoparticles (NPs) grafted on graphene oxide (GO-PdP2) are significantly more efficient than Pd4S NPs grafted on GO. Without grafting PdP2 and Pd4S both have low efficiency. This is the first report comparing the influence of P and S on the catalytic activity of Pd NPs. TEM, SEM-EDX and powder-XRD have been used to authenticate all NPs. The GO-PdP2 NPs have been found to be efficient catalysts for Suzuki-Miyaura coupling reactions (yield up to 96% in 30 min) at room temperature to 80 °C. Their recyclability has been found up to 6 cycles. In contrast, GO-Pd4S NPs are little active in comparison with GO-PdP2 NPs. The size of NPs and their distribution on GO appear to be key factors affecting the catalytic efficiency of the composite NPs. Leaching of Pd from GO-PdP2 NPs contributes significantly to the catalysis as evidenced by the three phase test, hot-filtration and recycling experiments. The catalysis is almost homogeneous. PMID:24626740

  9. Palladium-phosphorus/sulfur nanoparticles (NPs) decorated on graphene oxide: synthesis using the same precursor for NPs and catalytic applications in Suzuki-Miyaura coupling

    NASA Astrophysics Data System (ADS)

    Joshi, Hemant; Sharma, Kamal Nayan; Sharma, Alpesh K.; Singh, Ajai Kumar

    2014-04-01

    PdP2 and Pd4S nanoparticles (NPs) (size: ~2-6 and 9-15 nm respectively) have been prepared for the first time from a single source precursor complex [Pd(L)Cl2] (1) by its one pot thermolysis at 200 °C in TOP and OA/ODE (1 : 1) respectively. These NPs were stirred with graphene oxide (GO) at room temperature to prepare NP composites, GO-PdP2 and GO-Pd4S. The GO-PdP2 NPs have been synthesized for the first time. The thioether ligand L prepared by reaction of 1,3-dibromo-2-propanol with the in situ generated PhSNa reacts with [PdCl2(CH3CN)2] in CH3CN at 70 °C resulting in 1. The L and 1 have been characterized by 1H and 13C{1H} NMR and HR-MS. The single crystal structure of 1 determined by X-ray diffraction reveals nearly square planar geometry around the Pd metal centre. The catalytic activities of two palladium nano-phases having phosphorus and sulphur respectively as a co-constituent for Suzuki-Miyaura coupling have been found to be exceptionally different, as PdP2 nanoparticles (NPs) grafted on graphene oxide (GO-PdP2) are significantly more efficient than Pd4S NPs grafted on GO. Without grafting PdP2 and Pd4S both have low efficiency. This is the first report comparing the influence of P and S on the catalytic activity of Pd NPs. TEM, SEM-EDX and powder-XRD have been used to authenticate all NPs. The GO-PdP2 NPs have been found to be efficient catalysts for Suzuki-Miyaura coupling reactions (yield up to 96% in 30 min) at room temperature to 80 °C. Their recyclability has been found up to 6 cycles. In contrast, GO-Pd4S NPs are little active in comparison with GO-PdP2 NPs. The size of NPs and their distribution on GO appear to be key factors affecting the catalytic efficiency of the composite NPs. Leaching of Pd from GO-PdP2 NPs contributes significantly to the catalysis as evidenced by the three phase test, hot-filtration and recycling experiments. The catalysis is almost homogeneous.PdP2 and Pd4S nanoparticles (NPs) (size: ~2-6 and 9-15 nm respectively) have been prepared for the first time from a single source precursor complex [Pd(L)Cl2] (1) by its one pot thermolysis at 200 °C in TOP and OA/ODE (1 : 1) respectively. These NPs were stirred with graphene oxide (GO) at room temperature to prepare NP composites, GO-PdP2 and GO-Pd4S. The GO-PdP2 NPs have been synthesized for the first time. The thioether ligand L prepared by reaction of 1,3-dibromo-2-propanol with the in situ generated PhSNa reacts with [PdCl2(CH3CN)2] in CH3CN at 70 °C resulting in 1. The L and 1 have been characterized by 1H and 13C{1H} NMR and HR-MS. The single crystal structure of 1 determined by X-ray diffraction reveals nearly square planar geometry around the Pd metal centre. The catalytic activities of two palladium nano-phases having phosphorus and sulphur respectively as a co-constituent for Suzuki-Miyaura coupling have been found to be exceptionally different, as PdP2 nanoparticles (NPs) grafted on graphene oxide (GO-PdP2) are significantly more efficient than Pd4S NPs grafted on GO. Without grafting PdP2 and Pd4S both have low efficiency. This is the first report comparing the influence of P and S on the catalytic activity of Pd NPs. TEM, SEM-EDX and powder-XRD have been used to authenticate all NPs. The GO-PdP2 NPs have been found to be efficient catalysts for Suzuki-Miyaura coupling reactions (yield up to 96% in 30 min) at room temperature to 80 °C. Their recyclability has been found up to 6 cycles. In contrast, GO-Pd4S NPs are little active in comparison with GO-PdP2 NPs. The size of NPs and their distribution on GO appear to be key factors affecting the catalytic efficiency of the composite NPs. Leaching of Pd from GO-PdP2 NPs contributes significantly to the catalysis as evidenced by the three phase test, hot-filtration and recycling experiments. The catalysis is almost homogeneous. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr06586c

  10. Monitoring of phosphorus oxide ion for analytical speciation of phosphite and phosphate in transgenic plants by high-performance liquid chromatography-inductively coupled plasma mass spectrometry.

