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Sample records for on-line mass separator

  1. Application for the On-line Isotope Mass Separator ISOLDE Facility: the Mass Scan

    CERN Document Server

    Sánchez-Conejo, Jorge

    2003-01-01

    The purpose of the Mass Scan Application is to scan the mass of the ion beam that passes through the GPS (General Purpose Separator) on the On-Line Isotope Mass Separator ISOLDE facility. The application has been developed in Java, making use of the Java Development Kit 1.4 and the PS Java environment.

  2. Application for the On-line Isotope Mass Separator ISOLDE Facility: the Target Heater

    CERN Document Server

    Sánchez-Conejo, Jorge

    2003-01-01

    The purpose of the Heater Application is to heat and cool the target and line used on the On-Line Isotope Mass Separator ISOLDE facility up to a desired temperature selected by the user. The application has been developed in Java, making use of the Java Development Kit 1.4 and the PS Java environment.

  3. An Application for the On-Line Isotope Mass Separator ISOLDE facility: the Mass Control

    CERN Document Server

    Ovalle Gonzalez, E

    2003-01-01

    The Mass Control Application will calculate the magnetic field for both the HRS and GPS separators. The calculation will be carry out according to parameters either entered by the user or taken from other sources.

  4. MASS DEFLECTOR APPLICATION FOR CERN’s ON-LINE ISOTOPE SEPARATOR FACILITY 073

    CERN Document Server

    Sánchez-Conejo, J

    2004-01-01

    The mass deflector application for the General Purpose Separator GPS allows splitting a beam of particles, characterized by a central mass, into two particle beams, which are sent to a high-mass and low-mass beam lines.

  5. MASS DEFLECTOR APPLICATION FOR CERN’s ON-LINE ISOTOPE SEPARATOR FACILITY 077

    CERN Document Server

    Sánchez-Conejo, J

    2004-01-01

    The mass deflector application for the General Purpose Separator GPS allows splitting a beam of particles, characterized by a central mass, into two particle beams, which are sent to a high-mass and low-mass beam lines.

  6. The control system of the CERN-ISOLDE on-line mass-separator facility

    Energy Technology Data Exchange (ETDEWEB)

    Jonsson, O.C.; Bret, A.; Catherall, R.; Deloose, I.; Focker, G.J.; Forkel, D.; Kugler, E.; Olesen, G.; Pace, A.; Ravn, H.L.; Shering, G.; Tengblad, O. (CERN, Geneva (Switzerland)); Borch, O. (Aalborg Univ. (Denmark). Inst. of Electronic Systems); Richard-Serre, C. (IN2P3, 75 - Paris (France)); Torgersen, H.J. (Oslo Univ. (Norway). Dept. of Chemistry); ISOLDE Collaboration

    1992-08-01

    With the move of the ISOLDE facility to the PS-Booster from the now closed Synchro-Cyclotron at CERN, a new control system will be implented for the two separators. Personal computers, based on the Intel 80386 microprocessor running under MS-DOS and Microsoft Windows, are used. Network-wide distributed front end computers, which access the hardware for controls and measurements, are controlled by PC-consoles via a local area network with a PC file server used as a database. (orig.).

  7. The control system of the CERN-ISOLDE on-line mass-separator facility

    Science.gov (United States)

    Jonsson, O. C.; Borch, O.; Bret, A.; Catherall, R.; Deloose, I.; Focker, G. J.; Forkel, D.; Kugler, E.; Olesen, G.; Pace, A.; Ravn, H. L.; Richard-Serre, C.; Shering, G.; Tengblad, O.; Torgersen, H. J.; Isolde Collaboration

    1992-08-01

    With the move of the ISOLDE facility to the PS-Booster from the now closed Synchro-Cyclotron at CERN, a new control system will be implemented for the two separators. Personal computers, based on the Intel 80386 microprocessor running under MS-DOS and Microsoft Windows, are used. Network-wide distributed front end computers, which access the hardware for controls and measurements, are controlled by PC-consoles via a local area network with a PC file server used as a database.

  8. First on-line applications of multi-reflection time-of-flight mass separator at ISOLTRAP and the mass measurement of $^{82}$Zn

    CERN Document Server

    Wolf, Robert

    This thesis describes the implementation and first on-line application of a multi-reflection time-of-flight (MR-ToF) mass analyzer for high-resolution mass separation at the ISOLTRAP mass spectrometer at ISOLDE/CERN. On the one hand, the major objective was to improve ISOLTRAPs mass-measurement capabilities with respect to the ratio of delivered contaminating ions to ions of interest. On the other hand, the time necessary to purify wanted from unwanted species should be reduced as much as possible to enable access to even more exotic nuclei. The device has been set up, optimized and tested at the University of Greifswald before its move to ISOLTRAP. The achieved performance comprises mass resolving powers of up to 200000 reached at observation times of 30ms and a contamination suppression of about four orders of magnitude by use of a Bradbury-Nielsen gate. With the characteristics, it outperforms clearly the so far state-of-the-art purification method of a gas-filled Penning trap. To improve the utilization o...

  9. Solid-state Marx based two-switch voltage modulator for the On-Line Isotope Mass Separator accelerator at the European Organization for Nuclear Research.

    Science.gov (United States)

    Redondo, L M; Silva, J Fernando; Canacsinh, H; Ferrão, N; Mendes, C; Soares, R; Schipper, J; Fowler, A

    2010-07-01

    A new circuit topology is proposed to replace the actual pulse transformer and thyratron based resonant modulator that supplies the 60 kV target potential for the ion acceleration of the On-Line Isotope Mass Separator accelerator, the stability of which is critical for the mass resolution downstream separator, at the European Organization for Nuclear Research. The improved modulator uses two solid-state switches working together, each one based on the Marx generator concept, operating as series and parallel switches, reducing the stress on the series stacked semiconductors, and also as auxiliary pulse generator in order to fulfill the target requirements. Preliminary results of a 10 kV prototype, using 1200 V insulated gate bipolar transistors and capacitors in the solid-state Marx circuits, ten stages each, with an electrical equivalent circuit of the target, are presented, demonstrating both the improved voltage stability and pulse flexibility potential wanted for this new modulator.

  10. Development of the helium-jet fed on-line mass separator RAMA and its application to studies of T/sub z/ = -2 nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Moltz, D.M.

    1979-10-01

    The study of nuclei far from beta stability is hampered greatly when the nuclide of interest decays in a manner identical to that of a nuclide produced in greater yield in the same bombardment. One solution to this problem is through the use of an on-line mass separator. Development of the Berkelely helium-jet fed on-line mass separator RAMA is discussed as applied to studies of the A = 4n, T/sub z/ = -2 nuclides. RAMA (Recoil Atom Mass Analyzer) has typical efficiencies of 0.1% for approx. 75 elements with melting points less than or equal to 2000/sup 0/C. This efficiency permits decay studies to be readily performed on nuclei with production cross sections greater than or equal to 500 ..mu..b for ..gamma..-ray spectroscopy and greater than or equal to 1 ..mu..b for discrete energy charged particle spectroscopy. The mass range on the normalized RAMA focal plane is +- 10%. The quoted efficiency is for a mass resolution of M/..delta..M approx. 300. RAMA has been used to observe two members of the A = 4n, T/sub z/ = -2 series of beta-delayed proton emitters, /sup 20/Mg and /sup 24/Si. Observation of beta-delayed protons from a mass-separated sample of /sup 20/Mg(t/sub 1/2/ approx. 95 ms) establishes the mass-excess of the lowest T = 2 (0/sup +/) state in /sup 20/Na (13.42 +- .05 MeV), thereby completing the mass twenty isospin quintet. A similar measurement of the decay of /sup 24/Si (t/sub 1/2/ approx. 100 ms) establishes the mass-excess of the lowest T = 2 (0/sup +/) state in /sup 24/Al (5.903 +- 0.009 MeV). The mass 24 isospin quintet is incomplete because the mass of /sup 24/Si remains unknown. In both cases, excellent agreement is obtained using only the quadratic form of the isobaric multiplet mass equation (IMME). 79 references.

  11. Improvements to the on-line mass separator, RAMA, and the beta-delayed charged-particle emission of proton-rich sd shell nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Ognibene, Theodore Joseph [Lawrence Berkeley National Lab., CA (United States). Nuclear Science Div.

    1996-03-01

    To overcome the extreme difficulties encountered in the experimental decay studies of proton drip line nuclei, several techniques have been utilized, including a helium-jet transport system, particle identification detectors and mass separation. Improvements to the ion source/extraction region of the He-jet coupled on-line Recoil Atom Mass Analyzer (RAMA) and its target/ion source coupling resulted in significant increases in RAMA efficiencies and its mass resolution, as well as reductions in the overall transit time. At the 88-Inch Cyclotron at LBNL, the decays of 31Cl, 27P and 28P, with half-lives of 150 msec, 260 msec and 270.3 msec, respectively, were examined using a he-jet and low-energy gas ΔE-gas ΔE-silicon E detector telescopes. Total beta-delayed proton branches of 0.3% and 0.07% in 31Cl and 27P, respectively, were estimated. Several proton peaks that had been previously assigned to the decay of 31Cl were shown to be from the decay of 25Si. In 27P, two proton groups at 459 ± 14 keV and 610 ± 11 keV, with intensities of 7 ± 3% and 92 ± 4% relative to the main (100%) group were discovered. The Gamow-Teller component of the preceding beta-decay of each observed proton transition was compared to results from shell model calculations. Finally, a new proton transition was identified, following the β-decay of 28P, at 1,444 ± 12 keV with a 1.7 ± 0.5% relative intensity to the 100% group. Using similar low-energy detector telescopes and the mass separator TISOL at TRIUMF, the 109 msec and 173 msec activities, 17Ne and 33Ar, were studied. A new proton group with energy 729 ± 15 keV was observed following the beta-decay of 17Ne. Several discrepancies between earlier works as to the energies, intensities and assignments of several proton transitions from 17Ne and 33Ar were resolved.

  12. Improvements to the on-line mass separator, RAMA, and the beta-delayed charged-particle emission of proton-rich sd shell nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Ognibene, T.J. [Lawrence Berkeley National Lab., CA (United States). Nuclear Science Div.

    1996-03-01

    To overcome the extreme difficulties encountered in the experimental decay studies of proton drip line nuclei, several techniques have been utilized, including a helium-jet transport system, particle identification detectors and mass separation. Improvements to the ion source/extraction region of the He-jet coupled on-line Recoil Atom Mass Analyzer (RAMA) and its target/ion source coupling resulted in significant increases in RAMA efficiencies and its mass resolution, as well as reductions in the overall transit time. At the 88-Inch Cyclotron at LBNL, the decays of {sup 31}Cl, {sup 27}P and {sup 28}P, with half-lives of 150 msec, 260 msec and 270.3 msec, respectively, were examined using a he-jet and low-energy gas {Delta}E-gas {Delta}E-silicon E detector telescopes. Total beta-delayed proton branches of 0.3% and 0.07% in {sup 31}Cl and {sub 27}P, respectively, were estimated. Several proton peaks that had been previously assigned to the decay of {sup 31}Cl were shown to be from the decay of {sup 25}Si. In {sup 27}P, two proton groups at 459 {+-} 14 keV and 610 {+-} 11 keV, with intensities of 7 {+-} 3% and 92 {+-} 4% relative to the main (100%) group were discovered. The Gamow-Teller component of the preceding beta-decay of each observed proton transition was compared to results from shell model calculations. Finally, a new proton transition was identified, following the {beta}-decay of {sup 28}P, at 1,444 {+-} 12 keV with a 1.7 {+-} 0.5% relative intensity to the 100% group. Using similar low-energy detector telescopes and the mass separator TISOL at TRIUMF, the 109 msec and 173 msec activities, {sup 17}Ne and {sup 33}Ar, were studied. A new proton group with energy 729 {+-} 15 keV was observed following the beta-decay of {sup 17}Ne. Several discrepancies between earlier works as to the energies, intensities and assignments of several proton transitions from {sup 17}Ne and {sup 33}Ar were resolved.

  13. Stability of arsenic peptides in plant extracts: off-line versus on-line parallel elemental and molecular mass spectrometric detection for liquid chromatographic separation.

    Science.gov (United States)

    Bluemlein, Katharina; Raab, Andrea; Feldmann, Jörg

    2009-01-01

    The instability of metal and metalloid complexes during analytical processes has always been an issue of an uncertainty regarding their speciation in plant extracts. Two different speciation protocols were compared regarding the analysis of arsenic phytochelatin (As(III)PC) complexes in fresh plant material. As the final step for separation/detection both methods used RP-HPLC simultaneously coupled to ICP-MS and ES-MS. However, one method was the often used off-line approach using two-dimensional separation, i.e. a pre-cleaning step using size-exclusion chromatography with subsequent fraction collection and freeze-drying prior to the analysis using RP-HPLC-ICP-MS and/or ES-MS. This approach revealed that less than 2% of the total arsenic was bound to peptides such as phytochelatins in the root extract of an arsenate exposed Thunbergia alata, whereas the direct on-line method showed that 83% of arsenic was bound to peptides, mainly as As(III)PC(3) and (GS)As(III)PC(2). Key analytical factors were identified which destabilise the As(III)PCs. The low pH of the mobile phase (0.1% formic acid) using RP-HPLC-ICP-MS/ES-MS stabilises the arsenic peptide complexes in the plant extract as well as the free peptide concentration, as shown by the kinetic disintegration study of the model compound As(III)(GS)(3) at pH 2.2 and 3.8. But only short half-lives of only a few hours were determined for the arsenic glutathione complex. Although As(III)PC(3) showed a ten times higher half-life (23 h) in a plant extract, the pre-cleaning step with subsequent fractionation in a mobile phase of pH 5.6 contributes to the destabilisation of the arsenic peptides in the off-line method. Furthermore, it was found that during a freeze-drying process more than 90% of an As(III)PC(3) complex and smaller free peptides such as PC(2) and PC(3) can be lost. Although the two-dimensional off-line method has been used successfully for other metal complexes, it is concluded here that the fractionation and

  14. Development of an on-line flow injection Sr/matrix separation method for accurate, high-throughput determination of Sr isotope ratios by multiple collector-inductively coupled plasma-mass spectrometry.

    Science.gov (United States)

    Galler, Patrick; Limbeck, Andreas; Boulyga, Sergei F; Stingeder, Gerhard; Hirata, Takafumi; Prohaska, Thomas

    2007-07-01

    This work introduces a newly developed on-line flow injection (FI) Sr/Rb separation method as an alternative to the common, manual Sr/matrix batch separation procedure, since total analysis time is often limited by sample preparation despite the fast rate of data acquisition possible by inductively coupled plasma-mass spectrometers (ICPMS). Separation columns containing approximately 100 muL of Sr-specific resin were used for on-line FI Sr/matrix separation with subsequent determination of (87)Sr/(86)Sr isotope ratios by multiple collector ICPMS. The occurrence of memory effects exhibited by the Sr-specific resin, a major restriction to the repetitive use of this costly material, could successfully be overcome. The method was fully validated by means of certified reference materials. A set of two biological and six geological Sr- and Rb-bearing samples was successfully characterized for its (87)Sr/(86)Sr isotope ratios with precisions of 0.01-0.04% 2 RSD (n = 5-10). Based on our measurements we suggest (87)Sr/(86)Sr isotope ratios of 0.713 15 +/- 0.000 16 (2 SD) and 0.709 31 +/- 0.000 06 (2 SD) for the NIST SRM 1400 bone ash and the NIST SRM 1486 bone meal, respectively. Measured (87)Sr/(86)Sr isotope ratios for five basalt samples are in excellent agreement with published data with deviations from the published value ranging from 0 to 0.03%. A mica sample with a Rb/Sr ratio of approximately 1 was successfully characterized for its (87)Sr/(86)Sr isotope signature to be 0.718 24 +/- 0.000 29 (2 SD) by the proposed method. Synthetic samples with Rb/Sr ratios of up to 10/1 could successfully be measured without significant interferences on mass 87, which would otherwise bias the accuracy and uncertainty of the obtained data.

  15. On-line blind separation of non-stationary signals

    Directory of Open Access Journals (Sweden)

    Todorović-Zarkula Slavica

    2005-01-01

    Full Text Available This paper addresses the problem of blind separation of non-stationary signals. We introduce an on-line separating algorithm for estimation of independent source signals using the assumption of non-stationary of sources. As a separating model, we apply a self-organizing neural network with lateral connections, and define a contrast function based on correlation of the network outputs. A separating algorithm for adaptation of the network weights is derived using the state-space model of the network dynamics, and the extended Kalman filter. Simulation results obtained in blind separation of artificial and real-world signals from their artificial mixtures have shown that separating algorithm based on the extended Kalman filter outperforms stochastic gradient based algorithm both in convergence speed and estimation accuracy.

  16. The Leuven isotope separator on-line laser ion source

    CERN Document Server

    Kudryavtsev, Y; Franchoo, S; Huyse, M; Gentens, J; Kruglov, K; Müller, W F; Prasad, N V S; Raabe, R; Reusen, I; Van den Bergh, P; Van Duppen, P; Van Roosbroeck, J; Vermeeren, L; Weissman, L

    2002-01-01

    An element-selective laser ion source has been used to produce beams of exotic radioactive nuclei and to study their decay properties. The operational principle of the ion source is based on selective resonant laser ionization of nuclear reaction products thermalized and neutralized in a noble gas at high pressure. The ion source has been installed at the Leuven Isotope Separator On-Line (LISOL), which is coupled on-line to the cyclotron accelerator at Louvain-la-Neuve. sup 5 sup 4 sup , sup 5 sup 5 Ni and sup 5 sup 4 sup , sup 5 sup 5 Co isotopes were produced in light-ion-induced fusion reactions. Exotic nickel, cobalt and copper nuclei were produced in proton-induced fission of sup 2 sup 3 sup 8 U. The b decay of the sup 6 sup 8 sup - sup 7 sup 4 Ni, sup 6 sup 7 sup - sup 7 sup 0 Co, sup 7 sup 0 sup - sup 7 sup 5 Cu and sup 1 sup 1 sup 0 sup - sup 1 sup 1 sup 4 Rh isotopes has been studied by means of beta-gamma and gamma-gamma spectroscopy. Recently, the laser ion source has been used to produce neutron-d...

