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Sample records for tandem oxidation coupling

  1. Enantioselective synthesis of binaphthyl polymers using chiral asymmetric phenolic coupling catalysts: oxidative coupling and tandem glaser/oxidative coupling.

    PubMed

    Morgan, Barbara J; Xie, Xu; Phuan, Puay-Wah; Kozlowski, Marisa C

    2007-08-03

    A series of functionalized and optically active polybinaphthyls have been synthesized from achiral substrates by asymmetric oxidative phenolic coupling using a chiral 1,5-diaza-cis-decalin copper catalyst. In most cases, a copper tetrafluoroborate catalyst was found to be superior to the copper iodide catalyst, as ortho-iodination of the substrates could be prevented. Three methods for the formation of chiral polymers are described. In the first method, two 2-naphthols linked together at C-6 are subjected to the optimized asymmetric oxidative phenolic coupling conditions to form chiral polynaphthyls. A combination of NMR and HPLC measurements secured the selectivity of the asymmetric coupling. In the second method, substrates containing only one naphthalene were utilized. By incorporating a 2-naphthol and a terminal alkyne, the chiral copper catalysts effect both Glaser-Hay coupling of the alkyne and oxidative asymmetric coupling of the 2-naphthol with remarkable chemoselectivity. The relative reaction rates of various moieties with the chiral catalysts follows the order: benzyl cyanides > aryl alkynes > electron-rich 2-naphthols > electron-deficient 2-naphthols > alkyl alkynes. Because of high chemoselectivity, this approach is useful for the organized assembly of multifunctional substrates in a single operation. In all cases, no cross-coupling is observed between the alkyne and the 2-naphthol. This approach was thus applied to a set of highly functionalized precursors. In this third case, the biaryl coupling was performed first and a Glaser-Hay coupling was performed in a separate step to generate a highly functionalized polymer. In some cases, the resultant chiral polymers exhibit very large optical rotations.

  2. Characterization of the limonene oxidation products with liquid chromatography coupled to the tandem mass spectrometry

    NASA Astrophysics Data System (ADS)

    Witkowski, Bartłomiej; Gierczak, Tomasz

    2017-04-01

    Composition of the secondary organic aerosol (SOA) generated during ozonolysis of limonene was investigated with liquid chromatography coupled to the negative electrospray ionization (ESI), quadrupole tandem mass spectrometry (MS/MS) as well as high resolution Time-of-Flight mass spectrometry. Aerosol was generated in the flow-tube reactor. HR-MS/MS analysis allowed for proposing structures for the several up-to-date unknown limonene oxidation products. In addition to the low MW limonene oxidation products, significant quantities of oligomers characterized by elemental compositions: C19H30O5, C18H28O6, C19H28O7, C19H30O7 and C20H34O9 were detected in the SOA samples. It was concluded that these compounds are most likely esters, aldol reaction products and/or hemiacetals. In addition to detailed study of the limonene oxidation products, the reaction time as well as initial ozone concentration impact on the limonene SOA composition was investigated. The relative intensities of the two esters of the limonic acid and 7-hydroxy limononic acid increased as a result of lowering the initial ozone concentration and shortening the reaction time, indicating that esterification may be an important oligomerization pathway during limonene SOA formation.

  3. One-pot synthesis of thiazino[2,3,4-hi]indole derivatives through a tandem oxidative coupling/heteroannulation process.

    PubMed

    Mao, Xi; Tong, Tao; Fan, Senbao; Fang, Liting; Wu, Jingyi; Wang, Xiaoxia; Kang, Honglan; Lv, Xin

    2017-04-12

    A novel and expedient one-pot synthesis of thiazino[2,3,4-hi]indole derivatives from o-haloaryl enamines and o-bromothiophenols has been developed. The tandem oxidative coupling/heteroannulation reactions exhibit high selectivity and good efficiency. The polycyclic heterocyclic products obtained might be useful in medicinal chemistry and materials science.

  4. Online screening of nitric oxide scavengers in natural products using high performance liquid chromatography coupled with tandem diode array and fluorescence detection.

    PubMed

    Li, Dapeng; Wang, Ting; Guo, Yujie; Hu, Yuanjia; Yu, Boyang; Qi, Jin

    2015-12-18

    Nitric oxide (NO) is an important cellular signaling molecule with extensive physiological and pathophysiological effects. NO scavengers have the potential to treat inflammation, septic shock and other related diseases, and numerous examples have been chemically synthesized or isolated from natural products. The chemical diversity of natural products, however, means that a huge effort is necessary to efficiently screen and identify bioactive compounds, especially NO scavengers. In this article, we propose an effective analytical method to screen for NO scavengers in three natural products using an online system that couples high performance liquid chromatography with tandem diode array and fluorescence detection (HPLC-DAD-FLD). Eighteen compounds from radix of Scutellaria baicalensis Georgi and green tea displayed significant NO scavenging activity whereas components of Pueraria lobata (Willd.) Ohwi had no discernable activity. The structures of the active compounds were elucidated using Agilent Accurate-Mass Q-TOF LC/MS system. Preliminary analysis of structure-activity relationships indicated that, in flavonoids, a 2,3-double bond and a 3-H atom or a 3-OH group are essential for activity. In tannins, poly-hydroxyl groups are important for NO scavenging activity. Method validation indicated that the newly developed method is both reliable and repeatable. The online method that we present provides a simple, rapid and effective way to identify and characterize NO scavengers present in natural products.

  5. Planar graphene oxide-based magnetic ionic liquid nanomaterial for extraction of chlorophenols from environmental water samples coupled with liquid chromatography-tandem mass spectrometry.

    PubMed

    Cai, Mei-Qiang; Su, Jie; Hu, Jian-Qiang; Wang, Qian; Dong, Chun-Ying; Pan, Sheng-Dong; Jin, Mi-Cong

    2016-08-12

    A planar graphene oxide-based magnetic ionic liquid nanomaterial (PGO-MILN) was synthesized. The prepared PGO-MILN was characterized by transmission electronmicroscopy (TEM) and Fourier-transform infrared spectrometry (FTIR). The results of adsorption experiments showed that the PGO-MILN had great adsorption capacity for 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 the adsorption experimental data, a sensitive magnetic method for determination of the five CPs in environmental water samples was developed by an effective magnetic solid-phase extraction (MSPE) procedure coupled with high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS). The effects of main MSPE parameters including the solution pH, extraction time, desorption time, and volume of desorption solution on the extraction efficiencies had been investigated in detail. The recoveries ranged from 85.3 to 99.3% with correlation coefficients (r) higher than 0.9994 and the linear ranges were between 10 and 500ngL(-1). The limits of detection (LODs) and limits of quantification (LOQs) of the five CPs ranged from 0.2 to 2.6ngL(-1) and 0.6 to 8.7ngL(-1), respectively. The intra- and inter- day relative standard deviations (RSDs) were in the range from 0.6% to 7.4% and from 0.7% to 8.4%, respectively. It was confirmed that the PGO-MILN was a kind of highly effective MSPE materials used for enrichment of trace CPs in the environmental water.

  6. Simultaneous determination of trimethylamine and trimethylamine N-oxide in mouse plasma samples by hydrophilic interaction liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Mi, Si; Zhao, Yuan-Yuan; Jacobs, René L; Curtis, Jonathan M

    2017-02-01

    A method was developed that applies hydrophilic interaction liquid chromatography with tandem mass spectrometry in the multiple reaction monitoring mode to separate and accurately quantify trimethylamine and trimethylamine N-oxide in a single chromatographic run. This was achieved by converting trimethylamine to ethyl betaine, which is less volatile and hence results in greatly improved quantitation. Ethyl betaine also gives a similar response to trimethylamine N-oxide using positive-ion electrospray ionization mass spectrometry. It is readily separated from trimethylamine N-oxide by hydrophilic liquid chromatography in a 5 min run and with improved peak shape compared to underivatized trimethylamine. Validation of the method yielded a limit of detection (S/N ≥ 3) of 0.5 ng/mL for trimethylamine and 0.25 ng/mL for trimethylamine N-oxide. Method accuracies of 91.4-105.3% with precisions of 0.4-5.5% were obtained for standard mixtures over the range of 2.5-500 ng/mL. Recoveries measured for the extraction of trimethylamine and trimethylamine N-oxide spikes into mouse plasma were both >90%. The method, which simultaneously measures trimethylamine and trimethylamine N-oxide, was successfully applied to mouse plasma samples and could be adapted for use with other biological fluids.

  7. Influence of Ionic Liquids on an Iron(III) Catalyzed Three-Component Coupling/Hydroarylation/Dehydrogenation Tandem Reaction.

    PubMed

    Muntzeck, Maren; Wilhelm, René

    2016-06-01

    A three-component oxidative dehydrogenation tandem reaction via the coupling and hydroarylation of benzaldehyde, aniline and phenylacetylene to a quinoline derivate was catalyzed by an iron-containing ionic liquid. The reaction was air mediated and could be performed under neat conditions. The iron(III) of the ionic liquid was the oxidizing species.

  8. Influence of Ionic Liquids on an Iron(III) Catalyzed Three-Component Coupling/Hydroarylation/Dehydrogenation Tandem Reaction

    PubMed Central

    Muntzeck, Maren; Wilhelm, René

    2016-01-01

    A three-component oxidative dehydrogenation tandem reaction via the coupling and hydroarylation of benzaldehyde, aniline and phenylacetylene to a quinoline derivate was catalyzed by an iron-containing ionic liquid. The reaction was air mediated and could be performed under neat conditions. The iron(III) of the ionic liquid was the oxidizing species. PMID:27258264

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

    PubMed

    Mizuno, Keisuke; Kataoka, Hiroyuki

    2015-08-10

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

  10. Differential length measurement using low coherence coupled tandem interferometry

    NASA Astrophysics Data System (ADS)

    Smith, Martin D.; MacPherson, William N.; Maier, Robert R. J.

    2013-05-01

    This paper presents the use of low coherence coupled tandem interferometry to measure the differential length of two independent Fabry-Perot (F-P) type microcavities. The two discrete F-P type microcavities are formed between the cleaved end of a fibre and a reflective surface, which could for example, be a pressure sensing membrane or any other component of a transducing element. The technique is an all-optical fibre based sensing configuration in which the sensing cavities are at widely separated locations in an environment where strong temperature gradients may exist. The sensing system is based on two sequential cavities arranged in tandem. The lengths of the cavities are probed by a temperature stabilised fibre based Michelson interferometer operating with a broadband light source. One arm of the probing Michelson interferometer is scanned using a piezo fibre stretcher resulting in an optical path length difference (OPD) between the two arms. The optical interconnecting leads from the probing Michelson interferometer to the two F-P locations are not an active part of the sensor configuration and therefore this configuration is largely insensitive to temperature and strain effects on these interconnecting leads. It is only the probing Michelson interferometer which has to be temperature stabilised. This arrangement allows the F-P measurement cavities to be separated by distances in the range of tens of meters.

  11. Tandem ion mobility spectrometry coupled to laser excitation

    SciTech Connect

    Simon, Anne-Laure; Choi, Chang Min; Clavier, Christian; Barbaire, Marc; Maurelli, Jacques; Dagany, Xavier; MacAleese, Luke; Dugourd, Philippe; Chirot, Fabien

    2015-09-15

    This manuscript describes a new experimental setup that allows to perform tandem ion mobility spectrometry (IMS) measurements and which is coupled to a high resolution time-of-flight mass spectrometer. It consists of two 79 cm long drift tubes connected by a dual ion funnel assembly. The setup was built to permit laser irradiation of the ions in the transfer region between the two drift tubes. This geometry allows selecting ions according to their ion mobility in the first drift tube, to irradiate selected ions, and examine the ion mobility of the product ions in the second drift tube. Activation by collision is possible in the same region (between the two tubes) and between the second tube and the time-of-flight. IMS-IMS experiments on Ubiquitin are reported. We selected a given isomer of charge state +7 and explored its structural rearrangement following collisional activation between the two drift tubes. An example of IMS-laser-IMS experiment is reported on eosin Y, where laser irradiation was used to produce radical ions by electron photodetachment starting from doubly deprotonated species. This allowed measuring the collision cross section of the radical photo-product, which cannot be directly produced with an electrospray source.

  12. Reactivity and analytical performance of oxygen as cell gas in inductively coupled plasma tandem mass spectrometry

    NASA Astrophysics Data System (ADS)

    Virgilio, Alex; Amais, Renata S.; Amaral, Clarice D. B.; Fialho, Lucimar L.; Schiavo, Daniela; Nóbrega, Joaquim A.

    2016-12-01

    The reactivity and analytical performance of O2 as cell gas in inductively coupled plasma tandem mass spectrometry was investigated. Selected analytes in a wide mass range were divided in three groups according to their reactivity: G1 represents elements with high oxygen affinity (Ce, La, P, Sc, Ti, and Y), G2 contains elements that may partially react with oxygen (As, Ba, Mo, Si, Sr, and V), and G3 comprises elements expected to be less reactive towards oxygen (Al, Bi, Cu, Mg, Pb, and Pd). On-mass and mass-shift modes were evaluated by monitoring atomic and metal oxide ions, respectively. Analytical signal profiles, oxide percentages, sensitivities and limits of detection for oxygen flow rates varying from 0.1 to 1.0 mL min- 1 were also studied. Group 1 elements plus As and V presented better sensitivities and LODs when measuring oxides, which were the major species for all flow rates evaluated. Molybdenum and Si oxides presented intermediate behavior and MoO fraction was up to 47% and limit of detection was the same as that obtained in on-mass mode. For others G2 and G3 elements, on-mass mode presented higher sensitivity and better LODs, with estimated oxide contents lower than 10%. In most cases, increasing oxygen flow rates led to lower sensitivities and worse LODs.

  13. Perovskite catalysts for oxidative coupling

    DOEpatents

    Campbell, K.D.

    1991-06-25

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

  14. Perovskite catalysts for oxidative coupling

    DOEpatents

    Campbell, Kenneth D.

    1991-01-01

    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.

  15. Separation of intermediates of iron-catalyzed dopamine oxidation reactions using reversed-phase ion-pairing chromatography coupled in tandem with UV-visible and ESI-MS detections.

    PubMed

    Zhang, Lin; Yagnik, Gargey; Jiang, Dianlu; Shi, Shuyun; Chang, Peter; Zhou, Feimeng

    2012-12-12

    Reversed-phase ion-pairing chromatography (RP-IPC) is coupled on-line with electrospray ionization-mass spectrometry (ESI-MS) through an interface comprising a four-way switch valve and an anion exchange column. Regeneration of the anion exchange column can be accomplished on-line by switching the four-way switch valve to interconnect the column to a regeneration solution. Positioning the anion exchange column between the RP-IPC and ESI-MS instruments allows the ion-pairing reagent (IPR) sodium octane sulfonate to be removed. The IPC-ESI-MS method enabled us to separate and detect four intermediates of the Fe(III)-catalyzed dopamine oxidation. In particular, 6-hydroxydopamine, which is short-lived and highly neurotoxic, was detected and quantified. Together with the separation of other intermediates, gaining insight into the mechanism and kinetics of the Fe(III)-catalyzed dopamine oxidation becomes possible.

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

    NASA Technical Reports Server (NTRS)

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

    1957-01-01

    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.

  17. 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...

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

    PubMed

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

    2015-04-01

    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.

  19. Proteomic characterization of integral membrane proteins using thermostatted liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Moore, Sarah M; Wu, Christine C

    2012-01-01

    Due to the hydrophobicity and localization of integral membrane proteins, they are difficult to study using conventional biochemical methods that are compatible with proteomic analyses. This chapter describes the coupling of multiple crucial steps that lead to the optimized shotgun proteomic analysis of integral membrane proteins while maintaining empirical topology information. Namely, a membrane shaving method is utilized to separate protease accessible peptides from membrane embedded peptides and elevated temperatures during chromatographic separation is utilized to augment the recovery of hydrophobic peptides for in-line analysis using tandem mass spectrometry. This combination of steps facilitates increased identification of membrane proteins while also maintaining information regarding protein topology.

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

    SciTech Connect

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

    1981-01-01

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

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

    PubMed

    Kafka, František; Holan, Martin; Hidasová, Denisa; Pohl, Radek; Císařová, Ivana; Klepetářová, Blanka; Jahn, Ullrich

    2014-09-08

    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.

  2. Scandium analysis in silicon-containing minerals by inductively coupled plasma tandem mass spectrometry

    NASA Astrophysics Data System (ADS)

    Whitty-Léveillé, Laurence; Drouin, Elisabeth; Constantin, Marc; Bazin, Claude; Larivière, Dominic

    2016-04-01

    This article reports on the development of a new method for the accurate and precise determination of the amount of scandium, Sc, in silicon-containing minerals, based on the use of tandem quadrupole inductively coupled plasma mass spectrometry (ICP-MS/MS). The tandem quadrupole instrument enables new mass filtering configurations, which can reduce polyatomic interferences during the determination of Sc in mineral matrices. He and O2 were used and compared as collision and reaction gases for the removal of interferences at m/z 45 and 61. Using helium gas was ineffective to overcome all of the spectral interferences observed at m/z 45 and particularly for Si-based interferences. However, conversion of Sc+ ions into ScO+ ions (after bombardment with O2 in the octopole reaction system coupled with the use of the instrument in MS/MS mass-shift mode) provided interference-free conditions and sufficiently low limits of detection, down to 3 ng L- 1, to accurately detect Sc. The accuracy of the proposed methodology was assessed by analyzing five different reference materials (BX-N, OKA-2, NIM-L, SY-3 and GH).

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  4. Catalytic migratory oxidative coupling of nitrones.

    PubMed

    Hashizume, Shogo; Oisaki, Kounosuke; Kanai, Motomu

    2011-08-19

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

  5. Indium Zinc Oxide Mediated Wafer Bonding for III-V/Si Tandem Solar Cells

    SciTech Connect

    Tamboli, Adele C.; Essig, Stephanie; Horowitz, Kelsey A. W.; Woodhouse, Michael; van Hest, Maikel F. A. M.; Norman, Andrew G.; Steiner, Myles A.; Stradins, Paul

    2015-06-14

    Silicon-based tandem solar cells are desirable as a high efficiency, economically viable approach to one sun or low concentration photovoltaics. We present an approach to wafer bonded III-V/Si solar cells using amorphous indium zinc oxide (IZO) as an interlayer. We investigate the impact of a heavily doped III-V contact layer on the electrical and optical properties of bonded test samples, including the predicted impact on tandem cell performance. We present economic modeling which indicates that the path to commercial viability for bonded cells includes developing low-cost III-V growth and reducing constraints on material smoothness. If these challenges can be surmounted, bonded tandems on Si can be cost-competitive with incumbent PV technologies, especially in low concentration, single axis tracking systems.

  6. Base-catalyzed efficient tandem [3 + 3] and [3 + 2 + 1] annulation-aerobic oxidative benzannulations.

    PubMed

    Diallo, Aboubacar; Zhao, Yu-Long; Wang, He; Li, Sha-Sha; Ren, Chuan-Qing; Liu, Qun

    2012-11-16

    An efficient synthesis of substituted benzenes via a base-catalyzed [3 + 3] aerobic oxidative aromatization of α,β-unsaturated carbonyl compounds with dimethyl glutaconate was reported. All the reactions were carried out under mild, metal-free conditions to afford the products in high to excellent yields with molecular oxygen as the sole oxidant and water as the sole byproduct. Furthermore, a more convenient tandem [3 + 2 + 1] aerobic oxidative aromatization reaction was developed through the in situ generation of the α,β-unsaturated carbonyl compounds from aldehydes and ketones.

  7. A Tandem Catalyst with Multiple Metal Oxide Interfaces Produced by Atomic Layer Deposition.

    PubMed

    Ge, Huibin; Zhang, Bin; Gu, Xiaomin; Liang, Haojie; Yang, Huimin; Gao, Zhe; Wang, Jianguo; Qin, Yong

    2016-06-13

    Ideal heterogeneous tandem catalysts necessitate the rational design and integration of collaborative active sites. Herein, we report on the synthesis of a new tandem catalyst with multiple metal-oxide interfaces based on a tube-in-tube nanostructure using template-assisted atomic layer deposition, in which Ni nanoparticles are supported on the outer surface of the inner Al2 O3 nanotube (Ni/Al2 O3 interface) and Pt nanoparticles are attached to the inner surface of the outer TiO2 nanotube (Pt/TiO2 interface). The tandem catalyst shows remarkably high catalytic efficiency in nitrobenzene hydrogenation over Pt/TiO2 interface with hydrogen formed in situ by the decomposition of hydrazine hydrate over Ni/Al2 O3 interface. This can be ascribed to the synergy effect of the two interfaces and the confined nanospace favoring the instant transfer of intermediates. The tube-in-tube tandem catalyst with multiple metal-oxide interfaces represents a new concept for the design of highly efficient and multifunctional nanocatalysts.

  8. CFD-CAA Coupled Calculations of a Tandem Cylinder Configuration to Assess Facility Installation Effects

    NASA Technical Reports Server (NTRS)

    Redonnet, Stephane; Lockard, David P.; Khorrami, Mehdi R.; Choudhari, Meelan M.

    2011-01-01

    This paper presents a numerical assessment of acoustic installation effects in the tandem cylinder (TC) experiments conducted in the NASA Langley Quiet Flow Facility (QFF), an open-jet, anechoic wind tunnel. Calculations that couple the Computational Fluid Dynamics (CFD) and Computational Aeroacoustics (CAA) of the TC configuration within the QFF are conducted using the CFD simulation results previously obtained at NASA LaRC. The coupled simulations enable the assessment of installation effects associated with several specific features in the QFF facility that may have impacted the measured acoustic signature during the experiment. The CFD-CAA coupling is based on CFD data along a suitably chosen surface, and employs a technique that was recently improved to account for installed configurations involving acoustic backscatter into the CFD domain. First, a CFD-CAA calculation is conducted for an isolated TC configuration to assess the coupling approach, as well as to generate a reference solution for subsequent assessments of QFF installation effects. Direct comparisons between the CFD-CAA calculations associated with the various installed configurations allow the assessment of the effects of each component (nozzle, collector, etc.) or feature (confined vs. free jet flow, etc.) characterizing the NASA LaRC QFF facility.

  9. Tandem intermolecular Suzuki coupling/intramolecular vinyl triflate-arene coupling.

    PubMed

    Willis, Michael C; Claverie, Christelle K; Mahon, Mary F

    2002-04-21

    Treatment of a benzyl substituted meso-ditriflate with boronic acids in the presence of palladium acetate, triphenylphosphine and caesium fluoride results in intermolecular Suzuki coupling followed by vinyl triflate-arene cyclisation to provide, in high yields, single regioisomers of tricyclic-carbocycles.

  10. Characterization of crude oil biomarkers using comprehensive two-dimensional gas chromatography coupled to tandem mass spectrometry.

    PubMed

    Mogollón, Noroska Gabriela Salazar; Prata, Paloma Santana; Dos Reis, Jadson Zeni; Neto, Eugênio Vaz Dos Santos; Augusto, Fabio

    2016-09-01

    Oil samples from Recôncavo basin (NE Brazil), previously analyzed by traditional techniques such as gas chromatography coupled to tandem mass spectrometry, were evaluated using comprehensive two-dimensional gas chromatography coupled to quadrupole mass spectrometry and comprehensive two-dimensional gas chromatography coupled to tandem mass spectrometry along with simplified methods of samples preparation to evaluate the differences and advantages of these analytical techniques to better understand the development of the organic matter in this basin without altering the normal distribution of the compounds in the samples. As a result, the geochemical parameters calculated by comprehensive two-dimensional gas chromatography coupled to tandem mass spectrometry described better the origin, maturity, and biodegradation of both samples probably by increased selectivity, resolution, and sensitivity inherent of the multidimensional technique. Additionally, the detection of the compounds such as, the C(14α-) homo-26-nor-17α-hopane series, diamoretanes, nor-spergulanes, C19 -C26 A-nor-steranes and 4α-methylsteranes resolved and detected by comprehensive two-dimensional gas chromatography coupled to tandem mass spectrometry were key to classify and differentiate these lacustrine samples according to their maturity and deposition conditions.

  11. Zinc tin oxide as high-temperature stable recombination layer for mesoscopic perovskite/silicon monolithic tandem solar cells

    NASA Astrophysics Data System (ADS)

    Werner, Jérémie; Walter, Arnaud; Rucavado, Esteban; Moon, Soo-Jin; Sacchetto, Davide; Rienaecker, Michael; Peibst, Robby; Brendel, Rolf; Niquille, Xavier; De Wolf, Stefaan; Löper, Philipp; Morales-Masis, Monica; Nicolay, Sylvain; Niesen, Bjoern; Ballif, Christophe

    2016-12-01

    Perovskite/crystalline silicon tandem solar cells have the potential to reach efficiencies beyond those of silicon single-junction record devices. However, the high-temperature process of 500 °C needed for state-of-the-art mesoscopic perovskite cells has, so far, been limiting their implementation in monolithic tandem devices. Here, we demonstrate the applicability of zinc tin oxide as a recombination layer and show its electrical and optical stability at temperatures up to 500 °C. To prove the concept, we fabricate monolithic tandem cells with mesoscopic top cell with up to 16% efficiency. We then investigate the effect of zinc tin oxide layer thickness variation, showing a strong influence on the optical interference pattern within the tandem device. Finally, we discuss the perspective of mesoscopic perovskite cells for high-efficiency monolithic tandem solar cells.

  12. Characterization of four Phyllanthus species using liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Sprenger, Ricardo da Fontoura; Cass, Quezia Bezerra

    2013-05-24

    This paper reports a comparison of four Phyllanthus species (P. amarus, P. stipulatus, P. niruri and P. tenellus), commonly known as stone breaker, by the characterization of the chemical profile of their aqueous extracts. Such characterization was carried out using liquid chromatography coupled to ion trap tandem mass spectrometry (LC-IT-MS(n)) under reversed-phase gradient elution mode. The results of MS/MS and MS(3) on-line experiments, using the electrospray ionization source in the positive and negative mode, are extensively discussed. Furthermore, quercetin-3-O-β-d-glucuronopyranoside was isolated in multimilligram scale from the aqueous extract of P. stipulatus and characterized by mass spectrometry and NMR. Although it is an unusual flavonol in natural products, LC-IT-MS(n) experiments showed it to be present also in P. amarus.

  13. Benzene oxidation coupled to sulfate reduction

    USGS Publications Warehouse

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

    1995-01-01

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

  14. Copper-catalyzed tandem phosphination-decarboxylation-oxidation of alkynyl acids with H-phosphine oxides: a facile synthesis of β-ketophosphine oxides.

    PubMed

    Zhang, Pengbo; Zhang, Liangliang; Gao, Yuzhen; Xu, Jian; Fang, Hua; Tang, Guo; Zhao, Yufen

    2015-05-07

    The general method for the tandem phosphination-decarboxylation-oxidation of alkynyl acids under aerobic conditions has been developed. In the presence of CuSO4·5H2O and TBHP, the reactions provide a novel access to β-ketophosphine oxides in good to excellent yields. This transformation allows the direct formation of a P-C bond and the construction of a keto group in one reaction.

  15. External control of electron energy distributions in a dual tandem inductively coupled plasma

    SciTech Connect

    Liu, Lei; Sridhar, Shyam; Zhu, Weiye; Donnelly, Vincent M. Economou, Demetre J.; Logue, Michael D.; Kushner, Mark J.

    2015-08-28

    The control of electron energy probability functions (EEPFs) in low pressure partially ionized plasmas is typically accomplished through the format of the applied power. For example, through the use of pulse power, the EEPF can be modulated to produce shapes not possible under continuous wave excitation. This technique uses internal control. In this paper, we discuss a method for external control of EEPFs by transport of electrons between separately powered inductively coupled plasmas (ICPs). The reactor incorporates dual ICP sources (main and auxiliary) in a tandem geometry whose plasma volumes are separated by a grid. The auxiliary ICP is continuously powered while the main ICP is pulsed. Langmuir probe measurements of the EEPFs during the afterglow of the main ICP suggests that transport of hot electrons from the auxiliary plasma provided what is effectively an external source of energetic electrons. The tail of the EEPF and bulk electron temperature were then elevated in the afterglow of the main ICP by this external source of power. Results from a computer simulation for the evolution of the EEPFs concur with measured trends.

  16. Liquid chromatography coupled to tandem mass spectrometry for the analysis of acrylamide in typical Spanish products.

    PubMed

    Bermudo, E; Moyano, E; Puignou, L; Galceran, M T

    2008-07-15

    This paper describes the use of liquid chromatography coupled to tandem mass spectrometry for the determination of acrylamide in several typical foods produced and consumed in Spain. Christmas sweets, olives, traditionally made potato crisps, pastry products, sweet fritters ("churros") and one of Spain's most famous dishes, Spanish omelette, were selected. Using the mass spectra information provided by an ion trap analyzer in combination with the accurate mass measurements from time-of-flight (TOF) spectrometry a co-extractive interference present in some potato products was identified as valine. A porous graphitic carbon column, which enabled the co-extractive and acrylamide to be separated, and ion trap or triple quadrupole analyzers, depending on the acrylamide concentration, were used to determine this genotoxic compound in foodstuffs. The highest values were found in potato products, sweet fritters, Christmas sweets and pastry products, with values ranging between 70 and 2000 microg/g. Spanish omelette presented relatively low levels, similar to those obtained for dried fruits.

  17. External control of electron energy distributions in a dual tandem inductively coupled plasma

    NASA Astrophysics Data System (ADS)

    Liu, Lei; Sridhar, Shyam; Zhu, Weiye; Donnelly, Vincent M.; Economou, Demetre J.; Logue, Michael D.; Kushner, Mark J.

    2015-08-01

    The control of electron energy probability functions (EEPFs) in low pressure partially ionized plasmas is typically accomplished through the format of the applied power. For example, through the use of pulse power, the EEPF can be modulated to produce shapes not possible under continuous wave excitation. This technique uses internal control. In this paper, we discuss a method for external control of EEPFs by transport of electrons between separately powered inductively coupled plasmas (ICPs). The reactor incorporates dual ICP sources (main and auxiliary) in a tandem geometry whose plasma volumes are separated by a grid. The auxiliary ICP is continuously powered while the main ICP is pulsed. Langmuir probe measurements of the EEPFs during the afterglow of the main ICP suggests that transport of hot electrons from the auxiliary plasma provided what is effectively an external source of energetic electrons. The tail of the EEPF and bulk electron temperature were then elevated in the afterglow of the main ICP by this external source of power. Results from a computer simulation for the evolution of the EEPFs concur with measured trends.

  18. Determination of sulfonamides in beeswax by liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Mitrowska, Kamila; Antczak, Maja

    2015-12-01

    The manuscript presents the development of a new method for the quantification of 16 sulfonamides in beeswax. Different sample preparation techniques were tested and modified to maximise the recovery of the target analytes and minimise the amount of coeluted impurities under conditions that provide reproducible results. The proposed method consisted of melting and dilution of beeswax in a mixture of n-hexane and isopropanol followed by extraction with 2% acetic acid. The extract was cleaned up by solid-phase extraction using strong cation exchange phase. Determination of the sulfonamides was achieved by liquid chromatography coupled to tandem mass spectrometry with the use of a pentafluorophenyl analytical column and applying a gradient elution with acetonitrile and 0.01% acetic acid as mobile phases. The limits of detection and limits of quantification ranged from 1 to 2μg/kg and from 2 to 5μg/kg, respectively. The recoveries varied between 65.2% and 117.8% while coefficient of variation of the method was less than 24.2% under intermediate precision conditions. Finally, the method was applied to the analysis of real samples of beeswax from beekeepers and commercial foundations manufacturers.

  19. Ignition delay of a pulsed inductively coupled plasma (ICP) in tandem with an auxiliary ICP

    NASA Astrophysics Data System (ADS)

    Liu, Lei; Sridhar, Shyam; Donnelly, Vincent M.; Economou, Demetre J.

    2015-12-01

    Plasma ignition delays were observed in a ‘main’ inductively coupled plasma (ICP), in tandem with an ‘auxiliary’ ICP. The Faraday-shielded ICPs were separated by a grounded metal grid. Power (13.56 MHz) to the main ICP was pulsed with a frequency of 1 kHz, while the auxiliary ICP was operated in continuous wave (cw) mode. In chlorine plasmas, ignition delay was observed for duty cycles greater than 60% and, in contrast to expectation, the delay was longer with increasing duty cycle up to ~99.5%. The ignition delay could be varied by changing the auxiliary and/or main ICP power. Langmuir probe measurements provided the temporal evolution of electron temperature, and electron and positive ion densities. These measurements revealed that the plasma was ignited shortly after the decaying positive ion density (n +), in the afterglow of the main ICP, reached the density ({{n}+},\\text{aux} ) prevailing when only the auxiliary ICP was powered. At that time, production of electrons began to dominate their loss in the main ICP, due to hot electron injection from the auxiliary ICP. As a result, {{n}\\text{e}} increased from a value below {{n}\\text{e,\\text{aux}}} , improving inductive power coupling efficiency, further increasing plasma density leading to plasma ignition. Plasma ignition delay occurred when the afterglow of the pulsed plasma was not long enough for the ion density to reach {{n}+},\\text{aux} during the afterglow. Besides Cl2, plasma ignition delays were also observed in other electronegative gases (SF6, CF4/O2 and O2) but not in an electropositive gas (Ar).

  20. Tandem Suzuki-Miyaura coupling/acid-catalyzed cyclization between vinyl ether boronates and vinyl halides: a concise approach to polysubstituted furans.

    PubMed

    Butkevich, Alexey N; Meerpoel, Lieven; Stansfield, Ian; Angibaud, Patrick; Corbu, Andrei; Cossy, Janine

    2013-08-02

    Polysubstituted 2-(ω-hydroxyalkyl)furans were prepared by tandem Suzuki-Miyaura coupling/acid-catalyzed cyclization starting from appropriately substituted 3-haloallylic alcohols and dihydrofuran-, dihydropyran- or glycal-derived pinacol boronates.

  1. Gas-Phase Fragmentation Behavior of Oxidized Prenyl Peptides by CID and ETD Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Bhawal, Ruchika P.; Shahinuzzaman, A. D. A.; Chowdhury, Saiful M.

    2016-10-01

    Farnesylation and geranylgeranylation are the two types of prenyl modification of proteins. Prenylated peptides are highly hydrophobic and their abundances in biological samples are low. In this report, we studied the oxidized prenylated peptides by electrospray ionization mass spectrometry and identified them by collision-induced dissociation (CID) and electron-transfer dissociation (ETD) tandem mass spectrometry. Modified prenyl peptides were generated utilizing strong and low strength oxidizing agents to selectively oxidize and epoxidize cysteine sulfur and prenyl side chain. We selected three peptides with prenyl motifs and synthesized their prenylated versions. The detailed characteristic fragmentations of oxidized and epoxidized farnesylated and geranylgeranylated peptides were studied side by side with two popular fragmentation techniques. CID and ETD mass spectrometry clearly distinguished the modified version of these peptides. ETD mass spectrometry provided sequence information of the highly labile modified prenyl peptides and showed different characteristic fragmentations compared with CID. A detailed fragmentation of modified geranylgeranylated peptides was compared by CID and ETD mass spectrometry for the first time.

  2. Gas-Phase Fragmentation Behavior of Oxidized Prenyl Peptides by CID and ETD Tandem Mass Spectrometry.

    PubMed

    Bhawal, Ruchika P; Shahinuzzaman, A D A; Chowdhury, Saiful M

    2017-04-01

    Farnesylation and geranylgeranylation are the two types of prenyl modification of proteins. Prenylated peptides are highly hydrophobic and their abundances in biological samples are low. In this report, we studied the oxidized prenylated peptides by electrospray ionization mass spectrometry and identified them by collision-induced dissociation (CID) and electron-transfer dissociation (ETD) tandem mass spectrometry. Modified prenyl peptides were generated utilizing strong and low strength oxidizing agents to selectively oxidize and epoxidize cysteine sulfur and prenyl side chain. We selected three peptides with prenyl motifs and synthesized their prenylated versions. The detailed characteristic fragmentations of oxidized and epoxidized farnesylated and geranylgeranylated peptides were studied side by side with two popular fragmentation techniques. CID and ETD mass spectrometry clearly distinguished the modified version of these peptides. ETD mass spectrometry provided sequence information of the highly labile modified prenyl peptides and showed different characteristic fragmentations compared with CID. A detailed fragmentation of modified geranylgeranylated peptides was compared by CID and ETD mass spectrometry for the first time. Graphical Abstract ᅟ.

  3. Palladium-Catalyzed Ullmann Cross-Coupling/Tandem Reductive Cyclization Route to Key Members of the Uleine Alkaloid Family.

    PubMed

    Tang, Fei; Banwell, Martin G; Willis, Anthony C

    2016-04-01

    The trisubstituted cyclohexenone 12, generated through a palladium-catalyzed Ullmann cross-coupling reaction between o-iodonitrobenzene and a 4,5-trans-disubstituted 2-iodo-2-cyclohexen-1-one, engaged in a tandem reductive cyclization process upon exposure to hydrogen gas in the presence of Raney cobalt. As a result, the 1,5-methanoazocino[4,3-b]indole 13 was obtained and this could be readily elaborated to the racemic modifications of the alkaloids uleine, dasycarpidone, noruleine, and nordasycarpidone (1-4, respectively).

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

    SciTech Connect

    Krikorian, O.H.

    1980-10-10

    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.

  5. Iron-catalyzed oxidative coupling of alkylamides with arenes through oxidation of alkylamides followed by Friedel-Crafts alkylation.

    PubMed

    Shirakawa, Eiji; Uchiyama, Nanase; Hayashi, Tamio

    2011-01-07

    FeCl(3) in combination with t-BuOOt-Bu as an oxidant was found to be an efficient catalyst for oxidation of alkylamides to α-(tert-butoxy)alkylamides. FeCl(2) and CuCl showed, respectively, almost the same and slightly lower activities compared with FeCl(3) in the tert-butoxylation of N-phenylpyrrolidone (1a), whereas no tert-butoxylated product was obtained by use of Fe(OTf)(3), RuCl(3), or Zr(OTf)(4). FeCl(3) was found to be effective also as a catalyst for the Friedel-Crafts alkylation with thus obtained α-(tert-butoxy)alkylamides. The Friedel-Crafts alkylation proceeded smoothly also in the presence of a catalytic amount of Fe(OTf)(3), RuCl(3), or Zr(OTf)(4). In contrast, FeCl(2) and CuCl, which showed certain activity toward the tert-butoxylation, failed to promote the Friedel-Crafts alkylation. Among the transition metal complexes thus far examined, only FeCl(3) showed high catalytic activities for both the oxidation and the Friedel-Crafts alkylation. The bifunctionality of FeCl(3) was utilized for the oxidative coupling of alkylamides with arenes through a tandem reaction consisting of oxidation of alkylamides to α-(tert-butoxy)alkylamides and the following Friedel-Crafts alkylation. The FeCl(3)-catalyzed oxidative coupling is applicable to a wide variety of alkylamides and arenes, though a combination of FeCl(3) with Fe(OTf)(3) was found to be effective for the reaction of arenes with low nucleophilicity. A Fe(II)-Fe(III) catalytic cycle is concerned with the tert-butoxylation, whereas a Fe(III) complex as a Lewis acid catalyzes the Friedel-Crafts alkylation.

  6. IMPACT OF OXYGEN MEDIATED OXIDATIVE COUPLING ON ADSORPTION KINETICS

    EPA Science Inventory

    The presence of molecular oxygen in the test environment promotes oxidative coupling (polymer formation) of phenolic compounds on the surface of granular activated carbon (GAC). Both adsorption equilibria and adsorption kinetics are affected by these chemical reactions. Lack of...

  7. Tandem Silylformylation-Crotylsilylation/Tamao Oxidation of Internal Alkynes: A Remarkable Example of Generating Complexity from Simplicity

    PubMed Central

    Spletstoser, Jared T.; Zacuto, Michael J.; Leighton, James L.

    2009-01-01

    The rhodium-catalyzed tandem silylformylation-crotylsilylation reaction has been extended to include internal alkynes. Tamao oxidation of the initial product leads to the production of a substituted enol, which undergoes highly diastereoselective tautomerization. The resulting one-pot procedure fashions three new stereocenters, a ketone, and a terminal alkene from a butenyl group, a propynyl group, a silyl hydride, H2O2, and CO. PMID:19007175

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

    PubMed Central

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

    2014-01-01

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

  9. High ethylene to ethane processes for oxidative coupling

    DOEpatents

    Chafin, Richard B.; Warren, Barbara K.

    1991-01-01

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

  10. High ethylene to ethane processes for oxidative coupling

    DOEpatents

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

    1991-12-17

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

  11. Excitation of low-frequency waves via coupling between slow Alfven waves in the GAMMA 10 tandem mirror

    NASA Astrophysics Data System (ADS)

    Ikezoe, R.; Ichimura, M.; Okada, T.; Hirata, M.; Sakamoto, M.; Iwamoto, Y.; Sumida, S.; Jang, S.; Itagaki, J.; Onodera, Y.; Yoshikawa, M.; Kohagura, J.; Shima, Y.; Wang, X.; Nakashima, Y.

    2015-11-01

    In normal discharges of the GAMMA 10 tandem mirror, confined energy is saturated against heating power and unstable slow Alfven wave named as Alfven-Ion-Cyclotron (AIC) wave is observed in the saturated phase. This saturation may be partly related to (1) the decay of ICRF heating power, which is the main power source in GAMMA 10, due to the coupling with the AIC waves to produce difference-frequency waves and (2) the enhancement of axial transport of high-energy ions owing to nonlinearly excited low-frequency waves. To investigate these phenomena precisely, reflectometry is applied, which can provide assessment of nonlinear process at the location where the nonlinear process are taking place without any disturbance. Bispectral analysis applied to the density fluctuations measured at a wide radial region clearly shows the occurrence of various wave-wave couplings among the heating ICRF wave and the AIC waves. Generation of low-frequency waves via the coupling between coexisting AIC waves is found to be significant only near the core region. Details of measured nonlinear couplings are presented along with the observation showing the clear relation of generated low-frequency waves with the axial transport of high-energy ions. This work is partly supported by JSPS, Japan (25400531, 15K17797) and by NIFS, Japan (NIFS15KUGM101).

  12. Diastereoselective Synthesis of Highly Substituted Tetrahydrofurans by Pd-Catalyzed Tandem Oxidative Cyclization-Redox Relay Reactions Controlled by Intramolecular Hydrogen Bonding.

    PubMed

    Brooks, Joshua L; Xu, Liping; Wiest, Olaf; Tan, Derek S

    2017-01-06

    Palladium-catalyzed oxidative cyclization of alkenols provides a convenient entry into cyclic ethers but typically proceeds with little or no diastereoselectivity for cyclization of trisubstituted olefins to form tetrahydrofurans due to the similar energies of competing 5-membered transition-state conformations. Herein, a new variant of this reaction has been developed in which a PdCl2/1,4-benzoquinone catalyst system coupled with introduction of a hydrogen-bond acceptor in the substrate enhances both diastereoselectivity and reactivity. Cyclization occurs with 5-exo Markovnikov regioselectivity. Mechanistic and computational studies support an anti-oxypalladation pathway in which intramolecular hydrogen bonding increases the nucleophilicity of the alcohol and enforces conformational constraints that enhance diastereoselectivity. The cyclization is followed by a tandem redox-relay process that provides versatile side-chain functionalities for further derivatization.

  13. Identification of methylene diphenyl diisocyanate thermal degradation products in a generation chamber by liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Gagne, Sébastien; Cloutier, Yves

    2016-01-01

    Isocyanate thermal degradation characterization by liquid chromatography coupled with electrospray tandem mass spectrometry has been performed to elucidate the methylene diphenyl diisocyanate (MDI) thermal degradation structure emitted in a generation chamber using a temperature between 50°C and 180°C to produce MDI vapors. [M+H](+) ions containing an isocyanate functional group were studied by tandem mass spectrometry. The [M+H](+) ion analyses based on the combination of full scans and precursor ion scans were useful for identifying all structures. The compounds emitted were identified and validated as a mixture of compounds containing amine and isocyanate functions. Residual MDI, methylene diphenyl amino-isocyanate, and methylene diphenyl diamine were identified. Polymerized forms of these structures were also observed because amine and isocyanate chemical functions react rapidly to polymerize. These results must be used with special care by scientists establishing sensitization diagnostics and developing sampling devices using generation chambers as they must be related to MDI behavior in workplaces. Even if pure MDI is introduced in the generation chamber, several different compounds are generated when the MDI is heated at a high temperature. This can result in some misleading interpretations for non-specific isocyanate sampling device development and sensitization diagnostics as MDI is present in the chamber with other compounds with known adverse effects.

  14. Determination of azithromycin residue in pork using a molecularly imprinted monolithic microcolumn coupled to liquid chromatography with tandem mass spectrometry.

    PubMed

    Zhou, Tong; Yang, Haicui; Jin, Zhen; Liu, Qingying; Song, Xuqin; He, Limin; Fang, Binghu; Meng, Chenying

    2016-04-01

    Using spiramycin as a dummy template, a molecularly imprinted polymer monolithic micro-column with high selection to azithromycin was prepared in a micropipette tip. The imprinting factor of the monolithic micro-column prepared was approximately 2.67 and the morphological structure of the polymers was characterized by scanning electron microscopy. A simple, sensitive, and reproducible method based on the imprinted monolithic micro-column coupled to liquid chromatography with tandem mass spectrometry was developed for determining the residues of azithromycin in pork. Pork samples were extracted with acetonitrile, cleaned up under the optimal monolithic micro-column conditions, and analyzed using liquid chromatography with tandem mass spectrometry in the multiple reaction monitoring mode. The assay exhibited a linear dynamic range of 0.50-50 μg/L with the correlation coefficient (r(2) ) above 0.99. In the three spiking levels of 0.50, 1.0, and 10 μg/kg, the average recoveries of azithromycin from pork samples were between 85.8 and 96.5% with a relative standard deviation below 10%. The limit of detection and limit of quantitation were 0.03 and 0.1 μg/kg, respectively.

  15. Determination of Common Adulterants in Herbal Medicine and Food Samples using Core-shell Column Coupled to Tandem Mass Spectrometry.

    PubMed

    Al Lawati, Haider A J; Al Busaidi, Idris; Kadavilpparampu, Afsal M; Suliman, FakhrEldin O

    2017-03-01

    High-performance liquid chromatography coupled to tandem mass spectrometry was used to develop and validate a rapid method to qualitatively and quantitatively analyse 18 common adulterants in herbal medicine and food samples. Initially, the mobile phase composition was optimized in three different columns: core-shell, monolithic and standard 3.5-µm-particle-size columns. The results show that the core-shell column provides the best separation. Moreover, the tandem mass spectrometry was optimized. The linear range for all adulterants was 0.5-500 μg mL-1. Finally, the samples that were supplied by the Public Authority of Customer Protection, Ministry of Health, and those collected from the local market were analysed. The results indicate that 7 of 33 analysed samples contained adulterants. The adulterated samples mainly contain sildenafil, tadalafil or vardenafil. The concentrations of these three adulterants in the samples were 0.18-39 wt%. This study is the first report in the Sultanate of Oman about adulteration in herbal medicine and food samples. The results clearly raise some concern and require proper plan of action to increase public awareness about this serious issue.

  16. [High-sensitivity analysis of purines in alcoholic beverages using hydrophilic interaction chromatography coupled with tandem mass spectrometry].

    PubMed

    Kakigi, Yasuhiro; Yoshioka, Toshiaki; Nagatomi, Yasushi; Uyama, Atsuo; Mochizuki, Naoki

    2014-01-01

    In this study, we established a high-sensitivity analytical method for purines in alcoholic beverages using hydrophilic interaction chromatography coupled with tandem mass spectrometry. The alcoholic beverages were hydrolyzed with perchloric acid (60%) and subjected to strong cation exchange solid-phase extraction (Bond Elut SCX). The four purine bases (hypoxanthine, adenine, xanthine, guanine) in the extracted solution were separated by hydrophilic interaction chromatography with TSKgel Amide-80 as a separation column, 10 mM ammonium formate (pH 2.0) as mobile phase A, and acetonitrile/100 mM ammonium formate (pH 2.0) (90/10) as mobile phase B. The detection of purine bases was performed by tandem mass spectrometry with ESI. The linearity of this analytical method was not less than 0.996, and the repeatability was not more than 8.4% for each purine base. The recovery was in the range of 60-105%, and the detection limit was not more than 0.005 mg/100 mL. This established method is expected to be useful for quality control and surveillance of purines in alcoholic beverages.

  17. Tandem SN2' nucleophilic substitution/oxidative radical cyclization of aryl substituted allylic alcohols with 1,3-dicarbonyl compounds.

    PubMed

    Zhang, Zhen; Li, Cheng; Wang, Shao-Hua; Zhang, Fu-Min; Han, Xue; Tu, Yong-Qiang; Zhang, Xiao-Ming

    2017-03-23

    A novel and efficient tandem SN2' nucleophilic substitution/oxidative radical cyclization reaction of aryl substituted allylic alcohols with 1,3-dicarbonyl compounds has been developed by using Mn(OAc)3 as an oxidant, which enables the expeditious synthesis of polysubstituted dihydrofuran (DHF) derivatives in moderate to high yields. The use of weakly acidic hexafluoroisopropanol (HFIP) as the solvent rather than AcOH has successfully improved the yields and expanded the substrate scope of this type of radical cyclization reactions. Mechanistic studies confirmed the cascade reaction process involving a final radical cyclization.

  18. Qualitative analysis of phenolic compounds in apple pomace using liquid chromatography coupled to mass spectrometry in tandem mode.

    PubMed

    Sánchez-Rabaneda, Ferran; Jáuregui, Olga; Lamuela-Raventós, Rosa Maria; Viladomat, Francesc; Bastida, Jaume; Codina, Carles

    2004-01-01

    The occurrence of phenolic compounds in apple residues resulting from the juice industry was investigated to provide an alternative use for this raw material. For the identification of these compounds, liquid chromatography coupled to ionspray mass spectrometry in tandem mode (LC/MS/MS) with negative ion detection was used. The residues were first extracted and then chromatographed on Sephadex LH-20 to yield 13 fractions. Positive identification of the compounds was based on their retention times and mass spectra in full scan mode (MS), and in different MS/MS modes (product ion scan, precursor ion scan and neutral loss scan). In this way, 60 compounds, including cinnamic and benzoic acid derivatives and flavonoids, were identified, some of them not previously reported in apple waste.

  19. Hydrophilic interaction liquid chromatography-electrospray ionization-tandem mass spectrometry of a complex mixture of native and oxidized phospholipids.

    PubMed

    Losito, I; Facchini, L; Diomede, S; Conte, E; Megli, F M; Cataldi, T R I; Palmisano, F

    2015-11-27

    A mixture of native and oxidized phospholipids (PLs), generated by the soybean lipoxygenase type V-catalyzed partial oxidation of a lipid extract obtained from human platelets, was analyzed by Hydrophilic Interaction Liquid Chromatography-ElectroSpray Ionization-Tandem Mass Spectrometry (HILIC-ESI-MS/MS). The complexity of the resulting mixture was remarkable, considering that the starting lipid extract, containing (as demonstrated in a previous study) about 130 native PLs, was enriched with enzymatically generated hydroperoxylated derivatives and chemically generated hydroxylated forms of PLs bearing polyunsaturated side chains. Nonetheless, the described analytical approach proved to be very powerful; indeed, focusing on phosphatidylcolines (PCs), the most abundant PL class in human platelets, about fifty different native/oxidized species could be identified in a single HILIC-ESI-MS/MS run. Low-energy collision induced dissociation tandem MS (CID-MS/MS) experiments on chromatographically separated species showed single neutral losses of H2O2 and H2O to be typical fragmentation pathways of hydroperoxylated PCs, whereas a single H2O loss was observed for hydroxylated ones. Moreover, diagnostic losses of n-hexanal or n-pentanol were exploited to recognize PCs hydroperoxylated on the last but five carbon atom of a ɷ-6 polyunsaturated side chain. Despite the low resolution of the 3D ion trap mass analyzer used, the described HILIC-ESI-MS/MS approach appears very promising for the identification of oxidized lipids in oxidatively stressed complex biological systems.

  20. Nitric Oxide Enhances Charge-Coupled Device

    NASA Technical Reports Server (NTRS)

    Hecht, Michael H.; Poindexter, Edward H.

    1990-01-01

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

  1. Plasma lipid analysis by hydrophilic interaction liquid chromatography coupled with electrospray ionization tandem mass spectrometry.

    PubMed

    Sonomura, Kazuhiro; Kudoh, Shinobu; Sato, Taka-Aki; Matsuda, Fumihiko

    2015-06-01

    A novel method for the analysis of endogenous lipids and related compounds was developed employing hydrophilic interaction liquid chromatography with electrospray ionization tandem mass spectrometry. A hydrophilic interaction liquid chromatography with carbamoyl stationary phase achieved clear separation of phosphatidylcholine, lysophosphatidylcholine, sphingomyelin, ceramide, and mono-hexsosyl ceramide groups with good peak area repeatability (RSD% < 10) and linearity (R(2) > 0.99). The established method was applied to human plasma assays and a total of 117 endogenous lipids were successfully detected and reproducibly identified. In addition, we investigated the simultaneous detection of small polar metabolites such as amino and organic acids co-existing in the same biological samples processed in a single analytical run with lipids. Our results show that hydrophilic interaction liquid chromatography is a useful tool for human plasma lipidome analysis and offers more comprehensive metabolome coverage.

  2. Determination of salivary efavirenz by liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Theron, Anri; Cromarty, Duncan; Rheeders, Malie; Viljoen, Michelle

    2010-10-15

    A novel and robust screening method for the determination of the non-nucleoside reverse transcriptase inhibitor, efavirenz (EFV), in human saliva has been developed and validated based on high performance liquid chromatography tandem mass spectrometry (LC-MS/MS). Sample preparation of the saliva involved solid-phase extraction (SPE) on C18 cartridges. The analytes were separated by high performance liquid chromatography (Phenomenex Kinetex C18, 150mm×3mm internal diameter, 2.6μm particle size) and detected with tandem mass spectrometry in electrospray positive ionization mode with multiple reaction monitoring. Gradient elution with increasing methanol (MeOH) concentration was used to elute the analytes, at a flow-rate of 0.4mL/min. The total run time was 8.4min and the retention times for the internal standard (reserpine) was 5.4min and for EFV was 6.5min. The calibration curves showed linearity (r(2), 0.989-0.992) over the concentration range of 3.125-100μg/L. Mean intra- and inter-assay relative standard deviation, accuracy, mean extraction recovery, limit of detection (LOD) and limit of quantification (LOQ) were 0.46-9.43%, 80-120%, 60% (±7.95), 1.84 and 6.11μg/L respectively. The working range was defined as 6.25-100μg/L. This novel LC-MS/MS assay is suitable for reliable detection of low EFV concentrations in saliva and can be used as a screening tool for monitoring EFV compliance.

  3. Tandem mobile robot system

    DOEpatents

    Buttz, James H.; Shirey, David L.; Hayward, David R.

    2003-01-01

    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.

  4. 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...

  5. Proteomic analysis of Taenia ovis metacestodes by high performance liquid chromatography-coupled tandem mass spectrometry.

    PubMed

    Zheng, Yadong

    2017-03-15

    Taenia ovis metacestodes reside in the muscle of sheep and goats, and may cause great economic loss due to condemnation of carcasses if not effectively controlled. Although advances have been made in the control of T. ovis infection, our knowledge of T. ovis biology is limited. Herein the protein profiling of T. ovis metacestodes was determined by liquid chromatography-linked tandem mass spectrometry. A total of 966 proteins were identified and 25.1% (188/748) were annotated to be associated with metabolic pathways. Consistently, GO analysis returned a metabolic process (16.27%) as one of two main biological process terms. Moreover, it was found that 24 proteins, including very low-density lipoprotein receptor, enolase, paramyosin and endophilin B1, were abundant in T. ovis metacestodes. These proteins may be associated with motility, metabolism, signaling, stress, drug resistance and immune responses. Furthermore, comparative analysis of 5 cestodes revealed the presence of Taenia-specific enolases. These data provide clues for better understanding of T. ovis biology, which is informative for effective control of infection.

  6. Ignition Delay in a Pulsed Inductively Coupled Plasma (ICP) in Tandem with an Auxiliary ICP

    NASA Astrophysics Data System (ADS)

    Donnelly, Vincent M.; Liu, Lei; Sridhar, Shyam; Economou, Demetre J.

    2015-09-01

    Plasma ignition delays were observed in a ``main'' ICP, in tandem with an ``auxiliary'' ICP. The Faraday-shielded ICPs were separated by a grounded metal grid. Power (13.56 MHz) to the main ICP was pulsed with a frequency of 1 kHz, while the auxiliary ICP was operated in continuous wave (cw) mode. In chlorine plasmas, ignition delay was observed for duty cycles greater than 60% and, in contrast to expectation, the delay was longer with increasing duty cycle up to ~ 99.5%. The ignition delay could be manipulated by changing the auxiliary and/or main ICP power. Langmuir probe measurements provided the temporal evolution of electron temperature, and electron and positive ion (n+) densities. These measurements revealed that the plasma was re-ignited shortly after the decaying n+ in the main ICP reached the density (n+,aux) measured when only the auxiliary ICP was powered. At that time, the depressed electron density increased sharply resulting in plasma re-ignition. Plasma ignition delay occurred when the afterglow of the pulsed plasma was not long enough for n+ to reach n+,aux during the afterglow. Besides Cl2, plasma ignition delays were also observed in other electronegative gases (SF6, CF4/O2 and O2) but not in an electropositive gas (Ar).

  7. Multidimensional Liquid Chromatography Coupled with Tandem Mass Spectrometry for Identification of Bioactive Fatty Acyl Derivatives

    PubMed Central

    Divito, Erin B.; Kroniser, Kristin M.; Cascio, Michael

    2016-01-01

    Recognition of the contributions of lipids to cellular physiology, both as structural components of the membrane and as modulatory ligands for membrane proteins, has increased in recent years with the development of the biophysical and biochemical tools to examine these effects. Their modulatory roles in ion channels and transporters function have been extensively characterized, with the molecular mechanisms of these activities being the subject of intense scrutiny. The physiological significance of lipids in biochemistry is expanding as numerous fatty acyls are discovered to possess signaling properties. These bioactive lipids are often found in quantities of pmol/g of tissue and are co-extracted with numerous lipophilic molecules, making their detection and identification challenging. Common analytical methodologies involve chromatographic separation and mass spectrometric techniques; however, a single chromatographic step is typically ineffective due to the complexity of the biological samples. It is, therefore, essential to develop approaches that incorporate multiple dimensions of separation. Described in this manuscript are normal phase and reversed phase separation strategies for lipids that include detection of the bioactive primary fatty acid amides and N-acyl glycines via tandem mass spectrometry. Concerted utilization of these approaches are then used to separate and sensitively identify primary fatty acid amides extracted from homogenized tissue, using mouse brains as a test case. PMID:28018237

  8. Quantification of plasma homocitrulline using hydrophilic interaction liquid chromatography (HILIC) coupled to tandem mass spectrometry.

    PubMed

    Jaisson, Stéphane; Gorisse, Laëtitia; Pietrement, Christine; Gillery, Philippe

    2012-02-01

    Homocitrulline (HCit), an amino acid formed by the carbamylation of ε-amino groups of lysine residues, is considered a promising biomarker for monitoring diseases such as chronic renal failure and atherosclerosis. This paper describes a tandem mass spectrometric method for total, protein-bound and free HCit measurement in plasma samples. HCit was separated from other plasma components by hydrophilic interaction liquid chromatography. Detection was achieved by monitoring transitions of 190.1 > 127.1 and 190.1 > 173.1 for HCit, and 183.1 > 120.2 for d(7)-citrulline used as internal standard. This method allowed HCit quantification within 5.2 min and was precise (inter-assay CV < 5.85%), accurate (mean recoveries ranging from 97% to 106%), and exhibited a good linearity from 10 nmol/L to 1.6 μmol/L. Plasma samples from control and uremic mice (n = 10) were analyzed. In control mice, mean total plasma HCit concentration was 0.78 ± 0.12 μmol/mol amino acids, whereas it was increased 2.7-fold in uremic mice plasma, reaching 2.10 ± 0.50 μmol/mol amino acids (p < 0.001). In conclusion, this method exhibits good analytical performances and meets the criteria of sensitivity suitable for HCit concentration assessment in plasma samples.

  9. Fast quantification of endogenous carbohydrates in plasma using hydrophilic interaction liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Zhu, Bangjie; Liu, Feng; Li, Xituo; Wang, Yan; Gu, Xue; Dai, Jieyu; Wang, Guiming; Cheng, Yu; Yan, Chao

    2015-01-01

    Endogenous carbohydrates in biosamples are frequently highlighted as the most differential metabolites in many metabolomics studies. A simple, fast, simultaneous quantitative method for 16 endogenous carbohydrates in plasma has been developed using hydrophilic interaction liquid chromatography coupled with tandem mass spectrometry. In order to quantify 16 endogenous carbohydrates in plasma, various conditions, including columns, chromatographic conditions, mass spectrometry conditions, and plasma preparation methods, were investigated. Different conditions in this quantified analysis were performed and optimized. The reproducibility, precision, recovery, matrix effect, and stability of the method were verified. The results indicated that a methanol/acetonitrile (50:50, v/v) mixture could effectively and reproducibly precipitate rat plasma proteins. Cold organic solvents coupled with vortex for 1 min and incubated at -20°C for 20 min were the most optimal conditions for protein precipitation and extraction. The results, according to the linearity, recovery, precision, matrix effect, and stability, showed that the method was satisfactory in the quantification of endogenous carbohydrates in rat plasma. The quantified analysis of endogenous carbohydrates in rat plasma performed excellently in terms of sensitivity, high throughput, and simple sample preparation, which met the requirement of quantification in specific expanded metabolomic studies after the global metabolic profiling research.

  10. Coupling of tandem Smad ubiquitination regulatory factor (Smurf) WW domains modulates target specificity.

    PubMed

    Chong, P Andrew; Lin, Hong; Wrana, Jeffrey L; Forman-Kay, Julie D

    2010-10-26

    Smad ubiquitination regulatory factor 2 (Smurf2) is an E3 ubiquitin ligase that participates in degradation of TGF-β receptors and other targets. Smurf2 WW domains recognize PPXY (PY) motifs on ubiquitin ligase target proteins or on adapters, such as Smad7, that bind to E3 target proteins. We previously demonstrated that the isolated WW3 domain of Smurf2, but not the WW2 domain, can directly bind to a Smad7 PY motif. We show here that the WW2 augments this interaction by binding to the WW3 and making auxiliary contacts with the PY motif and a novel E/D-S/T-P motif, which is N-terminal to all Smad PY motifs. The WW2 likely enhances the selectivity of Smurf2 for the Smad proteins. NMR titrations confirm that Smad1 and Smad2 are bound by Smurf2 with the same coupled WW domain arrangement used to bind Smad7. The analogous WW domains in the short isoform of Smurf1 recognize the Smad7 PY peptide using the same coupled mechanism. However, a longer Smurf1 isoform, which has an additional 26 residues in the inter-WW domain linker, is only partially able to use the coupled WW domain binding mechanism. The longer linker results in a decrease in affinity for the Smad7 peptide. Interdomain coupling of WW domains enhances selectivity and enables the tuning of interactions by isoform switching.

  11. Screening and characterization of natural antioxidants in four Glycyrrhiza species by liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry.