    PubMed

    Torres Elguera, Julio Cesar; Yañez Barrientos, Eunice; Wrobel, Katarzyna; Wrobel, Kazimierz

    2013-07-10

    Large amounts of phosphate fertilizers utilized in agriculture and their relatively poor efficiency are of high ecological and economic concern. Therefore, transgenic plants capable of metabolizing phosphite are being engineered. In support of this biotechnological task, analytical speciation of phosphorus in biological tissues is required. In this study, plant extracts were analyzed by liquid chromatography-inductively coupled plasma mass spectrometry at m/z of elemental phosphorus and phosphorus oxide ions. Using polymeric-based anion exchange column and millimolar concentration of nitric acid in potassium phthalate mobile phase (pH 2.5), phosphite and phosphate ions were baseline resolved with retention times 6.95 ± 0.03 and 7.90 ± 0.03 min and with a total chromatographic run time 10 min. The detection limits were 1.58 and 1.74 ?g P L(-1) at m/z 47, as compared to 2.18 and 2.04 ?g P L(-1) at m/z 31, respectively. The results obtained in real world samples for the two detection modes were in good agreement, yet signal acquisition at m/z 47 enabled better precision without collision/reaction cell (RSD below 2%) as compared to RSD around 4% obtained at m/z 31 using He-pressurized cell (3.5 mL min(-1)). PMID:23782169

  11. Quantitative control of poly(ethylene oxide) surface antifouling and biodetection through azimuthally enhanced grating coupled-surface plasmon resonance sensing

    NASA Astrophysics Data System (ADS)

    Sonato, Agnese; Silvestri, Davide; Ruffato, Gianluca; Zacco, Gabriele; Romanato, Filippo; Morpurgo, Margherita

    2013-12-01

    Grating Coupled-Surface Plasmon reflectivity measurements carried out under azimuth and polarization control (GC-SPR ? ? 0°) were used to optimize the process of gold surface dressing with poly(ethylene oxide) (PEO) derivatives of different molecular weight, with the final goal to maximize the discrimination between specific and non-specific binding events occurring at the surface. The kinetics of surface deposition of thiol-ending PEOs (0.3, 2 and 5 kDa), introduced as antifouling layers, was monitored. Non-specific binding events upon immersion of the surfaces into buffers containing either 0.1% bovine serum albumin or 1% Goat Serum, were evaluated as a function of polymer size and density. A biorecognition event between avidin and biotin was then monitored in both buffers at selected low and high polymer surface densities and the contribution of analyte and fouling elements to the signal was precisely quantified. The 0.3 kDa PEO film was unable to protect the surface from non-specific interactions at any tested density. On the other hand, the 2 and 5 kDa polymers at their highest surface densities guaranteed full protection from non-specific interactions from both buffers. These densities were reached upon a long deposition time (24-30 h). The results pave the way toward the application of this platform for the detection of low concentration and small dimension analytes, for which both non-fouling and high instrumental sensitivity are fundamental requirements.

  12. Effect of ion-irradiation induced defects on the nanocluster Si/Er{sup 3+} coupling in Er-doped silicon-rich silicon oxide

    SciTech Connect

    Seo, Se-Young; Jeong, Hoon; Shin, Jung H.; Choi, Han Woo; Woo, Hyung Joo; Kim, Joon Kon [Department of Physics, Korea Advanced Institute of Science and Technology (KAIST), 373-1, Guseong-dong, Yuseong-gu, Daejeon 305-701 (Korea, Republic of); Ion Beam Application Group, Korean Institute of Geoscience and Mineral Resources, Daejeon 305-350 (Korea, Republic of)

    2007-07-09

    The effect of ion-irradiation induced defects on the nanocluster Si/Er{sup 3+} coupling in Er-doped silicon-rich silicon oxide (SRSO) thin film is investigated. Er-doped SRSO, which consists of silicon nanoclusters (nc-Si) in a SiO{sub 2} matrix, was fabricated using electron-cyclotron resonance plasma enhanced chemical vapor deposition using SiH{sub 4} and O{sub 2} with concurrent sputtering of Er followed by a high temperature annealing. Defects were introduced into the film via irradiation with 3 MeV Si ions and subsequently removed by high temperature annealings. The authors find that ion irradiation reduces Er{sup 3+} luminescence from SRSO films, even when the excitation cross section and luminescence efficiency of Er{sup 3+} ions are completely restored. On the other hand, ion irradiation increases the intrinsic nc-Si luminescence and has little effect on the Er{sup 3+} luminescence from a similarly prepared, Er-doped SiO{sub 2} film, indicating that the presence of irradiation induced defects in the initial amorphous film can reduce the number of Er{sup 3+} ions available for nc-Si mediated luminescence by as much as a factor of 3.

  13. Cisapride a green analytical reagent for rapid and sensitive determination of bromate in drinking water, bread and flour additives by oxidative coupling spectrophotometric methods

    NASA Astrophysics Data System (ADS)

    Al Okab, Riyad Ahmed

    2013-02-01

    Green analytical methods using Cisapride (CPE) as green analytical reagent was investigated in this work. Rapid, simple, and sensitive spectrophotometric methods for the determination of bromate in water sample, bread and flour additives were developed. The proposed methods based on the oxidative coupling between phenoxazine and Cisapride in the presence of bromate to form red colored product with max at 520 nm. Phenoxazine and Cisapride and its reaction products were found to be environmentally friendly under the optimum experimental condition. The method obeys beers law in concentration range 0.11-4.00 g ml-1 and molar absorptivity 1.41 × 104 L mol-1 cm-1. All variables have been optimized and the presented reaction sequences were applied to the analysis of bromate in water, bread and flour additive samples. The performance of these method was evaluated in terms of Student's t-test and variance ratio F-test to find out the significance of proposed methods over the reference method. The combination of pharmaceutical drugs reagents with low concentration create some unique green chemical analyses.

  14. Steroid Hormone Analysis by Tandem Mass Spectrometry

    PubMed Central

    Soldin, Steven J.; Soldin, Offie P.

    2013-01-01

    BACKGROUND New high-performance liquid chromatography/ tandem mass spectrometry (LC-MS/MS) methods are among the most successful approaches to improve specificity problems inherent in many immunoassays. CONTENT We emphasize problems with immunoassays for the measurement of steroids and review the emerging role of LC-MS/MS in the measurement of clinically relevant steroids. The latest generation of tandem mass spectrometers has superior limits of quantification, permitting omission of previously employed derivatization steps. The measurement of steroid profiles in the diagnosis and treatment of congenital adrenal hyperplasia, adrenal insufficiency, chronic pelvic pain and prostatitis, oncology (breast cancer), and athletes has important new applications. CONCLUSIONS LC-MS/MS now affords the specificity, imprecision, and limits of quantification necessary for the reliable measurement of steroids in human fluids, enhancing diagnostic capabilities, particularly when steroid profiles are available. PMID:19325015

  15. Tandem microwave waste remediation and decontamination system

    SciTech Connect

    Wicks, G.G.; Clark, D.E.; Schulz, R.L.