  17. Mass Separation by Metamaterials.

    Science.gov (United States)

    Restrepo-Flórez, Juan Manuel; Maldovan, Martin

    2016-02-25

    Being able to manipulate mass flow is critically important in a variety of physical processes in chemical and biomolecular science. For example, separation and catalytic systems, which requires precise control of mass diffusion, are crucial in the manufacturing of chemicals, crystal growth of semiconductors, waste recovery of biological solutes or chemicals, and production of artificial kidneys. Coordinate transformations and metamaterials are powerful methods to achieve precise manipulation of molecular diffusion. Here, we introduce a novel approach to obtain mass separation based on metamaterials that can sort chemical and biomolecular species by cloaking one compound while concentrating the other. A design strategy to realize such metamaterial using homogeneous isotropic materials is proposed. We present a practical case where a mixture of oxygen and nitrogen is manipulated using a metamaterial that cloaks nitrogen and concentrates oxygen. This work lays the foundation for molecular mass separation in biophysical and chemical systems through metamaterial devices.

  18. Separation of seven arsenic compounds by high-performance liquid chromatography with on-line detection by hydrogen–argon flame atomic absorption spectrometry and inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Hansen, S. H.; Larsen, E. H.; Pritzl, G.

    1992-01-01

    Seven molecular forms of arsenic were separated by anion- and cation-exchange high-performance liquid chromatography (HPLC) with on-line detection by flame atomic absorption spectrometry (FAAS). The interfacing was established by a vented poly(tetrafluoroethylene) capillary tubing connecting...... the HPLC column to the nebulizer of the atomic absorption spectrometer. Arsenite, arsenate, monomethylarsonate (MMA) and dimethylarsinate (DMA) were separated from each other and from the co-injected cationic arsenic compounds, arsenobetaine (AsB), arsenocholine (AsC) and the tetramethylarsonium ion (TMAs......-to-noise ratio of the on-line AAS detector was optimized. This involved the use of the hydrogen-argon-entrained air flame, a slotted tube atom trap in the flame for signal enhancement, electronic noise damping and a high-intensity light source. The detection limits in mu-g cm-3, using 100 mm3 injections...

  19. Separation of seven arsenic compounds by high performance liquid chromatography with on-line detection by hydrogen-argon flame atomic absorption spectrometry and inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Hansen, S. H.; Larsen, Erik Huusfeldt; Pritzl, G.

    1992-01-01

    Seven molecular forms of arsenic were separated by anion- and cation-exchange high-performance liquid chromatography (HPLC) with on-line detection by flame atomic absorption spectrometry (FAAS). The interfacing was established by a vented poly(tetrafluoroethylene) capillary tubing connecting......-to-noise ratio of the on-line AAS detector was optimized. This involved the use of the hydrogen-argon-entrained air flame, a slotted tube atom trap in the flame for signal enhancement, electronic noise damping and a high-intensity light source. The detection limits in mu-g cm-3, using 100 mm3 injections...... the HPLC column to the nebulizer of the atomic absorption spectrometer. Arsenite, arsenate, monomethylarsonate (MMA) and dimethylarsinate (DMA) were separated from each other and from the co-injected cationic arsenic compounds, arsenobetaine (AsB), arsenocholine (AsC) and the tetramethylarsonium ion (TMAs...

  20. On-line separation of refractory hafnium and tantalum isotopes at the ISOCELE separator

    CERN Document Server

    Liang, C F; Obert, J; Paris, P; Putaux, J C

    1981-01-01

    By chemical evaporation technique, neutron deficient hafnium nuclei have been on-line separated at the ISOCELE facility, from the isobar rare-earth elements, in the metal-fluoride HfF/sub 3//sup +/ ion form. Half-lives of /sup 162-165/Hf have been measured. Similarly, tantalum has been selectively separated on the TaF/sub 4//sup +/ form. (4 refs) .

  1. On-Line Synthesis and Analysis by Mass Spectrometry

    Science.gov (United States)

    Bain, Ryan M.; Pulliam, Christopher J.; Raab, Shannon A.; Cooks, R. Graham

    2015-01-01

    In this laboratory experiment, students learn how to use ESI to accelerate chemical synthesis and to couple it with on-line mass spectrometry for structural analysis. The Hantzsch synthesis of symmetric 1,4-dihydropyridines is a classic example of a one-pot reaction in which multiple intermediates can serve to indicate the progress of the reaction…

  2. On-Line Synthesis and Analysis by Mass Spectrometry

    Science.gov (United States)

    Bain, Ryan M.; Pulliam, Christopher J.; Raab, Shannon A.; Cooks, R. Graham

    2015-01-01

    In this laboratory experiment, students learn how to use ESI to accelerate chemical synthesis and to couple it with on-line mass spectrometry for structural analysis. The Hantzsch synthesis of symmetric 1,4-dihydropyridines is a classic example of a one-pot reaction in which multiple intermediates can serve to indicate the progress of the reaction…

  3. On-line multidimensional separation systems for peptide analysis

    NARCIS (Netherlands)

    Stroink, T.

    2005-01-01

    Today, there is an increasing interest in selective and sensitive analysis of proteins and peptides with a relatively high speed. The first chapter of this thesis describes several strategies for the on-line multidimensional analysis of peptides and proteins in biological samples. This overview of t

  4. Proceedings of the isotope separator on-line workshop

    Energy Technology Data Exchange (ETDEWEB)

    Chrien, R E [ed.

    1978-07-01

    Separate abstracts were prepared for thirteen of the papers in this volume. The remaining three have already been cited in ERA, and can be located by reference to the entry CONF-771078-- in the Report Number Index. (RWR)

  5. Recent great impact by an Isotope Separator On-Line (ISOL) in nuclear and radiochemistry.

    Science.gov (United States)

    Sakama, Minoru

    2016-01-01

    On April 9 2015, the Letter article titled "Measurement of the first ionization potential of lawrencium, element 103" is now published at News and Views on Nature (2015) which has been performed by our remarkably Japanese colleagues of nuclear and radiochemistry at JAEA (Japan Atomic Energy Agency). In this review, the author will state that the isotope separator on-line (ISOL) our regularly used, one of mass separation techniques, with a thermal surface ionization makes possible for determining the ionization potential of lawrencium based on the fruitful fundations of developing the ISOL system until now and also ever studying searches for unknown nuclei and these nuclear decay properties around actinide region in the past 20 years.

  6. On-line separation of short-lived beryllium isotopes

    CERN Document Server

    Köster, U; Catherall, R; Fedosseev, V; Georg, U; Huber, G; Jading, Y; Jonsson, O; Koizumi, M; Kratz, K L; Kugler, E; Lettry, Jacques; Mishin, V I; Ravn, H L; Sebastian, V; Tamburella, C; Wöhr, A

    1998-01-01

    With the development of a new laser ionization scheme, it became possible to ionize beryllium efficiently in the hot cavity of the ISOLDE laser ion source. The high target and ion source temperatures enable the release of short-lived beryllium isotopes. Thus all particle-stable beryllium isotopes could be extracted from a standard uranium carbide/graphite target. For the first time the short-lived isotopes /sup 12/Be and /sup 14/Be could be identified at an ISOL facility, /sup 14/Be being among the most short-lived isotopes separated so far at ISOLDE. The release time from the UC/graphite target was studied with several beryllium isotopes. Profiting from the element selectivity of laser ionization, the strong and isotopically pure beam of /sup 12/Be allowed to determine the half- life to T/sub 1/2 /=21.34(23) ms and the probability of beta-delayed neutron emission to P/sub n/=0.48/sub -0.10//sup +0.12/(23 refs).

  7. On-line I-/Te- separation for the AMS analysis of 125I

    Science.gov (United States)

    Charles, C. R. J.; Cornett, R. J.; Zhao, X.-L.; Litherland, A. E.; Kieser, W. E.

    2015-10-01

    The isobar separator for anions (ISA) was used together with a 3 MV tandem accelerator mass spectrometer (AMS) to demonstrate the real time (on-line) separation of Te- from I-. Following the ion source mass spectrometry and major retardation to tens of eV, the ISA uses a radiofrequency quadrupole (RFQ) ion guide to confine and direct I- and associated Te- isobar anions through a gas-reaction cell, where chemical reactions occur at eV energies with the electronegative gas NO2. Anions are subsequently reaccelerated out of the ISA to near original ion source extraction energies for AMS analysis. At 5 mTorr NO2 in the ISA gas-reaction cell, 125Te- was observed to be attenuated by a factor of ∼107 as compared to 127I- that did not experience significant (107 relative to 37Cl- under the same ISA-AMS conditions. The preferential destruction of Te- (and S-) at eV energies in the ISA is likely due to a larger favorable destruction cross-section with NO2. This study is the first demonstration of I-Te anion separation for AMS, and makes possible the use of 125I, free of the contaminant 125Te isobar after suitable sample purification, for future 129I/125I carrier-free analyses of natural samples at ultra-low trace levels.

  8. Optics of mass separator I

    Energy Technology Data Exchange (ETDEWEB)

    Balestrini, S.J.

    1981-07-01

    The ion optics of an existing mass separator are documented. The elctrostatic and magnetic stages are analyzed theoretically, both separately and in combination, by paying particular attention to the ion trajectories, the linear and angular magnifications, and the dispersion. The possibility of converting the magnet into a tunable unit by means of current-carrying elements in the gap is demonstrated. The feasibility of correction coils constructed from printed circuit board is shown.

  9. On-line blind source separation algorithm based on second order statistics

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    An on-line blind source separation (BSS) algorithm is presented in this paper under the assumption that sources are temporarily correlated signals. By using only some of the observed samples in a recursive calculation, the whitening matrix and the rotation matrix could be approximately obtained through the measurement of only one cost function. Simulations show good performance of the algorithm.

  10. On-line experimental results of an argon gas cell-based laser ion source (KEK Isotope Separation System)

    Science.gov (United States)

    Hirayama, Y.; Watanabe, Y. X.; Imai, N.; Ishiyama, H.; Jeong, S. C.; Jung, H. S.; Miyatake, H.; Oyaizu, M.; Kimura, S.; Mukai, M.; Kim, Y. H.; Sonoda, T.; Wada, M.; Huyse, M.; Kudryavtsev, Yu.; Van Duppen, P.

    2016-06-01

    KEK Isotope Separation System (KISS) has been developed at RIKEN to produce neutron rich isotopes with N = 126 to study the β -decay properties for application to astrophysics. The KISS is an element-selective mass-separation system which consists of an argon gas cell-based on laser ion source for atomic number selection and an ISOL mass-separation system. The argon gas cell of KISS is a key component to stop and collect the unstable nuclei produced in a multi-nucleon transfer reaction, where the isotopes of interest will be selectively ionized using laser resonance ionization. We have performed off- and on-line experiments to study the basic properties of the gas cell as well as of the KISS. We successfully extracted the laser-ionized stable 56Fe (direct implantation of a 56Fe beam into the gas cell) atoms and 198Pt (emitted from the 198Pt target by elastic scattering with a 136Xe beam) atoms from the KISS during the commissioning on-line experiments. We furthermore extracted laser-ionized unstable 199Pt atoms and confirmed that the measured half-life was in good agreement with the reported value.

  11. The ISOLDE on-line isotope separator at the 600 MeV Synchro-Cyclotron

    CERN Multimedia

    CERN PhotoLab

    1973-01-01

    Is at present being thoroughly modified and improved, in order to allow for the increased proton beam intensities, resulting from the SC improvement programme. This photograph, taken before the dismantinling of the facility in June 1973, shows the separator analysing magnet (centre background), the collector chamber of the mass-separated ion.

  12. Chemical investigations of isotope separation on line target units for carbon and nitrogen beams

    CERN Document Server

    Franberg, H; Gäggeler, H W; Köster, U

    2006-01-01

    Radioactive ion beams (RIBs) are of significant interest in a number of applications. Isotope separation on line (ISOL) facilities provide RIB with high beam intensities and good beam quality. An atom that is produced within the ISOL target will first diffuse out from the target material. During the effusion towards the transfer line and into the ion source the many contacts with the surrounding surfaces may cause unacceptable delays in the transport and, hence, losses of the shorter-lived isotopes. We performed systematic chemical investigations of adsorption in a temperature and concentration regime relevant for ISOL targets and ion source units, with regard to CO/sub x/ and NOmaterials are potential construction materials for the above-mentioned areas. Off-line and on-line tests have been performed using a gas thermochromatography setup with radioactive tracers. The experiments were performed at the production of tracers for atmospheric chemistry (PROTRAC) facility at the Paul Schener Institute in Villigen...

  13. Recent studies to improve release properties from thick isotope separator on-line fission targets

    CERN Document Server

    Lau, C; Verney, D; Bajeat, O; Ibrahim, F; Clapier, F; Cottereau, E; Donzaud, C; Ducourtieux, M; Essabaa, S; Guillemaud-Müller, D; Hosni, F; Lefort, H; Le Blanc, F; Müller, A C

    2003-01-01

    In the framework of the PARRNe program (Production d'Atomes Radioactifs Riches en Neutrons) of IPN Orsay, various techniques are currently used to characterize the release properties of elements of interest from a UC//X target. On-line studies have been carried out with two plasma ion sources: a Nier-Bernas and a hot plasma ISOLDE- type (the ISOLDE collaboration kindly supplied us a MK5 ion source for these studies). In parallel, the analysis of the chemical and structure properties of some UC//X samples as function of heating conditions has been carried out. Such data are essential to determine optimal conditions for the production of isotopes by the isotope separator on-line (ISOL) technique. First results are presented here for Kr and Ag. Investigations for other kinds of fission targets are planned.

  14. A rotating ball inlet for on-line MALDI mass spectrometry.

    Science.gov (United States)

    Orsnes, H; Graf, T; Degn, H; Murray, K K

    2000-01-01

    The rotating ball inlet (ROBIN) is presented in a new design for on-line matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS). This method uses a capillary to deliver a matrix and analyte solution to the surface of a rotating ball upon which MALDI is carried out. The ball is in contact with a polymer gasket surrounding the capillary. Sample adhering to the surface of the ball is dragged past the gasket into the vacuum of the mass spectrometer where it is irradiated by a pulsed UV laser, and the resulting ions are mass-separated in a linear time-of-flight mass spectrometer. The mechanical sample introduction prevents clogging of the vacuum interface by matrix crystals or frozen solvent. Preliminary results from flow injection analysis (FIA) suggest that the new interface does not introduce a significant peak-tailing or memory effect. The system is capable of 20-30 h of continuous operation with a flow rate of 2 microL/min before cleaning of the ball is needed. With the prototype inlet, concentration detection limits are at the low micromolar level.

  15. On-line cell mass monitoring of Saccharomyces cerevisiae cultivations by multi-wavelength fluorescence

    DEFF Research Database (Denmark)

    Haack, Martin Brian; Eliasson, Anna; Olsson, Lisbeth

    2004-01-01

    The catalyst in bioprocesses, i.e. the cell mass, is one of the most challenging and important variables to monitor in bioprocesses. In the present study, cell mass in cultivations with Saccharomyces cerevisiae was monitored on-line with a non-invasive in situ placed sensor measuring multi......-line monitoring of culture fluorescence can be used for estimation of the cell mass concentration during cultivations....... in a decomposition of the multivariate fluorescent landscape, whereby underlying spectra of the individual intrinsic fluorophors present in the cell mass were estimated. Furthermore, gravimetrically determined cell mass concentration was used together with the fluorescence spectra for calibration and validation...

  16. [Simultaneous determination of 16 organic acids in feed additives by on-line enrichment and ion chromatography-mass spectrometry].

    Science.gov (United States)

    Xiong, Zhiyu; Dong, Ying; Zhou, Hongbin; Yu, Yang; Li, Jing; Sun, Li

    2014-02-01

    A novel analytical method for simultaneous determination of sixteen organic acids by on-line enrichment and ion chromatography-mass spectrometry (IC-MS) was developed. Online enrichment and separation of the organic acids were performed by ion chromatography on a homemade enrichment column and a homemade separation column. The qualitative and quantitative analyses of the organic acids were performed by mass spectrometry in selected ion monitoring (SIM) mode on the basis of atmospheric pressure chemical ionization (APCI) source in negative mode. The sample of 200 microL was injected for the analysis, and the on-line enrichment time was 3 min. The sodium hydroxide solution was used as a gradient elution system. The two columns made it possible to have a low limit of detection due to the good enrichment and separation capability. The sixteen organic acids were separated completely within 30 min. All curves showed good linearity within the test concentration ranges. The limits of detection (LODs) were between 0.01 and 0.22 mg/L, and the average recoveries were between 70.6% and 110.8%. The relative standard deviations (RSDs) were less than 6.3%. The results indicate that this method is simple, rapid, sensitive and accurate for the determination of the organic acids in feed additives.