    PubMed

    Li, Yan-Jing; Chen, Jun; Li, Ying; Li, Qin; Zheng, Yun-Feng; Fu, Yu; Li, Ping

    2011-11-11

    Licorice, derived from the dried roots and rhizomes of several species of genus Glycyrrhiza L. (Leguminosae family), has been traditionally used in herbal medicine for over 4000 years. In recent years, the interest in antioxidative constituents in licorice has greatly increased. In this work, a new method based on 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) spiking test combined with HPLC coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (Q-TOF MS/MS) analysis was developed to screen and identify the antioxidants in licorice. The results of the method validation indicated that the developed method was reliable and repeatable. Compared with DPPH on-line method, the HPLC-Q-TOF MS/MS method combined with DPPH spiking test offered much higher sensitivity and resolution. Using this method, 35 radical scavengers were screened from four Glycyrrhiza species (G. inflata, G. glabra, G. pallidiflora and G. uralensis), and 21 of them were unambiguously or tentatively identified by HPLC-Q-TOF MS/MS. Among the 21 identified flavonoids, 10 compounds had been reported to possess antioxidative activities in the previous studies, and the radical scavenging activities of the other 11 compounds were reported for the first time. The effects of six purified flavonoids on DPPH radical and lipid peroxidation were evaluated for validation of the developed method. The results indicated that HPLC-Q-TOF MS/MS coupled with DPPH treatment is an efficient and powerful method to discover the potential antioxidative compounds from the complex natural product mixtures. In this study, the identified components with free radical scavenging activity, would help to explain the therapeutic benefit of licorice in the treatment of human disease associated with oxidative stress.

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

    PubMed

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

    2012-10-31

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

  13. Oxidation of aromatic contaminants coupled to microbial iron reduction

    USGS Publications Warehouse

    Lovley, D.R.; Baedecker, M.J.; Lonergan, D.J.; Cozzarelli, I.M.; Phillips, E.J.P.; Siegel, D.I.

    1989-01-01

    THE contamination of sub-surface water supplies with aromatic compounds is a significant environmental concern1,2. As these contaminated sub-surface environments are generally anaerobic, the microbial oxidation of aromatic compounds coupled to nitrate reduction, sulphate reduction and methane production has been studied intensively1-7. In addition, geochemical evidence suggests that Fe(III) can be an important electron acceptor for the oxidation of aromatic compounds in anaerobic groundwater. Until now, only abiological mechanisms for the oxidation of aromatic compounds with Fe(III) have been reported8-12. Here we show that in aquatic sediments, microbial activity is necessary for the oxidation of model aromatic compounds coupled to Fe(III) reduction. Furthermore, a pure culture of the Fe(III)-reducing bacterium GS-15 can obtain energy for growth by oxidizing benzoate, toluene, phenol or p-cresol with Fe(III) as the sole electron acceptor. These results extend the known physiological capabilities of Fe(III)-reducing organisms and provide the first example of an organism of any type which can oxidize an aromatic hydrocarbon anaerobically. ?? 1989 Nature Publishing Group.

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

    PubMed

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

    2012-10-01

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

  15. Determination of Flavonoids and Anthocyanins in Nitraria tangutorum by High Performance Liquid Chromatography Coupled with Tandem Mass Spectrometry.

    PubMed

    Zhe, Gao; Ying-Chun, Wang; Yan-Xu, Chang

    2016-01-01

    Using high-performance liquid chromatography coupled with diode array detection and electrospray ionization tandem mass spectrometry (HPLC-DAD-MSn) method, qualitative and quantitative analysis of flavonoids of stems, leaves, fruits and seeds, and anthocyanidin of fresh fruits in Nitraria tangutorum were performed. A total of 14 flavonoid components were identified from the seeds of N. tangutorum including three quercetin derivatives, three kaempferol derivatives, and eight isorhamnetin derivatives. A total of 12, 10, and 7 flavonoid components were identified from leaves, stems, and fruits of N. tangutorum, respectively; all were present in seeds also. The total content of flavonoids in leaves was the highest, up to 42.43 mg/g·dry weight. A total of 12 anthocyanidin components were identified from the fresh fruits of N. tangutorum, belonging to five anthocyanidin. The total content of anthocyanidin in fresh fruits was up to 45.83 mg/100 g· fresh weight, of which the acylated anthocyanidin accounted for 65.7%. The HPLC-DAD-MS(n) method can be operated easily, rapidly, and accurately, and is feasible for qualitative and quantitative analysis of flavone glycosides in N. tangutorum.

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

    PubMed

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

    2015-03-01

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

  17. Validation of determination of plasma metabolites derived from thyme bioactive compounds by improved liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Rubió, Laura; Serra, Aida; Macià, Alba; Borràs, Xenia; Romero, Maria-Paz; Motilva, Maria-José

    2012-09-15

    In the present study, a selective and sensitive method, based on microelution solid-phase extraction (μSPE) plate and ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS) was validated and applied to determine the plasma metabolites of the bioactive compounds of thyme. For validation process, standards of the more representative components of the phenolic and monoterpene fractions of thyme were spiked in plasma samples and then the quality parameters of the method were studied. Extraction recoveries (%R) of the studied compounds were higher than 75%, and the matrix effect (%ME) was lower than 18%. The LODs ranged from 1 to 65 μg/L, except for the thymol sulfate metabolite, which was 240 μg/L. This method was then applied for the analysis of rat plasma obtained at different times, from 0 to 6h, after an acute intake of thyme extract (5 g/kg body weight). Different thyme metabolites were identified and were mainly derived from rosmarinic acid (coumaric acid sulfate, caffeic acid sulfate, ferulic acid sulfate, hydroxyphenylpropionic acid sulfate, dihydroxyphenylpropionic acid sulfate and hydroxybenzoic acid) and thymol (thymol sulfate and thymol glucuronide). The most abundant thyme metabolites generated were hydroxyphenylpropionic acid sulfate and thymol sulfate, their respective concentrations in plasma being 446 and 8464 μM 1h after the intake of the thyme extract.

  18. Analysis of anabolic androgenic steroids as sulfate conjugates using high performance liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Rzeppa, S; Heinrich, G; Hemmersbach, P

    2015-01-01

    Improvements in doping analysis can be effected by speeding up analysis time and extending the detection time. Therefore, direct detection of phase II conjugates of doping agents, especially anabolic androgenic steroids (AAS), is proposed. Besides direct detection of conjugates with glucuronic acid, the analysis of sulfate conjugates, which are usually not part of the routine doping control analysis, can be of high interest. Sulfate conjugates of methandienone and methyltestosterone metabolites have already been identified as long-term metabolites. This study presents the synthesis of sulfate conjugates of six commonly used AAS and their metabolites: trenbolone, nandrolone, boldenone, methenolone, mesterolone, and drostanolone. In the following these sulfate conjugates were used for development of a fast and easy analysis method based on sample preparation using solid phase extraction with a mixed-mode sorbent and detection by high performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS). Validation demonstrated the suitability of the method with regard to the criteria given by the technical documents of the World Anti-Doping Agency (WADA). In addition, suitability has been proven by successful detection of the synthesized sulfate conjugates in excretion urines and routine doping control samples.

  19. Development of a comprehensive analytical method for phosphate metabolites in plants by ion chromatography coupled with tandem mass spectrometry.

    PubMed

    Sekiguchi, Yoko; Mitsuhashi, Naoto; Kokaji, Tetsuo; Miyakoda, Hidekazu; Mimura, Tetsuro

    2005-08-26

    This paper describes the development of a practical method for the analysis of phosphorus compounds with a focus on sugar phosphates from the model higher plant Arabidopsis thaliana by ion chromatography coupled to electrospray ionization tandem mass spectrometry (IC-ESI-MS-MS). After the analytical separation, the potassium hydroxide eluent was converted to water with an anion suppressor allowing the effluent from the IC to be connected to the mass spectrometer directly. In the optimized method, 17 phosphorous compounds (adenosine diphosphate (ADP), fructose 1,6-bisphosphate, fructose 2,6-bisphosphate, fructose 6-phosphate, galactose 1-phosphate, glucose 1-phosphate, glucose 1,6-bisphosphate, glucose 6-phosphate, mannose 6-phosphate, phosphoenol pyrvate, 3-phosphoglyceric acid, ribulose 1,5-bisphosphate, ribulose 5-phosphate, ribose 5-phosphate, sucrose 6-phosophate and uridine 5'-diphosphate-glucose (UDPG)) were determined. The linearity of response for these phosphorous compounds over the concentration range of 0 and 10 microM was better than 0.9993 in all cases. The minimum detection limit was between 0.01 and 2.50 microM for a 25 microL injection, and recovery rates for standard addition to the sample were within the range from 93% to 110%.

  20. Fast determination of four polar contaminants in soy nutraceutical products by liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Domingos Alves, Renata; Romero-González, Roberto; López-Ruiz, Rosalía; Jiménez-Medina, M L; Garrido Frenich, Antonia

    2016-11-01

    An analytical method based on a modified QuPPe (quick polar pesticide) extraction procedure coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was evaluated for the determination of four polar compounds (chlorate, fosetyl-Al, maleic hydrazide, and perchlorate) in nutraceutical products obtained from soy. Experimental conditions including extraction such as solvent, acidification, time, and clean-up sorbents were varied. Acidified acetonitrile (1 % formic acid, v/v) was used as extraction solvent instead of methanol (conventional QuPPe), which provides a doughy mixture which cannot be injected into the LC. Clean-up or derivatization steps were avoided. For analysis, several stationary phases were evaluated and Hypercarb (porous graphitic carbon) provided the best results. The optimized method was validated and recoveries ranged between 46 and 119 %, and correction factors can be used for quantification purposes bearing in mind that inter-day precision was equal to or lower than 17 %. Limits of quantification (LOQs) ranged from 4 to 100 μg kg(-1). Soy-based nutraceutical products were analyzed and chlorate was detected in five samples at concentrations between 63 and 1642 μg kg(-1). Graphical Abstract Analysis of polar compounds in soy-based nutraceutical products.

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

    PubMed

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

    2012-02-29

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

  2. Improvement of Mitochondria Extract from Saccharomyces cerevisiae Characterization in Shotgun Proteomics Using Sheathless Capillary Electrophoresis Coupled to Tandem Mass Spectrometry

    PubMed Central

    Ibrahim, Marianne; Gahoual, Rabah; Enkler, Ludovic; Becker, Hubert Dominique; Chicher, Johana; Hammann, Philippe; François, Yannis-Nicolas; Kuhn, Lauriane; Leize-Wagner, Emmanuelle

    2016-01-01

    In this work, we describe the characterization of a quantity-limited sample (100 ng) of yeast mitochondria by shotgun bottom-up proteomics. Sample characterization was carried out by sheathless capillary electrophoresis, equipped with a high sensitivity porous tip and coupled to tandem mass spectrometry (CESI–MS-MS) and concomitantly with a state-of-art nano flow liquid chromatography coupled to a similar mass spectrometry (MS) system (nanoLC–MS-MS). With single injections, both nanoLC–MS-MS and CESI–MS-MS 60 min-long separation experiments allowed us to identify 271 proteins (976 unique peptides) and 300 proteins (1,765 unique peptides) respectively, demonstrating a significant specificity and complementarity in identification depending on the physicochemical separation employed. Such complementary, maximizing the number of analytes detected, presents a powerful tool to deepen a biological sample's proteomic characterization. A comprehensive study of the specificity provided by each separating technique was also performed using the different properties of the identified peptides: molecular weight, mass-to-charge ratio (m/z), isoelectric point (pI), sequence coverage or MS–MS spectral quality enabled to determine the contribution of each separation. For example, CESI–MS-MS enables to identify larger peptides and eases the detection of those having extreme pI without impairing spectral quality. The addition of peptides, and therefore proteins identified by both techniques allowed us to increase significantly the sequence coverages and then the confidence of characterization. In this study, we also demonstrated that the two yeast enolase isoenzymes were both characterized in the CESI–MS-MS data set. The observation of discriminant proteotypic peptides is facilitated when a high number of precursors with high-quality MS–MS spectra are generated. PMID:26860395

  3. 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

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

    2012-06-01

    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.

  4. Oxidative-coupling reaction of TNT reduction products by manganese oxide.

    PubMed

    Kang, Ki-Hoon; Lim, Dong-Min; Shin, Hyunsang

    2006-03-01

    Abiotic transformation of TNT reduction products via oxidative-coupling reaction was investigated using Mn oxide. In batch experiments, all the reduction products tested were completely transformed by birnessite, one of natural Mn oxides present in soil. Oxidative-coupling was the major transformation pathway, as confirmed by mass spectrometric analysis. Using observed pseudo-first-order rate constants with respect to birnessite loadings, surface area-normalized specific rate constants, ksurf, were determined. As expected, ksurf of diaminonitrotoluenes (DATs) (1.49-1.91L/m2 d) are greater about 2 orders than that of dinitroaminotoluenes (DNTs) (1.15 x 10(-2)-2.09 x 10(-2)L/m2d) due to the increased number of amine group. In addition, by comparing the value of ksurf between DNTs or DATs, amine group on ortho position is likely to be more preferred for the oxidation by birnessite. Although cross-coupling of TNT in the presence of various mediator compounds was found not to be feasible, transformation of TNT by reduction using Fe0 followed by oxidative-coupling using Mn oxide was efficient, as evaluated by UV-visible spectrometry.

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

    PubMed

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

    2015-05-19

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

  6. High-performance liquid chromatography coupled with tandem mass spectrometry technology in the analysis of Chinese Medicine Formulas: A bibliometric analysis (1997-2015).

    PubMed

    He, Xi-Ran; Li, Chun-Guang; Zhu, Xiao-Shu; Li, Yuan-Qing; Jarouche, Mariam; Bensoussan, Alan; Li, Ping-Ping

    2017-01-01

    There is a recognized challenge in analyzing traditional Chinese medicine formulas because of their complex chemical compositions. The application of modern analytical techniques such as high-performance liquid chromatography coupled with a tandem mass spectrometry has improved the characterization of various compounds from traditional Chinese medicine formulas significantly. This study aims to conduct a bibliometric analysis to recognize the overall trend of high-performance liquid chromatography coupled with tandem mass spectrometry approaches in the analysis of traditional Chinese medicine formulas, its significance and possible underlying interactions between individual herbs in these formulas. Electronic databases were searched systematically, and the identified studies were collected and analyzed using Microsoft Access 2010, Graph Pad 5.0 software and Ucinet software package. 338 publications between 1997 and 2015 were identified, and analyzed in terms of annual growth and accumulated publications, top journals, forms of traditional Chinese medicine preparations and highly studied formulas and single herbs, as well as social network analysis of single herbs. There is a significant increase trend in using high-performance liquid chromatography coupled with tandem mass spectrometry related techniques in analysis of commonly used forms of traditional Chinese medicine formulas in the last 3 years. Stringent quality control is of great significance for the modernization and globalization of traditional Chinese medicine, and this bibliometric analysis provided the first and comprehensive summary within this field.

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

    SciTech Connect

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

    1986-08-01

    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.

  8. Combining novel device architecture and NIR dye towards the fabrication of transparent conductive oxide-less tandem dye sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Baranwal, Ajay Kumar; Fujikawa, Naotaka; Hayat, Azwar; Ogomi, Yuhei; Pandey, Shyam S.; Ma, Tingli; Hayase, Shuzi

    2015-10-01

    Tandem solar cells with different device architectures utilizing a back contact transparent conductive oxide-less bottom electrode (TCO-less tandem DSSC) that has better control of the optical transmission losses incurred by intermediate TCO layers with flexible Pt/tin-doped indium oxide (ITO)-polyethylene terephthalate film as an intermediate layer are reported. The proposed device architecture suppresses the optical loss to a greater extent (around 30%). Sensitizers were ruthenium-based N719 dye in the top electrode, while the newly synthesized phthalocyanine dye (PC25) corresponding to photon harvesting in the near infrared (NIR) region (up to 900 nm) was used in the TCO-less bottom cell. Open circuit voltage (Voc) ≥ 1.18 V (sum of top cell and bottom cell Voc) justifies the TCO-less tandem DSSC formation.

  9. Determination of phosphodiesterase type V inhibitors in wastewater by direct injection followed by liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Causanilles, Ana; Emke, Erik; de Voogt, Pim

    2016-09-15

    A simple, fast and reliable analytical method for the determination of phosphodiesterase type V inhibitors in wastewater was developed and validated. The method was based on direct injection followed by liquid chromatography coupled to tandem mass spectrometry with triple quadrupole as mass analyzer. Transformation products and analogues were included in the target list besides the three active pharmaceutical ingredients (sildenafil, vardenafil and tadalafil). The method performance was thoroughly investigated, including the analyte stability in wastewater and matrix effect. All target compounds presented linear fits between their LOD and 500ng/L. The quantification limits ranged from 1.6 to 30ng/L for all compounds except for n-octylnortadalafil (LOQ: 100ng/L); precision calculated as intraday repeatability was lower than 30%; accuracy calculated as procedural recovery ranged successfully between 85 and 105% in all cases. The method was applied to samples collected during three week-long monitoring campaigns performed in 2013, 2014 and 2015 in three Dutch cities. Only sildenafil and its two metabolites, desmethyl- and desethylsildenafil, were present with normalized loads ranging from LOQ to 8.3, 11.8 and 21.6mg/day/1000 inh, respectively. Two additional week-long sets of samples were collected in Amsterdam at the time that a festival event took place, bringing around 350,000 visitors to the city. The difference in drug usage patterns was statistically studied: "weekday" versus "weekend", "normal" versus "atypical" week; and results discussed. The metabolite to parent drug concentration ratio evolution during consecutive years was discussed, leading to several possible explanations that should be further investigated. Finally, wastewater-based epidemiology approach was applied to back-calculate sildenafil consumption.

  10. Simultaneous determination of eugenol, isoeugenol and methyleugenol in fish fillet using gas chromatography coupled to tandem mass spectrometry.

    PubMed

    Ke, Changliang; Liu, Qi; Li, Liudong; Chen, Jiewen; Wang, Xunuo; Huang, Ke

    2016-09-15

    Gas chromatography (GC) coupled with triple quadrupole tandem mass spectrometry (MS/MS) operated in electron ionization mode (EI) has been shown to have advantages in the trace analysis of chemical compounds. Employing the instrument, a method has been built to simultaneously determine eugenol, isoeugenol' and methyleugenol, which have been widely used as fish anesthetic, in the fish fillet. Procedure for the sample preparation was achieved by using hexane extraction followed by phenyl solid phase extraction (SPE) cleanup, which was free of such steps as rotary evaporation and nitrogen blowing by taking the volatility of eugenol and its isomers into consideration. The method was validated by conducting recovery studies on fortified fish fillet samples at four concentrations. The linearity in the range of 5-500μg·L(-1) was forced through the origin giving a coefficient of determination (r(2)) greater than 0.9982. Limits of detection (LODs) for eugenol, isoeugenol' and methyleugenol were 0.4, 1.2' and 0.2μg·kg(-1), respectively. The limits of quantification (LOQs) were 1.2, 4' and 0.7μg·kg(-1) for eugenol, isoeugenol' and methyleugenol, respectively. The recoveries for eugenol and its isomers ranged from 76.4 to 99.9% with relative standard deviations (RSD) in a range from 2.18 to 15.5%. This method is quick, simple and suitable for determining the residues of eugenol, isoeugenol and methyleugenol simultaneously in batch samples of fish fillet.

  11. Ethyl-glucuronide and ethyl-sulfate in placental and fetal tissues by liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Morini, Luca; Falcón, Maria; Pichini, Simona; Garcia-Algar, Oscar; Danesino, Paolo; Groppi, Angelo; Luna, Aurelio

    2011-11-01

    The aim of this study was to develop a method for the determination of ethyl-glucuronide (EtG) and ethyl-sulfate (EtS), two direct ethanol metabolites, in early placental and fetal human tissues, as potential biomarkers of transplacental ethanol transfer from the mother to the fetus. Placental and fetal tissue samples were obtained from women undergoing voluntary termination of pregnancy at 12 weeks of gestation. Samples were deproteinized and directly injected into a liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) system. Limits of detection of 13.0 and 23.0 pmol/g and lower limits of quantification of 22.0 and 40.0 pmol/g were reached for EtG and EtS, respectively. Inter- and intraday imprecision and accuracy were always lower than 15%. The method was applied to 70 samples (35 placentas and 35 fetal tissues). Of 35 samples, 4 samples collected from 4 women tested positive for EtG and EtS, always showing higher concentrations for EtG. The placenta/fetal tissue ratio for EtG was 2.9 ± 0.9, whereas EtS showed a ratio of 1.7 ± 0.7. Preliminary results suggest that these metabolites are present in both tissues. Further studies should now corroborate the hypothesis, not yet confirmed, that transplacental transfer of ethanol takes place not only for the parent compound but also for EtG and EtS.

  12. Determination of paroxetine in plasma by liquid chromatography coupled to tandem mass spectrometry for pharmacokinetic and bioequivalence studies.

    PubMed

    Jhee, Ok Hwa; Seo, Hee Kyoung; Lee, Min Ho; Jeon, Yong Cheol; Shaw, Leslie M; Lee, Seung Hoon; Hur, Yeon; Kim, Kwang-Hyun; Lee, Heon-Soo; Lee, Seo Eun; Kang, Ju Seop

    2007-01-01

    A rapid and validated liquid chromatography coupled to tandem mass spectrometric method (LC-MS-MS) has been developed and applied to pharmacokinetic and bioequivalence studies in 24 healthy male Korean volunteers. The procedure involves a liquid-liquid extraction of paroxetine (CAS 61869-08-7) and fluoxetine (internal standard, CAS 54910-89-3) with ether/methyl chloride (7:3, v/v) and separated by LC equipped with C18 column using acetonitrile: 5 mmol/L ammonium formate (4:3, v/v) as mobile phase. Detection is carried out on an API 2000 MS system by multiple reactions monitoring mode. The ionization was optimized using ESI(+) and selectivity was achieved by MS-MS analysis, mlz 330.0-->192.0 and m/ z 310-->148 for paroxetine and fluoxetine, respectively. The method has a total run time of 1.5 min and was linear over a working range of 0.05-20 ng/mL and the lower limit of quantification was 0.05 ng/ mL. No endogenous compounds were found to interfere with the analysis. The inter-day and intra-day accuracy was in the ranges of 102.69-107.79% and 102.07-109.57%, respectively and precision of inter-day and intra-day expressed as relative standard deviation were 1.86-9.99% and 1.52-6.28%, respectively. The validation of this method on linearity, specificity, accuracy, precision as well as applicability to pharmacokinetic and bioequivalence studies by analysis of blood samples taken up to 72 h after oral administration of 20 mg of paroxetine in 24 healthy volunteers were found to be good performance.

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

    PubMed

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

    2012-05-01

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

  14. Multi-class mycotoxins analysis in Angelica sinensis by ultra fast liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Liu, Qiutao; Kong, Weijun; Guo, Weiying; Yang, Meihua

    2015-04-15

    An ultra fast liquid chromatography coupled with tandem mass spectrometry (UFLC-MS/MS) method was developed and validated for simultaneous analysis of multi-class mycotoxins including aflatoxins (AFB1, AFB2, AFG1 and AFG2), ochratoxin A (OTA), fumonisins (FB1 and FB2) and zearalanone (ZEN) in 20 batches of Angelica sinensis samples collected from different markets and stores in China. The eight mycotoxins were extracted and cleaned up by using QuEChERS-based procedure, and then were quantified under the multiple reaction monitoring (MRM) together with positive and negative ionization modes. Focusing on the optimization of extraction and clean-up conditions, as well as UFLC separation and MS/MS parameters of targeted analytes, the developed method expressed good linearity for the eight mycotoxins within their respective linear ranges with correlation coefficients all higher than 0.9974. The limits of detection (LODs) and quantification (LOQs) ranged from 0.005 to 0.125 μg/kg and from 0.0625 to 0.25 μg/kg, respectively. Recoveries for spiked A. sinensis sample at three different levels were all above 78.9% with relative standard deviations (RSDs) below 6.36% for all analytes. Analysis of real samples demonstrated that two visibly moldy A. sinensis samples were detected with AFB1 of 2.07 and 2.92 μg/kg, and AFG1 of 2.84 and 1.53 μg/kg. The proposed quantitative method with significant advantages including simple pretreatment, rapid determination and high sensitivity would be the preferred candidate for the determination and quantification of multi-class mycotoxin contaminants in complex matrixes, which well fulfilled the maximum residue limits (MRLs) from various countries.

  15. Remarkably efficient synthesis of 2H-indazole 1-oxides and 2H-indazoles via tandem carbon-carbon followed by nitrogen-nitrogen bond formation.

    PubMed

    Bouillon, Isabelle; Zajícek, Jaroslav; Pudelová, Nadĕzda; Krchnák, Viktor

    2008-11-21

    Base-catalyzed tandem carbon-carbon followed by nitrogen-nitrogen bond formations quantitatively converted N-alkyl-2-nitro-N-(2-oxo-2-aryl-ethyl)-benzenesulfonamides to 2H-indazoles 1-oxides under mild conditions. Triphenylphosphine or mesyl chloride/triethylamine-mediated deoxygenation afforded 2H-indazoles.

  16. OXIDATIVE COUPLING OF METHANE USING INORGANIC MEMBRANE REACTORS

    SciTech Connect

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

    1998-04-01

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

  17. Simultaneous targeted analysis of trimethylamine-N-oxide, choline, betaine, and carnitine by high performance liquid chromatography tandem mass spectrometry.

    PubMed

    Liu, Jia; Zhao, Mingming; Zhou, Juntuo; Liu, Changjie; Zheng, Lemin; Yin, Yuxin

    2016-11-01

    Trimethylamine-N-oxide (TMAO) is a metabolite generated from choline, betaine and carnitine in a gut microbiota-dependent way. This molecule is associated with development of atherosclerosis and cardiovascular events. A sensitive liquid chromatographic electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) has been developed and validated for the simultaneous determination of TMAO related molecules including TMAO, betaine, choline, and carnitine in mouse plasma. Analytes are extracted after protein precipitation by methanol and subjected to LC-ESI-MS/MS without preliminary derivatization. Separation of analytes was achieved on an amide column with acetonitrile-water as the mobile phase. This method has been fully validated in this study in terms of selectivity, linearity, sensitivity, precision, accuracy, and carryover effect, and the stability of the analyte under various conditions has been confirmed. This developed method has successfully been applied to plasma samples of our mouse model.

  18. 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

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

    2014-06-01

    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.

  19. Characterization of acylated flavonoid-O-glycosides and methoxylated flavonoids from Tagetes maxima by liquid chromatography coupled to electrospray ionization tandem mass spectrometry.

    PubMed

    Parejo, Irene; Jáuregui, Olga; Viladomat, Francesc; Bastida, Jaume; Codina, Carles

    2004-01-01

    Liquid chromatography coupled to negative electrospray ionization (ESI) tandem mass spectrometry (MS/MS) employing a triple quadrupole mass spectrometer was used in the structural determination of acylated flavonoid-O-glycosides and methoxylated flavonoids occurring in Tagetes maxima. The compounds were identified by experiments in full scan mode (MS), and tandem mass experiments (MS/MS) of precursor ion scan, product ion scan, and neutral loss scan modes. In order to characterize the aglycones of the flavonoid glycosides, in-source fragmentation of the deprotonated molecule [M-H]- followed by product ion scan of the resulting aglycone [A-H]- were performed. This combined approach allowed the identification of 51 phenolic compounds, including flavonoid-O-glycosides acylated with galloyl, protocatechuoyl, coumaroyl or caffeoyl groups, methoxylated flavonoids, and hydroxycinnamic acid and phenolic acid derivatives, none of them previously reported in Tagetes maxima.

  20. Controlling Spatial Coupling in Catalytic CO Oxidation on Platinum

    NASA Astrophysics Data System (ADS)

    Lund, C. D.; Yamamoto, S. Y.; Surko, C. M.; Maple, M. B.

    1997-03-01

    Reaction-rate oscillations are known to occur in oxidation reactions on a variety of metal catalysts. The most extensively studied system of this type is the oxidation of carbon monoxide on platinum. Most studies have focused on temporal behavior. Recently, we constructed an experiment in which we can study both the spatial and temporal behavior of CO oxidation on Pt thin-film catalysts, using a continuous-flow reactor and infrared imaging techniques.(S.Y. Yamamoto, C.M. Surko, M.B. Maple, and R.K.Pina, J. Chem. Phys. 102, 8614 (1995).) In most experiments to date, all parts of the catalysts are found to oscillate in phase. By systematically blocking the possible spatial coupling mechanisms, we have shown that the various parts of the catalyst are coupled by diffusion of the reactants in the gas stream.(S.Y. Yamamoto, C.M. Surko, and M.B. Maple, J. Chem. Phys. 103, 8209 (1995).) Using argon instead of helium as the inert buffer gas and increasing the gas flow rate, we find that we are able to control the degree of spatial synchronization. This results in non-trivial spatial patterns which will be discussed.

  1. Oxidative coupling of methane using inorganic membrane reactor

    SciTech Connect

    Ma, Y.H.; Moser, W.R.; Dixon, A.G.

    1995-12-31

    The goal of this research is to improve the oxidative coupling of methane in a catalytic inorganic membrane reactor. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and relatively higher yields than in 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 formation of CO{sub x} products. Such gas phase reactions are a cause for decreased selectivity in 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. Modeling work which aimed at predicting the observed experimental trends in porous membrane reactors was also undertaken in this research program.

  2. Comparative proteomic analysis of sulfur-oxidizing Acidithiobacillus ferrooxidans CCM 4253 cultures having lost the ability to couple anaerobic elemental sulfur oxidation with ferric iron reduction.

    PubMed

    Kucera, Jiri; Sedo, Ondrej; Potesil, David; Janiczek, Oldrich; Zdrahal, Zbynek; Mandl, Martin

    2016-09-01

    In extremely acidic environments, ferric iron can be a thermodynamically favorable electron acceptor during elemental sulfur oxidation by some Acidithiobacillus spp. under anoxic conditions. Quantitative 2D-PAGE proteomic analysis of a resting cell suspension of a sulfur-grown Acidithiobacillus ferrooxidans CCM 4253 subculture that had lost its iron-reducing activity revealed 147 protein spots that were downregulated relative to an iron-reducing resting cell suspension of the antecedent sulfur-oxidizing culture and 111 that were upregulated. Tandem mass spectrometric analysis of strongly downregulated spots identified several physiologically important proteins that apparently play roles in ferrous iron oxidation, including the outer membrane cytochrome Cyc2 and rusticyanin. Other strongly repressed proteins were associated with sulfur metabolism, including heterodisulfide reductase, thiosulfate:quinone oxidoreductase and sulfide:quinone reductase. Transcript-level analyses revealed additional downregulation of other respiratory genes. Components of the iron-oxidizing system thus apparently play central roles in anaerobic sulfur oxidation coupled with ferric iron reduction in the studied microbial strain.

  3. Methane oxidation coupled to oxygenic photosynthesis in anoxic waters.

    PubMed

    Milucka, Jana; Kirf, Mathias; Lu, Lu; Krupke, Andreas; Lam, Phyllis; Littmann, Sten; Kuypers, Marcel M M; Schubert, Carsten J

    2015-09-01

    Freshwater lakes represent large methane sources that, in contrast to the Ocean, significantly contribute to non-anthropogenic methane emissions to the atmosphere. Particularly mixed lakes are major methane emitters, while permanently and seasonally stratified lakes with anoxic bottom waters are often characterized by strongly reduced methane emissions. The causes for this reduced methane flux from anoxic lake waters are not fully understood. Here we identified the microorganisms and processes responsible for the near complete consumption of methane in the anoxic waters of a permanently stratified lake, Lago di Cadagno. Interestingly, known anaerobic methanotrophs could not be detected in these waters. Instead, we found abundant gamma-proteobacterial aerobic methane-oxidizing bacteria active in the anoxic waters. In vitro incubations revealed that, among all the tested potential electron acceptors, only the addition of oxygen enhanced the rates of methane oxidation. An equally pronounced stimulation was also observed when the anoxic water samples were incubated in the light. Our combined results from molecular, biogeochemical and single-cell analyses indicate that methane removal at the anoxic chemocline of Lago di Cadagno is due to true aerobic oxidation of methane fuelled by in situ oxygen production by photosynthetic algae. A similar mechanism could be active in seasonally stratified lakes and marine basins such as the Black Sea, where light penetrates to the anoxic chemocline. Given the widespread occurrence of seasonally stratified anoxic lakes, aerobic methane oxidation coupled to oxygenic photosynthesis might have an important but so far neglected role in methane emissions from lakes.

  4. Methane oxidation coupled to oxygenic photosynthesis in anoxic waters

    PubMed Central

    Milucka, Jana; Kirf, Mathias; Lu, Lu; Krupke, Andreas; Lam, Phyllis; Littmann, Sten; Kuypers, Marcel MM; Schubert, Carsten J

    2015-01-01

    Freshwater lakes represent large methane sources that, in contrast to the Ocean, significantly contribute to non-anthropogenic methane emissions to the atmosphere. Particularly mixed lakes are major methane emitters, while permanently and seasonally stratified lakes with anoxic bottom waters are often characterized by strongly reduced methane emissions. The causes for this reduced methane flux from anoxic lake waters are not fully understood. Here we identified the microorganisms and processes responsible for the near complete consumption of methane in the anoxic waters of a permanently stratified lake, Lago di Cadagno. Interestingly, known anaerobic methanotrophs could not be detected in these waters. Instead, we found abundant gamma-proteobacterial aerobic methane-oxidizing bacteria active in the anoxic waters. In vitro incubations revealed that, among all the tested potential electron acceptors, only the addition of oxygen enhanced the rates of methane oxidation. An equally pronounced stimulation was also observed when the anoxic water samples were incubated in the light. Our combined results from molecular, biogeochemical and single-cell analyses indicate that methane removal at the anoxic chemocline of Lago di Cadagno is due to true aerobic oxidation of methane fuelled by in situ oxygen production by photosynthetic algae. A similar mechanism could be active in seasonally stratified lakes and marine basins such as the Black Sea, where light penetrates to the anoxic chemocline. Given the widespread occurrence of seasonally stratified anoxic lakes, aerobic methane oxidation coupled to oxygenic photosynthesis might have an important but so far neglected role in methane emissions from lakes. PMID:25679533

  5. Pyridine N-oxide and pyridine-d5 N-oxide: an electrospray/tandem mass spectrometric study carried out at high mass resolution.

    PubMed

    March, Raymond E; Stadey, Christopher J; Lewars, Errol G

    2005-01-01

    A mass spectrometric study of pyridine N-oxide and pyridine-d5 N-oxide was carried out with a hybrid quadrupole/time-of-flight (TOF) mass spectrometer coupled with an electrospray (ES) source. In addition to the observation of protonated, sodiated, and proton-bound dimers of pyridine N-oxide and pyridine-d5 N-oxide, mass scans revealed the presence of several doubly-charged ion species. Doubly-charged ions of m/z 191 were identified as diprotonated tetramers of pyridine N-oxide; a structure has been proposed for the diprotonated tetramer and its energy relative to that of protonated pyridine N-oxide has been obtained from geometry optimizations. The principal ion species observed were subjected to collision-induced dissociation; accurate mass measurements were made of each fragment ion so as to determine its elemental composition. On the basis of mass spectrometric evidence, it is suggested that dissociation of pyridine N-oxide may occur during the ES process and the resulting fragments become embedded in doubly-charged ions. The proton affinity for both pyridine N-oxide and pyridine-d5 N-oxide was calculated; the difference between these proton affinities was compared with an experimentally determined difference between the proton affinities of pyridine N-oxide and pyridine-d5 N-oxide.

  6. Simultaneous analysis of mono-, di-, and tri-ethanolamine in cosmetic products using liquid chromatography coupled tandem mass spectrometry.

    PubMed

    Shin, Kyong-Oh; Lee, Yong-Moon

    2016-01-01

    Alkanolamines such as monoethanolamine (MEA), diethanolamine (DEA), and triethanolamine (TEA) are used as wetting agents in shampoos, lotions, creams, and other cosmetics. DEA is widely used to provide lather in shampoos and maintain a favorable consistency in lotions and creams. Although DEA is not harmful, it may react with other ingredients in the cosmetic formula after extended storage periods to form an extremely potent carcinogen called nitrosodiethanolamine (NDEA), which is readily absorbed through the skin and has been linked to the development of stomach, esophagus, liver, and bladder cancers. The purpose of this study was to develop a simultaneous quantification method for measurement of MEA, DEA, and TEA in cosmetic products. Liquid chromatography coupled tandem mass spectrometry (LC-MS/MS) was performed using a hydrophilic interaction liquid chromatography (HILIC) column with isocratic elution containing acetonitrile and 5 mM ammonium formate in water (88:12, v/v). Identification and quantification of alkanolamines were performed using MS/MS monitoring to assess the transition from precursor to product ion of MEA (m/z, 61.1 → 44.0), DEA (m/z, 106.1 → 88.0), TEA (m/z, 150.1 → 130.0), and the internal standard triethylamine (m/z, 102.2 → 58.0). Alkanolamines extractions were simplified using a single extraction with acetonitrile in the cosmetic matrix. Performance of the method was evaluated with quality parameters such as specificity, carry-over, linearity and calibration, correlation of determination (R(2)), detection limit, precision, accuracy, and recovery. Calibration curves of MEA (2.9-1000 ppb), DEA (1-1000 ppb), and TEA (1-1000 ppb) were constructed by plotting concentration versus peak-area ratio (analyte/internal standard with a correlation coefficient greater than 0.99). The intra- and inter-assay accuracy ranged from 92.92 to 101.15 % for all analytes. The intra- and inter-assay precision for MEA, DEA, and TEA showed all

  7. Elucidating collision induced dissociation products and reaction mechanisms of protonated uracil by coupling chemical dynamics simulations with tandem mass spectrometry experiments.

    PubMed

    Molina, Estefanía Rossich; Ortiz, Daniel; Salpin, Jean-Yves; Spezia, Riccardo

    2015-12-01

    In this study we have coupled mixed quantum-classical (quantum mechanics/molecular mechanics) direct chemical dynamics simulations with electrospray ionization/tandem mass spectrometry experiments in order to achieve a deeper understanding of the fragmentation mechanisms occurring during the collision induced dissociation of gaseous protonated uracil. Using this approach, we were able to successfully characterize the fragmentation pathways corresponding to ammonia loss (m/z 96), water loss (m/z 95) and cyanic or isocyanic acid loss (m/z 70). Furthermore, we also performed experiments with isotopic labeling completing the fragmentation picture. Remarkably, fragmentation mechanisms obtained from chemical dynamics simulations are consistent with those deduced from isotopic labeling.

  8. Tandem Affinity Purification Approach Coupled to Mass Spectrometry to Identify Post-translational Modifications of Histones Associated with Chromatin-Binding Proteins.

    PubMed

    Beyer, Sophie; Robin, Philippe; Ait-Si-Ali, Slimane

    2017-01-01

    Protein purification by tandem affinity purification (TAP)-tag coupled to mass spectrometry analysis is usually used to reveal protein complex composition. Here we describe a TAP-tag purification of chromatin-bound proteins along with associated nucleosomes, which allow exhaustive identification of protein partners. Moreover, this method allows exhaustive identification of the post-translational modifications (PTMs) of the associated histones. Thus, in addition to partner characterization, this approach reveals the associated epigenetic landscape that can shed light on the function and properties of the studied chromatin-bound protein.

  9. Phonon-coupled trap-assisted charge injection in metal-nitride-oxide-silicon/silicon-oxide-nitride-oxide-silicon structures

    NASA Astrophysics Data System (ADS)

    Nasyrov, K. A.; Shaimeev, S. S.; Gritsenko, V. A.; Han, J. H.

    2009-06-01

    A phonon-coupled trap model is proposed for trap-assisted injection mechanism in silicon-oxide-nitride-oxide-silicon (SONOS)/metal-nitride-oxide-silicon (MNOS) structures at low voltages. On the basis of this model, a theory of charge injection in SONOS/MNOS has been developed. Charge injection experimental data was fitted by this theory. Obtained trap parameters are close to those previously reported [K. A. Nasyrov et al., J. Appl. Phys. 96, 4293 (2004)], where the current dependence on temperature and electric field was investigated in MNOS.

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

    PubMed

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

    2012-06-22

    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-d₄)) 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-d₄. 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 μg/L), and analyzed each in quintuplicate. Satisfactory accuracy and precision, with recoveries

  11. Quantitative multiresidue analysis of antibiotics in milk and milk powder by ultra-performance liquid chromatography coupled to tandem quadrupole mass spectrometry.

    PubMed

    Tian, He; Wang, Jiaqi; Zhang, Yangdong; Li, Songli; Jiang, Jindou; Tao, Dali; Zheng, Nan

    2016-10-15

    A simple and fast multiresidue extraction and purification method was developed for the determination of 61 veterinary drugs, belonging to seven classes, in milk and milk powder. The extraction depends on the acetonitrile solvent, followed by a single step to remove lipids with fatty acid chains using a new reversed phase SPE without traditional pre-equilibration and washing steps before eluting SPE. The purifying lipid effect of the present preparation method was evaluated by comparing the response changes of ion peak areas of the milk endogenous metabolites before and after SPE treatment using ultra-fast LC coupled to tandem quadrupole and TOF MS. Subsequently, UPLC coupled to tandem quadrupole MS was performed for the quantitative analysis of milk and milk powder samples spiked with 61 veterinary drugs, including β-lactam, macrolide, amide alcohol, forest amine, sulfanilamide, tetracyclines, and quinolones antibiotics. This method is very simple, fast, sensitive, and selective, and allows the good recoveries of all compounds, with a recovery range of 61.5-118.6%, and coefficients of variation of less than 11.6%. The 61 compounds behave in the dynamic range 0.01-200μgkg(-1), with correlation coefficient >0.99. The limits of quantification for the analytes are in the range 0.01-5.18μgkg(-1). Finally, this method has been successfully applied to the screening of veterinary drugs in 50 commercial bovine milk and milk powder samples, and ceftiofur and ciprofloxacin were detected in some brand samples.

  12. Determination of methandrostenolone and its metabolites in equine plasma and urine by coupled-column liquid chromatography with ultraviolet detection and confirmation by tandem mass spectrometry.

    PubMed

    Edlund, P O; Bowers, L; Henion, J

    1989-02-24

    Monitoring steroid use requires an understanding of the metabolism in the species in question and development of sensitive methods for screening of the steroid or its metabolites in urine. Qualitative information for confirmation of methandrostenolone and identification of its metabolites was primarily obtained by coupled-column high-performance liquid chromatography-tandem mass spectrometry. The steroids and a sulphuric acid conjugate were isolated and identified by their daughter ion mass spectra in the urine of both man and the horse following administration of methandrostenolone. Spontaneous hydrolysis of methandrostenolone sulphate gave 17-epimethandrostenolone and several dehydration products. This reaction had a half-life of 16 min in equine urine at 27 degrees C. Mono- and dihydroxylated metabolites were also identified. Several screening methods were evaluated for detection and confirmation of methandrostenolone use including thin-layer chromatography and high-performance liquid chromatography. Coupled-column liquid chromatography was used for automated clean-up of analytes difficult to isolate by manual methods. The recovery of methandrostenolone was 101 +/- 3.3% (mean +/- S.D.) at 6.5 ng/ml and both methandrostenolone and 17-epimethandrostenolone were quantified in urine by ultraviolet detection up to six days after a 250-mg intramuscular dose to a horse. The utility of on-line tandem mass spectrometry for confirmation of suspected metabolites is also shown.

  13. Chemical constituents of Meconopsis horridula and their simultaneous quantification by high-performance liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Liu, Jiajia; Wu, Haimei; Zheng, Feng; Liu, Wenyuan; Feng, Feng; Xie, Ning

    2014-09-01

    Meconopsis horridula Hook.f. Thoms has been used as a traditional Tibetan medicine to clear away heat, relieve pain, and mobilize static blood. In this study, a reliable method based on high-performance liquid chromatography with diode array detection and electrospray ionization quadrupole time-of-flight tandem mass spectrometry was established for the identification of components in this herb. A total of 40 compounds (including 17 flavonoids, 15 alkaloids, and eight phenylpropanoids) were identified or tentatively identified. Among them, 17 components were identified in the herb for the first time. Compound 39 appears to be a novel compound, which is confirmed as 3-(kaempferol-8-yl)-2,3-epoxyflavanone by NMR spectroscopy and mass spectrometry. Moreover, seven major constituents were simultaneously quantified by the developed high-performance liquid chromatography with tandem triple-quadrupole mass spectrometry method. The quantitative method was validated and quality parameters were established. The study provides a comprehensive approach for understanding this herbal medicine.

  14. [Oxidative efficiency of the system of electrolysis coupled ozonation].

    PubMed

    Zhou, Qi; Zhang, Rong; Wang, Xun-Hua; Tong, Shao-Ping; Ma, Chun-An

    2010-09-01

    The oxidation system of electrolysis coupled ozonation (electrolysis-ozonation) was used to degrade 4-chlorophenol (4-CP), and its mechanism was discussed on the basis of kinetic analysis. The experimental results indicated the electrolysis-ozonation system had a significant synergistic effect during degradation of 4-CP. For example, the electrolysis-ozonation had the 4-CP removal rate of 92.7% and the COD removal rate of 64.9% in 900 s, respectively; while electrolysis alone plus ozonation alone only had the 4-CP removal rate of 69.7% and the COD removal rate of 30.1% under the same conditions. The results of H2O2 concentration analysis and photocurrent test showed that the synergistic mechanism of electrolysis-ozonation included two factors: (1) production of *03- at the cathode; (2) H2O2 generation resulting from reduction of dissolved oxygen. The above two factors led to generation of *OH in system effectively.

  15. Coupling Oxygen Consumption with Hydrocarbon Oxidation in Bacterial Multicomponent Monooxygenases.

    PubMed

    Wang, Weixue; Liang, Alexandria D; Lippard, Stephen J

    2015-09-15

    A fundamental goal in catalysis is the coupling of multiple reactions to yield a desired product. Enzymes have evolved elegant approaches to address this grand challenge. A salient example is the biological conversion of methane to methanol catalyzed by soluble methane monooxygenase (sMMO), a member of the bacterial multicomponent monooxygenase (BMM) superfamily. sMMO is a dynamic protein complex of three components: a hydroxylase, a reductase, and a regulatory protein. The active site, a carboxylate-rich non-heme diiron center, is buried inside the 251 kDa hydroxylase component. The enzyme processes four substrates: O2, protons, electrons, and methane. To couple O2 activation to methane oxidation, timely control of substrate access to the active site is critical. Recent studies of sMMO, as well as its homologues in the BMM superfamily, have begun to unravel the mechanism. The emerging and unifying picture reveals that each substrate gains access to the active site along a specific pathway through the hydroxylase. Electrons and protons are delivered via a three-amino-acid pore located adjacent to the diiron center; O2 migrates via a series of hydrophobic cavities; and hydrocarbon substrates reach the active site through a channel or linked set of cavities. The gating of these pathways mediates entry of each substrate to the diiron active site in a timed sequence and is coordinated by dynamic interactions with the other component proteins. The result is coupling of dioxygen consumption with hydrocarbon oxidation, avoiding unproductive oxidation of the reductant rather than the desired hydrocarbon. To initiate catalysis, the reductase delivers two electrons to the diiron(III) center by binding over the pore of the hydroxylase. The regulatory component then displaces the reductase, docking onto the same surface of the hydroxylase. Formation of the hydroxylase-regulatory component complex (i) induces conformational changes of pore residues that may bring protons to the

  16. Postmortem screening for fatty acid oxidation disorders by analysis of Guthrie cards with tandem mass spectrometry in sudden unexpected death in infancy.

    PubMed

    Wilcox, Rebecca L; Nelson, Cliff C; Stenzel, Peter; Steiner, Robert D

    2002-12-01

    A protocol was developed for the detection of fatty acid oxidation disorders (FOD) in cases of sudden unexpected death in infancy (SUDI). Tandem mass spectrometry blood acylcarnitine analysis of Guthrie card blood spots was performed. In the first 5 years, 1.2% of Oregon's 247 SUDI cases were identified with FOD, 2 with medium-chain acyl-CoA dehydrogenase deficiency, and one with very long-chain acyl-CoA dehydrogenase deficiency.

  17. A formal anti-Markovnikov hydroamination of allylic alcohols via tandem oxidation/1,4-conjugate addition/1,2-reduction using a Ru catalyst.

    PubMed

    Nakamura, Yushi; Ohta, Tetsuo; Oe, Yohei

    2015-05-01

    A formal anti-Markovnikov hydroamination of allylic alcohols using a Ru catalyst via tandem oxidation/1,4-conjugate addition/1,2-reduction was developed. Thus, the reaction of allylic alcohols with amines was performed in the presence of the catalyst generated from RuClH(CO)(PPh3)3 and 2,6-bis(n-butyliminomethyl)pyridine in situ to afford the corresponding γ-amino alcohols efficiently.

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

    NASA Astrophysics Data System (ADS)

    Subedi, Kiran; Trejos, Tatiana; Almirall, José

    2015-01-01

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

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

    NASA Technical Reports Server (NTRS)

    Shanks, Robert E.

    1958-01-01

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

  20. Characterization of the potential new phthalides in Ligusticum chuanxiong Hort. using ultra performance liquid chromatography coupled with quadrupole time of flight tandem mass spectrometry.

    PubMed

    Zhang, Qingqing; Wang, Meiling; Wang, Qing; Zhao, Huizhen; Zhang, Zhixin; Yu, Honghong; Liu, Yuehong; Fu, Shuang; Lu, Zhiwei; Huang, Zhenghai; Xie, Ziye; Gao, Xiaoyan; Qiao, Yanjiang

    2017-03-29

    The characterization of unknown compounds is still a great challenge currently. A strategy for deduction of potential new phthalides through the characterization of isomers based on ultra performance liquid chromatography coupled with quadrupole time of flight tandem mass spectrometry was proposed here to characterize the unknown compounds of Ligusticum chuanxiong Hort. (Chuanxiong). This proposed strategy consisted of four steps: 1) the high resolution MS data was collected, and the peaks were screened preliminarily by UNIFI(TM) platform based on the in-house database; 2) the fragmentation patterns and the characteristic fragments were summarized based on the representative standards; 3) the target compounds were identified based on the fragmentation rules, standards comparison and false positive exclusion; 4) the unknown components were structurally characterized according to the accurate mass and fragmentation patterns analysis. This strategy was successfully applied to the identification and deduction of phthalides in Chuanxiong. A total of 81 phthalides were detected. 55 known phthalides were identified, and 26 potential new phthalides were characterized. This research enriched the material basis of Chuanxiong, and provided a liquid chromatography tandem mass spectrometry-oriented method for the discovery of the potential new compounds. This article is protected by copyright. All rights reserved.

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

    PubMed

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

    2015-01-01

    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 (100 mm × 2.1 mm × 1.7 μm) within 4.6 min 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 0.5 ng mL(-1) (limit of quantification - LOQ) to 50 ng mL(-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.

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

    PubMed

    Jiao, Zhe; Zhang, Suling; Chen, Hongwei

    2015-01-01

    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 μg/g and oxytetracycline was found at 0.14 and 0.21 μg/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.

  3. Sensitive analysis of anti-HIV drugs, efavirenz, lopinavir and ritonavir, in human hair by liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Huang, Yong; Gandhi, Monica; Greenblatt, Ruth M; Gee, Winnie; Lin, Emil T; Messenkoff, Nicholas

    2008-11-01

    A highly sensitive and selective method using liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS) was developed and validated for the measurement of three antiretroviral agents, efavirenz, lopinavir and ritonavir, in human hair. Hair samples from adherent HIV-infected patients on antiretroviral therapies were cut into about 1 mm length segments and drugs were extracted by first shaking the samples with methanol in a 37 degrees C water bath overnight (>14 h), followed by methyl tert-butyl ether/ethyl acetate (1:1) extraction under weak alkaline conditions. The extracted lopinavir and ritonavir were separated by reversed-phase chromatography and detected by tandem mass spectrometry in electrospray positive ionization mode with multiple reaction monitoring (MRM), while efavirenz was monitored in negative ionization MRM mode. This method was validated from 0.01 to 4.0 ng/mg hair for ritonavir and 0.05-20 ng/mg hair for lopinavir and efavirenz by using 2 mg of a human hair sample. The interday and intraday assay precision (coefficients of variation, CV) for spiked quality control (QC) samples at low, medium and high concentrations were within 15% and accuracy ranged from 89% to 110%. Assay reproducibility was also demonstrated by analysis of incurred hair QC samples (CV <14%). No significant matrix ionization suppression was observed. This developed method allowed for the monitoring of these target medications in the hair samples of HIV-infected women on antiretroviral therapy in an observational study using small amounts of hair.

  4. Surface Proton Hopping and Coupling Pathway of Water Oxidation on Cobalt Oxide Catalyst

    NASA Astrophysics Data System (ADS)

    Pham, Hieu; Cheng, Mu-Jeng; Frei, Heinz; Wang, Lin-Wang

    We propose an oxidation pathway of water splitting on cobalt oxide surface with clear thermodynamic and kinetic details. The density-functional theory studies suggest that the coupled proton-electron transfer is not necessarily sequential and implicit in every elementary step of this mechanistic cycle. Instead, the initial O-O bond could be formed by the landing of water molecule on the surface oxos, which is then followed by the dispatch of protons through the hopping manner and subsequent release of di-oxygen. Our theoretical investigations of intermediates and transition states indicate that all chemical conversions in this pathway, including the proton transfers, are possible with low activation barriers, in addition to their favorable thermodynamics. Our hypothesis is supported by recent experimental observations of surface superoxide that is stabilized by hydrogen bonding to adjacent hydroxyl group, as an intermediate on fast-kinetics catalytic site.

  5. Screening inhibitors of xanthine oxidase from natural products using enzyme immobilized magnetic beads by high-performance liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Wang, Ting; Li, Dapeng; Yu, Boyang; Qi, Jin

    2017-03-06

    In this study, high-performance liquid chromatography coupled with tandem mass spectrometry was used to assess the results of bioactive compound screening from natural products using immobilized enzyme magnetic beads. We compared three commercial magnetic beads with modified amino, carboxy and N-hydroxysuccinimide groups, respectively. Amino magnetic beads performed best for immobilization and were selected for further experiments. Xanthine oxidase was immobilized on amino magnetic beads and applied to screen potential inhibitors in fresh Zingiber officinale Roscoe, extracts of Scutellaria baicalensis Georgi and Pueraria lobata Ohwi. In total, 12 potential xanthine oxidase ligands were identified from fresh Zingiber root and Scutellaria root extracts, of which eight were characterized and the concentration required for 50% inhibition was determined. Preliminary structure-function relationships were discussed based on these results. A convenient and effective method was therefore developed for the identification of active compounds from complex natural product mixtures. This article is protected by copyright. All rights reserved.

  6. Determination of nucleosides and nucleotides in baby foods by hydrophilic interaction chromatography coupled to tandem mass spectrometry in the presence of hydrophilic ion-pairing reagents.

    PubMed

    Mateos-Vivas, María; Rodríguez-Gonzalo, Encarnación; Domínguez-Álvarez, Javier; García-Gómez, Diego; Carabias-Martínez, Rita

    2016-11-15

    In this work we propose a rapid and efficient method for the joint determination of nucleosides and nucleotides in dairy and non-dairy baby foods based on hydrophilic interaction chromatography coupled to tandem mass spectrometry in the presence of diethylammonium (DEA) as a hydrophilic ion-pairing reagent (IP-HILIC-MS/MS). Sample treatment of the baby food included dilution with water and centrifugal ultrafiltration (CUF) with an additional washing step that notably improved the global performance of the process. Later dilution of the extract with acetonitrile allowed adequate separation in the HILIC system. With the proposed treatment, we obtained extraction recoveries higher than 80% and, additionally, no matrix effects were observed. The CUF-IP-HILIC-MS/MS method was validated according to the 2002/657/EC decision and was used for the quantification of nucleotides and nucleosides in sixteen samples of commercial baby foods.

  7. The role of nitric oxide in neurovascular coupling.

    PubMed

    Dormanns, K; Brown, R G; David, T

    2016-04-07

    Nitric oxide (NO) is a neurotransmitter known to act as a potent cerebral vasodilator. Its role in neurovascular coupling (NVC) is discussed controversially and one of the main unanswered questions is which cell type provides the governing source of NO for the regulation of vasodynamics. Mathematical modelling can be an appropriate tool to investigate the contribution of NO towards the key components of NVC and analyse underlying mechanisms. The lumped parameter model of a neurovascular unit, including neurons (NE), astrocytes (AC), smooth muscle cells (SMC) and endothelial cells (EC), was extended to model the NO signalling pathway. Results show that NO leads to a general shift of the resting regional blood flow by dilating the arteriolar radius. Furthermore, dilation during neuronal activation is enhanced. Simulations show that potassium release is responsible for the fast onset of vascular response, whereas NO-modulated mechanisms maintain dilation. Wall shear stress-activated NO release from the EC leads to a delayed return to the basal state of the arteriolar radius. The governing source of vasodilating NO that diffuses into the SMC, which determine the arteriolar radius, depends on neuronal activation. In the resting state the EC provides the major contribution towards vasorelaxation, whereas during neuronal stimulation NO produced by the NE dominates.

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

    PubMed

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

    2014-07-01

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

  9. A direct temperature-resolved tandem mass spectrometry study of cholesterol oxidation products in light-aged egg tempera paints with examples from works of art

    NASA Astrophysics Data System (ADS)

    van den Brink, Oscar F.; Ferreira, Ester S. B.; van der Horst, Jerre; Boon, Jaap J.

    2009-07-01

    Cholesterol (1) constitutes approximately 5% of the lipid fraction of eggs. The compound is therefore abundant in fresh egg tempera paints. The fate of cholesterol upon light ageing of egg tempera paint binding medium was investigated by direct temperature resolved mass spectrometry (DTMS) and tandem mass spectrometry (DTMSMS). Cholesterol oxidation products (COPs) such as 5,6-epoxycholestan-3-ol (2) and 3-hydroxycholest-5-en-7-one (3) were positively identified in light-aged egg binding medium. Given the fast rate of oxidation of cholesterol, the corresponding oxidation products are better markers for egg tempera than the cholesterol molecule itself. Cholesterol and COPs were discovered in paints on German baroque altar pieces from the 16th and 18th C and in a 20th C glaze on a Mark Rothko Seagram Mural painting at Tate by DTMS fingerprinting analysis of paint microsamples.

  10. Determination of abacavir, tenofovir, darunavir, and raltegravir in human plasma and saliva using liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Yamada, Eiko; Takagi, Ritsuo; Sudo, Koji; Kato, Shingo

    2015-10-10

    A liquid chromatography-tandem mass spectrometry assay for the determination of abacavir (ABC), tenofovir (TFV), darunavir (DRV), and raltegravir (RAL) in human plasma and saliva was developed and validated to investigate the applicability of saliva as an appropriate specimen for therapeutic drug monitoring. As internal standards, TFV was chosen for ABC, ABC was chosen for TFV, RAL for DRV, and DRV for RAL. Sample preparation involved protein precipitation with acetonitrile, evaporation of solvent using a centrifugal evaporator, and reconstitution by dissolving the residue in mobile phase. Liquid chromatography was performed on a C18 reverse phase column (1.5 × 50 mm, 5 μm) isocratically at a flow rate of 0.2 mL/min using 5mM formic acid-3% (v/v) acetonitrile as the mobile phase for ABC and TFV and 5mM formic acid-35% (v/v) acetonitrile as the mobile phase for DRV and RAL. The run time was 6 min, and the retention time was approximately 2.0 min for TFV, 2.5 min for RAL, and 4-4.5 min for ABC and DRV. Analytes were detected using tandem mass spectrometry in positive electrospray ionization mode. The precursor/product ion transitions (m/z) were 287.3/191.2 for ABC, 288.5/176.2 for TFV, 548.3/392.3 for DRV, and 445.3/109.5 for RAL, and were monitored on a triple-quadrupole mass spectrometer operated in the multiple reaction monitoring mode. The linearity of the assay was assessed in the range 1-10,000 ng/mL for all four drugs. Within-run and between-run mean accuracy, precision, and the extraction recovery for all drugs were -14.5-18.1%, 1.2-13.1%, and 86.0-111.1%, respectively. The proposed assay is sufficiently sensitive and accurate to quantify these drugs in plasma and saliva, and is suitable for investigating the relationship between drug concentrations in plasma and saliva.

  11. Profiling and Preparation of Metabolites from Pyragrel in Human Urine by Online Solid-Phase Extraction Coupled with High Performance Liquid Chromatography Tandem Mass Spectrometry Followed by a Macroporous Resin-Based Purification Approach.

    PubMed

    Zhao, Xin; Jiang, Jingjing; Yang, Guang; Huang, Jie; Yang, Guoping; He, Guangwei; Chu, Zhaoxing; Hang, Taijun; Fan, Guorong

    2017-03-21

    Pyragrel, a new anticoagulant drug, is derived from the molecular combination of ligustrazine and ferulic acid. Pyragrel showed significant inhibitory activity against platelet aggregation induced by adenosine diphosphate (ADP), and had been approved for a phase I clinical trial by CFDA. To characterize the metabolites of Pyragrel in human urine after intravenous administration, a reliable online solid-phase extraction couple with high performance liquid chromatography tandem mass spectrometry (online SPE-HPLC-MS(n)) method was conceived and applied. Five metabolites were detected and tentatively identified, which suggested that the major metabolic pathways of Pyragrel in human were double-bond reduction, double-bond oxidation, and then followed by glucuronide conjugation. Two main metabolites were then prepared using β-glucuronide hydrolysis and macroporous resin purification approach followed by preparative high-performance liquid chromatography (PHPLC) method, with their structures confirmed on the basis of nuclear magnetic resonance (NMR) data. This study provided information for the further study of the metabolism and excretion of Pyragrel.

  12. Coupled biotic-abiotic Mn(II) oxidation pathway mediates the formation and structural evolution of biogenic Mn oxides

    NASA Astrophysics Data System (ADS)

    Learman, D. R.; Wankel, S. D.; Webb, S. M.; Martinez, N.; Madden, A. S.; Hansel, C. M.

    2011-10-01

    Manganese (Mn) oxides are among the strongest oxidants and sorbents in the environment, impacting the transport and speciation of metals, cycling of carbon, and flow of electrons within soils and sediments. The oxidation of Mn(II) to Mn(III/IV) oxides has been primarily attributed to biological processes, due in part to the faster rates of bacterial Mn(II) oxidation compared to observed mineral-induced and other abiotic rates. Here we explore the reactivity of biogenic Mn oxides formed by a common marine bacterium ( Roseobacter sp. AzwK-3b), which has been previously shown to oxidize Mn(II) via the production of extracellular superoxide. Oxidation of Mn(II) by superoxide results in the formation of highly reactive colloidal birnessite with hexagonal symmetry. The colloidal oxides induce the rapid oxidation of Mn(II), with dramatically accelerated rates in the presence of organics, presumably due to mineral surface-catalyzed organic radical generation. Mn(II) oxidation by the colloids is further accelerated in presence of both organics and light, implicating reactive oxygen species in aiding abiotic oxidation. Indeed, the enhancement of Mn(II) oxidation is negated when the colloids are reacted with Mn(II) in the presence of superoxide dismutase, an enzyme that scavenges the reactive oxygen species (ROS) superoxide. The reactivity of the colloidal phase is short-lived due to the rapid evolution of the birnessite from hexagonal to pseudo-orthogonal symmetry. The secondary particulate triclinic birnessite phase exhibits a distinct lack of Mn(II) oxidation and subsequent Mn oxide formation. Thus, the evolution of initial reactive hexagonal birnessite to non-reactive triclinic birnessite imposes the need for continuous production of new colloidal hexagonal particles for Mn(II) oxidation to be sustained, illustrating an intimate dependency of enzymatic and mineral-based reactions in Mn(II) oxidation. Further, the coupled enzymatic and mineral-induced pathways are linked

  13. Simultaneous determination of irbesartan and hydrochlorothiazide in human plasma using HPLC coupled with tandem mass spectrometry: Application to bioequivalence studies.