    1999-10-19

    The invention discloses a tandem microwave system consisting of a primary chamber in which microwave energy is used for the controlled combustion of materials. A second chamber is used to further treat the off-gases from the primary chamber by passage through a susceptor matrix subjected to additional microwave energy. The direct microwave radiation and elevated temperatures provide for significant reductions in the qualitative and quantitative emissions of the treated off gases. The tandem microwave system can be utilized for disinfecting wastes, sterilizing materials, and/or modifying the form of wastes to solidify organic or inorganic materials. The simple design allows on-site treatment of waste by small volume waste generators.

  16. Beyond the chemiosmotic theory: analysis of key fundamental aspects of energy coupling in oxidative phosphorylation in the light of a torsional mechanism of energy transduction and ATP synthesis--invited review part 1.

    PubMed

    Nath, Sunil

    2010-08-01

    In Part 1 of this invited article, we consider the fundamental aspects of energy coupling in oxidative phosphorylation. The central concepts of the chemiosmotic theory are re-examined and the major problems with its experimental verification are analyzed and reassessed from first principles. Several of its assumptions and interpretations (with regard, for instance, to consideration of the membrane as an inert barrier, the occurrence of energy transduction at thermodynamic equilibrium, the completely delocalized nature of the protonmotive force, and the notion of indirect coupling) are shown to be questionable. Important biological implications of this analysis for molecular mechanisms of biological energy transduction are enumerated. A fresh molecular mechanism of the uncoupling of oxidative phosphorylation by classical weak acid anion uncouplers and an adequate explanation for the existence of uncoupler-resistant mutants (which until now has remained a mystery) has been proposed based on novel insights arising from a new torsional mechanism of energy transduction and ATP synthesis. PMID:20490637

  17. Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane. Quarterly report, October 1--December 31, 1992

    SciTech Connect

    Heinemann, H.; Somorjai, G.A.; Perry, D.L.

    1992-12-01

    Work on catalytic steam gasification with chars and coals will be extended from atmospheric to elevated pressures using the newly built pressure unit. The novel finding that coking of petroleum in the presence of small amounts of caustic greatly improves the gasification rates and characteristics of the coke will be extended to chars; in the oxidative coupling of methane over ternary catalysts, emphasis will be placed on low temperature coupling and on the oxidative production of syngas from methane at low temperature. Experimental work will continue on the synthesis of the mixed catalyst, and they will be characterized by a number of techniques, including elemental analyses, x-ray diffraction, and surface area determination.

  18. Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane. Quarterly report, January 1--March 31, 1992

    SciTech Connect

    Heinemann, H.; Somorjai, G.A.; Perry, D.L.

    1992-03-01

    Work will continue on the oxidative coupling reaction of methane over ternary oxide catalysts to produce C{sub 2}, C{sub 3} and C{sub 4} hydrocarbons and particularly olefins with high selectivity. The work which has shown that close to 100% selectivity can be obtained has received wide attention and has resulted in collaborative efforts with industry (CRADA) towards the development of a commercial process. An immediate purpose of additional work is to increase the conversion without diminishing the extremely high selectivity of the reaction and also to permit operation at higher space velocity to reduce equipment size. The mechanism of this reaction is not understood and much additional work is needed to explain the role of carbon formation and of water as intermediates in the reaction and to investigate whether carbon oxides are intermediates. It has been found that oxides other than calcium-nickel-potassium oxides can be useful catalysts for this reaction in the presence of steam and at relatively low temperatures and long contact times. Better definition of the class of binary metal oxides is required and better catalyst characterization is needed to ensure reproducibility of catalyst preparation and operational results. Pretreatment of the catalyst should be shortened and higher space velocities must be obtained. Close collaboration with Orion ACT is required to advance the project toward the pilot plant stage. In the area of coal and char catalytic steam gasification, the large volume of data obtained at atmospheric pressure will be extended to operations at higher pressures.

  19. Fundamental studies of the mechanism of catalytic reactions with catalysts effective in the gasification of carbon solids and the oxidative coupling of methane. Quarterly report, July 1--September 30, 1992

    SciTech Connect

    Heinemann, H.; Somorjai, G.A.; Perry, D.L.

    1992-09-01

    Work will continue on the oxidative coupling reaction of methane over ternary oxide catalysts to produce C{sub 2}, C{sub 3} and C{sub 4} hydrocarbons and Particularly Olefins with high selectivity. The work which has shown that close to 100% selectivity can be obtained has received wide attention and has resulted in collaborative efforts with industry (CRADA) towards the development of a commercial process. An immediate purpose of additional work is to increase the conversion without diminishing the extremely high selectivity of the reaction and also to permit operation at higher space velocity to reduce equipment size. The mechanism of this reaction is not understood and much additional work is needed to explain the role of carbon formation and of water as intermediates in the reaction and to investigate whether carbon oxides are intermediates. It has been found that oxides other than calcium-nickel-potassium oxides can be useful catalysts for this reaction in the presence of steam and at relatively low temperatures and long contact times. Better definition of the class of binary metal oxides is required and better catalyst characterization is needed to ensure reproducibility Of catalyst preparation and operational results. Pretreatment of the catalyst should be shortened and higher space velocities must be obtained. Close collaboration with Orion ACT is required to advance the project toward the pilot plant stage. In the area of coal and char catalytic steam gasification, the large volume of data obtained at atmospheric pressure will be extended to operations at higher pressures.

  20. Tandem mirror next step: remote maintenance

    SciTech Connect

    Doggett, J.N.; Damm, C.C.; Hanson, C.L.