  17. Electrochemical oxidation and cleavage of peptides analyzed with on-line mass spectrometric detection

    NARCIS (Netherlands)

    Permentier, H.P.; Jurva, U; Barroso, B.; Bruins, A.P.

    2003-01-01

    An on-line electrochernistry/electrospray mass spectrometry system (EC/MS) is described that allows fast analysis of the oxidation products of peptides. A range of peptides was oxidized in an electrochemical cell by application of a potential ramp from 0 to 1.5 V during passage of the sample. Electr

  18. Resonance ionization laser ion sources for on-line isotope separators (invited).

    Science.gov (United States)

    Marsh, B A

    2014-02-01

    A Resonance Ionization Laser Ion Source (RILIS) is today considered an essential component of the majority of Isotope Separator On Line (ISOL) facilities; there are seven laser ion sources currently operational at ISOL facilities worldwide and several more are under development. The ionization mechanism is a highly element selective multi-step resonance photo-absorption process that requires a specifically tailored laser configuration for each chemical element. For some isotopes, isomer selective ionization may even be achieved by exploiting the differences in hyperfine structures of an atomic transition for different nuclear spin states. For many radioactive ion beam experiments, laser resonance ionization is the only means of achieving an acceptable level of beam purity without compromising isotope yield. Furthermore, by performing element selection at the location of the ion source, the propagation of unwanted radioactivity downstream of the target assembly is reduced. Whilst advances in laser technology have improved the performance and reliability of laser ion sources and broadened the range of suitable commercially available laser systems, many recent developments have focused rather on the laser/atom interaction region in the quest for increased selectivity and/or improved spectral resolution. Much of the progress in this area has been achieved by decoupling the laser ionization from competing ionization processes through the use of a laser/atom interaction region that is physically separated from the target chamber. A new application of gas catcher laser ion source technology promises to expand the capabilities of projectile fragmentation facilities through the conversion of otherwise discarded reaction fragments into high-purity low-energy ion beams. A summary of recent RILIS developments and the current status of laser ion sources worldwide is presented.

  19. A test-bench for isotope separator on-line of Beijing radioactive ion-beam facility

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Bing, E-mail: tangb364@126.com; Ma, Ruigang; Huang, Qinghua; Chen, Lihua; Ma, Yingjun; Cui, Baoqun; Jiang, Weisheng

    2013-12-15

    Highlights: • The modular design makes the maintenance of target station easily. • The diagnosis for low intensity beam is solved. • A positive surface ion source has been developed. -- Abstract: A test-bench for isotope separator on-line of Beijing radioactive ion-beam facility (BRISOL) has been built in China Institute of Atomic Energy (CIAE). The test-bench consists of target station, charge exchange cell, mass separator, quadrupole, hexapole, multipole and beam diagnostic system. It is nearly the same configuration as the first stage of BRISOL and all these components will be used on the BRISOL. A series of experiments have been carried out on this test-bench, and the primary results showed that all the components worked well. A Li{sup +} beam has been generated from the positive surface-ionization source and its emittance and the transmission of the beam line have been measured. The design, construction and experimental results of this test-bench have been presented.

  20. Different Ways to On-Line Hyphenate Centrifugal Partition Chromatography and Mass Spectrometry: Application to Prenylated Xanthones from Garcinia mangostana.

    Science.gov (United States)

    Destandau, Emilie; Michel, Thomas; Toribio, Alix; Elfakir, Claire

    2015-11-01

    Centrifugal partition chromatography is a liquid-liquid separation method well adapted for the fractionation or purification of natural compounds from plant extracts. However, following the preparative isolation, the fractions collected must be analysed by high-performance thin-layer chromatography or high-performance liquid chromatography to evaluate their composition and/or their purity. These additional steps are time-consuming and increase the risk of compound degradation. In order to get an instantaneous analysis of fraction content with structural information on the phytochemicals eluted, it is possible to hyphenate on-line centrifugal partition chromatography with mass spectrometry. Depending on the complexity of the extract, two different kinds of centrifugal partition chromatography-mass spectrometry coupling can be performed: centrifugal partition chromatography-mass spectrometry or centrifugal partition chromatography-high-performance liquid chromatography-mass spectrometry coupling. In the first case, one part of the centrifugal partition chromatography effluent is directly introduced in the mass spectrometry ionisation source to identify the eluted compounds, while in the second case, it is directed to a high-performance liquid chromatography-mass spectrometry system where compounds are first separated thanks to high-performance liquid chromatography and then identified using mass spectrometry.

  1. Mass transport and direction dependent battery modeling for accurate on-line power capability prediction

    Energy Technology Data Exchange (ETDEWEB)

    Wiegman, H.L.N. [General Electric Corporate Research and Development, Schenectady, NY (United States)

    2000-07-01

    Some recent advances in battery modeling were discussed with reference to on-line impedance estimates and power performance predictions for aqueous solution, porous electrode cell structures. The objective was to determine which methods accurately estimate a battery's internal state and power capability while operating a charge and sustaining a hybrid electric vehicle (HEV) over a wide range of driving conditions. The enhancements to the Randles-Ershler equivalent electrical model of common cells with lead-acid, nickel-cadmium and nickel-metal hydride chemistries were described. This study also investigated which impedances are sensitive to boundary layer charge concentrations and mass transport limitations. Non-linear impedances were shown to significantly affect the battery's ability to process power. The main advantage of on-line estimating a battery's impedance state and power capability is that the battery can be optimally sized for any application. refs., tabs., figs., append.

  2. Status report of the Jyvaskyla ion guide isotope separator on-line facility

    NARCIS (Netherlands)

    Penttila, H; Dendooven, P; Honkanen, A; Huhta, M; Jauho, PP; Jokinen, A; Lhersonneau, G; Oinonen, M; Parmonen, JM; Perajarvi, K; Aysto, J

    1997-01-01

    The ion guide isotope separator facility IGISOL of the University of Jyvaskyla has been moved to the new K-130 heavy ion cyclotron laboratory. The totally reconstructed facility is described in detail. The primary beams and targets, helium pumping, separator beam line construction and separator beam

  3. Continuation of Mass determinations through a Double Focusing Mass Spectrometer on Line with ISOLDE

    CERN Multimedia

    2002-01-01

    In a previous experiment (1976-77) we have demonstrated the interest and feasibility of atomic mass determinations from the direct measurements of mass ratios on Rb, Cs and Fr isotopes. Masses of long series of isotopes on both side of stability were determined with an accuracy of a few tens to 300 keV (for th exotic). Interesting nuclear structure features could be observed as for example the indication for an onset of deformation, at N~=~60 for Z~=~37, which stimulated further experiments and theoretical calculations. The many mass values, until then unknown, we obtained in our experiments, gave in addition the possibility to make detailed tests of the nuclear mass predictions. Due to improvements on our mass spectrometer (better transmission and higher resolving power) and increased ISOLDE production yields, some new and valuable measurements can be performed. We plan: \\item a) to continue the measurements towards even heavier isotopes and explore the deformation regions which start at |9|7Rb and |1|4|6Cs;...

  4. On-line high speed lipid extraction for nanoflow liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Lee, Ju Yong; Yang, Joon Seon; Park, Se Mi; Byeon, Seul Kee; Moon, Myeong Hee

    2016-09-16

    An on-line lipid extraction method is introduced by utilizing a short capillary extraction column using HILIC and C4 particles prior to nanoflow liquid chromatography-tandem mass spectrometry (nLC-MS/MS). The on-line extraction using a urine sample spiked with PL standards showed similar or slightly higher recovery values (86%-96%) of phospholipids (PLs) compared to those obtained by the conventional off-line extraction based on the Folch method with or without using the air-exposed drying process. In this study, we demonstrated that PL oxidation can occur during the air-exposed drying process of lipid extracts in standard liquid-liquid extraction procedures, which was confirmed by the oxidized PL (OxPL) molecules that were generated from an off-line extraction using a few PL standards. Quantitative comparison of these OxPL species between on- and off-line extraction followed by nLC-MS/MS with multiple reaction monitoring (MRM) analysis showed a significant decrease (2-10 fold) in unwanted OxPL species when on-line extraction was employed. While the number of identified PLs from a urine sample was somewhat lower than those by off-line extraction, the number of OxPLs was significantly reduced (from 70 to 22) with on-line extraction. The new method offers high speed (∼5min) automated extraction of PLs with nLC-MS/MS analysis and presents the possibility of handling a biological sample with a very limited amount of lipids.

  5. The Eurisol report. A feasibility study for a European isotope-separation-on-line radioactive ion beam facility

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2003-12-01

    The Eurisol project aims at a preliminary design study of the next-generation European isotope separation on-line (ISOL) radioactive ion beam (RIB) facility. In this document, the scientific case of high-intensity RIBs using the ISOL method is first summarised, more details being given in appendix A. It includes: 1) the study of atomic nuclei under extreme and so-far unexplored conditions of composition (i.e. as a function of the numbers of protons and neutrons, or the so-called isospin), rotational angular velocity (or spin), density and temperature, 2) the investigation of the nucleosynthesis of heavy elements in the Universe, an important part of nuclear astrophysics, 3) a study of the properties of the fundamental interactions which govern the properties of the universe, and in particular of the violation of some of their symmetries, 4) potential applications of RIBs in solid-state physics and in nuclear medicine, for example, where completely new fields could be opened up by the availability of high-intensity RIBs produced by the ISOL method. The proposed Eurisol facility is then presented, with particular emphasis on its main components: the driver accelerator, the target/ion-source assembly, the mass-selection system and post-accelerator, and the required scientific instrumentation. Special details of these components are given in appendices B to E, respectively. The estimates of the costs of the Eurisol, construction and running costs, have been performed in as much details as is presently possible. The total capital cost (installation manpower cost included) of the project is estimated to be of the order of 630 million Euros within 20%. In general, experience has shown that operational costs per annum for large accelerator facilities are about 10% of the capital cost. (A.C.)

  6. Status report of the Jyvaeskylaeion guide isotope separator on-line facility

    Energy Technology Data Exchange (ETDEWEB)

    Penttilae, H.; Dendooven, P.; Honkanen, A.; Huhta, M.; Jauho, P.P.; Jokinen, A.; Lhersonneau, G.; Oinonen, M.; Parmonen, J.-M.; Peraejaervi, K.; Aeystoe, J. [Jyvaeskylae Univ. (Finland). Dept. of Physics

    1997-04-01

    The ion guide isotope separator facility IGISOL of the University of Jyvaeskylaehas been moved to the new K-130 heavy ion cyclotron laboratory. The totally reconstructed facility is described in detail. The primary beams and targets, helium pumping, separator beam line construction and separator beam diagnostics are discussed. The spectroscopy stations are introduced with illustrative examples from the research program, including beta-delayed proton and neutron spectroscopy, gamma-ray spectroscopy with and without arrays, conversion electron spectroscopy, collinear laser spectroscopy and nuclear level lifetime spectroscopy. (orig.). 15 refs.

  7. High-performance liquid chromatography on-line coupled to high-field NMR and mass spectrometry for structure elucidation of constituents of Hypericum perforatum L

    DEFF Research Database (Denmark)

    Hansen, S. H.; Jensen, A. G.; Cornett, Claus

    1999-01-01

    The on-line separation and structure elucidation of naphthodianthrones, flavonoids, and other constituents of an extract from Hypericum perforatum L, using high performance liquid chromatography (HPLC) coupled on-line with ultraviolet-visible, nuclear magnetic resonance (NMR), and mass spectrometry...... (MS) is described. A conventional reversed-phase HPLC system using ammonium acetate as the buffer substance in the eluent tvas used, and proton NMR spectra were obtained on a 500 MHz NMR instrument. The MS and MS/MS analyses were performed using negative electrospray ionization, In the present study...

  8. Increasing of MERARG experimental performances: on-line fission gas release measurement by mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Pontillon, Y.; Capdevila, H.; Clement, S. [CEA, DEN, DEC, SA3C, LAMIR, F-13108 Saint Paul lez Durance, (France); Guigues, E.; Janulyte, A.; Zerega, Y.; Andre, J. [Aix-Marseille Universite, LISA EA 4672, 13397 MARSEILLE cedex 20, (France)

    2015-07-01

    The MERARG device - implemented at the LECASTAR Hot Laboratory, at the CEA Cadarache - allows characterizing nuclear fuels with respect to the behaviour of fission gases during thermal transients representative of normal or off normal operating nuclear power plant conditions. The fuel is heated in order to extract a part or the total gas inventory it contains. Fission Gas Release (FGR) is actually recorded by mean of both on-line gamma spectrometry station and micro gas chromatography. These two devices monitor the quantity and kinetics of fission gas release rate. They only address {sup 85}Kr radioactive isotope and the elemental quantification of Kr, Xe and He (with a relatively low detection limit in the latter case, typically 5-10 ppm). In order to better estimate the basic mechanisms that promote fission gas release from irradiated nuclear fuels, the CEA fuel study department decided to improve its experimental facility by modifying MERARG to extend the studies of gamma emitter fission gases to all gases (including Helium) with a complete isotopic distribution capability. To match these specifications, a Residual Gas Analyser (RGA) has been chosen as mass spectrometer. This paper presents a review of the main aspects of the qualification/calibration phase of the RGA type analyser. In particular, results recorded over three mass ranges 1-10 u, 80-90 u and 120-140 u in the two classical modes of MERARG, i.e. on-line and off-line measurements are discussed. Results obtained from a standard gas bottle show that the quantitative analysis at a few ppm levels can be achieved for all isotopes of Kr and Xe, as well as masses 2 and 4 u. (authors)

  9. On-line Identification of chiral ofloxacin in milk with an extraction/ionization device coupled to Electrospray Mass Spectrometry.

    Science.gov (United States)

    Wang, Jiang; Jiang, Xiao-Xiao; Zhao, Wei; Hu, Jun; Guan, Qi-Yuan; Xu, Jing-Juan; Chen, Hong-Yuan

    2017-08-15

    The direct separation and analysis of chiral drugs in the complex matrix systems are meaningful and challenging. As the most common broad-spectrum antibiotic, levofloxacin has a strong antibacterial ability, but its enantiomer, dextrofloxacin can cause serious harm to human health. In this work, we reported a rapid on-line extraction/ionization device coupled with Electrospray Mass Spectrometry (ESI-MS) for chiral analysis of ofloxacin enantiomers in complex matrix of milk. Since ofloxacin is difficult to dissolve in water and most organic solvents, the procedure of separating ofloxacin in complex system is often complicated. Using the homemade apparatus, the sample pretreatment process was greatly simplified. Milk sample was directly injected and chiral ofloxacin in the sample was extracted at PTFE membrane for further ionization. It took less than 10s to finish all the procedures including sampling, extraction, reagents mixing, ionization and mass analysis. Utilizing reaction thermodynamics method, trimeric cluster ion [Ni(ΙΙ)(ref)2Ofloxacin-H](+) was formed and collisionally dissociated to get chiral resolution of levofloxacin and dextrofloxacin due to the different relative stabilities of the two diastereomeric clusters produced through the dissociation of Ni(ΙΙ) bound trimeric clusters. With the proposed method, qualitative and quantitative chiral analysis of ofloxacin in milk was successfully achieved in a simple and fast way. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. On-line determination of oxygen isotope ratios of water or ice by mass spectrometry.

    Science.gov (United States)

    Leuenberger, M; Huber, C

    2002-09-15

    Oxygen isotope ratio determination on any of the water phases (water vapor, water, ice) is of great relevance in different research fields such as climate and paleoclimate studies, geological surveys, and hydrological studies. The conventional technique for oxygen isotope measurement involves equilibration with carbon dioxide gas for a given time with a subsequent isotope determination. The equilibration technique is available in different layouts, but all of them are rather time-consuming. Here we report a new on-line technique that processes water samples as well as ice samples. The same principal, CO2 hydration, is used but speeded up by (i) a direct injection and full dissolution of CO2 in the water, (ii) an increased isotope exchange temperature at 50 degrees C, and (iii) a rapid gas extraction by means of an air-permeable membrane into a continuous helium flux supplying the isotope ratio mass spectrometer with the sample gas. The precision is better than 0.1/1000 which is only slightly larger than with the conventional equilibration technique. This on-line technique allows analysis of 1 m of ice with a resolution of 1-3 cm, depending on the meltwater flux, within 1 h. Similarly, continuous and fast analysis can be performed for aqueous samples for hydrological, geological, and perhaps medical applications.

  11. On-line coupling of an ion chromatograph to the ICP-MS: Separations with a cation exchange chromatography column

    Energy Technology Data Exchange (ETDEWEB)

    Roellin, Stefan [Studsvik Nuclear AB, Nykoeping (Sweden)

    1999-12-01

    An ion chromatography system was coupled on-line to the ICP-MS. All separations were made with a cation exchange chromatography column. Fundamental laws about elution parameters affecting individual retention times and elution forms are explained by applying a proper ion exchange mechanism for the isocratic elution (separations with constant eluent concentration) of mono-, di-, tri-, and tetravalent cations and the actinide species MO{sub 2}{sup +} and MO{sub 2}{sup 2+}. A separation method with two eluents has been investigated to separate mono- from divalent ions in order to separate isobaric overlaps of Rb/Sr and Cs/Ba. The ions normally formed by actinides in aqueous solutions in the oxidation states III to VI are M{sup 3+}, M{sup 4+}, MO{sub 2}{sup +} and MO{sub 2}{sup 2+} respectively. Elution parameters were investigated to separate all four actinide species from each other in order to separate isobaric overlaps of the actinides Np, Pu, U and Am. A major question of concern over the possible release of actinides to the environment is the speciation of actinides within their four possible oxidation states. To check the possibility of speciation analysis with ion chromatography, a separation method was investigated to separate U{sup 4+} and UO{sub 2}{sup 2+} without changing the redox species composition during the separation. First results of Pu speciation analysis showed that Pu could be eluted as three different species. Pu(VI) was always eluting at the same time as Np(V). This was surprising as Pu(VI) is expected to have the same chemical characteristics as U(VI) and thus was expected to elute at the same time as U(VI)

  12. Liquid-chromatographic separation and on-line bioluminescence detection of creatine kinase isoenzymes

    Energy Technology Data Exchange (ETDEWEB)

    Bostick, W.D.; Denton, M.S.; Dinsmore, S.R.

