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1

Tandem catalysis of amines using porous graphene oxide.  

PubMed

Porous graphene oxide can be used as a metal-free catalyst in the presence of air for oxidative coupling of primary amines. Herein, we explore a GO-catalyzed carbon-carbon or/and carbon-heteroatom bond formation strategy to functionalize primary amines in tandem to produce a series of valuable products, i.e., ?-aminophosphonates, ?-aminonitriles, and polycyclic heterocompounds. Furthermore, when decorated with nano-Pd, the Pd-coated porous graphene oxide can be used as a bifunctional catalyst for tandem oxidation and hydrogenation reactions in the N-alkylation of primary amines, achieving good to excellent yields under mild conditions. PMID:25551171

Su, Chenliang; Tandiana, Rika; Balapanuru, Janardhan; Tang, Wei; Pareek, Kapil; Nai, Chang Tai; Hayashi, Tamio; Loh, Kian Ping

2015-01-21

2

Tandem Cycloisomerization/Suzuki Coupling of Arylethynyl MIDA Boronates  

PubMed Central

A tandem gold-catalyzed cycloisomerization/Suzuki cross coupling sequence involving arylethynyl-N-methyliminodiacetic acid boronates is described. Combining the mildness of homogeneous gold catalysis with the versatility of N-methyliminodiacetic acid (MIDA) boronates, this tandem two-step method enables the rapid assembly of various aryl-substituted heterocycles without having to isolate or purify any heterocyclic MIDA boronate intermediates. Another major advantage of this method is that a wide range of heterocycles bearing different aryl groups may be made from a single MIDA boronate alkyne precursor. PMID:21765556

Chan, Julian M. W.; Amarante, Giovanni W.; Toste, F. Dean

2011-01-01

3

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

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 1mL/min within a total analysis time of 17min. Using single reaction monitoring in the positive ion mode, the linear working ranges were 2.74-163pg/?L (Z-BOX A) and 2.12-162.4pg/?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 ± 5.1nM) and Z-BOX B (10.9±3.1nM) 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

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

2015-01-01

4

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

PubMed

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

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

2012-01-01

5

Photosensitized oxidation of phosphatidylethanolamines monitored by electrospray tandem mass spectrometry.  

PubMed

Photodynamic therapy combines visible light and a photosensitizer (PS) in the presence of molecular oxygen to generate reactive oxygen species able to modify biological structures such as phospholipids. Phosphatidylethanolamines (PEs), being major phospholipid constituents of mammalian cells and membranes of Gram-negative bacteria, are potential targets of photosensitization. In this work, the oxidative modifications induced by white light in combination with cationic porphyrins (Tri-Py(+)-Me-PF and Tetra-Py(+)-Me) were evaluated on PE standards. Electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS/MS) were used to identify and characterize the oxidative modifications induced in PEs (POPE: PE 16:0/18:1, PLPE: PE 16:0/18:2, PAPE: PE 16:0/20:4). Photo-oxidation products of POPE, PLPE and PAPE as hydroxy, hydroperoxy and keteno derivatives and products due to oxidation in ethanolamine polar head were identified. Hydroperoxy-PEs were found to be the major photo-oxidation products. Quantification of hydroperoxides (PE-OOH) allowed differentiating the potential effect in photodamage of the two porphyrins. The highest amounts of PE-OOH were notorious in the presence of Tri-Py(+)-Me-PF, a highly efficient PS against bacteria. The identification of these modifications in PEs is an important key point in the understanding cell damage processes underlying photodynamic therapy approaches. PMID:24338891

Melo, Tânia; Santos, Nuno; Lopes, Diana; Alves, Eliana; Maciel, Elisabete; Faustino, Maria A F; Tomé, João P C; Neves, Maria G P M S; Almeida, Adelaide; Domingues, Pedro; Segundo, Marcela A; Domingues, M Rosário M

2013-12-01

6

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

PubMed

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

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

2014-11-01

7

Quantification of fatty acid oxidation products using online high-performance liquid chromatography tandem mass spectrometry.  

PubMed

Oxidized fatty acids formed via lipid peroxidation are implicated in pathological processes such as inflammation and atherosclerosis. A number of methods may be used to detect specific oxidized fatty acids containing a single or multiple combinations of epoxide, hydroxyl, ketone, and hydroperoxide moieties on varying carbon chain lengths from C8 up to C30. Some of these methods are nonspecific and their use in biological systems is fraught with difficulty. Measures of specific oxidized fatty acid derivatives help in identifying oxidation pathways in pathological processes. We used liquid chromatography coupled with electrospray ionization tandem mass spectrometry as an efficient, selective, and sensitive method for identifying and analyzing multiple specific fatty acid peroxidation products in human plasma and other biological matrices. We then distilled the essential components of a number of these analyses to provide an efficient protocol by which fatty acid oxidation products and their parent compounds can be determined. In this protocol, addition of a synthetic internal standard to the sample, followed by base hydrolysis at elevated temperature and liquid-liquid phase sample extraction with lighter-than-water solvents, facilitates isolation of the oxidized fatty acid species. These species can be identified and accurately quantified using stable-isotope dilution and multiple-reaction monitoring. Use of a coupled multiplexed gradient HPLC system on the front end enables high-throughput chromatography and more efficient use of mass spectrometer time. PMID:23499838

Levison, Bruce S; Zhang, Renliang; Wang, Zeneng; Fu, Xiaoming; DiDonato, Joseph A; Hazen, Stanley L

2013-06-01

8

Auto-oxidative coupling of glycine derivatives.  

PubMed

The unprecedented title reaction between glycine derivatives and indoles, as well as the auto-oxidative Povarov/aromatization tandem reaction of glycine derivatives with olefins are described. The reactions were performed in the absence of redox-active catalysts and chemical oxidants under mild reaction conditions. Only simple organic solvents and air (or O2 ) were required. PMID:25288283

Huo, Congde; Yuan, Yong; Wu, Mingxia; Jia, Xiaodong; Wang, Xicun; Chen, Fengjuan; Tang, Jing

2014-12-01

9

Perovskite catalysts for oxidative coupling  

DOEpatents

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.

Campbell, Kenneth D. (Charleston, WV)

1991-01-01

10

Perovskite catalysts for oxidative coupling  

DOEpatents

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.

Campbell, K.D.

1991-06-25

11

Copper-mediated tandem oxidative C(sp2)-H/C(sp)-H alkynylation and annulation of arenes with terminal alkynes.  

PubMed

The copper-mediated tandem oxidative C(sp(2))-H/C(sp)-H cross-coupling and intramolecular annulation of arenes with terminal alkynes has been developed, which offers a highly efficient approach to the 3-methyleneisoindolin-1-one scaffold. In this oxidative coupling process, Cu(OAc)2 acts as both the promoter and the terminal oxidant. This protocol features a wide substrate scope; high functional group tolerance; exclusive chemo-, regio-, and stereoselectivity; and simple, easily available, and inexpensive reaction system. The transformation has demonstrated for the first time that Cu(OAc)2 can be renewable after undergoing an oxidative reaction. PMID:24855896

Dong, Jiaxing; Wang, Fei; You, Jingsong

2014-06-01

12

Synthesis of Pyrrolidines and Pyrroles via Tandem Amination/Cyanation/Alkylation and Amination/Oxidation Sequences.  

PubMed

Starting from a primary amine-tethered alkyne 1, a copper-catalyzed three-component tandem amination/cyanation/alkylation sequence gives ?-CN pyrrolidine 6 in good yield and regioselectivity. Also, a silver mediated tandem amination/oxidation of a secondary amine-tethered alkyne 7 produces functionalized pyrrole 8 in good yield. All reactions were conducted in one pot without any protection/deprotection steps. PMID:25386099

Han, Junbin; Lu, Zhichao; Hammond, Gerald B; Xu, Bo

2014-09-01

13

MEASUREMENT OF OXIDATIVE STRESS PARAMETERS USING LIQUID CHROMATOGRAPHY - TANDEM MASS SPECTROSCOPY (LC-MS/MS)  

EPA Science Inventory

What is the study? An invited review article. Measurement of oxidative stress parameters using liquid chromatography-tandem mass spectroscopy (LC-MS/MS) Why was it done? Although oxidative stress is frequently cited as a cause of various adverse biological eff...

14

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

NASA Astrophysics Data System (ADS)

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.

Strandberg, Rune

2015-01-01

15

Flight and Analytical Methods for Determining the Coupled Vibration Response of Tandem Helicopters  

NASA Technical Reports Server (NTRS)

Chapter one presents a discussion of flight-test and analysis methods for some selected helicopter vibration studies. The use of a mechanical shaker in flight to determine the structural response is reported. A method for the analytical determination of the natural coupled frequencies and mode shapes of vibrations in the vertical plane of tandem helicopters is presented in Chapter two. The coupled mode shapes and frequencies are then used to calculate the response of the helicopter to applied oscillating forces.

Yeates, John E , Jr; Brooks, George W; Houbolt, John C

1957-01-01

16

Aryl Ketone Synthesis via Tandem Orthoplatinated Triarylphosphite-Catalyzed Addition Reactions of Arylboronic Acids with Aldehydes Followed by Oxidation  

PubMed Central

Tandem orthoplatinated triarylphosphite-catalyzed addition reactions of arylboronic acids with aldehydes followed by oxidation to yield aryl ketones is described. 3-Pentanone was identified as a suitable oxidant for the tandem aryl ketone formation reaction. By using microwave energy, aryl ketones were obtained in high yields with the catalyst loading as low as 0.01%. PMID:20849092

Liao, Yuan-Xi; Hu, Qiao-Sheng

2010-01-01

17

Aryl ketone synthesis via tandem orthoplatinated triarylphosphite-catalyzed addition reactions of arylboronic acids with aldehydes followed by oxidation.  

PubMed

Tandem orthoplatinated triaryl phosphite-catalyzed addition reactions of arylboronic acids with aldehydes followed by oxidation to yield aryl ketones is described. 3-Pentanone was identified as a suitable oxidant for the tandem aryl ketone formation reaction. By using microwave energy, aryl ketones were obtained in high yields with the catalyst loading as low as 0.01%. PMID:20849092

Liao, Yuan-Xi; Hu, Qiao-Sheng

2010-10-15

18

Lewis acid catalysis and Green oxidations: sequential tandem oxidation processes induced by Mn-hyperaccumulating plants.  

PubMed

Among the phytotechnologies used for the reclamation of degraded mining sites, phytoextraction aims to diminish the concentration of polluting elements in contaminated soils. However, the biomass resulting from the phytoextraction processes (highly enriched in polluting elements) is too often considered as a problematic waste. The manganese-enriched biomass derived from native Mn-hyperaccumulating plants of New Caledonia was presented here as a valuable source of metallic elements of high interest in chemical catalysis. The preparation of the catalyst Eco-Mn1 and reagent Eco-Mn2 derived from Grevillea exul exul and Grevillea exul rubiginosa was investigated. Their unusual polymetallic compositions allowed to explore new reactivity of low oxidative state of manganese-Mn(II) for Eco-Mn1 and Mn(IV) for Eco-Mn2. Eco-Mn1 was used as a Lewis acid to catalyze the acetalization/elimination of aldehydes into enol ethers with high yields; a new green and stereoselective synthesis of (-)-isopulegol via the carbonyl-ene cyclization of (+)-citronellal was also performed with Eco-Mn1. Eco-Mn2 was used as a mild oxidative reagent and controlled the oxidation of aliphatic alcohols into aldehydes with quantitative yields. Oxidative cleavage was interestingly noticed when Eco-Mn2 was used in the presence of a polyol. Eco-Mn2 allowed direct oxidative iodination of ketones without using iodine, which is strongly discouraged by new environmental legislations. Finally, the combination of the properties in the Eco-Mn catalysts and reagents gave them an unprecedented potential to perform sequential tandem oxidation processes through new green syntheses of p-cymene from (-)-isopulegol and (+)-citronellal; and a new green synthesis of functionalized pyridines by in situ oxidation of 1,4-dihydropyridines. PMID:25263417

Escande, Vincent; Renard, Brice-Loïc; Grison, Claude

2014-09-30

19

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

PubMed

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

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

2014-09-01

20

Indium tin oxide-free tandem polymer solar cells on opaque substrates with top illumination.  

PubMed

Top-illuminated, indium tin oxide (ITO)-free, tandem polymer solar cells are fabricated on opaque substrates in an inverted device configuration. In the tandem cell, a wide band gap subcell, consisting of poly[N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT) blended with [70]PCBM is combined with a small band gap subcell consisting of a mixture of poly[{2,5-bis(2-hexyldecyl)-2,3,5,6-tetrahydro-3,6-dioxopyrrolo[3,4-c]pyrrole-1,4-diyl}-alt-{[2,2'-(1,4-phenylene)bisthiophene]-5,5'-diyl}] (PDPPTPT) and [60]PCBM. Compared to the more common bottom-illuminated inverted tandem polymer solar cells on transparent ITO substrates, the front and back cells must be reversed when using opaque substrates and a transparent and conductive top contact must be employed to enable top illumination. A high conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) layer in combination with Ag lines surrounding the active area as current collection electrode is used for this purpose. The tandem polymer solar cell on an opaque glass/metal substrate yields a power conversion efficiency of 6.1% when the thicknesses of the photoactive layers are balanced for optimum performance. This is similar to the equivalent inverted tandem device fabricated on a transparent glass/ITO substrate. PMID:25051293

Gupta, Dhritiman; Wienk, Martijn M; Janssen, René A J

2014-08-27

21

Tandem organic light-emitting diode with a molybdenum tri-oxide thin film interconnector layer  

NASA Astrophysics Data System (ADS)

A 10-nm-thick molybdenum tri-oxide (MoO3) thin film was used as the interconnector layer in tandem organic light-emitting devices (OLEDs). The tandem OLEDs with two identical emissive units consisting of N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine (NPB)/tris(8-hydroxyquinoline) aluminum (Alq3) exhibited current efficiency-current density characteristics superior to the conventional single-unit devices. At 20 mA/cm2, the current efficiency of the tandem OLEDs using the interconnector layers of MoO3 thin film was about 4.0 cd/A, which is about twice that of the corresponding conventional single-unit device (1.8 cd/A). The tandem OLED showed a higher power efficiency than the conventional single-unit device for luminance over 1200 cd/m2. The experimental results demonstrated that a MoO3 thin film with a proper thickness can be used as an effective interconnector layer in tandem OLEDs. Such an interconnector layer can be easily fabricated by simple thermal evaporation, greatly simplifying the device processing and fabrication processes required by previously reported interconnector layers. A possible explanation was proposed for the carrier generation of the MoO3 interconnector layer.

Lu, Fei-Ping; Wang, Qian; Zhou, Xiang

2013-03-01

22

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

PubMed

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

Miyamura, Hiroyuki; Kobayashi, Sh?

2014-04-15

23

Stir bar sorptive extraction coupled to liquid chromatography-tandem mass spectrometry for the2 determination of pesticides in water samples: method validation and measurement uncertainty3  

E-print Network

1 Title :1 Stir bar sorptive extraction coupled to liquid chromatography-tandem mass spectrometry sorptive extraction followed by liquid desorption and high performance liquid12 chromatography with tandem chromatography-tandem mass spectrometry (LC-30 MSMS), pesticides, surface water, validation, measurement

Paris-Sud XI, Université de

24

Automated surface sampling of lipids from worn contact lenses coupled with tandem mass spectrometry.  

PubMed

The deposition of biological material (biofouling) onto polymeric contact lenses is thought to be a major contributor to lens discomfort and hence discontinuation of wear. We describe a method to characterize lipid deposits directly from worn contact lenses utilizing liquid extraction surface analysis coupled to tandem mass spectrometry (LESA-MS/MS). This technique effected facile and reproducible extraction of lipids from the contact lens surfaces and identified lipid molecular species representing all major classes present in human tear film. Our data show that LESA-MS/MS is a rapid and comprehensive technique for the characterization of lipid-related biofouling on polymer surfaces. PMID:23181259

Brown, Simon H J; Huxtable, Liam H; Willcox, Mark D P; Blanksby, Stephen J; Mitchell, Todd W

2013-03-01

25

Catalytic migratory oxidative coupling of nitrones.  

PubMed

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

Hashizume, Shogo; Oisaki, Kounosuke; Kanai, Motomu

2011-08-19

26

Analysis of isomeric forms of oxidized triacylglycerols using ultra-high-performance liquid chromatography and tandem mass spectrometry.  

PubMed

Detailed studies on the regioisomeric structures of oxidized species of triacylglycerols (TAG), formed in food during storage and processing, have not been published thus far. In this study, an analytical approach based on efficient ultra-high-performance liquid chromatographic (UHPLC) separation of different isomers of oxidized TAG species and their tandem mass spectrometric analysis was created. A linear solvent gradient based on acetonitrile and acetone was used in the UHPLC method. A novel method utilizing positive ion ESI using ammonia supplemented in the nebulizer gas was used to produce ammonium adduct ions for mass spectrometric analysis. With the UHPLC method used, different regioisomers of TAG species containing oxidized linoleic or oleic acid could be efficiently resolved. Differences in the fragmentation patterns of many of the oxidized TAG isomers could be demonstrated by the tandem mass spectrometric method. On the basis of the results, the approach enables regiospecific analysis of oxidized TAG molecules. PMID:21702477

Suomela, Jukka-Pekka; Leskinen, Heidi; Kallio, Heikki

2011-08-10

27

Benzene oxidation coupled to sulfate reduction  

USGS Publications Warehouse

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.

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

1995-01-01

28

Rapid Characterization of Amyloid-? Side-Chain Oxidation by Tandem Mass Spectrometry and the Scoring Algorithm for Spectral Analysis  

Microsoft Academic Search

Purpose. Amyloid-ß (Aß) is a self-aggregating protein found in senile plaques in Alzheimer's disease (AD) brain and is thought to play a major role in the disease process. Oxidative stress may be a predominant cause of the formation of these Aß aggregates. This study aims at identifying possible sites of copper-catalyzed oxidation of Aß1-40 using liquid chromatography tandem mass spectrometry

Alexandra J. Schiewe; Lawrence Margol; Brian A. Soreghan; Stefani N. Thomas; Austin J. Yang

2004-01-01

29

Novel Mass Spectrometric Method for Phosphorylation Quantification Using Cerium Oxide Nanoparticles and Tandem Mass Tags  

PubMed Central

The stoichiometry of protein phosphorylation significantly impacts protein function. The development of quantitative techniques in mass spectrometry has generated the ability to systematically monitor the regulation levels of various proteins. This study reports an integrated methodology using cerium oxide nanoparticles and isobaric tandem mass tag (TMT) labeling to assess absolute stoichiometries of protein phosphorylation. This protocol was designed to directly measure the dephosphorylation levels for a known phosphorylation site therefore allowing for quantification of phosphosites. Both the accuracy and precision of the method were verified using standard peptides and protein tryptic digests. This novel method was then applied to quantify phosphorylations on eukaryotic initiation factor 3H (eIF3H), a protein integral to overall eukaryotic protein translation initiation. To date, this is the first report of assessment of protein phosphorylation quantification on eIF3. PMID:22304650

Jia, Weitao; Andaya, Armann; Leary, Julie A.

2012-01-01

30

Coupled tandem cavities based electro-absorption modulator with asymmetric tandem quantum well for high modulation performance at low driving voltage.  

PubMed

We propose and demonstrate a new electro-absorption modulator (EAM) based on coupled tandem cavities (CTC) having asymmetric tandem quantum well (ATQW) structure with separated electrode configuration to achieve large transmittance change over a broad spectral range at low driving voltage for high definition (HD) 3D imaging applications. Our theoretical calculations show that CTC with ATQW structure can provide large transmittance change over a wide spectral range at low driving voltage. By introducing separated electrode configuration, the fabricated EAM having CTC with ATQW structure shows a large transmittance change over 50%, almost three times larger spectral bandwidth compared to that of EAM having single cavity with a single thickness quantum well without significantly increasing the applied voltage. In addition, the CTC with ATQW structure also shows high speed modulation up to 28 MHz for the device having a large area of 2 mm x 0.5 mm. This high transmittance change, large spectral bandwidth and low voltage operation over a large device area for the EAM having CTC with ATQW demonstrates their huge potential as an optical image modulator for HD 3D imaging applications. PMID:24514307

Na, Byung Hoon; Ju, Gun Wu; Choi, Hee Ju; Lee, Soo Kyung; Ravindran, Sooraj; Cho, Yong Chul; Park, Yong Hwa; Park, Chang Young; Lee, Yong Tak

2013-11-18

31

Determination of anethole trithione in human plasma using high performance liquid chromatography coupled with tandem mass spectrometric detection  

Microsoft Academic Search

A rapid, sensitive and reliable high performance liquid chromatographic method coupled with tandem mass spectrometry via electrospray ionization (ESI) source (HPLC–MS\\/MS) has been developed and validated for the determination of anethole trithione (ATT) in human plasma. Diazepam was employed as the internal standard (IS). Sample extracts following liquid–liquid extraction were injected into the HPLC–MS\\/MS system. The analyte and IS were

Tianmin Li; Zunjian Zhang; Haoyan Jiao; Lu Zhang; Yuan Tian; Yun Chen; Xiaoyang Pang; Jie Zhuang

2007-01-01

32

Magnoelastic coupling in magnetic oxide nanoparticles  

NASA Astrophysics Data System (ADS)

Phonons are exquisitely sensitive to finite length scale effects in a wide variety of materials. To investigate confinement in combination with strong magnetoelastic interactions, we measured the infrared vibrational properties of MnO and CoFe2O4 nanoparticles and their parent compounds. For MnO, a charge and bonding analysis reveals that Born effective charge, local effective charge, total polarizability, and the force constant are overall lower in the nanoparticles compared to the bulk. We find that the spin-lattice coupling drops from ˜7 cm-1 in the single crystal to <1 cm-1 in the nanoparticles. For CoFe2O4, the spectroscopic response is sensitive to the size-induced crossover to the superparamagnetic state, which occurs between 7 and 10 nm, and a spin-phonon coupling analysis supports the core-shell model. Moreover, it provides an estimate of the thickness of the magnetically disordered shell, increasing from 0.4 nm in the 14 nm particles to 0.8 nm in the 5 nm particles, demonstrating that the associated local lattice distortions take place on the length scale of the unit cell. These findings are important for understanding finite length scale effects in magnetic oxides and other more complex functional oxides.

Sun, Qi; Baker, Sheila; Birkel, Christina; Seshadri, Ram; Tremel, Wolfgang; Christianson, Andrew; Musfeldt, Janice

2012-02-01

33

Tandem oxidative dearomatization/intramolecular Diels-Alder reaction for construction of the tricyclic core of palhinine A.  

PubMed

A concise construction of the 6/6/5 tricyclic core of Lycopodium alkaloid palhinine A (1) has been accomplished. The developed synthetic strategy featured a tandem oxidative dearomatization/intramolecular Diels-Alder reaction to construct C/D rings and an intramolecular 5-exo-trig radical cyclization to install the B ring of palhinine A (1). The developed approach paves the way for the total synthesis of palhinine A (1). PMID:22497445

Zhao, Changgui; Zheng, Huaiji; Jing, Peng; Fang, Bowen; Xie, Xingang; She, Xuegong

2012-05-01

34

[Research progress in microbial methane oxidation coupled to denitrification].  

PubMed

Methane oxidation coupled to denitrification is an essential bond to connect carbon- and nitrogen cycling. To deeply research this process will improve our understanding on the biochemical cycling of global carbon and nitrogen. As an exogenous gaseous carbon source of denitrification, methane can both regulate the balance of atmospheric methane to effectively mitigate the greenhouse effect caused by methane, and reduce the cost of exogenous carbon source input in traditional wastewater denitrification treatment process. As a result, great attention has being paid to the mechanical study of the process. This paper mainly discussed the two types of methane oxidation coupled to denitrification, i. e., aerobic methane oxidation coupled to denitrification (AME-D) and anaerobic methane oxidation coupled to denitrification (ANME-D), with the focus on the microbiological coupling mechanisms and related affecting factors. The existing problems in the engineering application of methane oxidation coupled to denitrification were pointed out, and the application prospects were approached. PMID:24697087

Zhu, Jing; Yuan, Meng-Dong; Liu, Jing-Jing; Huang, Xiao-Xiao; Wu, Wei-Xiang

2013-12-01

35

Magnetic coupling among spinel iron oxide microparticles by Mssbauer spectroscopy  

E-print Network

L-437 Magnetic coupling among spinel iron oxide microparticles by Mössbauer spectroscopy E. Tronc cristalline au sein d'agrégats est suggérée. Abstract 2014 Mössbauer spectra of hydrous spinel iron oxide to patterns of hydrous spinel iron oxide colloids worked correctly except for particles about 8 nm in size

Boyer, Edmond

36

Titanium oxidation by rf inductively coupled plasma  

NASA Astrophysics Data System (ADS)

The development of titanium dioxide (TiO2) films in the rutile and anatase phases is reported. The films have been obtained from an implantation/diffusion and sputtering process of commercially pure titanium targets, carried out in up to 500 W plasmas. The experimental outcome is of particular interest, in the case of anatase, for atmospheric pollution degradation by photocatalysis and, as to the rutile phase, for the production of biomaterials required by prosthesis and implants. The reactor employed consists in a cylindrical pyrex-like glass vessel inductively coupled to a 13.56 MHz RF source. The process takes place at a 5×10-2 mbar pressure with the target samples being biased from 0 to -3000 V DC. The anatase phase films were obtained from sputtering the titanium targets over glass and silicon electrically floated substrates placed 2 cm away from the target. The rutile phase was obtained by implantation/diffusion on targets at about 700 °C. The plasma was developed from a 4:1 argon/oxygen mixture for ~5 hour processing periods. The target temperature was controlled by means of the bias voltage and the plasma source power. The obtained anatase phases did not require annealing after the plasma oxidation process. The characterization of the film samples was conducted by means of x-ray diffraction, scanning electron microscopy, x-ray photoelectron spectroscopy and Raman spectroscopy.

Valencia-Alvarado, R.; de la Piedad-Beneitez, A.; López-Callejas, R.; Barocio, S. R.; Mercado-Cabrera, A.; Peña-Eguiluz, R.; Muñoz-Castro, A. E.; Rodríguez-Méndez, B. G.; de la Rosa-Vázquez, J. M.

2014-05-01

37

Materials considerations for the coupling of thermochemical hydrogen cycles to tandem mirror reactors  

SciTech Connect

Candidate materials are discussed and initial choices made for the critical elements in a liquid Li-Na Cauldron Tandem Mirror blanket and the General Atomic Sulfur-Iodine Cycle for thermochemical hydrogen production. V and Ti alloys provide low neutron activation, good radiation damage resistance, and good chemical compatibility for the Cauldron design. Aluminide coated In-800H and siliconized SiC are materials choices for heat exchanger components in the thermochemical cycle interface.

Krikorian, O.H.

1980-10-10

38

Tandem mobile robot system  

DOEpatents

A robotic vehicle system for terrain navigation mobility provides a way to climb stairs, cross crevices, and navigate across difficult terrain by coupling two or more mobile robots with a coupling device and controlling the robots cooperatively in tandem.

Buttz, James H. (Albuquerque, NM); Shirey, David L. (Albuquerque, NM); Hayward, David R. (Albuquerque, NM)

2003-01-01

39

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

PubMed

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

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

2013-07-17

40

Identification of the Related Substances in Ampicillin Capsule by Rapid Resolution Liquid Chromatography Coupled with Electrospray Ionization Tandem Mass Spectrometry  

PubMed Central

Rapid Resolution Liquid Chromatography coupled with Electrospray Ionization Tandem Mass Spectrometry (RRLC-ESI-MSn) was used to separate and identify related substances in ampicillin capsule. The fragmentation behaviors of related substances were used to identify their chemical structures. Finally, a total of 13 related substances in ampicillin capsule were identified, including four identified components for the first time and three groups of isomers on the basis of the exact mass, fragmentation behaviors, retention time, and chemical structures in the literature. This study avoided time-consuming and complex chemosynthesis of related substances of ampicillin and the results could be useful for the quality control of ampicillin capsule to guarantee its safety in clinic. In the meantime, it provided a good example for the rapid identification of chemical structures of related substances of drugs.

Cheng, Xian Long; Liu, Yang; Liang, Miao; Dong, Honghuan; Lv, Beiran; Luo, Zhiqiang; Tang, Mingmin

2014-01-01

41

Validation of antibiotics in catfish by on-line solid phase extraction coupled to liquid chromatography tandem mass spectrometry.  

PubMed

For the first time automated on-line solid phase extraction coupled to liquid chromatography tandem mass spectrometry was developed for the simultaneous determination of 13 antibiotics (sulfonamides and tetracyclines) in catfish. The method proposed was validated according to Commission Decision 2002/657/EC, showing good linearity between 2 and 350 ?g kg(-1), high recovery (80-99%) and reproducibility (13-20%) values, lower detection limits than 0.1 ?g kg(-1), and quantification limits under 2.4 ?g kg(-1) (between 39 and 84 times lower than the MRL fixed by the EU). Moreover, the proposed method was also used to determine sulfonamides and tetracyclines in 16 out of 107 samples, all previously analysed by microbiological screening that gave positive results. Five out of 13 antibiotics were found, having tetracycline the higher occurrence (10 samples); in all cases the concentrations were lower than the MRL established. PMID:23107742

Hurtado de Mendoza, Jorge; Maggi, Luana; Bonetto, Liliana; Rodríguez Carmena, Beatriz; Lezana, Alicia; Mocholí, Francisco A; Carmona, Manuel

2012-09-15

42

Multiclass determination of phytochemicals in vegetables and fruits by ultra high performance liquid chromatography coupled to tandem mass spectrometry.  

PubMed

In this study a simultaneous determination of several classes of phytochemicals (isoflavones, glucosinolates, flavones, flavonols and phenolic acids) in tomato, broccoli, carrot, eggplant and grape has been carried out by ultra high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). Solid-liquid extraction assisted by rotary agitator was utilised, using a mixture of methanol:water (80:20, v/v) as solvent. The analytical procedure was validated in all the matrices, obtaining recoveries ranging from 60% to 120% with repeatability values (expressed as relative standard deviations, RSDs) lower than 25%. Limits of quantification (LOQs) were always equal or lower than 50?g/kg, except for some glucosinolates (125?g/kg). Finally the method was applied to different matrices such as tomato, broccoli, carrot, grape and eggplant, observing that chlorogenic acid was detected in most of the samples at higher concentrations in relation to the other compounds. PMID:23790894

Alarcón-Flores, María Isabel; Romero-González, Roberto; Vidal, José Luis Martínez; Frenich, Antonia Garrido

2013-11-15

43

Oxidant-free dehydrogenative coupling reactions via hydrogen evolution.  

PubMed

Oxidant-free dehydrogenative coupling reactions: Recently, coupling reactions have followed a novel strategy for the construction of C==C, C==N, C==P, and S==S bonds by dehydrogenation without using any extra oxidant, via H2 evolution. These breakthroughs inspire a new direction in the construction of chemical bonds, towards more sustainable, highly atom-economical, and environmentally benign synthetic methods. PMID:25139249

He, Ke-Han; Li, Yang

2014-10-01

44

High ethylene to ethane processes for oxidative coupling  

DOEpatents

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.

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

1991-01-01

45

High ethylene to ethane processes for oxidative coupling  

DOEpatents

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.

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

1991-12-17

46

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...

47

Hydrogen Sulfide Oxidation is Coupled to Oxidative Phosphorylation in Mitochondria of Solemya reidi  

Microsoft Academic Search

Solemya reidi, a gutless clam found in sulfide-rich habitats, contains within its gills bacterial symbionts thought to oxidize sulfur compounds and provide a reduced carbon food source to the clam. However, the initial step or steps in sulfide oxidation occur in the animal tissue, and mitochondria isolated from both gill and symbiont-free foot tissue of the clam coupled the oxidation

Mark A. Powell; George N. Somero

1986-01-01

48

Hydrogen sulfide oxidation is coupled to oxidative phosphorylation in mitochondria of Solemya reidi  

Microsoft Academic Search

Solemya reidi, a gutless clam found in sulfide-rich habitats, contains within its gills bacterial symbionts thought to oxidize sulfur compounds and provide a reduced carbon food source to the clam. However, the initial step or steps in sulfide oxidation occur in the animal tissue, and mitochondria isolated from both gill and symbiont-free foot tissue of the clam coupled the oxidation

M. A. Powell; G. N. Somero

1986-01-01

49

Quantification of Neurotransmitters in Mouse Brain Tissue by Using Liquid Chromatography Coupled Electrospray Tandem Mass Spectrometry  

PubMed Central

A simple and rapid liquid chromatography tandem mass spectrometry method has been developed for the determination of BH4, DA, 5-HT, NE, EP, Glu, and GABA in mouse brain using epsilon-acetamidocaproic acid and isotopically labeled neurotransmitters as internal standards. Proteins in the samples were precipitated by adding acetonitrile, and then the supernatants were separated by a Sepax Polar-Imidazole (2.1?mm × 100?mm, i.d., 3??m) column by adding a mixture of 10?mM ammonium formate in acetonitrile/water (75?:?25, v/v, 300??l/min) for BH4 and DA. To assay 5-HT, NE, EP, Glu, and GABA; a Luna 3?? C18 (3.0?mm × 150?mm, i.d., 3??m) column was used by adding a mixture of 1% formic acid in acetonitrile/water (20?:?80, v/v, 350??l/min). The total chromatographic run time was 5.5?min. The method was validated for the analysis of samples. The calibration curve was linear between 10 and 2000?ng/g for BH4 (r2 = 0.995) , 10 and 5000?ng/g for DA (r2 = 0.997) , 20 and 10000?ng/g for 5-HT (r2 = 0.994) , NE (r2 = 0.993) , and EP (r2 = 0.993) , and 0.2 and 200??g/g for Glu (r2 = 0.996) and GABA (r2 = 0.999) in the mouse brain tissues. As stated above, LC-MS/MS results were obtained and established to be a useful tool for the quantitative analysis of BH4, DA, 5-HT, NE, EP, Glu, and GABA in the experimental rodent brain. PMID:25258696

Kim, Tae-Hyun; Choi, Juhee

2014-01-01

50

Tandem aldehyde–alkyne–amine coupling/cycloisomerization: A new synthesis of coumarins  

PubMed Central

Summary Cu-catalyzed A3 coupling of ethoxyacetylene, pyrrolidine and salicylaldehydes led to a concomitant cycloisomerization followed by hydrolysis of the resultant vinyl ether to afford coumarins in a cascade process. The reaction proceeded through exclusive 6-endo-dig cyclization and is compatible with halo and keto groups giving coumarins in good to moderate yields. PMID:23400373

Thirupathi, Nuligonda; Haribabu, Madala

2013-01-01

51

Sensitive determination of polychlorinated biphenyls in environmental water samples by headspace solid-phase microextraction with bamboo charcoal@iron oxide black fibers prior to gas chromatography with tandem mass spectrometry.  

PubMed

We have investigated the feasibility of bamboo charcoal@iron oxide black for the headspace solid-phase microextraction of polychlorinated biphenyls in environmental water samples. Bamboo charcoal@iron oxide black was prepared and used as a solid-phase microextraction coating material, and gas chromatography with tandem mass spectrometry was used for detection. Several important factors affecting the extraction efficiency were systematically investigated and optimized. Under the optimum conditions, the experimental data exhibited wide linear range over the range 0.2-1000 ng/L and low limits of detection in the range of 4.7-22.2 pg/L. The novel coating was successfully used for the enrichment and determination of polychlorinated biphenyls in real environmental water samples. All these results indicated that bamboo charcoal@iron oxide black-based headspace solid-phase microextraction coupled to gas chromatography with tandem mass spectrometry was an excellent alternative for the sensitive analysis of polychlorinated biphenyls at ultratrace levels in the environment. PMID:24723552

Liu, Yan-Long; Chen, Xiang-Feng; Wang, Xia; Zhou, Jia-Bin; Zhao, Ru-Song

2014-06-01

52

Quantification of endogenous brassinosteroids in sub-gram plant tissues by in-line matrix solid-phase dispersion-tandem solid phase extraction coupled with high performance liquid chromatography-tandem mass spectrometry.  

PubMed

A matrix solid-phase dispersion (MSPD)-tandem mixed mode anion exchange (MAX)-mixed mode cation exchange (MCX) solid phase extraction-high performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS) method was developed for quantification of six endogenous brassinosteroids (BRs) (24-epibrassinolide, 24-epicastasterone, 6-deoxo-24-epicastasterone, dolichosterone, teasterone and typhasterol) in rice plant tissues. Non-polar interferences were removed effectively by C8 dispersant used in MSPD, while the following tandem MAX-MCX process facilitated the elimination of polar and ionizable compounds. The weak reversed-phase retention feature of MAX-MCX leaded to good compatibility of the elution solvents in the in-line coupled MSPD-MAX-MCX system. This system was optimized for extraction and purification of BRs in plant samples. The effects of the type of solid phase, the elution solvent, the extraction temperature and the clean-up material were studied. Before HPLC separation, BRs purified were derivatized by m-aminophenylboronic acid to enhance the sensitivity of MS/MS to BRs. Compared with traditional liquid-liquid extraction and solid phase extraction (LLE-SPE), the proposed MSPD-MAX-MCX method showed higher extraction efficiency, lower matrix effect, and advantages of easy manipulation and time-saving. The in-line MSPD-MAX-MCX coupled with HPLC-MS/MS method provided a linear response over two orders of magnitude of BRs concentration with correlation coefficients above 0.9982, limits of detection between 0.008 and 0.04ngmL(-1), relative standard deviations (RSDs) below 29.4%, and recoveries above 77.8%. The proposed method has been successfully applied to analysis of endogenous BRs in rice plant at booting stage and maturity stage. PMID:25092597

Wang, Lu; Duan, Chunfeng; Wu, Dapeng; Guan, Yafeng

2014-09-12

53

Rapid isolation of new furostanol saponins from fenugreek seeds based on ultra-performance liquid chromatography coupled with a hybrid quadrupole time-of-flight tandem mass spectrometry.  

PubMed

An ultra-performance liquid chromatography coupled with a hybrid quadrupole time-of-flight tandem mass spectrometry method was established to rapidly identify and guide the isolation of target saponins from fenugreek seeds. Based on the online screening performance, totally forty-six furostanol saponins were detected and elucidated. Among them, twenty compounds were predicted to be new. To rapidly obtain new furostanol saponins from these seeds, a further phytochemical study was carried out under the guidance of the ultra-performance liquid chromatography coupled with a hybrid quadrupole time-of-flight tandem mass spectrometry. Finally, six new furostanol saponins, named as trigoneosides XIV (1), XV (2), XVI (3), XVIIa (4), XVIIb (5), and XIV (6), together with one known furostanol saponin, parvifloside (7), were rapidly obtained, and their definitive structures were determined by NMR and chemical evidence. PMID:22740265

Pang, Xu; Kang, Liping; Yu, Heshui; Zhao, Yang; Xiong, Chengqi; Zhang, Jie; Shan, Junjie; Ma, Baiping

2012-06-01

54

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

PubMed

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

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

2015-01-01

55

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

PubMed

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

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

2014-02-21

56

Simultaneous determination of five constituents in qinpijiegu capsule by high-performance liquid chromatography coupled with tandem mass spectrometry.  

PubMed

A rapid high-performance liquid chromatography coupled with tandem mass spectrometry method was developed for the simultaneous determination of five constituents in Qinpijiegu capsule (QJC), a classical Tibetan prescription. The separation of five compounds such as aesculin, aesculetin, fraxin, peimine and peiminine was performed on a Purospher STAR LP RP-C18 (250 × 4.6 mm, 5 ?m) column with linear gradient elution of acetonitrile-0.3‰ formic acid water in 13 min. Detection was carried out by multiple reaction monitoring mode using electrospray ionization in the positive and negative ion switching mode. The sample was prepared with ultrasound extraction with methanol, which could obtain higher extraction efficiency and shorter extraction time comparing to reflux extraction with alkalized chloroform-methanol. The proposed method was applied to analyze three batches of samples with acceptable linearity (r(2) > 0.9977), precision [relative standard deviation (RSD) < 7.40%], repeatability (RSD < 2.49%), stability [relative error (RE) < 9.15%] and recovery (RSD < 10.76%). This is the first development of a multicomponent quantitation method for the quality control of QJC. Furthermore, the new established method was proven to be highly sensitive and effective in evaluating the quality of QJC. PMID:24920654

Zhao, Minmin; Ding, Weijing; Wang, Shuang; Gao, Meng; Fu, Shan; Zhang, Juan; Li, Tao; Wu, Yin; Wang, Qiao

2015-02-01

57

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

PubMed

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

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

2014-11-01

58

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

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

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

2008-01-01

59

Evaluation of Multidimensional Chromatography Coupled with Tandem Mass Spectrometry (LC\\/LC?MS\\/MS) for Large-Scale Protein Analysis:  The Yeast Proteome  

Microsoft Academic Search

Highly complex protein mixtures can be directly analyzed after proteolysis by liquid chromatography coupled with tandem mass spectrometry (LC-MS\\/MS). In this paper, we have utilized the combination of strong cation exchange (SCX) and reversed-phase (RP) chromatography to achieve two-dimensional separation prior to MS\\/MS. One milligram of whole yeast protein was proteolyzed and separated by SCX chromatography (2.1 mm i.d.) with

Junmin Peng; Joshua E. Elias; Carson C. Thoreen; Larry J. Licklider; Steven P. Gygi

2003-01-01

60

Determination of Niacin and Its Metabolites Using Supercritical Fluid Chromatography Coupled to Tandem Mass Spectrometry  

PubMed Central

Niacin, a water-soluble vitamin belonging to the vitamin B group, has been known to cause various problems in the human body when deficient. The vitamin is derived from the diet and afterwards, niacin and its metabolites are secreted in blood or urine. It can be analyzed using liquid chromatography (LC) coupled to mass spectrometry, but niacin and its metabolites are very polar compounds. Recently, supercritical fluid chromatography (SFC) is gaining attention for polar compound analysis. To our best knowledge, the report on the analysis of endogenous-very hydrophilic metabolites in biofluids by SFC has not been found. In this study, we investigated whether the separation of hydrophilic metabolites in biofluids is achievable by SFC. In addition, we also examined the applicability of SFC coupled to MS in extrapolating unknown metabolites by means of spectra information. As a result, an analysis method to quantify the target compounds using SFC/MS/MS was constructed for niacin and its metabolites. Additional putative metabolites from niacin were also identified using the MS fragmentation spectra in plasma and urine. Consequently, the method using SFC/MS/MS allowed for the analysis of polar compounds with low log?P ranging from ?3.7 to 0.29. This study is the first report of the separation of niacin and its seven metabolites in human urine and these results showed that SFC-MS/MS can be an alternative technique for hydrophilic metabolite analysis. PMID:25386386

Taguchi, Kaori; Fukusaki, Eiichiro; Bamba, Takeshi

2014-01-01

61

COUPLING OF BIOTIC AND ABIOTIC ARSENITE OXIDATION IN SOIL  

E-print Network

: __________________________________________________________ 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

Sparks, Donald L.

62

Tear proteomic analysis of Sjögren syndrome patients with dry eye syndrome by two-dimensional-nano-liquid chromatography coupled with tandem mass spectrometry  

PubMed Central

We examined the tear film proteome of patients with Sjögren's syndrome (SS) and dry eye syndrome (group A), patients with dry eye symptoms (group B) and normal volunteers (group C). Tear samples were pooled from 8 subjects from each group and were subjected to two-dimensional-nano-liquid chromatography coupled with tandem mass spectrometry (2D-nano-LC-MS/MS). The tear breakup time for group A was significantly reduced compared with group B and C (P < 0.001). Group A (Schirmer I test, 2.13 ± 2.38?mm/5?min) had markedly lower tear volume than group B (5.94 ± 4.75?mm/5?min) and C (14.44 ± 6.57?mm/5?min) (P < 0.001). Group A had significantly higher normalized tear protein content (1.8291 ± 0.2241??g/mm) than group B (1.0839 ± 0.1120??g/mm) (P = 0.001) and C (0.2028 ± 0.0177??g/mm) (P = 0.001). The 2D-nano-LC-MS/MS analysis identified a total of 435 proteins, including 182 (54.8%), 247 (74.4%) and 278 (83.7%) in group A, B, and C, respectively, with 56 (16.7%) proteins including defensin ?1, clusterin and lactotransferrin unique to group A. In conclusion, dry eye syndrome in SS patients is associated with an altered proteomic profile with dysregulated expression of proteins involved in a variety of important cellular process including inflammation, immunity, and oxidative stress. PMID:25159733

Li, Bing; Sheng, Minjie; Li, Jianhua; Yan, Guoquan; Lin, Anjuan; Li, Min; Wang, Weifang; Chen, Yihui

2014-01-01

63

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

PubMed Central

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

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

2012-01-01

64

General approach on chemistry and stress coupling effects during oxidation  

NASA Astrophysics Data System (ADS)

In this paper, the mechanism of growth strain is discussed based on the irreversible evolving equations by considering the coupling effects of stress and chemical reaction during isothermal oxidation, and a simple model relating the growth strain and the oxide thickness is developed. If the effect of the stress on the chemical reaction is not taken into account, the model reduces to the Clarke assumption. The expression of Dox is exhibited, and its value can be determined by experiments. The stress evolving equations are derived, where the viscoplastic strain of the oxide and metal and the growth strain of the oxide are considered. Numerical results are given and compared with results from experiments and the existing model. There is good agreement between the proposed model and the experimental data.