    1980-10-27

    This study of the next proposed experiment in the Mirror Fusion Program, the Tandem Mirror Next Step (TMNS), has included serious consideration of the maintenance requirements of such a large source of high energy neutrons with its attendant throughput of tritium. Although maintenance will be costly in time and money, our conclusion is that with careful attention to a design for maintenance plan such a device can be reliably operated.

  1. Current and lattice matched tandem solar cell

    DOEpatents

    Olson, Jerry M. (Lakewood, CO)

    1987-01-01

    A multijunction (cascade) tandem photovoltaic solar cell device is fabricated of a Ga.sub.x In.sub.1-x P (0.505.ltoreq.X.ltoreq.0.515) top cell semiconductor lattice matched to a GaAs bottom cell semiconductor at a low-resistance heterojunction, preferably a p+/n+ heterojunction between the cells. The top and bottom cells are both lattice matched and current matched for high efficiency solar radiation conversion to electrical energy.

  2. Short Tandem Repeat DNA Internet Database

    NSDL National Science Digital Library

    This website contains comprehensive information relating to forensic DNA analysis. It has material from an introductory to an advanced level on forensic DNA technology. The material provides general information on DNA markers that are of interest to human identification. The site contains both introductory and in-depth discussions of short tandem repeats (STRs) and other DNA markers currently used by the forensic community. Powerpoint and PDF presentations on STR training material are available and can be readily downloaded.

  3. Small, octopole-stabilized tandem mirror reactor

    Microsoft Academic Search

    R. S. Devoto; D. E. Baldwin; B. G. Logan; G. W. Hamilton; B. W. Johnston

    1984-01-01

    It is shown that the use of octopole stabilization in a tandem mirror allows a large reduction in end-cell length. A novel feature of the method proposed is the placement of the minimum IBI region considerably off axis, thus rendering the core plasma more axisymmetric. The region from the core to the field minimum is bridged by a mirror-confined, hot-electron

  4. Proton-coupled electron transfer at the Qo-site of the bc1 complex controls the rate of ubihydroquinone oxidation.

    PubMed

    Crofts, Antony R

    2004-04-12

    The rate-limiting reaction of the bc(1) complex from Rhodobacter sphaeroides is transfer of the first electron from ubihydroquinone (quinol, QH(2)) to the [2Fe-2S] cluster of the Rieske iron-sulfur protein (ISP) at the Q(o)-site. Formation of the ES-complex requires participation of two substrates (S), QH(2) and ISP(ox). From the variation of rate with [S], the binding constants for both substrates involved in formation of the complex can be estimated. The configuration of the ES-complex likely involves the dissociated form of the oxidized ISP (ISP(ox)) docked at the b-interface on cyt b, in a complex in which N(epsilon) of His-161 (bovine sequence) forms a H-bond with the quinol -OH. A coupled proton and electron transfer occurs along this H-bond. This brief review discusses the information available on the nature of this reaction from kinetic, structural and mutagenesis studies. The rate is much slower than expected from the distance involved, likely because it is controlled by the low probability of finding the proton in the configuration required for electron transfer. A simplified treatment of the activation barrier is developed in terms of a probability function determined by the Brønsted relationship, and a Marcus treatment of the electron transfer step. Incorporation of this relationship into a computer model allows exploration of the energy landscape. A set of parameters including reasonable values for activation energy, reorganization energy, distances between reactants, and driving forces, all consistent with experimental data, explains why the rate is slow, and accounts for the altered kinetics in mutant strains in which the driving force and energy profile are modified by changes in E(m) and/or pK of ISP or heme b(L). PMID:15100020

  5. Combined Oxypalladation/C-H Functionalization: Palladium(II)-Catalyzed Intramolecular Oxidative Oxyarylation of Hydroxyalkenes

    E-print Network

    Zhu, Rong

    An efficient protocol has been developed for the intramolecular oxidative oxyarylation using a Pd[superscript II]-catalyzed tandem oxypalladation/C-H functionalization strategy. This methodology allows rapid access to ...

  6. Strain Balanced Quantum Well Monolithic Tandem Solar Cells

    Microsoft Academic Search

    A. Ioannides; T. N. D. Tibbits; J. P. Connolly; D. B. Bushnell; K. W. J. Barnham; C. Calder; G. Hill; J. S. Roberts; G. Smekens

    2006-01-01

    The effect of incorporating strain balanced multi-quantum well structures in InGaP\\/GaAs monolithic tandem solar cells is investigated. At present the majority of InGaP\\/GaAs tandem cells are current limited by the bottom GaAs junction. Incorporation of multi-quantum well structures in the GaAs bottom junction extends the cell absorption to longer wavelengths. This allows current matched dual junction tandem cells to achieve

  7. 47 CFR 36.124 - Tandem switching equipment-Category 2.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... false Tandem switching equipment-Category 2. 36.124 Section 36.124 Telecommunication...124 Tandem switching equipment—Category 2. (a) Tandem switching...included with Local Switching Equipment—Category 3. (1) At toll center...

  8. 47 CFR 36.124 - Tandem switching equipment-Category 2.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... false Tandem switching equipment-Category 2. 36.124 Section 36.124 Telecommunication...124 Tandem switching equipment—Category 2. (a) Tandem switching...included with Local Switching Equipment—Category 3. (1) At toll center...

  9. 47 CFR 69.713 - Common line, traffic-sensitive, and tandem-switched transport services.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ...traffic-sensitive, and tandem-switched transport services. 69.713 Section 69...traffic-sensitive, and tandem-switched transport services. (a) Scope. This paragraph...traffic-sensitive components of tandem-switched transport services, as described in §§...

  10. 47 CFR 69.713 - Common line, traffic-sensitive, and tandem-switched transport services.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ...Common line, traffic-sensitive, and tandem-switched transport services. 69...Common line, traffic-sensitive, and tandem-switched transport services. (a...The traffic-sensitive components of tandem-switched transport services, as...

  11. Microstability of the TMX tandem mirror experiments

    SciTech Connect

    Casper, T.A.; Berzins, L.V.