    1980-01-01

    Isoenzymes of creatine kinase were separated by anion-exchange chromatography, with use of an elution gradient containing lithium acetate (0.1 to 0.6 mol/L). A stream splitter was used to divert a 5% side stream of column effluent, which was subsequently mixed with the reagents necessary for bioluminescence assay of the separated isoenzymes. The use of the stream splitter greatly decreased the rate of consumption of reagent and, when combined with a peristaltic pumping system, permitted independent control of the side-stream flow rate. Thus both the residence interval in a delay coil in which the ATP reaction product is formed and the bioluminescence emission was monitored in a flow-through fluorometer without use of an external light source or filters. Separation and detection of the isoenzymes of creatine kinase were rapid, sensitive, and highly selective. The incremental decrease of bioluminescence response owing to inhibition by the ions in the eluent was less than 31% across the entire gradient.

  13. Development of an Ionization Scheme for Gold using the Selective Laser Ion Source at the On-Line Isotope Separator ISOLDE

    CERN Document Server

    Fedosseev, V; Marsh, B A; CERN. Geneva. AB Department

    2006-01-01

    At the ISOLDE on-line isotope separation facility, the resonance ionization laser ion source (RILIS) can be used to ionize reaction products as they effuse from the target. The RILIS process of laser step-wise resonance ionization of atoms in a hot metal cavity provides a highly element selective stage in the preparation of the radioactive ion beam. As a result, the ISOLDE mass separators can provide beams of a chosen isotope with greatly reduced isobaric contamination. The number of elements available at RILIS has been extended to 26, with the addition of a new three-step ionization scheme for gold. The optimal ionization scheme was determined during an extensive study of the atomic energy levels and auto-ionizing states of gold, carried out by means of in-source resonance ionization spectroscopy. Details of the ionization scheme and a summary of the spectroscopy study are presented.

  14. On line separation of overlapped signals from multi-time photons for the GEM-based detection system

    Science.gov (United States)

    Czarski, T.; Pozniak, K. T.; Chernyshova, M.; Malinowski, K.; Kasprowicz, G.; Kolasinski, P.; Krawczyk, R.; Wojenski, A.; Zabolotny, W.

    2015-09-01

    The Triple Gas Electron Multiplier (T-GEM) is presented as soft X-ray (SXR) energy and position sensitive detector for high-resolution X-ray diagnostics of magnetic confinement fusion plasmas. Multi-channel measurement system and serial data acquisition for X-ray energy and position recognition is described. Fundamental characteristics are presented for two dimensional detector structure. Typical signals of ADC - Analog to Digital Converter are considered for charge value and position estimation. Coinciding signals for high flux radiation cause the problem for cluster charge identification. The amplifier with shaper determines time characteristics and limits the pulses frequency. Separation of coincided signals was introduced and verified for simulation experiments. On line separation of overlapped signals was implemented applying the FPGA technology with relatively simple firmware procedure. Representative results for reconstruction of coinciding signals are demonstrated.

  15. First on-line mass measurements at SHIPTRAP and mass determinations of neutron-rich Fr and Ra isotopes at ISOLTRAP

    CERN Document Server

    Rahaman, Saidu

    SHIPTRAP is an ion trap facility behind the velocity filter SHIP at GSI/Darmstadt. Its aim are precision studies of transuranium nuclides produced in a fusion reaction and separated by SHIP. The current set-up for high-precision mass measurements consists of three main functional parts: (i) a gas cell for stopping the energetic ions from SHIP, (ii) radiofrequency quadrupole structures to cool and to bunch the ions extracted from the gas cell, and (iii) a superconducting magnet with two cylindrical Penning traps at a field strength of 7 T. In this work the Penning trap system has been installed and extensively characterized. The first on-line mass measurements of short-lived nuclides were carried out and the masses of $^{147}$Er and $^{148}$Er could be experimentally determined for the first time. Here a relative mass uncertainty of $\\delta$ m/m of about 1$\\times$ 10$^{-6}$ was achieved. Furthermore the masses of heavy neutron-rich $^{229-232}$Ra and $^{230}$Fr isotopes have been determined with a relative m...

  16. On-line monitoring of control rod integrity in BWRs using a mass spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Larsson, I., E-mail: irina@nephy.chalmers.se [Chalmers University of Technology, SE-412 96 Gothenburg (Sweden); Loner, H.; Ammon, K. [Kernkraftwerk Leibstadt, CH-5325 Leibstadt (Switzerland); Sihver, L. [Chalmers University of Technology, SE-412 96 Gothenburg (Sweden); Ledergerber, G. [Kernkraftwerk Leibstadt, CH-5325 Leibstadt (Switzerland)

    2013-01-11

    Surveillance of fuel and control rod integrity in the core of a boiling water reactor is essential for maintaining a safe and reliable operation. Control rods of a boiling water reactor are mainly filled with boron carbide as a neutron absorber. Due to the irradiation of boron with neutrons, a continuous production of lithium and helium will occur inside a control rod. Most of the created helium will be retained in the boron carbide lattice; however a small part will escape into the void volume of the control blade. Therefore the integrity of control rods during operation can efficiently be followed by on-line measurements of helium concentration in the reactor off-gas system using a mass spectrometer. Since helium is a fill gas in fuel rods, the same method is a useful early warning system for primary fuel failures. In this paper, we introduce an on-line helium detector system which is installed at the nuclear power plant in Leibstadt. Furthermore the measuring experiences of control rod failure detection at the plant are presented. Different causes of increased helium levels in the off-gas system have been distinguished. There are spontaneous helium releases as well as helium releases caused by changed conditions in the reactor (power reduction, control rod movement, etc.). Helium peaks can also be characterized according to the released amount of helium, the peak shape and the duration of the release, which leads to different interpretations of the release mechanisms. In addition, the measured amount of released helium from a 50 days period (280 l) is also compared to the calculated amount of produced helium from the washed out boron during the same time period (190 l).

  17. On-line monitoring of control rod integrity in BWRs using a mass spectrometer

    Science.gov (United States)

    Larsson, I.; Loner, H.; Ammon, K.; Sihver, L.; Ledergerber, G.

    2013-01-01

    Surveillance of fuel and control rod integrity in the core of a boiling water reactor is essential for maintaining a safe and reliable operation. Control rods of a boiling water reactor are mainly filled with boron carbide as a neutron absorber. Due to the irradiation of boron with neutrons, a continuous production of lithium and helium will occur inside a control rod. Most of the created helium will be retained in the boron carbide lattice; however a small part will escape into the void volume of the control blade. Therefore the integrity of control rods during operation can efficiently be followed by on-line measurements of helium concentration in the reactor off-gas system using a mass spectrometer. Since helium is a fill gas in fuel rods, the same method is a useful early warning system for primary fuel failures. In this paper, we introduce an on-line helium detector system which is installed at the nuclear power plant in Leibstadt. Furthermore the measuring experiences of control rod failure detection at the plant are presented. Different causes of increased helium levels in the off-gas system have been distinguished. There are spontaneous helium releases as well as helium releases caused by changed conditions in the reactor (power reduction, control rod movement, etc.). Helium peaks can also be characterized according to the released amount of helium, the peak shape and the duration of the release, which leads to different interpretations of the release mechanisms. In addition, the measured amount of released helium from a 50 days period (280 l) is also compared to the calculated amount of produced helium from the washed out boron during the same time period (190 l).

  18. SPIRAL2/DESIR high resolution mass separator

    Energy Technology Data Exchange (ETDEWEB)

    Kurtukian-Nieto, T., E-mail: kurtukia@cenbg.in2p3.fr [Centre d’Études Nucléaires de Bordeaux Gradignan, Université Bordeaux 1-CNRS/IN2P3, BP 120, F-33175 Gradignan Cedex (France); Baartman, R. [TRIUMF, 4004 Wesbrook Mall, Vancouver B.C., V6T 2A3 (Canada); Blank, B.; Chiron, T. [Centre d’Études Nucléaires de Bordeaux Gradignan, Université Bordeaux 1-CNRS/IN2P3, BP 120, F-33175 Gradignan Cedex (France); Davids, C. [Physics Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Delalee, F. [Centre d’Études Nucléaires de Bordeaux Gradignan, Université Bordeaux 1-CNRS/IN2P3, BP 120, F-33175 Gradignan Cedex (France); Duval, M. [GANIL, CEA/DSM-CNRS/IN2P3, Bd Henri Becquerel, BP 55027, F-14076 Caen Cedex 5 (France); El Abbeir, S.; Fournier, A. [Centre d’Études Nucléaires de Bordeaux Gradignan, Université Bordeaux 1-CNRS/IN2P3, BP 120, F-33175 Gradignan Cedex (France); Lunney, D. [CSNSM-IN2P3-CNRS, Université de Paris Sud, F-91405 Orsay (France); Méot, F. [BNL, Upton, Long Island, New York (United States); Serani, L. [Centre d’Études Nucléaires de Bordeaux Gradignan, Université Bordeaux 1-CNRS/IN2P3, BP 120, F-33175 Gradignan Cedex (France); Stodel, M.-H.; Varenne, F. [GANIL, CEA/DSM-CNRS/IN2P3, Bd Henri Becquerel, BP 55027, F-14076 Caen Cedex 5 (France); and others

    2013-12-15

    DESIR is the low-energy part of the SPIRAL2 ISOL facility under construction at GANIL. DESIR includes a high-resolution mass separator (HRS) with a designed resolving power m/Δm of 31,000 for a 1 π-mm-mrad beam emittance, obtained using a high-intensity beam cooling device. The proposed design consists of two 90-degree magnetic dipoles, complemented by electrostatic quadrupoles, sextupoles, and a multipole, arranged in a symmetric configuration to minimize aberrations. A detailed description of the design and results of extensive simulations are given.

  19. Proteolysis in microfluidic droplets: an approach to interface protein separation and peptide mass spectrometry

    OpenAIRE

    Ji, Ji; Nie, Lei; Qiao, Liang; Li, Yixin; Guo, Liping; Liu, Baohong; Yang, Pengyuan; Girault, Hubert H.

    2012-01-01

    A versatile microreactor protocol based on microfluidic droplets has been developed for on-line protein digestion. Proteins separated by liquid chromatography are fractionated in water-in-oil droplets and digested in sequence. The microfluidic reactor acts also as an electrospray ionization emitter for mass spectrometry analysis of the peptides produced in the individual droplets. Each droplet is an enzymatic micro-reaction unit with efficient proteolysis due to rapid mixing, enhanced mass tr...

  20. Hyphenating size-exclusion chromatography with electrospray mass spectrometry; using on-line liquid-liquid extraction to study the lipid composition of lipoprotein particles.

    Science.gov (United States)

    Osei, Michael; Griffin, Julian L; Koulman, Albert

    2015-11-15

    Lipoproteins belong to the most commonly measured clinical biochemical parameters. Lipidomics is an orthogonal approach and aims to profile the individual lipid molecules that jointly form the lipoprotein particles. However, in the first step of the extraction of lipid molecules from serum, an organic solvent is used leading to dissociation of the lipoproteins. Thus far it has been impossible to combine lipidomics and lipoprotein analysis in one analytical system. Human plasma was diluted in phosphate-buffered saline (PBS) and injected onto a Superose 6 PC 3.2 column with PBS as a mobile phase to separate lipoproteins. The eluent was led to a Syrris FLLEX module, which also received CHCl3 /MeOH (3:1). The two phases were mixed and subsequently separated using a Teflon membrane in an especially designed pressurized flow chamber. The organic phase was led to a standard electrospray source of an Orbitrap mass spectrometer. Size-exclusion chromatography (SEC) has been commonly applied to separate lipoproteins and is considered a practical alternative to ultracentrifugation. Through the on-line liquid-liquid extraction method it becomes possible to obtained detailed mass spectra of lipids across different lipoprotein fractions. The extracted ion chromatograms of specific lipid signals showed their distribution against the size of lipoprotein particles. The application of on-line liquid-liquid extraction allows for the continuous electrospray-based mass spectral analysis of SEC eluent, providing the detailed lipid composition of lipoprotein particles separated by size. This approach provides new possibilities for the study of the biochemistry of lipoproteins. © 2015 The Authors. Rapid Communications in Mass Spectrometry Published by John Wiley & Sons Ltd.

  1. First Responder Weapons of Mass Destruction Training Using Massively Multiplayer On-Line Gaming

    Science.gov (United States)

    2004-06-01

    Washington, DC. 1997. p. 16. 150 Kimery, Anthony. p. 24. 151 _____, “$7.7 Million Expansion for TEEX Training Complex.” Texas Engineering... TEEX Training Complex.” Texas Engineering Extension Service. 26 October 1999. Texas. Database available on line at http://teexweb.tamu.edu

  2. Operation of a high temperature ion source at the helium-jet on-line isotope separator facility HELIOS

    Energy Technology Data Exchange (ETDEWEB)

    Bruegger, M.; Hildebrand, N.; Karlewski, T.; Trautmann, N. (Mainz Univ. (Germany, F.R.). Inst. fuer Kernchemie); Mazumdar, A.K. (Marburg Univ. (Germany, F.R.). Fachbereich Physik); Herrmann, G. (Mainz Univ. (Germany, F.R.). Inst. fuer Kernchemie; Gesellschaft fuer Schwerionenforschung m.b.H., Darmstadt (Germany, F.R.))

    1985-02-01

    The performance of a high temperature ion source coupled to a helium gas-jet transport system for an efficient mass separation of neutron-rich alkaline earth and lanthanide isotopes is reported and the results of overall efficiency measurements using different cluster materials in the gas-jet are given. A fast, microprocessor controlled tape transport system for ..gamma..-spectroscopic studies on short-lived isotopes is described. Some results on the decay of 3.8sub(-s) /sup 152/Pr are presented.

  3. Production of chemically reactive radioactive ion beams through on-line separation; Production de faisceaux d'ions radioactifs chimiquement reactifs par separation en ligne

    Energy Technology Data Exchange (ETDEWEB)

    Joinet, A

    2003-10-01

    The ISOL (isotope separation on line) allows the production of secondary radioactive ion beams through spallation or fragmentation or fission reactions that take place in a thick target bombarded by a high intensity primary beam. The challenge is to increase the intensity and purity of the radioactive beam. The optimization of the system target/source requires the right choice of material for the target by taking into account the stability of the material, its reactivity and the ionization method used. The target is an essential part of the system because radioactive elements are generated in it and are released more or less quickly. Tests have been made in order to select the best fitted material for the release of S, Se, Te, Ge and Sn. Materials tested as target filling are: ZrO{sub 2}, Nb, Ti, V,TiO{sub 2}, CeO{sub x}, ThO{sub 2}, C, ZrC{sub 4} and VC). Other molecules such as: COSe, COS, SeS, COTe, GeS, SiS, SnS have been studied to ease the extraction of recoil nuclei (Se, S, Te, Ge and Sn) produced inside the target.

  4. Speciation of four selenium compounds using high performance liquid chromatography with on-line detection by inductively coupled plasma mass spectrometry or flame atomic absorption spectrometry

    DEFF Research Database (Denmark)

    Pedersen, Gitte Alsing; Larsen, Erik Huusfeldt

    1997-01-01

    An analytical method for the speciation of selenomethionine, selenocystine, selenite and selenate by high performance liquid chromatography (HPLC) with atomic spectrometric detection is presented. An organic polymeric strong anion exchange column was used as the stationary phase in combination...... with an aqueous solution of 6 mmol L-1 of salicylate ion at pH 8.5 as the mobile phase which allowed the isocratic separation of the four selenium analytes within 8 minutes. The separated selenium species were detected on-line by flame atomic absorption spectrometry (FAAS) or inductively coupled plasma mass...... spectrometry (ICP-MS). The signal-to-noise ratio of the FAAS detector was optimized using a hydrogen-argon entrained-air flame and a slotted-tube atom trap (STAT) in the flame. The limit of detection (3 sigma) achieved by the HPLC-FAAS system was 1 mg L-1 of selenium (100 mu L injections) for each of the four...

  5. On-line immunoaffinity solid-phase extraction capillary electrophoresis mass spectrometry for the analysis of large biomolecules: a preliminary report.

    Science.gov (United States)

    Medina-Casanellas, Silvia; Benavente, Fernando; Giménez, Estela; Barbosa, José; Sanz-Nebot, Victoria

    2014-08-01

    The analysis of large biomolecules by on-line immunoaffinity solid-phase extraction capillary electrophoresis mass spectrometry (IA-SPE-CE-MS) remains unexplored because of the complex issues that need to be addressed. In this preliminary study, we used the human glycoprotein transferrin (Tf) as a model of a large biomolecule. First, we established by CE-UV a novel method compatible with IA-SPE-CE-MS, based on the use of a fused silica capillary coated with an anionic derivative of polyacrylamide (UltraTrol(TM) Dynamic Pre-Coat High Normal, HN) to prevent protein adsorption. The methodology allowed the detection of the most abundant Tf sialoforms. Repeatability studies demonstrated high stability of the coated capillaries, which was required for on-line immunoextraction and MS detection. IA-SPE-CE-UV and IA-SPE-CE-MS methods were optimized for the analysis of Tf standards and human serum samples using a laboratory-made IA sorbent. Three peaks corresponding to Tf were detected with UV detection when on-line immunoextraction was applied to the standards. The use of MS detection, however, reduced the resolution of the electrophoretic separation. Finally, we demonstrated that it was possible to detect Tf in human serum samples, after off-line serum sample de-salting by centrifugal filtration.