Suo, Yaohong; Shen, Shengping

2013-10-01

65

Hydrogen sulfide oxidation is coupled to oxidative phosphorylation in mitochondria of Solemya reidi  

SciTech Connect

Solemya reidi, a gutless clam found in sulfide-rich habitats, contains within its gills bacterial symbionts thought to oxidize sulfur compounds and provide a reduced carbon food source to the clam. However, the initial step or steps in sulfide oxidation occur in the animal tissue, and mitochondria isolated from both gill and symbiont-free foot tissue of the clam coupled the oxidation of sulfide to oxidative phosphorylation (adenosine triphosphate (ATP) synthesis). The ability of Solemya reidi to exploit directly the energy in sulfide for ATP synthesis is unprecedented, and suggests that sulfide-habitat animals that lack bacterial symbionts may also use sulfide as an inorganic energy source.

Powell, M.A.; Somero, G.N.

1986-08-01

66

Enantiomeric analysis of drugs of abuse in wastewater by chiral liquid chromatography coupled with tandem mass spectrometry.  

PubMed

The manuscript concerns the development and validation of a method for enantiomeric analysis of structurally related amphetamines (amphetamine, methamphetamine, 4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyamphetamine (MDA) and 3,4-methylenedioxy-N-ethylamphetamine (MDEA)), ephedrines (ephedrine, pseudoephedrine and norephedrine) and venlafaxine in wastewater by means of chiral chromatography coupled with tandem mass spectrometry. Solid-phase extraction on Oasis HLB sorbent used for sample clean-up and concentration of analytes resulted in very good recoveries accounting for >70%. Signal suppression during MS analysis was negligible for most studied analytes. Resolution of enantiomers of chiral drugs was found to be higher than 1. Preliminary assay validation was undertaken. The mean correlation coefficients of the calibration curves, which were on average higher than 0.997 for all studied analytes, showed good linearity of the method in the studied range. Intra- and inter-day repeatabilities were on average less than 5%. The method quantification limits in wastewater were at low ppt levels and varied from 2.25 to 11.75ng/L. The method was successfully applied for the analysis of raw and treated wastewater samples collected from four wastewater treatment plants. A common occurrence of 1R,2S (-)-ephedrine, 1S,2S (+)-pseudoephedrine and venlafaxine in both raw and treated wastewater samples was observed. Amphetamine, methamphetamine, MDMA and MDEA were also detected in several wastewater samples. The study of enantiomeric fractions of these chiral drugs proved their variable non-racemic composition. The influence of wastewater treatment processes on the enantiomeric composition of chiral drugs was also noted and might indicate enantioselective processes occurring during treatment, although more comprehensive research has to be undertaken to support this hypothesis. PMID:20537654

Kasprzyk-Hordern, Barbara; Kondakal, Vishnu V R; Baker, David R

2010-07-01

67

OXIDATIVE COUPLING OF METHANE USING INORGANIC MEMBRANE REACTORS  

SciTech Connect

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.

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

1998-04-01

68

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

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

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

2015-01-22

69

Atomistic calculation of the thickness and temperature dependence of exchange coupling through a dilute magnetic oxide  

NASA Astrophysics Data System (ADS)

The exchange coupling of two magnetic layers via a diffuse oxide interlayer is studied with an atomistic spin model. We investigate the effect of magnetic concentration and oxide layer thickness on the effective exchange coupling strength and find an exponential dependence of the coupling strength on the oxide thickness without the need for magnetic pinholes. Furthermore we show that exchange coupling has a strong temperature dependence which is significant for the reversal dynamics during heat assisted magnetic recording.

Evans, R. F. L.; Coopman, Q.; Devos, S.; Fan, W. J.; Hovorka, O.; Chantrell, R. W.

2014-12-01

70

Noncollinear coupling of iron layers through native iron oxide spacers  

SciTech Connect

We have found a magnetic superstructure in multilayers that consist of iron and its native oxide. Employing nuclear resonant scattering of synchrotron radiation from {sup 57}Fe probe layers, this manifests as 1/2-order Bragg peaks in the reflectivity curve. From the field dependence of their intensity, we deduce the existence of two magnetic sublattices that are canted by an angle of almost 90 deg. and rotate as one unit in low fields. For higher fields, the two sets of moments gradually align collinear to the external field. This behavior can be explained by a coupling of two adjacent Fe layers that is mediated by an antiferromagnetic order in the oxide spacer between them.

Diederich, Thomas; Couet, Sebastien; Roehlsberger, Ralf [Hamburger Synchrotronstrahlungslabor (HASYLAB), Deutsches Elektronen-Synchrotron (DESY), Notkestrasse 85, 22603 Hamburg (Germany)

2007-08-01

71

Noxa couples lysosomal membrane permeabilization and apoptosis during oxidative stress.  

PubMed

The exact roles of lysosomal membrane permeabilization (LMP) in oxidative stress-triggered apoptosis are not completely understood. Here, we first studied the temporal relation between LMP and mitochondrial outer membrane permeabilization (MOMP) during the initial stage of apoptosis caused by the oxidative stress inducer H2O2. Despite its essential role in mediating apoptosis, the expression of the BH3-only Bcl-2 protein Noxa was dispensable for LMP. In contrast, MOMP was dependent on Noxa expression and occurred downstream of LMP. When lysosomal membranes were stabilized by the iron-chelating agent desferrioxamine, H2O2-induced increase in DNA damage, Noxa expression, and subsequent apoptosis were abolished by the inhibition of LMP. Importantly, LMP-induced Noxa expression increase was mediated by p53 and seems to be a unique feature of apoptosis caused by oxidative stress. Finally, exogenous iron loading recapitulated the effects of H2O2 on the expression of BH3-only Bcl-2 proteins. Overall, these data reveal a Noxa-mediated signaling pathway that couples LMP with MOMP and ultimate apoptosis during oxidative stress. PMID:23770082

Eno, Colins O; Zhao, Guoping; Venkatanarayan, Avinashnarayan; Wang, Bing; Flores, Elsa R; Li, Chi

2013-12-01

72

Coupling of nitrous oxide and methane by global atmospheric chemistry.  

PubMed

Nitrous oxide (N(2)O) and methane (CH(4)) are chemically reactive greenhouse gases with well-documented atmospheric concentration increases that are attributable to anthropogenic activities. We quantified the link between N(2)O and CH(4) emissions through the coupled chemistries of the stratosphere and troposphere. Specifically, we simulated the coupled perturbations of increased N(2)O abundance, leading to stratospheric ozone (O(3)) depletion, altered solar ultraviolet radiation, altered stratosphere-to-troposphere O(3) flux, increased tropospheric hydroxyl radical concentration, and finally lower concentrations of CH(4). The ratio of CH(4) per N(2)O change, -36% by mole fraction, offsets a fraction of the greenhouse effect attributable to N(2)O emissions. These CH(4) decreases are tied to the 108-year chemical mode of N(2)O, which is nine times longer than the residence time of direct CH(4) emissions. PMID:21071666

Prather, Michael J; Hsu, Juno

2010-11-12

73

Liquid chromatography coupled to tandem mass spectrometry for the residue determination of ethylenethiourea (ETU) and propylenethiourea (PTU) in water.  

PubMed

Ethylenethiourea (ETU) and propylenethiourea (PTU) are the main degradation products of dithiocarbamates fungicides, which are widely used in agriculture from several years ago. Their determination in water at low concentrations (e.g. sub-ppb levels) is highly problematic due to their polar character and low molecular size. In the present study, two analytical methodologies have been developed and compared for the selective and sensitive determination of ETU and PTU in various types of waters. Both approaches are based on liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) with electrospray ionization, using triple quadrupole analyzer. Whereas the first methodology used an on-line solid-phase extraction (SPE) step in order to reach the adequate sensitivity, the second one avoided sample treatment and was based on direct injection into an ultra high performance liquid chromatography (UHPLC-MS/MS) system, making use of a new-generation instrument in order to reach sub-ppb analyte levels in water. Strong matrix effects (typically leading to signal enhancement) were observed for most of the evaluated waters, especially when applying the on-line SPE method, surely due to the higher amount of sample injected into the system. The use of the own analyte (ETU-d?)) as isotope-labelled internal standard (ILIS) allowed to compensate these effects and to achieve an accurate ETU quantification at low concentrations. Moreover, three simultaneous transitions, operating in selected reaction monitoring mode, were acquired for both ETU and ETU-d?. This fact together with the evaluation of their relative intensity ratios assured the reliable identification of the analyte in the water samples. The two optimized methodologies were validated by analysis of six different samples (two drinking water, two groundwater and two surface water), spiked at two levels (0.1 and 1.0 ?g/L), and analyzed each in quintuplicate. Satisfactory accuracy and precision, with recoveries ranging from 73 to 104% and RSDs lower than 20%, were obtained for ETU. Limits of detection for ETU were found to be 0.058 ?g/L and 0.027 ?g/L with direct injection and with the on-line methodology, respectively. No satisfactory recoveries were obtained, in general, for PTU despite using its own deuterium-labelled molecule for matrix effects correction. Notable differences in the chemical behaviour between PTU and PTU-d? were observed, which lead to significant variation in their chromatographic retention time and ionization efficiency. Thus, no satisfactory correction of matrix effects could be reached illustrating that the use of deuterated ILIS can be problematic in some particular cases. Despite the poor correction, a semi-quantitative analysis would be feasible for PTU at sub-ppb levels in water. To the best of our knowledge, this is the first article reporting the use of LC-MS/MS for the trace level determination of these problematic analytes in water. PMID:22578799

Ripollés, Cristina; Sancho, Juan V; López, Francisco J; Hernández, Félix

2012-06-22

74

Structural elucidation of N-oxidized clemastine metabolites by liquid chromatography/tandem mass spectrometry and the use of Cunninghamella elegans to facilitate drug metabolite identification.  

PubMed

Cunninghamella elegans is a filamentous fungus that has been shown to biotransform drugs into the same metabolites as mammals. In this paper we describe the use of C. elegans to aid the identification of clemastine metabolites since high concentrations of the metabolites were produced and MS(n) experiments were facilitated. The combination of liquid chromatography and tandem mass spectrometry with two different ionization techniques and hydrogen/deuterium exchange were used for structural elucidation of the clemastine metabolites. Norclemastine, four isomers of hydroxylated clemastine, and two N-oxide metabolites were described for the first time in C. elegans incubations. The N-oxidations were confirmed by hydrogen/deuterium exchange and deoxygenation (-16 Da) upon atmospheric pressure chemical ionization mass spectrometry. By MS(n) fragmentation it was concluded that two of the hydroxylated metabolites were oxidized on the methylpyrridyl moiety, one on the aromatic ring with the chloro substituent, and one on the aromatic ring without the chlorine. PMID:20411584

Tevell Aberg, Annica; Löfgren, Helena; Bondesson, Ulf; Hedeland, Mikael

2010-05-30

75

Construction of N-containing heterocycles via oxidative intramolecular N-H/X-H coupling.  

PubMed

The preparation of N-containing heterocycles is always the core of synthetic chemistry. Recently, oxidative coupling between two R-H nucleophiles is gaining more attention due to its atom-economy and step-economy, thus there are numerous reports focusing on the N-heterocycle construction via oxidative coupling. This feature article is going to cover the methodology related to the construction of N-heterocycles through oxidative intramolecular N-H/X-H coupling. PMID:25373487

Yuan, Jiwen; Liu, Chao; Lei, Aiwen

2014-11-01

76

Determination of tetracycline antibiotics in fatty food samples by selective pressurized liquid extraction coupled with high-performance liquid chromatography and tandem mass spectrometry.  

PubMed

For the determination of trace residues of tetracycline antibiotics in fatty food samples, selective pressurized liquid extraction coupled with high-performance liquid chromatography and tandem mass spectrometry was applied in this study. Copper(II) isonicotinate was first used as online cleanup adsorbent in the selective pressurized liquid extraction process. The adsorbent to sample ratio, extraction temperature, extraction time, and recycle times, etc. were optimized. The tetracyclines in food samples of pork, chicken meat, and clam meat were detected by liquid chromatography with tandem mass spectrometry. Tetracycline was found at levels of 0.32 and 0.53 ?g/g and oxytetracycline was found at 0.14 and 0.21 ?g/g in chicken meat and clam meat, respectively, while chlorotetracycline and deoxytetracycline were below the detection limit. The detection limit (S/N = 3) for these four tetracyclines were from 0.2 to 3.3 ng/g, the recoveries were from 75.8 to 110.5%, and relative standard deviations were from 5.5 to 13.6%. Copper(II) isonicotinate showed a higher purification capacity than other cleanup adsorbents for extraction of antibiotics in fatty food and the recovery showed predominance compared with a pressurized liquid extraction method without adsorbent. The study demonstrated that copper(II) isonicotinate would be a promising cleanup adsorbent in pressurized liquid extraction for the analysis of trace organic pollutants in complicated samples. PMID:25394992

Jiao, Zhe; Zhang, Suling; Chen, Hongwei

2015-01-01

77

Determination of parabens in urine samples by microextraction using packed sorbent and ultra-performance liquid chromatography coupled to tandem mass spectrometry.  

PubMed

A simple, sensitive, and selective method using ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS) was developed and validated for simultaneous determination of parabens [methyl paraben (MeP), ethyl paraben (EtP), propyl paraben (PrP), butyl paraben (BuP), and benzyl paraben (BzP)] in human urine samples. After microextraction by packed sorbent (MEPS) using a C18 phase, the parabens were separated on a Kinetex C18 column (100mm×2.1mm×1.7?m) within 4.6min using isocratic elution. These compounds were detected on a triple quadrupole tandem mass spectrometer using the multiple reactions monitoring (MRM) mode via an electrospray ionization source operating in the negative ionization mode. Important factors that influence MEPS performance were evaluated, such as the sample pH, draw-eject sample volume, clean-up step, and desorption conditions. The proposed MEPS/UPLC-MS/MS method presented a linear range from 0.5ngmL(-1) (limit of quantification - LOQ) to 50ngmL(-1), and interassay precision with coefficients of variation lower than 15%, and relative standard error values of the accuracy ranged from -8.8% to 15%. The MEPS/UPLC-MS/MS method was applied successfully to determine parabens in urine samples from 30 postpartum volunteers, enabling assessment of human exposure to these compounds. PMID:25463195

Cristina Jardim, Valeria; de Paula Melo, Lidervan; Soares Domingues, Diego; Costa Queiroz, Maria Eugênia

2015-01-01

78

Analysis of sphingomyelin in meat based on hydrophilic interaction liquid chromatography coupled to electrospray ionization-tandem mass spectrometry (HILIC-HPLC-ESI-MS/MS).  

PubMed

The amount of sphingomyelin in different kinds of meat was analyzed by hydrophilic interaction liquid chromatography (HILIC-HPLC) coupled with electrospray ionization-tandem mass spectrometry (ESI-MS/MS). Analysis comprised sphingomyelin species with the five different sphingoid bases dihydrosphingosine (d18:0), sphingosine (d18:1(Delta4)), 4,8-sphingadienine (d18:2(Delta4,8)), 4-hydroxysphinganine (phytosphingosine (t18:0)), and 4-hydroxy-8-sphingenine (t18:1), and fatty acids with 12-26 carbon atoms as well as their (poly)unsaturated (up to four double bonds) and monohydroxylated analogues. Most sphingolipids contained sphingosine (d18:1) as the predominant sphingoid base, while stearic acid and palmitic acid were found as prevalent fatty acids. Total amounts vary from 361-471 mg/kg, whereas the meat of the wild animals showed considerably lower amounts. PMID:20175585

Fischbeck, Anne; Krüger, Melanie; Blaas, Nina; Humpf, Hans-Ulrich

2009-10-28

79

Analysis of chloramphenicol residues in the macroalgae Ulva lactuca through ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS).  

PubMed

Antibiotic use is a well-described practice to promote animal health whether for prevention or treatment. Nonetheless, it can also cause a number of potentially harmful effects that dictate the need to implement regulation to assure a reduction of hazards to the consumers and the environment. Chloramphenicol (CAP) is a broad-spectrum antibacterial excluded from use in animal food production but despite this, reports of illegal use still persist. More recently, awareness has risen that the surrounding natural ecosystems can potentially be contaminated by pharmaceuticals and the extent of their effects in non-target organisms is already under the scope of researchers. To face the demanding new challenges a methodology for the determination of CAP in the green macroalgae Ulva lactuca by ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) was developed, optimized and fully validated following the guidelines of the EC Decision 2002/657. PMID:25579630

Leston, Sara; Freitas, Andreia; Nunes, Margarida; Barbosa, Jorge; Pardal, Miguel Ângelo; Ramos, Fernando

2015-02-15

80

Quantification of apolipoprotein A-I mimetic peptide D-4F in rabbit plasma by high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry.  

PubMed

The apolipoprotein A-I mimetic peptide D-4F is a potential therapeutical agent effective in maintaining cardiovascular health. A bioanalytical assay based on high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (LC/MS/MS) to quantitate the D-4F amount in rabbit plasma was developed and validated. A compound with a close structure similarity to the D-4F (only one amino acid A-V altered) was used as an internal standard. Both D-4F and the internal standard were extracted by protein precipitation using acetonitrile/0.2% Triton XL 80N. The correlation coefficient of the calibration curve was 0.9991 in the range 20-40,000 ng/mL. This assay can be used for pharmacokinetic studies of the drug. Also, it may be adjusted for the quantification of other members of apolipoprotein A-I mimetic peptide family. PMID:19481508

Hu, Xiaoyi; Kamberi, Marika

2009-07-01

81

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

PubMed

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

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

2014-10-01

82

Stability of the proteasome inhibitor bortezomib in cell based assays determined by ultra-high performance liquid chromatography coupled to tandem mass spectrometry.  

PubMed

Bortezomib represents the first clinically approved proteasome inhibitor for multiple myeloma. Research conducted on its intracellular kinetics in target cells and on possibly related mechanisms of resistance is sparse so far. We therefore developed and validated a highly sensitive ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC/MS/MS) method for bortezomib quantification within cultured myeloma cells and media. Fast gradient UPLC based on a BEH C18 column (1.7 ?m particle size) with aqueous formic acid and acetonitrile as mobile phase. Selective extraction procedures using protein precipitation extraction (PPE) and liquid-liquid extraction (LLE) were established and compared. Extracted bortezomib was quantified by positive electrospray tandem mass spectrometry using deuterated D8-bortezomib as internal standard. The calibrated ranges were 0.5-2500 pg per sample. For LLE, overall accuracies varied between 99.2% and 112% (medium) and 89.9% and 111% (cells), while overall precision ranged from 1.13% to 13.0% (medium) and 2.80% to 12.7% (cells), respectively. Recovery rates (cells/medium) were >77%/>65% for LLE and >89%/63% for PPE. Matrix effects were generally lower for LLE compared to PPE. Regardless of the extraction method, retrievable amounts of bortezomib were considerably reduced after 24h of incubation (0.2, 1, 5, and 25 nM). Revealing greater dependence on the extent of acidification, retrieval of bortezomib can be increased distinctly in acidified solution or acidified culture medium. Thus, particular attention needs to be paid to the occurring bortezomib degradation in neutral culture medium since correct quantification of intracellular bortezomib can only be achieved in relation to the corresponding extracellular concentration. PMID:24780258

Clemens, Jannick; Longo, Magdalena; Seckinger, Anja; Hose, Dirk; Haefeli, Walter Emil; Weiss, Johanna; Burhenne, Jürgen

2014-06-01

83

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

PubMed

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

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

2007-01-30

84

Analysis of organochlorine pesticides in wine by solvent bar microextraction coupled with gas chromatography with tandem mass spectrometry detection.  

PubMed

A solvent bar microextraction (SBME) technique combined with gas chromatography/tandem mass spectrometry (GC/MS/MS), for the determination of selected organochlorine pesticides (OCPs) in wine samples, is described. In this work the OCPs were extracted and dissolved in a 2-microL aliquot of organic extraction solvent (n-tetradecane) confined within a 1.7-cm length of hollow fiber. Both ends of the hollow fiber (solvent bar) were sealed, and it was placed in an aqueous sample solution for extraction. The effects of solvent selection, sample agitation, extraction time, extraction temperature, and salt concentration on the SBME performance were optimized. The influence of aqueous sample/organic solvent phase ratio was further investigated in detail. High enrichments (1900-7100-fold) could be obtained at an aqueous sample/organic solvent volume ratio of 20 mL/2 microL in this study. Good extraction reproducibility was obtained with relative standard deviation (RSD) values below 12.6%. Comparisons of sensitivity and precision between SBME and dynamic hollow-fiber liquid-phase microextraction were also investigated. PMID:16331743

Chia, Kan-Jung; Huang, Shang-Da

2006-01-01

85

Determination of norcantharidin in mouse tissues by liquid chromatography coupled to tandem mass spectrometry and its tissue distribution study.  

PubMed

The purpose of this study is to determine the concentrations of norcantharidin (CAS NO: 5442-12-6) in mouse tissues and investigate its tissue distribution after intragastric administration of disodium norcantharidate solution. A highly sensitive and specific liquid chromatography-tandem mass spectrometric (LC-MS/MS) method was developed and validated, using ribavirin (CAS NO: 36791-04-5) as the internal standard (IS). Norcantharidin and IS were extracted from 0.3 mL tissue homogenates using protein precipitation with acetone under acid condition. The analyte was separated on a C18 reverse phase column and analyzed by MS/MS in the multiple reaction monitoring (MRM) mode using ESI with positive ionization, m/z 169?123 for norcantharidin and m/z 267?135 for IS. The developed method was validated over a linear range of concentrations 0.01~5 ?g·mL - 1 in liver, lung, kidney, stomach, small intestine, uterus and testis, 0.005~0.5 ?g·mL - 1 in heart, spleen and brain, the correlation coefficients (r2) were between 0.9918 and 0.9976. The tissue distribution study result was as follows: The AUC0-t of norcantharidin in tissues was in the order as follows: small intestine, stomach, uterus, kidney, testis, liver, lung, spleen, heart, brain. PMID:22473525

Zhang, R; Wang, J; Yuan, G; Wei, C; Liu, X; Wang, B; Gao, H; Guo, R

2012-06-01

86

Polyamines in biological samples: Rapid and robust quantification by solid-phase extraction online-coupled to liquid chromatography–tandem mass spectrometry  

PubMed Central

Polyamines are ubiquitous active biogenic amines which contribute to basic cellular functions. Hence, their quantification in samples of diverse biological origins is essential for understanding how they function, especially in disease-relevant conditions. We present here a robust, high-throughput solid-phase extraction online coupled to a liquid chromatography–tandem mass spectrometry (SPE–LC/MS/MS) approach for the simultaneous quantification of eight polyamines in various biological samples. The polyamines include 1,3-diaminopropane, putrescine, cadaverin, N-acetyl-putrescine, spermidine, spermine, N1-acetyl-spermine, and l-ornithine. The novelty of the work is the use of two SPE columns online coupled to LC/MS/MS, which minimizes the sample pretreatment to a single derivatization step. The analysis is complete within 4 min, making the method highly suitable for routine clinical analysis and high throughput screenings. The method was fully validated with serum samples. Dynamic ranges were 0.03 to 15 ?g/ml for ornithine and 1 to 500 ng/ml for other polyamines, which cover physiological concentrations in serum samples. Lower limits of quantification (LLoQ) were found to be between 0.1 and 5 ng/ml. As a proof of concept, we investigated gender differences in polyamine levels by analyzing the serum levels of 102 subjects. PMID:24485539

Magnes, Christoph; Fauland, Alexander; Gander, Edgar; Narath, Sophie; Ratzer, Maria; Eisenberg, Tobias; Madeo, Frank; Pieber, Thomas; Sinner, Frank

2014-01-01

87

Identification of 20(S)-protopanaxatriol metabolites in rats by ultra-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry and nuclear magnetic resonance spectroscopy.  

PubMed

20(S)-Protopanaxatriol (PPT), one of the aglycones of ginsenosides, has been shown to exert cardioprotective effects against myocardial ischemic injury. However, studies on PPT metabolism have rarely been reported. This study is the first to investigate the in vivo metabolism of PPT following oral administration by ultra-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (UPLC-Q/TOF-MS) and nuclear magnetic resonance (NMR) spectroscopy. The structures of the metabolites were identified based on the characteristics of their MS data, MS(2) data, and chromatographic retention times. A total of 22 metabolites, including 17 phase I and 5 phase II metabolites, were found and tentatively identified by comparing their mass spectrometry profiles with those of PPT. Two new monooxygenation metabolites, (20S,24S)-epoxy-dammarane-3,6,12,25-tetraol and (20S,24R)-epoxy-dammarane-3,6,12,25-tetraol, were chemicallly synthesized and unambiguously characterized according to the NMR spectroscopic data. The metabolic pathways of PPT were proposed accordingly for the first time. Results revealed that oxidation of (1) double bonds at ?((24,25)) to form 24,25-epoxides, followed by rearrangement to yield 20,24-oxide forms; and (2) vinyl-methyl at C-26/27 to form corresponding carboxylic acid were the predominant metabolic pathways. Phase II metabolic pathways were proven for the first time to consist of glucuronidation and cysteine conjugation. This study provides valuable and new information on the metabolism of PPT, which is indispensable for understanding the safety and efficacy of PPT, as well as its corresponding ginsenosides. PMID:24184656

He, Chunyong; Zhou, Dandan; Li, Jia; Han, Han; Ji, Guang; Yang, Li; Wang, Zhengtao

2014-01-01

88

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

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

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

2015-01-20

89

Quantitative trace analysis of eight chloramphenicol isomers in urine by chiral liquid chromatography coupled to tandem mass spectrometry.  

PubMed

Chloramphenicol is a broad-spectrum antibiotic with, apart from its human medicinal use, veterinary abuse in all major food-producing animals. Chloramphenicol occurs in four stereoisomers (all para-nitro substituted) and furthermore four meta-nitro analogs of chloramphenicol exist. In this paper these are referred to as eight chloramphenicol isomers. According to EU regulations an analytical method should be able to discriminate the analyte from interfering substances that might be present in the sample, including isomers. For the first time a quantitative method for the analysis of trace levels of eight chloramphenicol isomers in urine by chiral liquid chromatography in combination with tandem mass spectrometric detection is reported. The separation of the isomers on the analytical column, the clean-up of urine and the selectivity of the monitored product ions turned out to be critical parameters. To obtain reproducible retention isocratic elution on a chiral AGP column was applied. For urine samples matrix compounds present in the final extract caused decreased retention of the isomers on the chiral stationary phase and a lack of chromatographic resolution. Therefore an extended clean-up procedure that combines solid phase extraction and liquid-liquid extraction had to be developed. The final method was fully validated and showed satisfactory performance for all isomers with decision limits (CC?) ranging from 0.005 to 0.03 ?g L(-1) and within-laboratory reproducibility of all isomers below 20% at the minimum required performance limit level of 0.3 ?g L(-1). PMID:21893319

Berendsen, Bjorn J A; Essers, Martien L; Stolker, Linda A A M; Nielen, Michel W F

2011-10-14

90

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

PubMed Central

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

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

2013-01-01

91

Development of Analytical Methods Coupled to Microdialysis Sampling for Studying Biomarkers of Oxidative Stress  

E-print Network

This research describes the development of analytical methods based upon separation techniques coupled to microdialysis sampling for the detection of potential biomarkers of oxidative stress. The research focused on two ...

Hoque, Md Ehsanul

2007-12-18

92

[Determination of N-carbamyl-L-glutamic acid in feedstuff by high performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry].  

PubMed

A method was developed for the determination of N-carbamyl-L-glutamic acid (NCG) in feedstuff by high performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). The feedstuff samples were extracted with methanol, cleaned-up by a ProElut mixed-mode of strong anion exchange inverse column (PXA). Then the samples were separated with HPLC and detected with MS/MS in multiple reaction monitoring (MRM) mode via positive electrospray ionization (ESI+). The fragment ions of m/z 148.0 and m/z 84.0 were used for qualitative analysis, and m/z 130.0 was selected for quantitative analysis. The limit of detection for NCG was 24 microg/kg (S/N > 3), and the limit of quantification was 80 microg/kg (S/N > 10). The standard calibration curve was linear over the range of 20-1,000 microg/L, and the correlation coefficient was 0. 999 9. The recoveries of NCG in feedstuff were 104.0%, 103.5%, 95.3%, at the three spiked levels of 80, 200, 500 mg/kg with the relative standard deviations (RSDs) of 7.5%, 6.3% and 5.8%. The results showed that the method is simple, fast, highly sensitive, specific and with good purification effect. It can be applied to the analysis and determination of NCG in feedstuff. PMID:24822455

Tang, Shengyun; Wang, Yuanxing; Wen, Pingwei; Xin, Zhen

2014-02-01

93

Characterization of eight terpenoids from tissue cultures of the Chinese herbal plant, Tripterygium wilfordii, by high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry.  

PubMed

In this study, a reliable method for analysis and identification of eight terpenoids in tissue cultures of Tripterygium wilfordii has been established using high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (HPLC-ESI-MS). Our study indicated that sterile seedlings, callus cultures and cell-suspension cultures can rapidly increase the amount of biological materials. HPLC-ESI-MS was used to identify terpenoids from the extracts of these tissue cultures. Triptolide, triptophenolide, celastrol and wilforlide A were unambiguously determined by comparing the retention times, UV spectral data, and mass fragmentation behaviors with those of the reference compounds. Another four compounds were tentatively identified as triptonoterpenol, triptonoterpene, 22?-hydroxy-3-oxoolean-12-en-29-oic acid and wilforlide B, based on their UV and mass spectrometry spectra. The quantitative analysis showed that all three materials contain triptolide, triptophenolide, celastrol, wilforlide A, and the contents of the four compounds in the cell-suspension cultures were 53.1, 240, 129 and 964?µg/g, respectively, which were at least 2.0-fold higher than these in the sterile seedlings and callus cultures. Considering the known pharmacological activity of triptolide and celastrol, we recommend the cell-suspension cultures as biological materials for future studies, such as clinical and toxicological studies. The developed method was validated by the evaluation of its precision, linearity, detection limits and recovery, and it was successfully used to identify and quantify the terpenoids in the tissue cultures. PMID:25237706

Su, Ping; Cheng, Qiqing; Wang, Xiujuan; Cheng, Xiaoqing; Zhang, Meng; Tong, Yuru; Li, Fei; Gao, Wei; Huang, Luqi

2014-09-01

94

[Fingerprint analysis of Fritillaria thunbergii using rapid resolution liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry].  

PubMed

A fingerprint method for quality assessment of Fritillaria thunbergii was developed by rapid resolution liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (RRLC-Q-TOF-MS). The separation was performed using Agilent Eclipse Plus C18 column (2.1 mm x 100 mm, 1.8 microm) by gradient elution with acetonitrile and 0.1% formic acid aqueous solution (containing 10 mmol x L(-1) ammonium formate) as the mobile phase. Q-TOF-MS was used to obtain the accurate mass for precursor and product ions. Under this chromatographic and MS condition, 12 batches of F. thunbergii and its adulterants (F. hupehensis and F. pallidiflora) were analyzed by RRLC-Q-TOF-MS. Fifteen steroidal alkaloids were identified from F. thunbergii, F. hupehensis and F. pallidiflora and nine were assigned as the common characteristic peaks for F. thunbergii. The RRLC-Q-TOF-MS fingerprint of F. thunbergii was different significantly with those of F. hupehensis and F. pallidiflora. The quality of 12 batches of F. thunbergii samples were finally evaluated by hierarchical clustering analysis (HCA) and principle component analysis (PCA). This convenient and high specific method could be used to identify and evaluate the quality of the F. thunbergii. PMID:24380306

Zhou, Jian-Liang; Liu, Wei; Guo, Zeng-Xi; Chen, Bi-Lian

2013-09-01

95

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

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

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

2014-11-01

96

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

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

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

2013-07-01

97

Application of QuEChERS based method for the determination of pesticides in nutraceutical products (Camellia sinensis) by liquid chromatography coupled to triple quadrupole tandem mass spectrometry.  

PubMed

A QuEChERS (quick, easy, cheap, effective, rugged, and safe) based method has been evaluated and validated for the determination and quantification of approximately 100 LC-amenable pesticides in nutraceutical products obtained from green tea (Camellia sinensis). Extraction was performed with acidified acetonitrile (acetic acid 1% (v/v)), and additional clean-up steps were not necessary. Pesticides determination was achieved using ultra high performance liquid chromatography coupled to triple quadrupole tandem mass spectrometry (UHPLC-QqQ-MS/MS). Total running time was 11min. Pesticides were quantified using matrix-matched calibration. Recoveries ranged from 70% to 117% and relative standard deviation (RSD) was lower than 20% at concentration levels of 25, 50 and 100?g/kg for intra-day precision and equal or lower than 25% for inter-day precision. Limits of quantification (LOQ) were equal or lower than 25?g/kg. The validated method was applied to commercial nutraceutical products, detecting acetamiprid (56?g/kg) and carbendazim (13?g/kg) in two samples. PMID:25660875

Martínez-Domínguez, Gerardo; Nieto-García, Antonio José; Romero-González, Roberto; Frenich, Antonia Garrido

2015-06-15

98

Dissipation and residues determination of propamocarb in ginseng and soil by high-performance liquid chromatography coupled with tandem mass spectrometry.  

PubMed

Two-year field trials were performed at two experimental sites to investigate dissipation and terminal residues of propamocarb in ginseng root, stem, leaf, and soil by high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). Mean recoveries ranged from 80.5 to 95.6% with relative standard deviations (RSDs) of 5.5-9.1% at fortified levels of 0.01, 0.02, 0.05 and 0.20 mg kg(-1). The half-lives of propamocarb were 5.00-11.36 days in root, 5.07-11.46 days in stem, 6.83-11.31 days in leaf and 6.44-8.43 days in soil. The terminal residues of propamocarb were below the maximum residue limits (MRLs) of EU (0.20 mg kg(-1)) and South Korea (0.50 mg kg(-1) in fresh ginseng and 1.0 mg kg(-1) in dried ginseng) over 28 days after last spraying at recommended dosage. The results provide a quantitative basis for establishing the MRL and give a suggestion of safe and reasonable use of propamocarb in ginseng. PMID:24791956

Wang, Chunwei; Wang, Yan; Gao, Jie; Xu, Yuncheng; Cui, Lili

2014-09-01

99

Determination of pesticide residues in samples of green minor crops by gas chromatography and ultra performance liquid chromatography coupled to tandem quadrupole mass spectrometry.  

PubMed

A method was developed for pesticide analysis in samples of high chlorophyll content belonging to the group of minor crops. A new type of sorbent, known as ChloroFiltr, was employed for dispersive-solid phase extraction cleanup (dispersive-SPE) to reduce the unwanted matrix background prior to concurrent analysis by gas chromatography and ultra-performance liquid chromatography coupled to tandem quadrupole mass spectrometry (GC-MS/MS and UPLC-MS/MS). Validation experiments were carried out on green, unripe plants of lupin, white mustard and sorghum. The overall recoveries at the three spiking levels of 0.01, 0.05 and 0.5mgkg(-1) fell in the range between 68 and 120% (98% on average) and 72-104% (93% on average) with relative standard deviation (RSD) values between 2 and 19% (7% on average) and 3-16% (6% on average) by GC-MS/MS and UPLC-MS/MS technique, respectively. Because of strong enhancement or suppression matrix effects (absolute values >20%) which were exhibited by about 80% of the pesticide and matrix combinations, acceptably accurate quantification was achieved by using matrix-matched standards. Up to now, the proposed method has been successfully used to study the dissipation patterns of pesticides after application on lupin, white mustard, soya bean, sunflower and field bean in experimental plot trials conducted in Poland. PMID:25476298

Walorczyk, Stanis?aw; Dro?d?y?ski, Dariusz; Kierzek, Roman

2015-01-15

100

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

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

Terzopoulou, Evangelia; Voutsa, Dimitra; Kaklamanos, George

2014-08-12

101

Laccase catalyzed-oxidative coupling of 3-methyl 2-benzothiazolinone hydrazone and methoxyphenols  

Microsoft Academic Search

The reaction between o-, m-, and p-methoxyphenols and 3-methyl-2-benzothiazolinone hydrazone was studied in the presence of laccase from Pyricularia oryzae. The findings show that laccase (benzenediol:oxygen oxidoreductase, EC 1.10.3.2) catalyzes the oxidative coupling reaction between MBTH and phenols producing red colored azo-dye compounds. On the basis of kinetic parameters and optimum pH values, the mechanisms of the oxidative coupling reactions

Leonardo Setti; Silvia Giuliani; Giovanni Spinozzi; Pier Giorgio Pifferi

1999-01-01

102

An economical and environmentally friendly oxidative biaryl coupling promoted by activated MnO2.  

PubMed

An activated manganese dioxide (MnO2)-BF3·OEt2 oxidation system was developed to efficiently mediate the intramolecular as well as intermolecular biaryl coupling. The oxidative coupling proceeds smoothly at ambient temperature to deliver the corresponding five- to eight-membered tricyclic products in good to excellent yields. The employment of the combination of MnO2 and BF3·OEt2 is attractive on the basis of economical and environmental issues. PMID:25144866

Yang, Jingjing; Sun, Shutao; Zeng, Ziyu; Zheng, Hongbo; Li, Wei; Lou, Hongxiang; Liu, Lei

2014-10-21

103

Simultaneous determination of baicalin, baicalein, wogonin, berberine, palmatine and jatrorrhizine in rat plasma by liquid chromatography–tandem mass spectrometry and application in pharmacokinetic studies after oral administration of traditional Chinese medicinal preparations containing scutellaria–coptis herb couple  

Microsoft Academic Search

A sensitive, rapid and selective liquid chromatography–tandem mass spectrometry (LC–MS–MS) method was developed and validated for the simultaneous determination of baicalin, baicalein, wogonin, berberine, palmatine and jatrorrhizine in scutellaria–coptis herb couple in rat plasma. After protein precipitation with acetonitrile and 0.1% NaH2PO4, chromatography was performed using a C18 column, with gradient elution with 0.1% formic acid and acetonitrile at 0.25ml\\/min.

Jin Feng; Wen Xu; Xia Tao; Hua Wei; Fei Cai; Bo Jiang; Wansheng Chen

2010-01-01

104

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...

105

Effect of underlayer microstructure on the exchange coupling of Mumetal-Al oxide-Co multilayer  

Microsoft Academic Search

Exchange coupling of Mumetal(Ni77Fe14Mo5Cu4 wt%)-Al oxide-Co multilayers has been investigated as a function of Mumetal growth temperature. As Mumetal growth temperature increases from 20°C to 90°C, grain size and surface roughness increase simultaneously. The increase of grain size diminishes the exchange coupling up to 40°C, and increase of roughness increases exchange coupling after 40°C. It is thought that grain size

Young-woo Lee; T. H. Lee; C. G. Kim; C. O. Kim; T. S. Yoon

2002-01-01

106

Radical-Polar Crossover Reactions: Oxidative Coupling of 1,3-Dioxolanes with Electron-Deficient Alkenes and Vinylarenes Based on a Radical Addition and Kornblum-DeLaMare Rearrangement.  

PubMed

A new radical-polar crossover reaction has been developed involving the combination of a tandem radical reaction and Kornblum-DeLaMare rearrangement in a one-pot process. This simple methodology allows for the construction of polyfunctionalized carbonyl compounds via the oxidative coupling of 1,3-dioxolanes with electron-deficient alkenes and vinylarenes in the presence of Co(salen) and TBHP under mild conditions. This reaction also exhibited high functional group tolerance, wide substrate scope, and operational simplicity. PMID:25474618

Du, Peng; Li, Huihuang; Wang, Yaxiong; Cheng, Jiang; Wan, Xiaobing

2014-12-19

107

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

PubMed

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

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

2015-03-01

108

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....

109

Screening of drugs in equine plasma using automated on-line solid-phase extraction coupled with liquid chromatography-tandem mass spectrometry.  

PubMed

A rapid liquid chromatography-tandem mass spectrometry (LC-MS-MS) method was developed for the simultaneous screening of 19 drugs of different classes in equine plasma using automated on-line solid-phase extraction (SPE) coupled with a triple quadrupole mass spectrometer. Plasma samples were first protein precipitated using acetonitrile. After centrifugation, the supernatant was directly injected into the on-line SPE system and analysed by a triple quadrupole LC-MS-MS in positive electrospray ionisation (+ESI) mode with selected reaction monitoring (SRM) scan function. On-line extraction and chromatographic separation of the targeted drugs were performed using respectively a polymeric extraction column (2 cm L x 2.1mm ID, 25 microm particle size) and a reversed-phase C18 LC column (3 cm L x 2.1mm ID, 3 microm particle size) with gradient elution to provide fast analysis time. The overall instrument turnaround time was 9.5 min, inclusive of post-run and equilibration time. Plasma samples fortified with 19 targeted drugs including narcotic analgesics, local anaesthetics, antipsychotics, bronchodilators, mucolytics, corticosteroids, sedative and tranquillisers at sub-parts per billion (ppb) to low parts per trillion (ppt) levels could be consistently detected. No significant matrix interference was observed at the expected retention times of the targeted ion transitions. Over 70% of the drugs studied gave detection limits at or below 100 pg/mL, with some detection limits reaching down to 19 pg/mL. The method had been validated for extraction recovery, precision and sensitivity, and a blockage study had also been carried out. This method is used regularly in the authors' laboratory to screen for the presence of targeted drugs in pre-race plasma samples from racehorses. PMID:20122690

Kwok, W H; Leung, David K K; Leung, Gary N W; Wan, Terence S M; Wong, Colton H F; Wong, Jenny K Y

2010-05-01

110

Fully automated analysis of estrogens in environmental waters by in-tube solid-phase microextraction coupled with liquid chromatography-tandem mass spectrometry.  

PubMed

A simple, rapid and sensitive method for the determination of five estrogens, estrone, 17beta-estradiol, estriol, ethynyl estradiol, and diethylstilbestrol, was developed using a fully automated method consisting of in-tube solid-phase microextraction (SPME) coupled with liquid chromatography-tandem mass spectrometry (LC/MS/MS). These estrogens were separated within 8 min by HPLC using an XDB-C8 column and 0.01% ammonia/acetonitrile (60/40, v/v) at a flow rate of 0.2 mL/min. Electrospray ionization conditions in the negative ion mode were optimized for MS/MS detection of the estrogens. The optimum in-tube SPME conditions were 20 draw/eject cycles of 40 microL of sample using a Supel-Q PLOT capillary column as an extraction device. The extracted compounds were easily desorbed from the capillary by passage of the mobile phase, and no carryover was observed. Using the in-tube SPME LC/MS/MS method, good linearity of the calibration curve (r > or = 0.9996) was obtained in the concentration range from 10 to 200 pg/mL for all compounds examined. The limits of detection (S/N= 3) of the five estrogens examined ranged from 2.7 to 11.7 pg/mL. The in-tube SPME method showed 34-90-fold higher sensitivity than the direct injection method (5 microL injection). This method was applied successfully to the analysis of environmental water samples without any other pretreatment and interference peaks. Several surface water and wastewater samples were collected from the area around Asahi River, and estriol was detected at 35.7 pg/mL in the effluent of a sewage treatment plant. The recoveries of estrogens spiked into river waters were above 86%, except for estriol, and the relative standard deviations were below 0.9-8.8%. PMID:16038212

Mitani, K; Fujioka, M; Kataoka, H

2005-07-22

111

Determination of caffeine, myosmine, and nicotine in chocolate by headspace solid-phase microextraction coupled with gas chromatography-tandem mass spectrometry.  

PubMed

The occurrence of the bioactive components caffeine (xanthine alkaloid), myosmine and nicotine (pyridine alkaloids) in different edibles and plants is well known, but the content of myosmine and nicotine is still ambiguous in milk/dark chocolate. Therefore, a sensitive method for determination of these components was established, a simple separation of the dissolved analytes from the matrix, followed by headspace solid-phase microextraction coupled with gas chromatography-tandem mass spectrometry (HS-SPME-GC-MS/MS). This is the first approach for simultaneous determination of caffeine, myosmine, and nicotine with a convenient SPME technique. Calibration curves were linear for the xanthine alkaloid (250 to 3000 mg/kg) and the pyridine alkaloids (0.000125 to 0.003000 mg/kg). Residuals of the calibration curves were lower than 15%, hence the limits of detection were set as the lowest points of the calibration curves. The limits of detection calculated from linearity data were for caffeine 216 mg/kg, for myosmine 0.000110 mg/kg, and for nicotine 0.000120 mg/kg. Thirty samples of 5 chocolate brands with varying cocoa contents (30% to 99%) were analyzed in triplicate. Caffeine and nicotine were detected in all samples of chocolate, whereas myosmine was not present in any sample. The caffeine content ranged from 420 to 2780 mg/kg (relative standard deviation 0.1 to 11.5%) and nicotine from 0.000230 to 0.001590 mg/kg (RSD 2.0 to 22.1%). PMID:24446916

Müller, Christoph; Vetter, Florian; Richter, Elmar; Bracher, Franz

2014-02-01

112

Determination of peanut allergens in cereal-chocolate-based snacks: metal-tag inductively coupled plasma mass spectrometry immunoassay versus liquid chromatography/electrospray ionization tandem mass spectrometry.  