    PubMed

    Tutunji, Lara F; Tutunji, Maha F; Alzoubi, Mamoun I; Khabbas, Manal H; Arida, Adi I

    2010-03-11

    A sensitive, specific and selective liquid chromatography/tandem mass spectrometric method has been developed and validated for the simultaneous determination of irbesartan and hydrochlorothiazide in human plasma. Plasma samples were prepared using protein precipitation with acetonitrile, the two analytes and the internal standard losartan were separated on a reverse phase C(18) column (50mmx4mm, 3microm) using water with 2.5% formic acid, methanol and acetonitrile (40:45:15, v/v/v (%)) as a mobile phase (flow rate of 0.70mL/min). Irbesartan and hydrochlorothiazide were ionized using ESI source in negative ion mode, prior to detection by multiple reaction monitoring (MRM) mode while monitoring at the following transitions: m/z 296-->269 and m/z 296-->205 for hydrochlorothiazide, 427-->175 for irbesartan. Linearity was demonstrated over the concentration range 0.06-6.00microg/mL for irbesartan and 1.00-112.00ng/mL for hydrochlorothiazide. The developed and validated method was successfully applied to a bioequivalence study of irbesartan (300mg) with hydrochlorothiazide (12.5mg) tablet in healthy volunteers (N=36).

  14. Determination of polycyclic aromatic hydrocarbons in soy isoflavone nutraceutical products by gas chromatography coupled to triple quadrupole tandem mass spectrometry.

    PubMed

    Ruiz-Delgado, Ana; Martínez-Domínguez, Gerardo; Romero-González, Roberto; López-Ruiz, Rosalía; Frenich, Antonia Garrido

    2016-02-01

    Thirteen polycyclic aromatic hydrocarbons have been determined in soy-based nutraceutical products. First, an optimization of extraction procedure was performed, and a solid-liquid extraction assisted by sonication and a dilute and shoot procedure were compared, selecting the dilute and shoot approach for the extraction of target compounds, utilizing a mixture of acetone/n-hexane (1:1 v/v) as extractant solvent. After this, a clean-up step was needed bearing in mind the complexity of these matrices. Dispersive solid-phase extraction, using a mixture of C18 and Zr-Sep+ (25 mg/mL each) was used. The separation was achieved by gas chromatography and detection with triple quadrupole tandem mass spectrometry. For quantification purposes, matrix-matched calibration was used. The validation was applied at three concentration levels (20, 100 and 250 μg/kg), obtaining recoveries between 70 and 120% and precision values equal to or lower than 23%. Limits of detection and quantification were below 8 and 20 μg/kg, respectively. The method was applied in 11 samples, detecting five polycyclic aromatic hydrocarbons at concentrations ranging from 4.1 to 18.5 μg/kg.

  15. Determination of nicotine and its metabolites accumulated in fish tissue using hydrophilic interaction liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Chang, Yun-Wei; Nguyen, Hien P; Chang, Mike; Burket, S Rebekah; Brooks, Bryan W; Schug, Kevin A

    2015-07-01

    The determination of nicotine and its major metabolites (cotinine and anabasine) in fish tissue was performed using liquid chromatography and tandem mass spectrometry. Marine and freshwater fish were purchased from local grocery stores and were prepared based on a quick, easy, cheap, effective, rugged, and safe sample preparation protocol. To determine the highly polar compounds, hydrophilic interaction liquid chromatography was also used. There were modest suppressions on measured nicotine signals (10%) due to the matrix effects from marine fish but no obvious effects on freshwater fish signals. Method validation was incorporated with internal standards and carried out with matrix-matched calibration. The detection limits for nicotine, cotinine, and anabasine were 9.4, 3.0, and 1.5 ng/g in fish, respectively. Precision was quite acceptable returning less than 8% RSD at low, medium, and high concentrations. Acceptable and reproducible extraction recoveries (70-120%) of all three compounds were achieved, except for anabasine at low concentration (61%). The method was then applied to define nicotine bioaccumulation in a fathead minnow model, which resulted in rapid uptake with steady state internal tissue levels, reached within 12 h. This developed method offers a fast, easy, and sensitive way to evaluate nicotine and its metabolite residues in fish tissues.

  16. A graphene tip coupled with liquid chromatography tandem mass spectrometry for the determination of four synthetic adulterants in slimming supplements.

    PubMed

    Jin, Renyao; Li, Linqiu; Guo, Lianxian; Li, Weiqiao; Shen, Qing

    2017-06-01

    Slimming supplements were popularly sold online driven by the increasement of obesity and the development of social networking platform. However, events of drug abuse in slimming supplements were also frequently reported. In this study, a graphene tip solid-phase extraction (Gtip SPE) and ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method was established for determining fenfluramine, phenolphthalein, bumetanide, and sibutramine in slimming supplements. It was validated in terms of linearity (0.9985-0.9995), LOD (1.8ngmL(-1)), LOQ (5.6ngmL(-1)), intra-day precision (<5.1%), inter-day precision (<7.3%), and recovery (82.9-95.2%). Sibutramine is the most commonly used drug, which was detected in Bihais, Galong, and Aolist, with content 12.4, 3.6, 20.3mgg(-1), respectively. Phenolphthalein was also found with content lower than 5.2mgg(-1). The successful application of Gtip SPE and UPLC-MS/MS method indicated its advantage in analyzing low level of contaminates resulted from violation of regulation.

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

    PubMed

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

    2012-12-01

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

  18. [Determination of eight defoliant residues in cotton by accelerated solvent extraction coupled with ultra performance liquid chromatography-tandem mass spectrometry].

    PubMed

    Wu, Gang; Dong, Suozhuai; Pan, Lulu; Zhao, Shanhong; Wang, Lijun; Guo, Fanglong; Li, Dan

    2013-07-01

    A novel method has been developed for the rapid extraction and determination of eight defoliants including thidiazuron, butiphos, methabenzthiazuron, abscisic acid, carfentra-zone-ethyl, diuron, paraquat, and pyrithiobac-sodium in cotton by accelerated solvent extraction (ASE) coupled with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The defoliants in cotton were extracted by ASE and the extracts were dried by a rotavapor, then redissolved in the solvents of acetonitrile and water (1:9, v/v). The chromatographic analysis was performed on an Acquity UPLC HSS T3 column (50 mmx 2. 1 mm, 1. 8 microm) by a gradient elution employing of acetonitrile and 0.05% (v/v) formic acid as mobile phases. The analytes were detected by electrospray ionization (ESI) tandem mass spectrometry with multiple reaction monitoring (MRM) in positive ion mode. Good linearities (r >0.99) were observed between 0. 01 and 0. 3 mg/L for all the compounds. The recoveries and relative standard deviations (RSDs) were obtained by spiking untreated samples with the eight defoliants at 0. 1, 0. 5 and 1.0 mg/kg. The average recoveries of the eight defoliants were from (84. 18 +/- 8.04)% to (95.99 +/- 6.76)%. The precision values expressed as RSDs were from 7. 04% to 10. 60% (n = 6). The limits of detection were 0. 8 - 29 microg/kg and the limits of quantification were 2.5 - 96 1/4g/kg for the analytes. The results ahowed that the method is simple, rapid, sensitive and accurate, and is suitable for the quantitative determination and confirmation of the eight defoliants in cotton.

  19. Oxidative coupling of methane over oxide-supported sodium-manganese catalysts

    SciTech Connect

    Wang, Dingjun; Rosynek, M.P.; Lunsford, J.H.

    1995-09-01

    The oxidative coupling of methane over Mn/Na{sub 2}WO{sub 4}/SiO{sub 2}, Mn/Na{sub 2}WO{sub 4}/MgO, and NaMnO{sub 4}/MgO catalysts was studied using both a cofeed flow system and a pulse reactor. At 800{degrees}C and 1 atm, and using a CH{sub 4}/O{sub 2} ratio of ca. 8/1, a methane conversion of 20% was achieved at a C{sub 2+} selectivity of {ge}80%, with no diluent in the reagents. The similar catalytic behaviors of the three catalysts suggest that a common active site, consisting of an Na-O-Mn species, may be involved. Results from a pulse reaction sequence (an O{sub 2} pulse followed by a series of pure CH{sub 4} pulses) indicate that the active species are not stable under reaction conditions unless gas phase O{sub 2} is present, and that bulk lattice oxygen does not participate in the methane coupling reaction when carried out in the cofeed mode. There is a linear relationship between the specific activity for CH{sub 4} conversion and the concentration of surface Mn, which is believed to be responsible for the activation of O{sub 2}. The resulting form of oxygen then abstracts a hydrogen atom from CH{sub 4}. Sodium is essential for preventing the complete oxidation of CH{sub 4}, perhaps by isolating the Mn ions. The tungstate ions appear to impart stability to the catalysts. 39 refs., 11 figs., 5 tabs.

  20. Determination of ultratrace levels of tributyltin in waters by isotope dilution and gas chromatography coupled to tandem mass spectrometry.

    PubMed

    Rodríguez-Cea, Andrés; Rodríguez-González, Pablo; Font Cardona, Nuria; Aranda Mares, José Luís; Ballester Nebot, Salomé; García Alonso, J Ignacio

    2015-12-18

    The current EU legislation lays down the Environmental Quality Standards (EQS) of 45 priority substances in surface water bodies. In particular, the concentration of tributyltin (TBT) must not exceed 0.2ngL(-1) and analytical methodologies with a Limit of Quantification (LOQ) equal or below 0.06ngL(-1) are urged to be developed. This work presents a procedure for the determination of ultratrace levels of TBT in water samples by Isotope Dilution and GC-MS/MS operating in Selected Reaction Monitoring (SRM) mode which meets current EU requirements. The method requires the monitorization of five consecutive transitions (287>175 to 291>179) for the sensitive and selective detection of TBT. The measured isotopic distribution of TBT fragment ions was in agreement with the theoretical values computed by a polynomial expansion algorithm. The combined use of Tandem Mass Spectrometry, a sample volume of 250mL, the preconcentration of 1mL of organic phase to 30μL and an injection volume of 25μL by Programmed Temperature Vaporization provided a LOQ of 0.0426ngL(-1) for TBT (calculated as ten times the standard deviation of nine independent blanks). The recovery for TBT calculated in Milli-Q water at the EQS level was 106.3±4%. A similar procedure was also developed for the quantification of dibutyltin (DBT) and monobutyltin (MBT) in water samples showing satisfactory results. The method was finally implemented in a routine testing laboratory to demonstrate its applicability to real samples obtaining quantitative recoveries for TBT at the EQS level in mineral water, river water and seawater.

  1. Robust analysis of underivatized free amino acids in soil by hydrophilic interaction liquid chromatography coupled with electrospray tandem mass spectrometry.

    PubMed

    Gao, Jiajia; Helmus, Rick; Cerli, Chiara; Jansen, Boris; Wang, Xiang; Kalbitz, Karsten

    2016-06-03

    Amino acids are an important and highly dynamic fraction of organic N in soils and their determination in soil without derivatization is challenging due to the difficulties in separation and detection of trace amounts of these polar analytes. In the present work, we developed an analytical method to quantify 20 free amino acids in aqueous soil extracts without derivatization. The method employed hydrophilic interaction liquid chromatography-tandem mass spectrometry (HILIC-MS/MS) technique combined with a cation exchange solid phase extraction (SPE). Four stable isotope labelled amino acids were used as internal standards to improve the method performance. Good separation of 20 underivatized amino acids was achieved within 12min. The limit of detection (LODs) and limit of quantification (LOQs) were in the range of 13-384ngg(-1) and 43-1267ngg(-1) (dry soil basis), respectively. The results showed that overall recoveries with high precision were obtained for the extracted free amino acids from ten different soils. The overall recoveries of 18 amino acids were similar for the ten soils used, which differed substantially in organic C content and in other properties as soil texture and pH. For most of the amino acids, the average recoveries from soil extracts were between 74% and 117%, with the exception of Met (31%), Pro (52%) and Arg (68%). Variability was within acceptable limits (relative standard deviations were between 4% and 13%), with the exception of Met (relative standard deviation=90%) and Arg (relative standard deviation=53%). Thus the proposed method with high throughout and high analyte specificity shows great promise for consistent analysis of free amino acids extracted from soils and offers new horizons for the analysis of amino acids in terrestrial and aquatic ecosystem.

  2. Harmonized Collaborative Validation of Aflatoxins and Sterigmatocystin in White Rice and Sorghum by Liquid Chromatography Coupled to Tandem Mass Spectrometry

    PubMed Central

    Ok, Hyun Ee; Tian, Fei; Hong, Eun Young; Paek, Ockjin; Kim, Sheen-Hee; Kim, Dongsul; Chun, Hyang Sook

    2016-01-01

    An interlaboratory study was performed in eight laboratories to validate a liquid chromatography–tandem mass spectrometry (LC/MS/MS) method for the simultaneous determination of aflatoxins and sterigmatocystin (STC) in white rice and sorghum (Sorghum bicolor). Fortified samples (at three different levels) of white rice and sorghum were extracted, purified through a solid-phase extraction (SPE) column, and then analyzed by LC/MS/MS. The apparent recoveries (ARs) ranged from 78.8% to 95.0% for aflatoxins and from 85.3% to 96.7% for STC. The relative standard deviations for repeatability (RSDr) and reproducibility (RSDR) of aflatoxins were in the ranges 7.9%–33.8% and 24.4%–81.0%, respectively. For STC, the RSDr ranged from 7.1% to 40.2% and the RSDR ranged from 28.1% to 99.2%. The Horwitz ratio values for the aflatoxins and STC ranged from 0.4 to 1.2 in white rice and from 0.3 to 1.0 in sorghum, respectively. These results validated this method for the simultaneous determination of aflatoxins and STC by LC/MS/MS after SPE column cleanup. The percentages of satisfactory Z-score values (|Z| ≤ 2) were the following: for white rice, 100% for aflatoxins and STC; for sorghum, 100%, except in data from two laboratories for STC (0.3 μg/kg). This validated that the LC/MS/MS method was successfully applied for the determination of aflatoxins and STC in 20 white rice and 20 sorghum samples sourced from Korean markets. PMID:27983588

  3. Quantitative determination of the diastereoisomers of hexabromocyclododecane in human plasma using liquid chromatography coupled with electrospray ionization tandem mass spectrometry.

    PubMed

    Tang, Caiming

    2010-12-01

    A sensitive, simple and feasible method has been developed and validated for the simultaneous determination of three diastereoisomers of hexabromocyclododecane (HBCD) in human plasma using liquid chromatography tandem mass spectrometry (LC-MS/MS). The simple pretreatment generally involved protein precipitation with methanol (MeOH). The separation was performed with a C18 reverse phase column. The mobile phases were 5mM ammonium acetate (NH(4)AC) in water and acetonitrile (ACN). The mass spectrometer was operated using negative electrospray ionization (ESI) source and the data acquisition was carried out with multiple reaction monitoring (MRM) mode. The analyte quantifications were performed by external standard method with matrix-matched calibration curves. The method was partially validated with the evaluations of accuracy, precision, linearity, limit of quantification (LOQ), limit of detection (LOD), recovery, matrix effect and carryover effect. With the present method, the intra-batch accuracies were 94.7-104.3%, 91.9-109.3% and 89.8-105.0% for α-, β- and γ-HBCD, respectively. And the inter-batch accuracies were ranged from 94.2% to 109.7%. Both intra-batch and inter-batch precisions (relative standard deviation, RSD, %) of the analytes were no more than 11.2%. The recoveries were from 79.0% to 108.9% and the LOQ was 10pg/mL for each diastereoisomer. The linear range was 10-10,000pg/mL with the linear correlation coefficient R(2)>0.996. No significant matrix effect and carryover effect of the analytes were observed in this study. This method is in possession of sufficient resolution, high sensitivity as well as selectivity and convenient to be applied to the trace determination of HBCDs in human plasma.

  4. A Proteomic View of Desulfovibrio Vulgaris Metabolim as Determined by Liquid Chromatography Coupled with Tandem Mass Spectrometry

    SciTech Connect

    Zhang, Weiwen; Gritsenko, Marina A.; Moore, Ronald J.; Culley, David E.; Nie, Lei; Petritis, Konstantinos; Strittmatter, Eric F.; Camp, David G.; Smith, Richard D.; Brockman, Fred J.

    2006-08-15

    Direct liquid chromatography-tandem mass spectrometry (LC-MS/MS) was used to examine the proteins from Desulfovibrio vulgaris grown at exponential or stationary phase on a minimal medium containing either lactate or formate as the primary carbon source, with the goal of an initial characterization of the diversity of proteins synthesized under these conditions. Across all four growth conditions, 976 gene products were identified with high confidence, which is equal to approximately 28% of all predicted proteins in the D. vulgaris genome. Among these, fifty-two out of 55 predicted ribosomal proteins (~95%) were identified with high confidence. Functional analysis showed that the proteins identified were distributed among almost all functional classes, with the energy metabolism category containing the greatest number of identified proteins. At least 154 open reading frames (ORFs) originally annotated as hypothetical proteins were found to encode expressed proteins, which provided verification for the authenticity of these hypothetical proteins. Proteomic analysis showed that members of the proton gradient pathway, catalyzed by alcohol dehydrogenases and heterodisulfide reductases, and [NiFe] hydrogenase (HynAB-1) of the hydrogen cycling pathway were highly expressed in all four growth conditions, suggesting they may be the primary pathways for ATP synthesis in D. vulgaris. Most of the enzymes involved in substrate-level phosphorylation were also detected in all tested conditions. However, no enzyme involved in CO cycling or formate cycling was detected, suggesting these are not the primary pathways for ATP biosynthesis under the tested conditions. This study provides the first proteomic overview of the cellular metabolism of D. vulgaris.

  5. Analysis of Amaryllidaceae alkaloids from Crinum by high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry.

    PubMed

    Zhang, Xi; Huang, Hao; Liang, Xu; Huang, Haiqiang; Dai, WeiXing; Shen, YunHeng; Yan, ShiKai; Zhang, WeiDong

    2009-09-01

    A high-performance liquid chromatography/electrospray ionization multi-stage tandem mass spectrometry (HPLC/ESI-MS(n)) method was developed to analyze two structurally related groups of Amaryllidaceae alkaloids (AmAs), crinane- and tazettine-type alkaloids, in the species Crinum latifolium and C. asiaticum, as well as different organs of C. latifolium. In ESI-MS(n) spectra of the two types of alkaloids, characteristic fragmentation reactions were observed that allowed us to determine and differentiate them. Based on the fragmentation rules of reference standards, crinane-type alkaloids displayed concurrent neutral loss of C(2)H(5)N (43 u) and C(2)H(6)N (44 u) as well as characteristic ions of m/z 213 and 211, whereas tazettine-type alkaloids exhibited neutral loss of C(3)H(7)N (57 u) [or C(2)H(5)N (43 u), C(3)H(7)NO (73 u)] from the [M+H](+) and [M+H-H(2)O](+) ions. These were supported by quadrupole time-of-flight (Q-Tof)-MS/MS analysis. The chemical complexity of the mixture was resolved by profiling. The compositions of the main crinane- and tazettine-type alkaloids in the above-mentioned species and organs were also compared. Overall, 28 AmAs comprising 14 crinane-type and 14 tazettine-type alkaloids were identified and studied by MS. Among them, 14 AmAs were tentatively characterized from the two species for the first time. This method allowed a rapid analysis of alkaloid distribution and composition of Crinum species, and may also be used for quality control and screening of extracts designated for pharmaceutical application.

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

    PubMed

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

    2015-04-07

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

  7. Chalcocite Oxidation and Coupled Carbon Dioxide Fixation by Thiobacillus ferrooxidans.

    PubMed

    Nielsen, A M; Beck, J V

    1972-03-10

    The reaction of cell suspensions of Thiobacillus ferrooxidans with pulverized chalcocite (Cu(2)S) in a Warburg manometric apparatus resulted in oxygen uptake accompanied by increased solubilization of copper and fixation of carbon dioxide. Since the only detectable oxidized products were cupric ions and the more oxidized form of the sulfide mineral, that is, digenite or covellite, the apparent source of energy for the carbon dioxide fixation was provided by the oxidation of the cuprous copper of the chalcocite.

  8. 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

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

    2014-01-01

    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 Δ((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.

  9. Silicon isotope ratio measurements by inductively coupled plasma tandem mass spectrometry for alteration studies of nuclear waste glasses.

    PubMed

    Gourgiotis, Alkiviadis; Ducasse, Thomas; Barker, Evelyne; Jollivet, Patrick; Gin, Stéphane; Bassot, Sylvain; Cazala, Charlotte

    2017-02-15

    High-level, long-lived nuclear waste arising from spent fuel reprocessing is vitrified in silicate glasses for final disposal in deep geologic formations. In order to better understand the mechanisms driving glass dissolution, glass alteration studies, based on silicon isotope ratio monitoring of (29)Si-doped aqueous solutions, were carried out in laboratories. This work explores the capabilities of the new type of quadrupole-based ICP-MS, the Agilent 8800 tandem quadrupole ICP-MS/MS, for accurate silicon isotope ratio determination for alteration studies of nuclear waste glasses. In order to avoid silicon polyatomic interferences, a new analytical method was developed using O2 as the reaction gas in the Octopole Reaction System (ORS), and silicon isotopes were measured in mass-shift mode. A careful analysis of the potential polyatomic interferences on SiO(+) and SiO2(+) ion species was performed, and we found that SiO(+) ion species suffer from important polyatomic interferences coming from the matrix of sample and standard solutions (0.5M HNO3). For SiO2(+), no interferences were detected, and thus, these ion species were chosen for silicon isotope ratio determination. A number of key settings for accurate isotope ratio analysis like, detector dead time, integration time, number of sweeps, wait time offset, memory blank and instrumental mass fractionation, were considered and optimized. Particular attention was paid to the optimization of abundance sensitivity of the quadrupole mass filter before the ORS. We showed that poor abundance sensitivity leads to a significant shift of the data away from the Exponential Mass Fractionation Law (EMFL) due to the spectral overlaps of silicon isotopes combined with different oxygen isotopes (i.e. (28)Si(16)O(18)O(+), (30)Si(16)O(16)O(+)). The developed method was validated by measuring a series of reference solutions with different (29)Si enrichment. Isotope ratio trueness, uncertainty and repeatability were found to be <0

  10. Quantification of urinary o,o'-dityrosine, a biomarker for oxidative damage to proteins, by high performance liquid chromatography with triple quadrupole tandem mass spectrometry. A comparison with ion-trap tandem mass spectrometry.

    PubMed

    Orhan, Hilmi; Coolen, Stefan; Meerman, John H N

    2005-11-15

    We recently described an isotope dilution reversed-phase liquid chromatography-atmospheric pressure chemical ionization-ion-trap-tandem mass spectrometry (HPLC-APCI-MS/MS) method for the quantitative determination of oxidized amino acids in human urine, including o,o'-dityrosine, a specific marker of protein oxidation. In the present study, we investigated the possibility to use a triple quadrupole instrument for the analysis of this biomarker in urine. The two instruments were compared in terms of sensitivity, specificity and reproducibility. Results showed that the triple quadrupole instrument reaches 2.5-fold higher sensitivity (LOD=0.01 microM) compared to the previously used ion-trap instrument. Precision of the present assay is as follows: in-day variation is 4.6% and inter-day variation is 17%. The currently developed method was applied to a group of smoker urine samples. The mean urinary o,o'-dityrosine concentration was 0.08+/-0.01 microM. Expressed per urinary creatinine concentration, this corresponds to 10.1+/-0.4 micromol/mol creatinine. This is comparable to the previously reported values of 5.8+/-0.3 micromol/mol creatinine in non-smokers night-time urines, and 12.3+/-5 micromol/mol creatinine in day-time urines measured by the ion-trap instrument.

  11. Coupling UV-H2O2 to accelerate dimethyl phthalate (DMP) biodegradation and oxidation.

    PubMed

    Chen, Bin; Song, Jiaxiu; Yang, Lihui; Bai, Qi; Li, Rongjie; Zhang, Yongming; Rittmann, Bruce E

    2015-11-01

    Dimethyl phthalate (DMP), an important industrial raw material, is an endocrine disruptor of concern for human and environmental health. DMP exhibits slow biodegradation, and its coupled treatment by means of advanced oxidation may enhance its biotransformation and mineralization. We evaluated two ways of coupling UV-H2O2 advanced oxidation to biodegradation: sequential coupling and intimate coupling in an internal circulation baffled biofilm reactor (ICBBR). During sequential coupling, UV-H2O2 pretreatment generated carboxylic acids that depressed the pH, and subsequent biodegradation generated phthalic acid; both factors inhibited DMP biodegradation. During intimately coupled UV-H2O2 with biodegradation, carboxylic acids and phthalic acid (PA) did not accumulate, and the biodegradation rate was 13 % faster than with biodegradation alone and 78 % faster than with biodegradation after UV-H2O2 pretreatment. Similarly, DMP oxidation with intimate coupling increased by 5 and 39 %, respectively, compared with biodegradation alone and sequential coupling. The enhancement effects during intimate coupling can be attributed to the rapid catabolism of carboxylic acids, which generated intracellular electron carriers that directly accelerated di-oxygenation of PA and relieved the inhibition effect of PA and low pH. Thus, intimate coupling optimized the impacts of energy input from UV irradiation used together with biodegradation.

  12. Nickel/magnesium-lanthanum mixed oxide catalyst in the Kumada-coupling.

    PubMed

    Kiss, Arpád; Hell, Zoltán; Bálint, Mária

    2010-01-21

    A new, heterogeneous, magnesium-lanthanum mixed oxide solid base-supported nickel(ii) catalyst was developed. The catalyst was used successfully in the Kumada coupling of aryl halides, especially aryl bromides. The optimal reaction conditions of the coupling were determined.

  13. A capillary electrophoresis system with dual capacitively coupled contactless conductivity detection and electrospray ionization tandem mass spectrometry.

    PubMed

    Francisco, Kelliton José Mendonça; do Lago, Claudimir Lucio

    2016-07-01

    A commercial system that is comprised of a CE coupled to an ESI triple quadrupole mass spectrometer was equipped with two capacitively coupled contactless conductivity detectors (C(4) Ds). The first C(4) D was positioned inside the original cartridge, and the second C(4) D was positioned as close as possible to the ESI probe entrance by using a 3D-printed support. The C(4) Ds electropherograms were matched to the ESI-MS electropherogram by correcting their timescales by the factor LT /LD , where LT and LD are the total capillary length and the length until the C(4) D, respectively. A general approach for method development supporting the simultaneous conductivity and MS detection is discussed, while application examples are introduced. These examples include the use of C(4) D as a simple device that dismiss the use of an EOF marker, a low-selectivity detector that continuously provide information about unexpected features of the sample, and even a detector that can be more sensitive than ESI-MS. The C(4) D used in this setup proved to have a smaller contribution to the peak broadening than ESI-MS, which allowed that a C(4) D, positioned at 12 cm from the inlet of an 80-cm-long capillary, could be used to foresee position and shape of the peaks being formed 6.8 times slower at the ESI-MS electropherogram.

  14. A sensitive method for determination of allergenic fragrance terpene hydroperoxides using liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Rudbäck, Johanna; Islam, Nurul; Nilsson, Ulrika; Karlberg, Ann-Therese

    2013-04-01

    Different compositions of monoterpenes are utilized for their pleasant scent in cosmetics and perfumes. However, the most commonly used fragrance terpenes easily oxidize upon contact with air, forming strongly skin-sensitizing hydroperoxides. Due to their thermolability and low UV absorbance, detection methods for hydroperoxides are scarce. For the first time, a simple and sensitive method using LC/ESI-MS/MS was developed to quantitatively determine hydroperoxides from the common fragrance compounds linalool, linalyl acetate, and limonene. The method was applied to autoxidized petitgrain oil and sweet orange oil. A separation was accomplished using a C3 column. The method LOD for the investigated hydroperoxides in the essential oils was below 0.3 μg/mL, corresponding to 0.3 ppm. For prevention purposes and according to EU regulations, concentrations in cosmetics exceeding 100 ppm in "rinse-off" and 10 ppm in "stay-on" products of linalool and limonene must be labeled. However, the products may still contain allergens, such as hydroperoxides, formed by oxidative degradation of their parent terpenes. The sensitivity and selectivity of the presented LC/MS/MS method enables detection of hydroperoxides from the fragrance terpenes linalool, linalyl acetate, and limonene. However, for routine measurements, the method requires further validation.

  15. Transition-metal-free BF₃-mediated oxidative and non-oxidative cross-coupling of pyridines.

    PubMed

    Chen, Quan; León, Thierry; Knochel, Paul

    2014-08-11

    We report a BF3-mediated direct alkynylation of pyridines at C(2) by using a variety of alkynyllithium reagents (oxidative cross-coupling). Moreover, we have developed a novel transition-metal-free cross-coupling method between alkylmagnesium reagents and 4-substituted pyridines, such as isonicotinonitrile and 4-chloropyridine, by employing BF3⋅OEt2 as a promoter. The combination of these methods enabled us to efficiently prepare a range of di-, tri-, and tetrasubstituted pyridines.

  16. Determination of six chemotherapeutic agents in municipal wastewater using online solid-phase extraction coupled to liquid chromatography-tandem mass spectrometry.

    PubMed

    Rabii, Farida W; Segura, Pedro A; Fayad, Paul B; Sauvé, Sébastien

    2014-07-15

    Due to the increased consumption of chemotherapeutic agents, their high toxicity, carcinogenicity, their occurrence in the aquatic environment must be properly evaluated. An analytical method based on online solid-phase extraction coupled to liquid chromatography-tandem mass spectrometry was developed and validated. A 1 mL injection volume was used to quantify six of the most widely used cytotoxic drugs (cyclophosphamide, gemcitabine, ifosfamide, methotrexate, irinotecan and epirubicin) in municipal wastewater. The method was validated using standard additions. The validation results in wastewater influent had coefficients of determination (R(2)) between 0.983 and 0.998 and intra-day precision ranging from 7 to 13% (expressed as relative standard deviation %RSD), and from 9 to 23% for inter-day precision. Limits of detection ranged from 4 to 20 ng L(-1) while recovery values were greater than 70% except for gemcitabine, which is the most hydrophilic compound in the selected group and had a recovery of 47%. Matrix effects were interpreted by signal suppression and ranged from 55 to 118% with cyclophosphamide having the highest value. Two of the target anticancer drugs (cyclophosphamide and methotrexate) were detected and quantified in wastewater (effluent and influent) and ranged from 13 to 60 ng L(-1). The proposed method thus allows proper monitoring of potential environmental releases of chemotherapy agents.

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

    PubMed

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

    2014-07-01

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

  18. Identification of Polish cochineal (Porphyrophora polonica L.) in historical textiles by high-performance liquid chromatography coupled with spectrophotometric and tandem mass spectrometric detection.

    PubMed

    Lech, Katarzyna; Jarosz, Maciej

    2016-05-01

    The present work reports a method for identification of Polish cochineal (Porphyrophora polonica L.) in historical fabrics by the use of high-performance liquid chromatography coupled with diode array and tandem mass spectrometric detection with electrospray ionization (HPLC-DAD-ESI MS/MS). This hyphened technique allows detection and identification of 16 new minor colorants present in the discussed scale insect (including two previously observed by Wouters and Verhecken (Ann Soc Entomol Fr. 1989;25:393-410), but specified only as compounds of unknown structures) that do not occur (e.g., in American cochineal). The MS/MS experiments, complemented with UV-VIS data, enable identification of mono- and di-, C- and O-hexosides of kermesic and flavokermesic acids or their derivatives. The present paper introduces a fingerprint of color compounds present in Polish cochineal and defines them, particularly pp6 (ppI, O-hexoside of flavokermesic acid), as its markers allow distinguishing of Polish-cochineal reds from the American ones. Usefulness of the selected set of markers for identification of Polish cochineal has been demonstrated in the examination of textiles from the collection of the National Museum in Warsaw using the multiple reaction monitoring (MRM) method, originally elaborated on the basis of this study.

  19. In vivo study on the neurotransmitters and their metabolites change in depressive disorder rat plasma by ultra high performance liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Zhao, Longshan; Zheng, Shuning; Su, Guangyue; Lu, Xiumei; Yang, Jingyu; Xiong, Zhili; Wu, Chunfu

    2015-04-15

    A sensitive and versatile, ultra-high performance, liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method coupled to pre-column derivatization for the simultaneous determination of 5-hydroxytryptamine (5-HT), 5-hydroxyindoleacetic acid (5-HIAA), dopamine (DA), norepinephrine (NE), homovanillic acid (HVA), γ-aminobutyric acid (GABA) and glutamic acid (Glu) was developed and validated in rat plasma. The analytes were dansylated under strong alkaline conditions after protein precipitation extraction, which were analyzed on a BEH C18 column using a gradient elution. The lower limit of quantification (LLOQ) values for 5-HT, 5-HIAA, DA, NE, HVA, GABA and Glu were 1.00, 1.00, 0.991, 0.992, 1.02, 1000, and 5030 pmol/mL, respectively. Good linearity was obtained (r > 0.99) and the intra- and inter-day precisions of the method (relative standard deviation, RSD%) were lower than 12%. The method was novel, sensitive and specific which can provide an alternative method for the quantification of neurotransmitters and their metabolites in plasma samples.

  20. Characterization of the human salivary proteome by capillary isoelectric focusing/nanoreversed-phase liquid chromatography coupled with ESI-tandem MS.

    PubMed

    Guo, Tong; Rudnick, Paul A; Wang, Weijie; Lee, Cheng S; Devoe, Don L; Balgley, Brian M

    2006-06-01

    Saliva is a readily available body fluid with great diagnostic potential. The foundation for saliva-based diagnostics, however, is the development of a complete catalog of secreted and "leaked" proteins detectable in saliva. By employing a capillary isoelectric focusing-based multidimensional separation platform coupled with electrospray ionization tandem mass spectrometry (MS), a total of 5338 distinct peptides were sequenced, leading to the identification of 1381 distinct proteins. A search of bacterial protein sequences also identified many peptides unique to several organisms and unique to the NCBI nonredundant database. To the best of our knowledge, this proteome study represents the largest catalog of proteins measured from a single saliva sample to date. Data analysis was performed on individual MS/MS spectra using the highly specific peptide identification algorithm, OMSSA. Searches were conducted against a decoyed SwissProt human database to control the false-positive rate at 1%. Furthermore, the well-curated SwissProt sequences represent perhaps the least redundant human protein sequence database (12,484 records versus the 50,009 records found in the International Protein Index human database), therefore minimizing multiple protein inferences from single peptides. This combined bioanalytical and bioinformatic approach has established a solid foundation for building up the human salivary proteome for the realization of the diagnostic potential of saliva.

  1. Determination of illicit drugs in aqueous environmental samples by online solid-phase extraction coupled to liquid chromatography-tandem mass spectrometry.

    PubMed

    Yao, Bo; Lian, Lushi; Pang, Weihai; Yin, Daqiang; Chan, Shen-An; Song, Weihua

    2016-10-01

    In this study, a fully automated analytical method, based on online solid phase extraction coupled to liquid chromatography-triple quadrupole tandem mass spectrometry (online SPE-LC-MS/MS), has been developed and optimized for the quantification of 10 illicit drugs and metabolites in environmentally aqueous samples collected from China. The particular attention was devoted to minimize the matrix effects through a washing step, which washed out the interferences effectively and helped to reduce the matrix effect significantly. The key advantages of the method are high sensitivity, selectivity and reliability of results, smaller sample manipulation, full automation, and fairly high throughput. The whole procedure was then successfully applied in the analysis of various surface water and wastewater effluents samples. Pseudoephedrine have been detected at trace levels (several tens ng L(-1) or less), while MDA, MDMA, benzoylecgonine and methadone were below the LOQ in all samples. Caffeine, cotinine and paraxanthine, which may be derived from medicines and foods, were detected with the highest frequencies and concentrations.

  2. Simultaneous determination of four biogenic and three volatile amines in anchovy by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry.

    PubMed

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

    2012-05-30

    A new method has been developed and validated for the simultaneous determination of four biogenic (putrescine, cadaverine, histamine, and tyramine) and three volatile amines (trimethylamine, triethylamine, and tripropylamine) in anchovy. Separation and determination of the selected compounds were carried out by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS), using an electrospray ionization source (ESI) in positive ion mode. Chromatographic separation was carried out using an aqueous solution of formic acid (0.1%) and methanol as mobile phase in gradient mode. The method was validated, and mean recoveries were evaluated at three concentration levels (75, 150, and 250 μg/kg), ranging from 70 to 110% at the three levels assayed. Intra- and interday precision, expressed as relative standard deviation (RSD), were lower than 15% and 20%, respectively. Limits of quantitation (LOQs) were 25 μg/kg for all cases, except for that of TMA, which was set at 60 μg/kg. The developed procedure was applied to determine the target compounds in anchovy samples stored during 7 days at 4 °C, observing the increasing in the concentration of these compounds at longer storage time.

  3. 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

    Walorczyk, Stanisław; Drożdżyński, Dariusz; Kierzek, Roman

    2015-01-01

    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 0.5 mg kg(-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.

  4. Multiresidue method for simultaneous analysis of aflatoxin M1, avermectins, organophosphate pesticides and milbemycin in milk by ultra-performance liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Dos Anjos, Marianna Ramos; Castro, Izabela Miranda de; Souza, Maria de Lourdes Mendes de; de Lima, Virgínia Verônica; de Aquino-Neto, Francisco Radler

    2016-06-01

    A method developed for the simultaneous analysis of aflatoxin M1, abamectin, doramectin, eprinomectin, ivermectin, moxidectin, acephate, azinphos-ethyl, azinphos-methyl, diazinon, methamidophos, methidathion, mevinphos, pirimiphos-ethyl and pirimiphos-methyl in whole raw milk, based on the QuEChERS method for extraction and clean-up, with detection and quantification by ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS) is described. The method was validated according to parameters of the Analytical Quality Assurance Manual from the Brazilian Ministry of Agriculture and Commission Decision 2002/657/EC, and proved suitable for analysis of these analytes within the proposed working range, with recovery values between 77% and 110%, a standard deviation lower than 20%, limits of detection between 0.05 and 0.99 µg l(-)(1), and limits of quantification between 0.15 and 1.98 µg l(-1). Samples from animals treated with abamectin, doramectin, ivermectin and diazinon were analysed by the validated method. Residues of aflatoxin M1 were also found in field samples at levels below the established maximum residue limit.

  5. Simultaneous determination of urinary parabens, bisphenol A, triclosan, and 8-hydroxy-2'-deoxyguanosine by liquid chromatography coupled with electrospray ionization tandem mass spectrometry.

    PubMed

    Ren, Lu; Fang, Jianzhang; Liu, Guihua; Zhang, Jianqing; Zhu, Zhou; Liu, Honghe; Lin, Kai; Zhang, Huimin; Lu, Shaoyou

    2016-04-01

    A simple and fast method was developed for the simultaneous determination of five parabens, bisphenol A (BPA), triclosan (TCS), and 8-hydroxy-2'-deoxyguanosine (8-OHdG) in human urine using liquid chromatography coupled with electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). The solid-phase extraction (SPE) procedure, chromatographic conditions, and MS/MS parameters were optimized to achieve maximum sensitivity and accuracy for the analytes. The validation results showed that the correlation coefficients (R (2)) and recoveries ranged from 0.999 to 1 and 83.9 to 109.9 %, respectively, and the intra-day and inter-day precisions (relative standard deviation, RSD) were within the range of 1.3-8.5 % and 1.3-9.0 %, respectively. The limits of detection for the analytes ranged from 0.001 to 0.05 μg/L. The method was successfully employed to determine parabens, BPA, TCS, and 8-OHdG in urine samples from school students in Guangzhou, China. The results showed that methyl, ethyl, n-propyl parabens, BPA, TCS, and 8-OHdG were frequently detected in urine samples. n-Butyl and benzyl parabens were only detected in a part of the samples due to their low concentrations in urine.

  6. Direct and sensitive determination of glyphosate and aminomethylphosphonic acid in environmental water samples by high performance liquid chromatography coupled to electrospray tandem mass spectrometry.

    PubMed

    Guo, Hongyue; Riter, Leah S; Wujcik, Chad E; Armstrong, Daniel W

    2016-04-22

    A novel method based on high performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS) was developed for the sensitive determination of glyphosate and its major degradation product, AMPA in environmental water samples. The method involves the use of MS compatible mobile phases (0.1% formic acid in water and acetonitrile) for HPLC and direct analysis of water samples without sample derivatization. The method has been validated in different types of water matrices (drinking, surface and groundwater) by accuracy and precision studies with samples spiked at 0.1, 7.5 and 90 ppb. All mean accuracy values ranged from 85% to 112% for glyphosate and AMPA using both primary and secondary quantitative ion transitions (RSD ≤ 10%). Moreover, both primary and secondary ion transitions for glyphosate and AMPA can achieve the quantitation limits at 0.1 ppb. The linear dynamic range of the calibration curves were from 0.1 to 100 ppb for each analyte at each ion transitions with correlation coefficient higher than 0.997.

  7. Automated hollow-fiber liquid-phase microextraction coupled with liquid chromatography/tandem mass spectrometry for the analysis of aflatoxin M₁ in milk.

    PubMed

    Huang, Siming; Hu, Du; Wang, Ying; Zhu, Fang; Jiang, Ruifen; Ouyang, Gangfeng

    2015-10-16

    An automated hollow fiber liquid-phase microextraction (HF-LPME) coupled with liquid chromatography/tandem mass spectrometry (LC-MS/MS) method was developed for the extraction and determination of aflatoxin M1 (AFM1) in milk samples. Parameters affecting the extraction efficiency, such as the extraction phase, matrix conditions, extraction time and temperature, were investigated. Under the optimal conditions (ratio of water to milk, 4:1; extraction time, 50 min; extraction temperature, 50°C; extraction phase, 50 mg L(-1) anti-AFM1 antibody in PBS buffer solution; volume of HCl solution, 250 μL; agitation speed, 250 rpm), the matrix-matched calibration curve for AFM1 determination showed good linearity in the range of 0.25-5 μg kg(-1). The enrichment factor (EF) reached 48, and the limits of detection and quantification were 0.06 and 0.21 μg kg(-1), respectively. The developed method was successfully applied for the extraction of AFM1 from spiked milk samples, with recoveries from 61.0% to 106.7%. The method was highly specific to AFM1 analysis, and the results demonstrated that the method can be automated, inexpensive, and free from interference.

  8. A fast method for analysing six perfluoroalkyl substances in human serum by solid-phase extraction on-line coupled to liquid chromatography tandem mass spectrometry.

    PubMed

    Bartolomé, Mónica; Gallego-Picó, Alejandrina; Huetos, Olga; Lucena, Miguel Ángel; Castaño, Argelia

    2016-03-01

    We have developed and validated an on-line TurboFlow solid-phase extraction procedure coupled to high-performance liquid chromatography with tandem mass spectrometry for the analysis of six perfluoroalkyl substances (PFAS), two sulfonates (perfluorooctane sulfonate and perfluorohexane sulfonate), three carboxylates (perfluorooctanoic acid, perfluorononanoic acid and perfluorodecanoic acid), and one sulfonamide (N-methylperfluorooctane sulfonamide), in human serum samples. This method requires only 100 μL of sample and involves a short pre-treatment with acetonitrile followed by addition of a labelled internal standard for quantification and ultracentrifugation. All PFAS were detected with a run time of 8.5 min. Linearity ranges stay between 0.1 and 20 μg L(-1) (R (2) > 0.9960). Recoveries were determined by spiking blank serum samples with a mixture of six PFAS and found to be in the range 96-110 % for all compounds. Isotopic dilution was used to quantify the selected analytes. The low limits of quantification obtained, between 0.16 and 0.34 μg L(-1), small volume of sample required and short run time used (from two to three times shorter than any other described method), make this validated method highly recommended for human biomonitoring studies.

  9. Metabolism profiles of icariin in rats using ultra-high performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry and in vitro enzymatic study.

    PubMed

    Cheng, Tao; Sheng, Tingting; Yi, Yaxiong; Zhang, Tong; Han, Han

    2016-10-15

    Icariin (ICA), the major constituent of Epimedium brevicornu Maxim, is recognized as an effective agent for the treatment of osteoporosis. In our previous report, the relatively short half-life (74min) and poor bioavailability (approximately 0.1%) of ICA in rats suggested that not only ICA itself but also its metabolites could be responsible for the observed osteoporosis treatment effect. Therefore, the present study aimed at identifying the metabolites of ICA in rat plasma, bile, urine, and feces after the administration of a single oral dose of ICA (150mg/kg). In this work, ultra-high performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (UHPLC/Q-TOF-MS) method was established to identify the metabolic profiles following intragastric administration of pure ICA in rats. The blood, bile, urine, and feces samples of the rats were investigated to explore the complete metabolic pathway of ICA in vivo. A total of 14 metabolites were detected in the bile, revealing that the bile is the main excretion pathway for ICA and its metabolites. The conjugated metabolites as observed in vivo, was further confirmed by the in vitro enzymatic study. Five metabolites of ICA, including demethylicariin, icariside I-3-O-glucuronide, demethylicariside II, demethylicariside II-7-O-glucuronide, and dehydroxyicaritin-glucuronide, were reported for the first time in the literature. In addition, the results revealed that the principal metabolism pathways of ICA in rat were deglycosylation and glucuronidation after deglycosylation.

  10. Solution for blank and matrix difficulties encountered during phthalate analysis of edible oils by high performance liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Vavrouš, Adam; Pavloušková, Jana; Ševčík, Václav; Vrbík, Karel; Čabala, Radomír

    2016-07-22

    Worldwide production of phthalates has led to their undesirable presence in the food chain. Particularly edible oils have become an area of growing concern owing to numerous reported occurrences of phthalates. The analytical methods used in this field face difficulties associated mainly with matrix complexity or phthalate contamination which this study has aimed to describe and resolve. The proposed procedure consisting of liquid-liquid extraction, solid phase extraction and high performance liquid chromatography coupled with tandem mass spectrometry allowed us to analyze simultaneously 6 individual phthalates and 2 phthalate isomeric mixtures. DSC-18 SPE phase was selected for cleanup owing to the most efficient co-extract removal (assessed using high resolution mass spectrometry). Several sources of phthalate contamination were identified, however, the mobile phase was the most serious. The key improvement was achieved by equipping a contamination trap, a 50-mm reverse phase HPLC column, generating a delay between target and mobile phase peaks of the same compounds. RSDs ranging between 2.4 and 16 % confirm good precision and LOQs between 5.5 and 110μgkg(-1) reflect satisfactory blank management. With up to 19 occurrences in 25 analyzed edible oil samples and levels up to 33mgkg(-1), bis(2-ethylhexyl), diisononyl and diisodecyl phthalates were the most important contaminants.

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

    PubMed

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

    2014-11-01

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

  12. Identification and discrimination of three common Aloe species by high performance liquid chromatography-tandem mass spectrometry coupled with multivariate analysis.

    PubMed

    Zhao, Yan; Sun, Ya Nan; Lee, Min Jung; Kim, Young Ho; Lee, Wonjae; Kim, Kyeong Ho; Kim, Kyung Tae; Kang, Jong Seong

    2016-09-15

    Aloe arborescens, Aloe barbadensis and Aloe ferox are the most widely cultivated and used among 500 aloe species due to their potent bioactivity. However, the difference of aloe species is neglected and labeled only one name Aloe in the market without specifying aloe species discrimination in general. Furthermore, differences in bioactivity and side effects from different aloe species have not been well investigated. This study develops an effective method for simultaneous qualitative and quantitative determination of three common aloe species using high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) and high performance liquid chromatography-diode array detection (HPLC-DAD). The extraction conditions were optimized by response surface methodology (RSM) based on methanol concentration, extraction time and solvent-to-material ratio. A partial least squares-discriminant analysis (PLS-DA) was used to identify the three aloe species. The developed HPLC-MS/MS method coupled with multivariate analysis can be applied to discriminate three aloe species successfully.

  13. Development of immobilized-pepsin microreactors coupled to nano liquid chromatography and tandem mass spectrometry for the quantitative analysis of human butyrylcholinesterase.

    PubMed

    Bonichon, Maud; Combès, Audrey; Desoubries, Charlotte; Bossée, Anne; Pichon, Valérie

    2016-08-26

    Human butyrylcholinesterase is a serine hydrolase that reacts with organophosphorus compounds (OP) to form stable adducts. These adducts are valuable biomarkers for OP exposure and can be analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) after a preliminary digestion step in solution. However, this digestion step is time-consuming and cannot be directly coupled with LC-MS set ups. Therefore, the aim of this work was to develop pepsin-based immobilized enzyme microreactors (IMERs) for the rapid digestion of human butyrylcholinesterase (HuBuChE). Various IMERs were synthesized by grafting different amounts of pepsin on a CNBr-sepharose gel and the grafting yield was measured by a bicinchoninic acid assay (BCA). A sensitive nanoLC-MS/MS method was developed to evaluate the digestion yields of HuBuChE on IMERs which was made possible by a synthetic peptide which was used as a calibrant. The digestion was optimized by studying the impact of different parameters such as the digestion time, the temperature and the amount of pepsin grafted on IMER. This optimization allowed HuBuChE to be digested with-in 20min without pretreatment and with digestion yields up to 20%. The repeatability of the IMER synthesis and HuBuChE digestion was highlighted with the characterization of 3 similar IMERs. Finally, the digestion yields of HuBuChE were higher with IMERs when compared to a typical in solution digestion.

  14. Monitoring and determination of sulfonamide antibiotics (sulfamethoxydiazine, sulfamethazine, sulfamethoxazole and sulfadiazine) in imported Pangasius catfish products in Thailand using liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Jansomboon, Worawat; Boontanon, Suwanna Kitpati; Boontanon, Narin; Polprasert, Chongrak; Thi Da, Chau

    2016-12-01

    This research aimed to monitor the concentrations of sulfamethoxydiazine (SMD), sulfamethazine (SMT), sulfamethoxazole (SMX) and sulfadiazine (SDZ) in imported Pangasius catfish products in Thailand. The residues of the four sulfonamides (SAs) were analyzed by extraction process and liquid chromatography coupled with tandem mass spectrometry. The highest concentrations found were 10.97ng/g for SMD, 6.23ng/g for SMT, 11.13ng/g for SDZ and 245.91ng/g for SMX, which was higher than the European Union (EU) standard (100ng/g). Moreover, all samples contaminated with SMX also contained SMT, indicating that more than one antibiotic was used for production in the country of origin. Because Thai standards for antibiotics in food have not been completely set, all contaminated discovered would not be considered to be an illegal food, in which antibiotic residues may affect human health in the long term. Therefore, antibiotic residues in Pangasius catfish products should be continually regulated and monitored.

  15. 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

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

    2014-09-01

    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, 22β-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.

  16. Carbamazepine in municipal wastewater and wastewater sludge: ultrafast quantification by laser diode thermal desorption-atmospheric pressure chemical ionization coupled with tandem mass spectrometry.

    PubMed

    Mohapatra, D P; Brar, S K; Tyagi, R D; Picard, P; Surampalli, R Y

    2012-09-15

    In this study, the distribution of the anti-epileptic drug carbamazepine (CBZ) in wastewater (WW) and aqueous and solid phases of wastewater sludge (WWS) was carried out. A rapid and reliable method enabling high-throughput sample analysis for quicker data generation, detection, and monitoring of CBZ in WW and WWS was developed and validated. The ultrafast method (15s per sample) is based on the laser diode thermal desorption-atmospheric pressure chemical ionization (LDTD-APCI) coupled to tandem mass spectrometry (MS/MS). The optimization of instrumental parameters and method application for environmental analysis are presented. The performance of the novel method was evaluated by estimation of extraction recovery, linearity, precision and detection limit. The method detection limits was 12 ng L(-1) in WW and 3.4 ng g(-1) in WWS. The intra- and inter-day precisions were 8% and 11% in WW and 6% and 9% in WWS, respectively. Furthermore, three extraction methods, ultrasonic extraction (USE), microwave-assisted extraction (MAE) and accelerated solvent extraction (ASE) with three different solvent condition such as methanol, acetone and acetonitrile:ethyle acetate (5:1, v/v) were compared on the basis of procedural blank and method recovery. Overall, ASE showed the best extraction efficiency with methanol as compared to USE and MAE. Furthermore, the quantification of CBZ in WW and WWS samples showed the presence of contaminant in all stages of the treatment plant.

  17. Two-dimensional liquid chromatography coupled to tandem mass spectrometry for vitamin D metabolite profiling including the C3-epimer-25-monohydroxyvitamin D3.

    PubMed

    Mena-Bravo, A; Priego-Capote, F; Luque de Castro, M D

    2016-06-17

    A method based on automated on-line solid phase extraction coupled to two-dimensional liquid chromatography with tandem mass spectrometry detection (SPE-2DLC-MS/MS) is here reported for vitamin D metabolite profiling in human serum with absolute quantitation. Two-dimensional LC was configured with two complementary analytical columns, pentafluorophenyl (PFP) and C18 phases, for determination of 25 hydroxyvitamin D3 epimers and the resting bioactive metabolites of vitamin D (D3 and D2)-25-hydroxyvitamin D2, 1,25-dihydroxyvitamin D3, 1,25-dihydroxyvitamin D2 and 24,25-dihydroxyvitamin D3. Quantitative determination was supported on the use of a stable isotopic labelled internal standard for each analyte and the resulting method was validated by analysis of a standard reference material certified by the National Institute of Standards & Technology (NIST-972a) and 5 samples provided by the vitamin D External Quality Assurance Scheme (DEQAS). The limits of detection were between 9 and 90pg/mL for the eight analytes, and precision, expressed as relative standard deviation, was lower than 11.6%. Two-dimensional LC has shown to be the key to discriminate between 25 hydroxyvitamin D3 epimers in a quantitative analysis also involving dihydroxyvitamin D metabolites.

  18. Residue determination of glufosinate in plant origin foods using modified Quick Polar Pesticides (QuPPe) method and liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Han, Yongtao; Song, Le; Zhao, Pengyue; Li, Yanjie; Zou, Nan; Qin, Yuhong; Li, Xuesheng; Pan, Canping

    2016-04-15

    A sensitive and specific method for the determination of glufosinate in plant origin foods was developed. The method involves extraction using modified QuPPe method, clean-up by multi-walled carbon nanotubes (MWCNTs), derivatization with 9-fluorenylmethyl chloroformate (FMOC-Cl) and detection with liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The method was validated on twelve matrices spiked at 10 or 20, 100 and 500 μg/kg. The recovery ranged from 80% to 108% with intra-day RSDs (n=5) of 0.6-9.8% and inter-day RSDs (n=15) of 3.0-9.4%. Good linearities (R(2)⩾0.9991) were obtained for all matrices. The limit of detection (LOD) and limit of quantification (LOQ) for the selected matrices ranged from 0.3 to 3.3 μg kg(-1) and from 1 to 10 μg kg(-1), respectively. The method was demonstrated to be reliable and sensitive for the routine monitoring of glufosinate in plant origin foods.

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

    PubMed

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

    2013-09-01

    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.

  20. Advances in ultra-high performance liquid chromatography coupled to tandem mass spectrometry for sensitive detection of several food allergens in complex and processed foodstuffs.

    PubMed

    Planque, M; Arnould, T; Dieu, M; Delahaut, P; Renard, P; Gillard, N

    2016-09-16

    Sensitive detection of food allergens is affected by food processing and foodstuff complexity. It is therefore a challenge to detect cross-contamination in food production that could endanger an allergic customer's life. Here we used ultra-high performance liquid chromatography coupled to tandem mass spectrometry for simultaneous detection of traces of milk (casein, whey protein), egg (yolk, white), soybean, and peanut allergens in different complex and/or heat-processed foodstuffs. The method is based on a single protocol (extraction, trypsin digestion, and purification) applicable to the different tested foodstuffs: chocolate, ice cream, tomato sauce, and processed cookies. The determined limits of quantitation, expressed in total milk, egg, peanut, or soy proteins (and not soluble proteins) per kilogram of food, are: 0.5mg/kg for milk (detection of caseins), 5mg/kg for milk (detection of whey), 2.5mg/kg for peanut, 5mg/kg for soy, 3.4mg/kg for egg (detection of egg white), and 30.8mg/kg for egg (detection of egg yolk). The main advantage is the ability of the method to detect four major food allergens simultaneously in processed and complex matrices with very high sensitivity and specificity.

  1. Fluorocarbon-bonded magnetic mesoporous microspheres for the analysis of perfluorinated compounds in human serum by high-performance liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Liu, Xiaodan; Yu, Yingjia; Li, Yan; Zhang, Haiying; Ling, Jin; Sun, Xueni; Feng, Jianan; Duan, Gengli

    2014-09-24

    We report herein an extraction method for the analysis of perfluorinated compounds in human serum based on magnetic core-mesoporous shell microspheres with decyl-perfluorinated interior pore-walls (Fe3O4@mSiO2-F17). Thanks to the unique properties of the Fe3O4@mSiO2-F17 microspheres, macromolecules like proteins could be easily excluded from the mesoporous channels due to size exclusion effect, and perfluorinated compounds (PFCs) in protein-rich biosamples such as serum could thus be directly extracted with the fluorocarbon modified on the channel wall without any other pretreatment procedure. The PFCs adsorbed Fe3O4@mSiO2-F17 microspheres could then be simply and rapidly isolated by using a magnet, followed by being identified and quantified by LC-MS/MS (high-performance liquid chromatography coupled to tandem mass spectrometry). Five perfluorinatedcarboxylic acids (C6, C8-C11) and perfluorooctane sulfonate (PFOS) were selected as model analytes. In order to achieve the best extraction efficiency, some important factors including the amount of Fe3O4@mSiO2-F17 microspheres added, adsorption time, type of elution solvent, eluting solvent volume and elution time were investigated. The ranges of the LOD were 0.02-0.05 ng mL(-1) for the six PFCs. The recovery of the optimized method varies from 83.13% to 92.42% for human serum samples.

  2. Rapid residue analysis of fluoroquinolones in raw bovine milk by online solid phase extraction followed by liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Kantiani, Lina; Farré, Marinella; Barceló, Damià

    2011-12-16

    Online solid phase extraction followed by liquid chromatography coupled to tandem mass spectrometry was used for the determination of 15 fluoroquinolones and one quinolone antibiotic in raw bovine and skimmed commercial milk. Milk samples were partially deproteinized and defatted by 15 min centrifugation and then subjected to online solid phase extraction. Chromatographic separation was achieved in less than 15 min. Identification and quantification of the compounds of interest were performed by selected reaction monitoring, using an electrospray ionization source. Relative recoveries were calculated for raw milk (at 0.5, 1 and 1.5 times the MRL, or assuming 30 ng/mL for non permitted compounds) and skimmed milk (at 30 ng/mL) and ranged between 65% and 123% (raw milk) or 78% and 109% (skimmed milk). Matrix interferences were also assessed and yielded significant suppression and enhancement effects, which, at the time of quantification, were corrected by the use of six isotopically labeled standards. Quality parameters of the method were established, and limits of detection of selected antibiotics in raw milk ranged from 0.01 to 1.93 ng/mL, while in skimmed milk from 0.03 to 4.23 ng/mL. The validation of the method has been carried out according to the requirements set by the 2002/657/EC regulation. Finally, the applicability of the method was tested by analysing 28 milk samples.

  3. Analysis of sulfate metabolites of the doping agents oxandrolone and danazol using high performance liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Rzeppa, S; Viet, L

    2016-09-01

    The direct detection of sulfate conjugates of anabolic androgenic steroids (AAS) can be a powerful tool in doping control analysis. By skipping the solvolysis step analysis time can be reduced, and due to long term sulfate metabolites the detection time can be significantly extended as demonstrated for some AAS. This study presents the successful identification of sulfate metabolites of the doping agents oxandrolone and danazol in excretion urines by high performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS). The sulfate conjugate of 17β-hydroxymethyl-17α-methyl-18-nor-2-oxa-5α-androsta-13-en-3-one could be identified as a new metabolite of oxandrolone. Sulfate conjugates of the danazol metabolites ethisterone and 2α-hydroxymethylethisterone were identified in an excretion urine for the first time. In addition, these sulfate conjugates were synthesized successfully. For a confirmation analysis, the number of analytes can be increased by additional sulfate conjugates of danazol metabolites (2-hydroxymethyl-1,2-dehydroethisterone and 6β-hydroxy-2-hydroxymethylethisterone), which were also identified for the first time. The presented validation data underline the suitability of the identified sulfate conjugates for doping analysis with regard to the criteria given by the technical documents of the World Anti-Doping Agency (WADA).

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

    PubMed Central

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

    2015-01-01

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

  5. Graphene oxide modification of plexciton states in the strong coupling limit

    NASA Astrophysics Data System (ADS)

    Fedele, Stefano; Murphy, Antony; Pollard, Robert; Rice, James

    2017-03-01

    We demonstrate that gold nanorod arrays support LSPR modes which coincide with Frankel excitons in an organic J-aggregate complex forming plexciton hybrid states when tuned to within the strong coupling limit. The addition of graphene oxide modifies the strong coupling resonance conditions and Rabi frequency. This demonstrates that the formation of exciton–plasmon plexciton states in the strong coupling limit can be modified and potentially controlled through the introduction of graphene oxide which can have implications for energy harvesting or biosensor device design.

  6. Copper-catalyzed aerobic oxidative coupling: From ketone and diamine to pyrazine

    PubMed Central

    Wu, Kun; Huang, Zhiliang; Qi, Xiaotian; Li, Yingzi; Zhang, Guanghui; Liu, Chao; Yi, Hong; Meng, Lingkui; Bunel, Emilio E.; Miller, Jeffrey T.; Pao, Chih-Wen; Lee, Jyh-Fu; Lan, Yu; Lei, Aiwen

    2015-01-01

    Copper-catalyzed aerobic oxidative C–H/N–H coupling between simple ketones and diamines was developed toward the synthesis of a variety of pyrazines. Various substituted ketones were compatible for this transformation. Preliminary mechanistic investigations indicated that radical species were involved. X-ray absorption fine structure experiments elucidated that the Cu(II) species 5 coordinated by two N atoms at a distance of 2.04 Å and two O atoms at a shorter distance of 1.98 Å was a reactive one for this aerobic oxidative coupling reaction. Density functional theory calculations suggested that the intramolecular coupling of cationic radicals was favorable in this transformation. PMID:26601302

  7. Nitrous Oxide-dependent Iron-catalyzed Coupling Reactions of Grignard Reagents.

    PubMed

    Döhlert, Peter; Weidauer, Maik; Enthaler, Stephan

    2015-01-01

    The formation of carbon-carbon bonds is one of the fundamental transformations in chemistry. In this regard the application of palladium-based catalysts has been extensively investigated during recent years, but nowadays research focuses on iron catalysis, due to sustainability, costs and toxicity issues; hence numerous examples for iron-catalyzed cross-coupling reactions have been established, based on the coupling of electrophiles (R(1)-X, X = halide) with nucleophiles (R(2)-MgX). Only a small number of protocols deals with the iron-catalyzed oxidative coupling of nucleophiles (R(1)-MgX + R(2)-MgX) with the aid of oxidants (1,2-dihaloethanes). However, some issues arise with these oxidants; hence more recently the potential of the industrial waste product nitrous oxide (N(2)O) was investigated, because the unproblematic side product N(2) is formed. Based on that, we demonstrate the catalytic potential of easily accessible iron complexes in the oxidative coupling of Grignard reagents. Importantly, nitrous oxide was essential to obtain yields up to >99% at mild conditions (e.g. 1 atm, ambient temperature) and low catalyst loadings (0.1 mol%) Excellent catalyst performance is realized with turnover numbers of up to 1000 and turnover frequencies of up to 12000 h(-1). Moreover, a good functional group tolerance is observed (e.g. amide, ester, nitrile, alkene, alkyne). Afterwards the reaction of different Grignard reagents revealed interesting results with respect to the selectivity of cross-coupling product formation.

  8. Analysis of chlormequat and mepiquat by hydrophilic interaction chromatography coupled to tandem mass spectrometry in food samples.