    1987-08-01

    In the tandem mirror device, an efficient source of warm ions, the central cell, is available for stabilization of ion loss-cone instabilities. These instabilities previously limited ion confinement in single-cell mirror experiments. In the simple tandem mirror device, TMX, the drift cyclotron loss-cone (DCLC) mode was stabilized by plasma flow from the central cell into the end cell. However, to enhance the central-cell confinement and provide MHD stability, neutral beams were injected perpendicular to the magnetic field, which resulted in the excitation in the end cell of the Alfven ion-cyclotron (AIC) instability driven by plasma pressure and velocity distribution anisotropy. In the thermal-barrier experiment, TMX-U, the end-cell beams were injected at a 45/sup 0/ angle to the magnetic field to produce a sloshing-ion distribution, which is required to form the thermal barrier and the plugging potential. Ion distributions created by oblique injection were stable to the AIC mode and to the midplane (minimum magnetic field location) DCLC mode. However, an ion loss-cone instability remained at an axial location just outside the outboard peak of the sloshing-ion axial density profile, which is the density peak closest to the end wall. This mode can enhance the sloshing-ion loss rate, particularly at the lower levels of electron-cyclotron resonance heating (ECRH) used to form the thermal barrier. The stability to ion-cyclotron modes is critical to the performance of tandem mirrors and to designs for a mirror-based, high-fluence neutron source.

  12. Improved Isobaric Tandem Mass Tag Quantification by Ion Mobility-Mass Spectrometry

    PubMed Central

    Li, Lingjun

    2014-01-01

    Isobaric tandem mass tags are an attractive alternative to mass difference tags and label free approaches for quantitative proteomics due to the high degree of multiplexing that can be performed with their implementation. A drawback of tandem mass tags are that the co-isolation and co-fragmentation of labeled peptide precursors can result in chimeric MS/MS spectra that can underestimate the fold-change expression of each peptide. Two methods (QuantMode and MS3) have addressed this concern for ion trap and orbitrap instruments, but there is still a need to solve this problem for quadrupole time-of-flight (Q-TOF) instruments. Ion mobility (IM) separations coupled to Q-TOF instruments have the potential to mitigate MS/MS spectra chimeracy since IM-MS has the ability to separate ions based on charge, m/z, and collision cross section (CCS). This work presents results that showcase the power of IM-MS to improve tandem mass tag peptide quantitation accuracy by resolving co-isolated differently charged and same charged peptides prior to MS/MS fragmentation. PMID:24677527

  13. A Hybrid Approach To Tandem Cylinder Noise

    NASA Technical Reports Server (NTRS)

    Lockard, David P.

    2004-01-01

    Aeolian tone generation from tandem cylinders is predicted using a hybrid approach. A standard computational fluid dynamics (CFD) code is used to compute the unsteady flow around the cylinders, and the acoustics are calculated using the acoustic analogy. The CFD code is nominally second order in space and time and includes several turbulence models, but the SST k - omega model is used for most of the calculations. Significant variation is observed between laminar and turbulent cases, and with changes in the turbulence model. A two-dimensional implementation of the Ffowcs Williams-Hawkings (FW-H) equation is used to predict the far-field noise.

  14. The capacity of digital links in tandem

    NASA Technical Reports Server (NTRS)

    Posner, E. C.; Rubin, A. L.

    1984-01-01

    The present investigation is concerned with the error control strategy used in connection with digital data networks, taking into account the capacity of the end-to-end channel. It is assumed that the only source of noise is Gaussian and that bandwidth limitation on capacity can be ignored. Attention is given to L links in tandem with binary repeaters, the asymptotic capacity with a large number of links, some alternative repeater strategies, and approaches for lowering the bit error probability. Numerical results are presented, taking into consideration capacity versus link error probability for various numbers of links.

  15. Solid-state transformation of single precursor vanadium complex nanostructures to V?O? and VO?: catalytic activity of V?O? for oxidative coupling of 2-naphthol.

    PubMed

    Pradhan, Mukul; Roy, Anindita; Sinha, Arun Kumar; Sahoo, Ramkrishna; Deb, Dibakar; Pal, Tarasankar

    2015-01-28

    A vanadium complex, [(C5H5N)2V2O3·H2O], of different morphologies has been obtained via a modified hydrothermal procedure using pyridine and VOSO4 salt as the starting material. The evolved [(C5H5N)2V2O3·H2O] nanobelts are of 50-200 nm in width and of a length up to several millimeters. At higher temperatures (600 °C), the solid [(C5H5N)2V2O3·H2O] nanostructures are converted to vanadium pentoxide (V2O5) and vanadium dioxide (VO2) when heated in air and nitrogen atmosphere, respectively. During growth, the mechanism of the evolution of octahedra, truncated octahedra, and hollow truncated octahedra of [(C5H5N)2V2O3·H2O] are reported for the first time. These types of well-structured morphology are also isolated while V2O5 and VO2 are evolved. The as-grown belt-like and octahedral morphologies of [(C5H5N)2V2O3·H2O] are retained during the solid-state transformation, suggesting a route to evolve crystalline nanomaterials. Again, the morphological evolution of the [(C5H5N)2V2O3·H2O] nanostructures has been examined to be pyridine and precursor vanadyl sulfate (VS) concentration dependent. Thus, we are able to isolate truncated octahedra as an intermediate during the formation of [(C5H5N)2V2O3·H2O] nanobelts and nanoflowers with a high pyridine (Py) concentration. Interestingly, longer reaction times successively featured the transformation of truncated octahedra into nanobelts. Nanobelt evolution is not observed at low pyridine concentrations. However, the formation of octahedral morphology takes place at low pyridine concentration. All of the nanostructures were critically examined and characterized thoroughly by various physical techniques to ascertain their purity, structure and composition. An interesting, thermodynamically stable, single crystalline product from DMF soluble [(C5H5N)2V2O3·H2O] has been characterized, which indirectly supports the composition of [(C5H5N)2V2O3·H2O]. Selectively, vanadium pentoxide nanobelts have been found to be an efficient catalyst for the oxidative coupling of 2-naphthol to binaphthols under a molecular oxygen atmosphere. PMID:25486444

  16. The use of ultra-high pressure liquid chromatography with tandem mass spectrometric detection of analysis of agrochemical residues and mycotoxines in food - challenges and applications

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In the field of food contaminant analysis, the most significant development of recent years has been the integration of ultra-high pressure liquid chromatography (UHPLC), coupled to tandem quadrupole mass spectrometry (MS/MS), into analytical applications. In this review, we describe the emergence o...