PubMed

A comparison of two methods for the identification and determination of peanut allergens based on europium (Eu)-tagged inductively coupled plasma mass spectrometry (ICP-MS) immunoassay and on liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) with a triple quadrupole mass analyzer was carried out on a complex food matrix like a chocolate rice crispy-based snack. The LC/MS/MS method was based on the determination of four different peptide biomarkers selective for the Ara h2 and Ara h3/4 peanut proteins. The performance of this method was compared with that of a non-competitive sandwich enzyme-linked immunosorbent assay (ELISA) method with ICP-MS detection of the metal used to tag the antibody for the quantitative peanut protein analysis in food. The limit of detection (LOD) and quantitation of the ICP-MS immunoassay were 2.2 and 5 microg peanuts g(-1) matrix, respectively, the recovery ranged from 86 +/- 18% to 110 +/- 4% and linearity was proved in the 5-50 microg g(-1) range. The LC/MS/MS method allowed us to obtain LODs of 1 and 5 microg protein g(-1) matrix for Ara h3/4 and Ara h2, respectively, thus obtaining significantly higher values with respect to the ELISA ICP-MS method, taking into account the different expression for concentrations. Linearity was established in the 10-200 microg g(-1) range of peanut proteins in the food matrix investigated and good precision (RSD <10%) was demonstrated. Both the two approaches, used for screening or confirmative purposes, showed the power of mass spectrometry when used as a very selective detector in difficult matrices even if some limitations still exist, i.e. matrix suppression in the LC/ESI-MS/MS procedure and the change of the Ag/Ab binding with matrix in the ICP-MS method. PMID:18278822

Careri, Maria; Elviri, Lisa; Maffini, Monica; Mangia, Alessandro; Mucchino, Claudio; Terenghi, Mattia

2008-01-01

113

Thin-film octadecyl-silica glass coating for automated 96-blade solid-phase microextraction coupled with liquid chromatography-tandem mass spectrometry for analysis of benzodiazepines.  

PubMed

A thin-film octadecyl (C18)-silica glass coating was developed as the extraction phase for an automated 96-blade solid-phase microextraction (SPME) system coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS). Various factors (e.g., sol-gel composition and aging time, coating preparation speed, coating thickness, and drying conditions) affecting the quality of C18-silica glass thin-film coating were studied and optimized. The results showed that the stability and durability of the coating are functions of the coating thickness and drying conditions. Coating thickness is controlled by sol-gel composition, aging time and the withdrawal speed in the dipping method. Automated sample preparation was achieved using a robotic autosampler that enabled simultaneous preparation of 96 samples in a 96-well plate format. Under the optimum SPME conditions the proposed system requires a total of 140 min for preparation of all 96 samples (i.e., 30 min preconditioning, 40 min equilibrium extraction, 40 min desorption and 30 min carry over step). The performance of the C18-silica glass 96-blade SPME system was evaluated for high-throughput analysis of benzodiazepines from phosphate-buffered saline solution (PBS) and human plasma, and the reusability, repeatability, and validity of the system were evaluated. When analysing spiked PBS and human plasma, the inter-blade reproducibility for four benzodiazepines was obtained in the ranges of 4-8% and 9-11% RSD (relative standard deviation), respectively, and intra-blade reproducibility were in the ranges of 3-9% and 8-13% RSD, respectively. The limits of detection and quantitation for plasma analysis were in the ranges of 0.4-0.7 ng/mL and 1.5-2.5 ng/mL for all four analytes. PMID:22197254

Mirnaghi, Fatemeh S; Monton, Maria Rowena N; Pawliszyn, Janusz

2012-07-13

114

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

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

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

2012-07-20

115

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

PubMed

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

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

2014-08-01

116

Magnetoelectric coupling in multifunctional nanostructured complex oxide thin films  

NASA Astrophysics Data System (ADS)

The fabrication of magnetoelectric materials have long been sought as a means of expanding the ways in which engineers can interact with electronic devices, specifically in the area of driving magnetism directly with applied electric fields. While significant research has been conducted on thin-film heterostructure architectures, these systems are mired by non-ideal interface geometries, substrate clamping effects, and in-plane magnetic anisotropy. The research presented here seeks to explore the extent of magnetoelectric coupling in a nanostructured system, specifically exploring the BiFeO 3-NiFe2O4 composite system in the resonant-coupling regime, which has shown to produce the strongest magnetoelectric coupling to date. This dissertation reviews the materials selection process that led to the aforementioned system as the ideal one for these studies, the material deposition procedure, and subsequent process optimization with regard to structural, electrical, and magnetic properties, each of which is integral to understanding the magnetoelectric coupling in the system. Finally, the material system is characterized magnetoelectrically by studying the effect of applied electric fields on the ferromagnetic resonance condition of the composite thin films.

Crane, Steven Peter

117

Quantification of DNA damage products resulting from deamination, oxidation and reaction with products of lipid peroxidation by liquid chromatography isotope dilution tandem mass spectrometry  

PubMed Central

The analysis of damage products as biomarkers of inflammation has been hampered by a poor understanding of the chemical biology of inflammation, the lack of sensitive analytical methods, and a focus on single chemicals as surrogates for inflammation. To overcome these problems, we developed a general and sensitive liquid chromatographic tandem mass spectrometry (LC/MS-MS) method to quantify, in a single DNA sample, the nucleoside forms of seven DNA lesions reflecting the range of chemistries associated with inflammation: 2?-deoxyuridine, 2?-deoxyxanthosine, and 2?-deoxyinosine from nitrosative deamination; 8-oxo-2?-deoxyguanosine from oxidation; and 1,N2-etheno-2?-deoxyguanosine, 1,N6-etheno-2?-deoxyadenosine, and 3,N4-etheno-2?-deoxycytidine arising from reaction of DNA with lipid peroxidation products. Using DNA purified from cells or tissues under conditions that minimize artifacts, individual nucleosides are purified by HPLC and quantified by isotope-dilution, electrospray ionization LC/MS-MS. The method can be applied to other DNA damage products and requires 4-6 days to complete depending upon the number of samples. PMID:18714297

Taghizadeh, Koli; McFaline, Jose L.; Pang, Bo; Sullivan, Matthew; Dong, Min; Plummer, Elaine; Dedon, Peter C.

2009-01-01

118

Mixed-metal MIL-100(Sc,M) (M=Al, Cr, Fe) for Lewis acid catalysis and tandem C-C bond formation and alcohol oxidation.  

PubMed

The trivalent metal cations Al(3+) , Cr(3+) , and Fe(3+) were each introduced, together with Sc(3+) , into MIL-100(Sc,M) solid solutions (M=Al, Cr, Fe) by direct synthesis. The substitution has been confirmed by powder X-ray diffraction (PXRD) and solid-state NMR, UV/Vis, and X-ray absorption (XAS) spectroscopy. Mixed Sc/Fe MIL-100 samples were prepared in which part of the Fe is present as ?-Fe2 O3 nanoparticles within the mesoporous cages of the MOF, as shown by XAS, TGA, and PXRD. The catalytic activity of the mixed-metal catalysts in Lewis acid catalysed Friedel-Crafts additions increases with the amount of Sc present, with the attenuating effect of the second metal decreasing in the order Al>Fe>Cr. Mixed-metal Sc,Fe materials give acceptable activity: 40?% Fe incorporation only results in a 20?% decrease in activity over the same reaction time and pure product can still be obtained and filtered off after extended reaction times. Supported ?-Fe2 O3 nanoparticles were also active Lewis acid species, although less active than Sc(3+) in trimer sites. The incorporation of Fe(3+) into MIL-100(Sc) imparts activity for oxidation catalysis and tandem catalytic processes (Lewis acid+oxidation) that make use of both catalytically active framework Sc(3+) and Fe(3+) . A procedure for using these mixed-metal heterogeneous catalysts has been developed for making ketones from (hetero)aromatics and a hemiacetal. PMID:25348903

Mitchell, Laura; Williamson, Patrick; Ehrlichová, Barbora; Anderson, Amanda E; Seymour, Valerie R; Ashbrook, Sharon E; Acerbi, Nadia; Daniels, Luke M; Walton, Richard I; Clarke, Matthew L; Wright, Paul A

2014-12-15

119

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

PubMed Central

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

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

120

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

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

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

2014-10-01

121

Studies on oxidative coupling of methane using high-temperature proton-conducting membranes  

Microsoft Academic Search

A solid oxide proton conducting SrCe0.95Yb0.05O3?x (SCYO) membrane has been applied to methane oxidative coupling in a laboratory membrane reactor using disc-shaped membrane specimen equipped with porous silver electrodes. The investigations were carried out at 750°C and atmospheric pressure and covered variations of feed gases (methane versus helium or air), water vapor pressure, and electrical current. Under the conditions tested,

J. Langguth; R. Dittmeyer; H. Hofmann; G. Tomandl

1997-01-01

122

Horseradish peroxidase-catalyzed oxidative coupling of 3-methyl 2-benzothiazolinone hydrazone and methoxyphenols  

Microsoft Academic Search

The reaction between o-, m-, and p-methoxyphenols and 3-methyl-2-benzothiazolinone hydrazone (MBTH) is studied in the presence of horseradish peroxidase (HRP) and H2O2 as oxidative agent. The findings indicate that enzyme (H2O2 oxidoreductase; EC 1.11.1.7) catalyzes an oxidative coupling reaction between MBTH and phenols which produces azo dye compounds. On the basis of kinetic parameters and optimum pH values, a mechanism

Leonardo Setti; Sara Scali; Igor Degli Angeli; Pier Giorgio Pifferi

1998-01-01

123

Rh(III)-catalyzed traceless coupling of quinoline N-oxides with internal diarylalkynes.  

PubMed

Quinoline N-oxides were found to undergo Cp*Rh(III)-catalyzed coupling with internal diarylalkynes to provide 8-functionalized quinolines through a cascade process that involves remote C-H bond activation, alkyne insertion, and intramolecular oxygen atom transfer. In this reaction, the N-oxide plays a dual role, acting as a traceless directing group as well as a source of oxygen atom, as confirmed by an (18)O-labeling experiment. PMID:25263712

Sharma, Upendra; Park, Yoonsu; Chang, Sukbok

2014-10-17

124

Nanocrystal assembly for tandem catalysis  

DOEpatents

The present invention provides a nanocrystal tandem catalyst comprising at least two metal-metal oxide interfaces for the catalysis of sequential reactions. One embodiment utilizes a nanocrystal bilayer structure formed by assembling sub-10 nm platinum and cerium oxide nanocube monolayers on a silica substrate. The two distinct metal-metal oxide interfaces, CeO.sub.2--Pt and Pt--SiO.sub.2, can be used to catalyze two distinct sequential reactions. The CeO.sub.2--Pt interface catalyzed methanol decomposition to produce CO and H.sub.2, which were then subsequently used for ethylene hydroformylation catalyzed by the nearby Pt--SiO.sub.2 interface. Consequently, propanal was selectively produced on this nanocrystal bilayer tandem catalyst.

Yang, Peidong; Somorjai, Gabor; Yamada, Yusuke; Tsung, Chia-Kuang; Huang, Wenyu

2014-10-14

125

Nanocrystal bilayer for tandem catalysis  

NASA Astrophysics Data System (ADS)

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.

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

126

"Nanocrystal bilayer for tandem catalysis"  

SciTech Connect

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

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

127

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

Microsoft Academic Search

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

Tomoko Ohnishi; Takeshi Mori

1962-01-01

128

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

NASA Technical Reports Server (NTRS)

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.

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

1975-01-01

129

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

PubMed Central

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

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

2013-01-01

130

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

USGS Publications Warehouse

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.

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

1989-01-01

131

Observation of T-2 and HT-2 glucosides from Fusarium sporotrichioides by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS)  

Technology Transfer Automated Retrieval System (TEKTRAN)

Cultures of Fusarium sporotrichioides were extracted and subjected to evaluation by high performance liquid chromatography – tandem mass spectrometry (LC-MS/MS). Along with the expected T-2 and HT-2 toxins, compounds 162 m/z higher than the toxins were observed. Fragmentation behavior of the larger ...

132

Exploiting shape effects of La2O3 nanocatalysts for oxidative coupling of methane reaction.  

PubMed

High activity towards oxidative coupling of methane and high selectivity for C2 hydrocarbons could be achieved over La2O3 nanorods with a large surface area, strong surface basic sites, electron deficient surface oxygen species and defined surface structure compared with La2O3 nanoparticles at low temperature. PMID:24088951

Huang, Ping; Zhao, Yonghui; Zhang, Jun; Zhu, Yan; Sun, Yuhan

2013-11-21

133

Photo-oxidative tuning of individual and coupled GaAs photonic crystal cavities  

E-print Network

nanocavity modes by wet chemical digital etching," Appl. Phys. Lett. 87, 021108 (2005). 12. N. W. LPhoto-oxidative tuning of individual and coupled GaAs photonic crystal cavities Alexander Y Computing, University of Waterloo, Ontario, Canada piggott@stanford.edu Abstract: We demonstrate a photo

Vuckovic, Jelena

134

Substituent-enabled oxidative dehydrogenative cross-coupling of 1,4-naphthoquinones with alkenes.  

PubMed

A Rh-catalyzed oxidative dehydrogenative cross-coupling of 1,4-naphthquinones with alkenes was achieved by using a substituent-enabled C(sp(2))-H functionalization (SEF) strategy. The method shows high functional group tolerance, broad substrate scope, and great potential for further functional transformations. PMID:25075553

Zhang, Chi; Wang, Meining; Fan, Zhoulong; Sun, Li-Ping; Zhang, Ao

2014-08-15

135

Copper-catalyzed aerobic oxidative coupling of aromatic alcohols and acetonitrile to ?-ketonitriles.  

PubMed

A practical, convenient, and cheap copper-catalyzed aerobic oxidative coupling of aromatic alcohols and acetonitrile to ?-ketonitriles has been developed. The green C-C bond formation involving the loss of two hydrogen atoms from the corresponding two carbons, respectively, unlocks opportunities for markedly different synthetic strategies. PMID:24392889

Shen, Jiaxuan; Yang, Dejun; Liu, Yuxiao; Qin, Shuangshuang; Zhang, Jingwu; Sun, Jiangkai; Liu, Chunhui; Liu, Chaoyang; Zhao, Xiaomei; Chu, Changhu; Liu, Renhua

2014-01-17

136

The relative signs of the NMR coupling constants in styrene oxide by double resonance  

Microsoft Academic Search

The relative signs of the nuclear magnetic resonance spin-spin coupling constants between the three protons of the oxirane ring of styrene oxide have been determined to be the same by the audio side band phase detection proton-proton decoupling technique.

Daniel D. Elleman; Stanley L. Manatt

1962-01-01

137

Development of a scalable model for predicting arsenic transport coupled with oxidation and adsorption reactions  

E-print Network

systems contaminated by various natural and anthropogenic arsenic (As) sources has been a major manage and mitigate the overall risks posed by arsenic contamination. The predominant forms of arsenicDevelopment of a scalable model for predicting arsenic transport coupled with oxidation

Clement, Prabhakar

138

Ligand-free palladium-catalyzed aerobic oxidative coupling of carboxylic anhydrides with arylboronic acids.  

PubMed

We report a new, effective and environmentally friendly protocol for selective aerobic oxidative coupling of arylboronic acids with carboxylic anhydrides in the presence of ligand-free palladium catalyst. The aryl benzoates are obtained in good to excellent yields. PMID:24910234

Yin, Weiyan; He, Haifeng; Zhang, Yani; Long, Tong

2014-09-01

139

Oxidative cross-coupling/cyclization to build polysubstituted pyrroles from terminal alkynes and ?-enamino esters.  

PubMed

A novel silver-mediated highly selective synthesis of polysubstituted pyrroles by the C-H/C-H oxidative cross-coupling/cyclization of terminal alkynes with ?-enamino esters has been developed. This protocol represents a simple, efficient and selective way to construct polysubstituted pyrroles in good yields from basic chemical materials. PMID:23872924

Ke, Jie; He, Chuan; Liu, Huiying; Li, Mengjun; Lei, Aiwen

2013-09-01

140

Quantification of F 2-isoprostane isomers in cultured human lung epithelial cells after silica oxide and metal oxide nanoparticle treatment by liquid chromatography\\/tandem mass spectrometry  

Microsoft Academic Search

F2-isoprostanes are lipid peroxidation products of arachidonic acid in cell membrane and are reliable biomarkers for oxidative stress and cell membrane damage. Nanomaterials are widely used as raw materials in many industries and will have high potentials to be used in life science and medical fields. However, the human health impact of nanoparticles has caused people's great concern. Unfortunately, the

Xiaoqian Liu; Philip D. Whitefield; Yinfa Ma

2010-01-01

141

Simultaneous determination of morinidazole, its N-oxide, sulfate, and diastereoisomeric N(+)-glucuronides in human plasma by liquid chromatography-tandem mass spectrometry.  

PubMed

Morinidazole is a new third-generation 5-nitroimidazole antimicrobial drug. To investigate the pharmacokinetic profiles of morinidazole and its major metabolites in humans, a liquid chromatography-tandem mass spectrometry method was developed and validated for simultaneous determination of morinidazole, its N-oxide metabolite (M4-1), a sulfate conjugate (M7), and two diastereoisomeric N(+)-glucuronides (M8-1 and M8-2) in human plasma. A simple acetonitrile-induced protein precipitation was employed to extract five analytes and internal standard metronidazole from 50?L human plasma. To avoid the interference from the in-source dissociation of the sulfate and achieve the baseline-separation of diastereoisomeric N(+)-glucuronides, all the analytes were separated from each other with the mobile phase consisting of 10mM ammonium formate and acetonitrile using gradient elution on a Hydro-RP C(18) column (50mm×2mm, 4?m) with a total run time of 5min. The API 4000 triple quadrupole mass spectrometer was operated under the multiple reaction-monitoring mode using the electrospray ionization technique. The developed method was linear in the concentration ranges of 10.0-12,000ng/mL for morinidazole, 1.00-200ng/mL for M4-1, 2.50-500ng/mL for M7, 3.00-600ng/mL for M8-1, and 10.0-3000ng/mL for M8-2. The intra- and inter-day precisions for each analyte met the accepted value. Results of the stability of morinidazole and its metabolites in human plasma were also presented. The method was successfully applied to the clinical pharmacokinetic studies of morinidazole injection in healthy subjects, patients with moderate hepatic insufficiency, and patients with severe renal insufficiency, respectively. PMID:23122401

Gao, Ruina; Zhong, Dafang; Liu, Ke; Xia, Yu; Shi, Rongwei; Li, Hua; Chen, Xiaoyan

2012-11-01

142

Tandem Mirror Reactor Systems Code (Version I)  

SciTech Connect

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.

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

143

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

PubMed

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

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

2014-03-18

144

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

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

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

2005-11-01

145

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

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

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

146

Oxygen reduction electrocatalyst based on strongly coupled cobalt oxide nanocrystals and carbon nanotubes.  

PubMed

Electrocatalyst for oxygen reduction reaction (ORR) is crucial for a variety of renewable energy applications and energy-intensive industries. The design and synthesis of highly active ORR catalysts with strong durability at low cost is extremely desirable but remains challenging. Here, we used a simple two-step method to synthesize cobalt oxide/carbon nanotube (CNT) strongly coupled hybrid as efficient ORR catalyst by directly growing nanocrystals on oxidized multiwalled CNTs. The mildly oxidized CNTs provided functional groups on the outer walls to nucleate and anchor nanocrystals, while retaining intact inner walls for highly conducting network. Cobalt oxide was in the form of CoO due to a gas-phase annealing step in NH(3). The resulting CoO/nitrogen-doped CNT (NCNT) hybrid showed high ORR current density that outperformed Co(3)O(4)/graphene hybrid and commercial Pt/C catalyst at medium overpotential, mainly through a 4e reduction pathway. The metal oxide/carbon nanotube hybrid was found to be advantageous over the graphene counterpart in terms of active sites and charge transport. Last, the CoO/NCNT hybrid showed high ORR activity and stability under a highly corrosive condition of 10 M NaOH at 80 °C, demonstrating the potential of strongly coupled inorganic/nanocarbon hybrid as a novel catalyst system in oxygen depolarized cathode for chlor-alkali electrolysis. PMID:22957510

Liang, Yongye; Wang, Hailiang; Diao, Peng; Chang, Wesley; Hong, Guosong; Li, Yanguang; Gong, Ming; Xie, Liming; Zhou, Jigang; Wang, Jian; Regier, Tom Z; Wei, Fei; Dai, Hongjie

2012-09-26

147

Determination of rare earths in lanthanum oxide by inductively-coupled plasma emission derivative spectrometry.  

PubMed

Rare-earth elements (REE) at ppm levels in lanthanum oxide can be determined without prior separation and preconcentration by use of high-resolution inductively-coupled plasma emission derivative spectrometry (ICPEDS). The calibration graphs are all linear and pass through the origin, even in the presence of large amounts of lanthanum, except those for dysprosium, holmium and ytterbium. The detection limit for each REE is 1-10 mug g in lanthanum oxide. Investigation of various physical and/or spectral interferences shows that good selectivity is obtained by ICPEDS. PMID:18963327

Ishii, H; Satoh, K

1983-02-01

148

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

PubMed Central

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

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

2013-01-01

149

Ammonia oxidation coupled to CO2 fixation by archaea and bacteria in an agricultural soil.  

PubMed

Ammonia oxidation is an essential part of the global nitrogen cycling and was long thought to be driven only by bacteria. Recent findings expanded this pathway also to the archaea. However, most questions concerning the metabolism of ammonia-oxidizing archaea, such as ammonia oxidation and potential CO(2) fixation, remain open, especially for terrestrial environments. Here, we investigated the activity of ammonia-oxidizing archaea and bacteria in an agricultural soil by comparison of RNA- and DNA-stable isotope probing (SIP). RNA-SIP demonstrated a highly dynamic and diverse community involved in CO(2) fixation and carbon assimilation coupled to ammonia oxidation. DNA-SIP showed growth of the ammonia-oxidizing bacteria but not of archaea. Furthermore, the analysis of labeled RNA found transcripts of the archaeal acetyl-CoA/propionyl-CoA carboxylase (accA/pccB) to be expressed and labeled. These findings strongly suggest that ammonia-oxidizing archaeal groups in soil autotrophically fix CO(2) using the 3-hydroxypropionate-4-hydroxybutyrate cycle, one of the two pathways recently identified for CO(2) fixation in Crenarchaeota. Catalyzed reporter deposition (CARD)-FISH targeting the gene encoding subunit A of ammonia monooxygenase (amoA) mRNA and 16S rRNA of archaea also revealed ammonia-oxidizing archaea to be numerically relevant among the archaea in this soil. Our results demonstrate a diverse and dynamic contribution of ammonia-oxidizing archaea in soil to nitrification and CO(2) assimilation and that their importance to the overall archaeal community might be larger than previously thought. PMID:21368116

Pratscher, Jennifer; Dumont, Marc G; Conrad, Ralf

2011-03-01

150

Simultaneous determination of mercapturic acids derived from ethylene oxide (HEMA), propylene oxide (2-HPMA), acrolein (3-HPMA), acrylamide (AAMA) and N,N-dimethylformamide (AMCC) in human urine using liquid chromatography/tandem mass spectrometry.  

PubMed

Mercapturic acids are highly important and specific biomarkers of exposure to carcinogenic substances in occupational and environmental medicine. We have developed and validated a reliable, specific and very sensitive method for the simultaneous determination of five mercapturic acids derived from several high-production chemicals used in industry, namely ethylene oxide, propylene oxide, acrylamide, acrolein and N,N-dimethylformamide. Analytes are enriched and cleaned up from urinary matrix by offline solid-phase extraction. The mercapturic acids are subsequently separated by means of high-performance liquid chromatography on a Luna C8 (2) column and specifically quantified by tandem mass spectrometric detection using isotopically labelled analytes as internal standards. The limits of detection (LODs) for N-acetyl-S-2-carbamoylethylcysteine (AAMA) and N-acetyl-S-2-hydroxyethylcysteine (HEMA) were 2.5 microg/L and 0.5 microg/L urine, while for N-acetyl-S-3-hydroxypropylcysteine (3-HPMA), N-acetyl-S-2-hydroxypropylcysteine (2-HPMA) and N-acetyl-S-(N-methylcarbamoyl)cysteine (AMCC) it was 5 microg/L. These LODs were sufficient to detect the background exposure of the general population. We applied the method on spot urine samples of 28 subjects of the general population with no known occupational exposure to these substances. Median levels for AAMA, HEMA, 3-HPMA, 2-HPMA and AMCC in non-smokers (n = 14) were 52.6, 2.0, 155, 7.1 and 113.6 microg/L, respectively. In smokers (n = 14), median levels for AAMA, HEMA, 3-HPMA, 2-HPMA and AMCC were 243, 5.3, 1681, 41.7 and 822 microg/L, respectively. Due to the simultaneous quantification of these mercapturic acids, our method is well suited for the screening of workers with multiple chemical exposures as well as the determination of the background excretion of the general population. PMID:18666198

Schettgen, Thomas; Musiol, Anita; Kraus, Thomas

2008-09-01

151

Dual-channel-mediated spin coupling for one-electron-oxidized cobalt(II)-saddled porphyrin.  

PubMed

Saddle-shaped Co(II)[OET(p-R)PP] (R = CF3, H, CH3) can be readily oxidized with Cl2, Br2, and I2 to the corresponding one-electron-oxidation product Co[OET(p-R)PP]X (X = Cl, Br, I) with the clear character of a ring cation radical. With the series of (1)H and (13)C NMR spectra of these related complexes, both the axial ligand and peripheral substituent of the ring macrocycle are proven to act as a dual channel to tune spin coupling between low-spin Co(II) and a porphyrin ?-cation radical. Density functional theory calculations have shown that the antiferromagnetic coupling between spins residing in d(z)(2) and a(2u) are expected to exist as the ground state. The paramagnetic properties are attributed to an a(1u)-type ferromagnetic excited triplet state. PMID:25122190

Cheng, Ru-Jen; Chen, Yu-Hsuan; Chen, Ching-Chin; Lee, Gene-Hsiang; Peng, Shie-Ming; Chen, Peter Ping-Yu

2014-09-01

152

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

PubMed

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

Xu, Hai-Chao; Moeller, Kevin D

2010-04-16

153

Intramolecular Anodic Olefin Coupling Reactions: Using Competition Studies to Probe the Mechanism of Oxidative Cyclization Reactions  

PubMed Central

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

Xu, Hai-Chao; Moeller, Kevin D.

2014-01-01

154

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

Microsoft Academic Search

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

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

2011-01-01

155

Nanocellulose coupled flexible polypyrrole@graphene oxide composite paper electrodes with high volumetric capacitance.  

PubMed

A robust and compact freestanding conducting polymer-based electrode material based on nanocellulose coupled polypyrrole@graphene oxide paper is straightforwardly prepared via in situ polymerization for use in high-performance paper-based charge storage devices, exhibiting stable cycling over 16?000 cycles at 5 A g(-1) as well as the largest specific volumetric capacitance (198 F cm(-3)) so far reported for flexible polymer-based electrodes. PMID:25630958

Wang, Zhaohui; Tammela, Petter; Strømme, Maria; Nyholm, Leif

2015-02-12

156

Photoinitiated Coupling of Unmodified Monosaccharides to Iron Oxide Nanoparticles for Sensing Proteins and Bacteria  

PubMed Central

We report a versatile approach for the immobilization of unmodified monosaccharides onto iron oxide nanoparticles. Covalent coupling of the carbohydrate onto iron oxide nanoparticle surfaces was accomplished by the CH insertion reaction of photochemically activated phosphate-functionalized perfluorophenylazides (PFPAs), and the resulting glyconanoparticles were characterized by IR, TGA, and TEM. The surface-bound d-mannose showed the recognition ability towards Concanavalin A and Escherichia coli strain ORN178 that possesses mannose-specific receptor sites. Owing to the simplicity and versatility of the technique, together with the magnetic property of iron oxide nanoparticles, the methodology developed in this study serves as a general approach for the preparation of magnetic glyconanoparticles to be used in clinical diagnosis, sensing, and de-contamination. PMID:19534519

Liu, Li-Hong; Dietsch, Hervé; Schurtenberger, Peter; Yan, Mingdi

2009-01-01

157

Oxidative coupling of methane over lanthana catalysts. I. Identification and role of specific active sites  

SciTech Connect

The present work aims at coorelating the surface characteristics of a {open_quotes}working{close_quotes} catalyst under the conditions of the oxidative coupling of methane (OCM) with mechanistic aspects of the reaction deduced from transient experiments focused on the total oxidation pathway. Several lanthana samples with variable surface area and morphology are tested with a view to identifying the exact nature of OCM-specific active sites. The lanthana surface, characterized by XPS, TEM, XRD, FTIR, and in situ DRIFT spectroscopy, appears to be mostly decarbonated and dehydroxylated under reaction conditions. Low coordination sites localized on step edges are related to the total oxidation pathway, while basic sites associated with oxygen vacancies enable the oxygen activation leading to the initial methane activation. Structure sensitivity effects are explained within this proposal of differentiated sites on a typical OCM catalyst. 32 refs., 13 figs., 4 tabs.

Lacombe, S.; Geantet, C.; Mirodatos, C. [Institut de Recherches sur la Catalyse, Villeurbanne (France)] [Institut de Recherches sur la Catalyse, Villeurbanne (France)

1995-02-01

158

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

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. Copyright © 2014 John Wiley & Sons, Ltd. PMID:24811001

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

2014-12-01

159

Coupling between oxidation state and hydrogen bond conformation in heme proteins.  

PubMed

In all heme proteins for which crystal structures are available, the N(epsilon) of a histidyl residue is bonded to the heme iron and N(delta) is hydrogen bonded to a carbonyl oxygen of the peptide backbone. We investigate here the possibility that a change in oxidation state of the iron or a change in the geometry of this hydrogen bond might change the hydrogen bond strength in a functionally significant way. Dimerization energies obtained from ab initio molecular orbital calculations on the hydrogen-bonded dimer of imidazole and planar formamide are used to represent the strength of this hydrogen bond in heme proteins. The effect of a change in iron oxidation state is modeled by varying the positive charge on imidazole. The effect of a change in hydrogen bond geometry is studied by employing x-ray coordinates for reduced and oxidized cytochrome c, deoxy- and metmyoglobin, and deoxy- and methemoglobin. Our conclusions are that the strength of this hydrogen bond in heme proteins is sensitive to both the oxidation state of the iron atom and to geometry changes on the order of those obtained from the x-ray coordinates. We speculate that the changes in oxidation state may be functionally coupled with changes in hydrogen bond geometry and that this hydrogen bond represents a feasible pathway to link protein conformation with redox potential or reactivity of the iron atom. PMID:220604

Valentine, J S; Sheridan, R P; Allen, L C; Kahn, P C

1979-03-01

160

Effects of inductively coupled plasma oxidation on the properties of polycrystalline silicon films and thin film transistors  

Microsoft Academic Search

We investigated the effects of inductively coupled plasma (ICP) oxidation on the properties of polycrystalline silicon (poly-Si) films and thin film transistors (TFTs). The ICP oxidation in oxygen plasma passivated the dangling bonds in the poly-Si films, not by oxygen incorporation but by hydrogen incorporation; but the incorporated hydrogen diffused out during the TFT fabrication, so that the effect of

Yong Woo Choi; Sang Won Park; Byung Tae Ahn

1999-01-01

161

I?-catalyzed oxidative C(sp³)-H/S-H coupling: utilizing alkanes and mercaptans as the nucleophiles.  

PubMed

By using alkanes and mercaptans as the nucleophiles with di-tert-butyl peroxide (DTBP) as the oxidant, I2-catalyzed oxidative C(sp(3))-H/S-H coupling was achieved. This protocol provides a novel process to construct C(sp(3))-S bonds from commercially available hydrocarbons and mercaptans. PMID:25297879

Yuan, Jiwen; Ma, Xu; Yi, Hong; Liu, Chao; Lei, Aiwen

2014-11-28

162

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

PubMed

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

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

2014-01-15

163

Packed-fiber solid-phase extraction coupled with high performance liquid chromatography-tandem mass spectrometry for determination of diethylstilbestrol, hexestrol, and dienestrol residues in milk products.  

PubMed

A sensitive analytical method based on packed-fiber solid-phase extraction and high performance liquid chromatography-tandem mass spectrometry (PF SPE-HPLC-MS/MS) has been developed for determination of three synthetic stilbenes in milk. The stilbenes are extracted with acetonitrile, using sodium chloride, and purified with PF SPE using a cartridge containing electrospun polystyrene nanofibers. Parameters affecting the efficiency of PF SPE, such as pH and amount of salt, were optimized. Under optimal conditions, the limits of detection and quantification were 5-13pg/g and 15-37pg/g, respectively. Absolute recoveries varied between 60% and 85% at three different levels. The method was successfully applied for the determination of estrogenic stilbenes in a total of 69 milk samples. The method is sensitive and cost-effective in stilbene detection, and has potential in quality control of dairy products. PMID:24636894

Hu, Wen-Yan; Kang, Xue-Jun; Zhang, Chi; Yang, Jun; Ling, Rui; Liu, E-Hu; Li, Ping

2014-04-15

164

Tandem robot control system and method for controlling mobile robots in tandem  

SciTech Connect

A control system for controlling mobile robots provides a way to control mobile robots, connected in tandem with coupling devices, to navigate across difficult terrain or in closed spaces. The mobile robots can be controlled cooperatively as a coupled system in linked mode or controlled individually as separate robots.

Hayward, David R. (Albuquerque, NM); Buttz, James H. (Albuquerque, NM); Shirey, David L. (Albuquerque, NM)

2002-01-01

165

Copper-Catalyzed Difunctionalization of Activated Alkynes by Radical Oxidation-Tandem Cyclization/Dearomatization to Synthesize 3-Trifluoromethyl Spiro[4.5]trienones.  

PubMed

A copper-catalyzed difunctionalizing trifluoromethylation of activated alkynes with the cheap reagent sodium trifluoromethanesulfinate (NaSO2 CF3 or Langlois' reagent) has been developed incorporating a tandem cyclization/dearomatization process. This strategy affords a straightforward route to synthesis of 3-(trifluoromethyl)-spiro[4.5]trienones, and presents an example of difunctionalization of alkynes for simultaneous formation of two carbon-carbon single bonds and one carbon-oxygen double bond. PMID:25452200

Hua, Hui-Liang; He, Yu-Tao; Qiu, Yi-Feng; Li, Ying-Xiu; Song, Bo; Gao, Pin; Song, Xian-Rong; Guo, Dong-Hui; Liu, Xue-Yuan; Liang, Yong-Min

2014-11-28

166

Interchain coupled chain dynamics of poly(ethylene oxide) in blends with poly(methyl methacrylate): coupling model analysis.  

PubMed

Quasielastic neutron scattering and molecular dynamics simulation data from poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends found that for short times the self-dynamics of PEO chain follows the Rouse model, but at longer times past t(c) = 1-2 ns it becomes slower and departs from the Rouse model in dependences on time, momentum transfer, and temperature. To explain the anomalies, others had proposed the random Rouse model (RRM) in which each monomer has different mobility taken from a broad log-normal distribution. Despite the success of the RRM, Diddens et al. [Eur. Phys. Lett. 95, 56003 (2011)] extracted the distribution of friction coefficients from the MD simulations of a PEO/PMMA blend and found that the distribution is much narrower than expected from the RRM. We propose a simpler alternative explanation of the data by utilizing alone the observed crossover of PEO chain dynamics at t(c). The present problem is just a special case of a general property of relaxation in interacting systems, which is the crossover from independent relaxation to coupled many-body relaxation at some t(c) determined by the interaction potential and intermolecular coupling/constraints. The generality is brought out vividly by pointing out that the crossover also had been observed by neutron scattering from entangled chains relaxation in monodisperse homopolymers, and from the segmental ?-relaxation of PEO in blends with PMMA. The properties of all the relaxation processes in connection with the crossover are similar, despite the length scales of the relaxation in these systems are widely different. PMID:22112097

Ngai, K L; Wang, Li-Min

2011-11-21

167

Bioconjugation of gold nanoparticles through the oxidative coupling of ortho-aminophenols and anilines.  

PubMed

While there are a number of methods for attaching gold nanoparticles (AuNPs) to biomolecules, the existing strategies suffer from nonspecific AuNP adsorption, reagents that are unstable in aqueous solutions, and/or long reaction times. To improve upon existing AuNP bioconjugation strategies, we have adapted a recently reported potassium ferricyanide-mediated oxidative coupling reaction for the attachment of aniline-functionalized AuNPs to o-aminophenol-containing oligonucleotides, peptides, and proteins. The aniline-AuNPs are stable in aqueous solutions, show little-to-no nonspecific adsorption with biomolecules, and react rapidly (30 min) with o-aminophenols under mild conditions (pH 6.5, 1 mM oxidant). PMID:25275488

Capehart, Stacy L; ElSohly, Adel M; Obermeyer, Allie C; Francis, Matthew B

2014-10-15

168

Catalytic Properties of Oxygen Semipermeable Perovskite-Type Ceramic Membrane Materials for Oxidative Coupling of Methane  

Microsoft Academic Search

The catalytic properties for the oxidative coupling of methane (OCM) of La0.8Sr0.2CoO3(LSC) and SrCo0.8Fe0.2O3(SCF) in solid solution were studied and compared with those of 5 wt% Li\\/MgO, using a steady\\/unsteady state packed-bed reactor and a transient microbalance. The results of the steady-state cofeed experiments show that LSC possesses OCM catalytic properties similar to those of Li\\/MgO in terms of C2yield

Y. S. Lin; Y. Zeng

1996-01-01

169

Sensitivity of doping states in the copper oxides to electron-lattice coupling  

NASA Astrophysics Data System (ADS)

Doping states in a two-dimensional three-band Peierls-Hubbard model are investigated with inhomogeneous Hartree-Fock and random phase approximations. They are sensitive to small changes of electron-lattice and electron-electron interactions. For parameters relevant to the insulating copper oxides a small ferromagnetic polaron is found. Moderate intersite electron-lattice coupling triggers a nonlinear feedback mechanism resulting in a rapid crossover from a Zhang-Rice regime to a covalent molecular singlet state in which the local magnetic moment is quenched and local lattice distortion is large. Various states are characterized by distinct optical and infrared absorption spectra.

Yonemitsu, K.; Bishop, A. R.; Lorenzana, J.

1992-08-01

170

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

Microsoft Academic Search

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

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

1995-01-01

171

Directly-coupled dc-SQUID magnetometers made of Bi-Sr-Ca-Cu oxide films  

SciTech Connect

This paper reports on all high-T{sub c} dc- SQUID magnetometers made of Bi-Sr-Ca-Cu oxide films that were designed and fabricated. A directly-coupled scheme where a SQUID loop and a pick-up loop are connected directly in parallel was chosen to avoid fabricating the multi-layered structure. The flux noise which was measured in FLL operation at 4.2K increased in a form of 1/f as the frequency decreased below 20Hz.

Matsuda, M.; Murayama, Y.; Kiryu, S.; Kasai, N.; Kashiwaya, S.; Koyanagi, M.; Endo, T. (Electrotechnical Lab., 1-1-4 Umezono, Tsukuba, Ibaraki 305 (JP)); Kuriki, S. (Hokkaido Univ., Sapporo (Japan). Research Inst. of Applied Electricity)

1991-03-01

172

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

PubMed

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

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

2014-12-01

173

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

PubMed

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 La1.85Sr0.15CuO4 thin films develop weak ferromagnetism associated to the charge transfer of spin-polarised electrons from the La0.66Sr0.33MnO3 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

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

174

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

NASA Astrophysics Data System (ADS)

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 La1.85Sr0.15CuO4 thin films develop weak ferromagnetism associated to the charge transfer of spin-polarised electrons from the La0.66Sr0.33MnO3 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.

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.

2014-11-01

175

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

PubMed

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

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

2013-08-15

176

High-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry for the determination of flocoumafen and brodifacoum in whole blood.  

PubMed

A high-performance liquid chromatographic-tandem mass spectrometric (HPLC-MS-MS) assay was developed and validated to determine quantitatively flocoumafen and brodifacoum in whole blood using warfarin as an internal standard (IS). Liquid-liquid extraction, using ethyl acetate, was used to isolate flocoumafen, brodifacoum and the IS from the biological matrix. Detection was performed on a mass spectrometer by negative electrospray ionization (ESI) in multiple reaction monitoring (MRM) mode. The calibration curves were linear (r(2) > 0.998) in the concentration range of 0.1-100.0 ng ml(-1) with a lower limit of quantification of 0.05 ng ml(-1) for flocoumafen, and 0.1 ng ml(-1) for brodifacoum in whole blood. Intra-day and inter-day relative standard deviations (RSDs) were less than 8.0% and 10.8%, respectively. Recoveries of flocoumafen and brodifacoum ranged from 78.0% to 83.7%. This assay can be used to determine trace flocoumafen and brodifacoum in whole blood to investigate suspected poisoning of human and animals. PMID:17177169

Jin, Mi-Cong; OuYang, Xiao-Kun; Chen, Xiao-hong

2007-01-01

177

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

PubMed

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

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

2012-01-01

178

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

PubMed

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

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

2015-02-01

179

Simultaneous determination of ?-Hydroxybutyrate (GHB) and its analogues (GBL, 1.4-BD, GVL) in whole blood and urine by liquid chromatography coupled to tandem mass spectrometry.  

PubMed

A simple liquid chromatography-tandem mass spectrometry (LC-MS-MS) method has been developed and validated for simultaneous identification and quantification of ?-hydroxybutyrate (GHB), ?-butyrolactone (GBL), 1.4-butanediol (1.4-BD), and ?-valerolactone (GVL) in whole blood from forensic cases. The sample preparation of whole blood involved protein precipitation by acidic methanol. Urine samples were diluted and evaluated in relation to a control at the cutoff concentration. Hexadeutero GHB (GHB-d(6)) was used as the internal standard. Separation was achieved by reversed-phase chromatography, and detection was by MS-MS in MRM mode. The linear range for all compounds was from 1.0 to 100 mg/kg in whole blood with a limit of quantification of about 1 mg/kg. The method was validated with regards to selectivity, recovery, accuracy and precision, and stability. The method is currently applied to investigations on suspected drug-facilitated sexual assaults, driving under the influence of drugs, and general intoxication with these substances. PMID:21219697

Johansen, Sys Stybe; Windberg, Charlotte Norup

2011-01-01

180

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

PubMed

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

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

2013-02-01

181

Development and Validation of Amisulpride in Human Plasma by HPLC Coupled with Tandem Mass Spectrometry and its Application to a Pharmacokinetic Study  

PubMed Central

In this study, authors developed a simple, sensitive and specific liquid chromatography–tandem mass spectrometry (LC–MS/MS) method for quantification of Amisulpride in human plasma using Amisulpride-d5 as an internal standard (IS). Chromatographic separation was performed on Zorbax Bonus-RP C18, 4.6 × 75 mm, 3.5 ?m column with an isocratic mobile phase composed of 0.2% formic acid:methanol (35:65 v/v), at a flow-rate of 0.5 mL/min. Amisulpride, Amisulpride-d5 was detected at m/z 370.1?242.1 and 375.1?242.1. The drug and the IS were extracted by a liquid-liquid extraction method. The method was validated over a linear concentration range of 2.0–2500.0 ng/mL for Amisulpride with a correlation coefficient of (r2) ? 0.9982. This method demonstrated intra- and inter-day precision within 0.9 to 1.7 and 1.5 to 2.8 % and intra- and inter-day accuracy within 98.3 to 101.5 and 96.0 to 101.0 % for Amisulpride. Amisulpride was found to be stable at 3 freeze–thaw cycles, bench top and auto sampler stability studies. The developed method was successfully applied to a pharmacokinetic study. PMID:21886905

Mogili, Ramakotaiah; Kanala, Kanchanamala; Challa, Balasekhara Reddy; Chandu, Babu Rao; Bannoth, Chandrasekhar Kottapalli

2011-01-01

182

Determination of eight artificial sweeteners and common Stevia rebaudiana glycosides in non-alcoholic and alcoholic beverages by reversed-phase liquid chromatography coupled with tandem mass spectrometry.  

PubMed

The method for the determination of acesulfame-K, saccharine, cyclamate, aspartame, sucralose, alitame, neohesperidin dihydrochalcone, neotame and five common steviol glycosides (rebaudioside A, rebaudioside C, steviol, steviolbioside and stevioside) in soft and alcoholic beverages was developed using high-performance liquid chromatography and tandem mass spectrometry with electrospray ionisation (HPLC-ESI-MS/MS). To the best of our knowledge, this is the first work that presents an HPLC-ESI-MS/MS method which allows for the simultaneous determination of all EU-authorised high-potency sweeteners (thaumatin being the only exception) in one analytical run. The minimalistic sample preparation procedure consisted of only two operations; dilution and centrifugation. Linearity, limits of detection and quantitation, repeatability, and trueness of the method were evaluated. The obtained recoveries at three tested concentration levels varied from 97.0 to 105.7 %, with relative standard deviations lower than 4.1 %. The proposed method was successfully applied for the determination of sweeteners in 24 samples of different soft and alcoholic drinks. PMID:25471292

Kubica, Pawe?; Namie?nik, Jacek; Wasik, Andrzej

2014-12-01

183

Tandem hydrofoil system  

Microsoft Academic Search

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

Konstantin I. Matveev; Ivan Ivanovich Matveev

2001-01-01

184

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

PubMed

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

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

2014-03-01

185

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

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

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

2013-11-15

186

Liquid chromatography coupled to tandem mass spectrometry and high resolution mass spectrometry as analytical tools to characterize multi-class cytostatic compounds.  