    PubMed

    Esparza, X; Moyano, E; Galceran, M T

    2009-05-15

    In this work a LC-MS/MS method for the determination of two quaternary ammonium growth regulators (chlormequat and mepiquat) in food is reported. The separation was based on hydrophilic interaction liquid chromatography (HILIC) without the use of ion-pair reagents. A gradient elution of acetonitrile and formic acid/ammonium formate buffer from 60 to 40% acetonitrile was enough to achieve a resolution >1.5 in less than 4.0min. The HILIC system was coupled to a triple quadrupole mass spectrometer equipped with a heated electrospray probe (H-ESI) providing sub-pg LODs in SRM mode. A straightforward sample treatment (SPE C18 clean-up) was enough to provide MLODs at low ppb levels when analysing a range of food samples that covered different kinds of matrices such as fresh fruit, vegetables, fruit juices, baby food, bread, coffee and beer. Chlormequat was found in seven samples (0.8-126ng/g) but mepiquat was only detected in bread and coffee samples (0.9-166ng/g).

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

    PubMed

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

    2015-03-01

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

  10. Electrochemical production of hydrogen coupled with the oxidation of arsenite.

    PubMed

    Kim, Jungwon; Kwon, Daejung; Kim, Kitae; Hoffmann, Michael R

    2014-01-01

    The production of hydrogen accompanied by the simultaneous oxidation of arsenite (As(III)) was achieved using an electrochemical system that employed a BiOx-TiO2 semiconductor anode and a stainless steel (SS) cathode in the presence of sodium chloride (NaCl) electrolyte. The production of H2 was enhanced by the addition of As(III) during the course of water electrolysis. The synergistic effect of As(III) on H2 production can be explained in terms of (1) the scavenging of reactive chlorine species (RCS), which inhibit the production of H2 by competing with water molecules (or protons) for the electrons on the cathode, by As(III) and (2) the generation of protons, which are more favorably reduced on the cathode than water molecules, through the oxidation of As(III). The addition of 1.0 mM As(III) to the electrolyte at a constant cell voltage (E cell) of 3.0 V enhanced the production of H2 by 12% even though the cell current (I cell) was reduced by 5%. The net effect results in an increase in the energy efficiency (EE) for H2 production (ΔEE) by 17.5%. Furthermore, the value ΔEE, which depended on As(III) concentration, also depended on the applied E cell. For example, the ΔEE increased with increasing As(III) concentration in the micromolar range but decreased as a function of E cell. This is attributed to the fact that the reactions between RCS and As(III) are influenced by both RCS concentration depending on E cell and As(III) concentration in the solution. On the other hand, the ΔEE decreased with increasing As(III) concentration in the millimolar range due to the adsorption of As(V) generated from the oxidation of As(III) on the semiconductor anode. In comparison to the electrochemical oxidation of certain organic compounds (e.g., phenol, 4-chlorophenol, 2-chlorophenol, salicylic acid, catechol, maleic acid, oxalate, and urea), the ΔEE obtained during As(III) oxidation (17.5%) was higher than that observed during the oxidation of the above organic compounds

  11. Resonant Coupling between Molecular Vibrations and Localized Surface Plasmon Resonance of Faceted Metal Oxide Nanocrystals.

    PubMed

    Agrawal, Ankit; Singh, Ajay; Yazdi, Sadegh; Singh, Amita; Ong, Gary K; Bustillo, Karen; Johns, Robert W; Ringe, Emilie; Milliron, Delia J

    2017-04-12

    Doped metal oxides are plasmonic materials that boast both synthetic and postsynthetic spectral tunability. They have already enabled promising smart window and optoelectronic technologies and have been proposed for use in surface enhanced infrared absorption spectroscopy (SEIRA) and sensing applications. Herein, we report the first step toward realization of the former utilizing cubic F and Sn codoped In2O3 nanocrystals (NCs) to couple to the C-H vibration of surface-bound oleate ligands. Electron energy loss spectroscopy is used to map the strong near-field enhancement around these NCs that enables localized surface plasmon resonance (LSPR) coupling between adjacent nanocrystals and LSPR-molecular vibration coupling. Fourier transform infrared spectroscopy measurements and finite element simulations are applied to observe and explain the nature of the coupling phenomena, specifically addressing coupling in mesoscale assembled films. The Fano line shape signatures of LSPR-coupled molecular vibrations are rationalized with two-port temporal coupled mode theory. With this combined theoretical and experimental approach, we describe the influence of coupling strength and relative detuning between the molecular vibration and LSPR on the enhancement factor and further explain the basis of the observed Fano line shape by deconvoluting the combined response of the LSPR and molecular vibration in transmission, absorption and reflection. This study therefore illustrates various factors involved in determining the LSPR-LSPR and LSPR-molecular vibration coupling for metal oxide materials and provides a fundamental basis for the design of sensing or SEIRA substrates.

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

    PubMed

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

    2015-07-02

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

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

    PubMed

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

    2015-01-01

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

  14. Determination of eight nitrosamines in water at the ng L(-1) levels by liquid chromatography coupled to atmospheric pressure chemical ionization tandem mass spectrometry.

    PubMed

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

    2011-09-19

    In this work, we have developed a sensitive method for detection and quantification of eight N-nitrosamines, N-nitrosodimethylamine (NDMA), N-nitrosomorpholine (NMor), N-nitrosomethylethylamine (NMEA), N-nitrosopirrolidine (NPyr), N-nitrosodiethylamine (NDEA), N-nitrosopiperidine (NPip), N-nitroso-n-dipropylamine (NDPA) and N-nitrosodi-n-butylamine (NDBA) in drinking water. The method is based on liquid chromatography coupled to tandem mass spectrometry, using atmospheric pressure chemical ionization (APCI) in positive mode with a triple quadrupole analyzer (QqQ). The simultaneous acquisition of two MS/MS transitions in selected reaction monitoring mode (SRM) for each compound, together with the evaluation of their relative intensity, allowed the simultaneous quantification and reliable identification in water at ppt levels. Empirical formula of the product ions selected was confirmed by UHPLC-(Q)TOF MS accurate mass measurements from reference standards. Prior to LC-MS/MS QqQ analysis, a preconcentration step by off-line SPE using coconut charcoal EPA 521 cartridges (by passing 500 mL of water sample) was necessary to improve the sensitivity and to meet regulation requirements. For accurate quantification, two isotope labelled nitrosamines (NDMA-d(6) and NDPA-d(14)) were added as surrogate internal standards to the samples. The optimized method was validated at two concentration levels (10 and 100 ng L(-1)) in drinking water samples, obtaining satisfactory recoveries (between 90 and 120%) and precision (RSD<20%). Limits of detection were found to be in the range of 1-8 ng L(-1). The described methodology has been applied to different types of water samples: chlorinated from drinking water and wastewater treatment plants (DWTP and WWTP, respectively), wastewaters subjected to ozonation and tap waters.

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

    PubMed

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

    2014-02-01

    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%).

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

    PubMed

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

    2011-02-01

    In the present study, a novel, fast, sensitive and robust method to quantify budesonide in human plasma using 3-keto-desogestrel as the internal standard (IS) is described. The analyte and the IS were extracted from human plasma by liquid-liquid extraction (LLE) using ether. Extracted samples were analyzed by high performance liquid chromatography coupled to Atmospheric pressure photoionization tandem mass spectrometry (HPLC-APPI-MS/MS). Chromatography was performed isocratically on a C18, 5 μm analytical column. The temperature of the autosampler was kept at 6 °C and the run time was 4.00 min. A linear calibration curve over the range 7.5-1000 pg ml⁻¹ was obtained and the lowest concentration quantified was 7.5 pg ml⁻¹, demonstrating acceptable accuracy and precision. This analytical method was applied in a relative bioavailability study in order to compare a test budesonide 64 μg/dose nasal spray formulation vs. a reference 64 μg/dose nasal spray formulation (Budecort Aqua) in 48 volunteers of both sexes. The study was conducted in an open randomized two-period crossover design and with a one-week washout period. Plasma samples were obtained over a 14 h interval. Since the 90% CI for both C(max), AUC(last) and AUC(0-inf) were within the 80-125% interval proposed by the Food and Drug Administration and ANVISA, it was concluded that budesonide 64 μg/dose nasal spray was bioequivalent to Budecort Acqua® 64 μg/dose nasal spray, according to both the rate and extent of absorption.

  17. Cyproterone acetate quantification in human plasma by high-performance liquid chromatography coupled to atmospheric pressure photoionization tandem mass spectrometry. Application to a comparative pharmacokinetics study.

    PubMed

    Borges, Ney Carter; Mazuqueli, Ana; Moreno, Ronilson Agnaldo; Astigarraga, Rafael Barrientos; Sverdloff, Carlos Eduardo; Galvinas, Paulo Alexandre Rebelo; Sampaio, Maurício Rocha de Magalhães; da Silva, Washington Moreira

    2009-01-01

    A specific, fast and sensitive high performance liquid chromatography (HPLC) coupled to atmospheric pressure photoionization (APPI) tandem mass spectrometric (LC-MS/MS) assay was developed for the determination of cyproterone (CYP) acetate (CAS 427-51-0) in human plasma. The retention times were 3.26 and 2.90 min for CYP acetate and its internal standard (I. S.) finasteride (FIN), respectively. The overall mean recovery, using liquid/liquid extraction, was found to be 109.0, 107.7 and 100.3%, for low, medium and high concentrations, respectively. Calibration curves were linear in the concentration range of 0.1-50.0 ng/ml, and the lower limit of quantification (LLOQ) was 0.1 ng/ml. The LLOQ, 0.1 ng/ml, was sensitive enough for detecting terminal phase concentrations of the drug. Inter-batch precision of the method ranged from 2.2 to 5.55%, while Inter-batch accuracy ranged from 95.5 to 100.0%. Intra-batch precision ranged from 1.8 to 5.6%, while Intra-batch accuracy ranged from 92.0 to 99.4% at concentrations of 0.3 ng/ml, 20.0 and 40.0 ng/ml. The developed method was applied to a bioequivalenc study of CYP acetate in a group of 44 female volunteers at a single oral dose of a 2 mg tablet, in a combination of ethinylestradiol/CYP acetate (0.25/2 mg). The plasma concentration of CYP acetate did not differ significantly after administration of both formulations (test formulation and the reference one). The geometric mean and respective 90% CI of CYP acetate test/reference percent ratios were 90.66% (84.39-97.40%) for Cmax and 96.20% (90.45-102.33%) for AUC0-t.

  18. Quantification of cyproheptadine in human plasma by high-performance liquid chromatography coupled to electrospray tandem mass spectrometry in a bioequivalence study.

    PubMed

    Mendes, Gustavo Duarte; Arruda, André; Chen, Lu Shi; de Almeida Magalhães, José Cássio; Alkharfy, Khalid M; De Nucci, Gilberto

    2012-01-01

    A rapid, sensitive and specific method to quantify cyproheptadine in human plasma using amitriptyline as the internal standard (IS) is described. The analyte and the IS were extracted from plasma by liquid-liquid extraction using a diethyl-ether/dichloromethane (70/30; v/v) solvent. After removing and drying the organic phase, the extracts were reconstituted with a fixed volume of acetonitrile/water (50/50 v/v)+0.1% of acetic acid. The extracts were analyzed by high performance liquid chromatography coupled to electrospray tandem mass spectrometry (LC-MS/MS). Chromatography was performed isocratically using an Alltech Prevail C18 5 µm analytical column, (150 mm x 4.6 mm I.D.). The method had a chromatographic run time of 4 min and a linear calibration curve ranging from 0.05 to 10 ng/mL (r2 > 0.99). The limit of quantification was 0.05 ng/mL. This HPLC/MS/MS procedure was used to assess the bioequivalence of cyproheptadine in two cyproheptadine + cobamamide (4 mg + 1 mg) tablet formulations (Cobactin® [cyproheptadine + cobamamide] test formulation supplied from Zambon Laboratórios Farmacêuticos Ltda. and Cobavital® from Solvay Farma (standard reference formulation)). A single 4 mg + 1 mg [cyproheptadine + cobamamide] dose of each formulation was administered to healthy volunteers. The study was conducted using an open, randomized, two-period crossover design with a 1-week washout interval. Since the 90% CI for Cmax and AUCs ratios were all within the 80-125% bioequivalence limit proposed by the US Food and Drug Administration, it was concluded that the cyproheptadine test formulation (Cobactin®) is bioequivalent to the Cobavital® formulation for both the rate and the extent of absorption of cyproheptadine.

  19. Deoxynivalenol and its conjugates in beer: a critical assessment of data obtained by enzyme-linked immunosorbent assay and liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Zachariasova, Milena; Hajslova, Jana; Kostelanska, Marta; Poustka, Jan; Krplova, Alexandra; Cuhra, Petr; Hochel, Igor

    2008-09-05

    Enzyme-linked immunosorbent assays (ELISAs) are often employed for the control of deoxynivalenol (DON) in barley and other intermediates involved in beer production chain. Because of the occurrence of high levels of DON-3-glucoside (DON-3-Glc) in malt and beer that have been reported for the first time in our earlier study, research focused on the accuracy of DON determination by immunoassays in cereal-based matrices has been initiated. DON-3-Glc was strongly cross-reacting in all examined commercial ELISA test kits (Ridascreen) DON (R-Biopharm), Veratox 5/5 DON) (Neogen Corporation), Deoxynivalenol EIA (Euro-Diagnostica), and AgraQuant) DON Assay 0.25/5.0 Test Kit (Romer Labs). The highest overestimation in beer analysis, up to 1000%, when taking the DON content determined by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) as a reference method, was obtained by AgraQuant assay. Besides of DON-3-Glc and 3- and 15-acetyldeoxynivalenol (ADONs), also other, not known yet, matrix components contributed to false positive results. Similar phenomenon, although in a lesser extent due to lower content of these substances, was observed for using ELISA in the analysis of wheat. The relationship between a way of sample handling and DON overestimation was demonstrated; higher ELISA response was measured in an aqueous extract compared to that prepared by acetonitrile-water (84:16, v/v). Most of cross-reacting co-extracts were removed by MycoSep# 226 cartridge, what leads us to the hypothesis on the presence of currently unknown cross-reactive species.

  20. Comparison of hydrophilic interaction and reversed phase liquid chromatography coupled with tandem mass spectrometry for the determination of eight artificial sweeteners and common steviol glycosides in popular beverages.

    PubMed

    Kubica, Paweł; Namieśnik, Jacek; Wasik, Andrzej

    2016-08-05

    Hydrophilic interaction liquid chromatography (HILIC) coupled with tandem mass spectrometry (MS/MS) was used to separate artificial and natural sweeteners approved for use in European Union (EU). Among three tested HILIC columns (BlueOrchid PAL-HILIC, Ascentis Express Si and Acclaim™ Trinity™ P2) the last one was selected for the development of HILIC method due to the best results obtained with it. Early eluting and coeluting compounds in HILIC (acesulfame-K, saccharin, cyclamate, sucralose and aspartame) were successfully separated by the HILIC-based approach for the first time. The developed HILIC method allows for determination of all high potency sweeteners in one analytical run. The calibration curves for all analytes had good linearity within the tested ranges. The limits of detection and quantitation were in the range 0.81-3.30ng/mL and 2.32-9.89ng/mL, respectively. The obtained recoveries used for trueness and precision estimation were from 98.6% to 106.2% with standard deviation less than 4.1%. Sample preparation was reduced to a necessary minimum and contained only proper dilution and centrifugation. More than twenty samples of beverages were analyzed with the developed HILIC method. Finally, the chromatographic parameters of peaks (reduced retention time, width at baseline, width at 50% of peak height, tailing factor and efficiency) obtained in HILIC mode and in RPLC mode were compared. Developed HILIC method along with RPLC method can be applied for rapid evaluation of sweeteners' content, quality and safety control.

  1. Proteomic analysis of tears following acupuncture treatment for menopausal dry eye disease by two-dimensional nano-liquid chromatography coupled with tandem mass spectrometry

    PubMed Central

    Liu, Qingyu; Liu, Junling; Ren, Chengda; Cai, Wenting; Wei, Qingquan; Song, Yi; Yu, Jing

    2017-01-01

    Background The purpose of this study was to investigate whether acupuncture is effective at treating dry eye disease among postmenopausal women and to identify the possible mechanisms. Methods Twenty-eight postmenopausal women with dry eye disease were randomly divided into two groups: an acupuncture plus artificial tears (AC + AT) group and an artificial tears (AT) only group. After baseline examination of clinical parameters and tear sample collection, each patient received the designated modality of topical therapy for 2 months. Post-treatment documentation of clinical parameters was recorded, and tear samples were collected. Tear samples from the AC + AT group were subjected to two-dimensional nano-liquid chromatography coupled with tandem mass spectrometry (2D nano-LC-MS/MS). Western blot analysis was also performed on tear samples from both groups. Results After treatment, the Ocular Surface Disease Index scores, symptom assessment scores, scores of sign assessment, and tear break-up time were significantly improved in both groups (P=0.000). Symptom assessment scores were significantly improved in the AC + AT group (P=0.000) compared with the AT group. 2D nano-LC-MS/MS identified 2,411 proteins, among which 142 were downregulated and 169 were upregulated. After combined AC + AT treatment, the abundance of secreted proteins was increased, whereas that of cytoplasmic proteins decreased (Pearson’s χ2 test, P=0.000, P=0.000, respectively). Proteins involved in immunity and regulation were also more abundant (Pearson’s χ2 test, P=0.040, P=0.016, respectively), while components and proliferation-related proteins were downregulated (Pearson’s χ2 test, P=0.003, P=0.011, respectively). Conclusion AC + AT treatment increased protein synthesis and secretion, and improved clinical symptoms. These results indicate that acupuncture may be a complimentary therapy for treating postmenopausal dry eye disease. PMID:28280333

  2. Qualitative and quantitative analysis of polycyclic polyprenylated acylphloroglucinols from Garcinia species using ultra performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry.

    PubMed

    Zhou, Yan; Lee, Stephanie; Choi, Franky Fung Kei; Xu, Gang; Liu, Xin; Song, Jing-Zheng; Li, Song-Lin; Qiao, Chun-Feng; Xu, Hong-Xi

    2010-09-23

    Polycyclic polyprenylated acylphloroglucinols (PPAPs) are a group of natural products isolated from different Garcinia species with a wide range of important biological activities. In this study, an ultra performance liquid chromatography (UPLC) coupled to photodiode-array detection and quadrupole time-of-flight mass spectrometry (Q-TOF) method was developed to characterize 16 PPAPs in 10 Garcinia species. In source dissociation techniques based on cone voltage fragmentation were used to fragment the deprotonated molecules and multiple mass spectrometry (MS/MS) using ramping collision energy were used to further break down the resulting product ions. The resulting characteristic fragment ions were generated by cleavage of C1-C5 bond and C7-C8 bond through concerted pericyclic reaction, which is especially valuable for differentiating three types of PPAPs isomers. As such, two new PPAPs isomers present in minor amount in the extracts of Garcinia oblongifolia were tentatively characterized by comparing their tandem mass spectra to the known ones. In addition, an UPLC-Q-TOF-MS method was validated for the quantitative determination of PPAPs. The method exhibited limits of detection from 2.7 to 21.4 ng mL(-1) and intra-day and inter-day variations were less than 3.7% and the recovery was in the range of 89-107% with RSD less than 9.0%. This UPLC-Q-TOF-MS method has successfully been applied to quantify 16 PPAPs in 32 samples of 10 Garcinia species, which were found to be a rich source of PPAPs.

  3. Fast determination of hydroxylated polychlorinated biphenyls in human plasma by online solid phase extraction coupled to liquid chromatography-tandem mass spectrometry.

    PubMed

    Quinete, Natalia; Kraus, Thomas; Belov, Vladimir N; Aretz, Christina; Esser, André; Schettgen, Thomas

    2015-08-12

    Hydroxylated polychlorinated biphenyls (OH-PCBs) have been shown to be strongly retained in human blood causing endocrine-related toxicity, particularly on the thyroid system. Traditionally, analytical methods for the determination of OH-PCBs require labor-intensive and long-time consuming sample preparation with several extraction, evaporation and cleanup procedures steps and, in some cases, derivatization prior to the analysis by gas or liquid chromatography-mass spectrometry (GC-MS or LC-MS). The present study developed and validated a novel, sensitive and high throughput online solid phase extraction (SPE) method coupled to LC-tandem mass spectrometry (MS/MS) for the separation and quantitation of relevant congeners of OH-PCBs in human plasma. The developed method presented limits of quantification (LOQ) ranging from 0.02 to 0.5 ng mL(-1) and extraction recoveries from 71 to 134% for all congeners, requiring small amount of sample (only 100 μL) and minimal sample preparation. In order to evaluate the applicability of the method, preliminary tests (N = 93) were conducted in plasma from individuals occupationally exposed to very high levels of PCBs in a German cohort. Penta-through hepta-chlorinated OH-PCBs were the predominant congeners in human plasma with concentrations up to 44.5 ng mL(-1), while lower chlorinated OH-PCBs were occasionally detected. In addition, a new PCB 28 metabolite has been synthesized and identified for the first time in human plasma and associations between OH-PCBs and their parent compounds in the studied cohort were also assessed.

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

    PubMed

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

    2010-05-07

    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.

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

    PubMed

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

    2012-07-20

    A liquid-phase microextraction (LPME) methodology based on the use of porous polyvinylidene fluoride (PVDF) hollow fibres was developed for extracting seven pesticides from cucumbers. The seven pesticides include propoxur, carbofuran, atrazine, cyanatryn, metolachlor, prometryn and tebuconazole. The PVDF hollow fibre provides higher extraction efficiency due to its higher porosity and better solvent compatibility. A new desorption methodology was developed since some pesticides were absorbed by the wall pore of the PVDF. Ultra-high pressure liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) was used for pesticide analysis. In order to obtain high recoveries and enrichment factors of the analytes, several parameters such as method of sealing, acceptor phase (organic solvents), stirring speed, extraction time, salting out effect, desorption mode and time were optimized. A fast, simple method for closing fibre ends was practiced by using mechanical crimping. Pesticides were extracted from the sample to the organic solvent and then desorbed in a mixture of methanol:water (1:1 v/v) prior to chromatographic analysis. Limits of detection (LOD) for the multi-reaction-monitoring (MRM) mode of the method varies from 0.01 to 0.31 μg/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%.

  6. Bromazepam determination in human plasma by high-performance liquid chromatography coupled to tandem mass spectrometry: a highly sensitive and specific tool for bioequivalence studies.

    PubMed

    Laurito, Tiago L; Mendes, Gustavo D; Santagada, Vincenzo; Caliendo, Giuseppe; de Moraes, Maria Elisabete A; De Nucci, Gilberto

    2004-02-01

    A rapid, sensitive and specific method to quantify bromazepam in human plasma using diazepam as the internal standard (IS) is described. The analyte and the IS were extracted from plasma by liquid-liquid extraction using diethyl ether-hexane (80 : 20, v/v). The extracts were analyzed by high-performance liquid chromatography (HPLC) coupled to electrospray tandem mass spectrometry (MS/MS). Chromatography was performed isocratically on a Genesis C(18) analytical column (100 x 2.1 mm i.d., film thickness 4 microm). The method had a chromatographic run time of 5.0 min and a linear calibration curve over the range 5.0-150 ng ml(-1) (r(2) > 0.9952). The limit of quantification was 5 ng ml(-1). This HPLC/MS/MS procedure was used to assess the bioequivalence of two bromazepam 6 mg tablet formulations (bromazepam from Medley SA Indústria Farmacêutica as the test formulation and Lexotan from Produtos Roche Químico e Farmacêutico SA as the reference formulation). A single 6 mg dose of each formulation was administered to 24 healthy volunteers (12 males and 12 females). The study was conducted using an open, randomized, two-period crossover design with a 3 week washout interval. Since the 90% CI for C(max), AUC(last), AUC(0-240 h) (linear) and AUC((0- infinity )) ratios were all inside the 80-125% interval proposed by the US Food and Drug Administration, it was concluded that the bromazepam formulation from Medley is bioequivalent to the Lexotan formulation for both the rate and the extent of absorption.

  7. Simultaneous determination of eight neonicotinoid insecticide residues and two primary metabolites in cucumbers and soil by liquid chromatography-tandem mass spectrometry coupled with QuEChERS.

    PubMed

    Abdel-Ghany, Maha F; Hussein, Lobna A; El Azab, Noha F; El-Khatib, Ahmed H; Linscheid, Michael W

    2016-09-15

    A new, rapid, sensitive, precise and validated high performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS) method was developed for the simultaneous determination of eight neonicotinoid insecticides with their two primary metabolites in cucumbers and soil based on QuEChERS as a pretreatment procedure. In QuEChERS procedure, cucumber samples were extracted with acetonitrile and cleaned using (C18 sorbent material), while soil samples were extracted with a mixture of acetonitrile:dichloromethane (8.3:16.7v:v). The LC-MS/MS conditions were optimized to provide good selectivity and specificity of the developed method where neonicotinoids were separated using gradient elution of water and acetonitrile both containing 0.1% formic acid with Gemini C18 column where the last compound was eluted at 9.5min. Average recoveries of the eight neonicotinoids and their metabolites ranged between 81.6% and 95.7% in fortified cucumber samples with relative standard deviations (RSDs) lower than 13.18% and between 80.3% and 104% in fortified soil samples with relative standard deviations (RSDs) lower than 8.44%. The limits of detection (LODs) and quantification (LOQs) for the ten compounds were in the ranges of (0.08-6.06ng/g) and (0.26-20ng/g), respectively. The method was applied successfully to determine residues and rate of disappearance of the eight neonicotinoids from cucumber and soil and their half-lives where a safety pre-harvest interval of 5days for acetampirid, 12days for imidacloprid, 15days for nitenpyram, 12days for thiamethoxam, 5days for flonicamid, 8days for clothianidin, 2days for Dinotefuran, and 1day for thiacloprid were suggested.

  8. Simultaneous determination of dextromethorphan, dextrorphan and doxylamine in human plasma by HPLC coupled to electrospray ionization tandem mass spectrometry: application to a pharmacokinetic study.

    PubMed

    Donato, J L; Koizumi, F; Pereira, A S; Mendes, G D; De Nucci, G

    2012-06-15

    In the present study, a fast, sensitive and robust method to quantify dextromethorphan, dextrorphan and doxylamine in human plasma using deuterated internal standards (IS) is described. The analytes and the IS were extracted from plasma by a liquid-liquid extraction (LLE) using diethyl-ether/hexane (80/20, v/v). Extracted samples were analyzed by high performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). Chromatographic separation was performed by pumping the mobile phase (acetonitrile/water/formic acid (90/9/1, v/v/v) during 4.0min at a flow-rate of 1.5 mL min⁻¹ into a Phenomenex Gemini® C18, 5 μm analytical column (150 × 4.6 mm i.d.). The calibration curve was linear over the range from 0.2 to 200 ng mL⁻¹ for dextromethorphan and doxylamine and 0.05 to 10 ng mL⁻¹ for dextrorphan. The intra-batch precision and accuracy (%CV) of the method ranged from 2.5 to 9.5%, and 88.9 to 105.1%, respectively. Method inter-batch precision (%CV) and accuracy ranged from 6.7 to 10.3%, and 92.2 to 107.1%, respectively. The run-time was for 4 min. The analytical procedure herein described was used to assess the pharmacokinetics of dextromethorphan, dextrorphan and doxylamine in healthy volunteers after a single oral dose of a formulation containing 30 mg of dextromethorphan hydrobromide and 12.5mg of doxylamine succinate. The method has high sensitivity, specificity and allows high throughput analysis required for a pharmacokinetic study.

  9. Oxidative Coupling of Methane over Li/MgO: Catalyst and Nanocatalyst Performance

    NASA Astrophysics Data System (ADS)

    Farsi, Ali; Moradi, Ali; Ghader, Sattar; Shadravan, Vahid

    2011-02-01

    The Li/MgO catalyst and nanocatalyst were prepared by the incipient wetness impregnation and sol-gel method, respectively. The catalytic performance of the Li/MgO catalyst and nanocatalyst on oxidative coupling of methane was compared. The catalysts prepared in two ways were characterized by X-ray powder diffraction, Brunauer-Emmett-Teller surface and transmission electron microscope. The catalyst was tested at temperature of 973-1073 K with constant total pressure of 101 kPa. Experimental results showed that Li/MgO nanocatalyst in the oxidative coupling of methane would result in higher conversion of methane, higher selectivity, and higher yield of main products (ethane and ethylene) compared to ordinary catalyst. The results show the improved influence of nanoscale Li/MgO catalyst performance on oxidative coupling of methane.

  10. 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.

  11. Rapid and effective sample cleanup based on graphene oxide-encapsulated core-shell magnetic microspheres for determination of fifteen trace environmental phenols in seafood by liquid chromatography-tandem mass spectrometry.

    PubMed

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

    2016-05-05

    In this study, graphene oxide-encapsulated core-shell magnetic microspheres (GOE-CS-MM) were fabricated by a self-assemble approach between positive charged poly(diallyldimethylammonium) chloride (PDDA)-modified Fe3O4@SiO2 and negative charged GO sheets via electrostatic interaction. The as-prepared GOE-CS-MM was carefully characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibrating sample magnetometer analysis (VSM), and X-ray photoelectron spectroscopy (XPS), and was used as a cleanup adsorbent in magnetic solid-phase extraction (MSPE) for determination of 15 trace-level environmental phenols in seafood coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS). The obtained results showed that the GOE-CS-MM exhibited excellent cleanup efficiency and could availably reduce the matrix effect. The cleanup mechanisms were investigated and referred to π-π stacking interaction and hydrogen bond between GOE-CS-MM and impurities in the extracts. Moreover, the extraction and cleanup conditions of GOE-CS-MM toward phenols were optimized in detail. Under the optimized conditions, the limits of detection (LODs) were found to be 0.003-0.06 μg kg(-1), and satisfactory recovery values of 84.8-103.1% were obtained for the tested seafood samples. It was confirmed that the developed method is simple, fast, sensitive, and accurate for the determination of 15 trace environmental phenols in seafood samples.

  12. Simultaneous determination of ethanol's four types of non-oxidative metabolites in human whole blood by liquid chromatography tandem mass spectrometry.

    PubMed

    Zhang, Xinyu; Zheng, Feng; Lin, Zebin; Johansen, Sys Stybe; Yu, Tianfang; Liu, Yuming; Huang, Zhibin; Li, Jiaolun; Yan, Jie; Rao, Yulan

    2017-04-22

    The importance of ethanol non-oxidative metabolites as the specific biomarkers of alcohol consumption in clinical and forensic settings is increasingly acknowledged. Simultaneous determination of these metabolites can provide a wealth of information like drinking habit and history, but it was difficult to achieve because of their wide range of polarity. This work describes development and validation of a simple liquid chromatography tandem mass spectrometry (LC-MS/MS) assay for 4 types of ethanol non-oxidative metabolites (ethyl glucuronide, ethyl sulfate, fatty acid ethyl esters and phosphatidylethanols) in 50 μL of human whole blood. Pretreatment method, column and MS conditions were optimized. For the first time, the four types of ethanol non-oxidative metabolites with enormous discrepancies of property were simultaneously extracted and analyzed in one run within 40 min. The limits of detections (LODs) were among 0.1-10 ng/mL, and good linearity was obtained. Deviations in precision and accuracy were all lower than 15% at three QC levels. This method was then applied to two forensic samples, resulting in information on drinking habits and drinking time which were very useful for the interpretation of the blood alcohol results.

  13. Plasmon-exciton couplings in Al-CuCl nanoshells and the effects of oxidation

    NASA Astrophysics Data System (ADS)

    Yao, Jie; Ji, WenQian; Wu, DaJian; Cheng, Ying; Liu, XiaoJun

    2017-04-01

    The plasmon-exciton couplings in the Al-CuCl nanoshells have been investigated by using the Mie scattering theory. It is found that the bright dipole mode of the Al nanosphere can couple well with the exciton mode of the outer CuCl shell in the UV region by changing the geometry. The strong plasmon-exciton couplings in the Al-CuCl nanoshell lead to two hybrid plexcitonic modes and hence the Rabi splitting. We study the dispersion curves of the plexcitonic modes of the Al-CuCl nanoshells and obtain the splitting energy of about 135 meV. Furthermore, the influences of the metal oxide on the plasmon-exciton couplings in the Al-CuCl nanoshells have been studied. It is found that the Rabi splitting energy will shrink with the oxide.

  14. Transcription-coupled homologous recombination after oxidative damage.

    PubMed

    Wei, Leizhen; Levine, Arthur Samuel; Lan, Li

    2016-08-01

    Oxidative DNA damage induces genomic instability and may lead to mutagenesis and carcinogenesis. As severe blockades to RNA polymerase II (RNA POLII) during transcription, oxidative DNA damage and the associated DNA strand breaks have a profoundly deleterious impact on cell survival. To protect the integrity of coding regions, high fidelity DNA repair at a transcriptionally active site in non-dividing somatic cells, (i.e., terminally differentiated and quiescent/G0 cells) is necessary to maintain the sequence integrity of transcribed regions. Recent studies indicate that an RNA-templated, transcription-associated recombination mechanism is important to protect coding regions from DNA damage-induced genomic instability. Here, we describe the discovery that G1/G0 cells exhibit Cockayne syndrome (CS) B (CSB)-dependent assembly of homologous recombination (HR) factors at double strand break (DSB) sites within actively transcribed regions. This discovery is a challenge to the current dogma that HR occurs only in S/G2 cells where undamaged sister chromatids are available as donor templates.

  15. Treatment of pharmaceutical effluent by ultrasound coupled with dual oxidant system.

    PubMed

    Nachiappan, Senthilnathan; Muthukumar, Karuppan

    2013-01-01

    In this study, sonolysis (US), a dual oxidant system (DOX), and ultrasound coupled with a dual oxidant system (US/DOX) were employed to degrade real pharmaceutical effluent. In a DOX system, two effective oxidizing agents such as hydrogen peroxide and activated persulphate were used simultaneously. In this work, for the first time, an easily available waste material, iron swarf, was used as an activator for persulphate oxidation. Iron swarf coupled with an ultrasound system showed better activation. High iron dosage, acidic pH and high temperature favoured degradation with both DOX and US/DOX. Sequential addition of iron swarf produced better results compared to single-step addition. The activation energy was found to be 47.25 and 23.47 kJ/mol for DOX and US/DOX, respectively. The biodegradability index of the effluent was enhanced from 0.13 to 0.81 after treatment with US/DOX.

  16. Degradation of organic dyes via bismuth silver oxide initiated direct oxidation coupled with sodium bismuthate based visible light photocatalysis.

    PubMed

    Yu, Kai; Yang, Shaogui; Liu, Cun; Chen, Hongzhe; Li, Hui; Sun, Cheng; Boyd, Stephen A

    2012-07-03

    Organic dye degradation was achieved via direct oxidation by bismuth silver oxide coupled with visible light photocatalysis by sodium bismuthate. Crystal violet dye decomposition by each reagent proceeded via two distinct pathways, each involving different active oxygen species. A comparison of each treatment method alone and in combination demonstrated that using the combined methods in sequence achieved a higher degree of degradation, and especially mineralization, than that obtained using either method alone. In the combined process direct oxidation acts as a pretreatment to rapidly bleach the dye solution which substantially facilitates subsequent visible light photocatalytic processes. The integrated sequential direct oxidation and visible light photocatalysis are complementary manifesting a > 100% increase in TOC removal, compared to either isolated method. The combined process is proposed as a novel and effective technology based on one primary material, sodium bismuthate, for treating wastewaters contaminated by high concentrations of organic dyes.

  17. Impact of orthogonal exchange coupling on magnetic anisotropy in antiferromagnetic oxides/ferromagnetic systems

    NASA Astrophysics Data System (ADS)

    Kuświk, Piotr; Lana Gastelois, Pedro; Głowiński, Hubert; Przybylski, Marek; Kirschner, Jürgen

    2016-10-01

    The influence of interface exchange coupling on magnetic anisotropy in the antiferromagnetic oxide/Ni system is investigated. We show how interfacial exchange coupling can be employed not only to pin the magnetization of the ferromagnetic layer but also to support magnetic anisotropy to orient the easy magnetization axis perpendicular to the film plane. The fact that this effect is only observed below the Néel temperature of all investigated antiferromagnetic oxides with significantly different magnetocrystalline anisotropies gives evidence that antiferromagnetic ordering is a source of the additional contribution to the perpendicular effective magnetic anisotropy.

  18. Impact of orthogonal exchange coupling on magnetic anisotropy in antiferromagnetic oxides/ferromagnetic systems.

    PubMed

    Kuświk, Piotr; Gastelois, Pedro Lana; Głowiński, Hubert; Przybylski, Marek; Kirschner, Jürgen

    2016-10-26

    The influence of interface exchange coupling on magnetic anisotropy in the antiferromagnetic oxide/Ni system is investigated. We show how interfacial exchange coupling can be employed not only to pin the magnetization of the ferromagnetic layer but also to support magnetic anisotropy to orient the easy magnetization axis perpendicular to the film plane. The fact that this effect is only observed below the Néel temperature of all investigated antiferromagnetic oxides with significantly different magnetocrystalline anisotropies gives evidence that antiferromagnetic ordering is a source of the additional contribution to the perpendicular effective magnetic anisotropy.

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

    PubMed Central

    Guo, Fenghai; Clift, Michael D.

    2013-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1975-01-01

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

  1. TBHP-mediated highly efficient dehydrogenative cross-oxidative coupling of methylarenes with acetanilides

    PubMed Central

    Liu, Weibing; Zhou, Peng

    2016-01-01

    A TBHP-mediated dehydrogenative cross-oxidative-coupling approach has been developed for the synthesis of N-arylbenzamides from methylarenes and acetanilides. This cross-coupling method is free of transition metal catalysts and ligands, and no extra organic solvents are required, which make it an useful and attractive strategy for the straightforward construction of C–N bonds. Besides, this conversion is an important complement to the conventional C–N forming strategies. PMID:28144291

  2. Inductively coupled plasma - Tandem mass spectrometry (ICP-MS/MS): A powerful and universal tool for the interference-free determination of (ultra)trace elements – A tutorial review.

    PubMed

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

    2015-09-24

    This paper is intended as a tutorial review on the use of inductively coupled plasma - tandem mass spectrometry (ICP-MS/MS) for the interference-free quantitative determination and isotope ratio analysis of metals and metalloids in different sample types. Attention is devoted both to the instrumentation and to some specific tools and procedures available for advanced method development. Next to the more typical reaction gases, e.g., H2, O2 and NH3, also the use of promising alternative gases, such as CH3F, is covered, and the possible reaction pathways with those reactive gases are discussed. A variety of published applications relying on the use of ICP-MS/MS are described, to illustrate the added value of tandem mass spectrometry in (ultra)trace analysis.

  3. Coupled Mn(II) Oxidation Pathways by a Planktonic Roseobacter-like Bacterium

    NASA Astrophysics Data System (ADS)

    Hansel, C. M.; Francis, C. A.

    2005-12-01

    Bacteria belonging to the Roseobacter clade of the alpha-Proteobacteria are numerically abundant in coastal waters, ecologically significant in the cycling of (in)organic sulfur, and occupy a wide range of environmental niches. Here we reveal that Roseobacter-like bacteria may play a previously unrecognized role in the oxidation and cycling of manganese (Mn) in coastal waters. A diverse array of Mn(II)-oxidizing Roseobacter-like species were isolated from Elkhorn Slough, a coastal estuary adjacent to Monterey Bay, California. One isolate (designated AzwK-3b), in particular, rapidly oxidizes Mn(II) to insoluble Mn(III, IV) oxides. Interestingly, AzwK-3b is 100% identical (at the 16S rRNA level) to a previously reported Pfiesteria-associated Roseobacter-like bacterium, which does not posses the ability to oxidize Mn(II). Manganese(II) oxidation rates by live cultures and cell-free filtrates are substantially higher when incubated in the presence of light. Rates of oxidation by washed cell extracts, however, are light independent, which are actually identical to rates by cell-free filtrates incubated in the dark. Thus, AwwK-3b induces two Mn(II) oxidation mechanisms when incubated in the presence of light as opposed to predominantly direct enzymatic oxidation in the dark. Within the light, production of photochemically-active metabolites is coupled with initial direct enzymatic Mn(II) oxidation, resulting in substantially accelerated Mn(II) oxidation rates. Thus, Roseobacter-like bacteria may not only greatly influence Mn(II) oxidation and cycling within coastal surface waters, but may also induce a novel photo-oxidation pathway providing an alternative means of Mn(II) oxidation within the photic zone.

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

    USGS Publications Warehouse

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

    1989-01-01

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

  5. Hydrogen measurement during steam oxidation using coupled thermogravimetric analysis and quadrupole mass spectrometry

    SciTech Connect

    Parkison, Adam J.; Nelson, Andrew Thomas

    2016-01-11

    An analytical technique is presented with the goal of measuring reaction kinetics during steam oxidation reactions for three cases in which obtaining kinetics information often requires a prohibitive amount of time and cost. The technique presented relies on coupling thermogravimetric analysis (TGA) with a quantitative hydrogen measurement technique using quadrupole mass spectrometry (QMS). The first case considered is in differentiating between the kinetics of steam oxidation reactions and those for simultaneously reacting gaseous impurities such as nitrogen or oxygen. The second case allows one to independently measure the kinetics of oxide and hydride formation for systems in which both of these reactions are known to take place during steam oxidation. The third case deals with measuring the kinetics of formation for competing volatile and non-volatile oxides during certain steam oxidation reactions. In order to meet the requirements of the coupled technique, a methodology is presented which attempts to provide quantitative measurement of hydrogen generation using QMS in the presence of an interfering fragmentation species, namely water vapor. This is achieved such that all calibrations and corrections are performed during the TGA baseline and steam oxidation programs, making system operation virtually identical to standard TGA. Benchmarking results showed a relative error in hydrogen measurement of 5.7–8.4% following the application of a correction factor. Lastly, suggestions are made for possible improvements to the presented technique so that it may be better applied to the three cases presented.

  6. Hydrogen measurement during steam oxidation using coupled thermogravimetric analysis and quadrupole mass spectrometry

    DOE PAGES

    Parkison, Adam J.; Nelson, Andrew Thomas

    2016-01-11

    An analytical technique is presented with the goal of measuring reaction kinetics during steam oxidation reactions for three cases in which obtaining kinetics information often requires a prohibitive amount of time and cost. The technique presented relies on coupling thermogravimetric analysis (TGA) with a quantitative hydrogen measurement technique using quadrupole mass spectrometry (QMS). The first case considered is in differentiating between the kinetics of steam oxidation reactions and those for simultaneously reacting gaseous impurities such as nitrogen or oxygen. The second case allows one to independently measure the kinetics of oxide and hydride formation for systems in which both ofmore » these reactions are known to take place during steam oxidation. The third case deals with measuring the kinetics of formation for competing volatile and non-volatile oxides during certain steam oxidation reactions. In order to meet the requirements of the coupled technique, a methodology is presented which attempts to provide quantitative measurement of hydrogen generation using QMS in the presence of an interfering fragmentation species, namely water vapor. This is achieved such that all calibrations and corrections are performed during the TGA baseline and steam oxidation programs, making system operation virtually identical to standard TGA. Benchmarking results showed a relative error in hydrogen measurement of 5.7–8.4% following the application of a correction factor. Lastly, suggestions are made for possible improvements to the presented technique so that it may be better applied to the three cases presented.« less

  7. Catalyst-Free Three-Component Tandem CDC Cyclization: Convenient Access to Isoindolinones from Aromatic Acid, Amides, and DMSO by a Pummerer-Type Rearrangement.

    PubMed

    Wang, Peng-Min; Pu, Fan; Liu, Ke-Yan; Li, Chao-Jun; Liu, Zhong-Wen; Shi, Xian-Ying; Fan, Juan; Yang, Ming-Yu; Wei, Jun-Fa

    2016-04-25

    A catalyst-free multicomponent CDC reaction is rarely reported, especially for the intermolecular tandem CDC cyclization, which represents an important strategy for constructing cyclic compounds. Herein, a three-component tandem CDC cyclization by a Pummerer-type rearrangement to afford biologically relevant isoindolinones from aromatic acids, amides, and DMSO, is described. This intermolecular tandem reaction undergoes a C(sp(2) )-H/C(sp(3) )-H cross-dehydrogenative coupling, C-N bond formation, and intramolecular amidation. A notable feature of this novel protocol is avoiding a catalyst and additive (apart from oxidant).

  8. Simultaneous determination of diphenhydramine, its N-oxide metabolite and their deuterium-labeled analogues in ovine plasma and urine using liquid chromatography/electrospray tandem mass spectrometry.

    PubMed

    Kumar, S; Rurak, D W; Riggs, K W

    1998-12-01

    Our studies on drug disposition in chronically instrumented pregnant sheep involve simultaneous administration of the antihistamine diphenhydramine (DPHM), its deuterated analogue ([2H10]DPHM) and their metabolites to the mother or the fetus via various routes. Such studies require sensitive and selective mass spectrometric methods for quantitation of these labeled and unlabeled compounds in order to assess comparative maternal and fetal drug metabolism. The objective of this study was to develop and validate a liquid chromatographic/tandem mass spectrometric (LC/MS/MS) method for the simultaneous quantitation of DPHM, its N-oxide metabolite and their deuterium-labeled analogues in ovine plasma and urine. Samples spiked with the analytes and the internal standard, orphenadrine, were processed using liquid-liquid extraction. The extract was chromatographed on a propylamino LC column and MS/MS detection was performed in the positive ion electrospray mode using multiple reaction monitoring. The linear concentration ranges of the calibration curves for the N-oxides and the parent amines were 0.4-100.0 and 0.2-250.0 ng ml-1, respectively. In validation tests, the assay exhibited acceptable variability (< or = 15% at analyte concentrations below 2.0 ng ml-1 and < 10% at all other concentrations) and bias (< 15% at all concentrations), and the analytes were stable under a variety of sample handling conditions. Using this method, the labeled and unlabeled N-oxide metabolite was identified in fetal plasma after DPHM and [2H10]DPHM administration. This method will be used further to examine the comparative metabolism of diphenhydramine to its N-oxide metabolite in the mother and the fetus.

  9. Gold-catalyzed three-component coupling: oxidative oxyarylation of alkenes.

    PubMed

    Melhado, Asa D; Brenzovich, William E; Lackner, Aaron D; Toste, F Dean

    2010-07-07

    The three-component coupling of terminal alkenes with arylboronic acids and oxygen nucleophiles is described. The reaction employs a binuclear gold(I) bromide as a catalyst and Selectfluor reagent as the stoichiometric oxidant. Alcohols, carboxylic acids, and water can be employed as oxygen nucleophiles, thus providing an efficient entry into beta-aryl ethers, esters, and alcohols from alkenes.

  10. Microstructure and lateral conductivity control of hydrogenated nanocrystalline silicon oxide and its application in a-Si:H/a-SiGe:H tandem solar cells

    NASA Astrophysics Data System (ADS)

    Tian-Tian, Li; Tie, Yang; Jia, Fang; De-Kun, Zhang; Jian, Sun; Chang-Chun, Wei; Sheng-Zhi, Xu; Guang-Cai, Wang; Cai-Chi, Liu; Ying, Zhao; Xiao-Dan, Zhang

    2016-04-01

    Phosphorous-doped hydrogenated nanocrystalline silicon oxide (n-nc-SiO x :H) films are prepared via radio frequency plasma enhanced chemical vapor deposition (RF-PECVD). Increasing deposition power during n-nc-SiO x :H film growth process can enhance the formation of nanocrystalline and obtain a uniform microstructure of n-nc-SiO x :H film. In addition, in 20s interval before increasing the deposition power, high density small grains are formed in amorphous SiO x matrix with higher crystalline volume fraction (I c) and have a lower lateral conductivity. This uniform microstructure indicates that the higher I c can leads to better vertical conductivity, lower refractive index, wider optical band-gap. It improves the back reflection in a-Si:H/a-SiGe:H tandem solar cells acting as an n-nc-SiO x :H back reflector prepared by the gradient power during deposition. Compared with the sample with SiO x back reflector, with a constant power used in deposition process, the sample with gradient power SiO x back reflector can enhance the total short-circuit current density (J sc) and the initial efficiency of a-Si:H/a-SiGe:H tandem solar cells by 8.3% and 15.5%, respectively. Project supported by the Hi-Tech Research and Development Program of China (Grant No. 2013AA050302), the National Natural Science Foundation of China (Grant No. 61474065), Tianjin Municipal Research Key Program of Application Foundation and Advanced Technology, China (Grant No. 15JCZDJC31300), the Key Project in the Science & Technology Pillar Program of Jiangsu Province, China (Grant No. BE2014147-3), and the Specialized Research Fund for the Ph. D. Program of Higher Education, China (Grant No. 20120031110039).

  11. Differentiation between isomeric oxidative metabolites of a piperidine-containing drug by liquid chromatography-tandem mass spectrometry with stable-isotope tracer technique.

    PubMed

    Kato, Koji; Jingu, Shigeji; Ogawa, Naoyoshi; Higuchi, Shohei

    2002-02-01

    This report describes the application of a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method to differentiation of hydroxylations and N-oxidations and of two different aliphatic hydroxylations in the investigation of the metabolism of pibutidine hydrochloride, a novel H2 antagonist, the structure of which includes a piperidine ring. Pibutidine metabolites in urine samples from adult male volunteers after oral administration of pibutidine hydrochloride were separated by reversed-phase LC and ionized using an electrospray ionization (ESI) interface. A hydroxylated form of pibutidine was distinguished from the N-oxide by comparison of their product ion spectra, although their mass-to-charge ratios of protonated molecules were identical. Further, two hydroxylated compounds were present in rat microsomal incubation mixtures with pibutidine. The distinction between their positions of hydroxylation (beta- and gamma-carbon hydroxylation) on the piperidine ring was studied using [piperidine-2H10] pibutidine as incubation substrate. The production of the beta-hydroxylated form was accompanied by the elimination of three 2H, resulting from a mechanism including the formation of iminium/enamine. The participation of the iminium ion intermediate in the beta-hydroxylation was confirmed by the observation that a cyanide adduct of pibutidine was formed instead of the beta-hydroxylated form when another incubation was performed in the presence of cyanide.

  12. Electric coupling between distant nitrate reduction and sulfide oxidation in marine sediment.

    PubMed

    Marzocchi, Ugo; Trojan, Daniela; Larsen, Steffen; Meyer, Rikke Louise; Revsbech, Niels Peter; Schramm, Andreas; Nielsen, Lars Peter; Risgaard-Petersen, Nils

    2014-08-01

    Filamentous bacteria of the Desulfobulbaceae family can conduct electrons over centimeter-long distances thereby coupling oxygen reduction at the surface of marine sediment to sulfide oxidation in deeper anoxic layers. The ability of these cable bacteria to use alternative electron acceptors is currently unknown. Here we show that these organisms can use also nitrate or nitrite as an electron acceptor thereby coupling the reduction of nitrate to distant oxidation of sulfide. Sulfidic marine sediment was incubated with overlying nitrate-amended anoxic seawater. Within 2 months, electric coupling of spatially segregated nitrate reduction and sulfide oxidation was evident from: (1) the formation of a 4-6-mm-deep zone separating sulfide oxidation from the associated nitrate reduction, and (2) the presence of pH signatures consistent with proton consumption by cathodic nitrate reduction, and proton production by anodic sulfide oxidation. Filamentous Desulfobulbaceae with the longitudinal structures characteristic of cable bacteria were detected in anoxic, nitrate-amended incubations but not in anoxic, nitrate-free controls. Nitrate reduction by cable bacteria using long-distance electron transport to get privileged access to distant electron donors is a hitherto unknown mechanism in nitrogen and sulfur transformations, and the quantitative importance for elements cycling remains to be addressed.

  13. Oxide Defect Engineering Enables to Couple Solar Energy into Oxygen Activation.

    PubMed

    Zhang, Ning; Li, Xiyu; Ye, Huacheng; Chen, Shuangming; Ju, Huanxin; Liu, Daobin; Lin, Yue; Ye, Wei; Wang, Chengming; Xu, Qian; Zhu, Junfa; Song, Li; Jiang, Jun; Xiong, Yujie

    2016-07-20

    Modern development of chemical manufacturing requires a substantial reduction in energy consumption and catalyst cost. Sunlight-driven chemical transformation by metal oxides holds great promise for this goal; however, it remains a grand challenge to efficiently couple solar energy into many catalytic reactions. Here we report that defect engineering on oxide catalyst can serve as a versatile approach to bridge light harvesting with surface reactions by ensuring species chemisorption. The chemisorption not only spatially enables the transfer of photoexcited electrons to reaction species, but also alters the form of active species to lower the photon energy requirement for reactions. In a proof of concept, oxygen molecules are activated into superoxide radicals on defect-rich tungsten oxide through visible-near-infrared illumination to trigger organic aerobic couplings of amines to corresponding imines. The excellent efficiency and durability for such a highly important process in chemical transformation can otherwise be virtually impossible to attain by counterpart materials.

  14. Accurate determination of ultra-trace impurities, including europium, in ultra-pure barium carbonate materials through inductively coupled plasma-tandem mass spectrometry

    NASA Astrophysics Data System (ADS)

    Wu, Shuchao; Zeng, Xiangcheng; Dai, Xuefeng; Hu, Yongping; Li, Gang; Zheng, Cunjiang

    2016-09-01

    Impurities, especially ultra-trace europium (Eu), in ultra-pure barium carbonate materials were accurately determined through inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS). Two reaction modes, namely, mass shift (with O2 as reaction gas) and on-mass modes(with NH3/He and He as reaction gases), were extensively investigated using Eu+ as target analyte. The use of Eu+ → EuO2+, instead of Eu+ → EuO+, as ion pairs in mass shift mode eliminated polyatomic interferences based on Ba matrix ions (135Ba16O2+ on 151Eu16O+ and 137Ba16O2+ on 153Eu16O+). This procedure exhibited enhanced sensitivity and selectivity. When the ICP-MS/MS was operated in NH3 on-mass mode, Eu+ can be determined in its original mass in interference-free conditions because NH3 did not react with Eu+ but with BaO+ to form a neutral product (BaO). The two reaction modes, especially NH3 on mass mode, were validated to be accurate because their resultant isotope ratios of 153Eu/151Eu matched well with that of the natural abundance ratio. The proposed ICP-MS/MS method is a sensitive technique with a limit of detection as low as 2.0 ng L- 1 for 153Eu+. Compared with conventional single-quadrupole (SQ) ICP-MS, both NH3 on-mass mode and O2 mass shift mode in ICP-MS/MS can be used to accurately determine Eu+ in ultra-pure BaCO3 materials. The detected concentration of Eu+ was 4.0 ng L- 1 to 15 ng L- 1, with spiked recoveries ranging from 100%-110%. ICP-MS/MS was also used to eliminate polyatomic interferences, particularly Ba-based interferences, prior to measurement of Gd and Sm. Impurities, including Na, Mg, Al, K, Mn, Fe, Cr, Sr, and Cs, in ultra-pure BaCO3 materials were also determined using ICP-MS/MS in conventional SQ mode.

  15. Site-specific indolation of proline-based peptides via copper(II)-catalyzed oxidative coupling of tertiary amine N-oxides.

    PubMed

    Wu, Xiaowei; Zhang, Dengyou; Zhou, Shengbin; Gao, Feng; Liu, Hong

    2015-08-14

    The first site-specific and purely chemical method for modifying proline-based peptides was developed via a convenient, copper-catalyzed oxidative coupling of tertiary amine N-oxides with indoles. This novel approach features high regioselectivity and diastereoselectivity, mild conditions, and compatibility with various functional groups. In addition, a simplified process was realized in one pot and two steps via in situ oxidative coupling of tertiary amine and indoles.

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

    PubMed

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

    2014-08-01

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

  17. 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 ...

  18. Oxidative C-H/C-H Coupling Reactions between Two (Hetero)arenes.

    PubMed

    Yang, Yudong; Lan, Jingbo; You, Jingsong

    2017-01-13

    Transition metal-mediated C-H bond activation and functionalization represent one of the most straightforward and powerful tools in modern organic synthetic chemistry. Bi(hetero)aryls are privileged π-conjugated structural cores in biologically active molecules, organic functional materials, ligands, and organic synthetic intermediates. The oxidative C-H/C-H coupling reactions between two (hetero)arenes through 2-fold C-H activation offer a valuable opportunity for rapid assembly of diverse bi(hetero)aryls and further exploitation of their applications in pharmaceutical and material sciences. This review provides a comprehensive overview of the fundamentals and applications of transition metal-mediated/catalyzed oxidative C-H/C-H coupling reactions between two (hetero)arenes. The substrate scope, limitation, reaction mechanism, regioselectivity, and chemoselectivity, as well as related control strategies of these reactions are discussed. Additionally, the applications of these established methods in the synthesis of natural products and exploitation of new organic functional materials are exemplified. In the last section, a short introduction on oxidant- or Lewis acid-mediated oxidative Ar-H/Ar-H coupling reactions is presented, considering that it is a very powerful method for the construction of biaryl units and polycylic arenes.

  19. Ternary and coupled binary zinc tin oxide nanopowders: Synthesis, characterization, and potential application in photocatalytic processes

    SciTech Connect

    Ivetić, T.B.; Finčur, N.L.; Đačanin, Lj. R.; Abramović, B.F.; Lukić-Petrović, S.R.

    2015-02-15

    Highlights: • Mechanochemically synthesized nanocrystalline zinc tin oxide (ZTO) powders. • Photocatalytic degradation of alprazolam in the presence of ZTO water suspensions. • Coupled binary ZTO exhibits enhanced photocatalytic activity compared to ternary ZTO. - Abstract: In this paper, ternary and coupled binary zinc tin oxide nanocrystalline powders were prepared via simple solid-state mechanochemical method. X-ray diffraction, scanning electron microscopy, Raman and reflectance spectroscopy were used to study the structure and optical properties of the obtained powder samples. The thermal behavior of zinc tin oxide system was examined through simultaneous thermogravimetric-differential scanning calorimetric analysis. The efficiencies of ternary (Zn{sub 2}SnO{sub 4} and ZnSnO{sub 3}) and coupled binary (ZnO/SnO{sub 2}) zinc tin oxide water suspensions in the photocatalytic degradation of alprazolam, short-acting anxiolytic of the benzodiazepine class of psychoactive drugs, under UV irradiation were determined and compared with the efficiency of pure ZnO and SnO{sub 2}.

  20. Coupling Between and Among Ammonia Oxidizers and Nitrite Oxidizers in Grassland Mesocosms Submitted to Elevated CO2 and Nitrogen Supply.

    PubMed

    Simonin, Marie; Le Roux, Xavier; Poly, Franck; Lerondelle, Catherine; Hungate, Bruce A; Nunan, Naoise; Niboyet, Audrey

    2015-10-01

    Many studies have assessed the responses of soil microbial functional groups to increases in atmospheric CO2 or N deposition alone and more rarely in combination. However, the effects of elevated CO2 and N on the (de)coupling between different microbial functional groups (e.g., different groups of nitrifiers) have been barely studied, despite potential consequences for ecosystem functioning. Here, we investigated the short-term combined effects of elevated CO2 and N supply on the abundances of the four main microbial groups involved in soil nitrification: ammonia-oxidizing archaea (AOA), ammonia-oxidizing bacteria (AOB), and nitrite-oxidizing bacteria (belonging to the genera Nitrobacter and Nitrospira) in grassland mesocosms. AOB and AOA abundances responded differently to the treatments: N addition increased AOB abundance, but did not alter AOA abundance. Nitrobacter and Nitrospira abundances also showed contrasted responses to the treatments: N addition increased Nitrobacter abundance, but decreased Nitrospira abundance. Our results support the idea of a niche differentiation between AOB and AOA, and between Nitrobacter and Nitrospira. AOB and Nitrobacter were both promoted at high N and C conditions (and low soil water content for Nitrobacter), while AOA and Nitrospira were favored at low N and C conditions (and high soil water content for Nitrospira). In addition, Nitrobacter abundance was positively correlated to AOB abundance and Nitrospira abundance to AOA abundance. Our results suggest that the couplings between ammonia and nitrite oxidizers are influenced by soil N availability. Multiple environmental changes may thus elicit rapid and contrasted responses between and among the soil ammonia and nitrite oxidizers due to their different ecological requirements.

  1. Concurrent Formation of Carbon–Carbon Bonds and Functionalized Graphene by Oxidative Carbon-Hydrogen Coupling Reaction

    NASA Astrophysics Data System (ADS)

    Morioku, Kumika; Morimoto, Naoki; Takeuchi, Yasuo; Nishina, Yuta

    2016-05-01

    Oxidative C–H coupling reactions were conducted using graphene oxide (GO) as an oxidant. GO showed high selectivity compared with commonly used oxidants such as (diacetoxyiodo) benzene and 2,3-dichloro-5,6-dicyano-p-benzoquinone. A mechanistic study revealed that radical species contributed to the reaction. After the oxidative coupling reaction, GO was reduced to form a material that shows electron conductivity and high specific capacitance. Therefore, this system could concurrently achieve two important reactions: C–C bond formation via C–H transformation and production of functionalized graphene.

  2. Concurrent Formation of Carbon–Carbon Bonds and Functionalized Graphene by Oxidative Carbon-Hydrogen Coupling Reaction

    PubMed Central

    Morioku, Kumika; Morimoto, Naoki; Takeuchi, Yasuo; Nishina, Yuta

    2016-01-01

    Oxidative C–H coupling reactions were conducted using graphene oxide (GO) as an oxidant. GO showed high selectivity compared with commonly used oxidants such as (diacetoxyiodo) benzene and 2,3-dichloro-5,6-dicyano-p-benzoquinone. A mechanistic study revealed that radical species contributed to the reaction. After the oxidative coupling reaction, GO was reduced to form a material that shows electron conductivity and high specific capacitance. Therefore, this system could concurrently achieve two important reactions: C–C bond formation via C–H transformation and production of functionalized graphene. PMID:27181191

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

    PubMed Central

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

    2013-01-01

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

  4. Transient characteristics for proton gating in laterally coupled indium-zinc-oxide transistors.

    PubMed

    Liu, Ning; Zhu, Li Qiang; Xiao, Hui; Wan, Chang Jin; Liu, Yang Hui; Chao, Jin Yu

    2015-03-25

    The control and detection over processing, transport and delivery of chemical species is of great importance in sensors and biological systems. The transient characteristics of the migration of chemical species reflect the basic properties in the processings of chemical species. Here, we observed the field-configurable proton effects in a laterally coupled transistor gated by phosphorosilicate glass (PSG). The bias on the lateral gate would modulate the interplay between protons and electrons at the PSG/indium-zinc-oxide (IZO) channel interface. Due to the modulation of protons flux within the PSG films, the IZO channel current would be modified correspondingly. The characteristic time for the proton gating is estimated to be on the order of 20 ms. Such laterally coupled oxide based transistors with proton gating are promising for low-cost portable biosensors and neuromorphic system applications.

  5. Photocatalytic Dehydrogenative Cross-Coupling of Alkenes with Alcohols or Azoles without External Oxidant.

    PubMed

    Yi, Hong; Niu, Linbin; Song, Chunlan; Li, Yiying; Dou, Bowen; Singh, Atul K; Lei, Aiwen

    2017-01-19

    Direct cross-coupling between alkenes/R-H or alkenes/RXH is a dream reaction, especially without external oxidants. Inputting energy by photocatalysis and employing a cobalt catalyst as a two-electron acceptor, a direct C-H/X-H cross-coupling with H2 evolution has been achieved for C-O and C-N bond formation. A new radical alkenylation using alkene as the redox compound is presented. A wide range of aliphatic alcohols-even long chain alcohols-are tolerated well in this system, providing a new route to multi-substituted enol ether derivatives using simple alkenes. Additionally, this protocol can also be used for N-vinylazole synthesis. Mechanistic insights reveal that the cobalt catalyst oxidizes the photocatalyst to revive the photocatalytic cycle.