  6. On-line cell mass monitoring of Saccharomyces cerevisiae cultivations by multi-wavelength fluorescence

    DEFF Research Database (Denmark)

    Haack, Martin Brian; Eliasson, Anna; Olsson, Lisbeth

    2004-01-01

    -wavelength culture fluorescence. The excitation wavelength ranged from 270 to 550 nm with 20 nm steps and the emission wavelength range was from 310 to 590 nm also with 20 nm steps. The obtained spectra were analysed chemometrically with the multi-way technique, parallel factor analysis (PARAFAC), resulting...... in a decomposition of the multivariate fluorescent landscape, whereby underlying spectra of the individual intrinsic fluorophors present in the cell mass were estimated. Furthermore, gravimetrically determined cell mass concentration was used together with the fluorescence spectra for calibration and validation......-line monitoring of culture fluorescence can be used for estimation of the cell mass concentration during cultivations....

  7. On-line combination of high performance liquid chromatography with comprehensive two-dimensional gas chromatography-triple quadrupole mass spectrometry: a proof of principle study.

    Science.gov (United States)

    Zoccali, Mariosimone; Tranchida, Peter Quinto; Mondello, Luigi

    2015-02-03

    The present contribution is focused on the on-line combination of high performance liquid chromatography (HPLC), cryogenically modulated comprehensive two-dimensional gas chromatography (GC × GC), and triple quadrupole mass spectrometry (QqQ MS), generating a very powerful unified separation-science tool. The instrument can be used in seven different combinations ranging from one-dimensional HPLC with a photodiode array detector to on-line LC × GC × GC/QqQ MS. The main focus of the present research is directed to the LC-GC × GC/QqQ MS configuration, with its analytical potential shown in a proof-of-principle study involving a very complex sample, namely, coal tar. Specifically, a normal-phase LC process enabled the separation of three classes of coal tar compounds: (1) nonaromatic hydrocarbons; (2) unsaturated compounds (with and without S); (3) oxygenated constituents. The HPLC fractions were transferred to the GC × GC instrument via a syringe-based interface mounted on an autosampler. Each fraction was subjected to a specific programmed temperature vaporizer GC × GC/QqQ MS untargeted or targeted analysis. For example, the coal tar S-containing compounds were pinpointed through multiple-reaction-monitoring analysis, while full-scan information was attained for the oxygenated constituents.

  8. A Stable Isotope Mass Marker for On-line Isotope Separator

    Institute of Scientific and Technical Information of China (English)

    1996-01-01

    AStableIsotopeMassMarkerforOn-lineIsotopeSeparator¥ZhaoJinhua;WangTongqin;GuoBinandFanHongmeiSofarattheHIR,FLon-lilleisotopes...

  9. Continuous Determination of High-Vapor Phase Concentrations of Tetrachloroethylene Using On-Line Mass Spectrometry

    Science.gov (United States)

    A method was developed to determine the vapor concentration of tetrachloroethylene (PCE) at and below its equilibrium vapor phase concentration, 168,000 μg/L (25°C). Vapor samples were drawn by vacuum into a six-port sampling valve and injected through a jet separator into an io...

  10. Rotation and instabilities for isotope and mass separation

    Science.gov (United States)

    Rax, J.-M.; Gueroult, R.

    2016-10-01

    Rotating plasmas have the potential to offer unique capabilities for isotope and mass separation. Among the various electric and magnetic field configurations offering mass separation capabilities, rotating plasmas produced through static or oscillating fields are shown to be a leading candidate for tackling the unsolved problem of large-scale plasma separation. The successful development and deployment of industrial-scale plasma separation technologies could, among many other applications, provide an innovative path towards advanced sustainable nuclear energy. In this context, the potential and versatility of plasma rotation induced by rotating magnetic fields is uncovered and analysed. Analytical stability diagrams are derived from rotating ion orbits as a function of ion mass. Based on these findings, the basic principles of a rotating field plasma separator are then introduced. In light of these results, challenges associated with this original separation process are underlined, and the main directions for a future research program aimed at this important unsolved problem of applied plasma physics are identified.

  11. The on-line analysis of aerosol-delivered pharmaceuticals via single particle aerosol mass spectrometry.

    Science.gov (United States)

    Morrical, Bradley D; Balaxi, Maria; Fergenson, David

    2015-07-15

    The use of single particle aerosol mass spectrometry (SPAMS) was evaluated for the analysis of inhaled pharmaceuticals to determine the mass distribution of the individual active pharmaceutical ingredients (API) in both single ingredient and combination drug products. SPAMS is an analytical technique where the individual aerodynamic diameters and chemical compositions of many aerosol particles are determined in real-time. The analysis was performed using a Livermore Instruments SPAMS 3.0, which allowed the efficient analysis of aerosol particles with broad size distributions and can acquire data even under a very large particle load. Data similar to what would normally require roughly three days of experimentation and analysis was collected in a five minute period and analyzed automatically. The results were computed to be comparable to those returned by a typical Next Generation Impactor (NGI) particle size distribution experiment.

  12. On-line Electrogeneration of Copper-Peptide Complexes in Microspray Mass Spectrometry

    OpenAIRE

    Prudent, M; Girault, H H

    2008-01-01

    The interaction of copper ions with peptides was investigated by electrospray mass spectrometry. Two electrospray micro-emitters were compared, the first one with a platinum electrode using a copper(II) electrolyte solution containing a peptide sample, and the second one with a sacrificial copper anode in a water/methanol solution containing only a peptide (i.e., angiotensin III, bradykinin, or Leu-enkephalin). The former yielded mainly Cu2 complexes either with histidine residues or with th...

  13. Noninvasive Detection of the Gases Inside the Sealed Batteries by the On-line Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    Xiao Rong ZHOU; Pei Fang LIU; Lin ZHUANG; Jun Tao LU

    2004-01-01

    Mass spectrometer is connected through an adaptor to a sealed small battery to probe the gas phase changes inside the battery. The factors influencing the response time are analyzed with a simplified model. The feasibility of the new technique is demonstrated with a Ni-Cd battery, showing different profiles of MS intensities for O2 and H2. Compared with gas chromatography, this technique has the advantage of being noninvasive and should be useful for the study and diagnostic examination of small sealed batteries.

  14. Selective Fluorination and Separation of Metals with NF3 for Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Clark, Richard A.; Barinaga, Charles J.; McNamara, Bruce K.; Schwantes, Jon M.; Ballou, Nathan E.

    2016-03-01

    We report recent progress on the development of a new methodology based on the generation of volatile metal fluorides through the use of nitrogen trifluoride (NF3), and the separation and measurement of these metal fluorides by electron ionization mass spectrometry. Though unreactive under ambient conditions, NF3 reacts selectively at specified temperatures with various metal-containing species to form volatile metal fluorides. Utilizing these species-dependent traits, elements of a sample may be sequentially produced and thus separated on-line. Metals were reacted inside a thermogravimetric analyzer, the gas outlet of which was directly coupled to a quadrupole mass spectrometer with an electron impact ionization source via a molecular leak valve. We present results of this project including the electron ionization mass spectrum of gaseous tellurium hexafluoride.

  15. Theoretical and experimental comparison of one dimensional versus on-line comprehensive two dimensional liquid chromatography for optimized sub-hour separations of complex peptide samples.

    Science.gov (United States)

    Sarrut, Morgan; Rouvière, Florent; Heinisch, Sabine

    2017-05-19

    This study was devoted to the search for conditions leading to highly efficient sub-hour separations of complex peptide samples with the objective of coupling to mass spectrometry. In this context, conditions for one dimensional reversed phase liquid chromatography (1D-RPLC) were optimized on the basis of a kinetic approach while conditions for on-line comprehensive two-dimensional liquid chromatography using reversed phase in both dimensions (on-line RPLCxRPLC) were optimized on the basis of a Pareto-optimal approach. Maximizing the peak capacity while minimizing the dilution factor for different analysis times (down to 5min) were the two objectives under consideration. For gradient times between 5 and 60min, 15cm was found to be the best column length in RPLC with sub-2μm particles under 800bar as system pressure. In RPLCxRPLC, for less than one hour as first dimension gradient time, the sampling rate was found to be a key parameter in addition to conventional parameters including column dimension, particle size, flow-rate and gradient conditions in both dimensions. It was shown that the optimum sampling rate was as low as one fraction per peak for very short gradient times (i.e. below 10min). The quality descriptors obtained under optimized RPLCxRPLC conditions were compared to those obtained under optimized RPLC conditions. Our experimental results for peptides, obtained with state of the art instrumentation, showed that RPLCxRPLC could outperform 1D-RPLC for gradient times longer than 5min. In 60min, the same peak intensity (same dilution) was observed with both techniques but with a 3-fold lower injected amount in RPLCxRPLC. A significant increase of the signal-to-noise ratio mainly due to a strong noise reduction was observed in RPLCxRPLC-MS compared to the one in 1D-RPLC-MS making RPLCxRPLC-MS a promising technique for peptide identification in complex matrices. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. On-line electrogeneration of copper-peptide complexes in microspray mass spectrometry.

    Science.gov (United States)

    Prudent, Michel; Girault, Hubert H

    2008-04-01

    The interaction of copper ions with peptides was investigated by electrospray mass spectrometry. Two electrospray micro-emitters were compared, the first one with a platinum electrode using a copper(II) electrolyte solution containing a peptide sample, and the second one with a sacrificial copper anode in a water/methanol solution containing only a peptide (i.e., angiotensin III, bradykinin, or Leu-enkephalin). The former yielded mainly Cu(2+) complexes either with histidine residues or with the peptide backbone (Cu(+) complexes can be also formed due to gas-phase reactions), whereas the latter can generate a mixture of both Cu(+) and Cu(2+) aqueous complexes that yield different complexation patterns. This study shows that electrospray emitters with soluble copper anodes enable the study of Cu(I)-peptide complexes in solution.

  17. Precise Measurement of Separation Between Two Spherical Source Masses

    Institute of Scientific and Technical Information of China (English)

    陈德才; 罗俊; 胡忠坤; 赵亮

    2004-01-01

    A driving gauge method is performed to determine the separation between two spherical source masses in the measurement of Newtonian gravitational constant G. The experimental result shows that the uncertainty of determining the separation is about 0.35μm, which would contribute an uncertainty of 7.3ppm to the value of G.

  18. Analysis of recombinant Schistosoma mansoni antigen rSmp28 by on-line liquid chromatography-mass spectrometry combined with sodium dodecyl sulfate polyacrylamide gel electrophoresis

    NARCIS (Netherlands)

    Klarskov, K.; Roecklin, D.; Bouchon, B.; Sabatie, J.; Van Dorsselaer, A.; Bischoff, Rainer

    1994-01-01

    A recombinant Schistosoma mansoni antigen produced in Saccharomyces cerevisiae and purified by glutathione-Sepharose affinity chromatography was analyzed by tryptic peptide mapping using on-line reversed-phase high-performance liquid chromatography pneumatically assisted electrospray mass

  19. Membrane device and process for mass exchange, separation, and filtration

    Science.gov (United States)

    Liu, Wei; Canfield, Nathan L.

    2016-11-15

    A membrane device and processes for fabrication and for using are disclosed. The membrane device may include a number of porous metal membranes that provide a high membrane surface area per unit volume. The membrane device provides various operation modes that enhance throughput and selectivity for mass exchange, mass transfer, separation, and/or filtration applications between feed flow streams and permeate flow streams.

  20. Hybrid ion mobility and mass spectrometry as a separation tool.

    Science.gov (United States)

    Ewing, Michael A; Glover, Matthew S; Clemmer, David E

    2016-03-25

    Ion mobility spectrometry (IMS) coupled to mass spectrometry (MS) has seen spectacular growth over the last two decades. Increasing IMS sensitivity and capacity with improvements in MS instrumentation have driven this growth. As a result, a diverse new set of techniques for separating ions by their mobility have arisen, each with characteristics that make them favorable for some experiments and some mass spectrometers. Ion mobility techniques can be broken down into dispersive and selective techniques based upon whether they pass through all mobilities for later analysis by mass spectrometry or select ions by mobility or a related characteristic. How ion mobility techniques fit within a more complicated separation including mass spectrometry and other techniques such as liquid chromatography is of fundamental interest to separations scientists. In this review we explore the multitude of ion mobility techniques hybridized to different mass spectrometers, detailing current challenges and opportunities for each ion mobility technique and for what experiments one technique might be chosen over another. The underlying principles of ion mobility separations, including: considerations regarding separation capabilities, ion transmission, signal intensity and sensitivity, and the impact that the separation has upon the ion structure (i.e., the possibility of configurational changes due to ion heating) are discussed.

  1. Separation of proteins by zone electrophoresis on-line coupled with isotachophoresis on a column-coupling chip with conductivity detection.

    Science.gov (United States)

    Olvecká, Eva; Kaniansky, Dusan; Pollák, Branislav; Stanislawski, Bernd

    2004-11-01

    This feasibility study deals with the separations of proteins by an on-line combination of zone electrophoresis (ZE) with isotachophoresis (ITP) on a poly(methylmethacrylate) column-coupling (CC) chip with integrated conductivity detection. ITP and ZE provided specific analytical functions while performing the cationic mode of the separation. ITP served, mainly, for concentrations of proteins and its concentrating power was beneficial in reaching a low dispersion transfer (injection) of the proteinous constituents, loaded on the CC chip in a 960 nL volume, into the ZE separation stage. This was complemented by an electrophoretically driven removal of the sample constituents migrating in front of the focused proteins from the separation system before the ZE separation. On the other hand, ZE served as a final separation (destacking) method and it was used under the separating conditions providing the resolutions and sensitive conductivity detections of the test proteins. In this way, ITP and ZE cooperatively contributed to low- or sub-microg/mL concentration detectabilities of proteins and their quantitations at 1-5 microg/mL concentrations. However, a full benefit in concentration detectabilities of proteins, expected from the use of the ITP-ZE combination, was not reached in this work. Small adsorption losses of proteins and detection disturbances in the ZE stage of separation, very likely due to trace constituents concentrated by ITP, appear to set limits in the detection of proteins in our experiments. The ITP-ZE separations were carried out in a hydrodynamically closed separation compartment of the chip with suppressed hydrodynamic and electroosmotic flows of the electrolyte solutions. Such transport conditions, minimizing fluctuations of the migration velocities of the separated constituents, undoubtedly contributed to highly reproducible migrations of the separated proteins (fluctuations of the migration time of a particular protein were typically 0.5% RSD in

  2. Laser mass spectrometry as on-line sensor for industrial process analysis: process control of coffee roasting.

    Science.gov (United States)

    Dorfner, Ralph; Ferge, Thomas; Yeretzian, Chahan; Kettrup, Antonius; Zimmermann, Ralf

    2004-03-01

    The objective of the project is to develop on-line, real-time, and noninvasive process control tools of coffee roasting that help deliver a consistent and high-quality coffee aroma. The coffee roasting process was analyzed by direct injection of the roaster gas into a time-of-flight mass spectrometer and ionized either by resonance enhanced multiphoton ionization (REMPI) at 266 and 248 nm or vacuum ultraviolet single-photon ionization (VUV-SPI) at 118 nm. The VUV ionization scheme allows detecting mainly the most volatile and abundant compounds of molecular mass below 100 m/z, while REMPI ionizes mainly aromatic compounds of molecular mass larger than 100 m/z. Combining the compounds ionized by resonant and single-photon ionization, approximately 30 volatile organic compounds are monitored in real time. Time-intensity profiles of 10 important volatile coffee compounds were discussed in connection with their formation chemistry during roasting. Applying multivariate statistics (principle component analysis) on time-intensity traces of nine volatile coffee compounds, the roasting degree could be traced as a consistent path in the score plot of the two most significant principle components (including 68% of the total variance), for a range of roasting temperatures (200-250 degrees C).

  3. Determination of lycopene in food by on-line SFE coupled to HPLC using a single monolithic column for trapping and separation.

    Science.gov (United States)

    Pól, Jaroslav; Hyötylänen, Tuulia; Ranta-Aho, Outi; Riekkola, Marja-Liisa

    2004-10-15

    A method that would eliminate the degradation of lycopene during analysis was developed. Supercritical fluid extraction (SFE) with carbon dioxide as the extraction medium was connected on-line to high performance liquid chromatography (HPLC) where a single monolithic column was used for trapping and the subsequent separation of analytes. The method was linear over the studied range (0.1-2.5 microg), and it was repeatable (R.S.D. 3.9%), sensitive (LOD = 0.5 ng) and fast (35 min). Lycopene was determined in tomatoes, fruit and several food products. Because of the on-line construction, lycopene was not in contact with air or light during the whole procedure and the amount analysed should therefore correspond to the real amount in the sample.