PubMed

Cytostatic compounds used in the treatment of cancer have emerged as a new generation of water contaminants due to the continuous amounts administered to patients and to the fact that a variable proportion is excreted unchanged. In this study, we have evaluated the performance of liquid-chromatography-tandem mass spectrometry (LC-MS/MS) and high resolution mass spectrometry using an Orbitrap analyzer (LC-HRMS) for the multiresidue determination of multi-class cytostatic compounds. In a first step, ionization conditions were tested in positive electrospray mode and optimum fragmentation patterns were determined. For LC-MS/MS, two selected reaction monitoring (SRM) transitions were optimized and for LC-HRMS, the molecular ion with 5 ppm error and two product ions were defined. Following, the chromatographic conditions were optimized considering that compounds analyzed have a very different chemical structure and chromatographic behavior. The best performance was obtained with a Luna C18 column, which permitted the separation of the 26 compounds in 15 min. Finally, the performance of LC-MS/MS and LC-HRMS was compared in terms of linearity, sensitivity, intra and inter-day precision and overall robustness. While LC-MS/MS provided good identification capabilities due to selective SRM transitions, LC-Orbitrap proved to be 100 times more sensitive. This study provides a comprehensive overview on the MS conditions to determine the outmost used cytostatic compounds and provides a spectral library to be used for the identification of these compounds in water or biological matrices. PMID:23313302

Gómez-Canela, Cristian; Cortés-Francisco, Nuria; Ventura, Francesc; Caixach, Josep; Lacorte, Silvia

2013-02-01

187

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

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

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

2012-01-01

188

Separation of isomeric short-chain acyl-CoAs in plant matrices using ultra-performance liquid chromatography coupled with tandem mass spectrometry.  

PubMed

Acyl coenzyme A (acyl-CoA) thioesters are important intermediates in cellular metabolism and being able to distinguish among them is critical to fully understanding metabolic pathways in plants. Although significant advances have been made in the identification and quantification of acyl-CoAs using liquid chromatography tandem mass spectrometry (LC-MS/MS), separation of isomeric species such as isobutyryl- and n-butyrl-CoA has remained elusive. Here we report an ultra-performance liquid chromatography (UPLC)-MS/MS method for quantifying short-chain acyl-CoAs including isomeric species n-butyryl-CoA and isobutyryl-CoA as well as n-valeryl-CoA and isovaleryl-CoA. The method was applied to the analysis of extracts of hop (Humulus lupulus) and provided strong evidence for the existence of an additional structural isomer of valeryl-CoA, 2-methylbutyryl-CoA, as well as an unexpected isomer of hexanoyl-CoA. The results showed differences in the acyl-CoA composition among varieties of Humulus lupulus, both in glandular trichomes and cone tissues. When compared with the analysis of hemp (Cannabis sativa) extracts, the contribution of isobutyryl-CoAs in hop was greater as would be expected based on the downstream polyketide products. Surprisingly, branched chain valeryl-CoAs (isovaleryl-CoA and 2-methylbutyryl-CoA) were the dominant form of valeryl-CoAs in both hop and hemp. The capability to separate these isomeric forms will help to understand biochemical pathways leading to specialized metabolites in plants. PMID:25553535

Purves, Randy W; Ambrose, Stephen J; Clark, Shawn M; Stout, Jake M; Page, Jonathan E

2015-02-01

189

Determination and occurrence of phenoxyacetic Acid herbicides and their transformation products in groundwater using ultra high performance liquid chromatography coupled to tandem mass spectrometry.  

PubMed

A sensitive method was developed and validated for ten phenoxyacetic acid herbicides, six of their main transformation products (TPs) and two benzonitrile TPs in groundwater. The parent compounds mecoprop, mecoprop-p, 2,4-D, dicamba, MCPA, triclopyr, fluroxypr, bromoxynil, bentazone, and 2,3,6-trichlorobenzoic acid (TBA) are included and a selection of their main TPs: phenoxyacetic acid (PAC), 2,4,5-trichloro-phenol (TCP), 4-chloro-2-methylphenol (4C2MP), 2,4-dichlorophenol (DCP), 3,5,6-trichloro-2-pyridinol (T2P), and 3,5-dibromo-4-hydroxybenzoic acid (BrAC), as well as the dichlobenil TPs 2,6-dichlorobenzamide (BAM) and 3,5-dichlorobenzoic acid (DBA) which have never before been determined in Irish groundwater. Water samples were analysed using an efficient ultra-high performance liquid chromatography (UHPLC) method in an 11.9 min separation time prior to detection by tandem mass spectrometry (MS/MS). The limit of detection (LOD) of the method ranged between 0.00008 and 0.0047 µg·L-1 for the 18 analytes. All compounds could be detected below the permitted limits of 0.1 µg·L-1 allowed in the European Union (EU) drinking water legislation [1]. The method was validated according to EU protocols laid out in SANCO/10232/2006 with recoveries ranging between 71% and 118% at the spiked concentration level of 0.06 µg·L-1. The method was successfully applied to 42 groundwater samples collected across several locations in Ireland in March 2012 to reveal that the TPs PAC and 4C2MP were detected just as often as their parent active ingredients (a.i.) in groundwater. PMID:25514054

McManus, Sarah-Louise; Moloney, Mary; Richards, Karl G; Coxon, Catherine E; Danaher, Martin

2014-01-01

190

Amino acid derived Cu(II) compounds as catalysts for asymmetric oxidative coupling of 2-naphthol.  

PubMed

We report the synthesis and characterization of several novel aminopyridine - l-amino acid derived Cu(II)-complexes. The ligands are prepared by a one-pot reductive alkylation of the l-amino acid scaffold and the respective aminopyridine Cu(II)-complexes were obtained by reaction with CuCl2 or Cu(acetato)2. All compounds were characterized by spectroscopic techniques, as well as ESI-MS. Two of the Cu(II)-complexes were characterized by single-crystal X-ray diffraction, one of them, [Cu(II)(L)(CH3COO)] (HL = (S)-3-phenyl-2-(pyridin-2-ylmethylamino)propanoic acid), being the first ever reported aminopyridine-class Cu(II) complex bearing a tridentate N,N,O donor set and a monodentate acetato ligand. The complexes are tested as catalysts in the oxidative coupling of 2-naphthol in organic solvent-water mixtures using dioxygen as the terminal oxidant. The effect of variables such as ligand denticity and substituents, as well as solvent, temperature and oxidant intake, on the overall performance is studied. In general, moderate to low conversions of 2-naphthol to 1,1'-bi-2-naphthol (BINOL) are obtained. The catalysts also showed moderate to low enantioselectivity. Some aspects of the reaction mechanism were elucidated by spectroscopy, electrochemical and theoretical studies. It was found that basic additives are important for activity, but these also increase the formation of secondary oxidation products. The addition of peroxide scavengers such as KI resulted in an increase of conversion, the yield of BINOL and enantioselectivity. PMID:25434677

Adão, Pedro; Barroso, Sónia; Carvalho, M Fernanda N N; Teixeira, Carlos M; Kuznetsov, Maxim L; Costa Pessoa, João

2014-12-23

191

Effects of inductively coupled plasma oxidation on the properties of polycrystalline silicon films and thin film transistors  

NASA Astrophysics Data System (ADS)

We investigated the effects of inductively coupled plasma (ICP) oxidation on the properties of polycrystalline silicon (poly-Si) films and thin film transistors (TFTs). The ICP oxidation in oxygen plasma passivated the dangling bonds in the poly-Si films, not by oxygen incorporation but by hydrogen incorporation; but the incorporated hydrogen diffused out during the TFT fabrication, so that the effect of the dangling bond passivation was not obtained in the TFT. The ICP oxidation did not remove the intragranular defects such as microtwins and stacking faults, but it reduced the interface trap density and also improved the performance of the poly-Si TFT. The field effect mobility of TFT with an ICP oxide and low-pressure chemical vapor deposited (LPCVD) oxide double layer was 30.6 cm2/V s, while that of TFT with only a LPCVD oxide was 17.2 cm2/V s.

Choi, Yong Woo; Park, Sang Won; Ahn, Byung Tae

1999-05-01

192

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

USGS Publications Warehouse

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.

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

2008-01-01

193

Weathering of the Rio Blanco Quartz Diorite, Luquillo Mountains, Puerto Rico: Coupling Oxidation, Dissolution, And Fracturing  

SciTech Connect

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 ({approx}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 {Delta}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 {angstrom}, 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 x 10{sup -14} mol biotite m{sup -2} s{sup -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 {micro}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 x 10{sup -13} mol hornblende m{sup -2} s{sup -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 O{sub 2} at the bedrock-saprolite interface.

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

2009-05-12

194

Quantitative determination of perchlorate in bottled water and tea with online solid phase extraction high-performance liquid chromatography coupled to tandem mass spectrometry.  

PubMed

Due to the similarity in ionic radius, perchlorate has been reported to inhibit the iodide intake in the thyroid gland, which may lead to low heart rate, weight gain, and fatigue. In recent years, the presence of perchlorate in drinking water, surface water, soil, and food supplies in the United States has raised a great concern on establishing the maximum residue limit (MRL) for perchlorate to reduce its possible adverse influence on human health. US EPA currently puts perchlorate on the final third Contamination Candidate List (CCL3) and suggests a health reference level at 4.9 ?g L?¹. The MRL of perchlorate was therefore set at 5.0 ?g L?¹ by the authors for method validation. In this study, large volume injection (up to 1-mL) and online solid phase extraction (SPE) were utilized for pre-concentrating perchlorate ions and removing unretained matrix components prior to reversed-phase HPLC analysis using ESI-tandem MS under the negative mode. After eluting perchlorate from online SPE, 0.1% formic acid solution was utilized for isocratic HPLC analysis without any organic solvent. Multiple reaction monitoring (MRM) and the internal standard, Cl??O??, were utilized for quantitatively determining perchlorate in bottled water and bottled tea samples. Two linear ranges, 0.05-0.50 ?g L?¹ and 0.50-10.00 ?g L?¹, were established to better estimate the residual amounts of perchlorate in bottled water samples with a method detection limit (MDL, signal-to-noise ratio of 3) of 0.01 ?g L?¹. The linear range was 1.50-10.00 ?g L?¹ for bottled tea samples with a MDL of 0.5 ?g L?¹. In addition, the proposed method was further validated based on the EU Commission Decision 2002/657/EC, including within-laboratory reproducibility, decision limit (CC?), and detection capability (CC?) for bottled water and bottled tea samples. The intra-day/inter-day precision and accuracy as well as within-laboratory reproducibility were determined by calculating the relative standard deviation (RSD) at three spiked levels (0.5 MRL, 1 MRL, 1.5 MRL). The within-laboratory reproducibility (n=18) for both bottled water and bottled tea samples, spiked at MRL (5.0 ?g L?¹) of ClO??, was less than 10%. The values of CC?/CC? were reported as 5.43/5.74 ?g L?¹ and 5.03/5.75 ?g L?¹ for bottled water and bottled tea samples, respectively. PMID:22365567

Lin, Shu-Ling; Lo, Chih-Yu; Fuh, Ming-Ren

2012-07-13

195

Oxidative coupling of methane over lanthana catalysts: II. A mechanistic study using isotope transient kinetics  

SciTech Connect

The elementary steps dealing with the methane and oxygen activation in the reaction of oxidative coupling of methane (OCM) over lanthana catalysts have been investigated by means of state-of-the-art transient kinetic techniques. Methane and oxygen activation over lanthana catalysts are shown to combine reversible and irreversible steps, parallel for methane and consecutive for oxygen. In both processes, the surface residence time of activated species per active site is found to be below the time resolution of 1 ms, characteristic of the temporal analysis of products reactor. Evidence of a strong interaction between gaseous and lattice oxygen and of an inhibiting effect of carbon dioxide on both methane and oxygen activation is also provided. Specific sites pertaining to each of these routes are proposed, accounting for the various kinetic effects which are observed under the OCM conditions.

Lacombe, S.; Mirodatos, C. [Institut de Recherches sur la Catalyse, Villeurbanne (France)] [Institut de Recherches sur la Catalyse, Villeurbanne (France); Zanthoff, H. [Ruhr-Universitaet Bochum (Germany)] [Ruhr-Universitaet Bochum (Germany)

1995-08-01

196

Proteolytic cleavage of Opa1 stimulates mitochondrial inner membrane fusion and couples fusion to oxidative phosphorylation.  

PubMed

Mitochondrial fusion is essential for maintenance of mitochondrial function. The mitofusin GTPases control mitochondrial outer membrane fusion, whereas the dynamin-related GTPase Opa1 mediates inner membrane fusion. We show that mitochondrial inner membrane fusion is tuned by the level of oxidative phosphorylation (OXPHOS), whereas outer membrane fusion is insensitive. Consequently, cells from patients with pathogenic mtDNA mutations show a selective defect in mitochondrial inner membrane fusion. In elucidating the molecular mechanism of OXPHOS-stimulated fusion, we uncover that real-time proteolytic processing of Opa1 stimulates mitochondrial inner membrane fusion. OXPHOS-stimulated mitochondrial fusion operates through Yme1L, which cleaves Opa1 more efficiently under high OXPHOS conditions. Engineered cleavage of Opa1 is sufficient to mediate inner membrane fusion, regardless of respiratory state. Proteolytic cleavage therefore stimulates the membrane fusion activity of Opa1, and this feature is exploited to dynamically couple mitochondrial fusion to cellular metabolism. PMID:24703695

Mishra, Prashant; Carelli, Valerio; Manfredi, Giovanni; Chan, David C

2014-04-01

197

Determination of carbendazim in soil and lake water by immunoaffinity extraction and coupled-column liquid chromatography–tandem mass spectrometry  

Microsoft Academic Search

A method employing a high-performance protein G immunoaffinity column coupled to a reversed-phase analytical column through the use of a trapping column and INTEGRAL Micro-Analytical Workstation for the extraction of carbendazim from lake water samples and soil extracts is described. Characterization of the target analyte is achieved by on-line mass spectrometric analysis. The specificity of immunoaffinity extraction makes it possible

Karen A. Bean; Jack D. Henion

1997-01-01

198

Analysis of phospholipid species in human blood using normal-phase liquid chromatography coupled with electrospray ionization ion-trap tandem mass spectrometry  

Microsoft Academic Search

A narrow-bore normal-phase high-performance liquid chromatography (HPLC) method was developed for separation of phospholipid classes in human blood. The separation was obtained using an HPLC diol column and a gradient of chloroform and methanol with 0.1% formic acid, titrated to pH 5.3 with ammonia and added 0.05% triethylamine. The HPLC system was coupled on-line with an electrospray ionisation ion-trap mass

Steinar Uran; Åsmund Larsen; Petter Balke Jacobsen; Tore Skotland

2001-01-01

199

Mechanistic study of silver-mediated furan formation by oxidative coupling.  

PubMed

Density functional calculations and experiments have been carried out to unravel the mechanism of a silver-mediated furan formation by oxidative coupling. Various possible reaction paths were considered and the most favorable channel has been identified on the basis of the calculated solvent-corrected Gibbs free-energy profiles. The mechanism represented by this route consists of a radical and a subsequent ionic route. The silver cation has a double role in the mechanism: it is the oxidant in the radical steps and the catalyst for the ionic steps, which is in accordance with the experimental observations. The two most important aspects of the optimal route are the formation of a silver-acetylide, reacting subsequently with the enolate radical, and the aromatic furan-ring formation in a single step at the latter, ionic segment of the reaction path. Our findings could explain several experimental observations, including the "key-promoter role" of silver, the preference for ionic cyclization, and the reduced reactivity of internal acetylides. PMID:25284602

Daru, János; Benda, Zsuzsanna; Póti, Ádám; Novák, Zoltán; Stirling, András

2014-11-17

200

Report on three aliphatic dimethylarsinoyl compounds as common minor constituents in marine samples. An investigation using high-performance liquid chromatography/inductively coupled plasma mass spectrometry and electrospray ionisation tandem mass spectrometry.  

PubMed

Three water-soluble aliphatic arsenicals, dimethylarsinoyl acetate (DMAA), dimethylarsinoyl ethanol (DMAE), and dimethylarsinoyl propionate (DMAP), were identified in marine biological samples. Sample extracts in methanol/water (1 + 1) were analysed by cation-exchange high-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC/ICPMS). Eluate fractions from the HPLC/ICPMS analyses containing the compounds in question were collected and subjected to analysis by electrospray ionisation tandem mass spectrometry (ESI-MS/MS), which provided supportive evidence for the structures of the three compounds. The concentrations of the three arsenicals were determined in 37 marine organisms comprising algae, crustaceans, bivalves, fish and mammals by HPLC/ICPMS. The three arsenicals DMAA, DMAE and DMAP, which occurred at microg kg(-1) concentrations, were detected in 25, 23 and 17 of the 37 samples analysed, respectively. The limits of detection were 2-3 microg kg(-1) dry mass. The data illustrate that the three compounds are common minor constituents in marine samples. This is the first report on DMAE and DMAP as naturally occurring species in marine samples. The presence of DMAA and DMAE supports a proposed biosynthesis of arsenobetaine (AB) from dimethylarsinoylribosides. Alternative proposals, which explain the presence of the compounds in marine samples, are addressed briefly in the paper. PMID:15593252

Sloth, Jens J; Larsen, Erik H; Julshamn, Kåre

2005-01-01

201

A new approach for the estimation of expanded uncertainty of results of an analytical method developed for determining antibiotics in seawater using solid-phase extraction disks and liquid chromatography coupled with tandem mass spectrometry technique.  

PubMed

Although the uncertainty estimate should be a necessary component of an analytical result, the presentation of measurements together with their uncertainties is still a serious problem, especially in the monitoring of the presence of pharmaceuticals in the environment. Here we discuss the estimation of expanded uncertainty in analytical procedures for determining residues of twelve pharmaceuticals in seawaters using solid-phase extraction (SPE) with H2O-Philic BAKERBOND speed disks and liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Matrix effects, extraction efficiency and absolute recovery of the developed analytical method were determined. A validation was performed to obtain the method's linearity, precision, accuracy, limits of detection (LODs) and quantification (LOQs). The expanded uncertainty of the data obtained was estimated according to the Guide to the Expression of Uncertainty in Measurement and ISO 17025:2005 standard. We applied our method to the analysis of drugs in seawaters samples from the coastal area of the southern Baltic Sea. As a result, a new approach (concerning the uncertainty estimation as well as the development of analytical method) to the analysis of pharmaceutical residues in environmental samples is presented. The information given here should facilitate the introduction of uncertainty estimation in chromatographic measurements on a much greater scale than is currently the case. PMID:23885670

Borecka, Marta; Bia?k-Bieli?ska, Anna; Siedlewicz, Grzegorz; Kornowska, Kinga; Kumirska, Jolanta; Stepnowski, Piotr; Pazdro, Ksenia

2013-08-23

202

Rapid separation and characterization of diterpenoid alkaloids in processed roots of Aconitum carmichaeli using ultra high performance liquid chromatography coupled with hybrid linear ion trap-Orbitrap tandem mass spectrometry.  

PubMed

The lateral root of Aconitum carmichaeli, a popular traditional Chinese medicine, has been widely used to treat rheumatic diseases. For decades, diterpenoid alkaloids have dominated the phytochemical and biomedical research on this plant. In this study, a rapid and sensitive method based on ultra high performance liquid chromatography coupled with linear ion trap-Orbitrap tandem mass spectrometry was developed to characterize the diterpenoid alkaloids in Aconitum carmichaeli. Based on an optimized chromatographic condition, more than 120 diterpenoid alkaloids were separated with good resolution. Using a systematic strategy that combines high resolution separation, highly accurate mass measurements and a good understanding of the diagnostic fragment-based fragmentation patterns, these diterpenoid alkaloids were identified or tentatively identified. The identification of these chemicals provided essential data for further phytochemical studies and toxicity research of Aconitum carmichaeli. Moreover, the ultra high performance liquid chromatography with linear ion trap-Orbitrap mass spectrometry platform was an effective and accurate tool for rapid qualitative analysis of secondary metabolite productions from natural resources. PMID:25124198

Xu, Wen; Zhang, Jing; Zhu, Dayuan; Huang, Juan; Huang, Zhihai; Bai, Junqi; Qiu, Xiaohui

2014-10-01

203

On-line solid-phase extraction of large-volume injections coupled to liquid chromatography-tandem mass spectrometry for the quantitation and confirmation of 14 selected trace organic contaminants in drinking and surface water.  

PubMed

We describe the development and validation of an on-line solid-phase extraction of large-volume injections coupled to liquid chromatography-tandem mass spectrometry method for the simultaneous quantitation and confirmation of 14 selected trace organic contaminants in drinking and surface water. Selected compounds were: anti-infectives (clarithromycin, sulfamethoxazole and trimethoprim), an anticonvulsant (carbamazepine) and its transformation product 10,11-dihydrocarbamazepine, an antihypertensive (enalapril), antineoplastics (cyclophosphamide and methotrexate), herbicides (atrazine, cyanazine, and simazine) and two of their transformation products (deethylatrazine and deisopropylatrazine) and an antiseptic (triclocarban). The breakthrough volume determinations showed that out of all the investigated sorbents, the Strata-X on-line solid-phase extraction column showed the best performance. The method used a load volume of 10.0 mL and was validated using the corresponding matrices, yielding for most compounds, R(2)>0.99. Extraction recoveries ranged from 60 to 109%. The intra- and inter-day precision were <14 and <16%, respectively. The method detection limits ranged from 0.6 to 6 ng L(-1). Matrix effects were in general low. The performance of the on-line method was demonstrated with the analysis of real water samples. The application of alternative techniques of confirmation was also explored using accurate mass measurements on a time-of-flight mass spectrometer and the data-dependent reverse energy ramp scan on a triple quadrupole. PMID:19875124

Garcia-Ac, Araceli; Segura, Pedro A; Viglino, Liza; Fürtös, Alexandra; Gagnon, Christian; Prévost, Michèle; Sauvé, Sébastien

2009-11-27

204

Simultaneous determination of testosterone, cortisol, and dehydroepiandrosterone in saliva by stable isotope dilution on-line in-tube solid-phase microextraction coupled with liquid chromatography-tandem mass spectrometry.  

PubMed

We have developed a simple and sensitive method for the simultaneous determination of testosterone (TES), cortisol (CRT), and dehydroepiandrosterone (DHEA) in saliva by automated online in-tube solid-phase microextraction (SPME) coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) using a Discovery HS F5 column. The optimum in-tube SPME conditions were 25 draw/eject cycles of 40 ?L of sample at a flow rate of 200 ?L/min using a Supel-Q PLOT capillary column as an extraction device. The extracted compounds were easily desorbed from the capillary by passage of the mobile phase, and no carryover was observed. The in-tube SPME LC-MS/MS method showed good linearity with correlation coefficients r ? 0.9998 for TES, CRT, and DHEA using their respective stable isotope-labeled internal standards. The intra-day and inter-day precisions (relative standard deviations) were below 4.9 and 8.5 % (n = 5), respectively. This method was successfully utilized to analyze TES, CRT, and DHEA in saliva samples without any other pretreatment or interference peaks, and the quantification limits (S/N = 10) of TES, CRT and DHEA were about 0.01, 0.03 and 0.29 ng/mL saliva, respectively. The recoveries of these compounds spiked into saliva samples were each above 94%. This method was applied to analyze changes in salivary TES, CRT, and DHEA levels resulting from stress and fatigue load. PMID:23064711

Kataoka, Hiroyuki; Ehara, Kentaro; Yasuhara, Rie; Saito, Keita

2013-01-01

205

Solar water oxidation using nickel-borate coupled BiVO4 photoelectrodes.  

PubMed

A naturally abundant nickel-borate (Ni-Bi) complex is demonstrated to successfully catalyze the photoelectrochemical (PEC) water oxidation of BiVO4 electrodes at 1.23 VRHE with nearly 100% faradaic efficiency for oxygen evolution. Ni-Bi is electrodeposited (ED) and photodeposited (PD) for varying times on BiVO4 electrodes in the 0.1 M borate electrolyte with 1 mM Ni(2+) at pH 9.2. Surprisingly, optimally deposited Ni-Bi films (ED-10 s and PD-30 min) display the same layer thickness of ca. 40 nm. Both Ni-Bi films enhance the photocurrent generation of BiVO4 at 1.23 VRHE by a factor of 3-4 under AM 1.5-light irradiation (100 mW cm(-2)) along with ca. 250% increase in the incident and absorbed photon-to-current efficiencies. Impedance analysis further reveals that the charge transfer resistance at BiVO4 is markedly decreased by Ni-Bi deposits. The primary role of Ni-Bi has been suggested to be a hole-conductor making photogenerated electrons more mobile and catalyzing a four-hole transfer to water through cyclic changes between the lower and higher Ni oxidation states. However, thick Ni-Bi films (>~40 nm) significantly reduce the PEC performance of BiVO4 due to the kinetic bottleneck and charge recombination. Under identical PEC conditions (0.1 M, pH 9.2), the borate electrolyte (good proton acceptor) is found to be better than nitrate (poor proton acceptor), indicative of a proton-coupled electron transfer pathway in PEC water oxidation. PMID:23529529

Choi, Sung Kyu; Choi, Wonyong; Park, Hyunwoong

2013-05-01

206

Using ultrashort optical pulses to couple ferroelectric and ferromagnetic order in an oxide heterostructure  

NASA Astrophysics Data System (ADS)

A new approach to all-optical detection and control of the coupling between electric and magnetic order on ultrafast timescales is achieved using time-resolved second-harmonic generation (SHG) to study a ferroelectric (FE)/ferromagnet (FM) oxide heterostructure. We use femtosecond optical pulses to modify the spin alignment in a Ba0.1Sr0.9TiO3 (BSTO)/La0.7Ca0.3MnO3 (LCMO) heterostructure and selectively probe the ferroelectric response using SHG. In this heterostructure, the pump pulses photoexcite non-equilibrium quasiparticles in LCMO, which rapidly interact with phonons before undergoing spin–lattice relaxation on a timescale of tens of picoseconds. This reduces the spin–spin correlations in LCMO, applying stress on BSTO through magnetostriction. This then modifies the FE polarization through the piezoelectric effect, on a timescale much faster than laser-induced heat diffusion from LCMO to BSTO. We have thus demonstrated an ultrafast indirect magnetoelectric effect in a FE/FM heterostructure mediated through elastic coupling, with a timescale primarily governed by spin–lattice relaxation in the FM layer.

Sheu, Y. M.; Trugman, S. A.; Yan, L.; Jia, Q. X.; Taylor, A. J.; Prasankumar, R. P.

2014-12-01

207

Using ultrashort optical pulses to couple ferroelectric and ferromagnetic order in an oxide heterostructure.  

PubMed

A new approach to all-optical detection and control of the coupling between electric and magnetic order on ultrafast timescales is achieved using time-resolved second-harmonic generation (SHG) to study a ferroelectric (FE)/ferromagnet (FM) oxide heterostructure. We use femtosecond optical pulses to modify the spin alignment in a Ba0.1Sr0.9TiO3 (BSTO)/La0.7Ca0.3MnO3 (LCMO) heterostructure and selectively probe the ferroelectric response using SHG. In this heterostructure, the pump pulses photoexcite non-equilibrium quasiparticles in LCMO, which rapidly interact with phonons before undergoing spin-lattice relaxation on a timescale of tens of picoseconds. This reduces the spin-spin correlations in LCMO, applying stress on BSTO through magnetostriction. This then modifies the FE polarization through the piezoelectric effect, on a timescale much faster than laser-induced heat diffusion from LCMO to BSTO. We have thus demonstrated an ultrafast indirect magnetoelectric effect in a FE/FM heterostructure mediated through elastic coupling, with a timescale primarily governed by spin-lattice relaxation in the FM layer. PMID:25534775

Sheu, Y M; Trugman, S A; Yan, L; Jia, Q X; Taylor, A J; Prasankumar, R P

2014-01-01

208

Phase diagrams of voltage-gated oxide interfaces with strong Rashba coupling  

NASA Astrophysics Data System (ADS)

We propose a model for the two-dimensional electron gas formed at the interface of oxide heterostructures that includes a Rashba spin-orbit coupling proportional to an electric field oriented perpendicularly to the interface. Taking into account the electron density dependence of this electric field confining the electron gas at the interface, we report the occurrence of a phase separation instability (signaled by a negative compressibility) for realistic values of the spin-orbit coupling and of the electronic band-structure parameters at zero temperature. We extend the analysis to finite temperatures and in the presence of an in-plane magnetic field, thereby obtaining two phase diagrams that exhibit a phase separation dome. By varying the gating potential, the phase separation dome may shrink and vanish at zero temperature into a quantum critical point where the charge fluctuates dynamically. Similarly, the phase separation may be spoiled by a planar magnetic field even at zero temperature leading to a line of quantum critical points.

Bucheli, D.; Grilli, M.; Peronaci, F.; Seibold, G.; Caprara, S.

2014-05-01

209

Kinetic effects of increased proton transfer distance on proton-coupled oxidations of phenol-amines.  

PubMed

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 CPh(2)NH(2) substituent (1). Spectroscopic, structural, thermochemical, and computational studies show that the two amino-phenols are very similar, except that the O···N distance (d(ON)) is >0.1 Å longer in 2 than in 1. The difference in d(ON) 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-NH(3)(+) 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. 2 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(C(6)H(4)OMe)(3)(•+) (3a(+)) occurs at (1.4 ± 0.1) × 10(4) M(-1) s(-1), only a factor of 2 slower than the closely related reaction of 1 with N(C(6)H(4)OMe)(2)(C(6)H(4)Br)(•+) (3b(+)). This difference in rate constants is well accounted for by the slightly different free energies of reaction: ?G° (2 + 3a(+)) = +0.078 V versus ?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(K(eq))). 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

Markle, Todd F; Rhile, Ian J; Mayer, James M

2011-11-01

210

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

PubMed

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

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

2014-11-14

211

Probing catalytic activity of halide salts by electrical conductivity in the coupling reaction of CO2 and propylene oxide.  

PubMed

In the water-assisted coupling reaction of CO(2) and propylene oxide (PO) catalyzed by halide salts, the PO conversion was closely correlated with the electrical conductivity, suggesting that simple conductivity measurements might be used as a potential method for the selection of the catalyst. PMID:20625586

Guo, Liping; Wang, Congmin; Luo, Xiaoyan; Cui, Guokai; Li, Haoran

2010-08-28

212

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

PubMed Central

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

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

2014-01-01

213

A novel validated procedure for the determination of nicotine, eight nicotine metabolites and two minor tobacco alkaloids in human plasma or urine by solid-phase extraction coupled with liquid chromatography-electrospray ionization-tandem mass spectrometry.  

PubMed

A novel validated liquid chromatography-tandem mass spectrometry (LC-MS/MS) procedure was developed and fully validated for the simultaneous determination of nicotine-N-beta-D-glucuronide, cotinine-N-oxide, trans-3-hydroxycotinine, norcotinine, trans-nicotine-1'-oxide, cotinine, nornicotine, nicotine, anatabine, anabasine and cotinine-N-beta-D-glucuronide in human plasma or urine. Target analytes and corresponding deuterated internal standards were extracted by solid-phase extraction and analyzed by LC-MS/MS with electrospray ionization (ESI) using multiple reaction monitoring (MRM) data acquisition. Calibration curves were linear over the selected concentration ranges for each analyte, with calculated coefficients of determination (R(2)) of greater than 0.99. The total extraction recovery (%) was concentration dependent and ranged between 52-88% in plasma and 51-118% in urine. The limits of quantification for all analytes in plasma and urine were 1.0 ng/mL and 2.5 ng/mL, respectively, with the exception of cotinine-N-beta-D-glucuronide, which was 50 ng/mL. Intra-day and inter-day imprecision were < or = 14% and < or = 17%, respectively. Matrix effect (%) was sufficiently minimized to < or = 19% for both matrices using the described sample preparation and extraction methods. The target analytes were stable in both matrices for at least 3 freeze-thaw cycles, 24 h at room temperature, 24 h in the refrigerator (4 degrees C) and 1 week in the freezer (-20 degrees C). Reconstituted plasma and urine extracts were stable for at least 72 h storage in the liquid chromatography autosampler at 4 degrees C. The plasma procedure has been successfully applied in the quantitative determination of selected analytes in samples collected from nicotine-abstinent human participants as part of a pharmacokinetic study investigating biomarkers of nicotine use in plasma following controlled low dose (7 mg) transdermal nicotine delivery. Nicotine, cotinine, trans-3-hydroxycotinine and trans-nicotine-1'-oxide were detected in the particular sample presented herein. The urine procedure has been used to facilitate the monitoring of unauthorized tobacco use by clinical study participants at the time of physical examination (before enrollment) and on the pharmacokinetic study day. PMID:20097626

Miller, Eleanor I; Norris, Hye-Ryun K; Rollins, Douglas E; Tiffany, Stephen T; Wilkins, Diana G

2010-03-15

214

Palladium-Catalyzed Regioselective Benzylation-Annulation of Pyridine N-Oxides with Toluene Derivatives via Multiple C-H Bond Activations: Benzylation versus Arylation.  

PubMed

A palladium-catalyzed cross-dehydrogenative coupling (CDC) reaction of pyridine N-oxides with toluenes has been developed that operates under mild conditions. 2-Benzylpyridines can be obtained directly by this method via a CDC reaction between unactivated toluenes and pyridine N-oxides. In addition, azafluorene N-oxides, of value for future medicinal chemistry applications, can be obtained successfully by this procedure via four tandem C-H bond activations. PMID:25607468

Kianmehr, Ebrahim; Faghih, Nasser; Khan, Khalid Mohammed

2015-02-01

215

Nitric oxide contracts longitudinal smooth muscle of opossum oesophagus via excitation-contraction coupling  

PubMed Central

The effects of sodium nitroprusside (SNP) and diethylenetriamine/nitric oxide adduct (DETA/NO), putative nitric oxide (NO) donors, on opossum oesophageal longitudinal smooth muscle were investigated using isometric tension and intracellular micro-electrode recordings.SNP produced concentration-dependent contractions of oesophageal longitudinal smooth muscle with an EC50 of 239.6 ± 78.2 ?m (mean ±s.e.m., n = 10). Maximal contraction induced by SNP (1 mm) was about 75.5 ± 8.5 % (n = 10) of the 60 mm KCl-induced contraction. The SNP-induced contraction was resistant to tetrodotoxin (TTX; 1 ?m), but abolished by nifedipine (1 ?m), as well as by niflumic acid (300 ?m) and 9-anthroic acid (9-AC; 1 mm), Ca2+-activated Cl? channel blockers.DETA/NO at concentrations of 100 and 500 ?m induced 83.1 ± 24.4 and 104.1 ± 34.9 % of the 60 mm KCl-induced contraction (n = 4), respectively, which was abolished by nifedipine (1 ?m), niflumic acid (300 ?m) and 9-AC (1 mm).Pre-application of 1H-[1,2,4]oxidiazolo[4,3,-?]quinoxalin-1-one (ODQ) (10 ?m), a guanylate cyclase inhibitor, significantly inhibited the SNP-induced contraction, whereas 8-bromo-cGMP (1 mm), a membrane-permeable analogue of cGMP, mimicked the SNP-induced contraction.Intracellular recordings revealed that SNP (300 ?m) depolarized resting membrane potentials (RMPs) and increased the frequency of spontaneous spike-like action potentials. However, these electrical alterations were eliminated by pretreatment with niflumic acid (300 ?m).These results suggest that NO produces an excitation-contraction coupling in opossum oesophageal longitudinal smooth muscle via a cGMP-dependent signalling pathway. This contraction depends on extracellular Ca2+ entry through activation of L-type Ca2+ channels. PMID:11579163

Zhang, Yong; Paterson, William G

2001-01-01

216

Biological oxidation of Fe(II) in reduced nontronite coupled with nitrate reduction by Pseudogulbenkiania sp. Strain 2002  

NASA Astrophysics Data System (ADS)

The importance of microbial nitrate-dependent Fe(II) oxidation to iron biogeochemistry is well recognized. Past research has focused on oxidation of aqueous Fe2+ and structural Fe(II) in oxides, carbonates, and phosphate, but the importance of structural Fe(II) in phyllosilicates in this reaction is only recently studied. However, the effect of clay mineralogy on the rate and the mechanism of the reaction, and subsequent mineralogical end products are still poorly known. The objective of this research was to study the coupled process of microbial oxidation of Fe(II) in clay mineral nontronite (NAu-2), and nitrate reduction by Pseudogulbenkiania species strain 2002, and to determine mineralogical changes associated with this process. Bio-oxidation experiments were conducted using Fe(II) in microbially reduced nontronite as electron donor and nitrate as electron acceptor in bicarbonate-buffered medium under both growth and nongrowth conditions to investigate cell growth on this process. 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 NAu-2. The bio-oxidation extent under growth and nongrowth conditions reached 67% and 57%, respectively. Over the same time period, nitrate was completely reduced under both conditions to nitrogen gas (N2), via an intermediate product nitrite. Abiotic oxidation by nitrite partly accelerated Fe(II) oxidation rate under the growth condition. The oxidized Fe(III) largely remained in the nontronite structure, but secondary minerals such as vivianite, ferrihydrite, and magnetite formed depending on specific experimental conditions. 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 natural environments.

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

2013-10-01

217

Analysis of anthelmintics in surface water by ultra high performance liquid chromatography coupled to quadrupole linear ion trap tandem mass spectrometry.  

PubMed

A method based on ultra high performance liquid chromatography coupled to quadrupole linear ion trap mass spectrometry (UHPLC-QqLIT-MS) has been developed to investigate occurrence of 10 anthelmintic drugs from different structural groups (moxidectin, flubendazole, fenbendazole, levamisol, mebendazole, oxibendazole, albendazole, triclabendazole, febantel and praziquantel) in surface water. Analytes were pre-concentrated by solid phase extraction (SPE) using hydrophilic-lipophilic polymeric based sorbent. Quantification of investigated analytes was done using deuterated compounds as internal standards in order to minimize matrix effect. Analyte recoveries from spiked samples at two concentration levels were above 75% for most of the analytes. The main advantages of developed method are fast separation using UHPLC and therefore short analysis time, combined with good sensitivity which is demonstrated by low ngL(-1) detection limits. The developed method was applied for analysis of anthelmintics in the Llobregat River (NE Spain) and its main tributaries (rivers Anoia and Cardener). Eight out of ten anthelmintics were detected in all analyzed samples with the concentrations in low ngL(-1) level. The method fills the gap on analytical methodologies for determination of anthelmintic drugs in the environment. PMID:24289978

Zrn?i?, Mirta; Gros, Meritxell; Babi?, Sandra; Kaštelan-Macan, Marija; Barcelo, Damia; Petrovi?, Mira

2014-03-01

218

Fabrication of an on-line enzyme micro-reactor coupled to liquid chromatography-tandem mass spectrometry for the digestion of recombinant human erythropoietin.  

PubMed

Our aim was to develop a fast and efficient on-line method using micro-reactors for the digestion and deglycosylation of recombinant human erythropoietin extracted from equine plasma. The trypsin digestion micro reactors were fabricated using fused silica capillaries with either a dextran-modified coating or a porous monolith that was able to immobilise the enzyme. These were both found to be reasonably robust and durable, with the trypsin immobilised on dextran-modified fused silica capillaries offering better reproducibility than the micro-reactor based upon covalent attachment of this enzyme to the polymer. It is also evident that the enzyme attached micro reactors produced some tryptic peptides in a greater yield than in-solution digestion. A peptide-N-glycosidase F reactor was also fabricated and, when coupled with the trypsin reactor, the deaminated peptides T5 DAM and T9 DAM from recombinant human erythropoietin could also be detected by LC-ESI-MS/MS analysis. These results were better than those achieved using off-line digestion plus deglycosylation reactions and the analysis required far less time and effort to complete. The use of this on-line approach improved the sensitivity, efficiency and speed of our confirmation methodology that is based upon detecting the unique peptide segments of recombinant human erythropoietin that has been affinity extracted from positive equine plasma samples. PMID:25640120

Foo, Hsiao Ching; Smith, Norman W; Stanley, Shawn M R

2015-04-01

219

Multiresidue pesticide analysis of tuber and root commodities by QuEchERS extraction and ultra-performance liquid chromatography coupled to tandem mass spectrometry.  

PubMed

A simple, rapid, and reliable multiresidue method to determine 84 pesticides in potato and carrot samples by ultra-performance liquid chromatography coupled to MS/MS has been developed and fully validated for routine analysis according to ISO/IEC 17025:2005. The method makes use of a buffered Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) sample preparation procedure based on a single extraction with acidified acetonitrile, followed by partitioning with salts. Chromatographic conditions were optimized in order to achieve a rapid separation in the multiple reaction monitoring mode. Performance characteristics of the method, including an estimation of measurement uncertainty using validation data, are reported for both matrixes. Calibration curves were linear from 0.010 to 0.150 mg/kg for most compounds. The LOD and LOQ were 0.006 and 0.010 mg/kg, respectively, except for fluorocloridone, fluquinconazol, and hexitiazox, which were 0.030 and 0.050 mg/kg, respectively. Recoveries obtained were in the range 70-116%, with intraday precision values < or = 20% RSD and interday precision values < or = 25% RSD at two different concentration levels. The overall uncertainty of the method was estimated at two concentrations as being lower than 34% in all cases. The method has been applied to the analysis of 70 vegetable samples, and imidacloprid and linuron were the pesticides most frequently found in potato and carrot commodities, respectively. PMID:23175961

Garrido Frenich, Antonia; Martín Fernández, María del Mar; Díaz Moreno, Laura; Martínez Vidal, Jose Lúis; López-Gutiérrez, Noelia

2012-01-01

220

Online molecularly imprinted solid-phase extraction coupled to liquid chromatography-tandem mass spectrometry for the determination of hormones in water and sediment samples.  

PubMed

The molecularly imprinted SPE directly coupled to RP LC-MS/MS method has been developed and successfully validated for the determination of six hormones in water and sediment samples. The method is based on the use the home-made column filled with a molecularly imprinted sorbent (imprinted against estrogens) that was used under nonaqueous conditions. Thus, its high selectivity could be utilized resulting in low matrix components' coextraction. The method showed excellent recovery (92-105%) and satisfactory sensitivity (LOQs water: 1.9-4.0 ng/L; LOQs sediment: 0.2-0.5 ng/g). The intra- and interprecision for water and sediment was in the range of 4.0-6.0% and 4.4-7.6%, respectively. Finally, 20 water and sediment samples collected from the Svratka river were analyzed. Only estrone was quantified in eight water samples (4.4-7.1 ng/L); no analytes were found in sediment samples. PMID:23441059

Mat?jí?ek, David; Vl?ek, Ji?í; Burešová, Alena; Pelcová, Pavlína

2013-05-01

221

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

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

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

2014-08-22

222

Rapid and efficient purification of chrysophanol in Rheum Palmatum LINN by supercritical fluid extraction coupled with preparative liquid chromatography in tandem.  

PubMed

Chrysophanol has high pharmaceutical values. However, it was difficult to use the traditional extraction method to extract high-concentration chrysophanol. Therefore, the purpose of this study is to purify and separate chrysophanol in traditional herb, Rheum Palmatum LINN, by using supercritical fluid extraction (SFE) and preparative high-performance liquid chromatography (P-HPLC) for rapid and large-scale isolation. The method is efficient for selective extraction of chrysophanol from the herbs, which have complex compositions. The extraction efficiency of chrysophanol with SFE is 25 × higher than that of boiled water extraction under the same extraction time. The optimal conditions for SFE were 210 atm and 85 °C for 30 min; for P-HPLC, a C18 column was used with a gradient elution of methanol and 1% acetic acid at a flow rate of 10 mL/min. According to (1)H NMR and LC-MS analyses, the purity of the isolated chrysophanol was as high as 99%. The recovery for chrysophanol in Rheum after SPE/PHPLC processing was in the range of 88-91.5%. Compared with other extraction and purification methods, the sequential system (SFE/P-HPLC) achieved the highest amount of extracted chrysophanol from Rheum Palmatum LINN (0.38 mg/g) and the shortest run time (3h). Hence, this rapid and environmentally friendly method can separate compounds based on polarity with high efficiencies and, coupled with P-HPLC, it may be applicable in the large-scale production of foods and medicines in the future. PMID:22436825

Lo, Tiffany Chien-Ting; Nian, Hung-Chi; Chiu, Kong-Hwa; Wang, Ai-Yih; Wu, Ben-Zen

2012-04-15

223

Isolation and tandem mass fragmentations of an anti-inflammatory compound from Aralia elata.  

PubMed

One-step isolation of a saponin from Aralia elata was undertaken using high-speed countercurrent chromatography coupled with evaporative light scattering detection. A triterpenoid saponin, elatoside F, was purified with 96.8% purity using a two-phase-system comprising chloroform-methanol-water-isopropanol. The yield was 35.0 mg from 348.2 mg of the enriched saponin fraction. In vitro anti-inflammatory study demonstrated that elatoside F inhibited lipopolysaccharide-induced nitric oxide production, as well as nuclear factor kappaB activation, in a dose-dependent manner. Two types of mass ionization technique were compared on elatoside F to investigate characteristic fragmentation patterns. MALDI-TOF tandem mass spectrometric fragmentation patterns of sodiated ions provided structural information on glycosidic cleavages and on extensive cross-ring cleavages. Electrospray ionization multiple-stage tandem mass fragmentation of both sodiated and lithiated ions could provide information on glycosidic cleavages. All observed tandem mass fragmentation spectra provided valuable elatoside F structural information when unknown samples from crude extracts are under screening by mass spectrometry. PMID:19557359

Lee, Ju Hyeon; Ha, Young Wan; Jeong, Choon Sik; Kim, Yeong Shik; Park, Youmie

2009-06-01

224

Biogenesis of mitochondria. oli2 Mutations affecting the coupling of oxidation to phosphorylation in Saccharomyces cerevisiae.  