  6. Towards a zero-waste oxidative coupling of nonactivated aromatics by supported gold nanoparticles.

    PubMed

    Serna, Pedro; Corma, Avelino

    2014-08-01

    We show that gold nanoparticles are able to perform the direct oxidative coupling of nonactivated aromatics with O2 as the only co-reagent. In this reaction, the aromatic acts both as reactant and solvent. Biphenyl, for example, can be obtained from benzene with high selectivity and a turnover number (TON) of 230 per pass. Similarly, several substituted biaryls can be prepared. Pd performs only one TON and even when a second catalytic functionality is introduced, together with strong acidic conditions, TON is always lower than 100. Other catalysts require iodine for performing the reaction, leading to 2 kg of waste for 1 kg of biphenyl formed, whereas no waste is created by the oxidative coupling with gold nanoparticles.

  7. Spatially coupled catalytic ignition of CO oxidation on Pt: mesoscopic versus nano-scale

    PubMed Central

    Spiel, C.; Vogel, D.; Schlögl, R.; Rupprechter, G.; Suchorski, Y.

    2015-01-01

    Spatial coupling during catalytic ignition of CO oxidation on μm-sized Pt(hkl) domains of a polycrystalline Pt foil has been studied in situ by PEEM (photoemission electron microscopy) in the 10−5 mbar pressure range. The same reaction has been examined under similar conditions by FIM (field ion microscopy) on nm-sized Pt(hkl) facets of a Pt nanotip. Proper orthogonal decomposition (POD) of the digitized FIM images has been employed to analyze spatiotemporal dynamics of catalytic ignition. The results show the essential role of the sample size and of the morphology of the domain (facet) boundary in the spatial coupling in CO oxidation. PMID:26021411

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

    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.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. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr07251k

  9. [In-situ DRIFTS study of coupling partial oxidation of methane and carbon dioxide reforming].

    PubMed

    Ji, Hong-bing; Xu, Jian-hua; Xie, Jun-feng; Chen, Qing-lin

    2008-06-01

    8%Ru-5%Ce/gamma-Al2O3 catalyst exhibited excellent catalytic performance for low temperature activation of methane. Although the conversion rates of methane were 25.3% for exothermal partial oxidation of methane, and 0.8% for endothermal carbon dioxide reforming, whose activity was rather low, 38.8% of conversion rate of methane could be obtained for the obtained coupling reaction at 500 degrees C owing to the coupling intensification between endothermal carbon dioxide reforming reaction and exothermal partial oxidation of methane. The mechanism of coupling partial oxidation of methane and carbon dioxide reforming on supported Ru catalyst was investigated by in-situ DRIFTS. The adsorption of CO on 8%Ru-5%Ce/gamma-Al2O3 showed that two kinds of doublet peaks which were characteristic adsorption of the gaseous CO at 2167 cm(-1) (2118 cm(-1)) to form Ru(CO)2 at 2031 cm(-1) (2034 cm(-1)) to form Ce(CO)2 were observed. These CO adsorption species wee easy to be desorbed from the surface of the catalyst at high temperature. The results of in-situ DRIFTS showed that carbonate, formal (formate) and carbon monoxide formed on the surface of catalyst, and formal (formate) was intermediate for the methane partial oxidation. This intermediate was formed through the combination of the adsorption species of methane CHx and the lattice oxygen adsorption species on the surface of catalyst, and syngas was produced through the splitting of this intermediate. The DRIFTS researching on carbon dioxide reforming showed that there was no new adsorption species on the surface of the catalyst, which indicated that the mechanism for carbon dioxide reforming was through the dissociation of the adsorbed methane and carbon dioxide. During the reaction of the coupling of carbon dioxide reforming reaction and partial oxidation of methane, there was hydroxyl adsorption species on the surface of catalyst. The mechanism of coupling methane, carbon dioxide and oxygen might be composed of the above

  10. Development of oxidative coupling strategies for site-selective protein modification.

    PubMed

    ElSohly, Adel M; Francis, Matthew B

    2015-07-21

    As the need to prepare ever more complex but well-defined materials has increased, a similar need for reliable synthetic strategies to access them has arisen. Accordingly, recent years have seen a steep increase in the development of reactions that can proceed under mild conditions, in aqueous environments, and with low concentrations of reactants. To enable the preparation of well-defined biomolecular materials with novel functional properties, our laboratory has a continuing interest in developing new bioconjugation reactions. A particular area of focus has been the development of oxidative reactions to perform rapid site- and chemoselective couplings of electron rich aromatic species with both unnatural and canonical amino acid residues. This Account details the evolution of oxidative coupling reactions in our laboratory, from initial concepts to highly efficient reactions, focusing on the practical aspects of performing and developing reactions of this type. We begin by discussing our rationale for choosing an oxidative coupling approach to bioconjugation, highlighting many of the benefits that such strategies provide. In addition, we discuss the general workflow we have adopted to discover protein modification reactions directly in aqueous media with biologically relevant substrates. We then review our early explorations of periodate-mediated oxidative couplings between primary anilines and p-phenylenediamine substrates, highlighting the most important lessons that were garnered from these studies. Key mechanistic insights allowed us to develop second-generation reactions between anilines and anisidine derivatives. In addition, we summarize the methods we have used for the introduction of aniline groups onto protein substrates for modification. The development of an efficient and chemoselective coupling of anisidine derivatives with tyrosine residues in the presence of ceric ammonium nitrate is next described. Here, our logic and workflow are used to highlight

  11. Comparison of electron and chemical ionization modes for the quantification of thiols and oxidative compounds in white wines by gas chromatography-tandem mass spectrometry.

    PubMed

    Thibon, Cécile; Pons, Alexandre; Mouakka, Nadia; Redon, Pascaline; Méreau, Raphaël; Darriet, Philippe

    2015-10-09

    A rapid, sensitive method for assaying volatile impact compounds in white wine was developed using gas chromatography-tandem mass spectrometry (GC-MS/MS) technology, with a triple quadrupole analyzer operating in chemical ionization and electron impact mode. This GC-MS/MS method made it possible to assay volatile thiols (3SH: 3-sulfanylhexanol, formerly 3MH; 3SHA: 3-sulfanylhexyl acetate, formerly 3MHA; 4MSP: 4-methyl-4-sulfanylpentan-2-one, formerly 4MMP; BM: benzenemethanethiol; E2SA: ethyl 2-sulfanylacetate; and 2FM: 2-furanmethanethiol) and odoriferous oxidation markers (Sotolon: 4,5-dimethyl-3-hydroxy-2(5)H-furanone, methional, and phenylacetaldehyde) simultaneously in dry white wines, comparing electron impact (EI) and chemical ionization (CI) modes. More molecular ions were produced by CI than protonated molecules, despite the greater fragmentation caused by EI. So, even using the best reactant gas giving the highest signal for thiols, EI was the best ionization mode, with the lowest detection limits. For all compounds of interest, the limits of quantification (LOQ) obtained were well below their detection thresholds (ranging from 0.5 to 8.5ng/L for volatile thiols and 65-260ng/L for oxidation markers). Recovery rates ranged from 86% to 111%, reproducibility (in terms of relative standard deviation; RSD) was below 18% in all cases, with correlation coefficients above 0.991 for all analytes. The method was successfully applied to the analysis of compounds of interest in Sauvignon Blanc wines from a single estate and ten different vintages.

  12. Technical note: development and validation of a method using ultra performance liquid chromatography coupled with tandem mass spectrometry for determination of vitamin B12 concentrations in milk and dairy products.

    PubMed

    Zironi, E; Gazzotti, T; Barbarossa, A; Devicienti, C; Scardilli, M; Pagliuca, G

    2013-05-01

    A method using ultra performance liquid chromatography coupled with tandem mass spectrometry was developed to measure cobalamins in naturally enriched raw milk and to evaluate their fate during thermal treatments and along the process of cheese making. After addition of methotrexate as internal standard, samples were submitted to heat treatment in the presence of cyanide, which converts all the less-stable cobalamins into cyanocobalamin; then, purification was performed by a solid-phase extraction step. Reverse-phase ultra performance liquid chromatography separation coupled with tandem mass spectrometry provided a fast and reliable determination. Mass spectrometric analysis was carried out in multiple reaction monitoring mode. The monitored transitions were m/z 678.36 → 147.10 and 678.36 → 359.30 for vitamin B12 and m/z 455.22 → 175.13 and 455.22 → 308.22 for methotrexate (internal standard). The limit of quantification was 2 ng/g. The method showed good linearity from 2 to 20 ng/g (R(2) ≥ 0.98) and intra- and interday precisions were always less than 19%.

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

    PubMed

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

    2005-11-04

    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.

  14. Tandem betatron

    DOEpatents

    Keinigs, Rhonald K.

    1992-01-01

    Two betatrons are provided in tandem for alternately accelerating an electron beam to avoid the single flux swing limitation of conventional betatrons and to accelerate the electron beam to high energies. The electron beam is accelerated in a first betatron during a period of increasing magnetic flux. The eletron beam is extracted from the first betatron as a peak magnetic flux is reached and then injected into a second betatron at a time of minimum magnetic flux in the second betatron. The cycle may be repeated until the desired electron beam energy is obtained. In one embodiment, the second betatron is axially offset from the first betatron to provide for electron beam injection directly at the axial location of the beam orbit in the second betatron.

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

    PubMed Central

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

    2015-01-01

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

  16. Bimetallic oxidative addition involving radical intermediates in nickel-catalyzed alkyl-alkyl Kumada coupling reactions.

    PubMed

    Breitenfeld, Jan; Ruiz, Jesus; Wodrich, Matthew D; Hu, Xile

    2013-08-14

    Many nickel-based catalysts have been reported for cross-coupling reactions of nonactivated alkyl halides. The mechanistic understanding of these reactions is still primitive. Here we report a mechanistic study of alkyl-alkyl Kumada coupling catalyzed by a preformed nickel(II) pincer complex ([(N2N)Ni-Cl]). The coupling proceeds through a radical process, involving two nickel centers for the oxidative addition of alkyl halide. The catalysis is second-order in Grignard reagent, first-order in catalyst, and zero-order in alkyl halide. A transient species, [(N2N)Ni-alkyl(2)](alkyl(2)-MgCl), is identified as the key intermediate responsible for the activation of alkyl halide, the formation of which is the turnover-determining step of the catalysis.

  17. Topological phase transition coupled with spin-valley physics in ferroelectric oxide heterostructures

    NASA Astrophysics Data System (ADS)

    Yamauchi, Kunihiko; Barone, Paolo; Picozzi, Silvia

    2017-01-01

    The possibility to engineer the coupling of spin and valley physics is explored in ferroelectric oxide heterostructures with eg2 electronic configuration. We show that the polar structural distortion induces the appearance of spin-valley coupled properties, at the same time as being responsible for a topological transition from a quantum spin-Hall insulating phase to a trivial band insulator. The coupled spin-valley physics is affected by the topological band inversion in a nontrivial way; while the valley-dependent spin polarization of both conduction and valence bands is preserved, a change of the Berry curvature and of spin-valley selection rules is predicted, leading to different circular dichroic response as well as valley and spin Hall effects.

  18. Proton Coupled Electron Transfer Reactions at the Surface of Metal Oxide Nanomaterials

    NASA Astrophysics Data System (ADS)

    Braten, Miles N.

    Nanostructured metal oxide materials are found in many products and processes in our society today, but they play a particularly important role in the conversion and storage of energy. The materials are used as catalysts and redox active supports in devices such as dye sensitized solar cells, solid oxide fuel cells, and flow batteries, where they transfer and store electrons and charge balancing cations. Oftentimes electron transfer is modulated by the cations and when the cation is a proton, these redox reactions are known as proton coupled electron transfer (PCET) reactions. The work described in this dissertation focuses on understanding the PCET reactivity of nanocrystalline metal oxide materials. Chapter 1 introduces the concept of PCET and provides background information on the zinc oxide (ZnO) nanocrystals (NCs) which the majority of the research is focused on. Chapter 2 examines the chemistry that occurs during the photoreduction of ZnO NCs. Chapter 3 describes experiments probing how ZnO NC capping ligand concentration and NC size modulate PCET reaction rates. Chapter 4 describes experiments that compare the PCET reactivity of ZnO NCs with different numbers of electrons and protons stored on them. Chapter 5 describes attempts to observe the electrochemical reduction of ZnO NCs attached to gold electrodes. Finally, Chapter 6 contains attempts to identify a nanostructured metal oxide alkane oxidation catalyst for use in fuel cell.

  19. Ultrasensitive determination of DNA oxidation products by gas chromatography-tandem mass spectrometry and the role of antioxidants in the prevention of oxidative damage.

    PubMed

    Dawbaa, Sam; Aybastıer, Önder; Demir, Cevdet

    2017-04-15

    Oxidative stress is considered as one of the significant causes of DNA damage which in turn contributes to cell death through a series of intermediate processes such as cancer formation, mutation, and aging. Natural sources such as plant and fruit products have provided us with interesting substances of antioxidant activity that could be recruited in protecting the genetic materials of the cells. This study is an effort to discover some of those antioxidants effects in their standard and natural forms by performing an ultrasensitive determination of the products of DNA oxidation using GC-MS/MS. Experiments were used to determine the direct antioxidant activity of the substances contained in the tendrils of Vitis vinifera (var. alphonse) by extracting them and achieving Folin-Ciocalteau and CHROMAC analyses to determine the total phenolic content (TPC) and the antioxidant capacity of the extract, respectively; results revealed a phenolic content of 11.39±0.30mg Gallic Acid Equivalent (GAE)/g of the plant's fresh weight (FW) by Folin-Ciocalteau and 8.17±0.49mg Trolox Equivalent (TE)/g FW by CHROMAC assays. The qualitative analysis of the plant extract by HPLC-DAD technique revealed that two flavonoid glycosides namely rutin and isoquercitrin in addition to chlorogenic acid were contained in the extract. The determination of the DNA oxidation products was performed after putting DNA, rutin and isoquercitrin standard samples with different concentration, and the extract's sample under oxidative stress. Eighteen DNA oxidation products were traced using GC-MS/MS with ultra-sensitivity and the experiments proved a significant decrease in the concentration of the DNA oxidation products when the extract was used as a protectant against the oxidative stress. It is believed by conclusion that the extract of V. vinifera's (var. alphonse) tendrils has a good antioxidant activity; hence it is recommended to be used as a part of the daily healthy food list if possible.

  20. Sulfide oxidation coupled to arsenate reduction by a diverse microbial community in a soda lake.

    PubMed

    Hollibaugh, James T; Budinoff, Charles; Hollibaugh, Ryan A; Ransom, Briana; Bano, Nasreen

    2006-03-01

    We characterized the arsenate-reducing, sulfide-oxidizing population of Mono Lake, California, by analyzing the distribution and diversity of rrnA, cbbL, and dissimilatory arsenate reductase (arrA) genes in environmental DNA, arsenate-plus sulfide-amended lake water, mixed cultures, and isolates. The arsenate-reducing community was diverse. An organism represented by an rrnA sequence previously retrieved from Mono Lake and affiliated with the Desulfobulbaceae (Deltaproteobacteria) appears to be an important member of the arsenate-reducing, sulfide-oxidizing community. Sulfide oxidation coupled with arsenate reduction appears to proceed via a two-electron transfer, resulting in the production of arsenite and an intermediate S compound that is subsequently disproportionated. A realgar-like As/S mineral was formed in some experiments.

  1. Nanocrystal assembly for tandem catalysis

    DOEpatents

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

    2014-10-14

    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.

  2. Gold/Copper-Co-catalyzed Tandem Reactions of 2-Alkynylanilines: A Synthetic Strategy for the C2-Quaternary Indolin-3-ones.

    PubMed

    Li, Yi-Jin; Yan, Na; Liu, Chun-Hua; Yu, Yang; Zhao, Yu-Long

    2017-03-03

    A new strategy for direct and highly efficient synthesis of 2,3'-bisindolin-3-ones has been developed via a gold/copper-co-catalyzed tandem reactions of 2-alkynylanilines using TBHP as the terminal oxidant and oxygen-atom source. The single-step process involves a novel tandem intermolecular nucleophilic addition, intramolecular cyclization/oxidative cross-dehydrogenative coupling where up to four new bonds and two indole rings were created simultaneously in one-pot manner. The reaction features a broad substrate scope, good functional group tolerance, and high atom-economy.

  3. "Nanocrystal bilayer for tandem catalysis"

    SciTech Connect

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

    2011-01-24

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

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

    PubMed Central

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

    2010-01-01

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

  5. Enhanced spin-phonon-electronic coupling in a 5d oxide

    PubMed Central

    Calder, S.; Lee, J. H.; Stone, M. B.; Lumsden, M. D.; Lang, J. C.; Feygenson, M.; Zhao, Z.; Yan, J.-Q.; Shi, Y. G.; Sun, Y. S.; Tsujimoto, Y.; Yamaura, K.; Christianson, A. D.

    2015-01-01

    Enhanced coupling of material properties offers new fundamental insights and routes to multifunctional devices. In this context 5d oxides provide new paradigms of cooperative interactions that drive novel emergent behaviour. This is exemplified in osmates that host metal–insulator transitions where magnetic order appears intimately entwined. Here we consider such a material, the 5d perovskite NaOsO3, and observe a coupling between spin and phonon manifested in a frequency shift of 40 cm−1, the largest measured in any material. The anomalous modes are shown to involve solely Os–O interactions and magnetism is revealed as the driving microscopic mechanism for the phonon renormalization. The magnitude of the coupling in NaOsO3 is primarily due to a property common to all 5d materials: the large spatial extent of the ion. This allows magnetism to couple to phonons on an unprecedented scale and in general offers multiple new routes to enhanced coupled phenomena in 5d materials. PMID:26608626

  6. Enhanced spin-phonon-electronic coupling in a 5d oxide

    DOE PAGES

    Calder, Stuart A.; Yamaura, K.; Tsujimoto, Y.; ...

    2015-11-26

    Enhanced coupling of material properties offers new fundamental insights and routes to multifunctional devices. In this context 5d oxides provide new paradigms of cooperative interactions that drive novel emergent behaviour. This is exemplified in osmates that host metal insulator transitions where magnetic order appears intimately entwined. Here we consider such a material, the 5d perovskite NaOsO3, and observe a coupling between spin and phonon manifested in a frequency shift of 40 cm 1, the largest measured in any material. The anomalous modes are shown to involve solely Os O interactions and magnetism is revealed as the driving microscopic mechanism formore » the phonon renormalization. The magnitude of the coupling in NaOsO3 is primarily due to a property common to all 5d materials: the large spatial extent of the ion. This allows magnetism to couple to phonons on an unprecedented scale and in general offers multiple new routes to enhanced coupled phenomena in 5d materials.« less

  7. Enhanced spin-phonon-electronic coupling in a 5d oxide

    SciTech Connect

    Calder, Stuart A.; Yamaura, K.; Tsujimoto, Y.; Sun, Y. S.; Stone, Matthew B.; Shi, Y. G.; Lang, Jonathan; Christianson, Andrew D.; Lumsden, Mark D.; Lee, Jun Hee; Feygenson, Mikhail; Zhao, Zhiying; Yan, Jiaqiang

    2015-11-26

    Enhanced coupling of material properties offers new fundamental insights and routes to multifunctional devices. In this context 5d oxides provide new paradigms of cooperative interactions that drive novel emergent behaviour. This is exemplified in osmates that host metal insulator transitions where magnetic order appears intimately entwined. Here we consider such a material, the 5d perovskite NaOsO3, and observe a coupling between spin and phonon manifested in a frequency shift of 40 cm 1, the largest measured in any material. The anomalous modes are shown to involve solely Os O interactions and magnetism is revealed as the driving microscopic mechanism for the phonon renormalization. The magnitude of the coupling in NaOsO3 is primarily due to a property common to all 5d materials: the large spatial extent of the ion. This allows magnetism to couple to phonons on an unprecedented scale and in general offers multiple new routes to enhanced coupled phenomena in 5d materials.

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

    NASA Astrophysics Data System (ADS)

    Ngai, K. L.; Wang, Li-Min

    2011-11-01

    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 tc = 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 tc. 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 tc 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 α-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.

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

    PubMed

    Ngai, K L; Wang, Li-Min

    2011-11-21

    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 α-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.

  10. Ligand-Assisted Gold-Catalyzed Cross-Coupling with Aryldiazonium Salts: Redox Gold Catalysis without an External Oxidant.

    PubMed

    Cai, Rong; Lu, Mei; Aguilera, Ellen Y; Xi, Yumeng; Akhmedov, Novruz G; Petersen, Jeffrey L; Chen, Hao; Shi, Xiaodong

    2015-07-20

    Gold-catalyzed C(sp)-C(sp(2)) and C(sp(2))-C(sp(2)) cross-coupling reactions are accomplished with aryldiazonium salts as the coupling partner. With the assistance of bpy ligand, gold(I) species were oxidized to gold(III) by diazonium without any external oxidants. Monitoring the reaction with NMR and ESI-MS provided strong evidence for the nitrogen extrusion followed by Au(III) reductive elimination as the key step.

  11. Cu-catalyzed aerobic oxidative three-component coupling route to N-sulfonyl amidines via an ynamine intermediate.

    PubMed

    Kim, Jinho; Stahl, Shannon S

    2015-02-20

    Cu-catalyzed aerobic oxidative three-component coupling of a terminal alkyne, secondary amine, and sulfonamide enables efficient synthesis of amidines. The use of Cu(OTf)2 (5 mol %) produces amidines selectively without Glaser-Hay alkyne homocoupling products. Preliminary studies suggest that the reaction pathway involves initial oxidative coupling of the terminal alkyne with the secondary amine, followed by hydroamidation of the ynamine intermediate with the sulfonamide.

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

    PubMed

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

    2012-11-01

    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 50μL 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, 4μm) 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.

  13. Highly efficient and tunable spin-to-charge conversion through Rashba coupling at oxide interfaces

    NASA Astrophysics Data System (ADS)

    Lesne, E.; Fu, Yu; Oyarzun, S.; Rojas-Sánchez, J. C.; Vaz, D. C.; Naganuma, H.; Sicoli, G.; Attané, J.-P.; Jamet, M.; Jacquet, E.; George, J.-M.; Barthélémy, A.; Jaffrès, H.; Fert, A.; Bibes, M.; Vila, L.

    2016-12-01

    The spin-orbit interaction couples the electrons’ motion to their spin. As a result, a charge current running through a material with strong spin-orbit coupling generates a transverse spin current (spin Hall effect, SHE) and vice versa (inverse spin Hall effect, ISHE). The emergence of SHE and ISHE as charge-to-spin interconversion mechanisms offers a variety of novel spintronic functionalities and devices, some of which do not require any ferromagnetic material. However, the interconversion efficiency of SHE and ISHE (spin Hall angle) is a bulk property that rarely exceeds ten percent, and does not take advantage of interfacial and low-dimensional effects otherwise ubiquitous in spintronic hetero- and mesostructures. Here, we make use of an interface-driven spin-orbit coupling mechanism--the Rashba effect--in the oxide two-dimensional electron system (2DES) LaAlO3/SrTiO3 to achieve spin-to-charge conversion with unprecedented efficiency. Through spin pumping, we inject a spin current from a NiFe film into the oxide 2DES and detect the resulting charge current, which can be strongly modulated by a gate voltage. We discuss the amplitude of the effect and its gate dependence on the basis of the electronic structure of the 2DES and highlight the importance of a long scattering time to achieve efficient spin-to-charge interconversion.

  14. Electron-phonon coupling reflecting dynamic charge inhomogeneity in copper oxide superconductors

    NASA Astrophysics Data System (ADS)

    Reznik, D.; Pintschovius, L.; Ito, M.; Iikubo, S.; Sato, M.; Goka, H.; Fujita, M.; Yamada, K.; Gu, G. D.; Tranquada, J. M.

    2006-04-01

    The attempt to understand copper oxide superconductors is complicated by the presence of multiple strong interactions in these systems. Many believe that antiferromagnetism is important for superconductivity, but there has been renewed interest in the possible role of electron-lattice coupling. The conventional superconductor MgB2 has a very strong electron-lattice coupling, involving a particular vibrational mode (phonon) that was predicted by standard theory and confirmed quantitatively by experiment. Here we present inelastic scattering measurements that show a similarly strong anomaly in the Cu-O bond-stretching phonon in the copper oxide superconductors La2-xSrxCuO4 (with x = 0.07, 0.15). Conventional theory does not predict such behaviour. The anomaly is strongest in La1.875Ba0.125CuO4 and La1.48Nd0.4Sr0.12CuO4, compounds that exhibit spatially modulated charge and magnetic order, often called stripe order; it occurs at a wave vector corresponding to the charge order. These results suggest that this giant electron-phonon anomaly, which is absent in undoped and over-doped non-superconductors, is associated with charge inhomogeneity. It follows that electron-phonon coupling may be important to our understanding of superconductivity, although its contribution is likely to be indirect.

  15. Electron-phonon coupling reflecting dynamic charge inhomogeneity in copper oxide superconductors.

    PubMed

    Reznik, D; Pintschovius, L; Ito, M; Iikubo, S; Sato, M; Goka, H; Fujita, M; Yamada, K; Gu, G D; Tranquada, J M

    2006-04-27

    The attempt to understand copper oxide superconductors is complicated by the presence of multiple strong interactions in these systems. Many believe that antiferromagnetism is important for superconductivity, but there has been renewed interest in the possible role of electron-lattice coupling. The conventional superconductor MgB2 has a very strong electron-lattice coupling, involving a particular vibrational mode (phonon) that was predicted by standard theory and confirmed quantitatively by experiment. Here we present inelastic scattering measurements that show a similarly strong anomaly in the Cu-O bond-stretching phonon in the copper oxide superconductors La(2-x)Sr(x)CuO4 (with x = 0.07, 0.15). Conventional theory does not predict such behaviour. The anomaly is strongest in La(1.875)Ba(0.125)CuO4 and La(1.48)Nd(0.4)Sr(0.12)CuO4, compounds that exhibit spatially modulated charge and magnetic order, often called stripe order; it occurs at a wave vector corresponding to the charge order. These results suggest that this giant electron-phonon anomaly, which is absent in undoped and over-doped non-superconductors, is associated with charge inhomogeneity. It follows that electron-phonon coupling may be important to our understanding of superconductivity, although its contribution is likely to be indirect.

  16. Denitrification coupled to pyrite oxidation and changes in groundwater quality in a shallow sandy aquifer

    NASA Astrophysics Data System (ADS)

    Zhang, Yan-Chun; Slomp, Caroline P.; Broers, Hans Peter; Passier, Hilde F.; Cappellen, Philippe Van

    2009-11-01

    This study focuses on denitrification in a sandy aquifer using geochemical analyses of both sediment and groundwater, combined with groundwater age dating ( 3H/ 3He). The study sites are located underneath cultivated fields and an adjacent forested area at Oostrum, The Netherlands. Shallow groundwater in the region has high nitrate concentrations (up to 8 mM) due to intense fertilizer application. Nitrate removal from the groundwater below cultivated fields correlates with sulfate production, and the release of dissolved Fe 2+ and pyrite-associated trace metals (e.g. As, Ni, Co and Zn). These results, and the presence of pyrite in the sediment matrix within the nitrate removal zone, indicate that denitrification coupled to pyrite oxidation is a major process in the aquifer. Significant nitrate loss coupled to sulfate production is further confirmed by comparing historical estimates of regional sulfate and nitrate loadings to age-dated groundwater sulfate and nitrate concentrations, for the period 1950-2000. However, the observed increases in sulfate concentration are about 50% lower than would be expected from complete oxidation of pyrite to sulfate, possibly due to the accumulation of intermediate oxidation state sulfur compounds, such as elemental sulfur. Pollutant concentrations (NO 3, Cl, As, Co and Ni) measured in the groundwater beneath the agricultural areas in 1996 and 2006 show systematic decreases most likely due to declining fertilizer use.

  17. Simultaneous determination of tyrosine, phenylalanine and deoxyguanosine oxidation products by liquid chromatography-tandem mass spectrometry as non-invasive biomarkers for oxidative damage.

    PubMed

    Orhan, Hilmi; Vermeulen, Nico P E; Tump, Cornelis; Zappey, Herman; Meerman, John H N

    2004-01-25

    We developed an isotope dilution HPLC-atmospheric pressure chemical ionization-tandem mass spectrometry (HPLC-APCI-MS/MS) method for the simultaneous determination of p-tyrosine, phenylalanine, o,o'-dityrosine, m-tyrosine, o-tyrosine, 3-chlorotyrosine and 3-nitrotyrosine and 8-hydroxy-2'-deoxyguanosine (8-OHdG) that requires no extensive sample pre-treatment. p-[(2)H(4)]Tyrosine and o,o'-[(2)H(6)]dityrosine were used as internal standards. Calibration curves of the method were linear (r(2)=0.990-0.999) over a concentration range of 0.03-10 microM for o-tyrosine; 0.04-10 microM for 3-nitrotyrosine and 3-chlorotyrosine; 0.05-10 microM for o,o'-dityrosine; and for m-tyrosine; 1.0-100 microM for p-tyrosine and for phenylalanine; and 0.01-10 microM for 8-OHdG. The detection limits were from 0.025 to 0.05 microM for the tyrosine derivatives; 0.01 microM for 8-OHdG; and 0.5 microM for p-tyrosine and for phenylalanine, respectively. Within-day coefficients of variation (CV) for spiked human urine samples ranged from 2.7 to 7.0%, except for 8-OHdG (13.7%). Between-day variations ranged from 7.9 to 13.0%, except for o-tyrosine (CV = 18.2%), and for 8-OHdG (CV = 24.7%). The background levels of p-tyrosine, phenylalanine, o,o'-dityrosine, and o-tyrosine in morning urine of eight healthy volunteers were 3890+/-590, 3420+/-730, 5.8+/-0.3, and 9.2+/-1.5 micromol/mol creatinine, respectively. Using the present HPLC-APCI-MS/MS method, the urinary background levels of m-tyrosine, 3-chlorotyrosine, 3-nitrotyrosine and 8-OHdG were below the limit of detection.

  18. Coupled biotic-abiotic oxidation of organic matter by biogenic MnO_{2}

    NASA Astrophysics Data System (ADS)

    Gonzalez, Julia; Peña, Jasquelin

    2016-04-01

    Some reactive soil minerals are strongly implicated in stabilising organic matter. However, others can play an active role in the oxidation of organic molecules. In natural systems, layer-type manganese oxide minerals (MnO2) typically occur as biomineral assemblages consisting of mineral particles and microbial biomass. Both the mineral and biological fractions of the assemblage can be powerful oxidants of organic C. The biological compartment relies on a set of enzymes to drive oxidative transformations of reduced C-substrates, whereas MnO2 minerals are strong, less specific abiotic oxidants that are assumed to rely on interfacial interactions between C-substrates and the mineral surface. This project aims to understand the coupling between microbial C mineralization and abiotic C oxidation mediated by MnO2 in bacterial-MnO2 assemblages. Specifically, under conditions of high C turnover, microbial respiration can significantly alter local pH, dissolved oxygen and pool of available reductants, which may modify rates and mechanism of C oxidation by biotic and abiotic components. We first investigated changes in the solution chemistry of Pseudomonas putida suspensions exposed to varying concentrations of glucose, chosen to represent readily bioavailable substrates in soils. Glucose concentrations tested ranged between 0 and 5.5mM and changes in pH, dissolved oxygen and dissolved organic and inorganic carbon were tracked over 48h. We then combined literature review and wet-chemical experiments to compile the pH dependence of rates of organic substrate oxidation by MnO2, including glucose. Our results demonstrate a strong pH dependence for these abiotic reactions. In assemblages of P. putida - MnO2, kinetic limitations for abiotic C oxidation by MnO2 are overcome by changes in biogeochemical conditions that result from bacterial C metabolism. When extrapolated to a soil solution confronted to an input of fresh dissolved organic matter, bacterial C metabolism of the

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

    PubMed

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

    2014-12-01

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

  20. Tandem affinity purification of histones, coupled to mass spectrometry, identifies associated proteins and new sites of post-translational modification in Saccharomyces cerevisiae.

    PubMed

    Valero, M Luz; Sendra, Ramon; Pamblanco, Mercè

    2016-03-16

    Histones and their post-translational modifications contribute to regulating fundamental biological processes in all eukaryotic cells. We have applied a conventional tandem affinity purification strategy to histones H3 and H4 of the yeast Saccharomyces cerevisiae. Mass spectrometry analysis of the co-purified proteins revealed multiple associated proteins, including core histones, which indicates that tagged histones may be incorporated to the nucleosome particle. Among the many other co-isolated proteins there are histone chaperones, elements of chromatin remodeling, of nucleosome assembly/disassembly, and of histone modification complexes. The histone chaperone Rtt106p, two members of chromatin assembly FACT complex and Psh1p, an ubiquitin ligase, were the most abundant proteins obtained with both H3-TAP and H4-TAP, regardless of the cell extraction medium stringency. Our mass spectrometry analyses have also revealed numerous novel post-translational modifications, including 30 new chemical modifications in histones, mainly by ubiquitination. We have discovered not only new sites of ubiquitination but that, besides lysine, also serine and threonine residues are targets of ubiquitination on yeast histones. Our results show the standard tandem affinity purification procedure is suitable for application to yeast histones, in order to isolate and characterize histone-binding proteins and post-translational modifications, avoiding the bias caused by histone purification from a chromatin-enriched fraction.

  1. Synthesis of indazoles and azaindazoles by intramolecular aerobic oxidative C-N coupling under transition-metal-free conditions.

    PubMed

    Hu, Jiantao; Xu, Huacheng; Nie, Pengju; Xie, Xiaobo; Nie, Zongxiu; Rao, Yu

    2014-04-01

    A transition-metal-free oxidative C-N coupling method has been developed for the synthesis of 1H-azaindazoles and 1H-indazoles from easily accessible hydrazones. The procedure uses TEMPO, a basic additive, and dioxygen gas as the terminal oxidant. This reaction demonstrates better reactivity, functional group tolerance, and broader scope than comparable metal catalyzed reactions.

  2. Catalytic partial oxidation coupled with membrane purification to improve resource and energy efficiency in syngas production.

    PubMed

    Iaquaniello, G; Salladini, A; Palo, E; Centi, G

    2015-02-01

    Catalytic partial oxidation coupled with membrane purification is a new process scheme to improve resource and energy efficiency in a well-established and large scale-process like syngas production. Experimentation in a semi industrial-scale unit (20 Nm(3)  h(-1) production) shows that a novel syngas production scheme based on a pre-reforming stage followed by a membrane for hydrogen separation, a catalytic partial oxidation step, and a further step of syngas purification by membrane allows the oxygen-to-carbon ratio to be decreased while maintaining levels of feed conversion. For a total feed conversion of 40 %, for example, the integrated novel architecture reduces oxygen consumption by over 50 %, with thus a corresponding improvement in resource efficiency and an improved energy efficiency and economics, these factors largely depending on the air separation stage used to produce pure oxygen.

  3. A novel mechanism involved in the coupling of mitochondrial biogenesis to oxidative phosphorylation

    PubMed Central

    Ostojić, Jelena; Rago, Jean-Paul; Dujardin, Geneviève

    2014-01-01

    Mitochondria are essential organelles that are central to a multitude of cellular processes, including oxidative phosphorylation (OXPHOS), which produces most of the ATP in animal cells. Thus it is important to understand not only the mechanisms and biogenesis of this energy production machinery but also how it is regulated in both physiological and pathological contexts. A recent study by Ostojić et al. [Cell Metabolism (2013) 18, 567-577] has uncovered a regulatory loop by which the biogenesis of a major enzyme of the OXPHOS pathway, the respiratory complex III, is coupled to the energy producing activity of the mitochondria. PMID:28357209

  4. Coupled interactions between volatile activity and Fe oxidation state during arc crustal processes

    USGS Publications Warehouse

    Humphreys, Madeleine C.S.; Brooker, R; Fraser, D.C.; Burgisser, A; Mangan, Margaret T.; McCammon, C

    2015-01-01

    Arc magmas erupted at the Earth’s surface are commonly more oxidized than those produced at mid-ocean ridges. Possible explanations for this high oxidation state are that the transfer of fluids during the subduction process results in direct oxidation of the sub-arc mantle wedge, or that oxidation is caused by the effect of later crustal processes, including protracted fractionation and degassing of volatile-rich magmas. This study sets out to investigate the effect of disequilibrium crustal processes that may involve coupled changes in H2O content and Fe oxidation state, by examining the degassing and hydration of sulphur-free rhyolites. We show that experimentally hydrated melts record strong increases in Fe3+/∑Fe with increasing H2O concentration as a result of changes in water activity. This is relevant for the passage of H2O-undersaturated melts from the deep crust towards shallow crustal storage regions, and raises the possibility that vertical variations in fO2 might develop within arc crust. Conversely, degassing experiments produce an increase in Fe3+/∑Fe with decreasing H2O concentration. In this case the oxidation is explained by loss of H2 as well as H2O into bubbles during decompression, consistent with thermodynamic modelling, and is relevant for magmas undergoing shallow degassing en route to the surface. We discuss these results in the context of the possible controls on fO2 during the generation, storage and ascent of magmas in arc settings, in particular considering the timescales of equilibration relative to observation as this affects the quality of the petrological record of magmatic fO2.

  5. Mechanism of the cathodic process coupled to the oxidation of iron monosulfide by dissolved oxygen.

    PubMed

    Duinea, Mădălina I; Costas, Andreea; Baibarac, Mihaela; Chiriță, Paul

    2016-04-01

    This study investigated the mechanism of iron monosulfide (FeS) oxidation by dissolved oxygen (O2(aq)). Synthetic FeS was reacted with O2(aq) for 6days and at 25°C. We have characterized the initial and reacted FeS surface using Scanning Electron Microscopy coupled with Energy Dispersive X-ray (SEM/EDX) analysis, Raman spectroscopy and Fourier transform infrared spectroscopy (FTIR). It was found that during the aqueous oxidation of FeS new solid phases (disulfide, polysulfide, elemental sulfur, ferric oxyhydroxides and Fe3O4) develop on the mineral surface. The results of potentiodynamic polarization experiments show that after 2days of FeS electrode immersion in oxygen bearing solution (OBS) at initial pH 5.1 and 25°C the modulus of cathodic Tafel slopes dramatically decreases, from 393mV/dec to 86mV/dec. This decrease is ascribed to the change of the mechanism of electron transfer from cathodic sites to O2 (mechanism of cathodic process). The oxidation current densities (jox) indicate that mineral oxidative dissolution is not inhibited by pH increase up to 6.7. Another conclusion, which emerges from the analysis of jox, is that the dissolved Fe(3+) does not intermediate the aqueous oxidation of FeS. The results of electrochemical impedance spectroscopy (EIS) show that after 2days of contact between electrode and OBS the properties of FeS/water interface change. From the analysis of the EIS, FTIR spectroscopy, Raman spectroscopy and SEM/EDX data we can conclude that the change of FeS/water interface properties accompanies the formation of new solid phases on the mineral surface. The new characteristics of the surface layer and FeS/water interface do not cause the inhibition of mineral oxidation.

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

    PubMed Central

    Klatt, Judith M.; Polerecky, Lubos

    2015-01-01

    Chemolithoautotrophic sulfur oxidizing bacteria (SOB) couple the oxidation of reduced sulfur compounds to the production of biomass. Their role in the cycling of carbon, sulfur, oxygen, and nitrogen is, however, difficult to quantify due to the complexity of sulfur oxidation pathways. We describe a generic theoretical framework for linking the stoichiometry and energy conservation efficiency of autotrophic sulfur oxidation while accounting for the partitioning of the reduced sulfur pool between the energy generating and energy conserving steps as well as between the main possible products (sulfate vs. zero-valent sulfur). Using this framework, we show that the energy conservation efficiency varies widely among SOB with no apparent relationship to their phylogeny. Aerobic SOB equipped with reverse dissimilatory sulfite reductase tend to have higher efficiency than those relying on the complete Sox pathway, whereas for anaerobic SOB the presence of membrane-bound, as opposed to periplasmic, nitrate reductase systems appears to be linked to higher efficiency. We employ the framework to also show how limited rate measurements can be used to estimate the primary productivity of SOB without the knowledge of the sulfate-to-zero-valent-sulfur production ratio. Finally, we discuss how the framework can help researchers gain new insights into the activity of SOB and their niches. PMID:26052315

  7. Electrochemistry coupled to (LC-)MS for the simulation of oxidative biotransformation reactions of PAHs.

    PubMed

    Wigger, Tina; Seidel, Albrecht; Karst, Uwe

    2017-02-27

    Electrochemistry coupled to liquid chromatography and mass spectrometry was used for simulating the biological and environmental fate of polycyclic aromatic hydrocarbons (PAHs) as well as for studying the PAH degradation behavior during electrochemical remediation. Pyrene and benzo[a]pyrene were selected as model compounds and oxidized within an electrochemical thin-layer cell equipped with boron-doped diamond electrode. At potentials of 1.2 and 1.6 V vs. Pd/H2, quinones were found to be the major oxidation products for both investigated PAHs. These quinones belong to a large group of PAH derivatives referred to as oxygenated PAHs, which have gained increasing attention in recent years due to their high abundance in the environment and their significant toxicity. Separation of oxidation products allowed the identification of two pyrene quinone and three benzo[a]pyrene quinone isomers, all of which are known to be formed via photooxidation and during mammalian metabolism. The good correlation between electrochemically generated PAH quinones and those formed in natural processes was also confirmed by UV irradiation experiments and microsomal incubations. At potentials higher than 2.0 V, further degradation of the initial oxidation products was observed which highlights the capability of electrochemistry to be used as remediation technique.

  8. Tandem Mirror Reactor Systems Code (Version I)

    SciTech Connect

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

    1985-09-01

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

  9. Solventless oxidative coupling of amines to imines by using transition-metal-free metal-organic frameworks.

    PubMed

    Qiu, Xuan; Len, Christophe; Luque, Rafael; Li, Yingwei

    2014-06-01

    A highly efficient, simple, and versatile transition-metal-free metal-organic framework catalytic system is proposed for the oxidative coupling of amines to imines. The catalytic protocol features high activities and selectivities to target products; compatibility with a variety of substrates, including aliphatic amines and secondary amines; and the possibility to efficiently and selectively promote amine cross-coupling reactions. A high stability and recyclability of the catalyst is also observed under the investigated conditions. Insights into the reaction mechanism indicate the formation of a superoxide species able to efficiently promote oxidative couplings.

  10. Photo-induced oxidant-free oxidative C-H/N-H cross-coupling between arenes and azoles

    NASA Astrophysics Data System (ADS)

    Niu, Linbin; Yi, Hong; Wang, Shengchun; Liu, Tianyi; Liu, Jiamei; Lei, Aiwen

    2017-02-01

    Direct cross-coupling between simple arenes and heterocyclic amines under mild conditions is undoubtedly important for C-N bonds construction. Selective C(sp2)-H amination is more valuable. Herein we show a selective C(sp2)-H amination of arenes (alkyl-substituted benzenes, biphenyl and anisole derivatives) accompanied by hydrogen evolution by using heterocyclic azoles as nitrogen sources. The reaction is selective for C(sp2)-H bonds, providing a mild route to N-arylazoles. The KIE (kinetic isotope effect) experiment reveals the cleavage of C-H bond is not involved in the rate-determining step. Kinetic studies indicate the first-order behaviour with respect to the arene component. It is interesting that this system works without the need for any sacrificial oxidant and is highly selective for C(sp2)-H activation, whereas C(sp3)-H bonds are unaffected. This study may have significant implications for the functionalization of methylarenes which are sensitive to oxidative conditions.

  11. Photo-induced oxidant-free oxidative C–H/N–H cross-coupling between arenes and azoles

    PubMed Central

    Niu, Linbin; Yi, Hong; Wang, Shengchun; Liu, Tianyi; Liu, Jiamei; Lei, Aiwen

    2017-01-01

    Direct cross-coupling between simple arenes and heterocyclic amines under mild conditions is undoubtedly important for C–N bonds construction. Selective C(sp2)-H amination is more valuable. Herein we show a selective C(sp2)-H amination of arenes (alkyl-substituted benzenes, biphenyl and anisole derivatives) accompanied by hydrogen evolution by using heterocyclic azoles as nitrogen sources. The reaction is selective for C(sp2)-H bonds, providing a mild route to N-arylazoles. The KIE (kinetic isotope effect) experiment reveals the cleavage of C–H bond is not involved in the rate-determining step. Kinetic studies indicate the first-order behaviour with respect to the arene component. It is interesting that this system works without the need for any sacrificial oxidant and is highly selective for C(sp2)-H activation, whereas C(sp3)-H bonds are unaffected. This study may have significant implications for the functionalization of methylarenes which are sensitive to oxidative conditions. PMID:28145410

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

    PubMed

    Orčić, Dejan; Francišković, Marina; Bekvalac, Kristina; Svirčev, Emilija; Beara, Ivana; Lesjak, Marija; Mimica-Dukić, Neda

    2014-01-15

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

  13. Rapid identification of synthetic colorants in food samples by using indium oxide nanoparticle-functionalized porous polymer monolith coupled with HPLC-MS/MS.

    PubMed

    Qi, Ruifang; Zhou, Xiao; Li, Xiqian; Ma, Jiutong; Lu, Chunmei; Mu, Jun; Zhang, Xuguang; Jia, Qiong

    2014-12-07

    A synthetic protocol for the preparation of an indium oxide nanoparticle-functionalized poly(methacrylic acid-glycidyl methacrylate-ethylene dimethacrylate-ethanediamine) monolithic column is reported. Various techniques, including scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermal gravimetric analysis-derivative thermogravimetric analysis were employed to characterize the synthesized monolith. The modified monolithic column was coupled with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) for determining synthetic colorants in various food samples. Under optimized conditions, good linearity was obtained for all the targets with squared regression coefficients greater than 0.9982. The limits of detection (S/N = 3) for 12 synthetic colorants were in the range of 0.012-2.97 μg kg(-1). The intra-day and inter-day relative standard deviations, ranging from 2.7% to 8.5%, were within the acceptable range. The developed method was successfully applied to the determination of synthetic colorants in food samples (candy, milk, jelly, jam, canned food, juice, and carbonated drink). Target recoveries at different spiked levels ranged from 73.5% to 112.1% with relative standard deviations of less than 10.3%.

  14. Multi-residue method for the determination of pesticides and pesticide metabolites in honeybees by liquid and gas chromatography coupled with tandem mass spectrometry--Honeybee poisoning incidents.

    PubMed

    Kiljanek, Tomasz; Niewiadowska, Alicja; Semeniuk, Stanisław; Gaweł, Marta; Borzęcka, Milena; Posyniak, Andrzej

    2016-02-26

    A method for the determination of 200 pesticides and pesticide metabolites in honeybee samples has been developed and validated. Almost 98% of compounds included in this method are approved to use within European Union, as active substances of plant protection products or veterinary medicinal products used by beekeepers to control mites Varroa destructor in hives. Many significant metabolites, like metabolites of imidacloprid, thiacloprid, fipronil, methiocarb and amitraz, are also possible to detect. The sample preparation was based on the buffered QuEChERS method. Samples of bees were extracted with acetonitrile containing 1% acetic acid and then subjected to clean-up by dispersive solid phase extraction (dSPE) using a new Z-Sep+ sorbent and PSA. The majority of pesticides, including neonicotionoids and their metabolites, were analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS) but some of pesticides, especially pyrethroid insecticides, were analyzed by gas chromatography tandem mass spectrometry (GC-MS/MS). The procedure was validated according to the Guidance document SANCO/12571/2013 at four concentration levels: 1, 5, 10 and 100 ng/g bees and verified in the international proficiency test. The analysis of bee samples spiked at the limit of quantification (LOQ) showed about 98% mean recovery value (trueness) and 97% of analytes showed recovery in the required range of 70-120% and RSDr (precision) below 20%. Linearity and matrix effects were also established. The LOQs of pesticides were in the range of 1-100 ng/g. The developed method allows determination of insecticides at concentrations of 10 ng/g or less, except abamectin and tebufenozide. LOQ values are lower than the median lethal doses LD50 for bees. The method was used to investigate more than 70 honeybee poisoning incidents. Data about detected pesticides and their metabolites are included.

  15. Accelerated quantification of amphetamine enantiomers in human urine using chiral liquid chromatography and on-line column-switching coupled with tandem mass spectrometry.

    PubMed

    Hädener, Marianne; Bruni, Pia S; Weinmann, Wolfgang; Frübis, Matthias; König, Stefan

    2017-02-01

    Amphetamine (AM) is a powerful psychostimulant existing in two enantiomeric forms. Stereoselective analysis of AM in biosamples can assist clinicians and forensic experts in differentiating between abuse of illicitly synthesized racemic AM and ingestion of pharmaceutical AM formulations containing either S-AM or different proportions of the S- and R-enantiomers. Therefore, a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for quantifying AM enantiomers in urine was newly developed. The method comprised dilution with water, followed by injection of the diluted sample onto an achiral C18 trapping column for purification and subsequent backflush elution to a chiral Lux 3 μm AMP LC column by means of a switching valve. An isocratic mobile phase of 25 % acetonitrile in 0.1 M aqueous ammonia was used for enantiomeric separation. Injection, cleanup, and backflush of the next sample were performed before the previous sample had eluted from the analytical column, thus enabling simultaneous enantioseparation of up to three samples within the analytical column. This novel chromatographic concept allowed for increased sample throughput by accelerating both the sample preparation and the LC analysis. Analyte detection was accomplished by electrospray ionization in positive ion mode and selected reaction monitoring using a triple-stage quadrupole mass spectrometer. The method was successfully validated through assessment of its linearity, lower limit of quantification, accuracy and precision, selectivity, matrix effect, carry-over, dilution integrity, and re-injection reproducibility. Linearity ranged from 0.05 to 25 mg/L for both enantiomers. Proof of the method included analysis of urine samples obtained from drug abusers and patients receiving an S-AM prodrug. Graphical Abstract Enantioselective determination of amphetamine in human urine using liquid chromatography with achiral-chiral column-switching and tandem mass spectrometry.

  16. Control of the neurovascular coupling by nitric oxide-dependent regulation of astrocytic Ca2+ signaling

    PubMed Central

    Muñoz, Manuel F.; Puebla, Mariela; Figueroa, Xavier F.

    2015-01-01

    Neuronal activity must be tightly coordinated with blood flow to keep proper brain function, which is achieved by a mechanism known as neurovascular coupling. Then, an increase in synaptic activity leads to a dilation of local parenchymal arterioles that matches the enhanced metabolic demand. Neurovascular coupling is orchestrated by astrocytes. These glial cells are located between neurons and the microvasculature, with the astrocytic endfeet ensheathing the vessels, which allows fine intercellular communication. The neurotransmitters released during neuronal activity reach astrocytic receptors and trigger a Ca2+ signaling that propagates to the endfeet, activating the release of vasoactive factors and arteriolar dilation. The astrocyte Ca2+ signaling is coordinated by gap junction channels and hemichannels formed by connexins (Cx43 and Cx30) and channels formed by pannexins (Panx-1). The neuronal activity-initiated Ca2+ waves are propagated among neighboring astrocytes directly via gap junctions or through ATP release via connexin hemichannels or pannexin channels. In addition, Ca2+ entry via connexin hemichannels or pannexin channels may participate in the regulation of the astrocyte signaling-mediated neurovascular coupling. Interestingly, nitric oxide (NO) can activate connexin hemichannel by S-nitrosylation and the Ca2+-dependent NO-synthesizing enzymes endothelial NO synthase (eNOS) and neuronal NOS (nNOS) are expressed in astrocytes. Therefore, the astrocytic Ca2+ signaling triggered in neurovascular coupling may activate NO production, which, in turn, may lead to Ca2+ influx through hemichannel activation. Furthermore, NO release from the hemichannels located at astrocytic endfeet may contribute to the vasodilation of parenchymal arterioles. In this review, we discuss the mechanisms involved in the regulation of the astrocytic Ca2+ signaling that mediates neurovascular coupling, with a special emphasis in the possible participation of NO in this process

  17. Microscopic theory of Dzyaloshinsky-Moriya interaction in pyrochlore oxides with spin-orbit coupling

    NASA Astrophysics Data System (ADS)

    Arakawa, Naoya

    2016-10-01

    Pyrochlore oxides show several fascinating phenomena, such as the formation of heavy fermions and the thermal Hall effect. Although a key to understanding some phenomena may be the Dzyaloshinsky-Moriya (DM) interaction, its microscopic origin is unclear. To clarify the microscopic origin, we constructed a t2 g-orbital model with the kinetic energy, the trigonal-distortion potential, the multiorbital Hubbard interactions, and the L S coupling, and derived the low-energy effective Hamiltonian for a d1 Mott insulator with the weak L S coupling. We first show that lack of the inversion center of each nearest-neighbor V-V bond causes the odd-mirror interorbital hopping integrals. Those are qualitatively different from the even-mirror hopping integrals, existing even with the inversion center. We next show that the second-order perturbation using the kinetic terms leads to the ferromagnetic and the antiferromagnetic superexchange interactions, whose competition is controllable by tuning the Hubbard interactions. Then, we show the most important result: the third-order perturbation terms using the combination of the even-mirror hopping integral, the odd-mirror hopping integral, and the L S coupling causes the DM interaction due to the mirror-mixing effect, where those hopping integrals are necessary to obtain the antisymmetric kinetic exchange and the L S coupling is necessary to excite the orbital angular momentum at one of two sites. We also show that the magnitude and sign of the DM interaction can be controlled by changing the positions of the O ions and the strength of the Hubbard interactions. We discuss the advantages in comparison with the phenomenological theory and Moriya's microscopic theory, applicability of our mechanism, and the similarities and differences between our case and the strong-L S -coupling case.

  18. Control of the neurovascular coupling by nitric oxide-dependent regulation of astrocytic Ca(2+) signaling.

    PubMed

    Muñoz, Manuel F; Puebla, Mariela; Figueroa, Xavier F

    2015-01-01

    Neuronal activity must be tightly coordinated with blood flow to keep proper brain function, which is achieved by a mechanism known as neurovascular coupling. Then, an increase in synaptic activity leads to a dilation of local parenchymal arterioles that matches the enhanced metabolic demand. Neurovascular coupling is orchestrated by astrocytes. These glial cells are located between neurons and the microvasculature, with the astrocytic endfeet ensheathing the vessels, which allows fine intercellular communication. The neurotransmitters released during neuronal activity reach astrocytic receptors and trigger a Ca(2+) signaling that propagates to the endfeet, activating the release of vasoactive factors and arteriolar dilation. The astrocyte Ca(2+) signaling is coordinated by gap junction channels and hemichannels formed by connexins (Cx43 and Cx30) and channels formed by pannexins (Panx-1). The neuronal activity-initiated Ca(2+) waves are propagated among neighboring astrocytes directly via gap junctions or through ATP release via connexin hemichannels or pannexin channels. In addition, Ca(2+) entry via connexin hemichannels or pannexin channels may participate in the regulation of the astrocyte signaling-mediated neurovascular coupling. Interestingly, nitric oxide (NO) can activate connexin hemichannel by S-nitrosylation and the Ca(2+)-dependent NO-synthesizing enzymes endothelial NO synthase (eNOS) and neuronal NOS (nNOS) are expressed in astrocytes. Therefore, the astrocytic Ca(2+) signaling triggered in neurovascular coupling may activate NO production, which, in turn, may lead to Ca(2+) influx through hemichannel activation. Furthermore, NO release from the hemichannels located at astrocytic endfeet may contribute to the vasodilation of parenchymal arterioles. In this review, we discuss the mechanisms involved in the regulation of the astrocytic Ca(2+) signaling that mediates neurovascular coupling, with a special emphasis in the possible participation of NO in

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

    PubMed

    Nascimento, Ulisses M; Azevedo, Eduardo B

    2013-01-01

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

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

    NASA Astrophysics Data System (ADS)

    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

    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.

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

    PubMed

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

    2014-11-24

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

  2. Coupling membrane separation and photocatalytic oxidation processes for the degradation of pharmaceutical pollutants.

    PubMed

    Martínez, F; López-Muñoz, M J; Aguado, J; Melero, J A; Arsuaga, J; Sotto, A; Molina, R; Segura, Y; Pariente, M I; Revilla, A; Cerro, L; Carenas, G

    2013-10-01

    The coupling of membrane separation and photocatalytic oxidation has been studied for the removal of pharmaceutical pollutants. The retention properties of two different membranes (nanofiltration and reverse osmosis) were assessed. Comparable selectivity on the separation of pharmaceuticals were observed for both membranes, obtaining a permeate stream with concentrations of each pharmaceutical below 0.5 mg L(-)(1) and a rejected flux highly concentrated (in the range of 16-25 mg L(-)(1) and 18-32 mg L(-)(1) of each pharmaceutical for NF-90 and BW-30 membranes, respectively), when an initial stream of six pharmaceuticals was feeding to the membrane system (10 mg L(-)(1) of each pharmaceutical). The abatement of concentrated pharmaceuticals of the rejected stream was evaluated by means of heterogeneous photocatalytic oxidation using TiO2 and Fe2O3/SBA-15 in presence of hydrogen peroxide as photo-Fenton system. Both photocatalytic treatments showed remarkable removals of pharmaceutical compounds, achieving values between 80 and 100%. The nicotine was the most refractory pollutant of all the studied pharmaceuticals. Photo-Fenton treatment seems to be more effective than TiO2 photocatalysis, as high mineralization degree and increased nicotine removal were attested. This work can be considered an interesting approach of coupling membrane separation and heterogeneous photocatalytic technologies for the successful abatement of pharmaceutical compounds in effluents of wastewater treatment plants.

  3. COUPLING

    DOEpatents

    Frisch, E.; Johnson, C.G.

    1962-05-15

    A detachable coupling arrangement is described which provides for varying the length of the handle of a tool used in relatively narrow channels. The arrangement consists of mating the key and keyhole formations in the cooperating handle sections. (AEC)

  4. Novel approach to fast determination of cholesterol oxidation products in Cypriot foodstuffs using ultra-performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Georgiou, Christiana A; Constantinou, Michalis S; Andreou, Rafaella; Hapeshi, Evroula; Fatta-Kassinos, Despo; Kapnissi-Christodoulou, Constantina P

    2016-04-01

    This paper reports the development and validation of a new method based on ultra-performance LC coupled to MS/MS for the simultaneous determination of four cholesterol oxidation products (COPs) in foodstuffs in only 4.1 min. The COPs were detected by ESI in positive-ion mode with multiple reaction monitoring, and the mass spectrometric conditions were optimized in order to increase sensitivity. The developed method was validated in terms of linearity, precision, LODs, and LOQs. Recoveries of the extraction process ranged from 86 to 98.5% when the samples were fortified at 100, 500, and 1500 ng/mL. The applicability of the method was confirmed by analyzing different food samples. Considering the paucity of data regarding the content of COPs in Cypriot foods, particular attention was devoted, for the first time, to the determination of the profile of the main COPs in widely consumed, traditional Cypriot foodstuffs (halloumi cheese, hiromeri, snails, etc.).

  5. Competition Between Resonant Plasmonic Coupling and Electrostatic Interaction in Reduced Graphene Oxide Quantum Dots.

    PubMed

    Karna, Sanjay; Mahat, Meg; Choi, Tae-Youl; Shimada, Ryoko; Wang, Zhiming; Neogi, Arup

    2016-11-22

    The light emission from reduced graphene oxide quantum dots (rGO-QDs) exhibit a significant enhancement in photoluminescence (PL) due to localized surface plasmon (LSP) interactions. Silver and gold nanoparticles (NPs) coupled to rGO nanoparticles exhibit the effect of resonant LSP coupling on the emission processes. Enhancement of the radiative recombination rate in the presence of Ag-NPs induced LSP tuned to the emission energy results in a four-fold increase in PL intensity. The localized field due to the resonantly coupled LSP modes induces n-π* transitions that are not observed in the absence of the resonant interaction of the plasmons with the excitons. An increase in the density of the Ag-NPs result in a detuning of the LSP energy from the emission energy of the nanoparticles. The detuning is due to the cumulative effect of the red-shift in the LSP energy and the electrostatic field induced blue shift in the PL energy of the rGO-QDs. The detuning quenches the PL emission from rGO-QDs at higher concentration of Ag NPs due to non-dissipative effects unlike plasmon induced Joule heating that occurs under resonance conditions. An increase in Au nanoparticles concentration results in an enhancement of PL emission due to electrostatic image charge effect.

  6. Competition Between Resonant Plasmonic Coupling and Electrostatic Interaction in Reduced Graphene Oxide Quantum Dots

    PubMed Central

    Karna, Sanjay; Mahat, Meg; Choi, Tae-Youl; Shimada, Ryoko; Wang, Zhiming; Neogi, Arup

    2016-01-01

    The light emission from reduced graphene oxide quantum dots (rGO-QDs) exhibit a significant enhancement in photoluminescence (PL) due to localized surface plasmon (LSP) interactions. Silver and gold nanoparticles (NPs) coupled to rGO nanoparticles exhibit the effect of resonant LSP coupling on the emission processes. Enhancement of the radiative recombination rate in the presence of Ag-NPs induced LSP tuned to the emission energy results in a four-fold increase in PL intensity. The localized field due to the resonantly coupled LSP modes induces n-π* transitions that are not observed in the absence of the resonant interaction of the plasmons with the excitons. An increase in the density of the Ag-NPs result in a detuning of the LSP energy from the emission energy of the nanoparticles. The detuning is due to the cumulative effect of the red-shift in the LSP energy and the electrostatic field induced blue shift in the PL energy of the rGO-QDs. The detuning quenches the PL emission from rGO-QDs at higher concentration of Ag NPs due to non-dissipative effects unlike plasmon induced Joule heating that occurs under resonance conditions. An increase in Au nanoparticles concentration results in an enhancement of PL emission due to electrostatic image charge effect. PMID:27872487

  7. Competition Between Resonant Plasmonic Coupling and Electrostatic Interaction in Reduced Graphene Oxide Quantum Dots

    NASA Astrophysics Data System (ADS)

    Karna, Sanjay; Mahat, Meg; Choi, Tae-Youl; Shimada, Ryoko; Wang, Zhiming; Neogi, Arup

    2016-11-01

    The light emission from reduced graphene oxide quantum dots (rGO-QDs) exhibit a significant enhancement in photoluminescence (PL) due to localized surface plasmon (LSP) interactions. Silver and gold nanoparticles (NPs) coupled to rGO nanoparticles exhibit the effect of resonant LSP coupling on the emission processes. Enhancement of the radiative recombination rate in the presence of Ag-NPs induced LSP tuned to the emission energy results in a four-fold increase in PL intensity. The localized field due to the resonantly coupled LSP modes induces n-π* transitions that are not observed in the absence of the resonant interaction of the plasmons with the excitons. An increase in the density of the Ag-NPs result in a detuning of the LSP energy from the emission energy of the nanoparticles. The detuning is due to the cumulative effect of the red-shift in the LSP energy and the electrostatic field induced blue shift in the PL energy of the rGO-QDs. The detuning quenches the PL emission from rGO-QDs at higher concentration of Ag NPs due to non-dissipative effects unlike plasmon induced Joule heating that occurs under resonance conditions. An increase in Au nanoparticles concentration results in an enhancement of PL emission due to electrostatic image charge effect.

  8. Possible Superconductivity Induced by Strong Spin-Orbit Coupling in Carrier Doped Iridium Oxides Insulators

    NASA Astrophysics Data System (ADS)

    Nishiguchi, Kazutaka; Shirakawa, Tomonori; Watanabe, Hiroshi; Arita, Ryotaro; Yunoki, Seiji

    2014-03-01

    5 d transition metal oxide Sr2IrO4 and its relevant Iridium oxides have attracted much interest because of exotic properties arising from highly entangled spin and orbital degrees of freedom due to strong spin-orbit coupling (SOC). Sr2IrO4 crystalizes in the layered perovskite structure, similar to cuprates. Five 5 d electrons in Ir occupy its t2 g orbitals which are split by strong SOC, locally inducing an effective total angular momentum Jeff = 1 / 2 , analogous to a S = 1 / 2 state in cuprates. Because of the similarities to cuprates, the possibility of superconductivity (SC) in Iridium oxides has been expected theoretically once mobile carriers are introduced into the Jeff = 1 / 2 antiferromagnetic insulator. To study theoretically possible SC in carrier doped Sr2IrO4, we investigate a three-orbital Hubbard model with SOC. By solving the Eliashberg equation in the random phase approximation, we find that Jeff = 1 / 2 antiferromagnetic fluctuations favor dx2 -y2-wave SC with a mixture of singlet and triplet Cooper pairings. We will also discuss the particle-hole asymmetry of the SC induced by electron and hole doping.