  17. Characterisation by liquid chromatography-electrospray tandem mass spectrometry of anthocyanins in extracts of Myrtus communis L. berries used for the preparation of myrtle liqueur

    Microsoft Academic Search

    Paola Montoro; Carlo I. G. Tuberoso; Angela Perrone; Sonia Piacente; Paolo Cabras; Cosimo Pizza

    2006-01-01

    Anthocyanins in extracts of berries of Myrtus communis, prepared following a typical Sardinia myrtle liqueur recipe, were identified and quantified by HPLC coupled with electrospray\\/tandem mass spectrometry using, respectively, an ion trap and a triple quadrupole mass analyser. The fragmentation patterns of the anthocyanidins were dependent on the MS technique employed, and differed considerably from those previously reported. The anthocyanin

  18. Development and validation of sensitive method for determination of serum cotinine in smokers and nonsmokers by liquid chromatography\\/atmospheric pressure ionization tandem mass spectrometry

    Microsoft Academic Search

    John T. Bernert; Wayman E. Turner; James L. Pirkle; Connie S. Sosnoff; James R. Akins; Mary K. Waldrep; Qinghong Ann; Thomas R. Covey; Wanda E. Whitfield; Elaine W. Gunter; Barbara B. Miller; Donald G. Patterson; Larry L. Needham; W. Harry; Eric J. Sampson

    We describe a sensitive and specific method for measur- ing cotinine in serum by HPLC coupled to an atmo- spheric pressure chemical ionization tandem mass spec- trometer. This method can analyze 100 samples\\/day on a routine basis, and its limit of detection of 50 ng\\/L makes it applicable to the analysis of samples from nonsmok- ers potentially exposed to environmental

  19. Ultra-Trace Analysis of Nine Macrolides, including Tulathromycin A (Draxxin), in Edible Animal Tissues with Mini-Column Liquid Chromatography Tandem Mass Spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Analysis of 9 macrolides is presented, including tulathromycin A (Draxxin), in beef, poultry and pork muscle with a simple multi-residue extraction and analysis method using high performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. The extraction method inv...

  20. TassDB: a database of alternative tandem splice sites

    Microsoft Academic Search

    Michael Hiller; Swetlana Nikolajewa; Klaus Huse; Karol Szafranski; Philip Rosenstiel; Stefan Schuster; Rolf Backofen; Matthias Platzer

    2007-01-01

    Subtle alternative splice events at tandem splice sites are frequent in eukaryotes and substantially increase the complexity of transcriptomes and proteomes. We have developed a relational data- base, TassDB (TAndem Splice Site DataBase), which stores extensive data about alternative splice events at GYNGYN donors and NAGNAG acceptors. These splice events are of subtle nature since they mostly result in the

  1. Speckle-phase measurement in a tandem-vortex coronagraph.

    PubMed

    Serabyn, Eugene; Wallace, J Kent; Mawet, Dimitri

    2011-10-01

    A tandem-vortex coronagraph can in theory enable high-contrast imaging behind a classical on-axis telescope. Here we point out that a tandem-vortex coronagraph configuration can also directly enable the measurement of the phases of focal-plane speckles, thereby allowing for their suppression in the resultant high-contrast image. PMID:22016212

  2. Monitoring Bilingualism: Pedagogical Implications of the Bilingual Tandem Analyser

    ERIC Educational Resources Information Center

    Schwienhorst, Klaus; Borgia, Alexandre

    2006-01-01

    Tandem learning is the collaborative learning partnership of two language learners with complementary language combinations, for example an Irish student learning German and a German student learning English. One of the major principles in tandem learning, apart from reciprocity and learner autonomy, is balanced bilingualism. While learners may…

  3. The Shaft Torque of a Tandem Axial-Piston Pump

    E-print Network

    Manring, Noah D.

    The Shaft Torque of a Tandem Axial- Piston Pump Noah D. Manring Viral S. Mehta Mechanical of this study is to identify the best indexed position of two rotating groups within a tandem axial-piston pump characteristics of the pump, other vibration aspects of the machine are also expected to be reduced. In particular

  4. Tandem acoustic modeling in large-vocabulary recognition

    Microsoft Academic Search

    Daniel P. W. Ellis; Rita Singh; Sunil Sivadas

    2001-01-01

    In the tandem approach to modeling the acoustic signal, a neural-net preprocessor is first discriminatively trained to estimate posterior probabilities across a phone set. These are then used as feature inputs for a conventional hidden Markov model (HMM) based speech recognizer, which relearns the associations to subword units. We apply the tandem approach to the data provided for the first

  5. Linearbeschleuniger und Tandem-van-de-Graaffs: Werkzeuge der Schwerionenforschung

    NASA Astrophysics Data System (ADS)

    Brix, P.; Ingwersen, H.; Jaeschke, E.; Repnow, R.

    1980-06-01

    The basic principles of dc-tandem and high-frequency linear accelerator are discussed by referring to the pioneering work of H. Kallmann and R. Wideröe. The 30 MV Supertandem in Daresbury, the Heidelberg combination of tandem and linac, and the universal linear accelerator Unilac of the GSI at Darmstadt serve as examples of modern heavy-ion accelerators.