PubMed

1. Two oligomycin-resistant strains of Saccharomyces cerevisiae have been isolated and shown to have mutations in the oli2 region of the mitochondrial DNA. On solid media containing a non-fermentable energy source, the mutant strains were able to grow only slowly at 28 degrees C and not at all at 18 degrees C or 36 degrees C. 2. When grown in a glucose-limited chemostat at 28 degrees C, the mutant strains were almost completely defective in oxidative metabolism. The mutant mitochondria contained significant levels of all respiratory enzymes, and an active, oligomycin-sensitive ATPase, but the ATP-32Pi exchange activity and P : O ratio were very low. 3. The mutations in these strains are genetically closely linked to mit mutations which have been shown to affect a 20 000-dalton ATPase subunit (Roberts, H., Choo, W.M., Murphy, M., Marzuki, S., Lukins, H.B. and Linnane, A.W. (1979) FEBS Lett. 108, 501-504). Since the mitochondrial ATPase in these mutant strains appears to be fully assembled, the defect in the coupling mechanism is probably a result of a small alteration in the structure of the 20 000-dalton ATPase subunit. 4. When the mutant strains were grown at 18 degrees C, the mitochondria had very low cytochrome oxidase activities, and reduced levels of cytochrome aa3. The largest subunit (Mr 40 000) of this enzyme was not synthesized. PMID:6251866

Murphy, M; Roberts, H; Choo, W M; Macreadie, I; Marzuki, S; Lukins, H B; Linnane, A W

1980-10-01

225

Simvastatin Re-Couples Dysfunctional Endothelial Nitric Oxide Synthase in Experimental Subarachnoid Hemorrhage  

PubMed Central

Reduced endothelial nitric oxide synthase (eNOS) function has been linked to secondary complications of subarachnoid hemorrhage (SAH). We previously found that there is increased eNOS function after SAH but that it is uncoupled, leading to secondary complications such as vasospasm, microthromboembolism and neuronal apoptosis. Here we test the hypothesis that recoupling eNOS with simvastatin can prevent these complications. SAH was created in mice that were treated with vehicle or simvastatin starting 2 weeks before or 30 minutes after SAH. SAH increased phosphorylated eNOS which was prevented by pre- or post-treatment with simvastatin. Simvastatin pre-treatment also prevented the increase in eNOS monomer formation that was associated with SAH, decreased superoxide anion radical production and increased NO. These changes were associated with decreased vasospasm, microthromboemboli and neuronal injury. The data suggest that simvastatin re-couples eNOS after SAH, leading to decreased secondary complications such as vasospasm, microthromboemboli and neuronal injury. PMID:21373645

Sabri, Mohammed; Ai, Jinglu; Marsden, Philip A.; Macdonald, R. Loch

2011-01-01

226

Determination of melamine in animal feed based on liquid chromatography tandem mass spectrometry analysis and dynamic microwave-assisted extraction coupled on-line with strong cation-exchange resin clean-up.  

PubMed

In this work, a new method was developed for the determination of melamine (MEL) in animal feed. The method was based on the on-line coupling of dynamic microwave-assisted extraction (DMAE) to strong cation-exchange (SCX) resin clean-up. The MEL was first extracted by 90% acidified methanol aqueous solution (v/v, pH = 3) under the action of microwave energy, and then the extract was cooled and passed through the SCX resin. Thus, the protonated MEL was retained on the resin through ion exchange interaction and the sample matrixes were washed out. Some obvious benefits were achieved, such as acceleration of analytical process, together with reduction in manual handling, risk of contamination, loss of analyte, and sample consumption. Finally, the analyte was separated by a liquid chromatograph with a SCX analytical column, and then identified and quantitatived by a tandem mass spectrometry with positive ionization mode and multiple-reaction monitoring. The DMAE parameters were optimized by the Box-Behnken design. The linearity of quantification obtained by analyzing matrix-matched standards is in the range of 50-5,000 ng g(-1). The limit of detection and limit of quantification obtained are 12.3 and 41.0 ng g(-1), respectively. The mean intra- and inter-day precisions expressed as relative standard deviations with three fortified levels (50, 250, and 500 ng g(-1)) are 5.1% and 7.3%, respectively, and the recoveries of MEL are in the range of 76.1-93.5%. The proposed method was successfully applied to determine MEL in different animal feeds obtained from the local market. MEL was detectable with the contents of 279, 136, and 742 ng g(-1) in three samples. PMID:19756536

Chen, Ligang; Zeng, Qinglei; Du, Xiaobo; Sun, Xin; Zhang, Xiaopan; Xu, Yang; Yu, Aimin; Zhang, Hanqi; Ding, Lan

2009-11-01

227

Characterization of aromatic glycosides in the extracts of Trollius species by ultra high-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry.  

PubMed

Ultra high-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (UHPLC/ESI-Q-TOF MS/MS) was used to investigate the MS fragmentation behaviors of flavone C-glycosides present in the extracts of five Trollius species. In this study, the primary MS fragmentation pathways and key diagnostic fragment ions of flavone C-glycosides were systematically investigated and summarized to distinguish different types of derivatives and to trace other analogs in Trollius species. This method was useful, rapid, efficient and sensitive and allowed the simultaneous identification of different types of flavone C-glycosides present in other medicinal plants. The features of the MS fragmentation of these compounds indicated that the product ions were primarily the result of cleavage in the saccharide moiety, followed by hydrogen rearrangement and dehydration. In this study, thirty-six components including thirty-two flavone C-glycosides, two flavone O-glycosides and two phenylethanoid glycosides, were identified in the extracts of five Trollius species. Eleven of the flavone C-glycosides were identified by comparison with reference standards, and twenty-one flavone C-glycosides were tentatively identified based on their retention times, exact mass information and fragment ions. Two potentially new flavone C-glycosides (2?-O-vanilloylorientin and 2?-O-feruloylvitexin) were successfully characterized based on the summarized fragmentation pathways, and six known flavone C-glycosides (2?-O-glucosylvitexin, 2?-O-acetylorientin, 2?-O-acetylvitexin, 3?-O-acetylorientin, 3?-O-acetylvitexin and 6?-O-acetylvitexin) were identified in these plant species for the first time. In conclusion, the fragmentation pathways proposed in this paper were helpful for the identification of different types of flavone C-glycosides when no reference standards were available. PMID:23312385

Wu, Li-Zhen; Zhang, Xiao-Po; Xu, Xu-Dong; Zheng, Qing-Xia; Yang, Jun-Shan; Ding, Wan-Long

2013-03-01

228

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

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

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

2012-12-14

229

Quantitative analysis of PD 0332991 in mouse plasma using automated micro-sample processing and microbore liquid chromatography coupled with tandem mass spectrometry.  

PubMed

In the oncology therapeutic area, the mouse is the primary animal model used for efficacy studies. Often with mouse pharmacokinetic (PK) and pharmacokinetic/pharmacodynamic (PK/PD) studies, less than 20 ?L of total plasma sample volume is available for bioanalysis due to the small size of the animal and the need to split samples for other measurements such as biomarker analyses. The need to conduct automated "small volume" sample processing for quantitative bioanalysis has therefore increased. An automated fit for purpose protein precipitation (PPT) method using a Hamilton MicroLab Star (Reno, NV, USA) to support mouse PK and PK/PD studies for an oncology drug candidate PD 0332991, (a specific inhibitor of cyclin-dependent kinase 4 (CDK-4) currently in development) for processing "small volumes" was developed. The automated PPT method was achieved by extracting and processing 10 ?L out of a minimum sample volume of 15 ?L plasma utilizing the Hamilton MicroLab Star. A 96-conical shallow well plate by Agilent Technologies, Inc (Wilmington, DE, USA) was the labware of choice used in the automated Hamilton "small volume" method platform. Analyses of a 10 ?L plasma aliquot from 15 ?L of plasma study samples were conducted by both automated and manual PPT method. All plasma samples were quantitated using a Sciex API 4000 triple quadrupole mass spectrometer coupled with an Eksigent Express HT Ultra HPLC system. The chromatography was achieved using an Agilent microbore C(18) Extend, 1.0 × 50 mm, 3.5 ?m column at a flow rate of 0.150 mL/min with a total run time of 1.8 min. Accuracy and precision of standard and QC concentration levels were within 90-107% and <14%, respectively. Calibration curves were linear over the dynamic range of 1.0-1000 ng/mL. PK studies for PD 0332991 were conducted in female C3H mice following intravenous administration at 1mg/kg and oral administration at 2mg/kg. PK values such as area under curve (AUC), volume of distribution (Vd), clearance (Cl), half life (T(1/2)) and bioavailability (F%) demonstrated less than 11% difference between the automated Hamilton and manual PPT methods. The results demonstrate that the automated Hamilton PPT method can accurately and precisely aliquot 10 ?L of plasma from 15 ?L or larger volume plasma samples. The fit for purpose Hamilton PPT method is suitable for routine analyses of plasma samples from micro-sampling PK and PK/PD samples to support discovery studies. PMID:21889427

Smith, Danielle; Tella, Max; Rahavendran, Sadayappan V; Shen, Zhongzhou

2011-10-01

230

TRedD--a database for tandem repeats over the edit distance.  

PubMed

A 'tandem repeat' in DNA is a sequence of two or more contiguous, approximate copies of a pattern of nucleotides. Tandem repeats are common in the genomes of both eukaryotic and prokaryotic organisms. They are significant markers for human identity testing, disease diagnosis, sequence homology and population studies. In this article, we describe a new database, TRedD, which contains the tandem repeats found in the human genome. The database is publicly available online, and the software for locating the repeats is also freely available. The definition of tandem repeats used by TRedD is a new and innovative definition based upon the concept of 'evolutive tandem repeats'. In addition, we have developed a tool, called TandemGraph, to graphically depict the repeats occurring in a sequence. This tool can be coupled with any repeat finding software, and it should greatly facilitate analysis of results. Database URL: http://tandem.sci.brooklyn.cuny.edu/ PMID:20624712

Sokol, Dina; Atagun, Firat

2010-01-01

231

Quantification of ethylenediamine-N,N'-bis(hydroxysulfophenylacetic) acid regioisomers and structural characterisation of its related polycondensation products by porous graphitic carbon high-performance liquid chromatography coupled to electrospray tandem mass spectrometry.  

PubMed

Among the commercial ethylenediamine-N,N'-bis(2-hydroxy)phenylacetic acid/iron(III) derivatives, ethylenediamine-N,N'-bis(2-hydroxy-5-sulphophenylacetic) acid/iron(III) (EDDHSA/Fe) represents one of the promising chelates for the treatment of chlorotic plants. Industrial synthesis of EDDHSA/Fe leads to relevant amounts of o,o-EDDHSA condensation products (o,o-EDDHSAcps) and other secondary products that might have important relevance from the agronomic point of view. However, their chemical structures have remained unknown to date. Analysis of iron complexes by ion-pair reversed-phase chromatography, coupled with electrospray tandem mass spectrometry revealed the presence of the meso-o,o-EDDHSA/Fe, rac-o,o-EDDHSA/Fe, o,p-EDDHSA/Fe regioisomers, the hydroxyl derivative of o,o-EDDHSA/Fe, and the three main EDDHSA condensation products chelating the iron(III) (EDDHSAcps/nFe). However, the chromatographic peaks of EDDHSAcps/Fe are not well resolved due to the large numbers of stereoisomers and the poor efficiency of the ion-pair reversed-phase separation method. An alternative chromatographic method is based on porous graphitic carbon (PGC) separation after pre-column decomplexation of the chelates with trifluoracetic acid, which was developed to allow detection of EDDHSA stereo/regioisomers, EDDHSAcps, and low-molecular-weight by-products. This extensive PGC-HPLC-ESI-MS/MS investigation provides quantitative determination of meso-o,o-EDDHSA, rac-o,o-EDDHSA and o,p-EDDHSA, in addition to characterisation of EDDHSAcps and the low-molecular-weight by-products. PGC separation coupled to a triple quadrupole ESI-MS detector allowed characterisation of free ligands using collision-induced dissociation experiments in positive and negative ionisation mode, providing comparative evaluation of EDDHSAcps in three commercial samples. For detection, the PGC-HPLC-ESI-MS/MS is the best method according to the limit of quantification and limit of detection (picomolar and sub-picomolar detection, respectively) for determination of meso-EDDHSA and rac-o,o-EDDHSA. Synthesis, purification and quantification of o,o-EDDHSA and o,p-EDDHSA by (1)H-nuclear magnetic resonance are also reported. PMID:24028933

Biasone, Alessandro; Cianci, Giusto; Di Tommaso, Donata; Piaggesi, Alberto; D'Alessandro, Nicola

2013-10-18

232

Fast and simple screening for the simultaneous analysis of seven metabolites derived from five volatile organic compounds in human urine using on-line solid-phase extraction coupled with liquid chromatography-tandem mass spectrometry.  

PubMed

Recently, the International Agency for Research on cancer classified outdoor air pollution and particulate matter from outdoor air pollution as carcinogenic to humans (IARC Group 1), based on sufficient evidence of carcinogenicity in humans and experimental animals and strong mechanistic evidence. In particular, a wide variety of volatile organic compounds (VOCs) are volatized or released into the atmosphere and can become ubiquitous, as they originate from many different natural and anthropogenic sources, such as paints, pesticides, vehicle exhausts, cooking fumes, and tobacco smoke. Humans may be exposed to VOCs through inhalation, ingestion, or dermal contact, which may increase the risk of leukemia, birth defects, neurocognitive impairment, and cancer. Therefore, the focus of this study was the development of a simple, effective and rapid sample preparation method for the simultaneous determination of seven metabolites (6 mercaptic acids+t,t-muconic acid) derived from five VOCs (acrylamide, 1,3-butadiene, acrylonitrile, benzene, and xylene) in human urine by using automated on-line solid-phase extraction (SPE) coupled with liquid chromatography-electrospray tandem mass spectrometry (LC-MS/MS). An aliquot of each diluted urinary sample was directly injected into an autosampler through a trap column to reduce contamination, and then the retained target compounds were eluted by back-flush mode into an analytical column for separation. Negative electrospray ionization tandem mass spectrometry was utilized for quantification. The coefficients of correlation (r(2)) for the calibration curves were greater than 0.995. Reproducibility was assessed by the precision and accuracy of intra-day and inter-day precision, which showed results for coefficient of variation (CV) that were low 0.9 to 6.6% and 3.7 to 8.5%, respectively, and results for recovery that ranged from 90.8 to 108.9% and 92.1 to 107.7%, respectively. The limits of detection (LOD) and limits of quantification (LOQ) were determined to within 0.010 to 0.769ngmL(-1) and 0.033 to 2.564ngmL(-1) in this study. A stability study test included 3 freeze/thaw cycles during short-term storage at room temperature for 36h and long-term storage at -20°C for 1 month, and the CV (coefficient of variation) showed less than 8.4, 7.4 and 9.7%, respectively. To the best of our knowledge, this is the first study to provide simple, small injection volumes (40µL) and a rapid LC-MS/MS method combined with an on-line SPE step for the simultaneous detection, identification, and quantification of seven metabolites derived from five VOCs in human urine for evaluation of the future risk of human exposure to volatile organic compounds. PMID:25476333

Chiang, Wen-Chieh; Chen, Chao-Yu; Lee, Ting-Chen; Lee, Hui-Ling; Lin, Yu-Wen

2015-01-15

233

Coupled reductions in brain oxidative phosphorylation and synaptic function can be quantified and staged in the course of Alzheimer disease  

Microsoft Academic Search

In vivo, post-mortem and biopsy data suggest that coupled deelines occur in brain synaptic activity and brain energy consumption\\u000a during the evolution of Alzheimer disease. In the first stage of these declines, changes in synaptic structure and function\\u000a reduce neuronal energy demand and lead to potentially reversible downregulation of oxidative phosphorylation (OXPHOS) within\\u000a neuronal mitochondria. At this stage, measuring brain

Stanley I. Rapoport

2003-01-01

234

Direct oxidative coupling of N-acetyl indoles and phenols for the synthesis of benzofuroindolines related to phalarine.  

PubMed

Inspired by the biogenetic synthesis of benzofuroindoline-containing natural products, we designed an oxidative coupling between phenol and N-acetyl indoles. This straightforward and direct radical process, mediated by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and FeCl3 allowed the regioselective synthesis of benzofuro[3,2-b]indolines, whose structure is found in the natural product phalarine. PMID:25208884

Tomakinian, Terry; Guillot, Régis; Kouklovsky, Cyrille; Vincent, Guillaume

2014-10-27

235

Controlled surface modification of Ti-40Nb implant alloy by electrochemically assisted inductively coupled RF plasma oxidation.  

PubMed

Low temperature metal oxidation induced by plasma in the absence of liquid electrolytes can be useful for the surface preparation of orthopedic devices since residues from these may be harmful and need to be removed before implantation. In this study the oxidation of Ti-40Nb for biomedical application was achieved by employing an inductively coupled radio frequency oxygen plasma. The correlation between the growth mode of the surface oxide and the electric conductivity ratio of the plasma and the oxide phase were studied by varying the sample temperature, oxygen gas pressure and additional bias potential. The plasma treated samples were characterised by confocal laser microscopy, SEM, EBSD, XPS, TEM and ToF-SIMS. The surface energy was determined by contact angle measurements using the Owens-Wendt-Rabel-Kaelble method. Well adhering oxide layers consisting of TiO2 and Nb2O5 with thicknesses between 50 and 150 nm were obtained. Surface roughness values and microstructure indicate that the growth mode of the oxide can be well controlled by the sample temperature and oxygen gas pressure. At temperatures above 450°C a migration of Ti ions towards the surface controls the growth process. A bias potential higher than +50 V causes rough and defective surfaces with high surface energies. PMID:23891813

Göttlicher, Markus; Rohnke, Marcus; Helth, Arne; Leichtweiß, Thomas; Gemming, Thomas; Gebert, Annett; Eckert, Jürgen; Janek, Jürgen

2013-11-01

236

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

SciTech Connect

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.

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

2013-10-15

237

Biosynthesis of Hexahydroxyperylenequinone Melanin via Oxidative Aryl Coupling by Cytochrome P-450 in Streptomyces griseus  

PubMed Central

Dihydroxyphenylalanine (DOPA) melanins formed from tyrosine by tyrosinases are found in microorganisms, plants, and animals. Most species in the soil-dwelling, gram-positive bacterial genus Streptomyces produce DOPA melanins and melanogenesis is one of the characteristics used for taxonomy. Here we report a novel melanin biosynthetic pathway involving a type III polyketide synthase (PKS), RppA, and a cytochrome P-450 enzyme, P-450mel, in Streptomyces griseus. In vitro reconstitution of the P-450mel catalyst with spinach ferredoxin-NADP+ reductase/ferredoxin revealed that it catalyzed oxidative biaryl coupling of 1,3,6,8-tetrahydroxynaphthalene (THN), which was formed from five molecules of malonyl-coenzyme A by the action of RppA to yield 1,4,6,7,9,12-hexahydroxyperylene-3,10-quinone (HPQ). HPQ readily autopolymerized to generate HPQ melanin. Disruption of either the chromosomal rppA or P-450mel gene resulted in abolishment of the HPQ melanin synthesis in S. griseus and a decrease in the resistance of spores to UV-light irradiation. These findings show that THN-derived melanins are not exclusive in eukaryotic fungal genera but an analogous pathway is conserved in prokaryotic streptomycete species as well. A vivid contrast in THN melanin biosynthesis between streptomycetes and fungi is that the THN synthesized by the action of a type III PKS is used directly for condensation in the former, while the THN synthesized by the action of type I PKSs is first reduced and the resultant 1,8-dihydroxynaphthalene is then condensed in the latter. PMID:16291687

Funa, Nobutaka; Funabashi, Masanori; Ohnishi, Yasuo; Horinouchi, Sueharu

2005-01-01

238

Silylesterification of oxidized multi-wall carbon nanotubes by catalyzed dehydrogenative cross-coupling between carboxylic and hydrosilane functions  

NASA Astrophysics Data System (ADS)

Surface modification of oxidized carbon nanotubes (O-CNTs) with silicon based anchoring groups (R-SiR3) is a relatively uncommon approach of the CNTs functionalization. Hydrosilane derivatives constitute an attractive subclass of compounds for silanization reactions on the CNTs surface. In this work, we report on the ZnCl2 catalytically controlled reaction (hydrosilane dehydrogenative cross-coupling, DHCC) of fluorinated hydrosilane probes with the carboxylic functions present on the surface of oxidized multi-wall carbon nanotubes. Carbon nanotubes functionalized with essentially alcohol groups are also used to compare the selectivity of zinc chloride toward carboxylic groups. To assess the efficiency of functionalization, X-ray Photoelectron Spectroscopy is used to determine the qualitative and quantitative composition of the different samples. Solubility tests on the oxidized and silanized MWNTs are also carried out in the framework of the Hansen Solubility Parameters (HSP) theory to apprehend at another scale the effect of DHCC.

Seffer, J.-F.; Detriche, S.; Nagy, J. B.; Delhalle, J.; Mekhalif, Z.

2014-06-01

239

Identification of circulatory and excretory metabolites of a novel nitric oxide donor ZJM-289 in rat plasma, bile, urine and faeces by liquid chromatography-tandem mass spectrometry.  

PubMed

ZJM-289, [2-(1-diethylaminoacetoxy)pentyl] benzoic acid-{2-methoxy-4-[2-(4-nitrooxybutoxy carbonyl)-vinyl]}phenyl ester hydrochloride, is a novel nitric oxide-donating derivative of 3-n-butylphthalide synthesised on the hypothesis that it may be hydrolysed in vivo into 3-n-butylphthalide, ferulic acid and nitric oxide in hope that the three components may exert effects on the platelets as well as on central nervous system synergistically. In this study, ZJM-289 was extensively metabolised in rats. Eight major metabolites were identified by liquid chromatography (LC)-mass spectrometry (MS)/MS in rat plasma, bile, urine and faeces after intravenous administration. Metabolites M1, M2, M3, M4 and M5 were hydrolytic products of ZJM-289, M6 and M7 was a hydroxylation product of M5, and M8 was a glucuronide of M1. The pharmacologically active metabolite ferulic acid (M3) was a major metabolite in all the biological matrixes examined. 3-n-Butylphthalide was also present at a moderate level in the circulation. And along with the previous research, the anti-platelet activity of ZJM-289 was more potent than that of 3-n-butylphthalide both in vivo and in vitro. All these findings validated the theory of drug design. PMID:21561319

Li, Ning; Wang, Xuliang; Li, Tingting; Ji, Hui; Zhang, Yihua; Qiu, Zhixia; Zhao, Di; Chen, Xijing

2011-09-01

240

Remobilization of Cr(VI) from Cr(OH)3(s) coupled with heterogeneous Mn(II) oxidation  

NASA Astrophysics Data System (ADS)

Chromium(VI) is known to be the 2nd most common inorganic contaminant due to the wide range of applications of chromium in the industry. The most effective way to remove toxic Cr(VI) under natural conditions as well as in the engineered systems is to reduce it to less toxic Cr(III) using various reductants. Under circumneutral pH conditions, Cr(III) readily precipitates as sparingly soluble Cr(OH)3(s). This solid phase is generally considered as one of the most desirable remediation product of soil and groundwater contaminated by Cr(VI) because it is less toxic and less mobile form of chromium. In addition, this solid is usually believed to be relatively inert to natural oxidants such as dissolved oxygen and Mn oxides. The oxidation of Cr(III) by dissolved oxygen is known to be kinetically sluggish. Previous studies showed that dissolved Cr(III) could easily be oxidized by Mn oxides under acidic conditions but the oxidation became ineffective under neutral or higher pH conditions as a result of Cr(OH)3(s) precipitation. This study examines the potential remobilization of Cr(VI) from this solid by oxidation coupled with heterogeneous oxidation of Mn(II) by dissolved oxygen. 1.0 g/L Cr(OH)3(s) was reacted with 50 ?M Mn(II) in 50 mM NaNO3 at pH 7 to 9 in the presence or absence of dissolved oxygen. The pH was maintained with 10 or 50 mM buffers (MOPS for pH 7 and 8; CHES for pH 9). For the anaerobic conditions, the solutions were purged with N2 in sealed serum bottles. In the absence of dissolved oxygen, the oxidation of Cr(OH)3(s) did not occur either with or without dissolved Mn(II). When the solutions were open to atmosphere, by contrast, the oxidation of the solid did occur both in the presence and absence of Mn(II) when the pH was higher or at 8.0. The amounts of Cr(VI) released increased with increasing pH and were higher in the presence than the absence of Mn(II). At pH 9, Cr(VI) concentration rapidly increased for the first 130 hr and reached up to 300 ppb in the presence of Mn(II). The results of this study show that Cr(OH)3(s) can be oxidized by the product of heterogeneous Mn(II) oxidation and thereby would possibly become a source of toxic Cr(VI).

Lee, G.; Namgung, S.; Um, W.

2011-12-01

241

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

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

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

2013-02-15

242

Probabilistic approaches to alignment with tandem repeats  

PubMed Central

Background Short tandem repeats are ubiquitous in genomic sequences and due to their complex evolutionary history pose a challenge for sequence alignment tools. Results To better account for the presence of tandem repeats in pairwise sequence alignments, we propose a simple tractable pair hidden Markov model that explicitly models their presence. Using the framework of gain functions, we design several optimization criteria for decoding this model and describe resulting decoding algorithms, ranging from the traditional Viterbi and posterior decoding to block-based decoding algorithms tailored to our model. We compare the accuracy of individual decoding algorithms on simulated and real data and find that our approach is superior to the classical three-state pair HMM. Conclusions Our study illustrates versatility of pair hidden Markov models coupled with appropriate decoding criteria as a modeling tool for capturing complex sequence features. PMID:24580741

2014-01-01

243

Scope and Mechanistic Study of the Coupling Reaction of ?, ?-Unsaturated Carbonyl Compounds with Alkenes: Uncovering Electronic Effects on Alkene Insertion vs Oxidative Coupling Pathways  

PubMed Central

The cationic ruthenium-hydride complex [(C6H6)(PCy3)(CO)RuH]+BF4? (1) was found to be a highly effective catalyst for the intermolecular conjugate addition of simple alkenes to ?,?-unsaturated carbonyl compounds to give (Z)-selective tetrasubstituted olefin products. The analogous coupling reaction of cinnamides with electron-deficient olefins led to the oxidative coupling of two olefinic C–H bonds in forming (E)-selective diene products. The intramolecular version of the coupling reaction efficiently produced indene and bicyclic fulvene derivatives. The empirical rate law for the coupling reaction of ethyl cinnamate with propene was determined as: rate = k[1]1[propene]0[cinnamate]?1. A negligible deuterium kinetic isotope effect (kH/kD = 1.1±0.1) was measured from both (E)-C6H5CH=C(CH3)CONHCH3 and (E)-C6H5CD=C(CH3)CONHCH3 with styrene. In contrast, a significant normal isotope effect (kH/kD = 1.7±0.1) was observed from the reaction of (E)-C6H5CH=C(CH3)CONHCH3 with styrene and styrene-d10. A pronounced carbon isotope effect was measured from the coupling reaction of (E)-C6H5CH=CHCO2Et with propene (13C(recovered)/13C(virgin) at C? = 1.019(6)), while a negligible carbon isotope effect (13C(recovered)/13C(virgin) at C? = 0.999(4)) was obtained from the reaction of (E)-C6H5CH=C(CH3)CONHCH3 with styrene. Hammett plots from the correlation of para-substituted p-X-C6H4CH=CHCO2Et (X = OCH3, CH3, H, F, Cl, CO2Me, CF3) with propene and from the treatment of (E)-C6H5CH=CHCO2Et with a series of para-substituted styrenes p-Y-C6H4CH=CH2 (Y = OCH3, CH3, H, F, Cl, CF3) gave the positive slopes for both cases (? = +1.1±0.1 and +1.5±0.1, respectively). Eyring analysis of the coupling reaction led to the thermodynamic parameters, ? H‡ = 20±2 kcal mol?1 and S‡ = ?42±5 e.u. Two separate mechanistic pathways for the coupling reaction have been proposed on the basis of these kinetic and spectroscopic studies. PMID:22368318

Kwon, Ki-Hyeok; Lee, Do W.; Yi, Chae S.

2011-01-01

244

Tandem resonator reflectance modulator  

DOEpatents

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.

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

1994-09-06

245

Tandem resonator reflectance modulator  

DOEpatents

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.

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

1994-01-01

246

Monolithic tandem solar cell  

SciTech Connect

It is an object of the invention to provide a monolithic tandem photovoltaic solar cell which is highly radiation resistant and efficient; in which the energy bandgap of the lower subcell can be tailored for specific applications; solar cell comprising layers of InP and GaInAsP (or GaInAs), where said photovoltaic cell is useful, for example, in space power applications; having an improved power-to-mass ratio; in which subcells are lattice-matches; and are both two terminal and three terminal monolithic tandem photovoltaic solar cells. To achieve the foregoing and other objects and in accordance with the purpose of the present invention, as embodied and broadly described herein, the monolithic tandem photovoltaic solar cell may comprise; (a) an InP substrate having an upper surface; (b) a first photoactive subcell on the upper surface of the InP substrate; wherein the first subcell comprises GaInAs (which could include GaInAsP) and includes a homojunction; and (c) a second photoactive subcell on the first subcell; wherein the second subcell comprises InP and includes a homojunction. The cell is described in detail. 5 figs., 2 tabs.

Wanlass, M.W.

1989-11-03

247

Advancing tandem solar cells by spectrally selective multilayer intermediate reflectors.  

PubMed

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

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

2014-08-25

248

Separation and identification of underivatized plasma acylcarnitine isomers using liquid chromatography-tandem mass spectrometry for the differential diagnosis of organic acidemias and fatty acid oxidation defects.  

PubMed

A simple HPLC-MS/MS method has been established to separate and identify underivatized acylcarnitine isomers. Human plasma samples were deproteinized and concentrated. Acylcarnitines were separated on a reverse phase column and detected with triple quadrupole linear ion trap mass spectrometry. Deuterium-labeled internal standards were used for quantitation. To identify acylcarnitines without pure standards, information-dependent acquisition linking to enhanced product ion scan mode was used. 112 acylcarnitines, including stereoisomers, were found in samples of patients. Dicarboxylic acylcarnitines, such as methylmalonylcarnitine and glutarylcarnitine, were detected with high sensitivity. Three stereoisomers of (R,S)2-methyl-3-hydroxy butyrylcarnitine were detected in samples of patients with ?-ketothiolase deficiency. Validation results revealed excellent precision and accuracy of the method. In general the within- and between-run coefficients of variation (CV%) were less than 15%, and recoveries were in the range of 92.7-117.5%. In addition, the reference intervals of acylcarnitines for children aged 3-day to13-year old were established. Using the new method and reference intervals, we have correctly diagnosed 49 patients with fatty acid oxidation defects or organic acidemias in 176 high-risk patients. PMID:24169039

Peng, Minzhi; Fang, Xiefan; Huang, Yonglan; Cai, Yanna; Liang, Cuili; Lin, Ruizhu; Liu, Li

2013-12-01

249

A flow injection electrospray ionization tandem mass spectrometric method for the simultaneous measurement of trimethylamine and trimethylamine N-oxide in urine.  

PubMed

Key metabolites for the diagnosis of the genetic disorder trimethylaminuria are trimethylamine (TMA) and trimethylamine N-oxide (TMAO). A rapid, automatable flow injection ESI-MS/MS method for their measurement in urine has been developed. The TMA was derivatized with ethyl bromoacetate to form ethyl betaine bromide. The 2 min ESI-MS/MS analysis employed four multiple reaction monitoring (MRM) ion pairs for derivatized TMA (146.1, 118.1), derivatized (2)H(9)-TMA (155.1, 127.1), TMAO (76.1, 58.1) and (2)H(9)-TMAO (85.1, 66.1). In control urine samples (n = 27) referred for suspected metabolic problems TMA was 0.11-1.19 mmol/mol creatinine, TMAO was 13.5-181 mmol/mol creatinine and the TMA/TMAO ratio was 0.0025-0.055. In five patients with diagnosed trimethylaminuria, TMA was 5.3-230 mmol/mol creatinine, TMAO was 0.36-607 mmol/mol creatinine and the TMA/TMAO ratio was 0.20-134. PMID:17975851

Johnson, David W

2008-04-01

250

Mössbauer effect study of tight spin coupling in oxidized chloro-5,10,15,20- tetra(mesityl)porphyrinatoiron(III)  

NASA Astrophysics Data System (ADS)

Mössbauer spectra of a polycrystalline form of oxidized chloro-5,10,15,20-tetra(mesityl)porphyrin- atoiron(III) [Fe(TMP)Cl], compound A, were recorded over a range of temperatures (4.2-195 K) and magnetic fields (0-6 T). These spectra of compound A exhibit magnetic features which are markedly different from those of the analogous protein complexes, horse radish peroxidase compound I (HRP-I) and compound ES of cytochrome c peroxidase, even though chemical evidence and optical spectroscopy indicate that compound A is similar to the others in comprising a Fe(IV) complex within a porphyrin cation radical. We interpret the data by employing a spin Hamiltonian model in which the central Fe(IV) complex, with S=1, is tightly coupled to a S=1/2 system of the oxidized porphyrin to yield a net S=3/2 system as suggested by the susceptibility measurements. The theoretical treatment yields information on the d-electron energies which is similar to that more directly available in the peroxidase spectra. The strength of the axial crystal field is found to increase progressively in the series HRP-I, ES, compound A, while the spin coupling in A is the strongest of the three by several orders of magnitude. The good fits to experimental data confirm the efficacy of the theoretical treatment which may be applicable to a variety of other coupled systems.

Boso, Brian; Lang, George; McMurry, Thomas J.; Groves, John T.

1983-08-01

251

Oxidative photoredox-catalytic activation of aliphatic nucleophiles for C(sp(3))-C(sp(2)) cross-coupling reactions.  

PubMed

In the light you will find the road (Led Zeppelin): Visible-light photoredox catalysis leads the way in overcoming the reactivity limitations of alkyl nucleophiles in cross-coupling reactions. Iridium-triggered oxidative photoredox activation of alkyltrifluoroborate or carboxylic acids affords alkyl radicals, which undergo nickel-catalyzed cross-coupling reactions. PMID:25324184

Jahn, Emanuela; Jahn, Ullrich

2014-12-01

252

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

SciTech Connect

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.

Weber Jr., W. J.

2000-10-01

253

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...

254

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

PubMed

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

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

2014-11-01

255

Determination of selenomethionine by high-performance liquid chromatography-fluorescence detection coupled with on-line oxidation.  

PubMed

A simple and sensitive determination method for selenomethionine (Se-Met) using an HPLC-fluorescence detection system coupled with an on-line electrochemical reactor has been developed. NBD-F (4-fluoro-7-nitro-2,1,3-benzoxadiazole) was used as the fluorescent derivatization reagent for Se-Met. NBD-Se-Met was separated from NBD-derivatives of 22 other amino acids within 35 min. Applying an optimized oxidation potential enhanced the fluorescence intensity of NBD-Se-Met 10-fold. The calibration curve was linear in the range of 300 fmol to 30 pmol with a correlation coefficient of 0.997. Detection limit (S/N = 3) was calculated to be 50 fmol, which is comparable to that of inductively coupled plasma mass spectrometry. This simple and sensitive method should be useful for the determination of Se-Met in physiological samples, such as serum or urine. PMID:19139574

Aoyama, Chiaki; Tsunoda, Makoto; Funatsu, Takashi

2009-01-01

256

High-temperature catalytic oxidative conversion of propane to propylene and ethylene involving coupling of exothermic and endothermic reactions  

Microsoft Academic Search

Coupling of the exothermic catalytic oxidative conversion and endothermic thermal cracking (noncatalytic) reactions of propane to propylene and ethylene over the SrO\\/LaâOâ\\/SA5205 catalyst in the presence of steam and limited oxygen was investigated at different process conditions (temperature, 700--850 C; CâHâ\\/Oâ ratio in feed, 2.0--8.0; HâO\\/CâHâ ratio, 0.5--2.5; space velocity, 2,000--15,000 cm³\\/g h). In the presence of steam and limited

Vasant R. Choudhary; Vilas H. Rane; Amarjeet M. Rajput

2000-01-01

257

Monolithic tandem solar cell  

DOEpatents

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. 9 figs.

Wanlass, M.W.

1994-06-21

258

Monolithic tandem solar cell  

SciTech Connect

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.

Wanlass, Mark W. (Golden, CO)

1994-01-01

259

Monolithic tandem solar cell  

DOEpatents

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.

Wanlass, Mark W. (Golden, CO)

1991-01-01

260

Monolithic tandem solar cell  

SciTech Connect

This patent describes a single-crystal, monolithic, tandem, photovoltaic solar cell which includes an InP substrate having an upper and lower surfaces, a first photoactive subcell on the upper surface of the InP substrate, and a second photoactive subcell on the first subcell. The first photovoltaic 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.

Wanlass, M.W.

1991-05-28

261

Spin-fluctuation-induced superconductivity in the copper oxides: A strong coupling calculation  

NASA Astrophysics Data System (ADS)

We have carried out a strong coupling calculation of spin-fluctuation-induced superconductivity for YBa2Cu3O7 using the experimentally determined spin excitation spectrum. We find that it is extremely important to take full account of the momentum and frequency dependence of the interaction and that while lifetime effects substantially reduce Tc from its value calculated in a weak coupling approximation, it is still possible for spin fluctuations to give rise to high-temperature superconductivity.

Monthoux, P.; Pines, D.

1992-08-01

262

Tandem metal relay catalysis: from cyclopropene to polysubstituted furan.  

PubMed

Transmetalation is a key step in traditional coupling reactions. Herein we discuss the most recent progress in the metal-metal relay catalysis based on a transmetalation strategy. An efficient synthetic strategy for the formation of polysubstituted furan derivatives from cyclopropenes based on the tandem metal relay catalysis (TMRC reaction) is summarized. PMID:24962613

Song, Chuanling; Wang, Jianwu; Xu, Zhenghu

2014-08-21

263

Polymerization of humic substances by an enzyme-catalyzed oxidative coupling  

NASA Astrophysics Data System (ADS)

A novel understanding of the structural features of humic substances supports the self-assembly supramolecular association of relatively small molecules rather than their polymeric nature. An increase in the conformational stability of humus may thus be achieved through promotion of intermolecular covalent bondings between heterogeneous humic molecules by an enzyme-catalyzed oxidative reaction. We present evidence from high performance size exclusion chromatography (HPSEC) and diffuse reflectance infrared spectrometry (DRIFT) that oxidation of a humic material catalyzed by horseradish peroxidase stabilizes the humic structure by the formation of aryl and alkyl ethers and permanently enhances its molecular size.

Piccolo, A.; Cozzolino, A.; Conte, P.; Spaccini, R.

2000-10-01

264

Reduced Graphene Oxide-Supported CuPd Alloy Nanoparticles as Efficient Catalysts for the Sonogashira Cross-Coupling Reactions.  

PubMed

Monodisperse CuPd alloy nanoparticles (NPs) were prepared by using a typical high-temperature organic solution phase protocol comprising the coreduction of copper(II) acetylacetonate and palladium(II) acetylacetonate by morpholine-borane complex in oleylamine and 1-octadecene solution at 80 °C. The presented synthesis protocol allows us to control the composition of CuPd alloy NPs by simply tuning the initial ratio of metal precursors and the Cu-rich Cu75Pd25 NPs and Pd-rich Cu32Pd68 were synthesized besides the Cu48Pd52 NPs. Transmission electron microscopy studies revealed that most of the CuPd alloy NPs are polyhedral with an average diameter of 3.0 ± 0.3 nm. The alloy structure of CuPd NPs was confirmed by the detailed X-ray diffraction and X-ray photoelectron spectroscopy analysis. As-prepared CuPd NPs were deposited on reduced graphene oxide (rGO) by using a liquid self-assembly method (rGO-CuPd) and used as catalysts in the Sonogashira cross-couplings of various aryl iodides or bromides and phenyl acetylene under the optimized reaction conditions. Among the three compositions of CuPd alloy NPs tested in the Sonogashira couplings, the rGO-Cu48Pd52 gave the best yields in shorter reaction times and therefore it was used for further coupling reactions. The results demonstrated that rGO-Cu48Pd52 were efficient catalysts for the Sonogashira reaction of various aryl halides with phenylacetylene. The coupling reactions proceeded smoothly with both electron-rich and electron-deficient aryl iodides and aryl bromides, affording the desired biaryl products in high yields. This is the first example of the employment of monodisperse CuPd alloy NPs with composition control in the Sonogashira cross-coupling reactions. PMID:25594280

Diyarbakir, Sümeyra; Can, Hasan; Metin, Önder

2015-02-11

265

Light induced carbon dioxide reduction by water at binuclear ZrOCo(II) unit coupled to Ir oxide nanocluster catalyst.  

PubMed

An all-inorganic polynuclear unit consisting of an oxo-bridged binuclear ZrOCo(II) group coupled to an iridium oxide nanocluster (IrO(x)) was assembled on an SBA-15 silica mesopore surface. A photodeposition method was developed that affords coupling of the IrO(x) water oxidation catalyst with the Co donor center. The approach consists of excitation of the ZrOCo(II) metal-to-metal charge-transfer (MMCT) chromophore with visible light in the presence of [Ir(acac)3] (acac: acetylacetonate) precursor followed by calcination under mild conditions, with each step monitored by optical and infrared spectroscopy. Illumination of the MMCT chromophore of the resulting ZrOCo(II)-IrO(x) units in the SBA-15 pores loaded with a mixture of (13)CO2 and H2O vapor resulted in the formation of (13)CO and O2 monitored by FT-IR and mass spectroscopy, respectively. Use of (18)O labeled water resulted in the formation of (18)O2 product. This is the first example of a closed photosynthetic cycle of carbon dioxide reduction by water using an all-inorganic polynuclear cluster featuring a molecularly defined light absorber. The observed activity implies successful competition of electron transfer between the IrO(x) catalyst cluster and the transient oxidized Co donor center with back electron transfer of the ZrOCo light absorber, and is further aided by the instant desorption of the CO and O2 product from the silica pores. PMID:25033315

Kim, Wooyul; Yuan, Guangbi; McClure, Beth Anne; Frei, Heinz

2014-08-01

266

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

PubMed

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

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

2015-01-18

267

Selective binding of albumin on stearyl poly(ethylene oxide) coupling polymer-modified poly(ether urethane) surfaces.  

PubMed

A tri-block-coupling polymer of stearyl poly(ethylene oxide)-4,4'-methylene diphenyl diisocyanate-stearyl poly(ethylene oxide) (MSPEO), was used as a surface modifying additive (SMA) and the MSPEO-modified poly(ether urethane) (PEU) surfaces were prepared by the process of dip-coating. The surface analysis by XPS revealed the surface enrichment of poly(ethylene oxide) (PEO). On the coating-modified surfaces, the bovine serum albumin (BSA) adsorption, respectively, from the low and high BSA bulk concentration solutions was correspondingly characterized by the methods of radioactive 125I-probe and ATR-FTIR. The bovine serum fibrinogen (Fg)-adsorption from the Fg bulk solution and the BSA-Fg competing adsorption from the BSA-Fg binary solutions were also characterized by radioactive 125I-probe. The reversible BSA-selective in situ adsorption on MSPEO-modified PEU surfaces were achieved, and the performance of blood compatibility on the coating-modified surfaces was also confirmed, respectively, by plasma recalcification time (PRT) and prothrombin time (PT) tests. PMID:11853382

Wang, D A; Ji, J; Feng, L X

2001-01-01

268

Advanced oxidation processes coupled with electrocoagulation for the exhaustive abatement of Cr-EDTA.  

PubMed

Using Cr-EDTA as a model system, a two-step method has been investigated for the abatement of persistent chromium complexes in water. The treatment consists of an oxidative decomposition of the organic ligands by means of ozonization or electrochemical oxidation at a boron doped diamond (BDD) electrode, followed by removal of the metal via electrochemical coagulation. In the designed synthetic waste, EDTA has been used both as a chelating agent and as a mimic of the organic content of a typical wastewater provided by a purification leather plant. A crucial point evaluated is the influence of the oxidative pretreatment on the chemical modification of the synthetic waste and hence on the electrocoagulation efficacy. Because of the great stability of Cr complexes, such as Cr-EDTA, the classical coagulation methods, based on ligand exchange between Cr(III) and Fe(II) or Fe(III), are ineffective toward Cr abatement in the presence of organic substances. On the contrary, when advanced oxidation processes (AOPs), such as ozonization or electrooxidation at a BDD anode are applied in series with electrocoagulation (EC), complete abatement of the recalcitrant Cr fraction can be achieved. ECs have been carried out by using Fe sacrificial anodes, with alternating polarization and complete Cr abatement (over 99%) has been obtained with modest charge consumption. It has been found that Cr(III) is first oxidized to Cr(VI) in the AOP preceding EC. Then, during EC, Cr(VI) is mainly reduced back to Cr(III) by electrogenerated Fe(II). Thus, Cr is mainly eliminated as Cr(III). However, a small fraction of Cr(VI) goes with the precipitate as confirmed by XPS analysis of the sludge. PMID:21255817

Durante, Christian; Cuscov, Marco; Isse, Abdirisak Ahmed; Sandonà, Giancarlo; Gennaro, Armando

2011-02-01

269

Lateral-coupling coplanar-gate oxide-based thin-film transistors on bare paper substrates  

NASA Astrophysics Data System (ADS)

For conventional thin-film transistors (TFTs), bottom-gate or top-gate configuration is always adopted because the channel current is generally controlled by vertical capacitive coupling. In this article, depending on huge lateral electric-double-layer (EDL) capacitor induced by spatial movement of protons in phosphosilicate glass (PSG) solid electrolyte dielectrics, coplanar-gate indium–zinc–oxide (IZO)-TFTs based on the lateral capacitive coupling were fabricated on bare paper substrates. The PSG solid electrolyte films here were used at the same time as gate dielectrics and smooth buffer layers. These TFTs showed a low-voltage operation of only 1?V with a large field-effect mobility of 13.4?cm2?V?1·s, a high current on/off ratio of 6? × ?106 and a small subthreshold swing of 75?mV/decade. Furthermore, with introducing another coplanar gate, AND logic operation was also demonstrated on the coplanar dual-gate TFTs. These simple lateral-coupling coplanar-gate IZO-TFTs on bare paper substrates are very promising for low-cost portable sensors and bio-electronics.