  4. On-line desalting of crude oil in the source region of a Fourier transform ion cyclotron resonance mass spectrometer.

    Science.gov (United States)

    Chanthamontri, C Ken; Stopford, Andrew P; Snowdon, Ryan W; Oldenburg, Thomas B P; Larter, Stephen R

    2014-08-01

    The presence of dissolved metal ions in waters associated with crude oils has many negative implications for the transport, processing, and refining of petroleum. In addition, mass spectrometric analysis of sodium containing crude oil samples suffers from ionization suppression, unwanted adduct formation, and an increase in the complexity of data analysis. Here, we describe a method for the reduction/elimination of these adverse effects by modification of the source region gas-inlet system of a 12 T Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Several acids were examined as part of this study, with the most suitable for on-line desalting found to have both high vapor pressure and low pK(a); 12.1 M HCl showed the strongest desalting effect for crude oil samples with a sodium removal index (SRI) of 88%-100% ± 7% for the NaOS compound class. In comparison, a SRI of only 38% ± 9% was observed for a H₂O/toluene solution-phase extraction of oil 1. These results clearly demonstrate the increased efficacy of pseudo-vapor phase desalting with the additional advantages that initial sample solution conditions are preserved and no sample preparation is required prior to analysis.

  5. On-line liquid chromatography/tandem mass spectrometry simultaneous determination of opiates, cocainics and amphetamines in dried blood spots.

    Science.gov (United States)

    Saussereau, E; Lacroix, C; Gaulier, J M; Goulle, J P

    2012-02-15

    A novel approach has been developed for the illicit drugs quantitative determination using dried blood spots (DBS) on filter paper. The illicit drugs tested were opiates (morphine and its 3- and 6-glucuronide metabolites, codeine, 6-monoacetylmorphine), cocainics (ecgonine methylester, benzoylecgonine, cocaine, cocaethylene) and amphetamines (amphetamine, methamphetamine, MDA, MDMA, MDEA). The described method, requiring a small blood volume, is based on high performance liquid chromatography coupled to tandem mass spectrometry using on-line extraction. A Whatman card 903 was spotted with 30μL of whole blood and left overnight to dry at room temperature. A 3-mm diameter disk was removed using a manual punch, suspended in 150μL of water for 10min with ultrasonication, and then 100μL was injected in the on-line LC-MS/MS system. An Oasis HLB was used as an extraction column and a C18 Atlantis as an analytical column. The chromatographic cycle was performed with 20mM ammonium formate buffer (pH 2.8) (solvent A) and acetonitrile/solvent A (90:10, v/v) gradient in 16min. Detection was performed in positive electrospray ionization mode (ESI+) with a Quattro Micro (Waters). Recoveries of all analytes were up to 80%. DBS were stored in duplicate at 4°C and -20°C for up to 6 months. Illicit drugs seemed to be much more stabled at -20°C. Furthermore, it was tested whether analysis of DBS may be as reliable as that of whole blood investigating authentic samples; significant correlations were obtained. This DBS assay has potential as rapid, sensitive and inexpensive option for the illicit drugs determination in small blood volumes, which seems of great interest in suspected cases of driving under the influence of drugs.

  6. Proteolysis in microfluidic droplets: an approach to interface protein separation and peptide mass spectrometry.

    Science.gov (United States)

    Ji, Ji; Nie, Lei; Qiao, Liang; Li, Yixin; Guo, Liping; Liu, Baohong; Yang, Pengyuan; Girault, Hubert H

    2012-08-07

    A versatile microreactor protocol based on microfluidic droplets has been developed for on-line protein digestion. Proteins separated by liquid chromatography are fractionated in water-in-oil droplets and digested in sequence. The microfluidic reactor acts also as an electrospray ionization emitter for mass spectrometry analysis of the peptides produced in the individual droplets. Each droplet is an enzymatic micro-reaction unit with efficient proteolysis due to rapid mixing, enhanced mass transfer and automated handling. This droplet approach eliminates sample loss, cross-contamination, non-specific absorption and memory effect. A protein mixture was successfully identified using the droplet-based micro-reactor as interface between reverse phase liquid chromatography and mass spectrometry.

  7. Application and recovery of ionic liquids in the preparative separation of four flavonoids from Rhodiola rosea by on-line three-dimensional liquid chromatography.

    Science.gov (United States)

    Ma, Shufeng; Hu, Liming; Ma, Chaoyang; Lv, Wenping; Wang, Hongxin

    2014-09-01

    A novel on-line three-dimensional liquid chromatography method was developed to separate four main flavonoids from Rhodiola rosea. Ethyl acetate/0.5 mol/L ionic liquid 1-butyl-3-methylimidazolium chloride aqueous solution was selected as the solvent system. In the first-dimension separation, the target flavonoids were entrapped and subsequently desorbed into the second-dimension high-speed countercurrent chromatographic column for separation. In the third-dimension chromatography, the residual ionic liquid in the four separated flavonoids was removed and the used ionic liquid was recovered. As a result, 35.1 mg of compound 1, 20.4 mg of compound 2, 8.5 mg of compound 3, and 10.6 mg of compound 4 were obtained from 1.53 g R. rosea extract. They were identified as rhodiosin, rhodionin, herbacetin, and kaempferol, respectively. The recovery of ionic liquid reached 99.1% of the initial amount. The results showed that this method is a powerful technology for the separation of R. rosea flavonoids and that the ionic-liquid-based solvent system has advantages over traditional solvent systems in renewable and environmentally friendly properties.

  8. This picture was taken in 1967 during the first test of the Isotope On-Line Separator (ISOLDE) installation at the 600 MeV CERN Synchro Cyclotron.

    CERN Multimedia

    CERN PhotoLab

    1967-01-01

    When ISOLDE began operation, it was unique in the world. It used a new technique to overcome the problem of rapidly separating interesting atoms from the rest of the nuclear target. Through a combination of chemical and electromagnetic methods the different isotopes were separated and converted into an ion beam made of just one isotope. On-line production of radioactive nuclei, in this way, offered many new opportunities for physicists as it allowed them to perform previously impossible experiments on short-lived nuclei. ISOLDE has become one of CERN's major installations and it supports a broad scientific programme by providing beams to different experiments. The techniques developed at ISOLDE have opened up a new field of radioactive ion-beam accelerators, both at CERN and worldwide.

  9. High-Throughput Proteomics Using High Efficiency Multiple-Capillary Liquid Chromatography With On-Line High-Performance ESI FTICR Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Yufeng (BATTELLE (PACIFIC NW LAB)); Tolic, Nikola (BATTELLE (PACIFIC NW LAB)); Zhao, Rui (ASSOC WESTERN UNIVERSITY); Pasa Tolic, Ljiljana (BATTELLE (PACIFIC NW LAB)); Li, Lingjun (Illinois Univ Of-Urbana/Champa); Berger, Scott J.(ASSOC WESTERN UNIVERSITY); Harkewicz, Richard (BATTELLE (PACIFIC NW LAB)); Anderson, Gordon A.(BATTELLE (PACIFIC NW LAB)); Belov, Mikhail E.(BATTELLE (PACIFIC NW LAB)); Smith, Richard D.(BATTELLE (PACIFIC NW LAB))

    2000-12-01

    We report on the design and application of a high-efficiency multiple-capillary liquid chromatography (LC) system for high-throughput proteome analysis. The multiple-capillary LC system was operated at the pressure of 10,000 psi using commercial LC pumps to deliver the mobile phase and newly developed passive feedback valves to switch the mobile phase flow and introduce samples. The multiple-capillary LC system was composed of several serially connected dual-capillary column devices. The dual-capillary column approach was designed to eliminate the time delay for regeneration (or equilibrium) of the capillary column after its use under the mobile phase gradient condition (i.e. one capillary column was used in separation and the other was washed using mobile phase A). The serially connected dual-capillary columns and ESI sources were operated independently, and could be used for either''backup'' operation or with other mass spectrometer(s). This high-efficiency multiple-capillary LC system uses switching valves for all operations and is highly amenable to automation. The separations efficiency of dual-capillary column device, optimal capillary dimensions (column length and packed particle size), suitable mobile phases for electrospray, and the capillary re-generation were investigated. A high magnetic field (11.5 tesla) Fourier transform ion cyclotron resonance (FTICR) mass spectrometer was coupled on-line with this high-efficiency multiple-capillary LC system through an electrospray ionization source. The capillary LC provided a peak capacity of {approx}600, and the 2-D capillary LC-FTICR provided a combined resolving power of > 6 x 10 7 polypeptide isotopic distributions. For yeast cellular tryptic digests, > 100,000 polypeptides were typically detected, and {approx}1,000 proteins can be characterized in a single run.

  10. Quark Mass Correction to Chiral Separation Effect and Pseudoscalar Condensate

    CERN Document Server

    Guo, Er-dong

    2016-01-01

    We derived an analytic structure of the quark mass correction to chiral separation effect (CSE) in small mass regime. We confirmed this structure by a D3/D7 holographic model study in a finite density, finite magnetic field background. The quark mass correction to CSE can be related to correlators of pseudo-scalar condensate, quark number density and quark condensate in static limit. We found scaling relations of these correlators with spatial momentum in the small momentum regime. They characterize medium responses to electric field, inhomogeneous quark mass and chiral shift. Beyond the small momentum regime, we found existence of normalizable mode, which possibly leads to formation of spiral phase. The normalizable mode exists beyond a critical magnetic field, whose magnitude decreases with quark chemical potential.

  11. Two-dimensional liquid separations-mass mapping of proteins from human cancer cell lysates.

    Science.gov (United States)

    Lubman, David M; Kachman, Maureen T; Wang, Haixing; Gong, Siyuan; Yan, Fang; Hamler, Rick L; O'Neil, Kimberly A; Zhu, Kan; Buchanan, Nathan S; Barder, Timothy J

    2002-12-25

    A review of two-dimensional (2D) liquid separation methods used in our laboratory to map the protein content of human cancer cells is presented herein. The methods discussed include various means of fractionating proteins according to isoelectric point (pI) in the first dimension. The proteins in each pI fraction are subsequently separated using nonporous (NPS) reversed-phase high-performance liquid chromatography (RP-HPLC). The liquid eluent of the RP-HPLC separation is directed on-line into an electrospray ionization time-of-flight (ESI-TOF) mass spectrometer where an accurate value of the protein intact M(r) can be obtained. The result is a 2D map of pI versus M(r) analogous to 2D gel electrophoresis; however the highly accurate and reproducible M(r) serves as the basis for interlysate comparisons. In addition, the use of liquid separations allows for the collection of hundreds of purified proteins in the liquid phase for further analysis via peptide mass mapping using matrix assisted laser desorption ionization TOF MS. A description of the methodology used and its applications to analysis of several types of human cancer cell lines is described. The potential of the method for differential proteomic analysis for the identification of biomarkers of disease is discussed.

  12. Automated Analysis of Oxytocin by On-Line in-Tube Solid-Phase Microextraction Coupled with Liquid Chromatography-Tandem Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Eri Moriyama

    2015-06-01

    Full Text Available A simple and sensitive method for the analysis of oxytocin was developed using automated on-line in-tube solid-phase microextraction (SPME coupled with liquid chromatography-tandem mass spectrometry (LC–MS/MS. Oxytocin was separated within 3 min on a Zorbax Eclipse XDB-C8 column, with water/methanol (10/90, v/v as the mobile phase at a flow rate of 0.2 mL min−1. Electrospray ionization conditions in the positive ion mode were optimized for MS/MS detection by multiple reaction monitoring. The optimum in-tube SPME conditions were 20 draw/eject cycles of 40 µL sample at a flow rate of 250 µL min−1 using a Supel-Q PLOT capillary column as an extraction device. The extracted oxytocin was easily desorbed from the capillary by passage of the mobile phase, and no carryover was observed. The calibration curves for oxytocin were linear (r = 0.9981 in the range of 0−5.0 ng mL−1, and the relative standard deviations at each point were below 14.7% (n = 3. The limit of detection of this method was 4.0 pg mL−1, and its sensitivity was 58-fold higher than that of the direct injection method. This method was applied successfully to the analysis of oxytocin in saliva samples without any other interference peaks.

  13. Rapid recognition of irradiated dry-cured ham by on-line coupling of reversed-phase liquid chromatography with gas chromatography and mass spectrometry.

    Science.gov (United States)

    Martínez, R M; Barba, C; Calvo, M M; Santa-María, G; Herraiz, M

    2011-06-01

    The use of on-line coupling of reversed-phase liquid chromatography and gas chromatography (RPLC-GC) with the through oven transfer adsorption desorption (TOTAD) interface and mass spectrometry (MS) was proposed for testing different types of commercial Spanish dry-cured ham for irradiation treatment at various doses (0, 1.5, 2, and 4 kGy). The qualitative analysis of radiation-specific compounds (e.g., n-pentadecane, 1-hexadecene, 1,7-hexadecadiene, n-heptadecane, 8-heptadecene, and 2-dodecylcyclobutanone) can be simultaneously established in a single run with samples that have or have not been irradiated. The overall analysis, which takes less than 100 min, includes a rapid extraction step using a small amount of dichloromethane-methanol (1:1, vol/vol) and anhydrous sodium sulfate, the subsequent fractionation of the sample in the first dimension of the system (RPLC), the transfer of the target fraction to the second dimension, the GC separation, and the MS detection. The calculated limits of detection in ham were lower than 22 ng/g. Repeatability studies provided relative standard deviation values of 0.8 to 13.5%.

  14. On-line derivatization gas chromatography with furan chemical ionization tandem mass spectrometry for screening of amphetamines in urine.

    Science.gov (United States)

    Tzing, Shin-Hwa; Ghule, Anil; Liu, Jen-Yu; Ling, Yong-Chien

    2006-12-22

    A simple alternative method with minimal sample pretreatment is investigated for screening of amphetamines in small volume (using only 20 microL) of urine sample. The method is sensitive and selective. The method uses gas chromatography (GC) direct sample introduction (DSI) for on-line derivatization (acylation) of amphetamines to improve sensitivity. Furan as chemical ionization (CI) reagent in conjunction with tandem mass spectrometry (MS/MS) is used to improve selectivity. Low background with sharp protonated molecular ion peaks of analytes is the evidence of improvement in sensitivity and selectivity. Blank urine samples spiked with known amounts of amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine and 3,4-methylenedioxyethylamphetamine is analyzed. Selected ion monitoring of the characteristic product ions (m/z 119+136+150+163) using furan CI-MS/MS in positive ion mode is used for quantification. Limits of detection (LOD) between 0.4 and 1.0 ng mL(-1) and limits of quantitation (LOQ) between 1.0 and 2.0 ng mL(-1) are established. Linear response over the range of 1-1000 ng mL(-1) (r(2)>0.997) is observed for all analytes, except for methamphetamine (2.0-1000 ng mL(-1)). Good accuracy between 86 and 113% and precision ranging from 4 to 18% is obtained. The method is also tested on real samples of urine from suspected drug abusers. This method could be used for screening and determination of amphetamines in urine samples, however needs additional work for full validation.

  15. Recent developments at the GSI Online Mass Separator

    CERN Document Server

    Schmidt, K; Burkard, K; Döring, J; aGórska, M; Grawe, H; Hüller, W; Janas, Z; Kirchner, R; La Commara, M; Mazzocchi, C; Roeckl, E

    2002-01-01

    The research programme at the GSI Online Mass Separator focuses on the study of exotic nuclei far from the valley of stability. Special emphasis is placed on the investigation of decay properties of isotopes along the N=Z line between the double shell closures at sup 5 sup 6 Ni and sup 1 sup 0 sup 0 Sn. In this contribution, the major recent achievements along with the corresponding experimental methods are reviewed.

  16. Biomonitoring of essential and toxic metals in single hair using on-line solution-based calibration in laser ablation inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Dressler, Valderi L; Pozebon, Dirce; Mesko, Marcia Foster; Matusch, Andreas; Kumtabtim, Usarat; Wu, B; Sabine Becker, J

    2010-10-15

    Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been established as a powerful and sensitive surface analytical technique for the determination of concentration and distribution of trace metals within biological systems at micrometer spatial resolution. LA-ICP-MS allows easy quantification procedures if suitable standard references materials (SRM) are available. In this work a new SRM-free approach of solution-based calibration method in LA-ICP-MS for element quantification in hair is described. A dual argon flow of the carrier gas and nebulizer gas is used. A dry aerosol produced by laser ablation (LA) of biological sample and a desolvated aerosol generated by pneumatic nebulization (PN) of standard solutions are carried by two different flows of argon as carrier or nebulizer gas, respectively and introduced separately in the injector tube of a special ICP torch, through two separated apertures. Both argon flows are mixed directly in the ICP torch. External calibration via defined standard solutions before analysis of single hair was employed as calibration strategy. A correction factor, calculated using hair with known analyte concentration (measured by ICP-MS), is applied to correct the different elemental sensitivities of ICP-MS and LA-ICP-MS. Calibration curves are obtained by plotting the ratio of analyte ion M(+)/(34)S(+) ion intensities measured using LA-ICP-MS in dependence of analyte concentration in calibration solutions. Matrix-matched on-line calibration in LA-ICP-MS is carried out by ablating of human hair strands (mounted on a sticky tape in the LA chamber) using a focused laser beam in parallel with conventional nebulization of calibration solutions. Calibrations curves of Li, Na, Mg, Al, K, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Mo, Ag, Cd, I, Hg, Pb, Tl, Bi and U are presented. The linear correlation coefficients (R) of calibration curves for analytes were typically between 0.97 and 0.999. The limits of detection (LODs) of

  17. On-line SPE-UHPLC method using fused core columns for extraction and separation of nine illegal dyes in chilli-containing spices.