  6. Simple tandem DNA repeats and human genetic disease

    Microsoft Academic Search

    G. R. Sutherland; R. I. Richards

    1995-01-01

    The human genome contains many repeated DNA sequences that vary in complexity of repeating unit from a single nucleotide to a whole gene. The repeat sequences can be widely dispersed or in simple tandem arrays. Arrays of up to 5 or 6 nt are known as simple tandem repeats, and these are widely dispersed and highly polymorphic. Members of one

  7. Form-Focused Interaction in Online Tandem Learning

    ERIC Educational Resources Information Center

    O'Rourke, Breffni

    2005-01-01

    Tandem language learning--a configuration involving pairs of learners with complementary target/native languages--is an underexploited but potentially very powerful use of computer-mediated communication (CMC) in second-language pedagogy. Tandem offers the benefits of authentic, culturally grounded interaction, while also promoting a pedagogical…

  8. APPLICATION NOTE SILVER Helps Assign Peptides to Tandem

    E-print Network

    Roth, Frederick

    Pharmacology, Harvard Medical School, Boston, Massachusetts, USA Tandem mass spectrometry is commonly used" peptide-spectrum matches (PSMs). SILVER is web-based software that assists manual curation of tandem mass at http://llama.med.harvard.edu/Software.html. (J Am Soc Mass Spectrom 2004, 15, 910­912) © 2004 American

  9. Monolithic Tandem Organic Photovoltaic Cell Utilizing Transparent Carbon Nanotube Interlayer

    Microsoft Academic Search

    Kamil Mielczarek; Senku Tanaka; Raquel Ovalle Robles; Alexander Kuznetsov; Brian Wang; Dean Hsu; Ray Baughman; Anvar Zakhidov

    2009-01-01

    We demonstrate an organic photovoltaic multijunction cell in a monolithic parallel tandem structure in which transparent multi and single-walled nanotube sheets are used as an interlayer electrode connecting two cells; polymeric photovoltaic (PPV) cell or organic low molecular PV (OPV). Each cell is characterized independently and the short circuit current density of the tandem is shown to be larger than

  10. Quantification of peramivir (a novel anti-influenza drug) in human plasma by hydrophilic interaction chromatography\\/tandem mass spectrometry

    Microsoft Academic Search

    Ying Li; Xinzhong Zhang; Xiaoying Wang; Song Li; Jinxiu Ruan; Zhenqing Zhang

    2009-01-01

    Peramivir is a novel influenza neuraminidase inhibitor. In this article, hydrophilic interaction chromatography coupled with tandem mass spectrometry was developed to determine peramivir in human plasma. The positive ion MRM mode was performed and the precursor to the product ion transitions of m\\/z 329?100 and 285?138 were used to measure peramivir and Ro 64-0802 (I.S.). Chromatographic separation was performed on

  11. Analysis of catecholamines and related substances using porous graphitic carbon as separation media in liquid chromatography–tandem mass spectrometry

    Microsoft Academic Search

    Anna Törnkvist; Per J. R. Sjöberg; Karin E. Markides; Jonas Bergquist

    2004-01-01

    Capillary porous graphitic carbon (PGC) columns have been utilized for separation of several catecholamines and related compounds (i.e. l-tyrosine, l-DOPA, 3-O-methyl-DOPA, dopamine, 3,4-dihydroxy-phenyl-acetic acid (DOPAC), homovanillic acid, noradrenaline, vanillomandelic acid and adrenaline) on-line with electrospray ionization tandem mass spectrometry (ESI–MS\\/MS). The use of a mobile phase without ion-pairing agents and with high content of organic modifier facilitated the coupling to

  12. Chlorpromazine quantification in human plasma by UPLC–electrospray ionization tandem mass spectrometry. Application to a comparative pharmacokinetic study

    Microsoft Academic Search

    Ney Carter Borges; Vinicius Marcondes Rezende; Jose Marcos Santana; Ricardo Pereira Moreira; Roberto Fernandes Moreira; Patrícia Moreno; Diego Carter Borges; José Luiz Donato; Ronilson Agnaldo Moreno

    In the present study a method to quantify chlorpromazine in human plasma using cyclobenzaprine as the internal standard (IS) is described. The analyte and the IS were extracted from human plasma by a liquid–liquid extraction with diethyl ether\\/dichloromethane (70\\/30, v\\/v) and analyzed by an ultra performance liquid chromatography (UPLC) coupled to an electrospray tandem triple quadrupole mass spectrometer in positive

  13. 4C-3 Monolithically Integrated Tandem Waveguide-Type Acoustooptic Frequency Shifter Driven by Surface Acoustic Waves

    Microsoft Academic Search

    Shoji Kakio; Shinji Uotani; Yasuhiko Nakagawa; Takefumi Hara; Hiromasa Ito; Tetsuya Kobayashi; Masayuki Watanabe

    2006-01-01

    A waveguide-type acoustooptic frequency shifter (AOFS) using coplanar AO coupling due to a surface acoustic wave (SAW), that is, Bragg diffraction, in a tapered crossed-channel proton-exchanged (PE) optical waveguide on a 128deg-rotated Y-cut LiNbO3 substrate for an optical wavelength of 1.55 mum has been proposed. In this study, a monolithically integrated tandem waveguide-type AOFS driven by SAW was designed and

  14. Pharmacokinetics of HZ08 in rats by liquid chromatography–tandem mass spectrometry

    Microsoft Academic Search

    Jing-yan Weng; Min Song; Tai-jun Hang; Wen-long Huang; Yun Du

    2007-01-01

    A selective and sensitive liquid chromatographic method coupled with ion spray tandem mass spectrometry detection (LC–MS\\/MS) was developed for the determination and pharmacokinetic study of N-cyano-1-[(3,4-dimethoxyphenyl)methyl]-3,4-dihydro-6,7-dimethoxy-N?-octyl-2(1H)-isoquinoline-carboximidamide (HZ08, a candidate reversing agent for multidrug resistance of cancer) liposome injection in rat plasma. The analyte was extracted from plasma using liquid–liquid extraction by methyl tert-butyl ether with drotaverine as internal standard. The

  15. Asymmetric synthesis of ?-allyl-?-aryl ?-amino acids by tandem alkylation/?-allylation of ?-iminoesters.

    PubMed

    Curto, John M; Dickstein, Joshua S; Berritt, Simon; Kozlowski, Marisa C

    2014-04-01

    The first asymmetric synthesis of ?-allyl-?-aryl ?-amino acids by means of a three-component coupling of ?-iminoesters, Grignard reagents, and cinnamyl acetate is reported. Notably, the enolate from the tandem process provides a much higher level of reactivity and selectivity than the same enolate generated via direct deprotonation, presumably due to differences in the solvation/aggregation state. A novel method for removal of a homoallylic amine protecting group delivers the free amine congeners. The ?-allyl group offers a means to generate further valuable ?-amino acid structures as exemplified by ring closing metathesis to generate a higher ring homologue of ?-aryl-proline. PMID:24666394

  16. The Bucharest FN Tandem Accelerator: Modernization and Development

    NASA Astrophysics Data System (ADS)

    Dobrescu, S.; Mosu, D. V.; Moisa, D.; Papureanu, S.