Wu, Guodong; Wan, Xiang; Yang, Yi; Jiang, Shuanghe

2014-11-01

270

A global model of the coupled sulfur/oxidant chemistry in the troposphere: The sulfur cycle  

NASA Astrophysics Data System (ADS)

A sulfur cycle chemistry scheme with dimethyl sulfide (DMS), SO2, sulfate, H2S, and methanesulfonic acid (MSA) is included in the OsloCTM2 model, and concentrations of sulfur are calculated interactively with the oxidant chemistry. This allows more consistent estimates of aqueous phase oxidation of SO2 to sulfate by O3, H2O2, and HO2NO2. The year 1996 is chosen as the standard, and a model run with 1996 meteorology and emissions is compared with 1996 observations. The results agree well with observations overall, although the model tends to overestimate SO2 and underestimate sulfate in Northern Hemisphere winter owing to an oxidation limitation. A global budget for 1996 quantifying the various processes is investigated. Our model results give a global lifetime (global burden) of 1 day (0.25 Tg(S)) and 3.8 days (0.5 3 Tg(S)) for SO2 and sulfate. Differences between the Southern Hemisphere, characterized by natural emissions and by loss of SO2 by O3 and H2O2 oxidation, and the Northern Hemisphere, characterized by anthropogenic emissions and by large loss by dry deposition, are revealed. Significant changes in sulfur emissions have occurred over the last decades with decrease in the Unites States and Europe and increase in Southeast Asia. U.S., European, and Chinese SO2 emissions have changed by -17.6%, -47.5%, and +93%, respectively. To study the impact of emission changes on the atmospheric composition, we have calculated distributions using the Global Emissions Inventory Activity (GEIA) 1985 inventory. The changes in sulfur emissions have significant changes on the sulfur concentrations and also some effect upon the oxidants. Increased emissions of NOx and hydrocarbons in China enhance O3, but increased sulfur inhibit the increase. The SO2 oxidation by OH, which can lead to formation of new sulfate particles, is given special attention. The model run using GEIA 1985 anthropogenic emission inventory is compared with other model studies.

Berglen, Tore F.; Berntsen, Terje K.; Isaksen, Ivar S. A.; Sundet, Jostein K.

2004-10-01

271

Coupling Fenton and biological oxidation for the removal of nitrochlorinated herbicides from water.  

PubMed

The combination of Fenton and biological oxidation for the removal of the nitrochlorinated herbicides alachlor, atrazine and diuron in aqueous solution has been studied. The H2O2 dose was varied from 20 to 100% of the stoichiometric amount related to the initial chemical oxygen demand (COD). The effluents from Fenton oxidation were analyzed for ecotoxicity, biodegradability, total organic carbon (TOC), COD and intermediate byproducts. The chemical step resulted in a significant improvement of the biodegradability in spite of its negligible or even slightly negative effect on the ecotoxicity. Working at 60% of the stoichiometric H2O2 dose allowed obtaining highly biodegradable effluents in the cases of alachlor and atrazine. That dose was even lower (40% of the stoichiometric) for diuron. The subsequent biological treatment was carried out in a sequencing batch reactor (SBR) and the combined Fenton-biological treatment allowed up to around 80% of COD reduction. PMID:24333521

Sanchis, S; Polo, A M; Tobajas, M; Rodriguez, J J; Mohedano, A F

2014-02-01

272

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, 1993--March 31, 1993  

SciTech Connect

Work continued on the development of catalysts for the steam gasification of chars and for the oxidative coupling of methane. Testing of the catalysts Ni-Ca-K-oxides and Co-Ca-K-oxides are described for gasification research; results of the testing of a Co-Mg-oxide catalysts for methane conversion are also described.

Heinemann, H.; Somorjai, G.A.; Perry, D.L.

1993-03-01

273

Adsorption and reaction of acrolein on titanium oxide single crystal surfaces: coupling versus condensation  

Microsoft Academic Search

The reactions of acrolein have been investigated on TiO2(001) single crystal surfaces by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS). Two carbon–carbon bond-forming reactions were observed. The first, on defect-containing surfaces, is reductive coupling to form olefins. The high reaction yield of ca. 80% shows the high activity of such surfaces

A. B. Sherrill; H. Idriss; M. A. Barteau; J. G. Chen

2003-01-01

274

Dye Sensitized Tandem Photovoltaic Cells  

SciTech Connect

This work provided a new way to look at photoelectrochemical cells and their performance. Although thought of as low efficiency, a the internal efficiency of a 9% global efficiency dye sensitized solar cell is approximately equal to an 18% efficient silicon cell when each is compared to their useful spectral range. Other work undertaken with this contract also reported the first growth oriented titania and perovskite columns on a transparent conducting oxide. Other work has shown than significant performance enhancement in the performance of dye sensitized solar cells can be obtained through the use of coupling inverse opal photonic crystals to the nanocrystalline dye sensitized solar cell. Lastly, a quick efficient method was developed to bond titanium foils to transparent conducting oxide substrates for anodization.

Barber, Greg D.

2009-12-21

275

Coupling of exothermic and endothermic reactions in oxidative conversion of natural gas into ethylene\\/olefins over diluted SrO\\/LaâOâ\\/SA5205 catalyst  

Microsoft Academic Search

In the oxidative conversion of natural gas to ethylene\\/lower olefins over SrO (17.3 wt.%)\\/LaâOâ (17.9 wt.%)\\/SA5205 catalyst diluted with inert solid particles (inerts\\/catalyst(w\\/w) = 2.0) in the presence of limited Oâ, the exothermic oxidative conversion reactions of natural gas are coupled with the endothermic C{sub 2+} hydrocarbon thermal cracking reactions for avoiding hot spot formation and eliminating heat removal problems.

Vasant R. Choudhary; Shafeek A. R. Mulla

1997-01-01

276

Rapid access to 3-(aminomethyl)isoquinoline-fused polycyclic compounds by copper-catalyzed four-component coupling, cascade cyclization, and oxidation.  

PubMed

A novel copper-catalyzed synthesis of 3-(aminomethyl)isoquinoline-fused polycyclic compounds, through four-component coupling, cyclization, and oxidation, has been developed. A Mannich-type reaction of 2-ethynylbenzaldehyde with paraformaldehyde and a secondary amine followed by treatment with a diamine component gave tricyclic isoquinolines through cascade cyclization and oxidation. Construction of fused isoquinolines of various ring sizes is also presented. PMID:19572599

Ohta, Yusuke; Kubota, Yushi; Watabe, Tsuyoshi; Chiba, Hiroaki; Oishi, Shinya; Fujii, Nobutaka; Ohno, Hiroaki

2009-08-21

277

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

SciTech Connect

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.

Okamoto, Satoshi [ORNL

2013-01-01

278

Hexagonal Ag nanoarrays induced enhancement of blue light emission from amorphous oxidized silicon nitride via localized surface plasmon coupling.  

PubMed

A significant enhancement of blue light emission from amorphous oxidized silicon nitride (a-SiNx:O) films is achieved by introduction of ordered and size-controllable arrays of Ag nanoparticles between the silicon substrate and a-SiNx:O films. Using hexagonal arrays of Ag nanoparticles fabricated by nanosphere lithography, the localized surface plasmons (LSPs) resonance can effectively increase the internal quantum efficiency from 3.9% to 13.3%. Theoretical calculation confirms that the electromagnetic field-intensity enhancement is through the dipole surface plasma coupling with the excitons of a-SiNx:O films, which demonstrates a-SiNx:O films with enhanced blue emission are promising for silicon-based light-emitting applications by patterned Ag arrays. PMID:25402058

Ma, Zhongyuan; Ni, Xiaodong; Zhang, Wenping; Jiang, Xiaofan; Yang, Huafeng; Yu, Jie; Wang, Wen; Xu, Ling; Xu, Jun; Chen, Kunji; Feng, Duan

2014-11-17

279

High-temperature catalytic oxidative conversion of propane to propylene and ethylene involving coupling of exothermic and endothermic reactions  

SciTech Connect

Coupling of the exothermic catalytic oxidative conversion and endothermic thermal cracking (noncatalytic) reactions of propane to propylene and ethylene over the SrO/La{sub 2}O{sub 3}/SA5205 catalyst in the presence of steam and limited oxygen was investigated at different process conditions (temperature, 700--850 C; C{sub 3}H{sub 8}/O{sub 2} ratio in feed, 2.0--8.0; H{sub 2}O/C{sub 3}H{sub 8} ratio, 0.5--2.5; space velocity, 2,000--15,000 cm{sup 3}/g h). In the presence of steam and limited O{sub 2}, the endothermic thermal cracking and exothermic oxidative conversion reactions occur simultaneously and there is no coke formation on the catalyst. Because of the direct coupling of exothermic and endothermic reactions, this process occurs in a most energy efficient and safe manner. The propane conversion, selectivity for propylene, and net heat of reaction ({Delta}H{sub r}) in the process are strongly influenced by the temperature and concentration of O{sub 2} relative to the propane in the feed. The C{sub 3}H{sub 6}/C{sub 2}H{sub 4} product ratio is also strongly influenced by the temperature, C{sub 3}H{sub 8}/O{sub 2} feed ratio, and space velocity. The net heat of reaction can be controlled by manipulating the reaction temperature and C{sub 3}H{sub 8}/O{sub 2} ratio in the feed; the process exothermicity is reduced drastically with increasing the temperature and/or C{sub 3}H{sub 8}/O{sub 2} feed ratio.

Choudhary, V.R.; Rane, V.H.; Rajput, A.M.

2000-04-01

280

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

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

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

281

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

PubMed Central

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

Ramond, Elodie; Gesbert, Gael; Rigard, Mélanie; Dairou, Julien; Dupuis, Marion; Dubail, Iharilalao; Meibom, Karin; Henry, Thomas; Barel, Monique; Charbit, Alain

2014-01-01

282

Quantification of Arginine and its Methylated Derivatives in Healthy Children by Liquid Chromatography-Tandem Mass Spectrometry.  

PubMed

Asymmetric dimethylarginine (ADMA) is a competitive inhibitor of nitric oxide synthase, which is responsible for most of the vascular nitric oxide (NO) produced. NO is an important physiological mediator of vascular tone and structure in normally functioning endothelial cells. We report the optimization of a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for simultaneous determination of arginine (Arg) and its derivatives in biological samples. Chromatographic separation and mass detection were performed by reverse phase chromatography coupled with tandem mass spectrometry. For sample preparation, plasma proteins were removed by centrifugal filters. Positive electrospray ionization was performed and analytes were detected by multiple reaction monitoring. Inter- and intra-day repeatability, accuracy, recovery, and limits of detection and quantification were evaluated to validate the method. Plasma and urine levels were measured in healthy children to establish control values: 52.2-124.7 µM for Arg, 0.06-0.16 µM for MMA, 0.42-1.10 µM for ADMA and 0.41-0.96 µM for SDMA in plasma. Quantification of Arg and its methylated derivatives by LC-MS/MS can be carried out without the need of organic solvents for sample preparation, and be used as a valuable tool in research on endothelial dysfunction. PMID:25260846

Andrade, Fernando; Llarena, Marta; Lage, Sergio; Aldámiz-Echevarría, Luis

2014-09-25

283

Molecular characterization of a microbial consortium involved in methane oxidation coupled to denitrification under micro-aerobic conditions.  

PubMed

Methane can be used as an alternative carbon source in biological denitrification because it is nontoxic, widely available and relatively inexpensive. A microbial consortium involved in methane oxidation coupled to denitrification (MOD) was enriched with nitrite and nitrate as electron acceptors under micro-aerobic conditions. The 16S rRNA gene combined with pmoA phylogeny of methanotrophs and nirK phylogeny of denitrifiers were analysed to reveal the dominant microbial populations and functional microorganisms. Real-time quantitative polymerase chain reaction results showed high numbers of methanotrophs and denitrifiers in the enriched consortium. The 16S rRNA gene clone library revealed that Methylococcaceae and Methylophilaceae were the dominant populations in the MOD ecosystem. Phylogenetic analyses of pmoA gene clone libraries indicated that all methanotrophs belonged to Methylococcaceae, a type I methanotroph employing the ribulose monophosphate pathway for methane oxidation. Methylotrophic denitrifiers of the Methylophilaceae that can utilize organic intermediates (i.e. formaldehyde, citrate and acetate) released from the methanotrophs played a vital role in aerobic denitrification. This study is the first report to confirm micro-aerobic denitrification and to make phylogenetic and functional assignments for some members of the microbial assemblages involved in MOD. PMID:24245852

Liu, Jingjing; Sun, Faqian; Wang, Liang; Ju, Xi; Wu, Weixiang; Chen, Yingxu

2014-01-01

284

Molecular characterization of a microbial consortium involved in methane oxidation coupled to denitrification under micro-aerobic conditions  

PubMed Central

Methane can be used as an alternative carbon source in biological denitrification because it is nontoxic, widely available and relatively inexpensive. A microbial consortium involved in methane oxidation coupled to denitrification (MOD) was enriched with nitrite and nitrate as electron acceptors under micro-aerobic conditions. The 16S rRNA gene combined with pmoA phylogeny of methanotrophs and nirK phylogeny of denitrifiers were analysed to reveal the dominant microbial populations and functional microorganisms. Real-time quantitative polymerase chain reaction results showed high numbers of methanotrophs and denitrifiers in the enriched consortium. The 16S rRNA gene clone library revealed that Methylococcaceae and Methylophilaceae were the dominant populations in the MOD ecosystem. Phylogenetic analyses of pmoA gene clone libraries indicated that all methanotrophs belonged to Methylococcaceae, a type I methanotroph employing the ribulose monophosphate pathway for methane oxidation. Methylotrophic denitrifiers of the Methylophilaceae that can utilize organic intermediates (i.e. formaldehyde, citrate and acetate) released from the methanotrophs played a vital role in aerobic denitrification. This study is the first report to confirm micro-aerobic denitrification and to make phylogenetic and functional assignments for some members of the microbial assemblages involved in MOD. PMID:24245852

Liu, Jingjing; Sun, Faqian; Wang, Liang; Ju, Xi; Wu, Weixiang; Chen, Yingxu

2014-01-01

285

Design and Growth of III-V on Si Microwire Array Tandem Solar Cells Christopher T. Chen1  

E-print Network

Design and Growth of III-V on Si Microwire Array Tandem Solar Cells Christopher T. Chen1 , Daniel B Abstract -- Tandem Ga1-xInxP/Si microwire array solar cells are a route towards a high efficiency, low cost, flexible, wafer- free solar technology. Coupled full-field optical and device physics simulations of a Ga0

Atwater, Harry

286

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

Microsoft Academic Search

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

Stamatia I. Kotretsou; Aglaia Koutsodimou

2006-01-01

287

Oxidative Reactivity and Cytotoxic Properties of a Platinum(II) Complex Prepared by Outer-Sphere Amide Bond Coupling.  

PubMed

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 (1)H, (13)C, and (195)Pt 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

Wilson, Justin J; Lippard, Stephen J

2013-07-13

288

Nitric oxide mediates metabolic coupling of omentum-derived adipose stroma to ovarian and endometrial cancer cells.  

PubMed

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. Cancer Res; 75(2); 456-71. ©2014 AACR. PMID:25425006

Salimian Rizi, Bahar; Caneba, Christine; Nowicka, Aleksandra; Nabiyar, Ahmad W; Liu, Xinran; Chen, Kevin; Klopp, Ann; Nagrath, Deepak

2015-01-15

289

Plasma silicon oxide films on garnet substrates: measurement of their thickness and refractive index by the prism coupling technique.  

PubMed

The prism coupling technique has been used to measure the refractive index and thickness of plasma silicon oxide films deposited on garnet substrates. The film thickness is also measured with a mechanical stylus (Talystep) for comparison. A linearly polarized He-Ne laser at 632.8-nm wavelength or a He-Cd laser at 441.6-nm wavelength is used as the light source in the prism coupler. The use of the He-Ne laser is demonstrated to result in a fluctuation in the detector output due to light interference in the substrate. The He-Cd laser is shown to be superior because the substrate is sufficiently absorbing that interference is eliminated. It also permits thickness measurements on thinner films. The agreement between thickness measurements by the prism coupler and the mechanical stylus is within +/-0.015 microm for films of 0.4 microm or thicker and +/-0.010 microm for thinner films. The error in thickness measurement caused by an error in refractive index assumed or in determining the coupling angles for films thinner than 0.30 microm is also estimated. PMID:20333119

Hou, T W; Mogab, C J

1981-09-15

290

Thickness-dependent crossover from charge- to strain-mediated magnetoelectric coupling in ferromagnetic/piezoelectric oxide heterostructures.  

PubMed

Magnetoelectric oxide heterostructures are proposed active layers for spintronic memory and logic devices, where information is conveyed through spin transport in the solid state. Incomplete theories of the coupling between local strain, charge, and magnetic order have limited their deployment into new information and communication technologies. In this study, we report direct, local measurements of strain- and charge-mediated magnetization changes in the La0.7Sr0.3MnO3/PbZr0.2Ti0.8O3 system using spatially resolved characterization techniques in both real and reciprocal space. Polarized neutron reflectometry reveals a graded magnetization that results from both local structural distortions and interfacial screening of bound surface charge from the adjacent ferroelectric. Density functional theory calculations support the experimental observation that strain locally suppresses the magnetization through a change in the Mn-eg orbital polarization. We suggest that this local coupling and magnetization suppression may be tuned by controlling the manganite and ferroelectric layer thicknesses, with direct implications for device applications. PMID:24313563

Spurgeon, Steven R; Sloppy, Jennifer D; Kepaptsoglou, Despoina Maria Demie; Balachandran, Prasanna V; Nejati, Siamak; Karthik, J; Damodaran, Anoop R; Johnson, Craig L; Ambaye, Hailemariam; Goyette, Richard; Lauter, Valeria; Ramasse, Quentin M; Idrobo, Juan Carlos; Lau, Kenneth K S; Lofland, Samuel E; Rondinelli, James M; Martin, Lane W; Taheri, Mitra L

2014-01-28

291

Strongly coupled Pd nanotetrahedron/tungsten oxide nanosheet hybrids with enhanced catalytic activity and stability as oxygen reduction electrocatalysts.  

PubMed

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

Lu, Yizhong; Jiang, Yuanyuan; Gao, Xiaohui; Wang, Xiaodan; Chen, Wei

2014-08-20

292

Electro-optic switching in iron oxide nanoparticle embedded paramagnetic chiral liquid crystal via magneto-electric coupling  

SciTech Connect

The variation in optical texture, electro-optic, and dielectric properties of iron oxide nanoparticles (NPs) embedded ferroelectric liquid crystal (FLC) with respect to change in temperature and electrical bias conditions are demonstrated in the current investigations. Improvement in spontaneous polarization and response time in nanocomposites has been attributed to magneto-electric (ME) coupling resulting from the strong interaction among the ferromagnetic nanoparticle's exchange field (due to unpaired e{sup ?}) and the field of liquid crystal molecular director. Electron paramagnetic resonance spectrum of FLC material gives a broad resonance signal with superimposed components indicating the presence of a source of spin. This paramagnetic behavior of host FLC material had been a major factor in strengthening the guest host interaction by giving an additional possibility of (a) spin-spin interaction and (b) interactions between magnetic-dipole and electric-dipole moments (ME effects) in the composite materials. Furthermore, the phenomenon of dielectric and static memory effect in these composites are also observed which yet again confirms the coupling of magnetic NP's field with FLC's director orientation. We therefore believe that such advanced soft materials holding the optical and electrical properties of conventional LCs with the magnetic and electronic properties of ferromagnetic nanoparticles are going to play a key role in the development of futuristic multifunctional optical devices.

Goel, Puja, E-mail: pujagoel@gmail.com [Division of Agricultural Chemicals, Indian Agricultural Research Institute, New Delhi 110012 (India); Arora, Manju; Biradar, Ashok M. [Materials Physics and Engineering Division, CSIR-National Physical Laboratory, Dr. K. S. Krishnan Marg, New Delhi 110012 (India)

2014-03-28

293

Electro-optic switching in iron oxide nanoparticle embedded paramagnetic chiral liquid crystal via magneto-electric coupling  

NASA Astrophysics Data System (ADS)

The variation in optical texture, electro-optic, and dielectric properties of iron oxide nanoparticles (NPs) embedded ferroelectric liquid crystal (FLC) with respect to change in temperature and electrical bias conditions are demonstrated in the current investigations. Improvement in spontaneous polarization and response time in nanocomposites has been attributed to magneto-electric (ME) coupling resulting from the strong interaction among the ferromagnetic nanoparticle's exchange field (due to unpaired e-) and the field of liquid crystal molecular director. Electron paramagnetic resonance spectrum of FLC material gives a broad resonance signal with superimposed components indicating the presence of a source of spin. This paramagnetic behavior of host FLC material had been a major factor in strengthening the guest host interaction by giving an additional possibility of (a) spin-spin interaction and (b) interactions between magnetic-dipole and electric-dipole moments (ME effects) in the composite materials. Furthermore, the phenomenon of dielectric and static memory effect in these composites are also observed which yet again confirms the coupling of magnetic NP's field with FLC's director orientation. We therefore believe that such advanced soft materials holding the optical and electrical properties of conventional LCs with the magnetic and electronic properties of ferromagnetic nanoparticles are going to play a key role in the development of futuristic multifunctional optical devices.

Goel, Puja; Arora, Manju; Biradar, Ashok M.

2014-03-01

294

FEM simulation of oxidation induced stresses with a coupled crack propagation in a TBC model system  

NASA Astrophysics Data System (ADS)

Plasma sprayed thermal barrier coating systems are used on top of highly stressed components, e.g. on gas turbine blades, to protect the underlying substrate from the high surrounding temperatures. A typical coating system consists of the bond-coat (BC), the thermal barrier coating (TBC), and the thermally grown oxide (TGO) between the BC and the TBC. This study examines the failure mechanisms which are caused by the diffusion of oxygen through the TBC and the resulting growth of the TGO. To study the behaviour of the complex failure mechanisms in thermal barrier coatings, a simplified model system is used to reduce the number of system parameters. The model system consists of a bond-coat material (fast creeping Fecralloy or slow creeping MA956) as the substrate with a Y2O3 partially stabilised plasma sprayed zircon oxide TBC on top and a TGO between the two layers. Alongside the experimental studies a FEM simulation was developed to calculate the stress distribution inside the simplified coating system [1]. The simulation permits the identification of compression and tension areas which are established by the growth of the oxide layer. Furthermore a 2-dimensional finite element model of crack propagation was developed in which the crack direction is calculated by using short trial cracks in different directions. The direction of the crack in the model system is defined as the crack direction with the maximum energy release rate [2,3]. The simulated stress distributions and the obtained crack path provide an insight into the possible failure mechanisms in the coating and allow to draw conclusions for optimising real thermal barrier coating systems. The simulated growth stresses of the TGO show that a slow creeping BC may reduce lifetime. This is caused by stress concentration and cracks under the TGO. A slow creeping BC on the other hand reduces the stresses in the TBC. The different failure mechanisms emphasise the existence of a lifetime optimum which depends on the creep properties of the used bond-coat material. Experimental results show a good agreement with the predicted failure mechanisms.

Seiler, P.; Bäker, M.; Rösier, J.

2010-06-01

295

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

DOEpatents

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.

Parry, G.W.

1988-04-21

296

Proton conducting sodium alginate electrolyte laterally coupled low-voltage oxide-based transistors  

SciTech Connect

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.

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

297

Radical O-O coupling reaction in diferrate-mediated water oxidation studied using multireference wave function theory.  

PubMed

The O-O (oxygen-oxygen) bond formation is widely recognized as a key step of the catalytic reaction of dioxygen evolution from water. Recently, the water oxidation catalyzed by potassium ferrate (K2FeO4) was investigated on the basis of experimental kinetic isotope effect analysis assisted by density functional calculations, revealing the intramolecular oxo-coupling mechanism within a di-iron(vi) intermediate, or diferrate [Sarma et al., J. Am. Chem. Soc., 2012, 134, 15371]. Here, we report a detailed examination of this diferrate-mediated O-O bond formation using scalable multireference electronic structure theory. High-dimensional correlated many-electron wave functions beyond the one-electron picture were computed using the ab initio density matrix renormalization group (DMRG) method along the O-O bond formation pathway. The necessity of using large active space arises from the description of complex electronic interactions and varying redox states both associated with two-center antiferromagnetic multivalent iron-oxo coupling. Dynamic correlation effects on top of the active space DMRG wave functions were additively accounted for by complete active space second-order perturbation (CASPT2) and multireference configuration interaction (MRCI) based methods, which were recently introduced by our group. These multireference methods were capable of handling the double shell effects in the extended active space treatment. The calculations with an active space of 36 electrons in 32 orbitals, which is far over conventional limitation, provide a quantitatively reliable prediction of potential energy profiles and confirmed the viability of the direct oxo coupling. The bonding nature of Fe-O and dual bonding character of O-O are discussed using natural orbitals. PMID:24686771

Kurashige, Yuki; Saitow, Masaaki; Chalupský, Jakub; Yanai, Takeshi

2014-06-28

298

Weak-coupling theory of high-temperature superconductivity in the antiferromagnetically correlated copper oxides  

NASA Astrophysics Data System (ADS)

We show that the retarded interaction between quasiparticles on a two dimensional square lattice induced by the exchange of antiferromagnetic paramagnons leads uniquely to a transition to a superconducting state with d2x-y2 symmetry. We find that the effective quasiparticle interaction responsible for superconductivity possesses considerable structure in both momentum and frequency space, and show, by explicit calculations, that if one wishes to obtain quantitatively meaningful results it is essential to allow for that structure in solving the full integral equations that determine the superconducting transition temperature and the superconducting properties. With a spin-excitation spectrum and a quasiparticle-paramagnon coupling determined by fits to normal-state experiments, we obtain high transition temperatures and energy-gap behaviors comparable to those measured for YBa2Cu3O7, YBa2Cu3O6.63, and La1.85Sr0.15CuO4.

Monthoux, P.; Balatsky, A. V.; Pines, D.

1992-12-01

299

The efficacy of oxidative coupling for promoting in-situ immobilization of hydroxylated aromatics in contaminated soil and sediment systems. 1998 annual progress report  

Microsoft Academic Search

'Hydroxylated aromatic compounds (HAC''s) and their precursors are common contaminants of surface and subsurface systems at DOE facilities. The environmental fate and transport of such compounds, particularly in subsurface systems, is generally dominated by their sorption and desorption by soils and sediments. Certain secondary chemical reactions, most specifically abiotic and\\/or enzymatic oxidative coupling, may be significant in controlling the sorption

W. J. Weber; A. Bhandari

1998-01-01

300

Cu-catalysed oxidative C-H/C-H coupling polymerisation of benzodiimidazoles: an efficient approach to regioregular polybenzodiimidazoles for blue-emitting materials.  

PubMed

The Cu-catalysed oxidative C-H/C-H coupling reaction of azoles has been used for the first time to develop polymerisation, which provides an efficient method for the preparation of polybenzodiimidazoles. These polymers exhibit high molecular weights, regioregularity, blue-emitting performance and thermal stability. PMID:25248306

Huang, Quan; Qin, Xurong; Li, Bijin; Lan, Jingbo; Guo, Qiang; You, Jingsong

2014-11-18

301

Transition metal free intramolecular selective oxidative C(sp(3))-N coupling: synthesis of N-aryl-isoindolinones from 2-alkylbenzamides.  

PubMed

A synthetic method has been developed for the preparation of biologically important isoindolinones including indoprofen and DWP205190 drugs from 2-alkylbenzamide substrates by transition metal-free intramolecular selective oxidative coupling of C(sp(3))-H and N-H bonds utilizing iodine, potassium carbonate and di-tert-butyl peroxide in acetonitrile at 110-140 °C. PMID:25487732

Verma, Ajay; Patel, Saket; Meenakshi; Kumar, Amit; Yadav, Abhimanyu; Kumar, Shailesh; Jana, Sadhan; Sharma, Shubham; Prasad, Ch Durga; Kumar, Sangit

2014-12-23

302

New developments in the analysis of fragrances and earthy-musty compounds in water by solid-phase microextraction (metal alloy fibre) coupled with gas chromatography-(tandem) mass spectrometry.  

PubMed

Fragrances are widespread aquatic contaminants due to their presence in many personal care products used daily in developed countries. Levels of galaxolide and tonalide are commonly found in surface waters, urban wastewaters and river sediments. On the other hand, earthy-musty compounds confer bad odour to drinking water at levels that challenge the analytical capabilities. The combined determination of earthy-musty compounds and fragrances in water would be a breakthrough to make the traditional organoleptic evaluation of the water quality stricter and safer for the analyst. Two approaches were attempted to improve the analytical capabilities: analyte pre-concentration with a newly developed PDMS-DVB solid-phase microextraction fibre on metal alloy core and sensitive detection by tandem mass spectrometry (MS/MS). The optimization of SPME parameters was carried out using a central composite design and desirability functions. The final optimum extraction conditions were: headspace extraction at 70°C during 40 min adding 200 g L(-1) of NaCl. The detection limits in tandem MS (0.02-20 ng L(-1)) were marginally lower compared to full scan except for geosmin and trichloroanisol which go down to 0.1 and 0.02 ng L(-1), respectively. The analysis of different water matrices revealed that fragrances and earthy-musty compounds were absent from ground- and drinking waters. Surface waters of river Leça contained levels of galaxolide around 250 ng L(-1) in the 4 terminal sampling stations, which are downstream of WWTPs and polluted tributaries. Geosmine was ubiquitously distributed in natural waters similarly in rivers Leça and Douro at concentrations <7 ng L(-1). PMID:21530789

Machado, S; Gonçalves, C; Cunha, E; Guimarães, A; Alpendurada, M F

2011-05-30

303

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

DOEpatents

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.

Parry, Gareth W. (East Windsor, CT)

1989-01-01

304

Using Coupled Mesoscale Experiments and Simulations to Investigate High Burn-Up Oxide Fuel Thermal Conductivity  

NASA Astrophysics Data System (ADS)

Nuclear energy is a mature technology with a small carbon footprint. However, work is needed to make current reactor technology more accident tolerant and to allow reactor fuel to be burned in a reactor for longer periods of time. Optimizing the reactor fuel performance is essentially a materials science problem. The current understanding of fuel microstructure have been limited by the difficulty in studying the structure and chemistry of irradiated fuel samples at the mesoscale. Here, we take advantage of recent advances in experimental capabilities to characterize the microstructure in 3D of irradiated mixed oxide (MOX) fuel taken from two radial positions in the fuel pellet. We also reconstruct these microstructures using Idaho National Laboratory's MARMOT code and calculate the impact of microstructure heterogeneities on the effective thermal conductivity using mesoscale heat conduction simulations. The thermal conductivities of both samples are higher than the bulk MOX thermal conductivity because of the formation of metallic precipitates and because we do not currently consider phonon scattering due to defects smaller than the experimental resolution. We also used the results to investigate the accuracy of simple thermal conductivity approximations and equations to convert 2D thermal conductivities to 3D. It was found that these approximations struggle to predict the complex thermal transport interactions between metal precipitates and voids.

Teague, Melissa C.; Fromm, Bradley S.; Tonks, Michael R.; Field, David P.

2014-12-01

305

Carbohydrate oxidation coupled to Fe(III) reduction, a novel form of anaerobic metabolism  

USGS Publications Warehouse

An isolate, designated GC-29, that could incompletely oxidize glucose to acetate and carbon dioxide with Fe(III) serving as the electron acceptor was recovered from freshwater sediments of the Potomac River, Maryland. This metabolism yielded energy to support cell growth. Strain GC-29 is a facultatively anaerobic, Gram-negative motile rod which, in addition to glucose, also used sucrose, lactate, pyruvate, yeast extract, casamino acids or H2 as alternative electron donors for Fe(III) reduction. Stain GC-29 could reduce NO-3, Mn(IV), U(VI), fumarate, malate, S2O32-, and colloidal S0 as well as the humics analog, 2,6-anthraquinone disulfonate. Analysis of the almost complete 16S rRNA sequence indicated that strain GC-29 belongs in the Shewanella genus in the epsilon subdivision of the Proteobacteria. The name Shewanella saccharophilia is proposed. Shewanella saccharophilia differs from previously described fermentative microorganisms that metabolize glucose with the reduction of Fe(III) because it transfers significantly more electron equivalents to Fe(III); acetate and carbon dioxide are the only products of glucose metabolism; energy is conserved from Fe(III) reduction; and glucose is not metabolized in the absence of Fe(III). The metabolism of organisms like S. saccharophilia may account for the fact that glucose is metabolized primarily to acetate and carbon dioxide in a variety of sediments in which Fe(III) reduction is the terminal electron accepting process.

Coates, J.D.; Councell, T.; Ellis, D.J.; Lovley, D.R.

1998-01-01

306

Coupling of Propylene Oxide and Lactide at a Porphyrin Chromium(III) Center.  

PubMed

5,10,15,20-Tetraphenylporphyrin chromium chloride (TPPCrCl) with added [Ph3P?N?PPh3](+)Cl(-) (PPN(+)Cl(-)) selectively polymerizes lactide (l and rac) dissolved in neat propylene oxide (PO) to yield polylactide (PLA) terminated by the -OCHMeCH2Cl group. At 0 °C and below, rac-LA yields polymers highly enriched in isotactic tetrads (iii). At 25 °C, some stereoselectivity is lost as transesterification becomes significant, and at 60 °C and above, enchainment of PO leads to the formation of 3,6-dimethyl-1,4-dioxan-2-one by a backbiting mechanism. At 0 °C, after the enchainment of l-(S,S)-LA in neat (R)-(+)-PO, the formation of (3S,6R)-3,6-dimethyl-1,4-dioxan-2-one occurs, while at higher temperatures the ratio of (3S,6R)-3,6-dimethyl-1,4-dioxan-2-one to (3R,6R)-3,6-dimethyl-1,4-dioxan-2-one falls to 3:2. PMID:25629656

Balasanthiran, Vagulejan; Chatterjee, Chandrani; Chisholm, Malcolm H; Harrold, Nicole D; RajanBabu, T V; Warren, Grant A

2015-02-11

307

Tandem Cylinder Noise Predictions  

NASA Technical Reports Server (NTRS)

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.

Lockhard, David P.; Khorrami, Mehdi R.; CHoudhari, Meelan M.; Hutcheson, Florence V.; Brooks, Thomas F.; Stead, Daniel J.

2007-01-01

308

Carbon and sulfur back flux during anaerobic microbial oxidation of methane and coupled sulfate reduction.  

PubMed

Microbial degradation of substrates to terminal products is commonly understood as a unidirectional process. In individual enzymatic reactions, however, reversibility (reverse reaction and product back flux) is common. Hence, it is possible that entire pathways of microbial degradation are associated with back flux from the accumulating product pool through intracellular intermediates into the substrate pool. We investigated carbon and sulfur back flux during the anaerobic oxidation of methane (AOM) with sulfate, one of the least exergonic microbial catabolic processes known. The involved enzymes must operate not far from the thermodynamic equilibrium. Such an energetic situation is likely to favor product back flux. Indeed, cultures of highly enriched archaeal-bacterial consortia, performing net AOM with unlabeled methane and sulfate, converted label from (14)C-bicarbonate and (35)S-sulfide to (14)C-methane and (35)S-sulfate, respectively. Back fluxes reached 5% and 13%, respectively, of the net AOM rate. The existence of catabolic back fluxes in the reverse direction of net reactions has implications for biogeochemical isotope studies. In environments where biochemical processes are close to thermodynamic equilibrium, measured fluxes of labeled substrates to products are not equal to microbial net rates. Detection of a reaction in situ by labeling may not even indicate a net reaction occurring in the direction of label conversion but may reflect the reverse component of a so far unrecognized net reaction. Furthermore, the natural isotopic composition of the substrate and product pool will be determined by both the forward and back flux. This finding may have to be considered in the interpretation of stable isotope records. PMID:22160711

Holler, Thomas; Wegener, Gunter; Niemann, Helge; Deusner, Christian; Ferdelman, Timothy G; Boetius, Antje; Brunner, Benjamin; Widdel, Friedrich

2011-12-27

309

Carbon nanomaterials as charge collectors in dye sensitized solar cells and tandems  

NASA Astrophysics Data System (ADS)

This research has set out to understand the physical and electrochemical properties of carbon nanomaterials as charge collector, catalyst and energy transfer induced redox couple modifier in dye sensitized solar cells, which may one day be a major source of electric power generation. This research focuses on (1) characterizing the use of carbon nanotubes, both single walled and multi walled, as catalyst and charge carrier collector (2) improving the performance of the carbon nanotubes with modification by graphene, and various doping (3) testing 2-d carbon nanomaterials, such as graphene and few layer graphene nanoribbons, characterizing an interesting new side effect of photobleaching the iodide/triiodide redox couple, and (4) using the flexibility of dry spun carbon nanotubes sheets and carbon nanotubes sheets for tandem structures and novel fiber architecture. A major motivation in using carbon nanostructures in dye sensitized solar cells is that the standard dye solar cell uses platinum coated on a transparent conductive oxide as the counter electrode. Platinum, a rare and costly metal, is subject to scarcity issues. With proper application, the single walled carbon nanotubes mats could be used for as a substitute that would give efficiencies equivalent to the reference dye solar cells with platinum, and the dry spun multi-walled carbon nanotubes were capable of achieving performance equivalent to platinum with mild doping and nanomaterials additives. The novel architectural design work performed here used these multi-walled carbon nanotubes taken in the form of dry spun sheets. The sheet, possessing a structure of its own, obviates the need for solution processing to create films, which allows it to be used for architectures that demand a freestanding sheet of carbon nanotubes or drawn into a fiber of bundled carbon nanotubes. These freestanding carbon nanotubes were used specifically for the tandem devices and the proposed fiber-based dye solar cells.

Velten, Josef Aaron

310

Pulling in Tandem  

ERIC Educational Resources Information Center

Finding the perfect vendor partner for any campus initiative takes more than patience and planning; it takes an open mind. In the case of the two institutions and their software initiative leaders profiled in this article, a careful assessment of need--coupled with a good deal of out-of-the-box thinking--led to innovative approaches to vendor…

Heid, Susan D.

2007-01-01

311

Effects of inducible nitric oxide synthase inhibition or norepinephrine on the neurovascular coupling in an endotoxic rat shock model  

PubMed Central

Introduction The inducible nitric oxide synthase (iNOS) plays a crucial role in early sepsis-related microcirculatory dysfunction. Compared to a catecholamine therapy we tested effects of a specific iNOS-inhibitor (1400W) on the microcirculatory function in the brain. Methods Seventy SD-rats (280-310 g) were divided into 1 control and 6 sepsis groups. Sepsis groups received 1 or 5 mg/kg lipopolysaccharide (LPS) intravenously to induce a moderate or severe sepsis syndrome. Thirty minutes later rats were further randomized into subgroups receiving moderate volume therapy alone or additionally continuous norepinephrine (NE) or 1400W infusion. Separately, effects of 1400W on neurofunctional parameters were investigated in 3 rats without sepsis induction. Performing electric forepaw-stimulation evoked potentials (N2-P1 amplitude, P1-latency) and local hemodynamic responses were recorded with surface electrodes and laser Doppler over the somatosensory cortex at baseline and repeatedly after LPS administration. Cytokine levels (tumor necrosis factor-alpha (TNF?), interleukin-6 (IL6), interferon-gamma (IFN?)) and cell destruction markers (neuron-specific enolase (NSE), S-100 calcium binding protein B (S100B)) were obtained at the end of experiments. Results During sepsis progression resting cerebral blood flow increased and functionally activated hemodynamic responses decreased in a dose-dependent manner. Whereas 1400W and NE improved blood pressure, only 1400W stabilized resting flow levels. However, both regimens were ineffective on the functionally coupled flow responses and destruction markers were similar between groups. Conclusions NE and 1400W appeared to be ineffective in mitigating the effects of sepsis on the neurovascular coupling. Other regimens are needed to protect the cerebral microcirculation under septic conditions. PMID:19709421

2009-01-01

312

Developmental competence of bovine early embryos depends on the coupled response between oxidative and endoplasmic reticulum stress.  

PubMed

The stress produced by the coupling of reactive oxygen species (ROS) and endoplasmic reticulum (ER) has been explored extensively, but little is known regarding their roles in the early development of mammalian embryos. Here, we demonstrated that the early development of in vitro-produced (IVP) bovine embryos was governed by the cooperative action between ROS and ER stress. Compared with the tension produced by 5% O2, 20% O2 significantly decreased the blastocyst formation rate and cell survival, which was accompanied by increases in ROS and in levels of sXBP-1 transcript, which is an ER stress indicator. In addition, treatment with glutathione (GSH), a ROS scavenger, decreased ROS levels, which resulted in increased blastocyst formation and cell survival rates. Importantly, levels of sXBP-1 and ER stress-associated transcripts were reduced by GSH treatment in developing bovine embryos. Consistent with this observation, tauroursodeoxycholate (TUDCA), an ER stress inhibitor, improved blastocyst developmental rate, trophectoderm proportion, and cell survival. Moreover, ROS and sXBP-1 transcript levels were markedly decreased by supplementation with TUDCA, suggesting a possible mechanism governing the mutual regulation between ROS and ER stress. Interestingly, knockdown of XBP-1 transcripts resulted in both elevation of ROS and decrease of antioxidant transcripts, which ultimately reduced in vitro developmental competence of bovine embryos. Based on these results, in vitro developmental competence of IVP bovine embryos was highly dependent on the coupled response between oxidative and ER stresses. These results increase our understanding of the mechanism(s) governing early embryonic development and may improve strategies for the generation of IVP embryos with high developmental competence. PMID:24695629

Yoon, Seung-Bin; Choi, Seon-A; Sim, Bo-Woong; Kim, Ji-Su; Mun, Seong-Eun; Jeong, Pil-Soo; Yang, Hae-Jun; Lee, Youngjeon; Park, Young-Ho; Song, Bong-Seok; Kim, Young-Hyun; Jeong, Kang-Jin; Huh, Jae-Won; Lee, Sang-Rae; Kim, Sun-Uk; Chang, Kyu-Tae

2014-05-01

313

Exergy & Economic Analysis of Catalytic Coal Gasifiers Coupled with Solid Oxide Fuel Cells  

SciTech Connect

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.

Siefert, Nicholas; Litster, Shawn

2012-01-01

314

Platinum(II)-mediated dehydrosulfurization and oxidative carbon-carbon coupling in the gas-phase decomposition of thioethers  

NASA Astrophysics Data System (ADS)

The ion/molecule reaction (IMR) of "roll-over" cyclometalated [Pt(bipy-H)]+ (1) (bipy = 2,2'-bipyridine) with dimethyl sulfide (2) leads to the loss of ethene in the main reaction channel (55%); this corresponds to a formal dehydrosulfurization accompanied by the dehydrogenative ("oxidative") C-C coupling of the two methyl groups in dimethyl sulfide to form ethene. In order to obtain deeper insight into this rare reaction, the IMRs of 1 with several symmetric, asymmetric as well as cyclic thioethers and some thiols are probed. Common to many substrates is the formal transfer of H2S from the organic sulfur compound to the [Pt(bipy-H)]+ core accompanied by the expulsion of one or more alkene units. In contrast to the behavior of [Pt(bipy-H)]+ (1), bare Pt+, diatomic PtH+, and also the complex [Pt(phpy-H)]+ (phpy = 2-phenyl pyridine) are not able to bring about dehydrosulfurization. It is accordingly suggested that the (bipy-H)-ligand does not only affect the electronic structure of the platinum(II) core but, moreover, plays an active role as an acceptor in the initial hydrogen transfer from the thioether ligand to the LPt+ core (L = heterocyclic ligand).

Butschke, Burkhard; Schlangen, Maria; Schröder, Detlef; Schwarz, Helmut

2009-06-01

315

Mitochondrial myopathy with loosely coupled oxidative phosphorylation in a case of Zellweger syndrome. A cytochemical-ultrastructural study.  