    Science.gov (United States)

    Khalikova, Maria A; Satínský, Dalibor; Smidrkalová, Tereza; Solich, Petr

    2014-12-01

    The presented work describes the development of a simple, fast and effective on-line SPE-UHPLC-UV/vis method using fused core particle columns for extraction, separation and quantitative analysis of the nine illegal dyes, most frequently found in chilli-containing spices. The red dyes Sudan I-IV, Sudan Red 7B, Sudan Red G, Sudan Orange G, Para Red, and Methyl Red were separated and analyzed in less than 9 min without labor-consuming pretreatment procedure. The chromatographic separation was performed on Ascentis Express RP-Amide column with gradient elution using mixture of acetonitrile and water, as a mobile phase at a flow rate of 1.0 mL min(-1) and 55°C of temperature. As SPE sorbent for cleanup and pre-concentration of illegal dyes short guard fused core column Ascentis Express F5 was used. The applicability of proposed method was proven for three different chilli-containing commercial samples. Recoveries for all compounds were between 90% and 108% and relative standard deviation ranged from 1% to 4% for within- and from 2% to 6% for between-day. Limits of detection showed lower values than required by European Union regulations and were in the range of 3.3-10.3 µg L(-1) for standard solutions, 5.6-235.6 µg kg(-1) for chilli-containing spices.

  18. Combination of two different stationary phases for on-line pre-concentration and separation of basic drugs by using nano-liquid chromatography.

    Science.gov (United States)

    D'Orazio, Giovanni; Fanali, Salvatore

    2013-04-12

    Capillary columns were packed firstly with silica modified-teicoplanin (teico-CSP) particles for a short zone (1-5 cm) and then with a Cogent Bidentate C18 silica phase (25 cm). The first part of the column (inlet) was intended for focusing the sample model, consisted of selected basic compounds, while the second zone, containing RP18 particles, was used for their separation. For method optimization, some important experimental parameters were studied including the sample solvent, injected volume and teico-CSP particles length. 3 cm teico-CSP resulted to be effective for the on-line pre-concentration, before the separation, of acebutolol, alprenolol, nadolol, oxprenolol and terbutaline with limit of detection at levels of few ng/mL. The comparison of the data obtained in absence of the chiral stationary phase revealed that the use of this chiral short sector into the capillary allowed the increase of the sensitivity of 5-12 times. Injection of larger sample volumes were easily done using higher length of the teico-CSP into the capillary, however the use of 5 cm length was not appropriate because caused the partial chiral separation of some studied compounds.

  19. Determination of 2-propanol in surface cleaning solutions used for copper continuous casting process by flow injection-spectrophotometric detection with on-line column separation.

    Science.gov (United States)

    Hayashibe, Yutaka; Tokuda, Masahiro; Takeya, Minoru

    2003-09-01

    A flow-injection system has been developed for the determination of 2-propanol in the surface cleaning solutions used in the copper continuous cast rod making system. Adsorption chromatography in nitric acid medium was used for the on-line separation of oily substances in the sample solution. Cerium(IV) diammonium nitrate was utilized as the chromogenic reagent for the spectrophotometric detection of 2-propanol. The system permits a throughput of one sample per hour for the oily sample, and of 12 samples per hour for the none-oily sample. The reproducibility has been proven to be satisfactory with a relative standard deviation of less than 6.0% (2.2%(V/V) 2-propanol level, n = 23). The detection limit is 0.01% (V/V).

  20. Determination of thromboxanes, leukotrienes and lipoxins using high-temperature capillary liquid chromatography-tandem mass spectrometry and on-line sample preparation

    DEFF Research Database (Denmark)

    Dahl, Sandra Rinne; Kleiveland, Charlotte Ramstad; Kassem, Moustapha

    2009-01-01

    An on-line strong cation-exchange (SCX)-reversed-phase (RP) capillary liquid chromatographic (cLC) method with ion-trap tandem mass spectrometric (IT-MS/MS) detection for the simultaneous determination of thromboxane (TX) B(2), TXB(3), leukotriene (LT) B(4), LTD(4) and lipoxin (LX) A(4) in cell...

  1. Identification of glyceollin metabolites derived from conjugation with glutathione and glucuronic acid in rats by on-line liquid chromatography-electrospray ionization tandem mass spectrometry

    Science.gov (United States)

    Glyceollin-related metabolites produced in rats following oral glyceollin administration were screened and identified by precursor and product ion scanning using liquid chromatography, coupled on-line with electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS), to identify all glyceollin me...

  2. Electrochemical oxidation and cleavage of proteins with on-line mass spectrometric detection : Development of an instrumental alternative to enzymatic protein digestion

    NARCIS (Netherlands)

    Permentier, HP; Bruins, AP

    2004-01-01

    An electrochemical flow cell coupled on-line to a mass spectrometer is used to oxidize a range of proteins. Oxidation of tyrosine and tryptophan can give rise to peptide bond cleavage at their C-terminal side. This suggests the possible use of electrochemistry as an alternative protein digestion

  3. Data correlation in on-line solid-phase extraction-gas chromatography-atomic emission/mass spectrometric detection of unknown microcontaminants

    NARCIS (Netherlands)

    Hankemeier, Th.; Rozenbrand, J.; Abhadur, M.; Vreuls, J.J.; Brinkman, U.A.Th.

    1998-01-01

    A procedure is described for the (non-target) screening of hetero-atom-containing compounds in tap and waste water by correlating data obtained by gas chromatography (GC) using atomic emission (AED) and mass selective (MS) detection. Solid-phase extraction (SPE) was coupled on-line to both GC system

  4. The use of a polymer inclusion membrane in flow injection analysis for the on-line separation and determination of zinc.

    Science.gov (United States)

    Zhang, Lujia L; Cattrall, Robert W; Kolev, Spas D

    2011-06-15

    This paper reports the first use of a polymer inclusion membrane (PIM) for on-line separation in flow injection analysis (FIA) involving simultaneous extraction and back-extraction. The FIA system containing the PIM separation module was used for the determination of Zn(II) in aqueous samples in the presence of Mg(II), Ca(II), Cd(II), Co(II), Ni(II), Cu(II), and Fe(III). The Fe(III) and Cu(II) interferences were eliminated by off-line precipitation with phosphate and on-line complexation with chloride, respectively. The concentration of Zn(II) was determined spectrophotometrically using 4-(2-pyridylazo) resorcinol (PAR). The optimal composition of the PIM consisted of 40% (m/m) di(2-ethlyhexyl) phosphoric acid (D2EHPA) as carrier, 10% (m/m) dioctyl phthalate (DOP) as plasticizer and 50% (m/m) poly(vinyl chloride) (PVC) as the base polymer. The optimized FIA system was characterized by a linear calibration curve in the range from 1.0 to 30.0 mg L(-1) Zn(II), a detection limit of 0.05 mg L(-1) and a relative standard deviation of 3.4% with a sampling rate of 4h(-1). Reproducible results were obtained for 20 replicate injections over a 5h period which demonstrated a good membrane stability. The FIA system was applied to the determination of Zn(II) in pharmaceuticals and samples from the galvanizing industry and very good agreement with atomic absorption spectrometry was obtained.

  5. Mass selective separation applied to radioisotopes of cesium: Mass selective applied to radioisotopes

    Energy Technology Data Exchange (ETDEWEB)

    Dion, Michael [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland 99354 WA USA; Eiden, Greg [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland 99354 WA USA; Farmer, Orville [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland 99354 WA USA; Finch, Zach [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland 99354 WA USA; Liezers, Martin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland 99354 WA USA

    2016-07-22

    A developed technique that uses the intrinsic mass-based separation capability of a quadrupole mass spectrometer has been used to resolve spectral radiometric interference of two isotopes of the same element. In this work the starting sample was a combination of 137Cs and 134Cs and was (activity) dominated by 137Cs and this methodology separated and “implanted” 134Cs that was later quantified for spectral features and ac- tivity with traditional radiometric techniques. This work demonstrated a 134Cs/137Cs activity ratio enhancement of >4 orders of magnitude and complete removal of 137Cs spectral features from the implanted target mass (i.e., 134).

  6. High-throughput determination of cortisol, cortisone, and melatonin in oral fluid by on-line turbulent flow liquid chromatography interfaced with liquid chromatography/tandem mass spectrometry.

    Science.gov (United States)

    Fustinoni, Silvia; Polledri, Elisa; Mercadante, Rosa

    2013-07-15

    Cortisol, cortisone, and melatonin (CORTol, CORTone, and MELA, respectively) are hormones related to stress and sleep disorders. Their detection is relevant to epidemiological studies aimed at investigating the effects of circadian cycle disruption. The aim of this study was to develop and evaluate a high-throughput assay for the detection of CORTol, CORTone, and MELA concentrations in non-invasively collected oral fluid samples. A liquid chromatography/tandem mass spectrometry (LC/MS/MS) method to measure levels of CORTol, CORTone, and MELA in oral fluid samples in the presence of deuterated analogs was optimized and validated. A 50 μL aliquot of oral fluid sample, obtained by centrifugation of a chewed swab, was purified using on-line turbulent flow liquid chromatography. Analytes were then separated using C18 reversed-phase chromatography, subjected to positive ionization using an electrospray source, then quantitated using a triple quadrupole mass detector in the selected reaction monitoring mode. Limits of quantification and linear dynamic ranges were found to be 0.55 nmol/L, 5.5 nmol/L, and 0.004 nmol/L, and up to 28 nmol/L, 277 nmol/L, and 0.43 nmol/L for CORTol, CORTone, and MELA, respectively. Inter- and intra-run precisions as relative standard deviation values were <5%, and accuracies were within 95-106% of theoretical concentrations. An evaluation of matrix effects showed that the use of deuterated analogs controlled sources of bias. Furthermore, the total analysis time per sample was 13 min, resulting in a throughput of approximately 100 samples/day. To our knowledge, this is the first automated, high-throughput assay for the simultaneous quantification of CORTol, CORTone, and MELA in oral fluid specimens. Copyright © 2013 John Wiley & Sons, Ltd.

  7. Cyclic pentapeptide analogs based on endomorphin-2 structure: cyclization studies using liquid chromatography combined with on-line mass spectrometry and tandem mass spectrometry.

    Science.gov (United States)

    Piekielna, Justyna; Kluczyk, Alicja; Perlikowska, Renata; Janecka, Anna

    2014-05-01

    The cyclization of linear analogs based on endomorphin-2 structure, Tyr/Dmt-d-Lys-Phe-Phe-Asp-NH2 and Tyr/Dmt-d-Cys-Phe-Phe-Cys-NH2 (where Dmt=2',6'-dimethyltyrosine), resulting in obtaining lactam or disulfide derivatives, was studied using liquid chromatography combined with on-line mass spectrometry (LC-MS) and tandem mass spectrometry (LC-MS/MS). In case of cyclization via an amide bond, the formation of the cyclic monomers, cyclic but not linear dimers and even traces of cyclic trimers was observed. Disulfide bridge containing peptides was obtained by the solid-phase synthesis of the linear sequences, followed by either in-solution or on-resin cyclization. In case of the in-solution cyclization, the expected cyclic monomers were the only products. When oxidation of the cysteine residues was performed when the peptides were still on the resin, cyclic monomer and two cyclodimers, parallel and antiparallel, were found. Digestion of the isolated cyclodimers with α-chymotrypsin allowed for their unambiguous identification. The comparison of the cyclic monomer/dimer ratios for analogs with Tyr versus Dmt in position 1 revealed that the presence of the exocyclic Dmt favored formation of the cyclic monomer, most likely due to the increased steric bulk of this amino acid side-chain as compared with Tyr.

  8. Separation and quantification of {sup 238}U, {sup 232}Th and rare earths in monazite samples by ion chromatography coupled with on-line flow scintillation detector

    Energy Technology Data Exchange (ETDEWEB)

    Borai, E.H.; Mady, A.S

    2002-10-01

    An alternative procedure has been described for efficient separation and quantitative determination of uranium (U), thorium (Th) and rare earth elements (REEs) in monazite mineral by high performance ion chromatographic system (IC). Different variables affecting the distribution coefficient, the retention and hence separation efficiency such as eluent flow rate and concentrations of HCl and ammonium sulfate (NH{sub 4}){sub 2}SO{sub 4} containing the mobile phase were studied. The developed separation protocol of U, Th and REEs was optimized using an Ion Pac CS5 separation column followed by post-column derivatization reaction with Arsenaso III and UV-VIS spectrophotometeric detection. Comparative evaluation of U, Th and REEs concentration in monazite mineral was demonstrated using two different on-line detection modes including flow through cell scintillation detector (FSD) and UV-VIS spectrophotometer. Response of the FSD was found to be linear over the full range of activities investigated (4-100 Bq). The lower limits of detection (LLD) for the investigated radionuclides were 3.0{+-}0.1 Bq for {sup 238}U and 6.0{+-}0.1 Bq for {sup 232}Th. The detection of {sup 238}U and {sup 232}Th by FSD shows good agreement with the corresponding determination by UV-VIS spectrophotometer. The content of ThO{sub 2} and U{sub 3}O{sub 8} in monazite sample were found to be 4.7{+-}0.1% and 0.42{+-}0.04% using UV-VIS detector and 4.3{+-}0.1% and 0.45{+-}0.1% using FSD, respectively.

  9. On-line solid phase extraction using the Prospekt-2 coupled with a liquid chromatography/tandem mass spectrometer for the determination of dextromethorphan, dextrorphan and guaifenesin in human plasma.

    Science.gov (United States)

    Kuhlenbeck, Debbie L; Eichold, Thomas H; Hoke, Steven H; Baker, Timothy R; Mensen, Robert; Wehmeyer, Kenneth R

    2005-01-01

    An on-line liquid chromatography/tandem mass spectrometry (LC-MS/MS) procedure, using the Prospekt- 2 system, was developed and used for the determination of the levels of the active ingredients of cough/cold medications in human plasma matrix. The experimental configuration allows direct plasma injection by performing on- line solid phase extraction (SPE) on small cartridge columns prior to elution of the analyte(s) onto the analytical column and subsequent MS/MS detection. The quantitative analysis of three analytes with differing polarities, dextromethorphan (DEX), dextrorphan (DET) and guaifenesin (GG) in human plasma presented a significant challenge. Using stable-isotope-labeled internal standards for each analyte, the Prospekt-2 on-line methodology was evaluated for sensitivity, suppression, accuracy, precision, linearity, analyst time, analysis time, cost, carryover and ease of use. The lower limit of quantitation for the on-line SPE procedure for DEX, DET and GG was 0.05, 0.05 and 5.0 ng mL(-1), respectively, using a 0.1 mL sample volume. The linear range for DEX and DET was 0.05-50 ng mL(-1) and was 5-5,000 ng mL(-1) for GG. Accuracy and precision data for five different levels of QC samples were collected over three separate days. Accuracy ranged from 90% to 112% for all three analytes, while the precision, as measured by the %RSD, ranged from 1.5% to 16.0%

  10. Attomole quantitation of protein separations with accelerator mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Vogel, J S; Grant, P G; Buccholz, B A; Dingley, K; Turteltaub, K W

    2000-12-15

    Quantification of specific proteins depends on separation by chromatography or electrophoresis followed by chemical detection schemes such as staining and fluorophore adhesion. Chemical exchange of short-lived isotopes, particularly sulfur, is also prevalent despite the inconveniences of counting radioactivity. Physical methods based on isotopic and elemental analyses offer highly sensitive protein quantitation that has linear response over wide dynamic ranges and is independent of protein conformation. Accelerator mass spectrometry quantifies long-lived isotopes such as 14C to sub-attomole sensitivity. We quantified protein interactions with small molecules such as toxins, vitamins, and natural biochemicals at precisions of 1-5% . Micro-proton-induced-xray-emission quantifies elemental abundances in separated metalloprotein samples to nanogram amounts and is capable of quantifying phosphorylated loci in gels. Accelerator-based quantitation is a possible tool for quantifying the genome translation into proteome.

  11. Laser photodissociation and spectroscopy of mass-separated biomolecular ions

    CERN Document Server

    Polfer, Nicolas C

    2014-01-01

    This lecture notes book presents how enhanced structural information of biomolecular ions can be obtained from interaction with photons of specific frequency - laser light. The methods described in the book ""Laser photodissociation and spectroscopy of mass-separated biomolecular ions"" make use of the fact that the discrete energy and fast time scale of photoexcitation can provide more control in ion activation. This activation is the crucial process producing structure-informative product ions that cannot be generated with more conventional heating methods, such as collisional activation. Th

  12. [Determination of five avermectins in bovine liver by on-line solid-phase extraction with hydrophobic monolithic column coupled with high performance liquid chromatography-tandem mass spectrometry].

    Science.gov (United States)

    Li, Xin; Zhang, Yaoqin; Ai, Lianfeng; Wang, Xuesheng; Wang, Manman; Xu, Houjun; Hao, Yulan

    2015-06-01

    A method based on on-line solid-phase extraction (SPE) with hydrophobic monolithic column coupled with high performance liquid chromatography-tandem mass spectrometry was developed for the simultaneous determination of five avermectins in bovine liver. A poly(butyl methacrylate-co-ethylene dimethacrylate) monolithic column was used as the sorbent. The parameters influenced on on-line SPE and separation process such as the loading mobile phase, the eluting flow rate and the solvent for the separation were investigated in detail. Blank samples, spiked samples, matrix effect and recovery experiments were investigated to evaluate the extraction efficiency and potential interfering compounds originating from the matrix. Under the optimized conditions, the method showed a linear range of 1-100 µg/L and the quantification limit of 5 µg/kg for each analyte. The presented method gave recoveries of 77.4%-98.4%. The relative standard deviations of intra-day and inter-day were 4.46%-8.03% and 4.79%-8.68%, respectively. Moreover, no significant changes were found in the extraction performance after more than 400 usages on one monolithic column, and even on the monoliths with various batches. The feasibility of the developed poly (butyl methacrylate-coethylene dimethacrylate) monolithic column based on the on-line SPE method for the determination of avermectins was further demonstrated by the analysis of real samples.