  9. Sulfur-Bridged Terthiophene Dimers: How Sulfur Oxidation State Controls Interchromophore Electronic Coupling.

    PubMed

    Cruz, Chad D; Christensen, Peter R; Chronister, Eric L; Casanova, David; Wolf, Michael O; Bardeen, Christopher J

    2015-10-07

    Symmetric dimers have the potential to optimize energy transfer and charge separation in optoelectronic devices. In this paper, a combination of optical spectroscopy (steady-state and time-resolved) and electronic structure theory is used to analyze the photophysics of sulfur-bridged terthiophene dimers. This class of dimers has the unique feature that the interchromophore (intradimer) electronic coupling can be modified by varying the oxidation state of the bridging sulfur from sulfide (S), to sulfoxide (SO), to sulfone (SO2). Photoexcitation leads to the formation of a delocalized charge resonance state (S1) that relaxes quickly (<10 ps) to a charge-transfer state (S1*). The amount of charge-transfer character in S1* can be enhanced by increasing the oxidation state of the bridging sulfur group as well as the solvent polarity. The S1* state has a decreased intersystem crossing rate when compared to monomeric terthiophene, leading to an enhanced photoluminescence quantum yield. Computational results indicate that electrostatic screening by the bridging sulfur electrons is the key parameter that controls the amount of charge-transfer character. Control of the sulfur bridge oxidation state provides the ability to tune interchromophore interactions in covalent assemblies without altering the molecular geometry or solvent polarity. This capability provides a new strategy for the design of functional supermolecules with applications in organic electronics.

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

    PubMed

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

    2014-03-01

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

  11. Coupled molybdenum carbide and reduced graphene oxide electrocatalysts for efficient hydrogen evolution

    PubMed Central

    Li, Ji-Sen; Wang, Yu; Liu, Chun-Hui; Li, Shun-Li; Wang, Yu-Guang; Dong, Long-Zhang; Dai, Zhi-Hui; Li, Ya-Fei; Lan, Ya-Qian

    2016-01-01

    Electrochemical water splitting is one of the most economical and sustainable methods for large-scale hydrogen production. However, the development of low-cost and earth-abundant non-noble-metal catalysts for the hydrogen evolution reaction remains a challenge. Here we report a two-dimensional coupled hybrid of molybdenum carbide and reduced graphene oxide with a ternary polyoxometalate-polypyrrole/reduced graphene oxide nanocomposite as a precursor. The hybrid exhibits outstanding electrocatalytic activity for the hydrogen evolution reaction and excellent stability in acidic media, which is, to the best of our knowledge, the best among these reported non-noble-metal catalysts. Theoretical calculations on the basis of density functional theory reveal that the active sites for hydrogen evolution stem from the pyridinic nitrogens, as well as the carbon atoms, in the graphene. In a proof-of-concept trial, an electrocatalyst for hydrogen evolution is fabricated, which may open new avenues for the design of nanomaterials utilizing POMs/conducting polymer/reduced-graphene oxide nanocomposites. PMID:27032372

  12. Coupled Mercury–Cell Sorption, Reduction, and Oxidation on Methylmercury Production by Geobacter sulfurreducens PCA

    SciTech Connect

    Lin, Hui; Morrell-Falvey, Jennifer L.; Rao, Balaji; Liang, Liyuan; Gu, Baohua

    2014-09-30

    G. sulfurreducens PCA cells have been shown to reduce, sorb, and methylate Hg(II) species, but it is unclear whether this organism can oxidize and methylate dissolved elemental Hg(0) as shown for Desulfovibrio desulfuricans ND132. Using Hg(II) and Hg(0) separately as Hg sources in washed cell assays in phosphate buffered saline (pH 7.4), in this paper we report how cell-mediated Hg reduction and oxidation compete or synergize with sorption, thus affecting the production of toxic methylmercury by PCA cells. Methylation is found to be positively correlated to Hg sorption (r = 0.73) but negatively correlated to Hg reduction (r = -0.62). These reactions depend on the Hg and cell concentrations or the ratio of Hg to cellular thiols (-SH). Oxidation and methylation of Hg(0) are favored at relatively low Hg to cell–SH molar ratios (e.g., <1). Increasing Hg to cell ratios from 0.25 × 10–19 to 25 × 10–19 moles-Hg/cell (equivalent to Hg/cell–SH of 0.71 to 71) shifts the major reaction from oxidation to reduction. In the absence of five outer membrane c-type cytochromes, mutant ΔomcBESTZ also shows decreases in Hg reduction and increases in methylation. However, the presence of competing thiol-binding ions such as Zn2+ leads to increased Hg reduction and decreased methylation. Finally, these results suggest that the coupled cell-Hg sorption and redox transformations are important in controlling the rates of Hg uptake and methylation by G. sulfurreducens PCA in anoxic environments.

  13. Coupled mercury-cell sorption, reduction, and oxidation on methylmercury production by Geobacter sulfurreducens PCA.

    PubMed

    Lin, Hui; Morrell-Falvey, Jennifer L; Rao, Balaji; Liang, Liyuan; Gu, Baohua

    2014-10-21

    G. sulfurreducens PCA cells have been shown to reduce, sorb, and methylate Hg(II) species, but it is unclear whether this organism can oxidize and methylate dissolved elemental Hg(0) as shown for Desulfovibrio desulfuricans ND132. Using Hg(II) and Hg(0) separately as Hg sources in washed cell assays in phosphate buffered saline (pH 7.4), we report how cell-mediated Hg reduction and oxidation compete or synergize with sorption, thus affecting the production of toxic methylmercury by PCA cells. Methylation is found to be positively correlated to Hg sorption (r = 0.73) but negatively correlated to Hg reduction (r = -0.62). These reactions depend on the Hg and cell concentrations or the ratio of Hg to cellular thiols (-SH). Oxidation and methylation of Hg(0) are favored at relatively low Hg to cell-SH molar ratios (e.g., <1). Increasing Hg to cell ratios from 0.25 × 10(-19) to 25 × 10(-19) moles-Hg/cell (equivalent to Hg/cell-SH of 0.71 to 71) shifts the major reaction from oxidation to reduction. In the absence of five outer membrane c-type cytochromes, mutant ΔomcBESTZ also shows decreases in Hg reduction and increases in methylation. However, the presence of competing thiol-binding ions such as Zn(2+) leads to increased Hg reduction and decreased methylation. These results suggest that the coupled cell-Hg sorption and redox transformations are important in controlling the rates of Hg uptake and methylation by G. sulfurreducens PCA in anoxic environments.

  14. Coupled Mercury–Cell Sorption, Reduction, and Oxidation on Methylmercury Production by Geobacter sulfurreducens PCA

    DOE PAGES

    Lin, Hui; Morrell-Falvey, Jennifer L.; Rao, Balaji; ...

    2014-09-30

    G. sulfurreducens PCA cells have been shown to reduce, sorb, and methylate Hg(II) species, but it is unclear whether this organism can oxidize and methylate dissolved elemental Hg(0) as shown for Desulfovibrio desulfuricans ND132. Using Hg(II) and Hg(0) separately as Hg sources in washed cell assays in phosphate buffered saline (pH 7.4), in this paper we report how cell-mediated Hg reduction and oxidation compete or synergize with sorption, thus affecting the production of toxic methylmercury by PCA cells. Methylation is found to be positively correlated to Hg sorption (r = 0.73) but negatively correlated to Hg reduction (r = -0.62).more » These reactions depend on the Hg and cell concentrations or the ratio of Hg to cellular thiols (-SH). Oxidation and methylation of Hg(0) are favored at relatively low Hg to cell–SH molar ratios (e.g., <1). Increasing Hg to cell ratios from 0.25 × 10–19 to 25 × 10–19 moles-Hg/cell (equivalent to Hg/cell–SH of 0.71 to 71) shifts the major reaction from oxidation to reduction. In the absence of five outer membrane c-type cytochromes, mutant ΔomcBESTZ also shows decreases in Hg reduction and increases in methylation. However, the presence of competing thiol-binding ions such as Zn2+ leads to increased Hg reduction and decreased methylation. Finally, these results suggest that the coupled cell-Hg sorption and redox transformations are important in controlling the rates of Hg uptake and methylation by G. sulfurreducens PCA in anoxic environments.« less

  15. Qualitative screening of veterinary anti-microbial agents in tissues, milk, and eggs of food-producing animals using liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Chen, Dongmei; Yu, Jie; Tao, Yanfei; Pan, Yuanhu; Xie, Shuyu; Huang, Lingli; Peng, Dapeng; Wang, Xu; Wang, Yulian; Liu, Zhenli; Yuan, Zonghui

    2016-04-01

    A method for the analysis of 120 drugs in animal derived food was developed using liquid chromatography-tandem mass spectrometry (LC-MS/MS). These analytes belong to 12 families of veterinary anti-microbial agents (quinolones, macrolides, β-lactams, nitroimidazoles, sulfonamides, lincomycines, chloramphenicols, quinoxalines, tetracyclines, polypeptides, and antibacterial synergists) as well as other compounds not assigned to a particular drug family. The animal derived food samples include muscle and liver of swine, bovine, sheep, and chicken, as well as hen eggs and dairy milk. The sample preparation included ultrasound-assisted extraction (UAE) with acetonitrile-water and a final clean-up with auto solid-phase extraction (SPE) on HLB cartridges. The detection and quantification of 120 anti-microbial agents was performed using LC-MS/MS in positive and negative ion mode. The chromatographic separation was performed on a C18 column using acetonitrile and 0.1% formic acid as the mobile phase. The limit of detection (LOD) and limit of quantification (LOQ) of all drugs in food-producing animals were 0.5-3.0μg/kg and 1.5-10.0μg/kg, respectively. The developed method was successfully utilized to monitor real samples, which demonstrated that it is a simple, fast, and robust method, and could be used as a regulatory to screen for the presence of residues from veterinary anti-microbial drugs in animal-derived foods.

  16. Simultaneous detection of eight active components in Radix Tinosporae by ultra high performance liquid chromatography coupled with electrospray tandem mass spectrometry.

    PubMed

    Xiang, Qiuyue; Hashi, Yuki; Chen, Zilin

    2016-06-01

    A rapid and sensitive ultra high performance liquid chromatography with electrospray ionization tandem mass spectrometry method was developed and validated for the simultaneous determination of eight major active components (magnoflorine, menisperine, 20-hydroxyecdysone, cepharanthine, columbamine, jatrorrhizine, columbin, and palmatine) in Radix Tinosporae. The separation was performed on an InterSustainSwift C18 column (1.9 μm, 2.1 id × 100 mm) at 40 °C with a gradient elution. A mixture of acetonitrile and methanol (v/v = 1:1) and ammonium acetate buffer (25 mmol/L ammonium acetate with 0.2% formic acid) were used as mobile phases, and the flow rate was set at 0.4 mL/min. The recovery was tested in real samples and calculated to be 86.97-111.28%, and all the compounds showed good linearity (r > 0.998) in relatively wide concentration ranges. The developed method was applied to the determination of eight active compounds in real herb samples, which were collected from four different places. It has been demonstrated that the proposed method has great potential for the quality control of the traditional Chinese medicine Radix Tinosporae.

  17. Simultaneous determination of 16 brominated flame retardants in food and feed of animal origin by fast gas chromatography coupled to tandem mass spectrometry using atmospheric pressure chemical ionisation.

    PubMed

    Bichon, E; Guiffard, I; Vénisseau, A; Lesquin, E; Vaccher, V; Brosseaud, A; Marchand, P; Le Bizec, B

    2016-08-12

    A gas chromatography tandem mass spectrometry method using atmospheric pressure chemical ionisation was developed for the monitoring of 16 brominated flame retardants (7 usually monitored polybromodiphenylethers (PBDEs) and BDE #209 and 8 additional emerging and novel BFRs) in food and feed of animal origin. The developed analytical method has decreased the run time by three compared to conventional strategies, using a 2.5m column length (5% phenyl stationary phase, 0.1mm i.d., 0.1μmf.t.), a pulsed split injection (1:5) with carrier gas helium flow rate at 0.48mLmin(-1) in one run of 20 min. For most BFRs, analytical data were compared with the current analytical strategy relying on GC/EI/HRMS (double sector, R=10000 at 10% valley). Performances in terms of sensitivity were found to meet the Commission recommendation (118/2014/EC) for nBFRs. GC/APCI/MS/MS represents a promising alternative for multi-BFRs analysis in complex matrices, in that it allows the monitoring of a wider list of contaminants in a single injection and a shorter run time.

  18. Determination of 13 Organic Toxicants in Human Blood by Liquid-Liquid Extraction Coupling High-Performance Liquid Chromatography Tandem Mass Spectrometry.

    PubMed

    Song, Aiying

    2016-01-01

    Pesticides and antidepressants are frequently misused in drug-facilitated crime because of their toxicological effect and easy-availability. Therefore, it is essential for the development of a simple and reliable method for the determination of these organic toxicants in biological fluids. Here, we report on an applicable method by the combination of optimized liquid-liquid extraction (LLE) procedure and high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) to identify and quantify dimethoate, omethoate, dichlorvos, carbofuran, fenpropathrin, diazepam, estazolam, alprazolam, triazolamm, chlorpromazine, phenergan, barbitone and phenobarbital in human blood. The method demonstrated a linear calibration curve in range of 20 - 500 μg/L (r > 0.994). The accuracy evaluated by recovery spiked at three different concentrations (50, 100 and 200 μg/L) was in the range of 58.8 - 83.1% with a relative standard deviations (RSD) of 3.7 - 7.4%. The limits of quantification ranged over 6.7 - 33.3 μg/L. This method was proved to be simple and reliable, and was thus successfully applied to forensic toxicology.

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

    PubMed

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

    2013-10-15

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

  20. Method development and validation for the quantification of dasatinib, erlotinib, gefitinib, imatinib, lapatinib, nilotinib, sorafenib and sunitinib in human plasma by liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Lankheet, N A G; Hillebrand, M J X; Rosing, H; Schellens, J H M; Beijnen, J H; Huitema, A D R

    2013-04-01

    To support pharmacokinetic-guided dosing in individual patients, a fast and accurate method for simultaneous determination of anticancer tyrosine kinase inhibitors (TKIs) dasatinib, erlotinib, gefitinib, imatinib, lapatinib, nilotinib, sorafenib and sunitinib in human plasma was developed using high-performance liquid chromatography and detection with tandem mass spectrometry (HPLC-MS/MS). Stable isotopically labeled compounds of the eight different TKIs were used as internal standards. Plasma proteins were precipitated and an aliquot of supernatant was directly injected onto a reversed phase chromatography system consisting of a Gemini C18 column (50 × 2.0 mm i.d., 5.0 µm particle size) and then compounds were eluted with a gradient. The outlet of the column was connected to a triple quadrupole mass spectrometer with electrospray interface. Ions were detected in the positive multiple reaction monitoring mode. This method was validated over a linear range from 20.0 to 10,000 ng/mL for erlotinib, gefitinib, imatinib, lapatinib, nilotinib and sorafenib, and from 5.00 to 2500 ng/mL for dasatinib and sunitinib. Results from the validation study demonstrated good intra- and inter-assay accuracy (<13.1%) and precision (10.0%) for all analytes. This method was successfully applied for routine therapeutic drug monitoring purposes in patients treated with the investigated TKIs.

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

    PubMed

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

    2013-12-30

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

  2. A comprehensive profiling of sulfatides in myelin from mouse brain using liquid chromatography coupled to high-resolution accurate tandem mass spectrometry.

    PubMed

    Pintado-Sierra, M; García-Álvarez, I; Bribián, A; Medina-Rodríguez, E M; Lebrón-Aguilar, R; Garrido, L; de Castro, F; Fernández-Mayoralas, A; Quintanilla-López, J E

    2017-01-25

    Sulfatides are sulfoglycolipids found in the myelin sheath. The composition ratio of sulfatide molecular species changes with age, and it has also been associated with the pathogenesis of various human central nervous system diseases. However, profiling sulfatides in biological samples is difficult, due to the great variety of molecular species. In this work, a new, easy and reliable liquid chromatography-electrospray tandem mass spectrometry (LC-ESI(+)-MS/MS) method has been developed to profile sulfatide content in biological samples of myelin. The 'wrong-way-round' ionization effect has been described for this type of molecules for the first time, making it possible to correctly identify as many as 37 different sulfatides in mouse brain myelin samples, including molecules with different fatty acid chain lengths and varying degrees of unsaturation and hydroxylation. A chemometric analysis of their relative abundances showed that the main difference among individuals of different ages was the content of sulfatides with odd-numbered fatty acid chains, in addition to hydroxylated species.

  3. Determination of soyasaponins Ba and Bb in human serum by high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry.

    PubMed

    Jin, Micong; Yang, Yiwen; Su, Baogen; Ren, Qilong

    2007-02-01

    A rapid, sensitive and selective high-performance liquid chromatography-tandem mass spectrometric method (HPLC-MS-MS) has been developed and validated for the determination of soyasaponins Ba and Bb in human serum using glycyrrhizin as internal standard (I.S.). Soyasaponins Ba and Bb were extracted from human serum by liquid-liquid extraction and cleaned up by C(18) solid-phase extraction (SPE), followed by separation on a C(18) reversed-phase column using acetonitrile/water containing 0.025% acetic acid as a mobile phase for gradient elution. Soyasaponins Ba and Bb, and I.S. were ionized by negative ion pneumatically assisted electrospray and detected by HPLC-MS-MS in the multiple-reaction monitoring (MRM) mode using precursor-->product ion combinations at m/z 958-->940, 942-->924 and 822-->351, respectively. The calibration curves were linear (r(2)>0.991) in the concentration range of 0.5-100.0 ng/mL, with lower limits of quantification of 0.5 and 0.3 ng/mL for soyasaponins Ba and Bb, respectively, in human serum. Intra-day and inter-day relative standard deviations (R.S.D.) were less than 7.9 and 11.3%, respectively. The mean recoveries of soyasaponins Ba and Bb ranged from 92 to 101% and from 85 to 94%, respectively.

  4. Quantification of 2-acetyl-1-pyrroline in rice by stable isotope dilution assay through headspace solid-phase microextraction coupled to gas chromatography-tandem mass spectrometry.

    PubMed

    Maraval, Isabelle; Sen, Kemal; Agrebi, Abdelhamid; Menut, Chantal; Morere, Alain; Boulanger, Renaud; Gay, Frédéric; Mestres, Christian; Gunata, Ziya

    2010-08-24

    A new and convenient synthesis of 2-acetyl-1-pyrroline (2AP), a potent flavor compound in rice, and its ring-deuterated analog, 2-acetyl-1-d(2)-pyrroline (2AP-d(2)), was reported. A stable isotope dilution assay (SIDA), involving headspace solid-phase microextraction (HS-SPME) combined with gas chromatography-positive chemical ionization-ion trap-tandem mass spectrometry (GC-PCI-IT-MS-MS), was developed for 2AP quantification. A divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was used for HS-SPME procedure and parameters affecting analytes recovery, such as extraction time and temperature, pH and salt, were studied. The repeatability of the method (n=10) expressed as relative standard deviation (RSD) was 11.6%. A good linearity was observed from 5.9 to 779 ng of 2AP (r(2)=0.9989). Limits of detection (LOD) and quantification (LOQ) for 2AP were 0.1 and 0.4 ng g(-1) of rice, respectively. The recovery of spiked 2AP from rice matrix was almost complete. The developed method was applied to the quantification of 2AP in aerial parts and grains of scented and non-scented rice cultivars.

  5. Simultaneous determination of codeine, ephedrine, guaiphenesin and chlorpheniramine in beagle dog plasma using high performance liquid chromatography coupled with tandem mass spectrometric detection: application to a bioequivalence study.

    PubMed

    Hu, Ziyan; Zou, Qiaogen; Tian, Jixin; Sun, Lili; Zhang, Zunjian

    2011-12-15

    A rapid and sensitive method based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the simultaneous determination of codeine, ephedrine, guaiphenesin and chlorpheniramine in beagle dog plasma has been developed and validated. Following liquid-liquid extraction, the analytes were separated on a reversed-phase C(18) column (150 mm × 2.0 mm, 3 μm) using formic acid:10 mM ammonium acetate:methanol (0.2:62:38, v/v/v) as mobile phase at a flow rate of 0.2 mL/min and analyzed by a triple-quadrupole mass spectrometer in the selected reaction monitoring (SRM) mode. The method was linear for all analytes over the following concentration (ng/mL) ranges: codeine 0.08-16; ephedrine 0.8-160; guaiphenesin 80-16,000; chlorpheniramine 0.2-40. Acceptable precision and accuracy were obtained for concentrations over the standard curve range. It is the first time that the validated HPLC-MS/MS method was successfully applied to a bioequivalence study in 6 healthy beagle dogs.

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

    PubMed

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

    2012-01-01

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

  7. 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

    Kubica, Paweł; Namieśnik, Jacek; Wasik, Andrzej

    2015-02-01

    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.

  8. Elemental analysis of coal by tandem laser induced breakdown spectroscopy and laser ablation inductively coupled plasma time of flight mass spectrometry

    NASA Astrophysics Data System (ADS)

    Dong, Meirong; Oropeza, Dayana; Chirinos, José; González, Jhanis J.; Lu, Jidong; Mao, Xianglei; Russo, Richard E.

    2015-07-01

    The capabilities and analytical benefits of combined LIBS and LA-ICP-MS were evaluated for the analysis of coal samples. The ablation system consisted of a Nd:YAG laser operated 213 nm. A Czerny-turner spectrograph with ICCD detector and time-of-flight based mass spectrometer were utilized for LIBS and ICP-MS detection, respectively. This tandem approach allows simultaneous determination of major and minor elements (C, Si, Ca, Al, Mg), and trace elements (V, Ba, Pb, U, etc.) in the coal samples. The research focused on calibration strategies, specifically the use of univariate and multivariate data analysis on analytical performance. Partial least square regression (PLSR) was shown to minimize and compensate for matrix effects in the emission and mass spectra improving quantitative analysis by LIBS and LA-ICP-MS, respectively. The correlation between measurements from these two techniques demonstrated that mass spectral data combined with LIBS emission measurements by PLSR improved the accuracy and precision for quantitative analysis of trace elements in coal.

  9. Determination of Oxytetracycline and 4-Epi-Oxytetracycline Residues in Feathers and Edible Tissues of Broiler Chickens Using Liquid Chromatography Coupled with Tandem Mass Spectrometry.

    PubMed

    Cornejo, Javiera; Pokrant, Ekaterina; Krogh, Magdalena; Briceño, Cristóbal; Hidalgo, Héctor; Maddaleno, Aldo; Araya-Jordán, Carolina; Martín, Betty San

    2017-04-01

    Antibiotics have been widely used in poultry production for the treatment of bacterial diseases. However, drug residues can remain in products derived from animals after the cessation of the drug therapies. Feathers, in particular, have shown an affinity for antibiotics such as tetracycline, suggesting the persistence of these drugs in nonedible tissue. After the birds are slaughtered, feathers are ground into feather meals, which are used as organic fertilizer or an ingredient in animal diets, thereby entering into the food chain and becoming a potential risk for public health. To evaluate the depletion of oxytetracycline (OTC) and its metabolite 4-epi-oxytetracycline (4-epi-OTC) in the muscles, liver, and feathers, 64 broiler chickens, bred under controlled conditions, were treated orally with a commercial formulation of 10% OTC for 7 days. The analytes were quantified using liquid chromatography-tandem mass spectrometry. OTC and 4-epi-OTC were found in the feathers for 46 days, whereas they were found in the muscle and liver for only 12 and 6 days, respectively. These results prove that the analytes remain in feathers in higher concentrations than they do in edible tissues after treatment with tetracyclines. Thus, feather meals represent a potential source of antimicrobial residue contamination in the food chain.

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

    USGS Publications Warehouse

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

    2008-01-01

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

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

    SciTech Connect

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

    2009-05-12

    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

  12. A single marker choice strategy in simultaneous characterization and quantification of multiple components by rapid resolution liquid chromatography coupled with triple quadrupole tandem mass spectrometry (RRLC-QqQ-MS).

    PubMed

    Ning, Zhangchi; Liu, Zhenli; Song, Zhiqian; Zhao, Siyu; Dong, Yunzhuo; Zeng, Honglian; Shu, Yisong; Lu, Cheng; Liu, Yuanyan; Lu, Aiping

    2016-05-30

    Single standard to determine multi-components (SSDMC) method has been accepted as an efficient technique for the quality control of Traditional Chinese medicines (TCMs), especially for overcoming the shortage of reference standards. HPLC-UV methods have been applied to establish SSDMC method for quantitative analysis in several plant medicines and Chinese patent medicines, however, no LC-MS methods have been used. The purpose of this study is to put forward an improved strategy for the choice of single marker in SSDMC using rapid resolution liquid chromatography coupled with triple quadrupole tandem mass spectrometry (RRLC-QqQ-MS). Five different Panax genus plants, recorded in the Chinese Pharmacopeia 2015 edition, were used as research subjects. An improved SSDMC strategy for simultaneous characterization and determination of 18 bioactive saponins in five Panax plants was put forward, and which was validated to be more superior. Then, it was fully investigated with respect to linearity, LODs, LOQs, precision and accuracy. Coupling with multivariate statistical analysis, the established and validated SSDMC strategy could be successively used in discrimination of the five Panax genus plants.

  13. Analysis of 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) and its brominated analogues in chlorine-treated water by gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS).

    PubMed

    Planas, Carles; Ventura, Francesc; Caixach, Josep; Martín, Jordi; Boleda, M Rosa; Paraira, Miquel

    2015-11-01

    A simple, selective and sensitive method for the analysis of the strong mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) and its brominated analogues (BMXs) in chlorine-treated water has been developed. The method is based on gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS), previous liquid-liquid extraction (LLE) of a smaller sample volume compared to other methods and on-line derivatization with a silylation reactive. GC-QqQ-MS/MS has been raised as an alternative easier to perform than gas chromatography coupled to high resolution mass spectrometry (GC-HRMS) for the analysis of MX and BMXs, and it allows to achieve low LODs (0.3 ng/L for MX and 0.4-0.9 ng/L for BMXs). This technique had not been previously described for the analysis of MX and BMXs. Quality parameters were calculated and real samples related to 3 drinking water treatment plants (DWTPs), tap water and both untreated and chlorinated groundwater were analyzed. Concentrations of 0.3-6.6 ng/L for MX and 1.0-7.3 ng/L for BMXs were detected. Results were discussed according to five of the main factors affecting MX and BMXs formation in chlorine-treated water (organic precursors, influence of bromide ions, evolution of MX and BMXs in the drinking water distribution system, groundwater chlorination and infiltration of water coming from chlorination processes in groundwater).

  14. Evaluation of the capabilities of atmospheric pressure chemical ionization source coupled to tandem mass spectrometry for the determination of dioxin-like polychlorobiphenyls in complex-matrix food samples.

    PubMed

    Portolés, T; Sales, C; Abalos, M; Sauló, J; Abad, E

    2016-09-21

    The use of the novel atmospheric pressure chemical ionization (APCI) source for gas chromatography (GC) coupled to triple quadrupole using tandem mass spectrometry (MS/MS) and its potential for the simultaneous determination of the 12 dioxin-like polychlorobiphenyls (DL-PCBs) in complex food and feed matrices has been evaluated. In first place, ionization and fragmentation behavior of DL-PCBs on the APCI source under charge transfer conditions has been studied followed by their fragmentation in the collision cell. Linearity, repeatability and sensitivity have been studied obtaining instrumental limits of detection and quantification of 0.0025 and 0.005 pg μL(-1) (2.5 and 5 fg on column) respectively for every DL-PCB. Finally, application to real samples has been carried out and DL-PCB congeners (PCB 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189) have been detected in the different samples in the range of 0.40-10000 pg g(-1). GC-(APCI)MS/MS has been proved as a suitable alternative to the traditionally accepted confirmation method based on the use of high resolution mass spectrometry and other triple quadrupole tandem mass spectrometry techniques operating with electron ionization. The development of MS/MS methodologies for the analysis of dioxins and DL-PCBs is nowadays particularly important, since this technique was included as a confirmatory method in the present European Union regulations that establish the requirements for the determination of these compounds in food and feed matrices.

  15. Rapid analysis of multiclass antibiotic residues and some of their metabolites in hospital, urban wastewater and river water by ultra-high-performance liquid chromatography coupled to quadrupole-linear ion trap tandem mass spectrometry.

    PubMed

    Gros, Meritxell; Rodríguez-Mozaz, Sara; Barceló, Damià

    2013-05-31

    The present work describes the development of a fast and robust analytical method for the determination of 53 antibiotic residues, covering various chemical groups and some of their metabolites, in environmental matrices that are considered important sources of antibiotic pollution, namely hospital and urban wastewaters, as well as in river waters. The method is based on automated off-line solid phase extraction (SPE) followed by ultra-high-performance liquid chromatography coupled to quadrupole linear ion trap tandem mass spectrometry (UHPLC-QqLIT). For unequivocal identification and confirmation, and in order to fulfill EU guidelines, two selected reaction monitoring (SRM) transitions per compound are monitored (the most intense one is used for quantification and the second one for confirmation). Quantification of target antibiotics is performed by the internal standard approach, using one isotopically labeled compound for each chemical group, in order to correct matrix effects. The main advantages of the method are automation and speed-up of sample preparation, by the reduction of extraction volumes for all matrices, the fast separation of a wide spectrum of antibiotics by using ultra-high-performance liquid chromatography, its sensitivity (limits of detection in the low ng/L range) and selectivity (due to the use of tandem mass spectrometry) The inclusion of β-lactam antibiotics (penicillins and cephalosporins), which are compounds difficult to analyze in multi-residue methods due to their instability in water matrices, and some antibiotics metabolites are other important benefits of the method developed. As part of the validation procedure, the method developed was applied to the analysis of antibiotics residues in hospital, urban influent and effluent wastewaters as well as in river water samples.

  16. Optimal control strategies for hydrogen production when coupling solid oxide electrolysers with intermittent renewable energies

    NASA Astrophysics Data System (ADS)

    Cai, Qiong; Adjiman, Claire S.; Brandon, Nigel P.

    2014-12-01

    The penetration of intermittent renewable energies requires the development of energy storage technologies. High temperature electrolysis using solid oxide electrolyser cells (SOECs) as a potential energy storage technology, provides the prospect of a cost-effective and energy efficient route to clean hydrogen production. The development of optimal control strategies when SOEC systems are coupled with intermittent renewable energies is discussed. Hydrogen production is examined in relation to energy consumption. Control strategies considered include maximizing hydrogen production, minimizing SOEC energy consumption and minimizing compressor energy consumption. Optimal control trajectories of the operating variables over a given period of time show feasible control for the chosen situations. Temperature control of the SOEC stack is ensured via constraints on the overall temperature difference across the cell and the local temperature gradient within the SOEC stack, to link materials properties with system performance; these constraints are successfully managed. The relative merits of the optimal control strategies are analyzed.

  17. Infrared rectification in a nanoantenna-coupled metal-oxide-semiconductor tunnel diode.

    PubMed

    Davids, Paul S; Jarecki, Robert L; Starbuck, Andrew; Burckel, D Bruce; Kadlec, Emil A; Ribaudo, Troy; Shaner, Eric A; Peters, David W

    2015-12-01

    Direct rectification of electromagnetic radiation is a well-established method for wireless power conversion in the microwave region of the spectrum, for which conversion efficiencies in excess of 84% have been demonstrated. Scaling to the infrared or optical part of the spectrum requires ultrafast rectification that can only be obtained by direct tunnelling. Many research groups have looked to plasmonics to overcome antenna-scaling limits and to increase the confinement. Recently, surface plasmons on heavily doped Si surfaces were investigated as a way of extending surface-mode confinement to the thermal infrared region. Here we combine a nanostructured metallic surface with a heavily doped Si infrared-reflective ground plane designed to confine infrared radiation in an active electronic direct-conversion device. The interplay of strong infrared photon-phonon coupling and electromagnetic confinement in nanoscale devices is demonstrated to have a large impact on ultrafast electronic tunnelling in metal-oxide-semiconductor (MOS) structures. Infrared dispersion of SiO2 near a longitudinal optical (LO) phonon mode gives large transverse-field confinement in a nanometre-scale oxide-tunnel gap as the wavelength-dependent permittivity changes from 1 to 0, which leads to enhanced electromagnetic fields at material interfaces and a rectified displacement current that provides a direct conversion of infrared radiation into electric current. The spectral and electrical signatures of the nanoantenna-coupled tunnel diodes are examined under broadband blackbody and quantum-cascade laser (QCL) illumination. In the region near the LO phonon resonance, we obtained a measured photoresponsivity of 2.7 mA W(-1) cm(-2) at -0.1 V.

  18. Simultaneous determination of eight alkaloids and oleandrin in herbal cosmetics by dispersive solid-phase extraction coupled with ultra high performance liquid chromatography and tandem mass spectrometry.

    PubMed

    Xun, Zhiqing; Liu, Donghong; Huang, Rongrong; He, Shuang; Hu, Du; Guo, Xindong; Xian, Yanping

    2017-03-20

    We utilized ultra high performance liquid chromatography with tandem mass spectrometry and dispersive solid-phase extraction to develop a new method for the detection of nine analytes (scopolamine, cephaeline, strychnine, hyoscyamine, brucine, hydrastine, ajmalicine, colchicine and oleandrin) in herbal cosmetics. Acetonitrile/water and 2-propylaminoethylamine were used to disperse and purify during the dispersive solid-phase extraction step. The analytes were separated by a Waters UPLC HSS T3 column and detected through electrospray ionization source in the positive mode with multi-reaction monitoring conditions. Under the optimal conditions, the calibration curves were linear in the range of 0.2-100.0 μg L(-1) with the correlation coefficients higher than 0.995. The method limit of quantitation (S/N = 10) were 5.0 μg kg(-1) for oleandrin and 1.0 μg kg(-1) for the other eight alkaloids. The mean recoveries at three spiked concentration levels of 1.0-10.0 μg kg(-1) were in the range of 86.9-116.5% with the intra-day relative standard deviations (n = 6) ranging from 2.4 to 8.8%, and inter-day relative standard deviations ranging from 2.7 to 5.7%. This method is accurate, simple and rapid, and has been applied to the quality supervision of herbal cosmetics in Guangzhou. This article is protected by copyright. All rights reserved.

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

    PubMed

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

    2015-02-01

    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.

  20. Multi-residue enantiomeric analysis of human and veterinary pharmaceuticals and their metabolites in environmental samples by chiral liquid chromatography coupled with tandem mass spectrometry detection.

    PubMed

    Camacho-Muñoz, Dolores; Kasprzyk-Hordern, Barbara

    2015-12-01

    Enantiomeric profiling of chiral pharmacologically active compounds (PACs) in the environment has hardly been investigated. This manuscript describes, for the first time, a multi-residue enantioselective method for the analysis of human and veterinary chiral PACs and their main metabolites from different therapeutic groups in complex environmental samples such as wastewater and river water. Several analytes targeted in this paper have not been analysed in the environment at enantiomeric level before. These are aminorex, carboxyibuprofen, carprofen, cephalexin, 3-N-dechloroethylifosfamide, 10,11-dihydro-10-hydroxycarbamazepine, dihydroketoprofen, fenoprofen, fexofenadine, flurbiprofen, 2-hydroxyibuprofen, ifosfamide, indoprofen, mandelic acid, 2-phenylpropionic acid, praziquantel and tetramisole. The method is based on chiral liquid chromatography utilising a chiral α1-acid glycoprotein column and tandem mass spectrometry detection. Excellent chromatographic separation of enantiomers (Rs≥1.0) was achieved for chloramphenicol, fexofenadine, ifosfamide, naproxen, tetramisole, ibuprofen and their metabolites: aminorex and dihydroketoprofen (three of four enantiomers), and partial separation (Rs = 0.7-1.0) was achieved for ketoprofen, praziquantel and the following metabolites: 3-N-dechloroethylifosfamide and 10,11-dihydro-10-hydroxycarbamazepine. The overall performance of the method was satisfactory for most of the compounds targeted. Method detection limits were at low nanogram per litre for surface water and effluent wastewater. Method intra-day precision was on average under 20% and sample pre-concentration using solid phase extraction yielded recoveries >70% for most of the analytes. This novel, selective and sensitive method has been applied for the quantification of chiral PACs in surface water and effluent wastewater providing excellent enantioresolution of multicomponent mixtures in complex environmental samples. It will help with better understanding

  1. 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

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

    2014-12-10

    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. 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.

  2. Simultaneous determination of ten biogenic amines in a thymopolypeptides injection using ultra-performance liquid chromatography coupled with electrospray ionization tandem quadrupole mass spectrometry.

    PubMed

    Li, Yong; Yang, Huaxin; Liao, Haiming; Fan, Huihong; Liang, Chenggang; Deng, Lijuan; Jin, Shaohong

    2013-06-15

    A selective and sensitive ultra-performance liquid chromatography-electrospray ionization tandem mass spectrometry (UPLC-MS) method was developed for the simultaneous determination of ten biogenic amines (tryptamine, 2-phenylethylamine, putrescine, cadaverine, histamine, tyramine, spermidine, adrenaline, dopamine and spermine) in a thymopolypeptides injection from the Chinese market for the first time. Biogenic amines (BAs) were pre-column derivatised by dansyl chloride after direct sample dilution. Dansylated amines were separated on an ACQUITY UPLC BEH Shield RP18 column (2.1mm×150mm I.D., 1.7μm) using a gradient elution. Quantification was done by monitoring fragment ions of each derivative under the MS mode of multiple reaction monitoring (MRM). A satisfactory result of method validation was obtained. The linearity ranged from 0.32 to 1182.9μg/L and the correlation coefficients (r) for all amines were above 0.99. The LOD ranged from 0.08μg/L for 2-phenylethylamine and tyramine to 8.00μg/L for adrenaline; the LOQ ranged from 0.32μg/L for 2-phenylethylamine to 12.12μg/L for dopamine. The recovery ranged from 75.8 to 110.3% after spiking standard solutions of BAs to a sample at three levels. The intra and inter-day precision RSD were 0.78-8.85% and 1.39-9.93% respectively. Eighty-four injections were analyzed by this method. Nine biogenic amines were found in them except adrenaline. Moreover, the relationship between the result of test for depressor substances and the content of BAs was statistically analyzed.

  3. [Simultaneous determination of glyphosate and glufosinate-ammonium residues in tea by ultra performance liquid chromatography-tandem mass spectrometry coupled with pre-column derivatization].

    PubMed

    Wu, Xiaogang; Chen, Xiaoquan; Xiao, Haijun; Liu, Binqiu

    2015-10-01

    A method was developed for the determination of glyphosate (GLY) and glufosinate-ammonium (GLUF) in tea using ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The sample was extracted with ultrapure water and dichloromethane for 30 min under ultrasonication, followed by a simple cleanup with a C18 solid phase extraction (SPE) cartridge, and then GLY and GLUF were derivatized using 9-fluorenylmethoxycarbonyl (FMOC-Cl) in borate buffer for 2 h. The derivatives of GLY and GLUF were separated on a Waters C18 column (50 mm x 2.1 mm, 1.7 μm) in a gradient elution mode, and finally detected with positive electrospray ionization-mass spectrometry (ESI-MS/MS ) in multiple reaction monitoring (MRM) mode. The quantification analysis was performed by external standard method. The method showed a good linearity (r > 0. 990) in the range of 0.003 125-0.1 mg/L. The limits of detection (LODs) of GLY and GLUF were 0.03 mg/kg. At the spiked levels of 0.375, 1.5 and 4.5 mg/kg, the recoveries of GLY and GLUF were 87.37%-99.11% and 81.44% -86.17% respectively, and the relative standard deviations (RSDs) (n = 6) of GLY and GLUF were 0.68%-1.35% and 1.01%-2.33%, respectively. This method is simple, rapid and characterized with acceptable sensitivity and accuracy to meet the requirements for the analysis of GLY and GLUF simultaneously in tea.

  4. Terbinafine quantification in human plasma by high-performance liquid chromatography coupled to electrospray tandem mass spectrometry: application to a bioequivalence study.

    PubMed

    de Oliveira, C H; Barrientos-Astigarraga, R E; de Moraes, M O; Bezerra, F A; de Moraes, M E; de Nucci, G

    2001-12-01

    A method based on liquid chromatography with positive ion electrospray ionization and tandem mass spectrometry is described for the determination of terbinafine in human plasma using naftifine as internal standard. The method has a chromatographic run time of 5 minutes and was linear in the range 1.0 to 2000 ng/mL. The limit of quantification was 1.0 ng/mL; the intraday precision was 3.6%, 3.8%, 3.5%, and 4.1%; and the intraday accuracy was -2.7%, 7.7%, 4.8%, and -2.7% for 5.0, 80.0, 250.0, and 1500.0 ng/mL, respectively. The interday precision was 4.9%, 1.7%, 2.4%, and 4.6% and the interday accuracy was 0.3%, 5.8%, 6.5%, and -1.4% for the same concentrations. This method was used in a bioequivalence study of two tablet formulations of terbinafine. Twenty-four healthy volunteers (both sexes) received a single oral dose of terbinafine (250 mg) in an open, randomized, two-period crossover study. The 90% CI of geometric mean ratios between Terbinafina (Medley S/A Indústria Farmacêutica, Campinas, Brazil) and Lamisil (Novartis Biociências S/A, São Paulo, Brazil) were 90.5% to 110.0% for C max, 92.2% to 108.1% for AUC last, and 91.3% to 107.5% for AUC 0-inf. Because the 90% CI for the above-mentioned parameters were included in the 80% to 125% interval proposed by the US FDA, the two formulations were considered bioequivalent in terms of rate and extent of absorption.

  5. Rapid determination of 88 veterinary drug residues in milk using automated TurborFlow online clean-up mode coupled to liquid chromatography-tandem mass spectrometry.

    PubMed

    Zhu, Wei-xia; Yang, Ji-zhou; Wang, Zhao-xing; Wang, Cai-juan; Liu, Ya-feng; Zhang, Li

    2016-02-01

    A novel method based on TurborFlow online solid phase extraction (SPE) combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been established for simultaneous screening and confirmation of 88 wide-range veterinary drugs belonging to eight families (20 sulfonamides, 7 macrolides, 15 quinolones, 8 penicillins, 13 benzimidazoles, 4 tetracyclines, 2 sedatives, and 19 hormones) in milk. The preparation method consists of sample dilution and ultrasonic extraction, followed by an automated turbulent flow cyclone chromatography sample clean-up system. The detection was achieved in selected reaction monitoring mode (SRM). The total run time was within 39 min, including automated extraction, analytical chromatography and re-equilibration of the turboflow system. The optimization of different experimental parameters including extraction, purification, separation, and detection were evaluated separately in this study. The developed method was validated and good performing characteristics were obtained. The linear regression coefficients (R(2)) of matrix-match calibration standard curves established for quantification were higher than 0.9930. The limits of detection (LOD) were in the range of 0.2-2.0 μg/kg given by signal-noise ratio ≥3 (S/N) and the limits of quantification (LOQ, S/N≥10) ranged between 0.5 μg/kg and 10 μg/kg. Average recoveries of spiked target compounds with different levels were between 63.1% and 117.4%, with percentage relative standard deviations (RSD) in the range of 3.3-17.6%. The results indicated that the developed method has great potential for the routine laboratory analysis of large numbers of samples on measuring different classes of compounds. In comparison to traditional procedures, the automated sample clean-up ensures rapid, effective, sensitive analyses of veterinary drugs in milk.

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

    PubMed Central

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

    2012-01-01

    A liquid chromatography-tandem mass spectrometry method (LC-MS/MS) was developed for the determination of phenolic acids and flavonoids in a medicinal Chinese herb Taraxacum formosanum Kitam. Initially, both phenolic acids and flavonoids were extracted with 50% ethanol in a water-bath at 60 °C for 3 h and eventually separated into acidic fraction and neutral fraction by using a C18 cartridge. A total of 29 compounds were separated within 68 min by employing a Gemini C18 column and a gradient solvent system of 0.1% formic acid and acetonitrile at a flow rate of 1.0 mL/min. Based on the retention behavior as well as absorption and mass spectra, 19 phenolic acids and 10 flavonoids were identified and quantified in T. formosanum, with the former ranging from 14.1 μg/g to 10,870.4 μg/g, and the latter from 9.9 μg/g to 325.8 μg/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

  7. Liquid chromatography coupled to tandem and high resolution mass spectrometry for the characterisation of ofloxacin transformation products after titanium dioxide photocatalysis.

    PubMed

    Jimenez-Villarin, Javier; Serra-Clusellas, Anna; Martínez, Cristina; Conesa, Aleix; Garcia-Montaño, Júlia; Moyano, Encarnación

    2016-04-22

    The characterization of pharmaceutical drugs and their transformation products have become an important analytical research field because its presence in the environment could induce bacterial resistance. Despite all efforts made by the scientific community, detection and structure identification of unknown chemicals still remains the most challenging task in non-targeted analytics. Given that, the objective of the present study was to develop an untargeted workflow to detect, quantify, identify and characterize ofloxacin and its transformation products (OFX TPs) after photocatalytic treatments based on TiO2 nanoparticles and TiO2 nanofibers. For the characterization and chemical structure assignment of OFX TPs, mass defect filters, mass accurate measurements (HRMS), tandem mass spectrometry in a q-Orbitrap (MS/HRMS) and the photocatalysis of the isotopically labelled ofloxacin (OFX-d3) were used. Since a large set of data was obtained in each run, data treatment based on statistical analysis and mass defect filtering was used to reduce the number of potential TP candidates from 2497 m/z peaks to 70. Moreover, ions generated by in-source CID and by redox reactions in the electrospray source (ESI) were also detected and discarded from the TP candidate list. Moreover, the whole kinetics evolution of the generated TPs provided a deeper insight into the degradation mechanism and was used to propose a degradation pathway for the OFX in the aqueous phase. The time evolution of the TPs generated during the photocatalytic process using both types of catalysts (NPs and NFs) and different set-ups (suspended and supported conditions) indicated that OFX was completely removed from the aqueous solution in less than 4h. Among the condition tested TiO2 nanoparticles in suspended conditions showed the fastest kinetics (k: 0.161 min(-1)).

  8. Surrogate analyte approach for quantitation of endogenous NAD(+) in human acidified blood samples using liquid chromatography coupled with electrospray ionization tandem mass spectrometry.

    PubMed

    Liu, Liling; Cui, Zhiyi; Deng, Yuzhong; Dean, Brian; Hop, Cornelis E C A; Liang, Xiaorong

    2016-02-01

    A high-performance liquid chromatography tandem mass spectrometry (LC-MS/MS) assay for the quantitative determination of NAD(+) in human whole blood using a surrogate analyte approach was developed and validated. Human whole blood was acidified using 0.5N perchloric acid at a ratio of 1:3 (v:v, blood:perchloric acid) during sample collection. 25μL of acidified blood was extracted using a protein precipitation method and the resulting extracts were analyzed using reverse-phase chromatography and positive electrospray ionization mass spectrometry. (13)C5-NAD(+) was used as the surrogate analyte for authentic analyte, NAD(+). The standard curve ranging from 0.250 to 25.0μg/mL in acidified human blood for (13)C5-NAD(+) was fitted to a 1/x(2) weighted linear regression model. The LC-MS/MS response between surrogate analyte and authentic analyte at the same concentration was obtained before and after the batch run. This response factor was not applied when determining the NAD(+) concentration from the (13)C5-NAD(+) standard curve since the percent difference was less than 5%. The precision and accuracy of the LC-MS/MS assay based on the five analytical QC levels were well within the acceptance criteria from both FDA and EMA guidance for bioanalytical method validation. Average extraction recovery of (13)C5-NAD(+) was 94.6% across the curve range. Matrix factor was 0.99 for both high and low QC indicating minimal ion suppression or enhancement. The validated assay was used to measure the baseline level of NAD(+) in 29 male and 21 female human subjects. This assay was also used to study the circadian effect of endogenous level of NAD(+) in 10 human subjects.

  9. Asymmetric tandem organic solar cells

    NASA Astrophysics Data System (ADS)

    Howells, Thomas J.

    Organic photovoltaics (OPVs) is an area that has attracted much attention recently as a potential low cost, sustainable source of energy with a good potential for full-scale commercialisation. Understanding the factors that determine the efficiency of such cells is therefore a high priority, as well as developing ways to boost efficiency to commercially-useful levels. In addition to an intensive search for new materials, significant effort has been spent on ways to squeeze more performance out of existing materials, such as multijunction cells. This thesis investigates double junction tandem cells in the context of small molecule organic materials. . Two different organic electron donor materials, boron subphthalocyanine chloride (SubPc) and aluminium phthalocyanine chloride (ClAlPc) were used as donors in heterojunctions with C60 to create tandem cells for this thesis. These materials have been previously used for solar cells and the absorption spectra of the donor materials complement each other, making them good candidates for tandem cell architectures. The design of the recombination layer between the cells is considered first, with silver nanoparticles demonstrated to work well as recombination centres for charges from the front and back sub-cells, necessary to avoid a charge build-up at the interface. The growth conditions for the nanoparticles are optimised, with the tandem cells outperforming the single heterojunction architecture. Optical modelling is considered as a method to improve the understanding of thin film solar cells, where interference effects from the reflective aluminium electrode are important in determining the magnitude of absorption a cell can achieve. The use of such modelling is first demonstrated in hybrid solar cells based on a SubPc donor with a titanium oxide (TiOx) acceptor; this system is ideal for observing the effects of interference as only the SubPc layer has significant absorption. The modelling is then applied to tandem cells

  10. Diode Laser Measurements in an Inductively Coupled GEC Cell for Oxide Etching

    NASA Astrophysics Data System (ADS)

    Perry, Lee; Deering, Glen; Koltunski, Laure; Anderson, Harold

    1998-10-01

    Diode laser absorption measurements have been made on CF, CF2 and CO radicals in an inductively coupled GEC reference cell. The GEC reference cell was modified with a quartz confinement ring around the source region to stabilize the plasma. Optical emission and Langmuir probe studies indicated this modification resulted in fluorocarbon discharges with a plasma chemistry similar to that found in commercial etch tools. The experiments in this study focused on radical concentrations found in the reactor under typical high-density plasma etching conditions. In a 10 mTorr C_2F6 discharge at 300 W source power and 100 W bias power, etching proceeded at about 5000 Åmin-1. A range of source power and bias power conditions, from 100 to 400 W and from 0 to 130 W, respectively, was employed. The time evolution of CF, CF2 and CO in a C_2F6 plasma was monitored during an approximate 2 minute etch cycle. Chamber cleanliness and bias was found to exert a strong influence on radical densities. The data is expected to provide an important database for models of oxide etching in inductively coupled plasma tools. (This work has been supported by SEMATECH)

  11. Endothelial nitric oxide synthase interactions with G-protein-coupled receptors.

    PubMed Central

    Marrero, M B; Venema, V J; Ju, H; He, H; Liang, H; Caldwell, R B; Venema, R C

    1999-01-01

    The endothelial nitric oxide synthase (eNOS) is activated in response to stimulation of endothelial cells by a number of vasoactive substances including, bradykinin (BK), angiotensin II (Ang II), endothelin-1 (ET-1) and ATP. In the present study we have used in vitro activity assays of purified eNOS and in vitro binding assays with glutathione S-transferase fusion proteins to show that the capacity to bind and inhibit eNOS is a common feature of membrane-proximal regions of intracellular domain 4 of the BK B2, the Ang II AT1 and the ET-1 ETB receptors, but not of the ATP P2Y2 receptor. Phosphorylation of serine or tyrosine residues in the eNOS-interacting region of the B2 receptor results in a loss of eNOS inhibition due to a decrease in the binding affinity of the receptor domain for the eNOS enzyme. Furthermore, the B2 receptor is transiently phosphorylated on tyrosine residues in cultured endothelial cells in response to BK stimulation. Phosphorylation occurs during the time in which eNOS transiently dissociates from the receptor accompanied by a transient increase in nitric oxide production. Taken together, these data support the hypotheses that eNOS is regulated in endothelial cells by reversible and inhibitory interactions with G-protein-coupled receptors and that these interactions can be modulated by receptor phosphorylation. PMID:10510297

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

    PubMed

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

    2014-11-17

    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.

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

    PubMed

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

    2013-05-15

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

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

    DOEpatents

    Hayward, David R.; Buttz, James H.; Shirey, David L.

    2002-01-01

    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.

  15. Proton-Coupled Electron Transfer in a Strongly Coupled Photosystem II-Inspired Chromophore–Imidazole–Phenol Complex: Stepwise Oxidation and Concerted Reduction

    SciTech Connect

    Manbeck, Gerald F.; Fujita, Etsuko; Concepcion, Javier J.

    2016-08-18

    Proton-coupled electron-transfer (PCET) reactions were studied in acetonitrile for a Photosystem II (PSII) inspired [Ru(bpy)2(phen-imidazole-Ph(OH)(tBu)2)]2+, in which Ru(III) generated by a flash-quench sequence oxidizes the appended phenol and the proton is transferred to the hydrogen bonded imidazole base. In contrast to related systems, the donor and acceptor are strongly coupled, as indicated by the shift in the RuIII/IIcouple upon phenol oxidation, and intramolecular oxidation of the phenol by Ru(III) is energetically favorable by both stepwise or concerted pathways. The phenol oxidation occurs via a stepwise ET-PT mechanism with kET = 2.7 × 107 s₋1 and a kinetic isotope effect (KIE) of 0.99 ± 0.03. The electron transfer reaction was characterized as adiabatic with λDA = 1.16 eV and 280 < HDA < 540 cm₋1 consistent with strong electronic coupling and slow solvent dynamics. Reduction of the phenoxyl radical by the quencher radical was examined as the analogue of the redox reaction between the PSII tyrosyl radical and the oxygen evolving complex (OEC). In our PSII-inspired complex, the recombination reaction activation energy is < 2 kcal mol₋1. In conclusion, the reaction is nonadiabatic (VPCET ~ 22 cm₋1 (H) and 49 cm₋1 (D)), concerted, and exhibits an unexpected inverse KIE of 0.55 that is attributed to greater overlap of the reactant vibronic ground state with the OD vibronic states of the proton acceptor due to the smaller quantum spacing of the deuterium vibrational levels.

  16. Combined remediation of pyrene-contaminated soil with a coupled system of persulfate oxidation and phytoremediation with ryegrass.

    PubMed

    Chen, Xiao; Li, Hongbing; Liu, Xiaoyan; Zhang, Xinying; Liang, Xia; He, Chiquan; Cao, Liya

    2016-10-01

    The in situ chemical oxidation technology (ISCO) and phytoremediation for PAHs have been studied respectively, but few focus on the feasibility of combining persulfate with ryegrass. This literature revealed the effect of persulfate oxidation on the growth of ryegrass and the removal ratios of pyrene in the couple system of persulfate oxidation and phytoremediation. The results demonstrated that half of pyrene in test soil was oxidized by persulfate in 7 days and then the residual pyrene concentration was decreased to a lower level by ryegrass in the following 2 months in oxidation treatment and drip washing and plants (OWP) and oxidation treatment and drip washing and plants and fertilization (OWFP) treatment. Ryegrass could grow well after persulfate oxidation with the oxidized soil washed by water. Ryegrass in OWP and OWFP treatments had higher ratios of overground and underground biomass. However, the seeds of ryegrass cannot germinate when drip washing was omitted. Pyrene together with residual persulfate changed soil enzyme activities. Drip washing and the growth of ryegrass made soil enzyme activities tend to returned to normal levels. Persulfate oxidation and phytoremediation were compatible to make contributions to the dissipation of pyrene. Persulfate oxidation activated by heat had higher removal efficiency of PAHs and phytoremediation could further decrease the pyrene concentration in spiked soil.

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

    PubMed

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

    2015-08-15

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

  18. Nevirapine quantification in human plasma by high-performance liquid chromatography coupled to electrospray tandem mass spectrometry. Application to bioequivalence study.

    PubMed

    Laurito, Tiago L; Santagada, Vincenzo; Caliendo, Giuseppe; Oliveira, Celso H; Barrientos-Astigarraga, Rafael E; De Nucci, Gilberto

    2002-04-01

    A rapid, sensitive and specific method to quantify nevirapine in human plasma using dibenzepine as the internal standard (IS) was developed and validated. The method employed a liquid-liquid extraction. The analyte and the IS were chromatographed on a C(18) analytical column, (150 x 4.6 mm i.d. 4 microm) and analyzed by tandem mass spectrometry in the multiple reaction monitoring mode. The method had a chromatographic run time of 5.0 min and a linear calibration curve over the range 10-5000 ng ml(-1) (r(2) > 0.9970). The between-run precision, based on the relative standard deviation for replicate quality controls was 1.3% (30 ng ml(-1)), 2.8% (300 ng ml(-1)) and 3.6% (3000 ng ml(-1)). The between-run accuracy was 4.0, 7.0 and 6.2% for the above-mentioned concentrations, respectively. This method was employed in a bioequivalence study of two nevirapine tablet formulations (Nevirapina from Far-Manguinhos, Brazil, as a test formulation, and Viramune from Boehringer Ingelheim do Brasil Química e Farmacêutica, as a reference formulation) in 25 healthy volunteers of both sexes who received a single 200 mg dose of each formulation. The study was conducted using an open, randomized, two-period crossover design with a 3 week washout interval. The 90% confidence interval (CI) of the individual ratio geometric mean for Nevirapina/Viramune was 96.4-104.5% for AUC((0-last)), 91.4-105.1% for AUC((0-infinity)) and 95.3-111.6% for C(max) (AUC = area under the curve; C(max) = peak plasma concentration). Since both 90% CI for AUC((0-last)) and AUC((0-infinity)) and C(max) were included in the 80-125% interval proposed by the US Food and Drug Administration, Nevirapina was considered bioequivalent to Viramune according to both the rate and extent of absorption.

  19. Stereoselective synthesis of 1,3-disubstituted isoindolines via Rh(III)-catalyzed tandem oxidative olefination-cyclization of 4-aryl cyclic sulfamidates.

    PubMed

    Son, Se-Mi; Seo, Yeon Ji; Lee, Hyeon-Kyu

    2016-03-21

    Rh(III)-catalyzed tandem ortho C-H olefination of cyclic 4-aryl sulfamidates (1) and subsequent intramolecular cyclization are described. This reaction serves as a method for the direct and stereoselective synthesis of 1,3-disubstituted isoindolines (3) starting with enantiomerically enriched 4-aryl cyclic sulfamidates. In this process, the configurational integrity of the stereogenic center in the starting cyclic sulfamidate is completely retained. In addition, the process generates trans-1,3-disubstituted isoindolines exclusively.

  20. Copper-catalyzed difunctionalization of activated alkynes by radical oxidation-tandem cyclization/dearomatization to synthesize 3-trifluoromethyl spiro[4.5]trienones.

    PubMed

    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

    2015-01-19

    A copper-catalyzed difunctionalizing trifluoromethylation of activated alkynes with the cheap reagent sodium trifluoromethanesulfinate (NaSO2CF3 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.

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

    PubMed

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

    2011-11-02

    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: ΔG° (2 + 3a(+)) = +0.078 V versus ΔG° (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 α, Δ ln(k)/Δ 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

  2. Experimental coupling and modelling of wet air oxidation and packed-bed biofilm reactor as an enhanced phenol removal technology.

    PubMed

    Minière, Marine; Boutin, Olivier; Soric, Audrey

    2017-01-25

    Experimental coupling of wet air oxidation process and aerobic packed-bed biofilm reactor is presented. It has been tested on phenol as a model refractory compound. At 30 MPa and 250 °C, wet air oxidation batch experiments led to a phenol degradation of 97% and a total organic carbon removal of 84%. This total organic carbon was mainly due to acetic acid. To study the interest of coupling processes, wet air oxidation effluent was treated in a biological treatment process. This step was made up of two packed-bed biofilm reactors in series: the first one acclimated to phenol and the second one to acetic acid. After biological treatment, phenol and total organic carbon removal was 99 and 97% respectively. Thanks to parameters from literature, previous studies (kinetic and thermodynamic) and experimental data from this work (hydrodynamic parameters and biomass characteristics), both treatment steps were modelled. This modelling allows the simulation of the coupling process. Experimental results were finally well reproduced by the continuous coupled process model: relative error on phenol removal efficiency was 1 and 5.5% for wet air oxidation process and packed-bed biofilm reactor respectively.

  3. Hydrophilic interaction and reversed phase mixed-mode liquid chromatography coupled to high resolution tandem mass spectrometry for polar lipids analysis.

    PubMed

    Granafei, Sara; Azzone, Pietro; Spinelli, Vito Alessandro; Losito, Ilario; Palmisano, Francesco; Cataldi, Tommaso R I

    2016-12-16

    A hydrophilic interaction liquid chromatography (HILIC) fused-core column (150×2.1mm ID, 2.7μm particle size) and a short reversed-phase liquid chromatography (RPLC) column (20mm×2.1mm ID, 1.9μm) were serially coupled to perform mixed-mode chromatography (MMC) on complex mixtures of phospholipids (PL). Mobile phase composition and gradient elution program were, preliminarily, optimized using a mixture of phosphatidylcholines (PC), phosphatidylethanolamines (PE), their corresponding lyso-forms (LPC and LPE), and sphingomyelins (SM). Thus a mixture of PC extracted from soybean was characterized by MMC coupled to electrospray ionization (ESI) high-resolution Fourier-transform mass spectrometry (FTMS) using an orbital trap analyzer. Several previously undiscovered PC, including positional isomers (i.e. 16:0/19:1 and 19:1/16:0) of PC 35:1 and skeletal isomers (i.e. 18:1/18:2 and 18:0/18:3) of PC 36:3 were identified. Therefore, high-resolution MS/MS spectra unveiled the occurrence of isomers for several overall side chain compositions. The proposed MMC-ESI-FTMS/MS approach revealed an unprecedented capability in disclosing complexity of an actual lipid extract, thus representing a very promising approach to lipidomics.

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

    PubMed

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

    2012-07-13

    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 μg L⁻¹. The MRL of perchlorate was therefore set at 5.0 μg 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, Cl₁₈O₄⁻, were utilized for quantitatively determining perchlorate in bottled water and bottled tea samples. Two linear ranges, 0.05-0.50 μg L⁻¹ and 0.50-10.00 μg 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 μg L⁻¹. The linear range was 1.50-10.00 μg L⁻¹ for bottled tea samples with a MDL of 0.5 μg 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 (CCα), and detection capability (CCβ) 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

  5. Proton-Coupled Electron Transfer in a Strongly Coupled Photosystem II-Inspired Chromophore–Imidazole–Phenol Complex: Stepwise Oxidation and Concerted Reduction

    DOE PAGES

    Manbeck, Gerald F.; Fujita, Etsuko; Concepcion, Javier J.