PubMed

A newborn female, the second child of consanguineous parents, exhibited general muscle hypotonia, apathy, hepatomegaly and failure to thrive from birth and signs of craniofacial dysmorphia were present. Pipecolic and trihydroxicoprostanoic acid were excreted in the urine and serum transferrin, ferritin and iron were markedly elevated. At the age of 7 weeks the baby died of respiratory insufficiency. Besides malformations of the brain, renal cysts, liver damage with hypoplastic intrahepatic bile ducts and cholestasis, increased storage of iron and cytochemically proven deficiency of peroxisomes in liver and kidney, morphological studied provided evidence of a mitochondrial myopathy in striated muscle with the accumulation of enlarged bizarre mitochondria, showing only minor structural abnormalities. No defects of NADH-reductase, succinate-dehydrogenase or cytochrome-c-oxidase were demonstrated histochemically. Cytochemical-ultrastructural investigation of mitochondrial ATPase revealed activation of the ATP-synthesising enzyme even before the addition of an uncoupler, this indicating loosely coupled oxidative phosphorylation. In addition a high rate of subcellular autophagy with segregation of mitochondria and focal loss of fibrils was present. Muscle damage in Zellweger syndrome appears to be the consequence of complex, interacting metabolic processes. The mitochondrial myopathy thereby induced allows a better understanding of general muscle hypotonia, one of the leading symptoms of this disorder. PMID:6143441

Müller-Höcker, J; Walther, J U; Bise, K; Pongratz, D; Hübner, G

1984-01-01

316

Aerobic methane oxidation coupled to denitrification in a membrane biofilm reactor: treatment performance and the effect of oxygen ventilation.  

PubMed

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

Sun, Fei-yun; Dong, Wen-yi; Shao, Ming-fei; Lv, Xiao-mei; Li, Ji; Peng, Liang-yu; Wang, Hong-jie

2013-10-01

317

Magnetization States of All-Oxide Spin Valves Controlled by Charge-orbital Ordering of Coupled Ferromagnets  

PubMed Central

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

Wu, Han-Chun; Mryasov, Oleg N.; Abid, Mohamed; Radican, Kevin; Shvets, Igor V.

2013-01-01

318

Magnetization States of All-Oxide Spin Valves Controlled by Charge-orbital Ordering of Coupled Ferromagnets  

NASA Astrophysics Data System (ADS)

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.

Wu, Han-Chun; Mryasov, Oleg N.; Abid, Mohamed; Radican, Kevin; Shvets, Igor V.

2013-05-01

319

Chiral on-line solid phase extraction coupled to liquid chromatography-tandem mass spectrometry assay for quantification of (R) and (S) enantiomers of methadone and its main metabolite in plasma.  

PubMed

The authors aimed at developing a liquid chromatography tandem mass spectrometry (LC-MS/MS) method with online extraction to determine (R)- and (S)- methadone enantiomers and its main metabolite 2-ethylidine-1,5-dimethyl-3,3 diphenylpyrrolidine (EDDP) in plasma. The analysis combined straightforward sample preparation, consisting of protein precipitation with acetonitrile, and an online enrichment by a flush/back-flush cycle before the second dimension chromatography. Using D3-deuterated internal standards allows overcoming significant relative matrix effect. Our method was linear up to 2000ng/mL. This simple sample preparation provides sensitive (the limit of quantitation is 25ng/mL for (R,S)-methadone and EDDP and 12.5ng/mL for (R)- and (S)- methadone), accurate and precise (the intra-day and inter-day imprecision and inaccuracy are lower than 15%) quantification of the plasma concentration of these drugs. We have developed a reliable LC-MS/MS method for both routine therapeutic drug monitoring and pharmacokinetics studies and for toxicology analysis in the setting of methadone treatment or intoxication. PMID:25618682

Bouquié, Régis; Hélène Hernando; Guillaume Deslandes; Mostefa Daho, Amina Ben; Renaud, Christian; Grall-Bronnec, Marie; Dailly, Eric; Jolliet, Pascale

2015-03-01

320

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

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

Zhang, Cangman; Ren, Biao; Lin, Zongtao; Tong, Lingkun; Wang, Hong; Chen, Shizhong

2015-02-13

321

Direct analysis of 18 flavonol glycosides, aglycones and terpene trilactones in Ginkgo biloba tablets by matrix solid phase dispersion coupled with ultra-high performance liquid chromatography tandem triple quadrupole mass spectrometry.  

PubMed

Analysis and quality control of Ginkgo biloba have been comprehensively studied. However, little attention has been devoted to the simultaneous extraction and analysis of flavonols and terpene trilactones, especially for direct quantification of flavonol glycosides. This work described a rapid strategy for one-step extraction and quantification of the components. A matrix solid phase dispersion (MSPD) method was designed for the extraction of ginkgo ingredients and compared with the heat-reflux and ultrasonic extraction methods. An ultra-high performance liquid chromatography (UHPLC)-tandem-triple-quadrupole-mass spectrometry (QQQ-MS) method was developed for detection of the 18 components, including 10 original flavonol glycosides, 3 aglycones, and 5 lactones. Subsequently, the proposed strategy was used for the analysis of 12 G. biloba tablets. Results showed that MSPD produced comparable extraction efficiency but consumed less time and required lower solvent volumes compared with conventional methods. Without hydrolysis, the concentration detected was much closer to the original in the sample. The total flavonol glycoside contents in ginkgo tablets ranged from 3.59 to 125.21?gmg(-1), and the terpene trilactone varied from 3.45 to 57.8?gmg(-1) among different manufacturers. In conclusion, the proposed MSPD and UHPLC-QQQ-MS is rapid and sensitive in providing comprehensive profile of chemical constituents especially the genuine flavonol glycosides for improved quality control of ginkgo products. PMID:24876067

Liu, Xin-Guang; Yang, Hua; Cheng, Xiao-Lan; Liu, Lei; Qin, Yong; Wang, Qi; Qi, Lian-Wen; Li, Ping

2014-08-01

322

Multiresidue determination of fluoroquinolones in poultry muscle and kidney according to the regulation 2002/657/EC. A systematic comparison of two different approaches: Liquid chromatography coupled to high-resolution mass spectrometry or tandem mass spectrometry.  

PubMed

This work involved the optimization and validation of two methods according to the Commission Decision 2002/657/EC directives for determining fluoroquinolones residues in samples of poultry muscle and kidney: ciprofloxacin, danofloxacin, difloxacin, enrofloxacin, flumequine, marbofloxacin, nalidixic acid, norfloxacin, ofloxacin, oxolinic acid, pipemidic acid and sarafloxacin. The extraction procedure was based on a QuEChERS approach, whose optimization employed a Box-Behnken 3(3) factorial design. A liquid chromatography-tandem mass spectrometry method (LC-MS/MS) was developed for determining the twelve analytes using the multiple reaction monitoring mode (MRM). Accuracy, evaluated by recovery studies, varied from 88.8 to 112.2% for the selected levels with RSD values lower than 12.3%. The second validated method employed high resolution mass spectrometry (HRMS) performed in the single ion monitoring mode (SIM), determining nine among twelve analytes. The validation parameters were evaluated as satisfactory, with recoveries from 82.5 to 114.4% and RSD lower than 8.7%. Decision limits and detection capabilities for both methods were reported. The two methods were statistically compared using the Student's t test, at 95% confidence level, resulting in no significant difference. PMID:25577647

Rocha, Diego G; Santos, Flavio A; da Silva, Júlio César C; Augusti, Rodinei; Faria, Adriana F

2015-01-30

323

Ultrasound/microwave-assisted solid-liquid-solid dispersive extraction with high-performance liquid chromatography coupled to tandem mass spectrometry for the determination of neonicotinoid insecticides in Dendrobium officinale.  

PubMed

A one-step ultrasound/microwave-assisted solid-liquid-solid dispersive extraction procedure was used for the simultaneous determination of eight neonicotinoids (dinotefuran, nitenpyram, thiamethoxam, clothianidin, imidacloprid, acetamiprid, thiacloprid, imidaclothiz) in dried Dendrobium officinale by liquid chromatography combined with electrospray ionization triple quadrupole tandem mass spectrometry in multiple reaction monitoring mode. The samples were quickly extracted by acetonitrile and cleaned up by the mixed dispersing sorbents including primary secondary amine, C18 , and carbon-GCB. Parameters that could influence the ultrasound/microwave-assisted extraction efficiency such as microwave irradiation power, ultrasound irradiation power, temperature, and solvent were investigated. Recovery studies were performing well (70.4-113.7%) at three examined spiking levels (10, 50, and 100 ?g/kg). Meanwhile, the limits of quantification for the neonicotinoids ranged from 0.87 to 1.92 ?g/kg. The method showed good linearity in the concentration range of 1-100 ?g/L with correlation coefficients >0.99. This quick and useful analytical method could provide a basis for monitoring neonicotinoid insecticide residues in herbs. PMID:25348589

Zheng, Shuilian; Wu, Huizhen; Li, Zuguang; Wang, Jianmei; Zhang, Hu; Qian, Mingrong

2015-01-01

324

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

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

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

2005-01-01

325

Reduction of Matrix-Induced Oxide Interferences on Rare Earth Elements and Platinum Using a Desolvating Nebulizer System with Quadrupole Inductively Coupled Plasma Mass Spectrometry  

NASA Astrophysics Data System (ADS)

This paper will examine the use of a specialized low-flow desolvating nebulizer system for reduction of oxide mass spectral interferences that can occur in quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS). This nebulizer system uses an inert low-flow nebulizer (100 microliters/min) coupled to an inert, heated membrane desolvator for efficient water vapor removal before sample aerosol injection to the Q-ICP-MS instrument. Water vapor from conventional nebulizer / spray chamber systems used with Q-ICP-MS can cause numerous mass spectral interferences. One general example is metal oxides formed from the combination of oxygen (from injected water) with sample matrix components. Two specific examples of metal oxide interferences will be investigated with and without membrane desolvation: Ba and Ce oxides on several low-mass rare earth elements (Sm, Eu, and Gd) and Hf oxides on platinum. Rare earth elements are critically important components of modern electronics (ex. magnets, lasers, cell phones, computers) and platinum is a widely used catalyst. Figures of merit for both a conventional nebulizer/spray chamber and the desolvating nebulizer systems will include operating conditions, interference intensities and reduction factors, background equivalent concentrations (BECs), and instrument detection limits (IDLs).

Smith, F.

2013-12-01

326

Mobility platform coupling device and method for coupling mobility platforms  

DOEpatents

A coupling device for connecting a first mobility platform to a second mobility platform in tandem. An example mobility platform is a robot. The coupling device has a loose link mode for normal steering conditions and a locking position, tight link mode for navigation across difficult terrain and across obstacles, for traversing chasms, and for navigating with a reduced footprint in tight steering conditions.

Shirey, David L. (Albuquerque, NM); Hayward, David R. (Albuquerque, NM); Buttz, James H. (Albuquerque, NM)

2002-01-01

327

DNA Damage by Ionizing Radiation: Tandem Double Lesions by Charged Particles  

NASA Technical Reports Server (NTRS)

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.

Huo, Winifred M.; Chaban, Galina M.; Wang, Dunyou; Dateo, Christopher E.

2005-01-01

328

Improved tandem mirror fusion reactor  

Microsoft Academic Search

It is shown that the introduction of barrier potentials between the plugs and solenoid of a tandem mirror substantially reduce ion energy and density required in end plugs. Several means for creating barriers and some of the important physics issues are discussed.

D. E. Baldwin; B. G. Logan

1979-01-01

329

Magnetic order and interfacial coupling in oxide thin films and heterostructures probed with soft x-ray dichroism  

SciTech Connect

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.

Arenholz, Elke; van der Laan, G.

2009-02-01

330

Electrolytes Based on TEMPO-Co Tandem Redox Systems Outperform Single Redox Systems in Dye-sensitized Solar Cells.  

PubMed

A new TEMPO-Co tandem redox system with TEMPO and Co(bpy)3 (2+/3+) has been investigated for the use in dye-sensitized solar cells (DSSCs). A large open-circuit voltage (VOC ) increase, from 862?mV to 965?mV, was observed in the tandem redox system, while the short-circuit current density (JSC ) was maintained. The conversion efficiency was observed to increase from 7.1?% for cells containing the single Co(bpy)3 (2+/3+) redox couple, to 8.4?% for cells containing the TEMPO-Co tandem redox system. The reason for the increase in VOC and overall efficiency is ascribed to the involvement of partial regeneration of the sensitizing dye molecules by TEMPO. This assumption can be verified through the observed much faster regeneration dynamics exhibited in the presence of the tandem system. Using the tandem redox system, the faster recombination problem of the single TEMPO redox couple is resolved and the mass-transport of the metal-complex-based electrolyte is also improved. This TEMPO-Co tandem system is so far the most effienct tandem redox electrolyte reported not involving iodine. The current results show a promising future for tandem system as replacements for single redox systems in electrolytes for DSSCs. PMID:25504818

Cong, Jiayan; Hao, Yan; Boschloo, Gerrit; Kloo, Lars

2015-01-01

331

Simultaneous quantification of cyclophosphamide and its active metabolite 4-hydroxycyclophosphamide in human plasma by high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (LC-MS/MS).  

PubMed

Cyclophosphamide is a cytotoxic prodrug with a very narrow therapeutic index. To study the clinical pharmacology of cyclophosphamide in a large cohort of patients a previously published method for the simultaneous quantitative determination of cyclophosphamide and 4-hydroxycyclophosphamide in human plasma using liquid chromatography tandem mass spectrometry (LC-MS/MS) was optimized. Addition of an isotopically labelled internal standard and adaptation of the gradient resulted in a fast, robust and sensitive assay. Because 4-hydroxycyclophosphamide is not stable in plasma, the compound is derivatized with semicarbazide immediately after sample collection. Sample preparation was carried out by protein precipitation with methanol-acetonitrile (1:1, v/v), containing isotopically labelled cyclophosphamide and hexamethylphosphoramide as internal standards. The LC separation was performed on a Zorbax Extend C18 column (150 mm x 2.1 mm ID, particle size 5 microm) with 1 mM ammonium hydroxide in water-acetonitrile (90:10, v/v) as the starting gradient, at a flow-rate of 0.40 mL/min with a total run time of 6 min. The lower limit of quantification (LLQ, using a 100 microL sample volume) was 200 ng/mL and the linear dynamic range extended to 40,000 ng/mL for cyclophosphamide and 50-5000 ng/mL for 4-hydroxycyclophosphamide. Accuracies as well as precisions were lower than 20% at the LLQ concentration and lower than 15% for all other concentrations. This method has been successfully applied in our institute to support ongoing studies into the pharmacokinetics and pharmacogenetics of cyclophosphamide. PMID:17485255

Ekhart, Corine; Gebretensae, Abadi; Rosing, Hilde; Rodenhuis, Sjoerd; Beijnen, Jos H; Huitema, Alwin D R

2007-07-01

332

Dimeric 1,3-propanediaminetetraacetato lanthanides as the precursors of catalysts for the oxidative coupling of methane.  

PubMed

From neutral solutions, dimeric 1,3-propanediaminetetraacetato lanthanides (NH4)2[Ln2(1,3-pdta)2(H2O)4]·8H2O [Ln = La, 1; Ce, 2] and K2[Ln2(1,3-pdta)2(H2O)4]·11H2O [Ln = La, 3; Ce, 4] (1,3-H4pdta = 1,3-propanediaminetetraacetic acid, C11H18N2O8) were isolated in high yields. The reaction of excess strontium nitrate with 1 resulted in the formation of a two dimensional coordination polymer [La2(1,3-pdta)2(H2O)4]n·[Sr2(H2O)6]n·[La2(1,3-pdta)2(H2O)2]n·18nH2O (5) at 70 °C. Complexes 1-4 show a similar central molecular structure. The lanthanide ions are coordinated by two nitrogen atoms, four carboxy oxygen atoms from one 1,3-pdta ligand, two from the neighboring 1,3-pdta ligand forming a four-membered ring and two water molecules. Complex 5 has two kinds of dimeric lanthanum unit and extends into a 2D coordination polymer through strontium ions and bridged oxygen atoms, and forms a fourteen membered ring linked by oxygen atoms from carboxy groups of pdta. Complexes 1-4 are soluble in water. The (13)C{(1)H} NMR experiments for complex 1 were tested in solution. Thermal products from 1 and 5 show good catalytic activities towards the oxidative coupling reaction of methane (OCM). The conversion of methane and selectivity to C2 reached 29.7% and 51.7% at 750 °C for the product of 5. From TGA, XRD and SEM analyses, the thermal products from 1 and 5 are rod- and poly-shaped, which are assigned as lanthanum oxocarbonate and a mixture of La2O3, SrCO3 and La2O2CO3 for 1 and 5, respectively. The precursor method is favorable for the formation of regular shaped mixed oxides. PMID:24769659

Chen, Mao-Long; Hou, Yu-Hui; Xia, Wen-Sheng; Weng, Wei-Zheng; Cao, Ze-Xing; Zhou, Zhao-Hui; Wan, Hui-Lin

2014-06-21

333

Copper-mediated intramolecular oxidative C-H/N-H cross-coupling of ?-alkenoyl ketene N,S-acetals to synthesize pyrrolone derivatives.  

PubMed

CuCl2 and CuBr2-mediated intramolecular oxidative C-H/N-H cross-coupling/halogenation of ?-thioalkyl-substituted ?-alkenoyl ketene N,S-acetals occurred efficiently, affording 4-halo-5-thioalkyl-3-pyrrolones. Tunable C-S and C-halo bond transformations of the resultant pyrrolone derivatives led to highly functionalized N-heterocyclic compounds. PMID:25188605

Huang, Fei; Wu, Ping; Wang, Liandi; Chen, Jiping; Sun, Chenglin; Yu, Zhengkun

2014-10-25

334

Enhanced catalytic activity of zeolite encapsulated Fe(III)-Schiff-base complexes for oxidative coupling of 2-napthol.  

PubMed

Iron(III) Schiff-base complexes of general formula [Fe(L)(2)Cl]·2H(2)O, where L = N,?-bis(salicylidene)ethylenediamine and N,N?-disalicylidene-1,2-phenylenediamine have been encapsulated within various alkali exchanged zeolites viz. LiY, NaY, and KY by flexible ligand method. The encapsulated complexes are characterized by EDX, scanning electron microscopy (SEM), powder X-ray diffraction (XRD), FT-IR, UV-vis, diffuse reflectance spectroscopy (DRS), electron spin resonance spectroscopy (ESR) and cyclic voltammetry studies. The diffuse reflectance UV-vis spectra of encapsulated complexes show a dramatic red shift of the charge transfer band with increasing electropositivity of the exchangeable cations. The electrochemical analysis predicts the shifting of the reduction potential toward negative values with increasing size of the alkali exchanged cations. The zeolite encapsulated Schiff-base complexes of iron are found to be catalytically active toward the oxidative coupling of 2-napthol. Metal complexes incorporated in potassium exchanged zeolite-Y are found to be more effective for catalytic conversion of 2-naphthol to binaphthol and induces higher selectivity toward the R-conformation. The catalytic conversion of 2-napthol to BINOL is found to depend on the reduction potential of the catalyst, with a more negative reduction potential being better for the catalytic conversion. Density functional calculation is being carried out on both the neat Fe-Salen and Fe-Salophen complexes and those encapsulated in NaY zeolite to investigate change in structural parameters, energies of the HOMO and LUMO, and global hardness and softness. Fukui functions, as local descriptors, are used to analyze the hard-hard interaction at a particular site of the complexes. PMID:22256783

Bania, Kusum K; Bharali, Dipsikha; Viswanathan, B; Deka, Ramesh C

2012-02-01

335

Kinetic study of the transient phase of a chemical reaction system coupled to an enzymatically catalyzed step. Application to the oxidation of epinine by tyrosinase.  

PubMed

The present work deals with epinine oxidation by mushroom tyrosinase and sodium metaperiodate. Intermediates produced within short reaction times were characterized by repetitive scanning spectrophotometry and the stoichiometry of the appearance of the respective aminochrome was established. The oxidation pathway from epinine to aminochrome had the following steps: epinine----o-quinone-H+----o-quinone----leukoaminochrome----aminoc hrome. The stoichiometry for the conversion of o-quinone-H+ into the aminochrome of epinine followed the equation: 2 o-quinone-H+----epinine+aminochrome. A transient phase kinetic study has been developed for the system of chemical reactions coupled to an enzymatically catalyzed step, these taking place when epinine is oxidized by mushroom tyrosinase. Rate constants for the implied chemical steps at different temperature and pH values were calculated from analysis of the progress curves of aminochrome accumulation with time. The thermodynamic activation parameters of the chemical steps were also calculated. PMID:3111559

Escribano, J; García, M; García Cánovas, F; García Carmona, F; Varón, R; Tudela, J; Lozano, J A

1987-07-01

336

Simultaneous and enantioselective determination of cis-epoxiconazole and indoxacarb residues in various teas, tea infusion and soil samples by chiral high performance liquid chromatography coupled with tandem quadrupole-time-of-flight mass spectrometry.  

PubMed

A novel and sensitive method for simultaneous enantiomeric analysis of two pesticides-cis-epoxiconazole and indoxacarb-in various teas, black tea infusion, and soil samples has been developed. The samples were initially subjected to acetonitrile extraction followed by cleanup using lab-made florisil/graphitized carbon black mixed solid phase extraction (SPE) column (for the different teas and soil samples) and a BondElut C18-SPE column (for the black tea infusion samples). Separation of the analytes was performed on a chiral stationary phase using high performance liquid chromatography (HPLC) under a reversed-phase isocratic elution mode followed by tandem quadrupole time-of-flight mass spectrometry (Q-TOF/MS) detection. The mobile phase components, mobile phase ratios, flow rates, column temperatures, and MS parameters were all optimized to reach high sensitivity and selectivity, good peak shape, and satisfactory resolution. The performance of the method was evaluated based on the sensitivity, linearity, accuracy, precision, and matrix effects. Under optimal conditions, for the various teas (green tea, black tea, and puer tea), fresh tea leaf, soil and black tea infusion samples spiked at low, medium, and high levels, the mean recoveries for the four enantiomers ranged from 61.0% to 129.7% with most relative standard deviations (RSDs) being 17.1% or below. Good linearity can be achieved with regression coefficients (R) of 0.9915 or above for all target enantiomers, and matrix-matched calibration concentration ranging from 5.0 to 1000?g/L. The limits of detection (LODs) for all four target enantiomers were 1.4?g/kg or below in the different teas and soil samples and 0.05?g/kg or below in the black tea infusion, whereas the limits of quantification (LOQs) for those did not exceed 5.0?g/kg and 0.2?g/L, respectively. The proposed method is convenient and reliable and has been applied to real tea samples screening. It has also been extended for studies on the degradation kinetics and environmental behaviors in the field trials, providing additional information for reliable risk assessment of these chiral pesticides. PMID:25108768

Zhang, Xinzhong; Luo, Fengjian; Lou, Zhengyun; Lu, Meiling; Chen, Zongmao

2014-09-12

337

The efficacy of oxidative coupling for promoting in-situ immobilization of hydroxylated aromatics in contaminated soil and sediment systems. 1998 annual progress report  

SciTech Connect

'Hydroxylated aromatic compounds (HAC''s) and their precursors are common contaminants of surface and subsurface systems at DOE facilities. The environmental fate and transport of such compounds, particularly in subsurface systems, is generally dominated by their sorption and desorption by soils and sediments. Certain secondary chemical reactions, most specifically abiotic and/or enzymatic oxidative coupling, may be significant in controlling the sorption and subsequent desorption of such hydroxylated aromatics by soils and sediments. The principal objectives of this study are to investigate: (1) the role of abiotic/enzymatic coupling reactions on the immobilization of HAC''s; (2) the effects of environmental factors on such immobilization; and (3) preliminary engineering approaches utilizing enhanced abiotic/enzymatic coupling reactions to immobilize hydroxylated aromatics in-situ. Information gathered from the study will be useful in quantifying the behavior of this class of organic compounds in various subsurface contamination scenarios relevant to DOE facilities, and in specifying strategies for the selection and design of remediation technologies. Over the first two years of this three-year project, the authors have developed a significantly improved understanding of the mechanisms of hydroxylated aromatic compound sorption and immobilization by natural soils and sediments. Immobilization in this context is attributed to oxidative coupling of the hydroxylated aromatics subsequent to their sorption to a soil or sediment, and is quantified in terms of the amount of a sorbed target compound retained by a sorbent after a series of sequential water and solvent extractions. The presence of oxygen, metal oxides, and organic matter, all of which can potentially catalyze/facilitate the abiotic oxidative coupling of HAC''s, were investigated during these first two years. Three different HAC''s: phenol, trichlorophenol and o-cresol were included in the experimental program. Inorganic soil matrices were represented by a glacial wash sand (Wurtsmith sand) having very low organic content. Because the chemical nature of soil organic matter may potentially affect the extent of coupling or immobilization, sorbents having different organic matter compositions are being investigated. Two of the three studied to date are near-surface soils, characterized by geologically younger organic material (Fox Forest soil and Fox Grassland soil). The third sorbent is an older and diagenetically altered soil (Lachine Shale). Sorbent preparation, characterization and experimental protocol development were completed in the first year of the study while the second year of the project has focused primarily on experiments with natural systems, as planned. Preliminary work with engineered systems has been initiated earlier than scheduled in order to integrate and relate all aspects of the study.'

Weber, W.J. [Univ. of Michigan, Ann Arbor, MI (US); Bhandari, A. [Kansas State Univ., Manhattan, KS (US)

1998-06-01

338

High-field asymmetric waveform ion mobility spectrometry coupled with liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-FAIMS-MS/MS) multi-component bioanalytical method development, performance evaluation and demonstration of the constancy of the compensation voltage with change of mobile phase composition or flow rate.  

PubMed

The feasibility of developing a multi-component bioanalytical method using high-field asymmetric waveform ion mobility spectrometry coupled with liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-FAIMS-MS/MS) is demonstrated using nefazodone and its two metabolites as model compounds. The performance of the bioanalytical method for the three analytes, with three different compensation voltage (CV) values, is assessed using standard curves and quality control samples, which exhibited good accuracy, precision and ruggedness. The number of analytes with different CV values that can be quantitated simultaneously depends on the acquisition cycle time, which is a function of the FAIMS residence time (fixed), chromatographic peak width and selected reaction monitoring (SRM) dwell time. It is established that CV, the FAIMS selectivity parameter, is reproducible for at least 16 h, thus ensuring the constancy of the CV during a large-batch sample analysis. It is also established that change in mobile phase composition or of flow rate does not cause a shift in CV. Thus, CV values determined from a CV scan via infusion of a sample can be used for an LC/ESI-FAIMS-M/MS method based on isocratic or gradient elution. PMID:17939154

Wu, Steven T; Xia, Yuan-Qing; Jemal, Mohammed

2007-01-01

339

Multi-residue monitoring for the simultaneous determination of five nitrofurans (furazolidone, furaltadone, nitrofurazone, nitrofurantoine, nifursol) in poultry muscle tissue through the detection of their five major metabolites (AOZ, AMOZ, SEM, AHD, DNSAH) by liquid chromatography coupled to electrospray tandem mass spectrometry--in-house validation in line with Commission Decision 657/2002/EC.  

PubMed

Following the ban of four nitrofurans in the mid-90s (furazolidone, furaltadone, nitrofurantoine, nitrofurazone), the nifursol, a veterinary drug from the nitrofuran class of antibacterials which has been used prophylactically as feed additive for treating turkeys against histomoniasis (blackhead disease) was also declared in Annex IV of the European Union Directive no. 90/2377/EC in 2002 according to the Regulation no. 1756/2002/EC. As for the four other nitrofurans, nifursol disappears from tissues within a few days after treatment of food-producing animals. But toxic metabolites are still present for longer periods (several weeks or even months). The major metabolite that can readily be monitored in the tissues following nifursol abuse is the 3,5-dinitro-salicylic acid hydrazine (DNSAH). This article displays some improvements and the revalidation of the analytical method by liquid chromatography coupled to electrospray tandem mass spectrometry (LC-esiMS/MS) already in use in our laboratory for monitoring nitrofuran metabolites but also including the nifursol metabolite at the confirmatory minimum required performance level (MRPL) of 1 microg kg(-1). The validation is applied both to artificially and to naturally incurred turkey muscle. PMID:17386733

Verdon, Eric; Couedor, Pierrick; Sanders, Pascal

2007-03-14

340

Biological oxidation of Mn(II) coupled with nitrification for removal and recovery of minor metals by downflow hanging sponge reactor.  

PubMed

Biogenic manganese oxides (bio-MnO2) have been shown to absorb minor metals. Bioreactor cultivation of heterotrophic manganese oxidizing bacteria (MnOB), which produce bio-MnO2 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 (NH4(+)) 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-MnO2 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

Cao, Linh Thi Thuy; Kodera, Hiroya; Abe, Kenichi; Imachi, Hiroyuki; Aoi, Yoshiteru; Kindaichi, Tomonori; Ozaki, Noriatsu; Ohashi, Akiyoshi

2014-10-23

341

Sulfur and oxygen isotope fractionation during sulfate reduction coupled to anaerobic oxidation of methane is dependent on methane concentration  

NASA Astrophysics Data System (ADS)

Isotope signatures of sulfur compounds are key tools for studying sulfur cycling in the modern environment and throughout earth's history. However, for meaningful interpretations, the isotope effects of the processes involved must be known. Sulfate reduction coupled to the anaerobic oxidation of methane (AOM-SR) plays a pivotal role in sedimentary sulfur cycling and is the main process responsible for the consumption of methane in marine sediments - thereby efficiently limiting the escape of this potent greenhouse gas from the seabed to the overlying water column and atmosphere. In contrast to classical dissimilatory sulfate reduction (DSR), where sulfur and oxygen isotope effects have been measured in culture studies and a wide range of isotope effects has been observed, the sulfur and oxygen isotope effects by AOM-SR are unknown. This gap in knowledge severely hampers the interpretation of sulfur cycling in methane-bearing sediments, especially because, unlike DSR which is carried out by a single organism, AOM-SR is presumably catalyzed by consortia of archaea and bacteria that both contribute to the reduction of sulfate to sulfide. We studied sulfur and oxygen isotope effects by AOM-SR at various aqueous methane concentrations from 1.4±0.6 mM up to 58.8±10.5 mM in continuous incubation at steady state. Changes in the concentration of methane induced strong changes in sulfur isotope enrichment (?S34) and oxygen isotope exchange between water and sulfate relative to sulfate reduction (?O), as well as sulfate reduction rates (SRR). Smallest ?S34 (21.9±1.9‰) and ?O (0.5±0.2) as well as highest SRR were observed for the highest methane concentration, whereas highest ?S34 (67.3±26.1‰) and ?O (2.5±1.5) and lowest SRR were reached at low methane concentration. Our results show that ?S34, ?O and SRR during AOM-SR are very sensitive to methane concentration and thus also correlate with energy yield. In sulfate-methane transition zones, AOM-SR is likely to induce very large sulfur isotope fractionation between sulfate and sulfide (i.e. >60‰) and will drive the oxygen isotope composition of sulfate towards the sulfate-water oxygen isotope equilibrium value. Sulfur isotope fractionation by AOM-SR at gas seeps, where methane fluxes are high, will be much smaller (i.e. 20 to 40‰).

Deusner, Christian; Holler, Thomas; Arnold, Gail L.; Bernasconi, Stefano M.; Formolo, Michael J.; Brunner, Benjamin

2014-08-01

342

The construction of tandem dye-sensitized solar cells from chemically-derived nanoporous photoelectrodes  

NASA Astrophysics Data System (ADS)

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.

Choi, Hongsik; Hwang, Taehyun; Lee, Sangheon; Nam, Seunghoon; Kang, Joonhyeon; Lee, Byungho; Park, Byungwoo

2015-01-01

343

Hybrid tandem photovoltaic devices with a transparent conductive interconnecting recombination layer  

SciTech Connect

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.

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

344

Recent Activities at Tokai Tandem Accelerator  

SciTech Connect

Recent activities at the JAEA-Tokai tandem accelerator facility are presented. The terminal voltage of the tandem accelerator reached 19.1 MV by replacing acceleration tubes. The multi-charged positive-ion injector was installed in the terminal of the tandem accelerator, supplying high-current noble-gas ions. A superconducting cavity for low-velocity ions was developed. Radioactive nuclear beams of {sup 8,9}Li and fission products, produced by the tandem accelerator and separated by the ISOL, were supplied with experiment. Recent results of nuclear physics experiments are reported.

Ishii, Tetsuro [Department of Research Reactor and Tandem Accelerator, Japan Atomic Energy Agency (JAEA), Tokai, Ibaraki 319-1195 (Japan)

2010-05-12

345

Efficient Tandem Polymer Solar Cells Fabricated by All-Solution Processing  

Microsoft Academic Search

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.

Jin Young Kim; Kwanghee Lee; Nelson E. Coates; Daniel Moses; Thuc-Quyen Nguyen; Mark Dante; Alan J. Heeger

2007-01-01

346

Dearomatization strategy of ?-enamino ester: construction of indenoazepines via tandem Michael addition/polycyclization.  

PubMed

A dearomatization strategy of ?-enamino esters was developed to construct indenoazepine derivatives. The oxidative dearomatization was combined with a base-promoted tandem Michael addition/polycyclization and an acid-catalyzed aromatization. The nonaromatic structure of the Michael adducts might be essential to the realization of the 7-endo-dig cyclization. PMID:23795890

Yang, Min; Tang, Jie; Fan, Renhua

2013-07-01

347

Emerging catalytic applications of transition metal oxide nanomaterials under microwave and conventional heating  

NASA Astrophysics Data System (ADS)

Heterogeneous transition metal oxide catalysts have advantages over homogeneous catalysts, such as easy separations and efficient recycling and minimization of metal traces in the products. Transition metal oxide nanomaterials with different properties such as shapes and particle size were synthesized by hydrothermal, solvothermal, solvent-free and by energy efficient microwave heating methods and characterized using X-Ray and microscopic techniques. The synthesized catalysts were tested for tandem reactions to form quinoxalines, oxidations of hydrocarbons to form alcohols, aldehydes and ketones, epoxidation, epoxide ring opening, and N-aryl coupling reactions. The kinetics and energy consumption associated with these reactions were compared for both microwave and conventionally heated reactions. Further, Synchrotron radiation-based time-resolved XRD experiments under a wide variety of temperature and pressure conditions were conducted to study the reactions under working conditions. EXAFS and XANES data collections were performed to determine inter-atomic distances and oxidation states of the catalysts.

Sithambaram, Shanthakumar

348

On the effect of the Fe(2+)/Fe(3+) redox couple on oxidation of carbon in hot H3PO4  

NASA Technical Reports Server (NTRS)

Oxidation studies of graphite:glassy carbon composites have been carried out at 1 and 4.7 atm. pressures in conc. H3PO4 in the presence and absence of iron ions. The concentration of the acid was varied over 85-100 wt pct, and of the iron ions over 30-300 ppm; the temperature varied over 190-210 C. Unlike the effect of Fe, which has been observed to increase the corrosion of carbon in sulphuric acid, the corrosion in phosphoric acid was observed to be slightly decreased or not at all affected. This result arises because of the catalytic reduction of the oxidized surface groups of carbon by Fe(2+) ions. The catalytic reduction is possible because under the experimental conditions the redox potential of the Fe(2+)/Fe(3+) couple is lower than the open-circuit voltage of carbon.

Dhar, H. P.; Christner, L. G.; Kush, A. K.

1986-01-01

349

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

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

Yang, Min; Sun, Peide; Wang, Ruyi; Han, Jingyi; Wang, Jianqiao; Song, Yingqi; Cai, Jing; Tang, Xiudi

2013-09-01

350

A comprehensive theoretical study on the coupling reaction mechanism of propylene oxide with carbon dioxide catalyzed by copper(I) cyanomethyl.  

PubMed

The mechanistic details of the coupling reaction of propylene oxide with carbon dioxide catalyzed by copper(I) cyanomethyl to yield cyclic carbonate were elucidated by density functional theory (DFT) calculations at the B3LYP/6-311G** level. Our results reveal that the overall reaction is stepwise and considered to include two processes. In process 1, CO(2) insertion into the Cu(I)-C bond of copper(I) cyanomethyl affords activated carbon dioxide carriers. In process 2, O-coordination of propylene oxide molecule to the electrophilic copper center of carriers occurs. Herein, three possible pathways were investigated, and the calculated reaction free energy profiles were compared. It was found that carrier 8 reacting with propylene oxide is more favored than the other two carriers (6 and 7) both kinetically and thermodynamically. Several factors, such as the composition of catalyst, the coordinate environment of copper, and the symmetry of frontier molecular orbitals, affected the reaction mechanisms, and the outcomes were identified. The overall reaction is exothermic. In addition, natural bond orbital (NBO) analysis has been performed to study the effects of charge transfer and understand the nature of different interactions between atoms and groups. The present theoretical study explains satisfactorily the early reported experimental observations well and provides a clear profile for the cycloaddition of carbon dioxide with propylene oxide promoted by NCCH(2)Cu. PMID:19469523

Guo, Cai-Hong; Wu, Hai-Shun; Zhang, Xian-Ming; Song, Jiang-Yu; Zhang, Xiang

2009-06-18

351

Demonstrating Advanced Oxidation Coupled with Biodegradation for Removal of Carbamazepine, WERF Report INFR6SG09, ISBN: 9781780400426  

EPA Science Inventory

Carbamazepine is an anthropogenic pharmaceutical found in wastewater effluents that is quite resistant to removal by conventional wastewater treatment processes. Hydroxyl radical-based advanced oxidation processes can transform carbamazepine into degradation products but cannot m...

352

Tandem mirror technology demonstration facility  

SciTech Connect

This report describes a facility for generating engineering data on the nuclear technologies needed to build an engineering test reactor (ETR). The facility, based on a tandem mirror operating in the Kelley mode, could be used to produce a high neutron flux (1.4 MW/M/sup 2/) on an 8-m/sup 2/ test area for testing fusion blankets. Runs of more than 100 h, with an average availability of 30%, would produce a fluence of 5 mW/yr/m/sup 2/ and give the necessary experience for successful operation of an ETR.

Not Available

1983-10-01

353

Improved monolithic tandem solar cell  

SciTech Connect

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.

Wanlass, M.W.

1991-04-23

354

Iridium Catalyzed C-C Coupling via Transfer Hydrogenation: Carbonyl Addition from the Alcohol or Aldehyde Oxidation Level Employing 1,3-Cyclohexadiene  

PubMed Central

Under hydrogen auto-transfer conditions employing a catalyst derived from [Ir(cod)Cl]2 and BIPHEP, 1,3-cyclohexadiene (CHD) couples to benzylic alcohols 1a-9a to furnish carbonyl addition products 1c-9c, which appear as single diastereomers with variable quantities of regioisomeric adducts 1d-9d. Under related transfer hydrogenation conditions employing isopropanol as terminal reductant, identical carbonyl adducts 1c-9c are obtained from the aldehyde oxidation level. Isotopic labeling studies corroborate a mechanism involving hydrogen donation from the reactant alcohol or sacrificial alcohol (i-PrOH). PMID:18254642

Bower, John F.; Patman, Ryan L.; Krische, Michael J.

2010-01-01

355

Exchange bias and antiferromagnetic interfacial exchange coupling in the mixed-spin oxide Li{sub 2/7}Ni{sub 5/7}O  

SciTech Connect

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.

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

356

Tandem mass spectrometry: analysis of complex mixtures  

SciTech Connect

Applications of tandem mass spectrometry (MS/MS) for the analysis of complex mixtures results in increased specificity and selectivity by using a variety of reagent gases in both negative and positive ion modes. Natural isotopic abundance ratios were examined in both simple and complex mixtures using parent, daughter and neutral loss scans. MS/MS was also used to discover new compounds. Daughter scans were used to identify seven new alkaloids in a cactus species. Three of these alkaloids were novel compounds, and included the first simple, fully aromatic isoquinoline alkaloids reported in Cactaceae. MS/MS was used to characterize the chemical reaction products of coal in studies designed to probe its macromolecular structure. Negative ion chemical ionization was utilized to study reaction products resulting from the oxidation of coal. Possible structural units in the precursor coal were predicted based on the reaction products identified, aliphatic and aromatic acids and their anhydrides. The MS/MS method was also used to characterize reaction products resulting from coal liquefaction and/or extraction. These studies illustrate the types of problems for which MS/MS is useful. Emphasis has been placed on characterization of complex mixtures by selecting experimental parameters which enhance the information obtained. The value of using MS/MS in conjunction with other analytical techniques as well as the chemical pretreatment is demonstrated.

Singleton, K.E.

1985-01-01

357

Characterization and quantification of racemic and meso-ethylenediamine-N,N'-bis(2-hydroxy-5-sulfophenylacetic) acid/iron (III) by ion-pair ultra-high performance liquid chromatography coupled with diode array detector and electrospray tandem mass spectrometry.  

PubMed

EDDHSA/Fe is a promising substitute of EDDHA/Fe to fight iron chlorosis. o,o-EDDHSA structure contains two chiral carbons giving the racemic and meso couples of stereoisomers. Ion-pair HPLC and UHPLC-UV/Vis-ESI-MS/MS methods were developed for the determination of racemic and meso-o,o-EDDHSA/Fe in commercial samples of chelates. The lack of a commercial EDDHSA standard was overcome by sulfonation of a commercial available o,o-EDDHA standard and subsequent quantification by (1)H-NMR. Assignment of configurations was carried out starting from racemic and meso-o,o-EDDHA/Fe by direct sulfonation to give the corresponding o,o-EDDHSA/Fe isomers. The performances of these methods were assessed in terms of intra and inter-day precision, linearity and selectivity. The high selectivity and lower detection limit (nanomolar) of the UHPLC-ESI-MS/MS method could allow to deepen the knowledge relative to meso and rac-o,o-EDDHSA/Fe interactions with plants, its fate in different soil conditions, its mobility and other environmental aspects. PMID:23411145

Biasone, Alessandro; Cianci, Giusto; Di Tommaso, Donata; Piaggesi, Alberto; Tagliavini, Emilio; Galletti, Paola; Moretti, Fabio

2013-03-22

358

Synthesis of substituted azafluorenones from dihalogeno diaryl ketones by palladium-catalyzed auto-tandem processes.  

PubMed

Substituted azafluorenones were synthesized from different dihalogeno diaryl ketones under palladium catalysis by combining either Suzuki or Heck coupling with direct cyclizing arylation. Conditions were identified to allow both auto-tandem processes to proceed successfully from 3-(bromobenzoyl)- or 3-benzoyl-4-bromo-2-chloropyridines, as well as 4-benzoyl-2,3- and 4-benzoyl-2,5-dichloropyridines. PMID:25233952

Marquise, Nada; Dorcet, Vincent; Chevallier, Floris; Mongin, Florence

2014-11-01

359

RUTHENIUM-CATALYZED TANDEM OLEFIN MIGRATION-ALDOL AND MANNICH-TYPE REACTIONS IN IONIC LIQUID.  

EPA Science Inventory

In the presence of a catalytic amount of RuCl2(PPh3)3, a cross-coupling of 3-buten-2-ol with aldehydes and imines was developed via a tandem olefin migration--aldol--Mannich reaction in bmim[PF6]. With In(OAc)3 as a co-catalyst, a-vinylbenzyl alcohol and aldehydes underwent sim...

360

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...

361

Identification of the antidiarrhoeal components in official rhubarb using liquid chromatography–tandem mass spectrometry  

Microsoft Academic Search

Though the purgative components in official rhubarb are well documented as anthraquinone glycosides and sennosides, the antidiarrhoeal effect and its chemical basis have not been reported before. In this study, liquid chromatography coupled with electrospray ionisation tandem mass spectrometry was used to investigate the main chemicals in the antidiarrhoeal fraction previously isolated from Rheum palmatum L. In total 10 compounds

Jia-bo Wang; Yi Qin; Wei-jun Kong; Zhe-wei Wang; Ling-na Zeng; Fang Fang; Cheng Jin; Yan-ling Zhao; Xiao-he Xiao

2011-01-01

362

FABRICATION OF FUEL RODS BY TANDEM ROLLING  

Microsoft Academic Search

The tandem rolling process used industrially to manufacture tubular ; resistance heating elements was investigated to determine its applicability for ; fabricating rod-type fuel elements. Approximately 90 stainless steel clad fuel ; rods containing natural UOâ were tandem-rolled to establish optimum rolling ; parameters and fuel rod design. Fuel rod diameter, cladding wall thickness, UO\\/; sub 2\\/ particle size, rolling

Lingafelter

1961-01-01

363

Tandem junction amorphous silicon solar cells  

DOEpatents

An amorphous silicon solar cell has an active body with two or a series of layers of hydrogenated amorphous silicon arranged in a tandem stacked configuration with one optical path and electrically interconnected by a tunnel junction. The layers of hydrogenated amorphous silicon arranged in tandem configuration can have the same bandgap or differing bandgaps.

Hanak, Joseph J. (Lawrenceville, NJ)

1981-01-01

364

Gold-catalyzed tandem cycloisomerization/functionalization of in situ generated ?-oxo gold carbenes in water.  

PubMed

A gold-catalyzed tandem cycloisomerization/functionalization of in situ generated ?-oxo gold carbenes in water has been developed, which provides ready access to highly functionalized indole derivatives from o-alkynyl anilines and ynamides. Importantly, gold serves dual catalytic roles to mediate both the cycloisomerization of o-alkynyl anilines and the intermolecular oxidation of ynamides at the same time, thus providing a new type of concurrent tandem catalysis. The use of readily available starting materials, a simple procedure, and mild reaction conditions are other notable features of this method. PMID:25229883

Shen, Cang-Hai; Li, Long; Zhang, Wei; Liu, Shuang; Shu, Chao; Xie, Yun-Er; Yu, Yong-Fei; Ye, Long-Wu

2014-10-01

365

Photoelectrochemical and photovoltaic characteristics of amorphous-silicon-based tandem cells as photocathodes for water splitting.  