    2009-03-01

    The Bucharest FN tandem accelerator, installed in 1973 and upgraded in 1983 to 9 MV, has been used for atomic and nuclear physics studies as well as for different applications using accelerated ion beams. In the last three years a program of modernization of the tandem accelerator including the replacement of the old accelerator equipment by new ones, installation of a pelletron system for the Van de Graaff generator and installation of new negative ion injectors was undertaken. In parallel a development of the tandem accelerator was started. In 2009, a beam pulsing system in the nanosecond range is scheduled to be installed. All these works aimed to transform the tandem accelerator in a reliable and efficient tool for research and applications are presented. The main lines of the research program at the Bucharest tandem accelerator are shortly presented too.

  17. Speciation of trace elements in human serum by micro anion exchange chromatography coupled with inductively coupled plasma mass spectrometry.

    PubMed

    Malavolta, Marco; Piacenza, Francesco; Basso, Andrea; Giacconi, Robertina; Costarelli, Laura; Pierpaoli, Sara; Mocchegiani, Eugenio

    2012-02-01

    Speciation analysis of essential trace elements in human serum provides important information on nutritional status and homeostatic mechanisms regulating transport processes, acute phase reactions, and protection against oxidative damage. Anion exchange high-performance liquid chromatography (HPLC) combined with inductively coupled plasma mass spectrometry (ICP-MS) has proved to be a useful tool in speciation. Here we describe a fast method that can be applied to carry out the speciation of Fe, Cu, Zn, and Se in as little as 1 microl [corrected] of serum. The method employs monolithic anion exchange micro columns installed on a tandem HPLC system coupled on-line with an ICP-MS detector. The chromatographic separation is similar to those reported previously but with considerable gain in terms of time and sample requirement. Reproducibility is acceptable for most species. Using our method, we were able to find species-specific differences between different commercially available trace element reference materials. Because the method chosen to collect blood might interfere with speciation, the proposed methodology was used to compare heparinized plasma, ethylenediaminetetraacetic acid (EDTA) plasma, and serum from adult healthy volunteers. As expected, EDTA strongly affects speciation analysis (especially for Fe and Zn), whereas changes due to the use of lithium-heparin (Li-He) as anticoagulant appear to be minimized. PMID:22155148

  18. Magnetoelectric coupling at metal surfaces

    Microsoft Academic Search

    Lukas Gerhard; T. K. Yamada; T. Balashov; A. F. Takács; R. J. H. Wesselink; M. Däne; M. Fechner; S. Ostanin; Arthur Ernst; I. Mertig; Wulf Wulfhekel

    2010-01-01

    Magnetoelectric coupling allows the magnetic state of a material to be changed by an applied electric field. To date, this phenomenon has mainly been observed in insulating materials such as complex multiferroic oxides. Bulk metallic systems do not exhibit magnetoelectric coupling, because applied electric fields are screened by conduction electrons. We demonstrate strong magnetoelectric coupling at the surface of thin

  19. Depth-related coupling relation between methane-oxidizing bacteria (MOBs) and sulfate-reducing bacteria (SRBs) in a marine sediment core from the Dongsha region, the South China Sea.

    PubMed

    Xu, Xiao-Ming; Fu, Shao-Ying; Zhu, Qing; Xiao, Xi; Yuan, Jian-Ping; Peng, Juan; Wu, Chou-Fei; Wang, Jiang-Hai

    2014-12-01

    The vertical distributions of methane-oxidizing bacteria (MOBs) and sulfate-reducing bacteria (SRBs) in the marine sediment core of DH-CL14 from the Dongsha region, the South China Sea, were investigated. To enumerate MOBs and SRBs, their specific genes of pmoA and apsA were quantified by a culture-independent molecular biological technique, real-time polymerase chain reaction (RT-PCR). The result shows that the pmoA gene copies per gram of sediments reached the maximum of 1,118,679 at the depth of 140-160 cm. Overall considering the detection precision, sample amount, measurement cost, and sensitivity to the seepage of methane from the oil/gas reservoirs or gas hydrates, we suggest that the depth of 140-160 cm may be the optimal sampling position for the marine microbial exploration of oils, gases, and gas hydrates in the Dongsha region. The data of the pmoA and apsA gene copies exhibit an evident coupling relation between MOBs and SRBs as illustrated in their vertical distributions in this sediment core, which may well be interpreted by a high sulfate concentration inhibiting methane production and further leading to the reduction of MOBs. In comparison with the numbers of the pmoA and apsA copies at the same sediment depth, we find out that there were two methane-oxidizing mechanisms of aerobic and anaerobic oxidation in this sediment core, i.e., the aerobic oxidation with free oxygen dominantly occurred above the depth of 210-230 cm, while the anaerobic oxidation with the other electron acceptors such as sulfates and manganese-iron oxides happened below the depth of 210-230 cm. PMID:25064353

  20. Electronic Tandem Language Learning (eTandem): A Third Approach to Second Language Learning for the 21st Century

    ERIC Educational Resources Information Center

    Cziko, Gary A.

    2004-01-01

    Tandem language learning occurs when two learners of different native languages work together to help each other learn the other language. First used in face-to-face contexts, Tandem is now increasingly being used by language-learning partners located in different countries who are linked via various forms of electronic communication, a context…