    2016-08-18

    Proton-coupled electron-transfer (PCET) reactions were studied in acetonitrile for a Photosystem II (PSII) inspired [Ru(bpy)2(phen-imidazole-Ph(OH)(tBu)2)]2+, in which Ru(III) generated by a flash-quench sequence oxidizes the appended phenol and the proton is transferred to the hydrogen bonded imidazole base. In contrast to related systems, the donor and acceptor are strongly coupled, as indicated by the shift in the RuIII/IIcouple upon phenol oxidation, and intramolecular oxidation of the phenol by Ru(III) is energetically favorable by both stepwise or concerted pathways. The phenol oxidation occurs via a stepwise ET-PT mechanism with kET = 2.7 × 107 s₋1 and a kinetic isotope effect (KIE)more » of 0.99 ± 0.03. The electron transfer reaction was characterized as adiabatic with λDA = 1.16 eV and 280 < HDA < 540 cm₋1 consistent with strong electronic coupling and slow solvent dynamics. Reduction of the phenoxyl radical by the quencher radical was examined as the analogue of the redox reaction between the PSII tyrosyl radical and the oxygen evolving complex (OEC). In our PSII-inspired complex, the recombination reaction activation energy is < 2 kcal mol₋1. In conclusion, the reaction is nonadiabatic (VPCET ~ 22 cm₋1 (H) and 49 cm₋1 (D)), concerted, and exhibits an unexpected inverse KIE of 0.55 that is attributed to greater overlap of the reactant vibronic ground state with the OD vibronic states of the proton acceptor due to the smaller quantum spacing of the deuterium vibrational levels.« less

  6. A novel mechanism of bisphenol A removal during electro-enzymatic oxidative process: chain reactions from self-polymerization to cross-coupling oxidation.

    PubMed

    Li, Haitao; Zhao, He; Liu, Chenming; Li, Yuping; Cao, Hongbin; Zhang, Yi

    2013-08-01

    The catalyzed removal of bisphenol A (BPA) by a horseradish peroxidase (HRP) cathode in the presence of humic acid (HA) was investigated. At an optimal condition, the removal of BPA achieved 100% within 2min reaction. In the electro-enzymatic process, products were analyzed by high performance liquid chromatography with diode array detector (HPLC-DAD) and high performance size exclusion chromatography (HPSEC). HPLC-DAD results showed that BPA was oxidized into self-polymers and then self-polymers as important intermediate products decreased and disappeared. HPSEC results showed the order of molecular weight (MW): HA+BPA cross-coupling products>HA self-coupling products>initial HA. According to above results, a novel mechanism of BPA transformation in the presence of HA was proposed in electro-enzymatic process. In summary, under oxidation of in situ hydrogen peroxide on HRP electrode, the BPA first are polymerized into self-polymers, and then, the polymers may be incorporated into HA matrix and finally larger MW of BPAn-HA might be formed. The presence of HA can provide chain reactions from BPA self-polymerization to cross-coupling oxidation. Therefore, in the presence of HA, the electro-enzymatic oxidation is an effective way to improve BPA removal.

  7. Determination and purification of sesamin and sesamolin in sesame seed oil unsaponified matter using reversed-phase liquid chromatography coupled with photodiode array and tandem mass spectrometry and high-speed countercurrent chromatography.

    PubMed

    Takahashi, Miki; Nishizaki, Yuzo; Sugimoto, Naoki; Takeuchi, Hiroaki; Nakagawa, Kazuya; Akiyama, Hiroshi; Sato, Kyoko; Inoue, Koichi

    2016-10-01

    In Asian countries, sesame seed oil unsaponified matter is used as a natural food additive due to its associated antioxidant effects. We determined and purified the primary lignans sesamin and sesamolin in sesame seed oil unsaponified matter using reversed-phase liquid chromatography coupled with photodiode array and tandem mass spectrometry and high-speed countercurrent chromatography. Calibration curves showed good correlation coefficients (r(2) > 0.999, range 0.08 and/or 0.15 to 5 μg/mL) with a limit of detection (at 290 nm) of 0.02 μg/mL for sesamin and 0.04 μg/mL for sesamolin. Sesame seed oil unsaponified matter contained 2.82% sesamin and 2.54% sesamolin, respectively. Direct qualitative analysis of sesamin and sesamolin was achieved using quadrupole mass spectrometry with positive-mode electrospray ionization. Pure (>99%) sesamin and sesamolin standards were obtained using high-speed countercurrent chromatographic purification (hexane/ethyl acetate/methanol/water; 7:3:7:3). An effective method for determining and purifying sesamin and sesamolin from sesame seed oil unsaponified matter was developed by combining these separation techniques for standardized food additives.

  8. Simultaneous Determination of 16 Nucleosides and Nucleobases in Euryale ferox Salisb. by Liquid Chromatography Coupled with Electro Spray Ionization Tandem Triple Quadrupole Mass Spectrometry (HPLC-ESI-TQ-MS/MS) in Multiple Reaction Monitoring (MRM) Mode.

    PubMed

    Wang, Hong; Wu, Qinan; Wu, Chengying; Jiang, Zheng

    2015-09-01

    In this study, a simple, rapid, efficient analytical method was established for the qualification and quantification of 16 nucleosides and nucleobases in Euryale ferox Salisb. by using liquid chromatography coupled with electrospray ionization tandem triple quadrupole mass spectrometry (HPLC-ESI-TQ-MS/MS) in multiple-reaction monitoring (MRM) mode. Ideal separation of 16 target compounds was achieved on Xbridge Amide HILIC column (4.6 × 150 mm, 3.5 μm) with gradient elution in 11 min by optimized conditions. Variations of nucleosides and nucleobase in samples from different cultivation regions ranging from 190.50 to 1594.30 μg/g were obvious. The total nucleoside contents were higher than total nucleobases, especially in the compositions of guanosine, cytidine and 2'-deoxyguanosine. Samples 1-18 with dense thorns were better characters than samples 19-26 without thorns in terms of nucleosides and nucleobases concentrations in general. The limits of detection (LODs) and quantification (LOQs) for 16 analytical substances were investigated to be 0.11-6.33 ng/mL and 0.35-21.1 ng/mL, respectively. And the method was first applied to large aquatic plants with good linearity, precision, repeatability and accuracy. All present information provided a scientific and rational reference for quality assessment and control of Euryale ferox Salisb.

  9. Bioequivalence study between a fixed-dose single-pill formulation of nebivolol plus hydrochlorothiazide and separate formulations in healthy subjects using high-performance liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Vespasiano, Celso Francisco Pimentel; Laurito, Tiago Luders; Iwamoto, Renan Donomae; Moreno, Ronilson Agnaldo; Mendes, Gustavo D; De Nucci, Gilberto

    2016-11-03

    Systemic arterial hypertension is a major risk factor for cerebrovascular disease. Therefore, adequate control of blood pressure is of enormous importance. One of the many fixed-dose single-pill antihypertensive formulations available on the market is the combination of nebivolol and hydrochlorothiazide. The objective of this study was to develop two distinct high-performance liquid chromatography coupled to tandem mass spectrometry methods to simultaneously quantify nebivolol and hydrochlorothiazide in human plasma. The methods were employed in a bioequivalence study, the first assay involving a nebivolol fixed-dose single-pill formulation based on healthy Brazilian volunteers. Nebilet HCT™ (nebivolol 5 mg + hydrochlorothiazide 12.5 mg tablet, manufactured by Menarini) was the test formulation. The reference formulations were Nebilet™ (nebivolol 5 mg tablet, manufactured by Menarini) and Clorana™ (hydrochlorothiazide 25 mg tablet, manufactured by Sanofi). For both analytes, liquid-liquid extraction was employed for sample preparation and the chromatographic run time was 3.5 min. The limits of quantification validated were 0.02 ng/mL for nebivolol and 1 ng/mL for hydrochlorothiazide. Since the 90% CI for Cmax , AUC(0-last) and AUC(0-inf) individual test/reference ratios were within the 80-125% interval indicative of bioequivalence, it was concluded that Nebilet HCT™ is bioequivalent to Nebilet™ and Clorana™.

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

    PubMed

    Leung, Elvis M K; Chan, Wan

    2014-01-01

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

  11. Qualitative and quantitative analysis of multiple components for quality control of Deng-Zhan-Sheng-Mai capsules by ultra high performance liquid chromatography tandem mass spectrometry method coupled with chemometrics.

    PubMed

    Jiang, Pin; Lu, Yan; Chen, Daofeng

    2017-02-01

    Deng-Zhan-Sheng-Mai capsules are a well-known traditional Chinese patent medicine that was developed in China for the treatment of ischemic stroke. Its quality control focuses on Erigerontis Herba but ignores the contributions of Ginseng Radix et Rhizoma, Schisandrae Chinensis Fructus, and Ophiopogonis Radix. To improve the quality standards for this medicine, this work reports the application of a systematic ultra high performance liquid chromatography tandem mass spectrometric method coupled with chemometrics. Three qualitative and quantitative parameters are established for the evaluation of quality: chemical profiling, the relationship between the contents of 18 compounds and the antioxidant activity, and chemometric analysis. A total of 55 compounds, including 20 phenolic acids, 10 flavonoids, 15 saponins, and 10 lignans, were identified. The method for the quantitative determination of the aforementioned 18 compounds was validated. The limit of quantification ranged from 0.13 to 9.60 ng/mL. The overall recoveries ranged from 95.31 to 103.54%. Hierarchical cluster analysis and principal component analysis were applied to the data of 18 components in ten batches of samples. Nine compounds, including scutellarin, 3,5-O-dicaffeoylquinic acid, 4,5-O-dicaffeoylquinic acid, ginsenoside Rb1, ginsenoside Re, ginsenoside Rg1, ophiopogonin D, schisandrin, and schisandrol B, are suggested as chemical markers for evaluating the quality.

  12. Dispersive micro-solid-phase extraction using mesoporous hybrid materials for simultaneous determination of semivolatile compounds from plant tea by ultra-high-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry.

    PubMed

    Cao, Wan; Hu, Shuai-Shuai; Ye, Li-Hong; Cao, Jun

    2014-10-08

    This report described the use of mesoporous hybrid materials (MHM) in a dispersive micro-solid-phase extraction procedure to extract semivolatile compounds from plant tea that were then analyzed by ultra-high-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry. Dihydrotanshinone I, tanshinone I, cryptotanshinone, and tanshinone IIA were selected as the model compounds, and the extraction parameters, including mesoporous concentration, extraction time, sample agitation and desorption solvents, were optimized. The interaction with the analytes and the large surface area of the MHM facilitated the adsorption of analytes. The method showed good linearity, with correlation coefficients >0.9980 in the range 0.25-100 ng/mL, and low limits of detection (0.012-0.046 pg). Finally, the recovery values were 91-103% for Danshen tea, 89-102% for Danshen, and 88-96% for tanshinone capsules. The results showed that the proposed method was suitable for the extraction and determination of tanshinones in complex samples.

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

    PubMed

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

    2014-08-05

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

  14. Dual ultrasonic-assisted dispersive liquid-liquid microextraction coupled with microwave-assisted derivatization for simultaneous determination of 20(S)-protopanaxadiol and 20(S)-protopanaxatriol by ultra high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Zhao, Xian-En; Lv, Tao; Zhu, Shuyun; Qu, Fei; Chen, Guang; He, Yongrui; Wei, Na; Li, Guoliang; Xia, Lian; Sun, Zhiwei; Zhang, Shijuan; You, Jinmao; Liu, Shu; Liu, Zhiqiang; Sun, Jing; Liu, Shuying

    2016-03-11

    This paper, for the first time, reported a speedy hyphenated technique of low toxic dual ultrasonic-assisted dispersive liquid-liquid microextraction (dual-UADLLME) coupled with microwave-assisted derivatization (MAD) for the simultaneous determination of 20(S)-protopanaxadiol (PPD) and 20(S)-protopanaxatriol (PPT). The developed method was based on ultra high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) detection using multiple-reaction monitoring (MRM) mode. A mass spectrometry sensitizing reagent, 4'-carboxy-substituted rosamine (CSR) with high reaction activity and ionization efficiency was synthesized and firstly used as derivatization reagent. Parameters of dual-UADLLME, MAD and UHPLC-MS/MS conditions were all optimized in detail. Low toxic brominated solvents were used as extractant instead of traditional chlorinated solvents. Satisfactory linearity, recovery, repeatability, accuracy and precision, absence of matrix effect and extremely low limits of detection (LODs, 0.010 and 0.015ng/mL for PPD and PPT, respectively) were achieved. The main advantages were rapid, sensitive and environmentally friendly, and exhibited high selectivity, accuracy and good matrix effect results. The proposed method was successfully applied to pharmacokinetics of PPD and PPT in rat plasma.

  15. Automated and sensitive determination of four anabolic androgenic steroids in urine by online turbulent flow solid-phase extraction coupled with liquid chromatography-tandem mass spectrometry: a novel approach for clinical monitoring and doping control.

    PubMed

    Guo, Feng; Shao, Jing; Liu, Qian; Shi, Jian-Bo; Jiang, Gui-Bin

    2014-07-01

    A novel method for automated and sensitive analysis of testosterone, androstenedione, methyltestosterone and methenolone in urine samples by online turbulent flow solid-phase extraction coupled with high performance liquid chromatography-tandem mass spectrometry was developed. The optimization and validation of the method were discussed in detail. The Turboflow C18-P SPE column showed the best extraction efficiency for all the analytes. Nanogram per liter (ng/L) level of AAS could be determined directly and the limits of quantification (LOQs) were 0.01 ng/mL, which were much lower than normally concerned concentrations for these typical anabolic androgenic steroids (AAS) (0.1 ng/mL). The linearity range was from the LOQ to 100 ng/mL for each compound, with the coefficients of determination (r(2)) ranging from 0.9990 to 0.9999. The intraday and interday relative standard deviations (RSDs) ranged from 1.1% to 14.5% (n=5). The proposed method was successfully applied to the analysis of urine samples collected from 24 male athletes and 15 patients of prostate cancer. The proposed method provides an alternative practical way to rapidly determine AAS in urine samples, especially for clinical monitoring and doping control.

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

    PubMed

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

    2014-06-11

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

  17. Simultaneous determination of penflufen and one metabolite in vegetables and cereals using a modified quick, easy, cheap, effective, rugged, and safe method and liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Tian, Fajun; Liu, Xingang; Wu, Yanbing; Xu, Jun; Dong, Fengshou; Wu, Xiaohu; Zheng, Yongquan

    2016-12-15

    The present study attempts to investigate a rapid, effective and sensitive analytical method to determine a new fungicide penflufen and its metabolite residues in potato, cowpea, corn, wheat and rice using ultra-performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS). The compounds were extracted using acetonitrile and cleaned up by primary secondary amine (PSA) and octadecylsilane (C18). Both compounds were determined in less than 5.0min using an electrospray ionization source in positive mode (ESI+). The calculated limits of detection and quantification were below 0.018μgkg(-1) and 0.060μgkg(-1) in different matrices. The method revealed excellent linearity (R(2)>0.9957) for both compounds. The recoveries ranged from 76.1 to 101.0% for both compounds with RSD values lower than 9.8% in all matrices. The results demonstrated that the method is reliable and effective enough for the routine detecting penflufen and its metabolite residues in vegetables and cereals.

  18. 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

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

    2014-10-01

    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.

  19. Selectively adsorptive extraction of phenylarsonic acids in chicken tissue by carboxymethyl α-cyclodextrin immobilized Fe3O4 magnetic nanoparticles followed ultra performance liquid chromatography coupled tandem mass spectrometry detection.

    PubMed

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

    2014-01-01

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

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

    PubMed Central

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

    2012-01-01

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

  1. Enantiomeric Profiling of Chiral Pharmacologically Active Compounds in the Environment with the Usage of Chiral Liquid Chromatography 
Coupled with Tandem Mass Spectrometry

    PubMed Central

    Camacho-Muñoz, Dolores; Petrie, Bruce; Castrignanò, Erika; Kasprzyk-Hordern, Barbara

    2016-01-01

    The issue of drug chirality is attracting increasing attention among the scientific community. The phenomenon of chirality has been overlooked in environmental research (environmental occurrence, fate and toxicity) despite the great impact that chiral pharmacologically active compounds (cPACs) can provoke on ecosystems. The aim of this paper is to introduce the topic of chirality and its implications in environmental contamination. Special attention has been paid to the most recent advances in chiral analysis based on liquid chromatography coupled with mass spectrometry and the most popular protein based chiral stationary phases. Several groups of cPACs of environmental relevance, such as illicit drugs, human and veterinary medicines were discussed. The increase in the number of papers published in the area of chiral environmental analysis indicates that researchers are actively pursuing new opportunities to provide better understanding of environmental impacts resulting from the enantiomerism of cPACs. PMID:27713682

  2. Dynamic headspace coupled to perevaporation for the analysis of anisoles in wine by gas chromatography-ion-trap tandem mass spectrometry.

    PubMed

    Gómez-Ariza, J L; García-Barrera, T; Lorenzo, F

    2004-11-12

    Off-flavours in wines are mainly due to the presence of 2,4,6-trichloroanisole and other haloanisoles. The purpose of this study was to develop a method based on the coupling of dynamic headspace and perevaporation to GC-MS-MS to attain better analyte sensitivity and selectivity. The approach has been applied to the analysis of 2,6-dichloroanisole, 2,4,6-trichloroanisole and 2,4,6-tribromoanisole in various wines. For these compounds that cause taste and odour problems, the method was linear from the quantification limit to 3 ng for all the analytes with recoveries greater than 80% and satisfactory precision. Detection limits were as low as 2-36 ng l(-1).

  3. Enantiomeric Profiling of Chiral Pharmacologically Active Compounds in the Environment with the Usage of Chiral Liquid Chromatography 
Coupled with Tandem Mass Spectrometry.

    PubMed

    Camacho-Muñoz, Dolores; Petrie, Bruce; Castrignanò, Erika; Kasprzyk-Hordern, Barbara

    2016-08-01

    The issue of drug chirality is attracting increasing attention among the scientific community. The phenomenon of chirality has been overlooked in environmental research (environmental occurrence, fate and toxicity) despite the great impact that chiral pharmacologically active compounds (cPACs) can provoke on ecosystems. The aim of this paper is to introduce the topic of chirality and its implications in environmental contamination. Special attention has been paid to the most recent advances in chiral analysis based on liquid chromatography coupled with mass spectrometry and the most popular protein based chiral stationary phases. Several groups of cPACs of environmental relevance, such as illicit drugs, human and veterinary medicines were discussed. The increase in the number of papers published in the area of chiral environmental analysis indicates that researchers are actively pursuing new opportunities to provide better understanding of environmental impacts resulting from the enantiomerism of cPACs.

  4. Fast and simultaneous determination of eleven synthetic color additives in flour and meat products by liquid chromatography coupled with diode-array detector and tandem mass spectrometry.

    PubMed

    Qi, Ping; Lin, Zi-hao; Chen, Gui-yun; Xiao, Jian; Liang, Zhi-an; Luo, Li-ni; Zhou, Jun; Zhang, Xue-wu

    2015-08-15

    In this study, an efficient, fast and sensitive method for the simultaneous determination of eleven synthetic color additives (Allura red, Amaranth, Azo rubine, Brilliant blue, Erythrosine, Indigotine, Ponceau 4R, New red, Sunset yellow, Quinoline yellow and Tartrazine) in flour and meat foodstuffs is developed and validated using HPLC coupled with DAD and MS/MS. The color additives were extracted with ammonia-methanol and was further purified with SPE procedure using Strata-AW column in order to reduce matrix interference. This HPLC-DAD method is intended for a comprehensive survey of color additives in foods. HPLC-MS/MS method was used as the further confirmation and identification. Validation data showed the good recoveries in the range of 75.2-113.8%, with relative standard deviations less than 15%. These methods are suitable for the routine monitoring analysis of eleven synthetic color additives due to its sensitivity, reasonable time and cost.

  5. Analysis of coupled Sr/Ca and 87Sr/ 86Sr variations in enamel using laser-ablation tandem quadrupole-multicollector ICPMS

    NASA Astrophysics Data System (ADS)

    Balter, Vincent; Telouk, Philippe; Reynard, Bruno; Braga, José; Thackeray, Francis; Albarède, Francis

    2008-08-01

    We present in this study results obtained with a laser-ablation coupled with both a quadrupole and a multi-collector ICPMS. The simultaneous in situ Sr/Ca and 87Sr/ 86Sr measurements along growth profiles in enamel allows the concomitant diet and migration patterns in mammals to be reconstructed. Aliquots of the powdered international standard NIST "SRM1400 Bone Ash" with certified Sr and Ca contents, was sintered at high pressure and temperature and was adopted as the reference material for external reproducibility and calibration of the results. A total of 145 coupled elemental and isotopic measurements of herbivores enamel from the Kruger National Park, South Africa, gives intra-tooth Sr/Ca and 87Sr/ 86Sr variations that are well larger than external reproducibility. Sr/Ca profiles systematically decrease from the dentine-enamel junction to the outer enamel whereas 87Sr/ 86Sr profiles exhibit variable patterns. Using a simple geometric model of hypsodont teeth growth, we demonstrate that a continuous recording of the 87Sr/ 86Sr variations can be reconstructed in the tooth length axis. This suggests that the mobility of a mammal can be reconstructed over a period of more than a year with a resolution of a ten of days, by sampling enamel along growth profiles. Our geometric model of hypsodont teeth growth predicts that an optimal distance between two successive profiles is equal to the enamel thickness. However, this model does not apply to the Sr/Ca signal which is likely to be altered during the enamel maturation stage due to differential maturation processes along enamel thickness. Here, the observed constant decreases of the Sr/Ca ratios in the ungulates of Kruger National Park suggests that they did not changed of diet, while some of them were migrating.

  6. Hydrogen production by coupled catalytic partial oxidation and steam methane reforming at elevated pressure and temperature

    NASA Astrophysics Data System (ADS)

    Chen, Luwei; Hong, Qi; Lin, Jianyi; Dautzenberg, F. M.

    Hydrogen production by coupled catalytic partial oxidation (CPO) and steam methane reforming of methane (OSMR) at industrial conditions (high temperatures and pressures) have been studied over supported 1 wt.% NiB catalysts. Mixture of air/CH 4/H 2O was applied as the feed. The effects of O 2:CH 4 ratio, H 2O:CH 4 ratio and the gas hourly space velocity (GHSV) on oxy-steam reforming (OSRM) were also studied. Results indicate that CH 4 conversion increases significantly with increasing O 2:CH 4 or H 2O:CH 4 ratio. However, the hydrogen mole fraction goes through a maximum, depending on reaction conditions, e.g., pressure, temperature and the feed gases ratios. Carbon deposition on the catalysts has been greatly decreased after steam addition. The supported 1 wt.% NiB catalysts exhibit high stability with 85% methane conversion at 15 bar and 800 °C during 70 h time-on-stream reaction (CH 4:O 2:H 2O:N 2 = 1:0.5:1:1.887). The thermal efficiency was increased from 35.8% by CPO (without steam) to 55.6%. The presented data would be useful references for further design of enlarged scale hydrogen production system.

  7. New insights into the first oxidative phenol coupling reaction during vancomycin biosynthesis.

    PubMed

    Geib, Nina; Woithe, Katharina; Zerbe, Katja; Li, Dong Bo; Robinson, John A

    2008-05-15

    OxyB catalyzes the first oxidative phenol coupling reaction in vancomycin biosynthesis. OxyB is a P450 hemoprotein whose activity is strictly dependent upon the presence of molecular oxygen. Here, it was shown that label from (18)O(2) is not incorporated into the monocyclic product during catalysis by OxyB. In addition, it was shown that OxyB can convert a model hexapeptide substrate containing (R)-Tyr6, instead of (S)-Tyr6, covalently linked as a C-terminal thioester to a peptidyl carrier protein (PCP-7S) derived from the vancomycin non-ribosomal peptide synthetase (NRPS), into the corresponding epimeric monocyclic product. The binding of this epimeric hexapeptide-PCP conjugate to the Fe(III) form of OxyB, as monitored by UV-vis spectroscopy, revealed a K(d)=35+/-5 microM. Thus, the enzyme reveals a surprising lack of stereospecificity in the binding and transformation of these epimeric substrates.

  8. Stoichiometry of mitochondrial H+ translocation coupled to succinate oxidation at level flow.

    PubMed

    Costa, L E; Reynafarje, B; Lehninger, A L

    1984-04-25

    The mechanistic stoichiometry of vectorial H+ translocation coupled to succinate oxidation by rat liver mitochondria in the presence of a permeant cation has been determined under level flow conditions with a membraneless fast responding O2 electrode kinetically matched with a glass pH electrode. The reactions were initiated by rapid injection of O2 into the anaerobically preincubated test system under conditions in which interfering H+ backflow was minimized. The rates of O2 uptake and H+ ejection, obtained from computer-fitted regression lines, were monotonic and first order over 75% of the course of O2 consumption. Extrapolation of the observed rates to zero time, at which zero delta mu H+ and thus level flow prevails, yielded vectorial H+/O flow ratios above 7 and closely approaching 8. The mitochondria undergo no irreversible change and give identical H+/O ratios on repeated tests. In a further refinement, the lower and upper limits of the mechanistic H+/O ratio were determined to be 7.55 and 8.56, respectively, from plots of the rates of O2 uptake versus H+ ejection at increasing malonate and increasing valinomycin concentrations, respectively. It is therefore concluded that the mechanistic H+/O ratio for energy-conserving sites 2 + 3 is 8, in confirmation of earlier measurements. KCl concentration is critical for maximal observed H+/O ratios. Optimum conditions and possible errors in determination of mechanistic H+/O translocation ratios are discussed.

  9. Coupling of bias-induced crystallographic shear planes with charged domain walls in ferroelectric oxide thin films

    NASA Astrophysics Data System (ADS)

    Han, Myung-Geun; Garlow, Joseph A.; Bugnet, Matthieu; Divilov, Simon; Marshall, Matthew S. J.; Wu, Lijun; Dawber, Matthew; Fernandez-Serra, Marivi; Botton, Gianluigi A.; Cheong, Sang-Wook; Walker, Frederick J.; Ahn, Charles H.; Zhu, Yimei

    2016-09-01

    Polar discontinuity at interfaces plays deterministic roles in charge transport, magnetism, and even superconductivity of functional oxides. To date, most polar discontinuity problems have been explored in heterointerfaces between two dissimilar materials. Here, we show that charged domain walls (CDWs) in epitaxial thin films of ferroelectric PbZ r0.2T i0.8O3 are strongly coupled to polar interfaces through the formation of 1/2 <101 > {h 0 l } - type crystallographic shear planes (CSPs). Using atomic resolution imaging and spectroscopy we illustrate that the CSPs consist of both conservative and nonconservative segments when coupled to the CDWs where necessary compensating charges for stabilizing the CDWs are associated with vacancies at the CSPs. The CDW/CSP coupling yields an atomically narrow domain wall, consisting of a single atomic layer of oxygen. This study shows that the CDW/CSP coupling is a fascinating venue to develop emergent material properties.

  10. Computer simulation of spatial coupling in chemical oscillations of CO oxidation on two Pd(110) single crystals

    NASA Astrophysics Data System (ADS)

    Park, I. J.; Woo, S. I.

    1993-09-01

    Gas-phase coupling between two Pd(110) single crystals in a UHV CO oxidation reaction in a continuous stirred tank reactor (CSTR) has been simulated by solving gas-phase mass balance equations with kinetic rate equations. This work was motivated by the experimental results which show that the frequency of partial pressure change in carbon monoxide is the same as the frequency of the work function change in the oscillation region and that the coupling between the two crystals occurred entirely via CO partial pressure. The computer simulation described here gives qualitative agreement with the experimental results. The change in the oscillatory region originating from the coupling of chemical oscillators which are slightly different to each other is successfully demonstrated by this model. The coupling of two oscillators having a simple periodic oscillation to produce mixed-mode oscillation was also successfully simulated.

  11. Coupling of bias-induced crystallographic shear planes with charged domain walls in ferroelectric oxide thin films

    DOE PAGES

    Han, Myung-Geun; Garlow, Joseph A.; Bugnet, Matthieu; ...

    2016-09-02

    Polar discontinuity at interfaces plays deterministic roles in charge transport, magnetism, and even superconductivity of functional oxides. To date, most polar discontinuity problems have been explored in hetero-interfaces between two dissimilar materials. Here, we show that charged domain walls (CDWs) in epitaxial thin films of ferroelectric PbZr0.2Ti0.8O3 are strongly coupled to polar interfaces through the formation of ½<101>{h0l} type crystallographic shear planes (CSPs). Using atomic resolution imaging and spectroscopy we illustrate that the CSPs consist of both conservative and nonconservative segments when coupled to the CDWs, where necessary compensating charges for stabilizing the CDWs are associated with vacancies at themore » CSPs. Lasly, the CDW/CSP coupling yields an atomically narrow domain walls, consisting of a single atomic layer of oxygen. This study shows that the CDW/CSP coupling is a fascinating venue to develop emergent material properties.« less

  12. Quantitative determination of buprenorphine, naloxone and their metabolites in rat plasma using hydrophilic interaction liquid chromatography coupled with tandem mass spectrometry.

    PubMed

    Joshi, Anand; Parris, Brian; Liu, Yongzhen; Heidbreder, Christian; Gerk, Phillip M; Halquist, Matthew

    2017-02-01

    A rapid and sensitive LC-MS/MS method was developed and validated for the simultaneous determination of buprenorphine and its three metabolites (buprenorphine glucuronide, norbuprenorphine and norbuprenorphine glucuronide) as well as naloxone and its metabolite naloxone glucuronide in the rat plasma. A hydrophilic interaction chromatography column and a mobile phase containing acetonitrile and ammonium formate buffer (pH 3.5) were used for the chromatographic separation. Mass spectrometric detection was achieved by an electrospray ionization source in the positive mode coupled to a triple quadrupole mass analyzer. The calibration curves for the six analytes displayed good linearity over the concentration range 1.0 or 5.0-1000 ng/mL. The intra and inter-day precision (CV) ranged from 2.68 to 16.4% and from 9.02 to 14.5%, respectively. The intra- and inter-day accuracy (bias) ranged from -14.2 to 15.2% and from -9.00 to 4.80%, respectively. The extraction recoveries for all the analytes ranged from 55 to 86.9%. The LC-MS/MS method was successfully applied to a pharmacokinetic study of buprenorphine-naloxone combination in rats.

  13. Metabolite profiling of licorice (Glycyrrhiza glabra) from different locations using comprehensive two-dimensional liquid chromatography coupled to diode array and tandem mass spectrometry detection.

    PubMed

    Montero, Lidia; Ibáñez, Elena; Russo, Mariateresa; di Sanzo, Rosa; Rastrelli, Luca; Piccinelli, Anna Lisa; Celano, Rita; Cifuentes, Alejandro; Herrero, Miguel

    2016-03-24

    Profiling of the main metabolites from several licorice (Glycyrrhiza glabra) samples collected at different locations is carried out in this work by using comprehensive two-dimensional liquid chromatography (LC × LC) coupled to diode array (DAD) and mass spectrometry (MS) detectors. The optimized method was based on the application of a HILIC-based separation in the first dimension combined with fast RP-based second dimension separation. This set-up was shown to possess powerful separation capabilities allowing separating as much as 89 different metabolites in a single sample. Identification and grouping of metabolites according to their chemical class were achieved using the DAD, MS and MS/MS data. Triterpene saponins were the most abundant metabolites followed by glycosylated flavanones and chalcones, whereas glycyrrhizic acid, as expected, was confirmed as the main component in all the studied samples. LC × LC-DAD-MS/MS was able to resolve these complex licorice samples providing with specific metabolite profiles to the different licorice samples depending on their geographical origin. Namely, from 19 to 50 specific compounds were exclusively determined in the 2D-chromatograms from the different licorice samples depending on their geographical origin, which can be used as a typical pattern that could potentially be related to their geographical location and authentication.

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

    PubMed

    Uran, S; Larsen, A; Jacobsen, P B; Skotland, T

    2001-07-15

    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 spectrometer. Chromatographic baseline separation was obtained between phosphatidylglycerol, phosphatidylcholine, phosphatidylethanolamine, lyso-phosphatidylcholine, phosphatidylinositol and phosphatidylserine, eluting in that order. The total run time was 30 min. Plasmalogen phosphatidylethanolamine and sphingomyelin, which both are substances with structural similarities to the glycerophospholipids, had similar retention time as phosphatidylethanolamine, but were well separated from the other glycerophospholipid classes. The species from each class were identified using MS2 or MS3, which forms characteristic lyso-fragments. The combination of lyso-fragment mass, molecular ion and chromatographic retention time was used to identify each species, including 20 species of phosphatidylglycerol. The mass spectra obtained for the phospholipid classes are presented. Using this system 17 disaturated phospholipid species not earlier described to be present in blood were identified. The limit of detection varied between different phospholipid classes and was in the range 0.1-5 ng of injected substance.

  15. Rate enhancement of photocatalytic cyanide oxidation by the application of an anodic bias/coupled semiconductor configuration

    SciTech Connect

    Munroe, N.D.H.; Tilleux, R.

    1996-12-31

    In this study, photocatalytic cyanide degradation was investigated utilizing ultraviolet light (UV), an increase in titanium (IV) oxide (TiO{sub 2}) photocatalyst surface area, platinization of the photocatalyst, appropriate adjustment of pH, and the immobilization of TiO{sub 2}/ tin (IV) oxide (SnO{sub 2}) coupled semi-conductor film on an optically transparent electrode. The cyanide concentration was monitored using an ion selective electrode. The focus of this study was to explore the possibility of a viable process for the effective and complete photodegradation of cyanide ion. The long-term goal is the application of this process to industry. Cyanide detoxification has been successfully achieved in recent years. Research has shown that photocatalytic oxidation can completely degrade cyanide to nitrate via nitrite. However, the rate at which this oxidation occurs is not yet suitable for application in industry. Therefore, the need for an effective treatment is most urgent.

  16. Solid phase extraction coupled to liquid chromatography-tandem mass spectrometry analysis of sulfonamides, tetracyclines, analgesics and hormones in surface water and wastewater in Luxembourg.

    PubMed

    Pailler, J-Y; Krein, A; Pfister, L; Hoffmann, L; Guignard, C

    2009-08-01

    In the early 1990s different studies highlighted the relationship between pharmaceuticals, human health and the environment. Among the emerging contaminants, antibiotics are obviously of high concern, because of their potential for inducing antibiotic resistance. In addition, natural and synthetic hormones are relevant because of their potential endocrine-disrupting effects on wildlife. This investigation focuses on the analysis of four classes of veterinary and human pharmaceuticals (sulfonamides, tetracyclines, analgesics and hormones) in surface water and wastewater in Luxembourg. The selected eleven pharmaceuticals include four sulfonamides (sulfathiazole, sulfamethoxazole, sulfadimethoxine and sulfamethazine), two tetracyclines (tetracycline and oxytetracycline), two analgesics (ibuprofen and diclofenac), and three hormones (2 naturals, estrone and beta-estradiol, and a synthetic one, 17-alpha-ethinyl estradiol). The most innovative parts of this study are the simultaneous extraction of the above-mentioned pharmaceuticals as well as tracking their behaviour during flood events in a small river catchment. The method includes pre-concentration by solid phase extraction using Oasis HLB (Hydrophilic Lipophilic Balance) which gave superior results compared to Chromabond C-18EC, Chromabond(R) EASY and Bond Elut PLEXA cartridges, also evaluated in this investigation. The analysis of the investigated pharmaceutical compounds is carried out by high performance liquid chromatography coupled to a triple quadrupole mass spectrometer. The limits of quantification were 1 ng L(-1), except for beta-estradiol (2 ng L(-1)) and 17-alpha-ethinyl estradiol (6 ng L(-1)). Recovery rates range from 70 to 94%, with relative standard deviations between 4 and 19%. Application of this method to river concentration and flood events revealed high concentrations of ibuprofen (10-4000 ng L(-1)), with highest levels during flood events, while concentrations of estrogens (1-240 ng L(-1)) and

  17. Determination of Ochratoxin A in wine by packed in-tube solid phase microextraction followed by high performance liquid chromatography coupled to tandem mass spectrometry.

    PubMed

    Andrade, Mariane A; Lanças, Fernando M

    2017-04-14

    Ochratoxin A (OTA), a widely studied mycotoxin, can be found in a variety of food matrices. As its concentration in food is generally low (in the order of μg kg(-1)), sample preparation techniques are necessary for the analyte purification and pre-concentration in order to achieve the required low detection limits. The separation and detection methods used for OTA analysis should also offer proper sensitivity in order to allow the adequate quantification of the analyte. This manuscript addresses the development of a methodology aiming the analysis of OTA in wine samples by packed in-tube SPME in flow through extraction mode coupled to HPLC-MS/MS. The in-tube SPME set up utilized a PEEK tube packed with C18 particles as the extraction column. The method was optimized by a central composite design 2(2)+3 extra central points, having as factors the percentage of ACN and time in the sample load step. The functionalities of the method were attested and its analytical conditions, enhanced by using 22% of ACN and 6min in the sample load step. Validation of the method was also accomplished prior to analyses of both dry red wine and dry white wine samples. The method demonstrated proper sensitivity, with detection and quantification limits equal to 0.02 and 0.05μgL(-1), respectively. Linearity and precision exhibited a 0.996 correlation coefficient and RSD under 6%, respectively. The method proved to be accurate at medium and higher concentration levels with a maximum recovery of 73% at higher concentration levels. OTA was not detected in either dry red and dry white wine samples evaluated in this work. If present, it would be at concentrations lower than the detection and quantification limits established for the proposed method, and considered not a potential danger to human health according to our present knowledge.

  18. Interactions of soil-derived dissolved organic matter with phenol in peroxidase-catalyzed oxidative coupling reactions.

    PubMed

    Huang, Qingguo; Weber, Walter J

    2004-01-01

    The influence of dissolved soil organic matter (DSOM) derived from three geosorbents of different chemical composition and diagenetic history on the horseradish peroxidase (HRP) catalyzed oxidative coupling reactions of phenol was investigated. Phenol conversion and precipitate-product formation were measured, respectively, by HPLC and radiolabeled species analysis. Fourier transform infrared (FTIR) spectroscopy and capillary electrophoresis (CE) were used to characterize the products of enzymatic coupling, and the acute toxicities of the soluble products were determined by Microtox assay. Phenol conversion and precipitate formation were both significantly influenced by cross-coupling of phenol with dissolved organic matter, particularly in the cases of the more reactive and soluble DSOMs derived from two diagenetically "young" humic-type geosorbents. FTIR and CE characterizations indicate that enzymatic cross-coupling in these two cases leads to incorporation of phenol in DSOM macromolecules, yielding nontoxic soluble products. Conversely, cross-coupling appears to proceed in parallel with self-coupling in the presence of the relatively inert and more hydrophobic DSOM derived from a diagenetically "old" kerogen-type shale material. The products formed in this system have lower solubility and precipitate more readily, although their soluble forms tend to be more toxic than those formed by dominant cross-coupling reactions in the humic-type DSOM solutions. Several of the findings reported may be critically important with respect to feasibility evaluations and the engineering design of associated remediation schemes.

  19. Tuning the Reactivity of Radical through a Triplet Diradical Cu(II) Intermediate in Radical Oxidative Cross-Coupling

    PubMed Central

    Zhou, Liangliang; Yi, Hong; Zhu, Lei; Qi, Xiaotian; Jiang, Hanpeng; Liu, Chao; Feng, Yuqi; Lan, Yu; Lei, Aiwen

    2015-01-01

    Highly selective radical/radical cross-coupling is paid more attention in bond formations. However, due to their intrinsic active properties, radical species are apt to achieve homo-coupling instead of cross-coupling, which makes the selective cross-coupling as a great challenge and almost untouched. Herein a notable strategy to accomplish direct radical/radical oxidative cross-coupling has been demonstrated, that is metal tuning a transient radical to a persistent radical intermediate followed by coupling with another transient radical. Here, a transient nitrogen-centered radical is tuned to a persistent radical complex by copper catalyst, followed by coupling with a transient allylic carbon-centered radical. Firstly, nitrogen-centered radical generated from N-methoxybenzamide stabilized by copper catalyst was successfully observed by EPR. Then DFT calculations revealed that a triplet diradical Cu(II) complex formed from the chelation N-methoxybenzamide nitrogen-centered radical to Cu(II) is a persistent radical species. Moreover, conceivable nitrogen-centered radical Cu(II) complex was observed by high-resolution electrospray ionization mass spectrometry (ESI-MS). Ultimately, various allylic amides derivatives were obtained in good yields by adopting this strategy, which might inspire a novel and promising landscape in radical chemistry. PMID:26525888

  20. Characterization of procyanidin B2 oxidation products in an apple juice model solution and confirmation of their presence in apple juice by high-performance liquid chromatography coupled to electrospray ion trap mass spectrometry.

    PubMed

    Poupard, Pascal; Sanoner, Philippe; Baron, Alain; Renard, Catherine M G C; Guyot, Sylvain

    2011-11-01

    Procyanidins (i.e. condensed tannins) are polyphenols commonly found in fruits. During juice and cider making, apple polyphenol oxidase catalyzes the oxidation of caffeoylquinic acid (CQA) into its corresponding o-quinone which further reacts with procyanidins and other polyphenols, leading to the formation of numerous oxidation products. However, the structure and the reaction pathways of these neoformed phenolic compounds are still largely unknown. Experiments were carried out on a model system to gain insights into the chemical processes occurring during the initial steps of fruit processing. Procyanidin B2 was oxidized by caffeoylquinic acid o-quinone (CQAoq) in an apple juice model solution. The reaction products were monitored using high performance liquid chromatography (HPLC) coupled to ultraviolet (UV)-visible and electrospray tandem mass spectrometry (ESI-MS/MS) in the negative mode. Oxidative conversion of procyanidin B2 ([M-H](-) at m/z 577) into procyanidin A2 at m/z 575 was unambiguously confirmed. In addition, several classes of products were characterized by their deprotonated molecules ([M-H](-)) and their MS/MS fragmentation patterns: hetero-dimers (m/z 929) and homo-dimers (m/z 1153 and 705) resulting from dimerization involving procyanidin and CQA molecules; intramolecular addition products at m/z 575, 573, 927, 1151 and 703. Interestingly, no extensive polymerization was observed. Analysis of a cider apple juice enabled comparison with the results obtained on a biosynthetic model solution. However, procyanidin A2 did not accumulate but seemed to be an intermediate in the formation of an end-product at m/z 573 for which two structural hypotheses are given. These structural modifications of native polyphenols as a consequence of oxidation probably have an impact on the organoleptic and nutritional properties of apple juices and other apple-derived foods.

  1. Acetaldehyde partial oxidation on the Au(111) model catalyst surface: C-C bond activation and formation of methyl acetate as an oxidative coupling product

    NASA Astrophysics Data System (ADS)

    Karatok, Mustafa; Vovk, Evgeny I.; Shah, Asad A.; Turksoy, Abdurrahman; Ozensoy, Emrah

    2015-11-01

    Partial oxidation of acetaldehyde (CH3CHO) on the oxygen pre-covered Au(111) single crystal model catalyst was investigated via Temperature Programmed Desorption (TPD) and Temperature Programmed Reaction Spectroscopy (TPRS) techniques, where ozone (O3) was utilized as the oxygen delivery agent providing atomic oxygen to the reacting surface. We show that for low exposures of O3 and small surface oxygen coverages, two partial oxidation products namely, methyl acetate (CH3COOCH3) and acetic acid (CH3COOH) can be generated without the formation of significant quantities of carbon dioxide. The formation of methyl acetate as the oxidative coupling reaction product implies that oxygen pre-covered Au(111) single crystal model catalyst surface can activate C-C bonds. In addition to the generation of these products; indications of the polymerization of acetaldehyde on the gold surface were also observed as an additional reaction route competing with the partial and total oxidation pathways. The interplay between the partial oxidation, total oxidation and polymerization pathways reveals the complex catalytic chemistry associated with the interaction between the acetaldehyde and atomic oxygen on catalytic gold surfaces.

  2. Catalytic Chan–Lam coupling using a ‘tube-in-tube’ reactor to deliver molecular oxygen as an oxidant

    PubMed Central

    Mallia, Carl J; Burton, Paul M; Smith, Alexander M R; Walter, Gary C

    2016-01-01

    Summary A flow system to perform Chan–Lam coupling reactions of various amines and arylboronic acids has been realised employing molecular oxygen as an oxidant for the re-oxidation of the copper catalyst enabling a catalytic process. A tube-in-tube gas reactor has been used to simplify the delivery of the oxygen accelerating the optimisation phase and allowing easy access to elevated pressures. A small exemplification library of heteroaromatic products has been prepared and the process has been shown to be robust over extended reaction times. PMID:27559412

  3. Characterization and evaluation of two-dimensional microfluidic chip-HPLC coupled to tandem mass spectrometry for quantitative analysis of 7-aminoflunitrazepam in human urine.

    PubMed

    Bai, Hsin-Yu; Lin, Shu-Ling; Chan, Shen-An; Fuh, Ming-Ren

    2010-10-01

    Microfluidic chip-based high-performance-liquid-chromatography coupled to mass spectrometry (chip-HPLC-MS) has been widely used in proteomic research due to its enhanced sensitivity. We employed a chip-HPLC-MS system for determining small molecules such as drug metabolites in biological fluids. This chip-HPLC-MS system integrates a microfluidic switch, a 2-dimensional column design including an enrichment column (160 nL) for sample pre-concentration and an analytical column for chromatographic separation, as well as a nanospray emitter on a single polyimide chip. In this study, a relatively large sample volume (500 nL) was injected into the enrichment column for pre-concentration and an additional 4 μL of the initial mobile phase was applied to remove un-retained components from the sample matrix prior to chromatographic separation. The 2-dimensional column design provides the advantages of online sample concentration and reducing matrix influence on MS detection. 7-Aminoflunitrazepam (7-aminoFM2), a major metabolite of flunitrazepam (FM2), was determined in urine samples using the integrated chip-HPLC-MS system. The linear range was 0.1-10 ng mL(-1) and the method detection limit (signal-to-noise ratio of 3) was 0.05 ng mL(-1) for 7-aminoFM2. After consecutive liquid-liquid extraction (LLE) and solid-phase extraction (SPE), the chip-HPLC-MS exhibited high correlation between 7-aminoFM2 spiked Milli-Q water and 7-aminoFM2 spiked urine samples. This system also showed good precision (n = 5) and recovery for spiked urine samples at the levels of 0.1, 1.0, and 10 ng mL(-1). Intra-day and inter-day precision were 2.0-7.1% and 4.3-6.0%, respectively. Clinical urine samples were also analyzed by this chip-HPLC-MS system and acceptable relative differences (-1.3 to -13.0%) compared with the results using a GC-MC method were determined. Due to its high sensitivity and ease of operation, the chip-HPLC-MS system can be utilized for the determination of small molecules such

  4. Analysis of the Benzene Oxide-DNA Adduct 7-Phenylguanine by Liquid Chromatography-Nanoelectrospray Ionization-High Resolution Tandem Mass Spectrometry-Parallel Reaction Monitoring: Application to DNA from Exposed Mice and Humans

    PubMed Central

    Zarth, Adam; Cheng, Guang; Zhang, Zhaobin; Wang, Mingyao; Villalta, Peter W.; Balbo, Silvia; Hecht, Stephen S.

    2014-01-01

    Benzene oxide, the initial metabolite of the human carcinogen benzene, reacts with DNA producing 7-phenylguanine (7-PhG) and other products. We developed a highly sensitive liquid chromatography-nanoelectrospray ionization-high resolution tandem mass spectrometry-parallel reaction monitoring method for the analysis of 7-PhG in DNA. Accuracy and precision of the method were established and the detection limit was about 8 amol of 7-PhG injected on the column and less than 1 adduct per 109 nucleotides in DNA. 7-PhG was detected in calf thymus DNA reacted with 1 μM to 10 mM benzene oxide. The method was applied for the analysis of DNA isolated from bone marrow, lung, and liver of B6C3F1 mice treated by gavage with 50 mg/kg benzene in corn oil 5 times weekly for 4 weeks. 7-PhG was not detected in any of these DNA samples. The method was applied to DNA from mouse hepatocytes exposed to 100 μM benzene oxide and human TK-6 lymphoblasts exposed to 100 μM, 1 mM, and 10 mM benzene oxide. 7-PhG was only detected in TK-6 cell DNA from the 10 mM exposure. The method was also applied to leukocyte DNA from 10 smokers and 10 nonsmokers. 7-PhG was detected in only one DNA sample, from a nonsmoker. The results of this study do not support the hypothesis that the benzene oxide-DNA adduct 7-PhG is involved in carcinogenesis by benzene. PMID:24632417

  5. Coupling between crystal structure and magnetism in transition-metal oxides

    NASA Astrophysics Data System (ADS)

    Barton, Phillip Thomas

    Transition-metal oxides exhibit a fascinating array of phenomena ranging from superconductivity to negative thermal expansion to catalysis. This dissertation focuses on magnetism, which is integral to engineering applications such as data storage, electric motors/generators, and transformers. The investigative approach follows structure-property relationships from materials science and draws on intuition from solid-state chemistry. The interplay between crystal structure and magnetic properties is studied experimentally in order to enhance the understanding of magnetostructural coupling mechanisms and provide insight into avenues for tuning behavior. A combination of diffraction and physical property measurements were used to study structural and magnetic phase transitions as a function of chemical composition, temperature, and magnetic field. The systems examined are of importance in Li-ion battery electrochemistry, condensed-matter physics, solid-state chemistry, and p-type transparent conducting oxides. The materials were prepared by solid-state reaction of powder reagents at high temperatures for periods lasting tens of hours. The first project discussed is of a solid solution between NiO, a correlated insulator, and LiNiO2, a layered battery cathode. Despite the deceptive structural and compositional simplicity of this system, a complete understanding of its complex magnetic properties has remained elusive. This study shows that nanoscale domains of chemical order form at intermediate compositions, creating interfaces between antiferromagnetism and ferrimagnetism that give rise to magnetic exchange bias. A simple model of the magnetism is presented along with a comprehensive phase diagram. The second set of investigations focus on the Ge-Co-O system where the spin-orbit coupling of Co(II) plays a significant role. GeCo2O 4 is reported to exhibit unusual magnetic behavior that arises from Ising spin in its spinel crystal structure. Studies by variable

  6. Synthesis of eight-shaped poly(ethylene oxide) by the combination of Glaser coupling with ring-opening polymerization.

    PubMed

    Wang, Guowei; Fan, Xiaoshan; Hu, Bin; Zhang, Yannan; Huang, Junlian

    2011-10-18

    The eight-shaped poly(ethylene oxide) (PEO) is synthesized by a combination of Glaser coupling with ring-opening polymerization (ROP). Firstly, the star-shaped (PEO-OH)(4) is synthesized by ROP of ethylene oxide (EO) using pentaerythritol as an initiator and diphenylmethyl potassium (DPMK) as a deprotonated agent, and then the alkyne group is introduced onto the PEO arm-end to give (PEO-Alkyne)(4) in a NaH/tetrahydrofuran (THF) system. The intramolecular cyclization is carried out by a Glaser coupling reaction in a pyridine/CuBr/N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA) system at room temperature in an air atmosphere, and eight-shaped PEO was formed with high efficiency (almost 100%). The target polymers and intermediates were well characterized by SEC, MALDI-TOF MS, (1)H NMR and FT-IR in detail.

  7. Femtosecond snapshots of the electron-boson coupling in copper oxides and other correlated materials

    NASA Astrophysics Data System (ADS)

    Giannetti, Claudio

    One of the pivotal questions in the physics of unconventional superconductors is whether the low-energy dynamics of the charge carriers is mediated by bosons with a characteristic timescale. This issue has remained elusive as electronic correlations are expected to greatly accelerate the electron-boson scattering processes, confining them to the very femtosecond timescale. Recent advances in ultrafast spectroscopy allowed us to simultaneously push the time resolution and frequency range of transient reflectivity measurements, up to the point of direct observing the effective electron-boson interaction in doped copper oxides. The extremely fast timescale (~15 fs) is in agreement with numerical calculations based on the t - J model and the repulsive Hubbard model, in which the relaxation of the photo-excited charges is achieved via inelastic scattering with short-range antiferromagnetic excitations with an energy spectrum extending up to ~300 meV. Our results support a scenario in which the strong local magnetic correlations provide a dissipative channel that is effective on the 10 fs timescale. Secondly, we will present very recent results on the model system Na2IrO3, in which the interplay of the spin-orbit coupling, the onsite Coulomb repulsion and the hopping within the Ir hexagons gives rise to a complex magnetic ground state, characterized by strong antiferromagnetic correlations below 100 K and the emergence of a zig-zag magnetic phase at T =12 K. The energy exchange between the photoexcited charge carriers and the antiferromagnetic background is observed by monitoring a specific high-energy quasi-molecular orbital, which turns out to be sensitive to the magnetization of the system.

  8. 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

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

    2013-03-05

    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.

  9. On-line solid-phase extraction coupled with high-performance liquid chromatography and tandem mass spectrometry (SPE-HPLC-MS-MS) for quantification of bromazepam in human plasma: an automated method for bioequivalence studies.

    PubMed

    Gonçalves, José Carlos Saraiva; Monteiro, Tânia Maria; Neves, Claúdia Silvana de Miranda; Gram, Karla Regina da Silva; Volpato, Nádia Maria; Silva, Vivian A; Caminha, Ricardo; Gonçalves, Maria do Rocio Bencke; Santos, Fábio Monteiro Dos; Silveira, Gabriel Estolano da; Noël, François

    2005-10-01

    A validated method for on-line solid-phase extraction coupled with high-performance liquid chromatography tandem mass spectrometry (SPE-HPLC-MS-MS) is described for the quantification of bromazepam in human plasma. The method involves a dilution of 300 muL of plasma with 100 muL of carbamazepine (2.5 ng/mL), used as internal standard, vortex-mixing, centrifugation, and injection of 100 muL of the supernate. The analytes were ionized using positive electrospray mass spectrometry then detected by multiple reaction monitoring (MRM). The m/z transitions 316-->182 (bromazepam) and 237-->194 (carbamazepine) were used for quantification. The calibration curve was linear from 1 ng/mL (limit of quantification) to 200 ng/mL. The retention times of bromazepam and carbamazepine were 2.6 and 3.2 minutes, respectively. The intraday and interday precisions were 3.43%-15.45% and 5.2%-17%, respectively. The intraday and interday accuracy was 94.00%-103.94%. This new automated method has been successfully applied in a bioequivalence study of 2 tablet formulations of 6 mg bromazepam: Lexotan(R) from Produtos Roche Químicos e Farmacêuticos SA, Rio de Janeiro, Brazil (reference) and test formulation from Laboratórios Biosintética Ltda, São Paulo, Brazil. Because the 90% CI of geometric mean ratios between reference and test were completely included in the 80%-125% interval, the 2 formulations were considered bioequivalent. The comparison of different experimental conditions for establishing a dissolution profile in vitro along with our bioavailability data further allowed us to propose rationally based experimental conditions for a dissolution test of bromazepam tablets, actually lacking a pharmacopeial monograph.

  10. Molecularly imprinted polymer coupled with dispersive liquid-liquid microextraction and injector port silylation: a novel approach for the determination of 3-phenoxybenzoic acid in complex biological samples using gas chromatography-tandem mass spectrometry.

    PubMed

    Mudiam, Mohana Krishna Reddy; Chauhan, Abhishek; Jain, Rajeev; Dhuriya, Yogesh Kumar; Saxena, Prem Narain; Khanna, Vinay Kumar

    2014-01-15

    A novel analytical approach based on molecularly imprinted solid phase extraction (MISPE) coupled with dispersive liquid-liquid microextraction (DLLME), and injector port silylation (IPS) has been developed for the selective preconcentration, derivatization and analysis of 3-phenoxybenzoic acid (3-PBA) using gas chromatography-tandem mass spectrometry (GC-MS/MS) in complex biological samples such as rat blood and liver. Factors affecting the synthesis of MIP were evaluated and the best monomer and cross-linker were selected based on binding affinity studies. Various parameters of MISPE, DLLME and IPS were optimized for the selective preconcentration and derivatization of 3-PBA. The developed method offers a good linearity over the calibration range of 0.02-2.5ngmg(-1) and 7.5-2000ngmL(-1) for liver and blood respectively. Under optimized conditions, the recovery of 3-PBA in liver and blood samples were found to be in the range of 83-91%. The detection limit was found to be 0.0045ngmg(-1) and 1.82ngmL(-1) in liver and blood respectively. SRM transition of 271→227 and 271→197 has been selected as quantifier and qualifier transition for 3-PBA derivative. Intra and inter-day precision for five replicates in a day and for five, successive days was found to be less than 8%. The method developed was successfully applied to real samples, i.e. rat blood and tissue for quantitative evaluation of 3-PBA. The analytical approach developed is rapid, economic, simple, eco-friendly and possess immense utility for the analysis of analytes with polar functional groups in complex biological samples by GC-MS/MS.

  11. Quantification of endogenous brassinosteroids in plant by on-line two-dimensional microscale solid phase extraction-on column derivatization coupled with high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Wu, Qian; Wu, Dapeng; Shen, Zheng; Duan, Chunfeng; Guan, Yafeng

    2013-07-05

    An on-line two-dimensional microscale solid phase extraction (2DμSPE)-on column derivatization (OCD)-high performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS) method was developed for quantification of brassinosteroids (BRs) in plant tissues. Five BRs with widest distribution in plant species and high bioactivity (24-epibrassinolide, 24-epicastasterone, 6-deoxo-24-epicastasterone, teasterone and typhastero) were selected as target analytes. 2DμSPE column packed sequentially with phenyl boronic acid silica sorbent (the first dimension) and C18 silica sorbent (the second dimension) was used to selectively extract and enrich BRs by 110-146 times. OCD was carried out on the second dimension of 2DμSPE column with m-aminophenylboronic acid (m-APBA) as a derivatization reagent, enhancing the sensitivity of MS/MS to BRs by 13-8437 times. It was also found that pre-trap of derivatization reagent on the C18 section of 2DμSPE column could increase reaction efficiency by 3-10 times. The whole process time of the on-line system was less than 30min. The detection limits of the method for five BRs were between 1.4 and 6.6pg with RSDs less than 10%. Endogeneous BRs in tomato leaves were analyzed by using this method. Owing to the high selectivity of this on-line 2DμSPE system, BRs in plant extracts could be quantified using matrix-free standard calibration method with relative recoveries in the range of 80-124%.

  12. High-throughput determination of multi-mycotoxins in Chinese yam and related products by ultra fast liquid chromatography coupled with tandem mass spectrometry after one-step extraction.

    PubMed

    Li, Menghua; Kong, Weijun; Li, Yanjun; Liu, Hongmei; Liu, Qiutao; Dou, Xiaowen; Ou-Yang, Zhen; Yang, Meihua

    2016-06-01

    A simple, accurate and sensitive ultra fast liquid chromatography coupled with tandem mass spectrometry (UFLC-MS/MS) method was developed for high-throughput determination of aflatoxins (AFB1, AFB2, AFG1 and AFG2), ochratoxin A (OTA), fumonisins (FB1 and FB2) and zearalenone (ZEA) in Chinese yam, yam flours and yam-derived products. Mycotoxins were extracted from the samples with methanol-water-formic acid (79:20:1, v/v/v) and no further cleanup step before analysis. After optimization of some crucial parameters including sample preparation, chromatographic separation and MS/MS conditions, the method was successfully validated to exhibit excellent performance in terms of satisfactory linearity (r≥0.9977), limits of detection (≤0.15ngmL(-1)) and quantification (≤0.5ngmL(-1)) with good precision (RSD for intra- and inter-day variations of ≤4.65% and 6.31%, respectively), good accuracy (recoveries of 71.0-106.0%) and robustness, together with short run time (8min/sample). The developed method was applied for simultaneous detection and quantification of the above 8 mycotaxins in 27 batches of Chinese yam and related products collected from different markets and pharmacies in China. The results revealed that 1 normal sample and 4 moldy samples were found to be contaminated with different mycotoxins. The detected concentrations of AFB1 in 2 moldy samples exceeded the regulatory maximum residue levels. The proposed method was capable for simultaneous determination of mycotoxins in this and other types of complex matrices.

  13. Active fragments-guided drug discovery and design of selective tropane alkaloids using ultra-high performance liquid chromatography-quadrupole time-of-flight tandem mass spectrometry coupled with virtual calculation and biological evaluation.

    PubMed

    Zhou, Mengge; Ma, Xiaoyao; Sun, Jixue; Ding, Guoyu; Cui, Qingxin; Miao, Yan; Hou, Yuanyuan; Jiang, Min; Bai, Gang

    2017-02-01

    Tropane alkaloids (TAs), rich in the plant of Physochlaina infundibularis Kuang, which is named Huashanshen (HSS) in China, showed good effects on types of spasms. However, no data were collected to explore the relationship between the specificity for muscarinic receptor subtypes and the structures of these TAs. To address this issue, an extracted ion chromatogram (EIC) strategy using ultra-high performance liquid chromatography-quadrupole time-of-flight tandem mass spectrometry (UPLC-Q/TOF-MS) based on the fragmentation behavior of the TA standards was established to rapidly capture the varied TAs from HSS. Based on the provided structural information of diagnostic ions or neutral loss, 29 TAs were efficiently profiled, especially some trace ingredients. In additional, via virtual validation combined with molecular dynamic simulation, approximately a dozen alkaloids were found with high selectivity for muscarinic receptors. In additional, N-acetyl convolicine was chosen for selectivity evaluation of M2 or M3 receptors through the use of a dual-luciferase reporter assay system at the cellular level and an ACh-induced constricted strip test in vitro. After summarizing the active fragments and the structure-activity relationship (SAR) information, a new modified TA that takes advantage of both the high affinity and high selectivity for M3 receptors was proposed and evaluated successfully. This study provided an effective approach for the discovery and design of natural products based on highly selective drugs by UPLC-Q/TOF-MS coupled with virtual calculation and biological evaluation. Graphical Abstract Active fragments-guided strategy for selective inhibitors from HSS.

  14. Determination of stavudine in human serum by on-line solid-phase extraction coupled to high-performance liquid chromatography with electrospray ionization tandem mass spectrometry: application to a bioequivalence study.

    PubMed

    Raices, Renata S L; Salvadori, Myriam C; de Cassia E Estrela, Rita; de Aquino Neto, Francisco R; Suarez-Kurtz, Guilherme

    2003-01-01

    A method based on solid-phase extraction (SPE) coupled to high-performance liquid chromatography (HPLC) with positive ion electrospray ionization tandem mass spectrometry (ESI-MS/MS) detection was developed for the determination of stavudine in human serum, using didanosine as internal standard. The acquisition was performed in multiple reaction monitoring (MRM) mode. The method was linear over the studied range (10-2000 ng/mL), with r(2) > 0.99, and the run time was 4 min. The intra- and inter-assay precisions (%) were in the ranges 0.1-13.6 and 2.6-9.9, respectively, and the intra- and inter-assay accuracies were >92%. The absolute recoveries were approximately 100% (10 ng/mL), 98% (30 ng/mL), 105% (750 ng/mL) and 105% (1500 ng/mL). The limits of detection and quantitation were 4 and 10 ng/mL, respectively. The analytical method was applied to a bioequivalence study, in which 24 healthy adult volunteers (12 men) received single oral doses (40 mg) of reference and two test stavudine formulations, in an open, three-period, randomized, crossover protocol. The 90% confidence interval of the individual ratios (test formulation/reference formulation) for C(max) (peak serum concentration), AUC(0-10) and AUC(0-inf) (areas under the serum concentration vs. time curve from time zero to 10 h and to infinity, respectively), were in the range 80-125%, which supports the conclusion that the two test formulations are bioequivalent to the reference formulation with respect to the rate and extent of stavudine absorption.

  15. Determination of didanosine in human serum by on-line solid-phase extraction coupled to high-performance liquid chromatography with electrospray ionization tandem mass spectrometric detection: application to a bioequivalence study.