PubMed

In this study amorphous silicon tandem solar cells are successfully utilized as photoelectrodes in a photoelectrochemical cell for water electrolysis. The tandem cells are modified with various amounts of platinum and are combined with a ruthenium oxide counter electrode. In a two-electrode arrangement this system is capable of splitting water without external bias with a short-circuit current of 4.50 mA?cm(-2) . On the assumption that no faradaic losses occur, a solar-to-hydrogen efficiency of 5.54?% is achieved. In order to identify the relevant loss processes, additional three-electrode measurements were performed for each involved half-cell. PMID:25335095

Ziegler, Jürgen; Kaiser, Bernhard; Jaegermann, Wolfram; Urbain, Félix; Becker, Jan-Philipp; Smirnov, Vladimir; Finger, Friedhelm

2014-12-15

366

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

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.

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

367

Photochemical Tyrosine Oxidation in the Structurally Well-Defined ?3Y Protein: Proton-Coupled Electron Transfer and a Long-Lived Tyrosine Radical  

PubMed Central

Tyrosine oxidation–reduction involves proton-coupled electron transfer (PCET) and a reactive radical state. These properties are effectively controlled in enzymes that use tyrosine as a high-potential, one-electron redox cofactor. The ?3Y model protein contains Y32, which can be reversibly oxidized and reduced in voltammetry measurements. Structural and kinetic properties of ?3Y are presented. A solution NMR structural analysis reveals that Y32 is the most deeply buried residue in ?3Y. Time-resolved spectroscopy using a soluble flash-quench generated [Ru(2,2?-bipyridine)3]3+ oxidant provides high-quality Y32–O• absorption spectra. The rate constant of Y32 oxidation (kPCET) is pH dependent: 1.4 × 104 M–1 s–1 (pH 5.5), 1.8 × 105 M–1 s–1 (pH 8.5), 5.4 × 103 M–1 s–1 (pD 5.5), and 4.0 × 104 M–1 s–1 (pD 8.5). kH/kD of Y32 oxidation is 2.5 ± 0.5 and 4.5 ± 0.9 at pH(D) 5.5 and 8.5, respectively. These pH and isotope characteristics suggest a concerted or stepwise, proton-first Y32 oxidation mechanism. The photochemical yield of Y32–O• is 28–58% versus the concentration of [Ru(2,2?-bipyridine)3]3+. Y32–O• decays slowly, t1/2 in the range of 2–10 s, at both pH 5.5 and 8.5, via radical–radical dimerization as shown by second-order kinetics and fluorescence data. The high stability of Y32–O• is discussed relative to the structural properties of the Y32 site. Finally, the static ?3Y NMR structure cannot explain (i) how the phenolic proton released upon oxidation is removed or (ii) how two Y32–O• come together to form dityrosine. These observations suggest that the dynamic properties of the protein ensemble may play an essential role in controlling the PCET and radical decay characteristics of ?3Y. PMID:25121576

2014-01-01

368

Photochemical tyrosine oxidation in the structurally well-defined ?3Y protein: proton-coupled electron transfer and a long-lived tyrosine radical.  

PubMed

Tyrosine oxidation-reduction involves proton-coupled electron transfer (PCET) and a reactive radical state. These properties are effectively controlled in enzymes that use tyrosine as a high-potential, one-electron redox cofactor. The ?3Y model protein contains Y32, which can be reversibly oxidized and reduced in voltammetry measurements. Structural and kinetic properties of ?3Y are presented. A solution NMR structural analysis reveals that Y32 is the most deeply buried residue in ?3Y. Time-resolved spectroscopy using a soluble flash-quench generated [Ru(2,2'-bipyridine)3](3+) oxidant provides high-quality Y32-O• absorption spectra. The rate constant of Y32 oxidation (kPCET) is pH dependent: 1.4 × 10(4) M(-1) s(-1) (pH 5.5), 1.8 × 10(5) M(-1) s(-1) (pH 8.5), 5.4 × 10(3) M(-1) s(-1) (pD 5.5), and 4.0 × 10(4) M(-1) s(-1) (pD 8.5). k(H)/k(D) of Y32 oxidation is 2.5 ± 0.5 and 4.5 ± 0.9 at pH(D) 5.5 and 8.5, respectively. These pH and isotope characteristics suggest a concerted or stepwise, proton-first Y32 oxidation mechanism. The photochemical yield of Y32-O• is 28-58% versus the concentration of [Ru(2,2'-bipyridine)3](3+). Y32-O• decays slowly, t1/2 in the range of 2-10 s, at both pH 5.5 and 8.5, via radical-radical dimerization as shown by second-order kinetics and fluorescence data. The high stability of Y32-O• is discussed relative to the structural properties of the Y32 site. Finally, the static ?3Y NMR structure cannot explain (i) how the phenolic proton released upon oxidation is removed or (ii) how two Y32-O• come together to form dityrosine. These observations suggest that the dynamic properties of the protein ensemble may play an essential role in controlling the PCET and radical decay characteristics of ?3Y. PMID:25121576

Glover, Starla D; Jorge, Christine; Liang, Li; Valentine, Kathleen G; Hammarström, Leif; Tommos, Cecilia

2014-10-01

369

A coupled transport and solid mechanics formulation with improved reaction kinetics parameters for modeling oxidation and decomposition in a uranium hydride bed.  

SciTech Connect

Modeling of reacting flows in porous media has become particularly important with the increased interest in hydrogen solid-storage beds. An advanced type of storage bed has been proposed that utilizes oxidation of uranium hydride to heat and decompose the hydride, releasing the hydrogen. To reduce the cost and time required to develop these systems experimentally, a valid computational model is required that simulates the reaction of uranium hydride and oxygen gas in a hydrogen storage bed using multiphysics finite element modeling. This SAND report discusses the advancements made in FY12 (since our last SAND report SAND2011-6939) to the model developed as a part of an ASC-P&EM project to address the shortcomings of the previous model. The model considers chemical reactions, heat transport, and mass transport within a hydride bed. Previously, the time-varying permeability and porosity were considered uniform. This led to discrepancies between the simulated results and experimental measurements. In this work, the effects of non-uniform changes in permeability and porosity due to phase and thermal expansion are accounted for. These expansions result in mechanical stresses that lead to bed deformation. To describe this, a simplified solid mechanics model for the local variation of permeability and porosity as a function of the local bed deformation is developed. By using this solid mechanics model, the agreement between our reacting bed model and the experimental data is improved. Additionally, more accurate uranium hydride oxidation kinetics parameters are obtained by fitting the experimental results from a pure uranium hydride oxidation measurement to the ones obtained from the coupled transport-solid mechanics model. Finally, the coupled transport-solid mechanics model governing equations and boundary conditions are summarized and recommendations are made for further development of ARIA and other Sandia codes in order for them to sufficiently implement the model.

Salloum, Maher N.; Shugard, Andrew D.; Kanouff, Michael P.; Gharagozloo, Patricia E.

2013-03-01

370

In vitro demonstration of anaerobic oxidation of methane coupled to sulphate reduction in sediment from a marine gas hydrate area  

Microsoft Academic Search

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

Katja Nauhaus; Antje Boetius; Martin Kruger; Friedrich Widdel

2002-01-01

371

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...

372

Coupled Dynamics of Iron and Phosphorus in Sediments of an Oligotrophic Coastal Basin and the Impact of Anaerobic Oxidation of Methane  

PubMed Central

Studies of phosphorus (P) dynamics in surface sediments of lakes and coastal seas typically emphasize the role of coupled iron (Fe), sulfur (S) and P cycling for sediment P burial and release. Here, we show that anaerobic oxidation of methane (AOM) also may impact sediment P cycling in such systems. Using porewater and sediment profiles for sites in an oligotrophic coastal basin (Bothnian Sea), we provide evidence for the formation of Fe-bound P (possibly vivianite; Fe3(PO4)2.8H2O) below the zone of AOM with sulfate. Here, dissolved Fe2+ released from oxides is no longer scavenged by sulfide and high concentrations of both dissolved Fe2+ (>1 mM) and PO4 in the porewater allow supersaturation with respect to vivianite to be reached. Besides formation of Fe(II)-P, preservation of Fe-oxide bound P likely also contributes to permanent burial of P in Bothnian Sea sediments. Preliminary budget calculations suggest that the burial of Fe-bound P allows these sediments to act as a major sink for P from the adjacent eutrophic Baltic Proper. PMID:23626815

Slomp, Caroline P.; Mort, Haydon P.; Jilbert, Tom; Reed, Daniel C.; Gustafsson, Bo G.; Wolthers, Mariette

2013-01-01

373

Serial coupling of RP and zwitterionic hydrophilic interaction LC-MS: suspects screening of diclofenac transformation products by oxidation with a boron-doped diamond electrode.  

PubMed

The presence of pollutants and their transformation products (TPs) in the water system is a big concern because of possible adverse effects on the aquatic environment. Their identification is still a challenge that requires the combination of different chromatographic techniques. In the current research, serial coupling of RPLC and zwitterionic hydrophilic interaction LC with TOF-MS was investigated as a single separation technique for the screening of suspected TPs from electrochemical oxidation of diclofenac using a boron-doped diamond electrode. Diclofenac oxidation was performed in three water matrices in order to study its transformation in different chemical contexts. 47 TPs resulting from similar oxidation methods were selected from the literature. As in most cases standards were not available, an identification procedure based on accurate mass data and chromatographic behavior was proposed. According to this procedure, 11 suspected TPs, previously analyzed by LC, GC, or ion chromatography, were detected in a single injection. The method was proved to be reliable and versatile and it could be efficiently employed as a comprehensive analytical tool for the simultaneous analysis of compounds in a wide polarity range. PMID:23857646

Rajab, Mohamad; Greco, Giorgia; Heim, Carolin; Helmreich, Brigitte; Letzel, Thomas

2013-09-01

374

The development of copper-catalyzed aerobic oxidative coupling of H-tetrazoles with boronic acids and an insight into the reaction mechanism.  

PubMed

The development of a highly efficient and practical protocol for the direct C-N coupling of H-tetrazole and boronic acid was presented. A careful and patient optimization of a variety of reaction parameters revealed that this conventionally challenge reaction could indeed proceed efficiently in a very simple system, that is, just by stirring the tetrazoles and boronic acids under oxygen in the presence of different Cu(I) or Cu(II) salts with only 5?mol?% loading in DMSO at 100?°C. Most significantly, the reaction could proceed very smoothly in a regiospecific manner to afford the 2,5-disubstituted tetrazoles in high to excellent yields. A mechanistic study revealed that both tetrazole and DMSO are crucial for the generation of catalytically active copper species in the reaction process in addition to their role as reactant and solvent, respectively. It is demonstrated that in the reaction cycle, the Cu(I) catalyst could be oxidized to Cu(II) by oxygen to form a [CuT2D] complex (T = tetrazole anion; D = DMSO) through an oxidative copper amination reaction. The Cu(II) complex thus formed was confirmed to be the real catalytically active copper species. Namely, the Cu(II) complex disproportionates to aryl Cu(III) and Cu(I) in the presence of boronic acid. Facile elimination of the Cu(III) species delivers the C-N-coupled product. The results presented herein not only provide a reliable and efficient protocol for the synthesis of 2,5-disubstituted tetrazoles, but most importantly, the mechanistic results would have broad implications for the de novo design and development of new methods for Cu-catalyzed coupling reactions. PMID:24449340

Liu, Chao-You; Li, Yu; Ding, Jin-Ying; Dong, De-Wen; Han, Fu-She

2014-02-17

375

Enhancing light out-coupling of organic light-emitting devices using indium tin oxide-free low-index transparent electrodes  

NASA Astrophysics Data System (ADS)

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.

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

2014-05-01

376

Enhancing light out-coupling of organic light-emitting devices using indium tin oxide-free low-index transparent electrodes  

SciTech Connect

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.

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

377

Isoproterenol Induces Vascular Oxidative Stress and Endothelial Dysfunction via a Gi?-Coupled ?2-Adrenoceptor Signaling Pathway  

PubMed Central

Objective Sustained ?-adrenergic stimulation is a hallmark of sympathetic hyperactivity in cardiovascular diseases. It is associated with oxidative stress and altered vasoconstrictor tone. This study investigated the ?-adrenoceptor subtype and the signaling pathways implicated in the vascular effects of ?-adrenoceptor overactivation. Methods and Results Mice lacking the ?1- or ?2-adrenoceptor subtype (?1KO, ?2KO) and wild-type (WT) were treated with isoproterenol (ISO, 15 ?g.g?1.day?1, 7 days). ISO significantly enhanced the maximal vasoconstrictor response (Emax) of the aorta to phenylephrine in WT (+34%) and ?1KO mice (+35%) but not in ?2KO mice. The nitric oxide synthase (NOS) inhibitor L-NAME abolished the differences in phenylephrine response between the groups, suggesting that ISO impaired basal NO availability in the aorta of WT and ?1KO mice. Superoxide dismutase (SOD), pertussis toxin (PTx) or PD 98,059 (p-ERK 1/2 inhibitor) incubation reversed the hypercontractility of aortic rings from ISO-treated WT mice; aortic contraction of ISO-treated ?2KO mice was not altered. Immunoblotting revealed increased aortic expression of Gi?-3 protein (+50%) and phosphorylated ERK1/2 (+90%) and decreased eNOS dimer/monomer ratio in ISO-treated WT mice. ISO enhanced the fluorescence response to dihydroethidium (+100%) in aortas from WT mice, indicating oxidative stress that was normalized by SOD, PTx and L-NAME. The ISO effects were abolished in ?2KO mice. Conclusions The ?2-adrenoceptor/Gi? signaling pathway is implicated in the enhanced vasoconstrictor response and eNOS uncoupling-mediated oxidative stress due to ISO treatment. Thus, long-term ?2-AR activation might results in endothelial dysfunction. PMID:24622771

Davel, Ana P.; Brum, Patricia C.; Rossoni, Luciana V.

2014-01-01

378

Quantitation of carbon in oil shale process wastewaters: coulometry coupled with ultraviolet-peroxydisulfate and high-temperature oxidation  

SciTech Connect

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.

Langlois, G.W.; Jones, B.M.; Sakaji, R.H.; Daughton, C.G.

1984-07-01

379

Advances in Tandem Mirror fusion power reactors  

Microsoft Academic Search

The Tandem Mirror exhibits several distinctive features which make the reactor embodiment of the principle very attractive: Simple low-technology linear central cell; steady-state operation; high-..beta.. operation; no driven current or disruptions; divertorless operation; direction conversion of end-loss power; low-surface heat loads; and advanced fusion fuel capability. In this paper, we examine these features in connection with two tandem mirror reactor

L. J. Perkins; B. G. Logan

1986-01-01

380

Time-delay-and-integration charge-coupled devices using tin oxide gate technology. [for Landsat MSS  

NASA Technical Reports Server (NTRS)

Doped tin oxide gates are used in a time-delay-and-integration (TDI) CCD scheme in an effort to develop a stable transparent gate technology. Design characteristics of the system are discussed, including 2 sections of 10 by 9 integration stages, four-phase buried channel construction, and 10 input parallel-in/serial-out output shift register at a video rate of 1.25 MHz. A quantum efficiency of 65% with smooth spectral response is attained by front surface imaging. The suitability of the system for the Landsat program is discussed in terms of TDI-CCD operating parameters.

Thompson, L. L.; Mccann, D. H.; Tracy, R. A.; Kub, F. J.; White, M. H.

1978-01-01

381

Application of modified direct denitration to support the ORNL coupled-end-to-end demonstration in production of mixed oxides suitable for pellet fabrication  

SciTech Connect

The current and future development of the Modified Direct Denitration (MDD) process is in support of Oak Ridge National Laboratory's (ORNL) Coupled End-to-End (CETE) research, development, and demonstration (R and D) of proposed advanced fuel reprocessing and fuel fabrication processes. This work will involve the co-conversion of the U/Pu/Np product streams from the UREX+3 separation flow sheet utilizing the existing MDD glove-box setup and the in-cell co-conversion of the U/Pu/Np/Am/Cm product streams from the UREX+1a flow sheet. Characterization equipment is being procured and installed. Oxide powder studies are being done on calcination/reduction variables, as well as pressing and sintering of pellets to permit metallographic examinations. (authors)

Walker, E.A.; Vedder, R.J.; Felker, L.K.; Marschman, S.C. [Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, TN 37831 (United States)

2007-07-01

382

Application of Modified Direct Denitration to Support the ORNL Coupled-End-to-End Demonstration in Production of Mixed Oxides Suitable for Pellet Fabrication  

SciTech Connect

The current and future development of the Modified Direct Denitration (MDD)process is in support of Oak Ridge National Laboratory's (ORNL) Coupled End-to-End (CETE) research, development, and demonstration (R&D) of proposed advanced fuel reprocessing and fuel fabrication processes. This work will involve the co-conversion of the U/Pu/Np product streams from the UREX+3 separation flow sheet utilizing the existing MDD glove-box setup and the in-cell co-conversion of the U/Pu/Np/Am/Cm product streams from the UREX+1a flow sheet. Characterization equipment is being procured and installed. Oxide powder studies are being done on calcination/reduction variables, as well as pressing and sintering of pellets to permit metallographic examinations.

Walker, Elisabeth A [ORNL; Vedder, Raymond James [ORNL; Felker, Leslie Kevin [ORNL; Marschman, Steve [ORNL

2007-01-01

383

Allelic polymorphism in the promoter (T–786?C), but not in exon 7 (G894?T) or the variable number tandem repeat in intron 4, of the endothelial nitric oxide synthase gene is positively associated with acute coronary syndrome in the Ukrainian population  

PubMed Central

BACKGROUND Different allelic variants of endothelial nitric oxide synthase (eNOS) can have different effects on the development of certain forms of ischemic heart disease, depending on the specific human population. The frequency of the polymorphism T–786 ? C in the promoter, G894?T in exon 7 and the variable number tandem repeat in intron 4 were assayed in patients with acute coronary syndrome compared with clinically healthy individuals in the Ukrainian population. METHODS Polymerase chain reaction and restriction fragment length polymorphism analysis were used to detect the above mentioned variants of the eNOS gene in 221 patients with acute coronary syndrome and in 83 control subjects. RESULTS It was shown that the percentage of normal homozygotes, heterozygotes and pathological homozygotes for the T–786?C promoter polymorphism was 47.5%, 36.2% and 16.3%, respectively (controls: 48.2%, 45.8% and 6.0%; P<0.05 by ?2 test); for the G894?T polymorphism in exon 7, the percentages were 34.4%, 57.9% and 7.7%, respectively (controls: 28.9%, 67.5% and 3.6%; P>0.05); and, for the 4a/4b polymorphism in intron 4, the percentages were 64.7%, 31.2% and 4.1%, respectively (controls: 62.7%, 32.5% and 4.8%; P>0.05). CONCLUSIONS The C/C promoter variant of eNOS can be considered a risk factor for acute coronary syndrome in the Ukrainian population. PMID:18651012

Dosenko, Victor E; Zagoriy, Vyacheslav Yu; Lutay, Yaroslav M; Parkhomenko, Alexandr N; Moibenko, Alexey A

2006-01-01

384

FORUM: Bioinspired Heme, Heme/non-heme Diiron, Heme/copper and Inorganic NOx Chemistry: ·NO(g) Oxidation, Peroxynitrite-Metal Chemistry and ·NO(g) Reductive Coupling  

PubMed Central

The focus of this Forum review highlights work from our own laboratories and those of others in the area of biochemical and biologically inspired inorganic chemistry dealing with nitric oxide (nitrogen monoxide, ·NO(g)) and its biological roles and reactions. The latter focus is on (i) oxidation of ·NO(g) to nitrate by nitric oxide dioxygenases (NOD’s), and (ii) reductive coupling of two molecules of ·NO(g) to give N2O(g). In the former case, NOD’s are described and the highlighting of possible peroxynitrite-heme intermediates and consequences of this are given by discussion of recent works with myoglobin and a synthetic heme model system for NOD action. Summaries of recent copper complex chemistries with ·NO(g) and O2(g) leading to peroxynitrite species are given. The coverage of biological reductive coupling of ·NO(g) deals with bacterial nitric oxide reductases (NOR’s) with heme/non-heme diiron active sites, and on heme/Cu oxidases such as cytochrome c oxidase which can mediate the same chemistry. Recent designed protein and synthetic model compound (heme/non-heme diiron or heme/copper) as functional mimics are discussed in some detail. We also highlight examples from the chemical literature, not necessarily involving biologically relevant metal ions, which describe the oxidation of ·NO(g) to nitrate (or nitrite) and possible peroxynitrite intermediates, or reductive coupling of ·NO(g) to give nitrous oxide. PMID:20666386

Schopfer, Mark P.; Wang, Jun; Karlin, Kenneth D.

2010-01-01

385

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)

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.

Marin, I. S.; Molson, J. W.

2013-05-01

386

Neuronal nitric oxide synthase-dependent elevation in adiponectin in the rostral ventrolateral medulla underlies g protein-coupled receptor 18-mediated hypotension in conscious rats.  

PubMed

Direct activation of the endocannabinoid receptor G protein-coupled receptor 18 (GPR18) in the rostral ventrolateral medulla (RVLM) of conscious rats by abnormal cannabidiol (Abn CBD; trans-4-[3-methyl-6-(1-methylethenyl)-2-cyclohexen-1-yl]-5-pentyl-1,3-benzenediol) elevates local nitric oxide (NO) and adiponectin (ADN) levels and reduces oxidative stress and blood pressure (BP). However, the molecular mechanisms for GPR18-mediated neurochemical responses, including the nitric oxide synthase isoform that generates NO, and their potential causal link to the BP reduction are not known. We hypothesized that GPR18-mediated enhancement of Akt, extracellular signal-regulated kinase 1/2 (ERK1/2), and neuronal nitric oxide synthase (nNOS) phosphorylation, triggered by a reduction in cAMP, accounts for the NO/ADN-dependent reductions in RVLM oxidative stress and BP. Intra-RVLM GPR18 activation (Abn CBD; 0.4 ?g) enhanced RVLM Akt, ERK1/2, and nNOS phosphorylation as well as ADN levels during the hypotensive response. Prior GPR18 blockade with O-1918 (1,3-dimethoxy-5-methyl-2-[(1R,6R)-3-methyl-6-(1-methylethenyl)-2-cyclohexen-1-yl]benzene) produced the opposite effects and abrogated Abn CBD-evoked neurochemical and BP responses. Pharmacological inhibition of RVLM phosphoinositide 3-kinase (PI3K)/Akt (wortmannin), ERK1/2 (PD98059 [2-?(2-?amino-?3-?methoxyphenyl)-?4H-?1-?benzopyran-?4-?one]), or nNOS (N(?)-propyl-l-arginine), or activation of adenylyl cyclase (forskolin) virtually abolished intra-RVLM Abn CBD-evoked hypotension and the increases in Akt, ERK1/2, and nNOS phosphorylation and in ADN levels in the RVLM. Our pharmacological and neurochemical findings support a pivotal role for PI3K, Akt, ERK1/2, nNOS, and adenylyl cyclase, via modulation of NO, ADN, and cAMP levels, in GPR18 regulation of the RVLM redox state and BP in conscious rats. PMID:25100751

Penumarti, Anusha; Abdel-Rahman, Abdel A

2014-10-01

387

Aerobic oxidation of methanol to formic acid on Au8-: benchmark analysis based on completely renormalized coupled-cluster and density functional theory calculations.  

PubMed

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

Hansen, Jared A; Ehara, Masahiro; Piecuch, Piotr

2013-10-10

388

Graphene oxide liquid crystals as a versatile and tunable alignment medium for the measurement of residual dipolar couplings in organic solvents.  

PubMed

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

Lei, Xinxiang; Xu, Zhen; Sun, Han; Wang, Shun; Griesinger, Christian; Peng, Li; Gao, Chao; Tan, Ren X

2014-08-13

389

The Delta band dissociation of nitric oxide - A potential mechanism for coupling thermospheric variations to the mesosphere and stratosphere  

NASA Technical Reports Server (NTRS)

Depletion of solar radiation at discrete wavelengths by nitric oxide has a significant impact on the dissociation rate of this gas in the delta(0, 0) and delta(1, 0) bands. Inclusion of the opacity provided by a typical NO profile reduces the dissociation rate in the upper stratosphere to 50-75 pct of that predicted when the optical depth calculation omits this contribution. A substantial fraction of the NO column abundance as measured near the stratopause resides in the lower thermosphere where correlations of NO with solar and magnetic activity are well documented. Variations in the thermospheric NO abundance therefore modulate the radiation field at the precise wavelengths absorbed by this molecule in the mesosphere and upper stratosphere. Predicted changes in the dissociation rate arising from a varying thermospheric opacity exceed 8 pct throughout the mesosphere and reach 15 pct between 65 km and 95 km.

Frederick, J. E.; Abrams, R. B.; Crutzen, P. J.

1983-01-01

390

Nogo-A couples with Apg-1 through interaction and co-ordinate expression under hypoxic and oxidative stress.  

PubMed

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

Kern, Florian; Stanika, Ruslan I; Sarg, Bettina; Offterdinger, Martin; Hess, Daniel; Obermair, Gerald J; Lindner, Herbert; Bandtlow, Christine E; Hengst, Ludger; Schweigreiter, Rüdiger

2013-10-15

391

Coupling of solar-assisted advanced oxidative and biological treatment for degradation of agro-residue-based soda bleaching effluent.  

PubMed

This study evaluates the effect of integrated solar-assisted advanced oxidation process (AOP) and biological treatment on the extent of degradation of effluents from chlorination (C) and first alkaline extraction (E(1)) stages of soda pulp bleaching in agro-residue-based pulp and paper mill. Biodegradation of the effluents was attempted in suspended mode using activated sludge from the functional pulp and paper industry effluent treatment plant acclimatized to effluents in question. The photocatalytic treatment was employed using zinc oxide (ZnO) in slurry mode for decontamination of effluents in a batch manner and the degradation was evaluated in terms of reduction in chemical oxygen demand. The biological treatment (24 h) of C and E(1) effluent resulted in 30 and 57 % of degradation, respectively. Solar-induced AOP of C and E(1) effluents resulted in 53 and 43 % degradation under optimized conditions (2.5 g L(-1) ZnO at pH 8.0) after 6 h of exposure. For C effluent, a short duration of solar/ZnO (1 h) prior to biological treatment reduced the time required at biological step from 24 to 12 h for almost same extent (92 %) of degradation. However, sequential biological treatment (24 h) followed by solar/ZnO (2 h) resulted in 85.5 % degradation. In contrast, in the case of E(1) effluent, sequential biological (24 h)-solar/ZnO (2 h) system effectively degrades effluent to 95.4 % as compared to 84.8 % degradation achieved in solar/ZnO (2 h)-biological treatment (24 h) system. In the present study, the sequencing of photocatalysis with the biological treatment is observably efficient and technically viable process for the complete mineralization of the effluents. PMID:22645007

Dhir, Amit; Prakash, Nagaraja Tejo; Sud, Dhiraj

2012-11-01

392

Aminocatalytic Cross-Coupling Approach via Iminium Ions to Different C?C Bonds.  

PubMed

Given the attractive ability of iminium ions to functionalize molecules directly at ostensibly unreactive positions, the reactivity of iminium ions, in which an ? CH2 group is replaced by C?O was explored. Background studies on the ability of such iminium cations to promote reactions via an iminium-catalyzed or iminium-equivalent pathway are apparently unavailable. Previously, tandem cross-coupling reactions were reported, in which an iminium ion undergoes nucleophilic 1,2-addition to give a putative three-component intermediate that abstracts a proton in situ and undergoes self-deamination followed by unprecedented DMSO/aerobic oxidation to generate ?-ketoamides. However, later it was observed that iminium ions can generate valuable ?-ketoamides through simple aerobic oxidation. In all reactions, iminium ions were generated in situ by reaction of 2-oxoaldehydes with secondary amines. PMID:25524296

Mupparapu, Nagaraju; Battini, Narsaiah; Battula, Satyanarayana; Khan, Shahnawaz; Vishwakarma, Ram A; Ahmed, Qazi Naveed

2015-02-01

393

White organic light-emitting diodes based on tandem structures  

NASA Astrophysics Data System (ADS)

White organic light-emitting diodes made of two electroluminescent (EL) units connected by a charge generation layer were fabricated. Thus, with a tandem structure of indium tin oxide/N ,N'-di(naphthalene-1-yl)-N ,N'-diphenyl-benzidine (NPB)/9,10-bis-(?-naphthyl)-anthrene (ADN)/2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP)/tris(8-hydroxyquinoline) aluminum (Alq3)/BCP:Li/V2O5/NPB/Alq3:4-(dicyanomethylene)-2-t-butyle-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)4H-pyran (DCJTB)/Alq3/LiF/Al, a stable white light with Commission Internationale De L'Eclairage chromaticity coordinates from (0.35, 0.32) at 18V to (0.36, 0.36) at 50V was generated. It was clearly seen that the EL spectra consist of red band at 600nm due to DCJTB, green band at 505nm due to Alq3, and blue band at 435nm due to ADN, and the current efficiency and brightness equal basically to the sum of the two EL units. As a result, the tandem devices showed white light emission with a maximum brightness of 10200cd /m2 at a bias of 40V and a maximum current efficiency of 10.7cd/A at a current density of 3.5mA/cm2.

Guo, Fawen; Ma, Dongge

2005-10-01

394

Graphene oxide-silica composite coating hollow fiber solid phase microextraction online coupled with inductively coupled plasma mass spectrometry for the determination of trace heavy metals in environmental water samples.  

PubMed

In this work, a novel graphene oxide-silica (GO-silica) composite coating was prepared for hollow fiber solid phase microextraction (HF-SPME) of trace Mn, Co, Ni, Cu, Cd and Pb followed by on-line inductively coupled plasma mass spectrometry (ICP-MS) detection. The structure of the prepared graphene oxide and GO-silica composite was studied and elucidated by atomic force microscopy (AFM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The GO-silica composite coated hollow fiber was characterized by scanning electron microscope (SEM), and the results show that the GO-silica composite coating possessed a homogeneous and wrinkled structure. Various experimental parameters affecting the extraction of the target metal ions by GO-silica composite coated HF-SPME have been investigated carefully. Under the optimum conditions, the limits of detection (LODs, 3?) for Mn, Co, Ni, Cu, Cd and Pb were 7.5, 0.39, 20, 23, 6.7 and 28 ng L(-1) and the relative standard deviations (RSDs, c(Mn, Co, Cd)=0.05 ?g L(-1), c(Ni, Cu, Pb)=0.2 ?g L(-1), n=7) were 7.2, 7.0, 5.6, 7.3, 7.8 and 4.6%, respectively. The accuracy of the proposed method was validated by the analysis of Certified Reference Material of GSBZ 50009-88 environmental water and the determined values were in a good agreement with the certified values. The proposed method has been successfully applied for the determination of trace metals in real environmental water samples with recoveries ranging from 85 to 119%. PMID:24725857

Su, Shaowei; Chen, Beibei; He, Man; Hu, Bin

2014-06-01

395

{[K.18Crown6]Br 3} n : a unique tribromide-type and columnar nanotube-like structure for the oxidative coupling of thiols and bromination of some aromatic compounds  

Microsoft Academic Search

Reaction of 18-crown-6 with KBr and then with bromine (Br2) afforded a unique tribromide salt with a nanotube-like structure ({[K.18-crown-6]Br3}n). Oxidative coupling of thiols and bromination of some aromatic compounds is the first report on the chemistry of this reagent.

Mohammad Ali Zolfigol; Gholamabbas Chehardoli; Sadegh Salehzadeh; Harry Adams; Michael D. Ward

2007-01-01

396

Synfuels from fusion: using the tandem mirror reactor and a thermochemical cycle to produce hydrogen  

SciTech Connect

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)

Werner, R.W. (ed.)

1982-11-01

397

Metal-oxide interfaces: Where the action is  

NASA Astrophysics Data System (ADS)

Heterogeneous catalyst systems comprising metals supported on oxides are widespread. Evidence now suggests that it is the interfacial regions that are most catalytically active, and this has been exploited to create a tandem nanocatalyst system.

Stair, Peter C.

2011-05-01

398

Ant search strategies after interrupted tandem runs.  

PubMed

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

Franks, Nigel R; Richardson, Thomas O; Keir, Samantha; Inge, Stephen J; Bartumeus, Frederic; Sendova-Franks, Ana B

2010-05-01

399

Understanding tandem organic photovoltaic cell performance  

NASA Astrophysics Data System (ADS)

We develop a framework to understand the performance of tandem organic photovoltaic (OPV) cells consisting of a series-connected stack of an arbitrary number of sub-cells. The power conversion efficiency penalty, ??, is defined as the loss incurred when the tandem cell is at its maximum power point (MPP) but one or more sub-cells are not operating at their individual MPPs. To minimize ??, the current at the MPP for each sub-cell must be equal. We also develop a method to calculate the tandem cell spectral mismatch factor and fill factor, showing that they are related to both the fill factors and short circuit currents of all the constituent sub-cells. By including the current generated in the dark, exciton dissociation at the donor-acceptor heterojunction, and photoconductivity, along with current losses due to polaron-pair and bimolecular recombination, we simulate the operation of small molecule bilayer and mixed-layer sub-cells used in the tandem, and from these results derive the behavior of the integrated device. This analysis is used to understand and optimize tandem OPV cell performance.

Lassiter, Brian E.; Kyle Renshaw, C.; Forrest, Stephen R.

2013-06-01

400

Inductively coupled plasma torch efficiency at atmospheric pressure for organo-chlorine liquid waste removal: chloroform destruction in oxidative conditions.  

PubMed

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

Kamgang-Youbi, Georges; Poizot, Karine; Lemont, Florent

2013-01-15

401

Structure and Notch Receptor Binding of the Tandem WWE Domain of Deltex  

SciTech Connect

Deltex is a cytosolic effector of Notch signaling thought to bind through its N-terminal domain to the Notch receptor. Here we report the structure of the Drosophila Deltex N-terminal domain, which contains two tandem WWE sequence repeats. The WWE repeats, which adopt a novel fold, are related by an approximate two-fold axis of rotation. Although the WWE repeats are structurally distinct, they interact extensively and form a deep cleft at their junction that appears well suited for ligand binding. The two repeats are thermodynamically coupled; this coupling is mediated in part by a conserved segment that is immediately C-terminal to the second WWE domain. We demonstrate that although the Deltex WWE tandem is monomeric in solution, it forms a heterodimer with the ankyrin domain of the Notch receptor. These results provide structural and functional insight into how Deltex modulates Notch signaling, and how WWE modules recognize targets for ubiquitination.

Zweifel,M.; Leahy, D.; Barrick, D.

2005-01-01

402

Sulphur hexafluoride as a stripper gas for tandem accelerators  

NASA Astrophysics Data System (ADS)

We have investigated sulphur hexafluoride as a stripper gas in tandem accelerators by using the ANTARES accelerator system at ANSTO to measure charge state distributions for this gas. Results are reported at 4 MV terminal voltage for injected negative ions ranging from carbon to uranium oxide. For iodine and thorium the distributions are extended across a range of energies of practical use for accelerator mass spectrometry, ion beam analysis and other accelerator applications. Charge state distributions using sulphur hexafluoride are found to have mean charge states up to 1 charge unit higher than, and to be broader than, corresponding distributions for argon gas, except in the case of carbon beams. As a result, SF6 is shown to provide significantly higher yields for charge states of heavy ions above the mean charge state. We now perform actinide AMS measurements with 9% yield to the 5+ charge state, compared to 4-5% achieved previously with argon gas.

Hotchkis, M. A. C.; Child, D.; Fink, D.; Garton, D.; Levchenko, V.; Wilcken, K.

2013-05-01

403

Multiresidue pesticide analysis of fruits by ultra-performance liquid chromatography tandem mass spectrometry  

Microsoft Academic Search

Ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC–MS–MS) has been used for screening and quantification\\u000a of 32 pesticides and metabolites in two fruit matrices. The compounds investigated belonged to different chemical families\\u000a of insecticides, acaricides, fungicides, and herbicides; several metabolites were also included. Quantification was conducted\\u000a using matrix-matched standards calibration; response was a linear function of concentration in the

O. J. Pozo; M. Barreda; J. V. Sancho; F. Hernández; J. Ll. Lliberia; M. A. Cortés; B. Bagó

2007-01-01

404

Quantification of rabeprazole in human plasma by liquid chromatography–tandem mass spectrometry  

Microsoft Academic Search

An analytical method based on liquid chromatography coupled with tandem mass spectrometry detection has been developed and validated for the determination of rabeprazole in human plasma using omeprazole as the internal standard. The analyte and internal standard was extracted with n-hexane–dichloromethane–isopropanol (20:10:1, v\\/v) and chromatographed isocratically on a Diamonsil C18 analytical column. Methanol was used as the mobile phase to

Yong Zhang; Xiaoyan Chen; Qi Gu; Dafang Zhong

2004-01-01

405

The validation of short tandem repeat (STR) loci for use in forensic casework  

Microsoft Academic Search

A quadruplex reaction has been developed which amplifies the short tandem repeat (STR) loci HUMVWA31\\/A, HUMTHO1, HUMF13A1 and HUMFES\\/FPS. Detection of the PCR products employs denaturing poly-acrylamide gels coupled with fluorescent-based technology. This system has been evaluated for use in routine forensic casework and has been shown to be both robust and reproducible. The quadruplex reaction is as sensitive as

J. E. Lygo; P. E. Johnson; D. J. Holdaway; S. Woodroffe; C. P. Kimpton; P. Gill; J. P. Whitaker; T. M. Clayton

1994-01-01

406

Thermodynamic Modeling of a Solid Oxide Fuel Cell to Couple with an Existing Gas Turbine Engine Model  

NASA Technical Reports Server (NTRS)

The Controls and Dynamics Technology Branch at NASA Glenn Research Center are interested in combining a solid oxide fuel cell (SOFC) to operate in conjunction with a gas turbine engine. A detailed engine model currently exists in the Matlab/Simulink environment. The idea is to incorporate a SOFC model within the turbine engine simulation and observe the hybrid system's performance. The fuel cell will be heated to its appropriate operating condition by the engine s combustor. Once the fuel cell is operating at its steady-state temperature, the gas burner will back down slowly until the engine is fully operating on the hot gases exhausted from the SOFC. The SOFC code is based on a steady-state model developed by The U.S. Department of Energy (DOE). In its current form, the DOE SOFC model exists in Microsoft Excel and uses Visual Basics to create an I-V (current-voltage) profile. For the project's application, the main issue with this model is that the gas path flow and fuel flow temperatures are used as input parameters instead of outputs. The objective is to create a SOFC model based on the DOE model that inputs the fuel cells flow rates and outputs temperature of the flow streams; therefore, creating a temperature profile as a function of fuel flow rate. This will be done by applying the First Law of Thermodynamics for a flow system to the fuel cell. Validation of this model will be done in two procedures. First, for a given flow rate the exit stream temperature will be calculated and compared to DOE SOFC temperature as a point comparison. Next, an I-V curve and temperature curve will be generated where the I-V curve will be compared with the DOE SOFC I-V curve. Matching I-V curves will suggest validation of the temperature curve because voltage is a function of temperature. Once the temperature profile is created and validated, the model will then be placed into the turbine engine simulation for system analysis.

Brinson, Thomas E.; Kopasakis, George

2004-01-01

407

Tandem mirror thermal barrier experimental program plan  

SciTech Connect

This report describes an experimental plan for the development of the Tandem Mirror Thermal Barrier. Included is: (1) a description of thermal barrier related physics experiments; (2) thermal barrier related experiments in the existing TMX and Phaedrus experiments; (3) a thermal barrier TMX upgrade; and (4) initiation of investigations of axisymmetric magnetic geometry. Experimental studies of the first two items are presently underway. Results are expected from the TMX upgrade by the close of 1981 and from axisymmetric tandem mirror experiments at the end of 1983. Plans for Phaedrus upgrades are developing for the same period.

Coensgen, F.H.; Drake, R.P.; Simonen, T.C.

1980-01-02

408

High voltage series connected tandem junction solar battery  

DOEpatents

A high voltage series connected tandem junction solar battery which comprises a plurality of strips of tandem junction solar cells of hydrogenated amorphous silicon having one optical path and electrically interconnected by a tunnel junction. The layers of hydrogenated amorphous silicon, arranged in a tandem configuration, can have the same bandgap or differing bandgaps. The tandem junction strip solar cells are series connected to produce a solar battery of any desired voltage.

Hanak, Joseph J. (Lawrenceville, NJ)

1982-01-01

409

Micromorph tandem solar cells: optimization of the microcrystalline silicon bottom cell in a single chamber system  

NASA Astrophysics Data System (ADS)

We report on the development of single chamber deposition of microcrystalline and micromorph tandem solar cells directly onto low-cost glass substrates. The cells have pin single-junction or pin/pin double-junction structures on glass substrates coated with a transparent conductive oxide layer such as SnO2 or ZnO. By controlling boron and phosphorus contaminations, a single-junction microcrystalline silicon cell with a conversion efficiency of 7.47% is achieved with an i-layer thickness of 1.2 ?m. In tandem devices, by thickness optimization of the microcrystalline silicon bottom solar cell, we obtained an initial conversion efficiency of 9.91% with an aluminum (Al) back reflector without a dielectric layer. In order to enhance the performance of the tandem solar cells, an improved light trapping structure with a ZnO/Al back reflector is used. As a result, a tandem solar cell with 11.04% of initial conversion efficiency has been obtained.

Zhang, Xiao-Dan; Zheng, Xin-Xia; Xu, Sheng-Zhi; Lin, Quan; Wei, Chang-Chun; Sun, Jian; Geng, Xin-Hua; Zhao, Ying

2011-10-01

410

Tandem repeats finder: a program to analyze DNA sequences  

Microsoft Academic Search

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

Gary Benson

1999-01-01

411

Vacuum insulation tandem accelerator for B. Bayanov1  

E-print Network

-exchange tube in the center of high-voltage electrode, a proton beam is formed at the outlet of the tandem neutron therapy facility [1]. The main idea of tandem accelerator is providing high rate acceleration, as a powerful source of high voltage. Negative hydrogen ion beam is injected into electrostatic tandem

Taskaev, Sergey Yur'evich

412

Atmospheric pressure chemical ionisation normal phase liquid chromatography mass spectrometry and tandem mass spectrometry of chlorophyll a allomers.  

PubMed

Four oxidation products formed during the allomerisation reaction of chlorophyll a in methanol have been separated and identified using normal phase high-performance liquid chromatography (NP-HPLC) coupled with atmospheric pressure chemical ionisation (APCI) tandem mass spectrometry (MS/MS) and photodiode array detection. Fragmentation pathways of the main stereoisomers of the four major products, Mg-purpurin-7 dimethyl phytyl ester, 15(1)-MeO-lact-chl a, 13(2)-MeO-chl a and 13(2)-HO-chl a, have been assigned using APCI-MS(n) aided by examination of deuteriated counterparts of the purpurin and the lactone. Diagnostic fragmentations have been determined, including those for Mg-purpurin-7 dimethyl phytyl ester and 15(1)-MeO-lact-chl a, which display very similar full MS and MS/MS spectra. The use of NP-HPLC offers a rapid and efficient method which, combined with MS/MS, reduces reliance on precursor ion mass for assignment of structure in the allomerisation reaction where major and minor components are often isobaric. PMID:11857734

Jie, Chi; Walker, J Stuart; Keely, Brendan J

2002-01-01

413

Oligochitosan stimulated phagocytic activity of macrophages from blunt snout bream (Megalobrama amblycephala) associated with respiratory burst coupled with nitric oxide production.  

PubMed

The immunostimulating effects of oligochitosan have been proven in several fish, however, the mechanisms underlying the stimulation are not characterized. In the present study, the effects of oligochitosan were investigated using macrophages isolated from blunt snout bream (Megalobrama amblycephala). The results showed that the phagocytic activity of the macrophages was enhanced by the addition of oligochitosan in vitro and in vivo. The two of the most important antimicrobial pathways of macrophages, NADPH oxidase and iNOS pathways were included for further studies. The amounts of superoxide anion and the mRNAs of the five subunits of NADPH oxidase genes were significantly enhanced in the oligochitosan-treated macrophages and macrophages isolated from fish fed with feed containing oligochitosan. In addition, the NO production, iNOS activity and iNOS gene expression were all significantly increased in the presence of oligochitosan. Furthermore, the mRNA levels of the TNF-? and IL-1? were also significantly increased in the macrophages derived from fish fed with oligochitosan. In conclusion, the stimulation effects of oligochitosan on the phagocytic activity of the fish macrophages were associated with respiratory burst coupled with nitric oxide production. PMID:24968077

Liu, Lichun; Zhou, Yang; Zhao, Xiaoheng; Wang, Hong; Wang, Li; Yuan, Gailing; Asim, Muhammad; Wang, Weimin; Zeng, Lingbing; Liu, Xiaoling; Lin, Li

2014-11-01

414

Effect of ion-irradiation induced defects on the nanocluster Si/Er{sup 3+} coupling in Er-doped silicon-rich silicon oxide  

SciTech Connect

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.

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

415

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

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

Torres Elguera, Julio Cesar; Yañez Barrientos, Eunice; Wrobel, Katarzyna; Wrobel, Kazimierz

2013-07-10

416

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)

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 develop