    PubMed

    Estrela, Rita de Cassia E; Salvadori, Myriam C; Raices, Renata S L; Suarez-Kurtz, Guilherme

    2003-04-01

    A method based on solid-phase extraction coupled to liquid chromatography with positive ion electrospray ionization and tandem mass spectrometric detection was developed for the determination of didanosine in human serum, using lamivudine as internal standard. The acquisition was performed in the multiple reaction monitoring mode, monitoring the transitions m/z 237 --> 136.7 for didanosine and m/z 230 --> 111.7 for lamivudine. The method was linear over the range studied (10-1500 ng ml(-1)), with r(2) > 0.98, and the run time was 5 min. The intra- and inter-assay precisions were < or =10% and the intra- and inter-assay accuracies were >95%. The absolute recoveries were 99.8% (10 ng ml(-1)), 98.4% (30 ng ml(-1)), 91.5% (700 ng ml(-1)) and 94.7% (1200 ng ml(-1)). The limits of detection and quantitation were 5 and 10 ng ml(-1), respectively. The method was applied to a bioequivalence study, in which 24 healthy adult volunteers (12 men) received single oral doses (200 mg) of reference and test didanosine formulations (buffered powder for oral solutions), in an open, two-way, randomized, crossover protocol. The 90% confidence interval of the individual ratios (test formulation/reference formulation) for C(max) (peak serum concentration) and AUC(0-inf) (area under the serum concentration versus time curve from time zero to infinity) were within the range 80-125%, which supports the conclusion that the two formulations are bioequivalent regarding the rate and extent of didanosine absorption.

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

    PubMed

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

    2015-05-28

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

  17. I₂-TBHP-catalyzed oxidative cross-coupling of N-sulfonyl hydrazones and isocyanides to 5-aminopyrazoles.

    PubMed

    Senadi, Gopal Chandru; Hu, Wan-Ping; Lu, Ting-Yi; Garkhedkar, Amol Milind; Vandavasi, Jaya Kishore; Wang, Jeh-Jeng

    2015-03-20

    I2-TBHP-catalyzed oxidative cross coupling of N-sulfonyl hydrazones with isocyanides has been realized for the synthesis of 5-aminopyrazoles through formal [4 + 1] annulation via in situ azoalkene formation. Notable features are the metal/alkyne-free strategy, C-C and C-N bond formation, atom economy, catalytic I2, broad functional group tolerance, good reaction yields, shorter time, and also applicability to one-pot methodology.

  18. Synthesis and Application of Chiral Spiro Cp Ligands in Rhodium-Catalyzed Asymmetric Oxidative Coupling of Biaryl Compounds with Alkenes.

    PubMed

    Zheng, Jun; Cui, Wen-Jun; Zheng, Chao; You, Shu-Li

    2016-04-27

    The vastly increasing application of chiral Cp ligands in asymmetric catalysis results in growing demand for novel chiral Cp ligands. Herein, we report a new class of chiral Cp ligands based on 1,1'-spirobiindane, a privileged scaffold for chiral ligands and catalysts. The corresponding Rh complexes are shown to be excellent catalysts in asymmetric oxidative coupling reactions, providing axially chiral biaryls in 19-97% yields with up to 98:2 er.

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

    PubMed

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

    2014-05-14

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

  20. Platinum Metal-Free Catalysts for Selective Soft Oxidative Methane → Ethylene Coupling. Scope and Mechanistic Observations.

    PubMed

    Peter, Matthias; Marks, Tobin J

    2015-12-09

    Using abundant soft oxidants, a high methane-to-ethylene conversion might be achievable due to the low thermodynamic driving force for over-oxidation. Here we report on the oxidative coupling of methane by gaseous S2 (SOCM). The catalytic properties of Pd/Fe3O4 are compared with those of Fe3O4, and it is found that high ethylene selectivities can be achieved without noble metals; conversion and selectivity on Fe3O4 are stable for at least 48 h at SOCM conditions. SOCM data for 10 oxides are compared, and ethylene selectivities as high as 33% are found; the C2H4/C2H6 ratios of 9-12 observed at the highest S2 conversions are significantly higher than the C2H4/C2H6 ratios usually found in the CH4 coupling with O2. Complementary in-detail analytical studies show that, on Mg, Zr, Sm, W, and La catalysts, which strongly coke during the reaction, lower ethylene selectivities are observed than on Fe, Ti, and Cr catalysts, which only coke to a minor extent. Further catalyst-dependent changes during SOCM in surface area, surface composition, and partial conversion to oxysulfides and sulfides are discussed. Evidence concerning the reaction mechanism is obtained taking into account the selectivity for the different reaction products versus the contact time. CH4 coupling proceeds non-oxidatively with the evolution of H2 on some catalysts, and evidence is presented that C2H4 and C2H2 formation occur via C2H6 and C2H4 dehydrogenation, respectively.

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

    SciTech Connect

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

    2013-10-15

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

  2. Mitochondrial coupling and capacity of oxidative phosphorylation in skeletal muscle of Inuit and Caucasians in the arctic winter.

    PubMed

    Gnaiger, E; Boushel, R; Søndergaard, H; Munch-Andersen, T; Damsgaard, R; Hagen, C; Díez-Sánchez, C; Ara, I; Wright-Paradis, C; Schrauwen, P; Hesselink, M; Calbet, J A L; Christiansen, M; Helge, J W; Saltin, B

    2015-12-01

    During evolution, mitochondrial DNA haplogroups of arctic populations may have been selected for lower coupling of mitochondrial respiration to ATP production in favor of higher heat production. We show that mitochondrial coupling in skeletal muscle of traditional and westernized Inuit habituating northern Greenland is identical to Danes of western Europe haplogroups. Biochemical coupling efficiency was preserved across variations in diet, muscle fiber type, and uncoupling protein-3 content. Mitochondrial phenotype displayed plasticity in relation to lifestyle and environment. Untrained Inuit and Danes had identical capacities to oxidize fat substrate in arm muscle, which increased in Danes during the 42 days of acclimation to exercise, approaching the higher level of the Inuit hunters. A common pattern emerges of mitochondrial acclimatization and evolutionary adaptation in humans at high latitude and high altitude where economy of locomotion may be optimized by preservation of biochemical coupling efficiency at modest mitochondrial density, when submaximum performance is uncoupled from VO2max and maximum capacities of oxidative phosphorylation.

  3. Anoxic nitrate reduction coupled with iron oxidation and attenuation of dissolved arsenic and phosphate in a sand and gravel aquifer

    NASA Astrophysics Data System (ADS)

    Smith, Richard L.; Kent, Douglas B.; Repert, Deborah A.; Böhlke, J. K.

    2017-01-01

    Nitrate has become an increasingly abundant potential electron acceptor for Fe(II) oxidation in groundwater, but this redox couple has not been well characterized within aquifer settings. To investigate this reaction and some of its implications for redox-sensitive groundwater contaminants, we conducted an in situ field study in a wastewater-contaminated aquifer on Cape Cod. Long-term (15 year) geochemical monitoring within the contaminant plume indicated interacting zones with variable nitrate-, Fe(II)-, phosphate-, As(V)-, and As(III)-containing groundwater. Nitrate and phosphate were derived predominantly from wastewater disposal, whereas Fe(II), As(III), and As(V) were mobilized from the aquifer sediments. Multiple natural gradient, anoxic tracer tests were conducted in which nitrate and bromide were injected into nitrate-free, Fe(II)-containing groundwater. Prior to injection, aqueous Fe(II) concentrations were approximately 175 μM, but sorbed Fe(II) accounted for greater than 90% of the total reactive Fe(II) in the aquifer. Nitrate reduction was stimulated within 1 m of transport for 100 μM and 1000 μM nitrate additions, initially producing stoichiometric quantities of nitrous oxide (>300 μM N). In subsequent injections at the same site, nitrate was reduced even more rapidly and produced less nitrous oxide, especially over longer transport distances. Fe(II) and nitrate concentrations decreased together and were accompanied by Fe(III) oxyhydroxide precipitation and decreases in dissolved phosphate, As(III), and As(V) concentrations. Nitrate N and O isotope fractionation effects during nitrate reduction were approximately equal (ε15N/ε18O = 1.11) and were similar to those reported for laboratory studies of biological nitrate reduction, including denitrification, but unlike some reported effects on nitrate by denitrification in aquifers. All constituents affected by the in situ tracer experiments returned to pre-injection levels after several weeks

  4. 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

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

    2013-10-18

    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

  5. Rapid and automated analysis of aflatoxin M1 in milk and dairy products by online solid phase extraction coupled to ultra-high-pressure-liquid-chromatography tandem mass spectrometry.

    PubMed

    Campone, Luca; Piccinelli, Anna Lisa; Celano, Rita; Pagano, Imma; Russo, Mariateresa; Rastrelli, Luca

    2016-01-08

    This study reports a fast and automated analytical procedure for the analysis of aflatoxin M1 (AFM1) in milk and dairy products. The method is based on the simultaneous protein precipitation and AFM1 extraction, by salt-induced liquid-liquid extraction (SI-LLE), followed by an online solid-phase extraction (online SPE) coupled to ultra-high-pressure-liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis to the automatic pre-concentration, clean up and sensitive and selective determination of AFM1. The main parameters affecting the extraction efficiency and accuracy of the analytical method were studied in detail. In the optimal conditions, acetonitrile and NaCl were used as extraction/denaturant solvent and salting-out agent in SI-LLE, respectively. After centrifugation, the organic phase (acetonitrile) was diluted with water (1:9 v/v) and purified (1mL) by online C18 cartridge coupled with an UHPLC column. Finally, selected reaction monitoring (SRM) acquisition mode was applied to the detection of AFM1. Validation studies were carried out on different dairy products (whole and skimmed cow milk, yogurt, goat milk, and powder infant formula), providing method quantification limits about 25 times lower than AFM1 maximum levels permitted by EU regulation 1881/2006 in milk and dairy products for direct human consumption. Recoveries (86-102%) and repeatability (RSD<3, n=6) meet the performance criteria required by EU regulation N. 401/2006 for the determination of the levels of mycotoxins in foodstuffs. Moreover, no matrix effects were observed in the different milk and dairy products studied. The proposed method improves the performance of AFM1 analysis in milk samples as AFM1 determination is performed with a degree of accuracy higher than the conventional methods. Other advantages are the reduction of sample preparation procedure, time and cost of the analysis, enabling high sample throughput that meet the current concerns of food safety and the public

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

    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.

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

    PubMed

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

    2014-12-01

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

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

    SciTech Connect

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

    2003-03-26

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

  9. Distant electric coupling between nitrate reduction and sulphide oxidation investigated by an improved nitrate microscale biosensor

    NASA Astrophysics Data System (ADS)

    Marzocchi, U.; Revsbech, N. P.; Nielsen, L. P.; Risgaard-Petersen, N.

    2012-04-01

    Bacteria are apparently able to transmit electrons to other bacteria (Summers et al. 2010) or to electrodes (Malvankar et al. 2011) by some kind of nanowires (Reguera et al. 2005, Gorbi et al. 2006). Lately it has been shown that such transfer may occur over distances of centimetres in sediments, thereby coupling sulphide oxidation in deeper layers with oxygen reduction near the surface (Nielsen 2011). The finding of these long-distance electrical connections originated from analysis of O2, H2S, and pH profiles measured with microsensors. Nitrate is thermodynamically almost as good an electron acceptor as O2, and we therefore set up an experiment to investigate whether long-distance electron transfer also happens with NO3-. Aquaria were filled with sulphidic marine sediment from Aarhus Bay that was previously used to show long-distance electron transfer to O2. The aquaria were equipped with a lid so that they could be completely filled without a gas phase. Anoxic seawater with 300 μM NO3- was supplied at a constant rate resulting in a steady state concentration in the aquatic phase of 250 μM NO3-. The reservoir with the nitrate-containing water was kept anoxic by bubbling it with a N2/CO2 mixture and was kept at an elevated temperature. The water was cooled on the way to the aquaria to keep the water in the aquaria undersaturated with gasses, so that bubble formation by denitrification in the sediment could be minimised. Profiles of NO3-, H2S, and pH were measured as a function of time (2 months) applying commercial sensors for H2S and pH and an improved microscale NO3- biosensor developed in our laboratory. The penetration of NO3- in the sediment was 4-5 mm after 2 months, whereas sulphide only could be detected below 8-9 mm depth. The electron acceptor and electron donor were thus separated by 4-5 mm, indicating long distance electron transfer. A pH maximum of about 8.6 pH units at the NO3- reduction zone similar to a pH maximum observed in the O2 reduction

  10. Anoxic nitrate reduction coupled with iron oxidation and attenuation of dissolved arsenic and phosphate in a sand and gravel aquifer

    USGS Publications Warehouse

    Smith, Richard L.; Kent, Douglas B.; Repert, Deborah A.; Böhlke, J.K.

    2017-01-01

    Nitrate has become an increasingly abundant potential electron acceptor for Fe(II) oxidation in groundwater, but this redox couple has not been well characterized within aquifer settings. To investigate this reaction and some of its implications for redox-sensitive groundwater contaminants, we conducted an in situ field study in a wastewater-contaminated aquifer on Cape Cod. Long-term (15 year) geochemical monitoring within the contaminant plume indicated interacting zones with variable nitrate-, Fe(II)-, phosphate-, As(V)-, and As(III)-containing groundwater. Nitrate and phosphate were derived predominantly from wastewater disposal, whereas Fe(II), As(III), and As(V) were mobilized from the aquifer sediments. Multiple natural gradient, anoxic tracer tests were conducted in which nitrate and bromide were injected into nitrate-free, Fe(II)-containing groundwater. Prior to injection, aqueous Fe(II) concentrations were approximately 175 μM, but sorbed Fe(II) accounted for greater than 90% of the total reactive Fe(II) in the aquifer. Nitrate reduction was stimulated within 1 m of transport for 100 μM and 1000 μM nitrate additions, initially producing stoichiometric quantities of nitrous oxide (>300 μM N). In subsequent injections at the same site, nitrate was reduced even more rapidly and produced less nitrous oxide, especially over longer transport distances. Fe(II) and nitrate concentrations decreased together and were accompanied by Fe(III) oxyhydroxide precipitation and decreases in dissolved phosphate, As(III), and As(V) concentrations. Nitrate N and O isotope fractionation effects during nitrate reduction were approximately equal (ε15N/ε18O = 1.11) and were similar to those reported for laboratory studies of biological nitrate reduction, including denitrification, but unlike some reported effects on nitrate by denitrification in aquifers. All constituents affected by the in situ tracer experiments returned to pre-injection levels after several

  11. 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

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

    2015-01-01

    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

  12. Simultaneous removal and degradation characteristics of sulfonamide, tetracycline, and quinolone antibiotics by laccase-mediated oxidation coupled with soil adsorption.

    PubMed

    Ding, Huijun; Wu, Yixiao; Zou, Binchun; Lou, Qian; Zhang, Weihao; Zhong, Jiayou; Lu, Lei; Dai, Guofei

    2016-04-15

    The uses of laccase in the degradation and removal of antibiotics have recently been reported because of the high efficiency and environmental friendliness of laccase. However, these removal studies mostly refer to a limited number of antibiotics. In this study, soil adsorption was introduced into the laccase-oxidation system to assist the simultaneous removal of 14 kinds of sulfonamide, tetracycline, and quinolone antibiotics, which differed in structures and chemical properties. The complementary effects of laccase-mediated oxidation and soil adsorption enabled the simultaneous removal. Removal characteristics were determined by a comprehensive consideration of the separate optimum conditions for laccase oxidation and soil adsorption removal experiments. With concentrations of laccase, syringaldehyde (SA), and soil of 0.5mg/mL, 0.5mmol/L, and 50g/L, respectively, and at pH 6 and 25°C, the removal rates of each antibiotic exceeded 70% in 15min and were close to 100% in 180min. Sulfonamide antibiotics (SAs) were removed mainly by laccase oxidation and quinolone antibiotics (QUs) mainly by soil adsorption. Tetracycline antibiotics (TCs) were removed by both treatments in the coupled system, but laccase oxidation dominated. Electrostatic adsorption was speculated to be one of the adsorption mechanisms in soil adsorption with QUs and TCs.

  13. Coupling of Fe(II) oxidation in illite with nitrate reduction and its role in clay mineral transformation

    NASA Astrophysics Data System (ADS)

    Zhao, Linduo; Dong, Hailiang; Edelmann, Richard E.; Zeng, Qiang; Agrawal, Abinash

    2017-03-01

    In pedogenic and diagenetic processes, clay minerals transform from pre-existing phases to other clay minerals via intermediate interstratified clays. Temperature, pressure, chemical composition of fluids, and time are traditionally considered to be the important geological variables for clay mineral transformations. Nearly ten years ago, the role of microbes was recognized for the first time, where microbial reduction of structural Fe(III) in smectite resulted in formation of illite under ambient conditions within two weeks. However, the opposite process, the oxidation of structural Fe(II) in illite has not been studied and it remains unclear whether or not this process would result in the back reaction, e.g., from illite to smectite. The overall objective of this study was to investigate biological oxidation of structural Fe(II) in illite coupled with nitrate reduction and the effect of this process on clay mineral transformation. Laboratory incubations were set up, where structural Fe(II) in illite served as electron donor, nitrate as electron acceptor, and Pseudogulbenkiania sp. strain 2002 as mediator. Solution chemistry and gas composition were monitored over time. Mineralogical transformation resulting from bio-oxidation was characterized with X-ray diffraction and scanning and transmission electron microscopy. Our results demonstrated that strain 2002 was able to couple oxidation of structural Fe(II) in illite with reduction of nitrate to N2 with nitrite as a transient intermediate. This oxidation reaction resulted in transformation of illite to smectite and ultimately to kaolinite (illite → smectite → kaolinite transformations). This study illustrates the importance of Fe redox process in mediating the smectite-illite mineral cycle with important implications for Fe redox cycling and mineral evolution in surficial earth environments.

  14. Highly efficient and tunable spin-to-charge conversion through Rashba coupling at oxide interfaces.

    PubMed

    Lesne, E; Fu, Yu; Oyarzun, S; Rojas-Sánchez, J C; Vaz, D C; Naganuma, H; Sicoli, G; Attané, J-P; Jamet, M; Jacquet, E; George, J-M; Barthélémy, A; Jaffrès, H; Fert, A; Bibes, M; Vila, L

    2016-12-01

    The spin-orbit interaction couples the electrons' motion to their spin. As a result, a charge current running through a material with strong spin-orbit coupling generates a transverse spin current (spin Hall effect, SHE) and vice versa (inverse spin Hall effect, ISHE). The emergence of SHE and ISHE as charge-to-spin interconversion mechanisms offers a variety of novel spintronic functionalities and devices, some of which do not require any ferromagnetic material. However, the interconversion efficiency of SHE and ISHE (spin Hall angle) is a bulk property that rarely exceeds ten percent, and does not take advantage of interfacial and low-dimensional effects otherwise ubiquitous in spintronic hetero- and mesostructures. Here, we make use of an interface-driven spin-orbit coupling mechanism-the Rashba effect-in the oxide two-dimensional electron system (2DES) LaAlO3/SrTiO3 to achieve spin-to-charge conversion with unprecedented efficiency. Through spin pumping, we inject a spin current from a NiFe film into the oxide 2DES and detect the resulting charge current, which can be strongly modulated by a gate voltage. We discuss the amplitude of the effect and its gate dependence on the basis of the electronic structure of the 2DES and highlight the importance of a long scattering time to achieve efficient spin-to-charge interconversion.

  15. Evidence of Nitrogen Loss from Anaerobic Ammonium Oxidation Coupled with Ferric Iron Reduction in an Intertidal Wetland.

    PubMed

    Li, Xiaofei; Hou, Lijun; Liu, Min; Zheng, Yanling; Yin, Guoyu; Lin, Xianbiao; Cheng, Lv; Li, Ye; Hu, Xiaoting

    2015-10-06

    Anaerobic ammonium oxidation coupled with nitrite reduction is an important microbial pathway of nitrogen removal in intertidal wetlands. However, little is known about the role of anaerobic ammonium oxidation coupled with ferric iron reduction (termed Feammox) in intertidal nitrogen cycling. In this study, sediment slurry incubation experiments were combined with an isotope-tracing technique to examine the dynamics of Feammox and its association with tidal fluctuations in the intertidal wetland of the Yangtze Estuary. Feammox was detected in the intertidal wetland sediments, with potential rates of 0.24-0.36 mg N kg(-1) d(-1). The Feammox rates in the sediments were generally higher during spring tides than during neap tides. The tidal fluctuations affected the growth of iron-reducing bacteria and reduction of ferric iron, which mediated Feammox activity and the associated nitrogen loss from intertidal wetlands to the atmosphere. An estimated loss of 11.5-18 t N km(-2) year(-1) was linked to Feammox, accounting for approximately 3.1-4.9% of the total external inorganic nitrogen transported into the Yangtze Estuary wetland each year. Overall, the co-occurrence of ferric iron reduction and ammonium oxidation suggests that Feammox can act as an ammonium removal mechanism in intertidal wetlands.

  16. A novel and sensitive method for ethinylestradiol quantification in human plasma by high-performance liquid chromatography coupled to atmospheric pressure photoionization (APPI) tandem mass spectrometry: application to a comparative pharmacokinetics study.

    PubMed

    Borges, Ney Carter; Astigarraga, Rafael Barrientos; Sverdloff, Carlos Eduardo; Galvinas, Paulo Rabelo; da Silva, Washington Moreira; Rezende, Vinícius Marcondes; Moreno, Ronilson Agnaldo

    2009-11-01

    In the present study, a novel, fast, sensitive and robust method to quantify ethinylestradiol in human plasma using 17alpha-ethinylestradiol-d4 as the internal standard (IS) is described. The analyte and the IS were extracted from acidified plasma by liquid-liquid extraction (LLE) using diethyl ether-hexane followed by online solid phase extraction (SPE) using online C18 cartridges. Extracted samples were analyzed by high-performance liquid chromatography coupled to atmospheric pressure photoionization tandem mass spectrometry (HPLC-APPI-MS/MS). Chromatography was performed isocratically on a C18, 5 microm analytical column. The method had a chromatographic run time of 2.50 min and a linear calibration curve over the range 5-500 pg ml(-1) (r(2)>0.9992). The lowest concentration quantified was 5 pg ml(-1), demonstrating acceptable accuracy and precision. The intra-assay precisions ranged from 2.1 to 14.6%, while inter-assay precisions ranged from 4.4 to 11.4%. The intra-assay accuracies ranged from 94.6 to 103.8%, while the inter-assay accuracies ranged from 98.9 to 101.6%. The recovery of ethinylestradiol was determined as part of the assay validation process and was 73.1 and 79.0% for the concentrations 15 and 375 pg ml(-1), respectively. Short-term stability showed that ethinylestradiol was stable in plasma for at least 19 h at room temperature or for at least 385 days when stored at -20 degrees C. In the study of bioequivalence conducted in Brazil, healthy volunteers received two ethinylestradiol 0.035 mg tablet formulations using an open, randomized, two-period crossover design with a 2-week washout interval. Since the 90% confidence interval for C(max) and area under the curve ratios were all inside the 80-125% interval proposed by the US Food and Drug Administration, it was concluded that the two ethinylestradiol formulations are bioequivalent with respect to both the rate and the extent of absorption.

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

    PubMed

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

    2013-02-15

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

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

    PubMed

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

    2014-05-01

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

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

    SciTech Connect

    Weber Jr., W. J.

    2000-10-01

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

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

    PubMed

    Jahn, Emanuela; Jahn, Ullrich

    2014-12-01

    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.

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

    PubMed

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

    2015-10-01

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

  2. Direct preparation of N-quaternized and N-oxidized polycyclic azines by palladium-catalyzed cross-coupling. An unequivocal isomer synthesis

    SciTech Connect

    Zoltewicz, J.A.; Cruskie, M.P. Jr.; Dill, C.D.

    1995-01-13

    The authors report several examples of unequivocal isomer preparations using palladium-catalyzed cross-coupling to yield N-oxides and N-quaternized polycyclic azines. This approach serves as a model for such syntheses where selective N-quaternization, N-oxidation, or other types of N-functionalization of several rings is now possible in a regioncontrolled manner.

  3. nBu4NI-catalyzed oxidative cross-coupling of carbon dioxide, amines, and aryl ketones: access to O-β-oxoalkyl carbamates.

    PubMed

    Peng, Youbin; Liu, Juan; Qi, Chaorong; Yuan, Gaoqing; Li, Jiawei; Jiang, Huanfeng

    2017-02-28

    The first nBu4NI-catalyzed oxidative cross-coupling reaction of carbon dioxide, amines and arylketones has been successfully developed by using TBHP as the oxidant, providing an efficient, atom-economical and metal-free strategy for the synthesis of a range of O-β-oxoalkyl carbamates.

  4. Salicylic acid degradation by advanced oxidation processes. Coupling of solar photoelectro-Fenton and solar heterogeneous photocatalysis.

    PubMed

    Garza-Campos, Benjamin; Brillas, Enric; Hernández-Ramírez, Aracely; El-Ghenymy, Abdellatif; Guzmán-Mar, Jorge Luis; Ruiz-Ruiz, Edgar J

    2016-12-05

    A 3.0 L solar flow plant with a Pt/air-diffusion (anode/cathode) cell, a solar photoreactor and a photocatalytic photoreactor filled with TiO2-coated glass spheres has been utilized to couple solar photoelectro-Fenton (SPEF) and solar heterogeneous photocatalysis (SPC) for treating a 165mgL(-1) salicylic acid solution of pH 3.0. Organics were destroyed by OH radicals formed on the TiO2 photocatalyst and at the Pt anode during water oxidation and in the bulk from Fenton's reaction between added Fe(2+) and cathodically generated H2O2, along with the photolytic action of sunlight. Poor salicylic acid removal and mineralization were attained using SPC, anodic oxidation with electrogenerated H2O2 (AO-H2O2) and coupled AO-H2O2-SPC. The electro-Fenton process accelerated the substrate decay, but with low mineralization by the formation of byproducts that are hardly destroyed by OH. The mineralization was strongly increased by SPEF due to the photolysis of products by sunlight, being enhanced by coupled SPEF-SPC due to the additional oxidation by OH at the TiO2 surface. The effect of current density on the performance of both processes was examined. The most potent SPEF-SPC process at 150mAcm(-2) yielded 87% mineralization and 13% current efficiency after consuming 6.0AhL(-1). Maleic, fumaric and oxalic acids detected as final carboxylic acids were completely removed by SPEF and SPEF-SPC.

  5. Phenol oxidative coupling in the biogenesis of the macrocyclic spermine alkaloids aphelandrine and orantine in Aphelandra sp.

    PubMed

    Nezbedová, L; Hesse, M; Drandarov, K; Bigler, L; Werner, C

    2001-07-01

    A crucial step in the biosynthesis of the spermine alkaloid aphelandrine and its diastereoisomer orantine is an intramolecular cyclization of the intermediate (S)-dihydroxyverbacine. In order to elucidate this step of the biosynthetic pathway, microsomes from the roots of Aphelandra squarrosa Nees were incubated with unlabeled and (D8)-labeled (S)-dihydroxyverbacine. It was shown that the microsomal fraction catalyzes the intramolecular coupling of (S)-dihydroxyverbacine to aphelandrine. This was proven by microsomal transformation of (D8)-labeled (S)-dihydroxyverbacine to (D8)-labeled aphelandrine. The reaction absolutely requires NAPDH and O2. The underlying reaction mechanism is probably an oxidative phenol coupling catalyzed by an aphelandrine synthase. This enzyme is proposed to be a cytochrome P-450 oxidase. The intramolecular cyclization of (S)-dihydroxyverbacine represents an important point in the biogenesis of the aphelandrine-type alkaloids.

  6. Solar-powered electrochemical oxidation of organic compounds coupled with the cathodic production of molecular hydrogen.

    PubMed

    Park, Hyunwoong; Vecitis, Chad D; Hoffmann, Michael R

    2008-08-21

    A Bi-doped TiO2 anode, which is prepared from a mixed metal oxide coating deposited on Ti metal, is shown to be efficient for conventional water splitting. In this hybrid photovoltaic-electrochemical system, a photovoltaic (PV) cell is used to convert solar light to electricity, which is then used to oxidize a series of phenolic compounds at the semiconductor anode to carbon dioxide with the simultaneous production of molecular hydrogen from water/proton reduction at the stainless steel cathode. Degradation of phenol in the presence of a background NaCl electrolyte produces chlorinated phenols as reaction intermediates, which are subsequently oxidized completely to carbon dioxide and low-molecular weight carboxylic acids. The anodic current efficiency for the complete oxidation of phenolic compounds ranges from 3% to 17%, while the cathodic current efficiency and the energy efficiency for hydrogen gas generation range from 68% to 95% and 30% to 70%, respectively.

  7. 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...

  8. Demonstrating Advanced Oxidation Coupled with Biodegradation for Removal of Carbamazepine (WERF Report INFR6SG09)

    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...

  9. Coupling of bias-induced crystallographic shear planes with charged domain walls in ferroelectric oxide thin films

    SciTech Connect

    Han, Myung-Geun; Garlow, Joseph A.; Bugnet, Matthieu; Divilov, Simon; Marshall, Matthew S. J.; Wu, Lijun; Dawber, Matthew; Fernandez-Serra, Marivi; Botton, Gianluigi A.; Cheong, Sang-Wook; Walker, Frederick J.; Ahn, Charles H.; Zhu, Yimei

    2016-09-02

    Polar discontinuity at interfaces plays deterministic roles in charge transport, magnetism, and even superconductivity of functional oxides. To date, most polar discontinuity problems have been explored in hetero-interfaces between two dissimilar materials. Here, we show that charged domain walls (CDWs) in epitaxial thin films of ferroelectric PbZr0.2Ti0.8O3 are strongly coupled to polar interfaces through the formation of ½<101>{h0l} type crystallographic shear planes (CSPs). Using atomic resolution imaging and spectroscopy we illustrate that the CSPs consist of both conservative and nonconservative segments when coupled to the CDWs, where necessary compensating charges for stabilizing the CDWs are associated with vacancies at the CSPs. Lasly, the CDW/CSP coupling yields an atomically narrow domain walls, consisting of a single atomic layer of oxygen. This study shows that the CDW/CSP coupling is a fascinating venue to develop emergent material properties.

  10. Analysis of Chlorination, Nitration, and Nitrosylation of Tyrosine and Oxidation of Methionine and Cysteine in Hemoglobin from Type 2 Diabetes Mellitus Patients by Nanoflow Liquid Chromatography Tandem Mass Spectrometry.

    PubMed

    Chen, Hauh-Jyun Candy; Yang, Ya-Fen; Lai, Pang-Yen; Chen, Pin-Fan

    2016-09-20

    The post-translational modification (PTM) of proteins by endogenous reactive chlorine, nitrogen, and oxygen species is implicated in certain pathological conditions, including diabetes mellitus. Evidence showed that the extents of modifications on a number of proteins are elevated in diabetic patients. Measuring modification on hemoglobin has been used to monitor the extent of exposure. This study develops an assay for simultaneous quantification of the extent of chlorination, nitration, and oxidation in human hemoglobin and to examine whether the level of any of these modifications is higher in poorly controlled type 2 diabetic mellitus patients. This mass spectrometry-based assay used the bottom-up proteomic strategy. Due to the low amount of endogenous modification, we first characterized the sites of chlorination at tyrosine in hypochlorous acid-treated hemoglobin by an accurate mass spectrometer. The extents of chlorination, nitration, and oxidation of a total of 12 sites and types of modifications in hemoglobin were measured by nanoflow liquid chromatography-nanospray ionization tandem mass spectrometry under the selected reaction monitoring mode. Relative quantification of these PTMs in hemoglobin extracted from blood samples shows that the extents of chlorination at α-Tyr-24, nitration at α-Tyr-42, and oxidation at the three methionine residues are significantly higher in diabetic patients (n = 19) than in nondiabetic individuals (n = 18). After excluding the factor of smoking, chlorination at α-Tyr-24, nitration at α-Tyr-42, and oxidation at the three methionine residues are significantly higher in the nonsmoking diabetic patients (n = 12) than in normal nonsmoking subjects (n = 11). Multiple regression analysis performed on the combined effect of age, body-mass index (BMI), and HbA1c showed that the diabetes factor HbA1c contributes significantly to the extent of chlorination at α-Tyr-24 in nonsmokers. In addition, age contributes to oxidation at

  11. Three-dimensional fully-coupled electrical and thermal transport model of dynamic switching in oxide memristors

    DOE PAGES

    Gao, Xujiao; Mamaluy, Denis; Mickel, Patrick R.; ...

    2015-09-08

    In this paper, we present a fully-coupled electrical and thermal transport model for oxide memristors that solves simultaneously the time-dependent continuity equations for all relevant carriers, together with the time-dependent heat equation including Joule heating sources. The model captures all the important processes that drive memristive switching and is applicable to simulate switching behavior in a wide range of oxide memristors. The model is applied to simulate the ON switching in a 3D filamentary TaOx memristor. Simulation results show that, for uniform vacancy density in the OFF state, vacancies fill in the conduction filament till saturation, and then fill outmore » a gap formed in the Ta electrode during ON switching; furthermore, ON-switching time strongly depends on applied voltage and the ON-to-OFF current ratio is sensitive to the filament vacancy density in the OFF state.« less

  12. Three-dimensional fully-coupled electrical and thermal transport model of dynamic switching in oxide memristors

    SciTech Connect

    Gao, Xujiao; Mamaluy, Denis; Mickel, Patrick R.; Marinella, Matthew

    2015-09-08

    In this paper, we present a fully-coupled electrical and thermal transport model for oxide memristors that solves simultaneously the time-dependent continuity equations for all relevant carriers, together with the time-dependent heat equation including Joule heating sources. The model captures all the important processes that drive memristive switching and is applicable to simulate switching behavior in a wide range of oxide memristors. The model is applied to simulate the ON switching in a 3D filamentary TaOx memristor. Simulation results show that, for uniform vacancy density in the OFF state, vacancies fill in the conduction filament till saturation, and then fill out a gap formed in the Ta electrode during ON switching; furthermore, ON-switching time strongly depends on applied voltage and the ON-to-OFF current ratio is sensitive to the filament vacancy density in the OFF state.

  13. Novel Mode of Microbial Energy Metabolism: Organic Carbon Oxidation Coupled to Dissimilatory Reduction of Iron or Manganese

    PubMed Central

    Lovley, Derek R.; Phillips, Elizabeth J. P.

    1988-01-01

    A dissimilatory Fe(III)- and Mn(IV)-reducing microorganism was isolated from freshwater sediments of the Potomac River, Maryland. The isolate, designated GS-15, grew in defined anaerobic medium with acetate as the sole electron donor and Fe(III), Mn(IV), or nitrate as the sole electron acceptor. GS-15 oxidized acetate to carbon dioxide with the concomitant reduction of amorphic Fe(III) oxide to magnetite (Fe3O4). When Fe(III) citrate replaced amorphic Fe(III) oxide as the electron acceptor, GS-15 grew faster and reduced all of the added Fe(III) to Fe(II). GS-15 reduced a natural amorphic Fe(III) oxide but did not significantly reduce highly crystalline Fe(III) forms. Fe(III) was reduced optimally at pH 6.7 to 7 and at 30 to 35°C. Ethanol, butyrate, and propionate could also serve as electron donors for Fe(III) reduction. A variety of other organic compounds and hydrogen could not. MnO2 was completely reduced to Mn(II), which precipitated as rhodochrosite (MnCO3). Nitrate was reduced to ammonia. Oxygen could not serve as an electron acceptor, and it inhibited growth with the other electron acceptors. This is the first demonstration that microorganisms can completely oxidize organic compounds with Fe(III) or Mn(IV) as the sole electron acceptor and that oxidation of organic matter coupled to dissimilatory Fe(III) or Mn(IV) reduction can yield energy for microbial growth. GS-15 provides a model for how enzymatically catalyzed reactions can be quantitatively significant mechanisms for the reduction of iron and manganese in anaerobic environments. Images PMID:16347658

  14. Microbiology and potential applications of aerobic methane oxidation coupled to denitrification (AME-D) process: A review.

    PubMed

    Zhu, Jing; Wang, Qian; Yuan, Mengdong; Tan, Giin-Yu Amy; Sun, Faqian; Wang, Cheng; Wu, Weixiang; Lee, Po-Heng

    2016-03-01

    Aerobic methane oxidation coupled to denitrification (AME-D) is an important link between the global methane and nitrogen cycles. This mini-review updates discoveries regarding aerobic methanotrophs and denitrifiers, as a prelude to spotlight the microbial mechanism and the potential applications of AME-D. Until recently, AME-D was thought to be accomplished by a microbial consortium where denitrifying bacteria utilize carbon intermediates, which are excreted by aerobic methanotrophs, as energy and carbon sources. Potential carbon intermediates include methanol, citrate and acetate. This mini-review presents microbial thermodynamic estimations and postulates that methanol is the ideal electron donor for denitrification, and may serve as a trophic link between methanotrophic bacteria and denitrifiers. More excitingly, new discoveries have revealed that AME-D is not only confined to the conventional synergism between methanotrophic bacteria and denitrifiers. Specifically, an obligate aerobic methanotrophic bacterium, Methylomonas denitrificans FJG1, has been demonstrated to couple partial denitrification with methane oxidation, under hypoxia conditions, releasing nitrous oxide as a terminal product. This finding not only substantially advances the understanding of AME-D mechanism, but also implies an important but unknown role of aerobic methanotrophs in global climate change through their influence on both the methane and nitrogen cycles in ecosystems. Hence, further investigation on AME-D microbiology and mechanism is essential to better understand global climate issues and to develop niche biotechnological solutions. This mini-review also presents traditional microbial techniques, such as pure cultivation and stable isotope probing, and powerful microbial techniques, such as (meta-) genomics and (meta-) transcriptomics, for deciphering linked methane oxidation and denitrification. Although AME-D has immense potential for nitrogen removal from wastewater, drinking

  15. Rapid Mobilization of Noncrystalline U(IV) Coupled with FeS Oxidation.

    PubMed

    Bi, Yuqiang; Stylo, Malgorzata; Bernier-Latmani, Rizlan; Hayes, Kim F

    2016-02-02

    The reactivity of disordered, noncrystalline U(IV) species remains poorly characterized despite their prevalence in biostimulated sediments. Because of the lack of crystalline structure, noncrystalline U(IV) may be susceptible to oxidative mobilization under oxic conditions. The present study investigated the mechanism and rate of oxidation of biogenic noncrystalline U(IV) by dissolved oxygen (DO) in the presence of mackinawite (FeS). Previously recognized as an effective reductant and oxygen scavenger, nanoparticulate FeS was evaluated for its role in influencing U release in a flow-through system as a function of pH and carbonate concentration. The results demonstrated that noncrystalline U(IV) was more susceptible to oxidation than uraninite (UO2) in the presence of dissolved carbonate. A rapid release of U occurred immediately after FeS addition without exhibiting a temporary inhibition stage, as was observed during the oxidation of UO2, although FeS still kept DO levels low. X-ray photoelectron spectroscopy (XPS) characterized a transient surface Fe(III) species during the initial FeS oxidation, which was likely responsible for oxidizing noncrystalline U(IV) in addition to oxygen. In the absence of carbonate, however, the release of dissolved U was significantly hindered as a result of U adsorption by FeS oxidation products. This study illustrates the strong interactions between iron sulfide and U(IV) species during redox transformation and implies the lability of biogenic noncrystalline U(IV) species in the subsurface environment when subjected to redox cycling events.

  16. Nickel-doped zinc aluminate oxides: starch-assisted synthesis, structural, optical properties, and their catalytic activity in oxidative coupling of methane

    NASA Astrophysics Data System (ADS)

    Visinescu, Diana; Papa, Florica; Ianculescu, Adelina C.; Balint, Ioan; Carp, Oana

    2013-03-01

    Nanosized nickel-substituted zinc aluminate oxides were obtained by the gradual insertion of nickel cations within the zinc aluminate lattice, using starch as active ingredient. The obtained (Ni x Zn1- x Al2)-starch ( x = 0.1, 0.2, 0.4, 0.6, 0.8, 1) gel precursors were characterized through infrared spectroscopy and thermal analysis. The thermal behavior of the precursors are influenced by the nickel content, the DTA curves for the richer nickel samples revealing stronger, faster and overlapping exothermic reactions, that can be completed at lower temperatures. The corresponding spinelic oxides were obtained after calcination treatments at 800 °C and analyzed by means of NIR-UV-Vis spectroscopy, XRD measurements, SEM, TEM, and HRTEM investigations. The spinelic structure for all oxide samples is confirmed by XRD analysis, although small amounts of NiO cannot be neglected. TEM/HRTEM analysis revealed mesopores embedded in plate-like large (68.8 nm) particles of Ni0.2Zn0.8Al2O4 sample and smaller (15.7 nm) uniform equiaxial particles, with a more pronounced tendency of agglomeration for Ni0.8Zn0.2Al2O4 oxide. A formation mechanism for Ni0.2Zn0.8Al2O4 oxides was proposed based on DTA/TG, XRD, and SEM analyses. NIR-UV-Vis spectra for Ni x Zn1- x Al2O4 showed a significant presence of tetrahedral nickel cations that augments with nickel concentration increase. CIE- L * a * b * color parameters shown a variation of the lightness and also of the green and blue color components with x, the best color characteristics being obtained for x = 0.6. The oxides with a substitution degree x = 0.2 and 0.8 tested in the oxidative coupled of methane reaction (OCM) showed positive catalytic activity and selectivity due to an interesting synergetic effect of Zn(II) and Ni(II) ions.

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

    PubMed

    Largeron, Martine; Fleury, Maurice-Bernard

    2015-02-23

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

  18. Sulfur oxidation to sulfate coupled with electron transfer to electrodes by Desulfuromonas strain TZ1.

    PubMed

    Zhang, Tian; Bain, Timothy S; Barlett, Melissa A; Dar, Shabir A; Snoeyenbos-West, Oona L; Nevin, Kelly P; Lovley, Derek R

    2014-01-01

    Microbial oxidation of elemental sulfur with an electrode serving as the electron acceptor is of interest because this may play an important role in the recovery of electrons from sulfidic wastes and for current production in marine benthic microbial fuel cells. Enrichments initiated with a marine sediment inoculum, with elemental sulfur as the electron donor and a positively poised (+300 mV versus Ag/AgCl) anode as the electron acceptor, yielded an anode biofilm with a diversity of micro-organisms, including Thiobacillus, Sulfurimonas, Pseudomonas, Clostridium and Desulfuromonas species. Further enrichment of the anode biofilm inoculum in medium with elemental sulfur as the electron donor and Fe(III) oxide as the electron acceptor, followed by isolation in solidified sulfur/Fe(III) medium yielded a strain of Desulfuromonas, designated strain TZ1. Strain TZ1 effectively oxidized elemental sulfur to sulfate with an anode serving as the sole electron acceptor, at rates faster than Desulfobulbus propionicus, the only other organism in pure culture previously shown to oxidize S° with current production. The abundance of Desulfuromonas species enriched on the anodes of marine benthic fuel cells has previously been interpreted as acetate oxidation driving current production, but the results presented here suggest that sulfur-driven current production is a likely alternative.

  19. Sulfur oxidation to sulfate coupled with electron transfer to electrodes by Desulfuromonas strain TZ1

    SciTech Connect

    Zhang, T; Bain, TS; Barlett, MA; Dar, SA; Snoeyenbos-West, OL; Nevin, KP; Lovley, DR

    2014-01-02

    Microbial oxidation of elemental sulfur with an electrode serving as the electron acceptor is of interest because this may play an important role in the recovery of electrons from sulfidic wastes and for current production in marine benthic microbial fuel cells. Enrichments initiated with a marine sediment inoculum, with elemental sulfur as the electron donor and a positively poised (+300 mV versus Ag/AgCl) anode as the electron acceptor, yielded an anode biofilm with a diversity of micro-organisms, including Thiobacillus, Sulfurimonas, Pseudomonas, Clostridium and Desulfuromonas species. Further enrichment of the anode biofilm inoculum in medium with elemental sulfur as the electron donor and Fe(III) oxide as the electron acceptor, followed by isolation in solidified sulfur/Fe(III) medium yielded a strain of Desulfuromonas, designated strain TZ1. Strain TZ1 effectively oxidized elemental sulfur to sulfate with an anode serving as the sole electron acceptor, at rates faster than Desulfobulbus propionicus, the only other organism in pure culture previously shown to oxidize S with current production. The abundance of Desulfuromonas species enriched on the anodes of marine benthic fuel cells has previously been interpreted as acetate oxidation driving current production, but the results presented here suggest that sulfur-driven current production is a likely alternative.

  20. Tandem Air Propellers

    NASA Technical Reports Server (NTRS)

    Lesley, E.P.

    1937-01-01

    Tests of 2-blade, adjustable-pitch, counterrotating tandem model propellers, adjusted to absorb equal power at maximum efficiency, were made at Stanford University. The characteristics, for 15 degrees, 25 degrees, 35 degrees, and 45 degrees pitch settings at 0.75 R of the forward propeller and for 8 1/2%, 15% and 30% diameter spacings, were compared with those of 2-blade and 4-blade propellers of the same blade form. The tests showed that the efficiency of the tandem propellers was from 0.5% to 4% greater than that of a 4-blade propeller and, at the high pitch settings, not appreciable inferior to that of a 2-blade propeller. It was found that the rear tandem propeller should be set at a pitch angle slightly less than that of the forward propeller to realize the condition of equal power at maximum efficiency. Under this condition the total power absorbed by the tandem propellers was from 3% to 9% more than that absorbed by the 4-blade propeller and about twice that absorbed by a 2-blade propeller.

  1. Respiratory Ammonification of Nitrate Coupled to Anaerobic Oxidation of Elemental Sulfur in Deep-Sea Autotrophic Thermophilic Bacteria

    PubMed Central

    Slobodkina, Galina B.; Mardanov, Andrey V.; Ravin, Nikolai V.; Frolova, Anastasia A.; Chernyh, Nikolay A.; Bonch-Osmolovskaya, Elizaveta A.; Slobodkin, Alexander I.

    2017-01-01

    Respiratory ammonification of nitrate is the microbial process that determines the retention of nitrogen in an ecosystem. To date, sulfur-dependent dissimilatory nitrate reduction to ammonium has been demonstrated only with sulfide as an electron donor. We detected a novel pathway that couples the sulfur and nitrogen cycles. Thermophilic anaerobic bacteria Thermosulfurimonas dismutans and Dissulfuribacter thermophilus, isolated from deep-sea hydrothermal vents, grew autotrophically with elemental sulfur as an electron donor and nitrate as an electron acceptor producing sulfate and ammonium. The genomes of both bacteria contain a gene cluster that encodes a putative nitrate ammonification enzyme system. Nitrate reduction occurs via a Nap-type complex. The reduction of produced nitrite to ammonium does not proceed via the canonical Nrf system because nitrite reductase NrfA is absent in the genomes of both microorganisms. The genome of D. thermophilus encodes a complete sulfate reduction pathway, while the Sox sulfur oxidation system is missing, as shown previously for T. dismutans. Thus, in high-temperature environments, nitrate ammonification with elemental sulfur may represent an unrecognized route of primary biomass production. Moreover, the anaerobic oxidation of sulfur compounds coupled to growth has not previously been demonstrated for the members of Thermodesulfobacteria or Deltaproteobacteria, which were considered exclusively as participants of the reductive branch of the sulfur cycle. PMID:28194142

  2. Allele-specific transcriptional activity of the variable number of tandem repeats of the inducible nitric oxide synthase gene is associated with idiopathic achalasia

    PubMed Central

    Grosso, Michela; Palumbo, Ilaria; Pesce, Marcella; D’Alessandro, Alessandra; Zaninotto, Giovanni; Annese, Vito; Petruzzelli, Raffaella; Izzo, Paola; Sepulveres, Rossana; Bruzzese, Dario; Esposito, Giuseppe; Cuomo, Rosario

    2016-01-01

    Background Polymorphisms of genes involved in the regulation of the immune response are risk factors for achalasia, but their contribution to disease pathogenesis is unknown. Nitric oxide is involved both in immune function and inhibitory neurotransmission. Objective The objective of this article is to assess the association and the functional relevance of the CCTTT-inducible nitric oxide synthase (NOS2) gene promoter polymorphism in achalasia. Methods Genomic DNA was isolated from 181 achalasia patients and 220 controls. Genotyping of the (CCTTT)n repeats was performed by PCR and capillary electrophoresis, and data analyzed by considering the frequency of the different alleles. HT29 cells were transfected with iNOS luciferase promoter-reporter plasmids containing different (CCTTT)n. Results The alleles’ distribution ranged from 7 to 18, with a peak frequency at 12 repeats. Analysis of the allele frequencies revealed that individuals carrying 10 and 13 CCTTT repeats were respectively less and more frequent in achalasia (OR 0.5, 95% CI 0.3–0.5 and OR 1.6, 95% CI 1–2.4, all p < 0.05). Long repeats were also significantly associated with an earlier onset of the disease (OR 1.69, 95% CI 1.13–2.53, p = 0.01). Transfection experiments revealed a similar allele-specific iNOS transcriptional activity. Conclusion The functional polymorphism (CCTTT) of NOS2 promoter is associated with achalasia, likely by an allele-specific modulation of nitric oxide production. PMID:28344787

  3. Size determination and quantification of engineered cerium oxide nanoparticles by flow field-flow fractionation coupled to inductively coupled plasma mass spectrometry.

    PubMed

    Sánchez-García, L; Bolea, E; Laborda, F; Cubel, C; Ferrer, P; Gianolio, D; da Silva, I; Castillo, J R

    2016-03-18

    Facing the lack of studies on characterization and quantification of cerium oxide nanoparticles (CeO2 NPs), whose consumption and release is greatly increasing, this work proposes a method for their sizing and quantification by Flow Field-flow Fractionation (FFFF) coupled to Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). Two modalities of FFFF (Asymmetric Flow- and Hollow Fiber-Flow Field Flow Fractionation, AF4 and HF5, respectively) are compared, and their advantages and limitations discussed. Experimental conditions (carrier composition, pH, ionic strength, crossflow and carrier flow rates) are studied in detail in terms of NP separation, recovery, and repeatability. Size characterization of CeO2 NPs was addressed by different approaches. In the absence of feasible size standards of CeO2 NPs, suspensions of Ag, Au, and SiO2 NPs of known size were investigated. Ag and Au NPs failed to show a comparable behavior to that of the CeO2 NPs, whereas the use of SiO2 NPs provided size estimations in agreement to those predicted by the theory. The latter approach was thus used for characterizing the size of CeO2 NPs in a commercial suspension. Results were in adequate concordance with those achieved by transmission electron microscopy, X-ray diffraction and dynamic light scattering. The quantification of CeO2 NPs in the commercial suspension by AF4-ICP-MS required the use of a CeO2 NPs standards, since the use of ionic cerium resulted in low recoveries (99 ± 9% vs. 73 ± 7%, respectively). A limit of detection of 0.9 μg L(-1) CeO2 corresponding to a number concentration of 1.8 × 1012 L(-1) for NPs of 5 nm was achieved for an injection volume of 100 μL.

  4. Identification and quantification of adducts between oxidized rosmarinic acid and thiol compounds by UHPLC-LTQ-Orbitrap and MALDI-TOF/TOF tandem mass spectrometry.

    PubMed

    Tang, Chang-bo; Zhang, Wan-gang; Dai, Chen; Li, Hui-xia; Xu, Xing-lian; Zhou, Guang-hong

    2015-01-28

    LTQ Orbitrap MS/MS was used to identify the adducts between quinones derived from rosmarinic acid (RosA) and thiol compounds, including cysteine (Cys), glutathione (GSH), and peptides digested from myosin. Two adducts of quinone-RosA/Cys and quinone-RosA/2Cys, one quinone-RosA/GSH adduct, and three quinone-RosA/peptide adducts were identified by extracted ion and MS(2) fragment ion chromatograms. By using MALDI-TOF/TOF MS, the adduction reaction between RosA and myosin in myofibrillar protein isolates was determined, demonstrating that the accurate reaction site was at Cys949 of myosin. The effect of reaction conditions, including stirring time, temperature, and oxidative stress, on the formation of adducts was further investigated. The formation of quinone-RosA/Cys and quinone-RosA/GSH increased with stirring time. Both adducts increased with temperature, whereas the reactivity of the addition reaction of GSH was higher than that of Cys. With increasing oxidation stress, the formation of quinone-RosA/GSH adduct increased and that of quinone-RosA/Cys adduct decreased.

  5. Ultrathin Limit of Exchange Bias Coupling at Oxide Multiferroic/Ferromagnetic Interfaces

    DTIC Science & Technology

    2013-07-12

    control of exchange bias was also shown for an all oxide heterostructure consisting of BFO and La 0.7 Sr 0.3 MnO 3 (LSMO), [ 22 , 23 ] where epitaxial...drastically. This is generally interpreted by considering a strain-induced distortion of MnO 6 octahedra based on the Jahn-Teller distortion theory. [ 39

  6. Photoinduced Cross-Linking of Dynamic Poly(disulfide) Films via Thiol Oxidative Coupling.

    PubMed

    Feillée, Noémi; Chemtob, Abraham; Ley, Christian; Croutxé-Barghorn, Céline; Allonas, Xavier; Ponche, Arnaud; Le Nouen, Didier; Majjad, Hicham; Jacomine, Léandro

    2016-01-01

    Initially developed as an elastomer with an excellent record of barrier and chemical resistance properties, poly(disulfide) has experienced a revival linked to the dynamic nature of the S-S covalent bond. A novel photobase-catalyzed oxidative polymerization of multifunctional thiols to poly(disulfide) network is reported. Based solely on air oxidation, the single-step process is triggered by the photodecarboxylation of a xanthone acetic acid liberating a strong bicyclic guanidine base. Starting with a 1 μm thick film based on trithiol poly(ethylene oxide) oligomer, the UV-mediated oxidation of thiols to disulfides occurs in a matter of minutes both selectively, i.e., without overoxidation, and quantitatively as assessed by a range of spectroscopic techniques. Thiolate formation and film thickness determine the reaction rates and yield. Spatial control of the photopolymerization serves to generate robust micropatterns, while the reductive cleavage of S-S bridges allows the recycling of 40% of the initial thiol groups.

  7. Destruction of commercial pesticides by cerium redox couple mediated electrochemical oxidation process in continuous feed mode.

    PubMed

    Balaji, Subramanian; Chung, Sang Joon; Ryu, Jae-Yong; Moon, Il Shik

    2009-12-30

    Mediated electrochemical oxidation was carried out for the destruction of commercial pesticide formulations using cerium(IV) in nitric acid as the mediator electrolyte solution in a bench scale set up. The mediator oxidant was regenerated in situ using an electrochemical cell. The real application of this sustainable process for toxic organic pollutant destruction lies in its ability for long term continuous operation with continuous organic feeding and oxidant regeneration with feed water removal. In this report we present the results of fully integrated MEO system. The task of operating the continuous feed MEO system for a long time was made possible by continuously removing the feed water using an evaporator set up. The rate of Ce(IV) regeneration in the electrochemical cell and the consumption for the pesticide destruction was matched based on carbon content of the pesticides. It was found that under the optimized experimental conditions for Ce(III) oxidation, organic addition and water removal destruction efficiency of ca. 99% was obtained for all pesticides studied. It was observed that the Ce(IV) concentration was maintained nearly the same throughout the experiment. The stable operation for 6h proved that the process can be used for real applications and for possible scale up for the destruction of larger volumes of toxic organic wastes.

  8. Metallic nanoparticle shape and size effects on aluminum oxide-induced enhancement of exciton-plasmon coupling and quantum dot emission

    SciTech Connect

    Wing, Waylin J.; Sadeghi, Seyed M. Gutha, Rithvik R.; Campbell, Quinn; Mao, Chuanbin

    2015-09-28

    We investigate the shape and size effects of gold metallic nanoparticles on the enhancement of exciton-plasmon coupling and emission of semiconductor quantum dots induced via the simultaneous impact of metal-oxide and plasmonic effects. This enhancement occurs when metallic nanoparticle arrays are separated from the quantum dots by a layered thin film consisting of a high index dielectric material (silicon) and aluminum oxide. Our results show that adding the aluminum oxide layer can increase the degree of polarization of quantum dot emission induced by metallic nanorods by nearly two times, when these nanorods have large aspect ratios. We show when the aspect ratio of these nanorods is reduced to half, the aluminum oxide loses its impact, leading to no improvement in the degree of polarization. These results suggest that a silicon/aluminum oxide layer can significantly enhance exciton-plasmon coupling when quantum dots are in the vicinity of metallic nanoantennas with high aspect ratios.

  9. Metallic nanoparticle shape and size effects on aluminum oxide-induced enhancement of exciton-plasmon coupling and quantum dot emission.

    PubMed

    Wing, Waylin J; Sadeghi, Seyed M; Gutha, Rithvik R; Campbell, Quinn; Mao, Chuanbin

    2015-09-28

    We investigate the shape and size effects of gold metallic nanoparticles on the enhancement of exciton-plasmon coupling and emission of semiconductor quantum dots induced via the simultaneous impact of metal-oxide and plasmonic effects. This enhancement occurs when metallic nanoparticle arrays are separated from the quantum dots by a layered thin film consisting of a high index dielectric material (silicon) and aluminum oxide. Our results show that adding the aluminum oxide layer can increase the degree of polarization of quantum dot emission induced by metallic nanorods by nearly two times, when these nanorods have large aspect ratios. We show when the aspect ratio of these nanorods is reduced to half, the aluminum oxide loses its impact, leading to no improvement in the degree of polarization. These results suggest that a silicon/aluminum oxide layer can significantly enhance exciton-plasmon coupling when quantum dots are in the vicinity of metallic nanoantennas with high aspect ratios.

  10. Ergosterone-coupled Triazol molecules trigger mitochondrial dysfunction, oxidative stress, and acidocalcisomal Ca2+ release in Leishmania mexicana promastigotes

    PubMed Central

    Figarella, K; Marsiccobetre, S; Arocha, I; Colina, W; Hasegawa, M; Rodriguez, M; Rodriguez-Acosta, A; Duszenko, M; Benaim, G; Uzcategui, NL

    2015-01-01

    The protozoan parasite Leishmania causes a variety of sicknesses with different clinical manifestations known as leishmaniasis. The chemotherapy currently in use is not adequate because of their side effects, resistance occurrence, and recurrences. Investigations looking for new targets or new active molecules focus mainly on the disruption of parasite specific pathways. In this sense, ergosterol biosynthesis is one of the most attractive because it does not occur in mammals. Here, we report the synthesis of ergosterone coupled molecules and the characterization of their biological activity on Leishmania mexicana promastigotes. Molecule synthesis involved three steps: ergosterone formation using Jones oxidation, synthesis of Girard reagents, and coupling reaction. All compounds were obtained in good yield and high purity. Results show that ergosterone-triazol molecules (Erg-GTr and Erg-GTr2) exhibit an antiproliferative effect in low micromolar range with a selectivity index ~10 when compared to human dermic fibroblasts. Addition of Erg-GTr or Erg-GTr2 to parasites led to a rapid [Ca2+]cyt increase and acidocalcisomes alkalinization, indicating that Ca2+ was released from this organelle. Evaluation of cell death markers revealed some apoptosis-like indicators, as phosphatidylserine exposure, DNA damage, and cytosolic vacuolization and autophagy exacerbation. Furthermore, mitochondrion hyperpolarization and superoxide production increase were detected already 6 hours after drug addition, denoting that oxidative stress is implicated in triggering the observed phenotype. Taken together our results indicate that ergosterone-triazol coupled molecules induce a regulated cell death process in the parasite and may represent starting point molecules in the search of new chemotherapeutic agents to combat leishmaniasis. PMID:28357313

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

    PubMed

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

    2011-02-01

    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.

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

    PubMed Central

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

    2015-01-01

    COFs represent a class of polymers with designable crystalline structures capable of interacting with active metal nanoparticles to form excellent heterogeneous catalysts. Many valuable ligands/monomers employed in making coordination/organic polymers are prepared via Heck and C-C couplings. Here, we report an amphiphilic triazine COF and the facile single-step loading of Pd0 nanoparticles into it. An 18–20% nano-Pd loading gives highly active composite working in open air at low concentrations (Conc. Pd(0) <0.05 mol%, average TON 1500) catalyzing simultaneous multiple site Heck couplings and C-C couplings using ‘non-boronic acid’ substrates, and exhibits good recyclability with no sign of catalyst leaching. As an oxidation catalyst, it shows 100% conversion of CO to CO2 at 150 °C with no loss of activity with time and between cycles. Both vapor sorptions and contact angle measurements confirm the amphiphilic character of the COF. DFT-TB studies showed the presence of Pd-triazine and Pd-Schiff bond interactions as being favorable. PMID:26057044

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

    PubMed

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

    2015-06-09

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

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

    PubMed

    Honda, Masashi; Oaki, Yuya; Imai, Hiroaki

    2015-06-21

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

  15. Reactive ion etching of indium-tin oxide films by CCl4-based Inductivity Coupled Plasma

    NASA Astrophysics Data System (ADS)

    Juneja, Sucheta; Poletayev, Sergey D.; Fomchenkov, Sergey; Khonina, Svetlana N.; Skidanov, Roman V.; Kazanskiy, Nikolay L.

    2016-08-01

    Indium tin oxide (ITO) films have been a subject of extensive studies in fabrication of micro-electronic devices for opto-electronic applications ranging from anti-reflection coatings to transparent contacts in photovoltaic devices. In this paper, a new and effective way of reactive ion etching of a conducting indium-tin oxide (ITO) film with Carbon tetrachloride (CCl4) has been investigated. CCl4 plasma containing an addition of gases mixture of dissociated argon and oxygen were used. Oxygen is added to increase the etchant percentage whereas argon was used for stabilization of plasma. The etching characteristics obtained with these gaseous mixtures were explained based on plasma etch chemistry and etching regime of ITO films. An etch rate as high as ∼20 nm/min can be achieved with a controlled process parameter such as power density, total flow rate, composition of reactive gases gas and pressure. Our Investigation represents some of the extensive work in this area.

  16. Coupling Graphene Sheets with Iron Oxide Nanoparticles for Energy Storage and Microelectronics

    DTIC Science & Technology

    2015-08-13

    tetrafluoroborate TEA : Triethylamine IPA: Isopropyl alcohol DMF: N,N-Dimethylformamide Distribution A: Approved for public release; distribution is...ligand exchanged nanoparticles is changed as expected due to their interaction with the oxidic surface of the MNP. TEA , DMF RT, 10 h TBTU, TEA ...IPA EtOAc TBTU: O-(Benzotriazol-1-yl)-N,N,N’,N’-tetramethyluronium tetrafluoroborate TEA : Triethylamine IPA: Isopropyl alcohol DMF: N,N

  17. Coupling Graphene Sheets with Iron Oxide Nanoparticles for Energy Storage and Microelectronics

    DTIC Science & Technology

    2015-12-18

    N’,N’-tetramethyluronium tetrafluoroborate TEA : Triethylamine IPA: Isopropyl alcohol DMF: N,N-Dimethylformamide DISTRIBUTION A: Distribution...peak in the ligand exchanged nanoparticles is changed as expected due to their interaction with the oxidic surface of the MNP. TEA , DMF RT...10 h TBTU, TEA , IPA EtOAc TBTU: O-(Benzotriazol-1-yl)-N,N,N’,N’-tetramethyluronium tetrafluoroborate TEA : Triethylamine IPA: Isopropyl alcohol

  18. Lactate Oxidation Coupled to Iron or Electrode Reduction by Geobacter sulfurreducens PCA▿

    PubMed Central

    Call, Douglas F.; Logan, Bruce E.

    2011-01-01

    Geobacter sulfurreducens PCA completely oxidized lactate and reduced iron or an electrode, producing pyruvate and acetate intermediates. Compared to the current produced by Shewanella oneidensis MR-1, G. sulfurreducens PCA produced 10-times-higher current levels in lactate-fed microbial electrolysis cells. The kinetic and comparative analyses reported here suggest a prominent role of G. sulfurreducens strains in metal- and electrode-reducing communities supplied with lactate. PMID:22003020

  19. Microbial nitrate-dependent cyclohexane degradation coupled with anaerobic ammonium oxidation.

    PubMed

    Musat, Florin; Wilkes, Heinz; Behrends, Astrid; Woebken, Dagmar; Widdel, Friedrich

    2010-10-01

    An anaerobic nitrate-reducing enrichment culture was established with a cyclic saturated petroleum hydrocarbon, cyclohexane, the fate of which in anoxic environments has been scarcely investigated. GC-MS showed cyclohexyl