  13. Parallel extraction columns and parallel analytical columns coupled with liquid chromatography/tandem mass spectrometry for on-line simultaneous quantification of a drug candidate and its six metabolites in dog plasma.

    Science.gov (United States)

    Xia, Y Q; Hop, C E; Liu, D Q; Vincent, S H; Chiu, S H

    2001-01-01

    A method with parallel extraction columns and parallel analytical columns (PEC-PAC) for on-line high-flow liquid chromatography/tandem mass spectrometry (LC/MS/MS) was developed and validated for simultaneous quantification of a drug candidate and its six metabolites in dog plasma. Two on-line extraction columns were used in parallel for sample extraction and two analytical columns were used in parallel for separation and analysis. The plasma samples, after addition of an internal standard solution, were directly injected onto the PEC-PAC system for purification and analysis. This method allowed the use of one of the extraction columns for analyte purification while the other was being equilibrated. Similarly, one of the analytical columns was employed to separate the analytes while the other was undergoing equilibration. Therefore, the time needed for re-conditioning both extraction and analytical columns was not added to the total analysis time, which resulted in a shorter run time and higher throughput. Moreover, the on-line column extraction LC/MS/MS method made it possible to extract and analyze all seven analytes simultaneously with good precision and accuracy despite their chemical class diversity that included primary, secondary and tertiary amines, an alcohol, an aldehyde and a carboxylic acid. The method was validated with the standard curve ranging from 5.00 to 5000 ng/mL. The intra- and inter-day precision was no more than 8% CV and the assay accuracy was between 95 and 107%.

  14. Continuous-flow separation and pre-concentration coupled on-line to solid-surface fluorescence spectroscopy for the simultaneous determination of o-phenylphenol and thiabendazole.

    Science.gov (United States)

    García Reyes, J F; Llorent Martínez, E J; Ortega Barrales, P; Molina Díaz, A

    2004-01-01

    A novel and single flow-injection system combined with solid-surface fluorescence detection is proposed in this work for the resolution of a mixture of two widely used pesticides (o-phenylphenol and thiabendazole). The continuous-flow methodology is based on the implementation of on-line pre-concentration and separation of both analytes on the surface of C18 silica gel beads placed just inside the flow cell, implemented with gel-phase fluorimetric multi-wavelength detection (using 305/358 and 250/345 nm as excitation/emission wavelengths for thiabendazole and o-phenylphenol, respectively). The separation of the pesticides was possible owing to the different retention/desorption kinetics of their interactions with the solid support in the zone where the stream impinges on the solid material. No previous separation of the analytes before they reach the flow cell is needed thereby simplifying substantially both the procedure and the manifold. By using a sample volume of 2,600 microL, the system was calibrated in the range 0.5-16 and 5-120 ng mL(-1) with detection limits of 0.09 and 0.60 ng mL(-1) for thiabendazole and o-phenylphenol, respectively. The RSD values (n=10) were about 1% for both analytes. The proposed methodology was applied to environmental water samples and also to various commercial pesticide formulations containing both analytes. Recovery percentages were 97-103% and 98-102% for thiabendazole and o-phenylphenol, respectively.

  15. The Cryo-Thermochromatographic Separator (CTS) A new rapid separation and alpha-detection system for on-line chemical studies of highly volatile osmium and hassium (Z=108) tetroxides

    CERN Document Server

    Kirbach, U W; Gregorich, K E; Lee, D M; Ninov, V; Omtvedt, J P; Patin, J B; Seward, N K; Strellis, D A; Sudowe, R; Türler, A; Wilk, P A; Zielinski, P M; Hoffman, D C; Nitsche, H

    2002-01-01

    The Cryo-Thermochromatographic Separator (CTS) was designed and constructed for rapid, continuous on-line separation and simultaneous detection of highly volatile compounds of short-lived alpha-decaying isotopes of osmium and hassium (Hs, Z=108). A flowing carrier gas containing the volatile species is passed through a channel formed by two facing rows of 32 alpha-particle detectors, cooled to form a temperature gradient extending from 247 K at the channel entrance down to 176 K at the exit. The volatile species adsorb onto the SiO sub 2 -coated detector surfaces at a characteristic deposition temperature and are identified by their observed alpha-decay energies. The CTS was tested on-line with OsO sub 4 prepared from sup 1 sup 6 sup 9 sup - sup 1 sup 7 sup 3 Os isotopes produced in sup 1 sup 1 sup 8 sup , sup 1 sup 2 sup 0 Sn( sup 5 sup 6 Fe, 3,4,5n) reactions. An adsorption enthalpy for OsO sub 4 of -40.2+-1.5 kJ/mol on SiO sub 2 was deduced by comparing the measured deposition distribution with Monte Carlo...

  16. On-line gas chromatography combustion/pyrolysis isotope ratio mass spectrometry (HRGC-C/P-IRMS) of pineapple (Ananas comosus L. Merr.) volatiles.

    Science.gov (United States)

    Preston, Christina; Richling, Elke; Elss, Sandra; Appel, Markus; Heckel, Frank; Hartlieb, Ariane; Schreier, Peter

    2003-12-31

    By use of extracts prepared by liquid-liquid separation of the volatiles from self-prepared juices of pineapple fruits (Ananas comosus) (n = 14) as well as commercial pineapple recovery aromas/water phases (n = 3), on-line capillary gas chromatography-isotope ratio mass spectrometry was employed in the combustion (C) and the pyrolysis (P) modes (HRGC-C/P-IRMS) to determine the delta(13)C(VPDB) and delta(2)H(VSMOW) values of selected pineapple flavor constituents. In addition to methyl 2-methylbutanoate 1, ethyl 2-methylbutanoate 2, methyl hexanoate 3, ethyl hexanoate 4, and 2,5-dimethyl-4-methoxy-3[2H]-furanone 5, each originating from the fruit, the delta(13)C(VPDB) and delta(2)H(VSMOW) data of commercial synthetic 1-5 and "natural" (biotechnologically derived) 1-4 were determined. With delta(13)C(VPDB) data of pineapple volatiles 1-4 varying from -12.8 to -24.4 per thousand, the range expected for CAM metabolism was observed. Compound 5 showed higher depletion from -20.9 to -28.6 per thousand. A similar situation was given for the delta(2)H(VSMOW) values of 3-5 from pineapple ranging from -118 to -191 per thousand, whereas 1 and 2 showed higher depleted values from -184 to -263 per thousand. In nearly all cases, analytical differentiation of 1-5 from pineapple and natural as well as synthetic origin was possible. In general, natural and synthetic 1-5 exhibited delta(13)C(VPDB) data ranging from -11.8 to -32.2 per thousand and -22.7 to -35.9 per thousand, respectively. Their delta(2)H(VSMOW) data were in the range from -242 to -323 per thousand and -49 to -163 per thousand, respectively.

  17. An efficient VLSI implementation of on-line recursive ICA processor for real-time multi-channel EEG signal separation.

    Science.gov (United States)

    Shih, Wei-Yeh; Liao, Jui-Chieh; Huang, Kuan-Ju; Fang, Wai-Chi; Cauwenberghs, Gert; Jung, Tzyy-Ping

    2013-01-01

    This paper presents an efficient VLSI implementation of on-line recursive ICA (ORICA) processor for real-time multi-channel EEG signal separation. The proposed design contains a system control unit, a whitening unit, a singular value decomposition unit, a floating matrix multiply unit and, and an ORICA weight training unit. Because the input sample rate of the ORICA processor is 128 Hz, the ORICA processor should produce independent components before the next sample is input in 1/128 s. Under the timing constraints of commutating multi-channel ORICA in real time, the design of the ORICA processor is a mixed architecture, which is designed as different hardware parallelism according to the complexity of processing units. The shared arithmetic processing unit and shared register can reduce hardware complexity and power consumption. The proposed design is implemented used TSMC 90 nm CMOS technology with 8-channel EEG processing in 128 Hz sample rate of raw data and consumes 2.827 mW at 50 MHz clock rate. The performance of the proposed design is also shown to reach 0.0078125 s latency after each EEG sample time, and the average correlation coefficient between the original source signals and extracted ORICA signals for each 1 s frame is 0.9763.

  18. Dynamic etching of soluble surface layers with on-line inductively coupled plasma mass spectrometry detection - a novel approach for determination of complex metal oxide surface cation stoichiometry

    OpenAIRE

    Limbeck, A; Rupp, GM; M. Kubicek; Tellez, H.; Druce, J; Ishihara, T.; Kilner, JA; Fleig, J.

    2016-01-01

    In this work, an innovative approach for determining the surface stoichiometry of complex metal oxide (CMO) thin films is presented. The procedure is based on treatment of the sample surface with different etching solutions, followed by on-line analysis of the derived eluates using inductively coupled plasma ? mass spectrometry (ICP-MS). Via consecutive treatment of the sample surface with water and diluted HCl, a differentiation between water soluble and acid soluble parts of near surface re...

  19. An On-Line Solid Phase Extraction-Liquid Chromatography-Tandem Mass Spectrometry Method for the Determination of Perfluoroalkyl Acids in Drinking and Surface Waters

    Directory of Open Access Journals (Sweden)

    Michela Mazzoni

    2015-01-01

    Full Text Available An UHPLC-MS/MS multiresidue method based on an on-line solid phase extraction (SPE procedure was developed for the simultaneous determination of 9 perfluorinated carboxylates (from 4 to 12 carbon atoms and 3 perfluorinated sulphonates (from 4 to 8 carbon atoms. This work proposes using an on-line solid phase extraction before chromatographic separation and analysis to replace traditional methods of off-line SPE before direct injection to LC-MS/MS. Manual sample preparation was reduced to sample centrifugation and acidification, thus eliminating several procedural errors and significantly reducing time-consuming and costs. Ionization suppression between target perfluorinated analytes and their coeluting SIL-IS were detected for homologues with a number of carbon atoms less than 9, but the quantitation was not affected. Total matrix effect corrected by SIL-IS, inclusive of extraction efficacy, and of ionization efficiency, ranged between −34 and +39%. The percentage of recoveries, between 76 and 134%, calculated in different matrices (tap water and rivers impacted by different pollutions was generally satisfactory. LODs and LOQs of this on-line SPE method, which also incorporate recovery losses, ranged from 0.2 to 5.0 ng/L and from 1 to 20 ng/L, respectively. Validated on-line SPE-LC/MS/MS method has been applied in a wide survey for the determination of perfluoroalkyl acids in Italian surface and ground waters.

  20. Elemental ratios for characterization of quantum-dots populations in complex mixtures by asymmetrical flow field-flow fractionation on-line coupled to fluorescence and inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Menendez-Miranda, Mario; Fernandez-Arguelles, Maria T.; Costa-Fernandez, Jose M., E-mail: jcostafe@uniovi.es; Encinar, Jorge Ruiz; Sanz-Medel, Alfredo, E-mail: asm@uniovi.es

    2014-08-11

    Highlights: • The hyphenated system allows unequivocal identification of nanoparticle populations. • AF4 separation permitted detection of unexpected nanosized species in a sample. • ICP-QQQ provides elemental ratios with adequate accuracy in every nanoparticle. • Purity and chemical composition of different quantum dot samples were assessed. - Abstract: Separation and identification of nanoparticles of different composition, with similar particle diameter, coexisting in heterogeneous suspensions of polymer-coated CdSe/ZnS quantum dots (QDs) have been thoroughly assessed by asymmetric flow field-flow fractionation (AF4) coupled on-line to fluorescence and inductively coupled plasma mass spectrometry (ICPMS) detectors. Chemical characterization of any previously on-line separated nanosized species was achieved by the measurement of the elemental molar ratios of every element involved in the synthesis of the QDs, using inorganic standards and external calibration by flow injection analysis (FIA). Such elemental molar ratios, strongly limited so far to pure single nanoparticles suspensions, have been achieved with adequate accuracy by coupling for the first time an ICP-QQQ instrument to an AF4 system. This hyphenation turned out to be instrumental to assess the chemical composition of the different populations of nanoparticles coexisting in the relatively complex mixtures, due to its capabilities to detect the hardly detectable elements involved in the synthesis. Interestingly such information, complementary to that obtained by fluorescence, was very valuable to detect and identify unexpected nanosized species, present at significant level, produced during QDs synthesis and hardly detectable by standard approaches.

  1. On-line coupling of macroporous resin column chromatography with direct analysis in real time mass spectrometry utilizing a surface flowing mode sample holder.

    Science.gov (United States)

    Zeng, Shanshan; Wang, Lu; Chen, Teng; Qu, Haibin

    2014-02-06

    A surface flowing mode sample holder was designed as an alternative sampling strategy for direct analysis in real time mass spectrometry (DART-MS). With the sample holder, the on-line coupling of macroporous resin column chromatography with DART-MS was explored and the new system was employed to monitor the column chromatography elution process of Panax notoginseng. The effluent from macroporous resin column was first diluted and mixed with a derivatization reagent on-line, and the mixture was then directly transferred into the ionization region of DART-MS by the sample holder. Notoginsenosides were methylated and ionized in a metastable helium gas stream, and was introduced into MS for detection. The on-line system showed reasonable repeatability with a relative standard deviation of 12.3% for the peak area. Three notoginsenosides, i.e. notoginsenoside R1, ginsenoside Rb1 and ginsenoside Rg1, were simultaneously determined during the eluting process. The alteration of the chemical composition in the effluent was accurately identified in 9 min, agreeing well with the off-line analysis. The presented technique is more convenient compared to the traditional UPLC method. These results suggest that the surface flowing mode DART-MS has a good potential for the on-line process monitoring in the pharmaceutical industry.

  2. Fast determination of the relative elemental and organic carbon content of aerosol samples by on-line single-particle aerosol time-of-flight mass spectrometry.

    Science.gov (United States)

    Ferge, T; Karg, E; Schröppel, A; Coffee, K R; Tobias, H J; Frank, M; Gard, E E; Zimmermann, R

    2006-05-15

    Different particulate matter (PM) samples were investigated by on-line single-particle aerosol time-of-flight mass spectrometry (ATOFMS). The samples consist of soot particulates made by a diffusion flame soot generator (combustion aerosol standard, CAST), industrially produced soot material (printex), soot from a diesel passenger car as well as ambient particulates (urban dust (NIST) and road tunnel dust). Five different CAST soot particle samples were generated with different elemental carbon (EC) and organic carbon (OC) content. The samples were reaerosolized and on-line analyzed by ATOFMS, as well as precipitated on quartz filters for conventional EC/OC analysis. For each sample ca. 1000 ATOFMS single-particle mass spectra were recorded and averaged. A typical averaged soot ATOFMS mass spectrum shows characteristic carbon cluster peak progressions (Cn+) as well as hydrogen-poor carbon cluster peaks (CnH(1-3)+). These peaks are originated predominately from the elemental carbon (EC) content of the particles. Often additional peaks, which are not due to carbon clusters, are observed, which either are originated from organic compounds (OC-organic carbon), or from the non-carbonaceous inorganic content of the particles. By classification of the mass spectral peaks as elemental carbon (i.e., the carbon cluster progression peaks) or as peaks originated from organic compounds (i.e., molecular and fragment ions), the relative abundance of elemental (EC) and organic carbon (OC) can be determined. The dimensionless TC/EC values, i.e., the ratio of total carbon content (TC, TC = OC + EC) to elemental carbon (EC), were derived from the ATOFMS single-particle aerosol mass spectrometry data. The EC/TC values measured by ATOFMS were compared with the TC/EC values determined by the thermal standard techniques (thermooptical and thermocoulometric method). A good agreement between the EC/TC values obtained by on-line ATOFMS and the offline standard method was found.

  3. Application of matrix-assisted laser desorption/ionization to on-line aerosol time-of-flight mass spectrometry

    NARCIS (Netherlands)

    Stowers, M.A.; Wuijckhuijse, A.L. van; Marijnissen, J.C.M.; Scarlett, B.; Baar, B.L.M. van; Kientz, Ch.E.

    2000-01-01

    Matrix-assisted laser desorption/ionization (MALDI) mass spectra were obtained from single biological aerosol particles using an aerosol time-of- flight mass spectrometer (ATOFMS). The inlet to the ATOFMS was coupled with an evaporation/condensation flow cell that allowed the aerosol to be coated wi

  4. Flow injection on-line dilution for multi-element determination in human urine with detection by inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Wang, J.H.; Hansen, E.H.; Gammelgaard, Bente

    2001-01-01

    A simple flow injection on-line dilution procedure with detection by inductively coupled plasma mass spectrometry (ICP-MS) was developed for the determination of copper, zinc, arsenic, lead, selenium, nickel and molybdenum in human urine. Matrix effects were minimized by employing a dilution fact...... of 16.5 with on-line standard addition, and Rh-103 was used as internal standard to compensate for signal fluctuation. The procedure was validated by the analysis of two standard reference materials SRM 2670 (NIST) and Seronorm (TM) Trace Elements in Urine. Recovery experiments were pet...... human urine samples. No correlations between the concentrations of the elements were observed. (C) 2001 Elsevier Science B.V. All rights reserved...

  5. A miniature condensed-phase membrane introduction mass spectrometry (CP-MIMS) probe for direct and on-line measurements of pharmaceuticals and contaminants in small, complex samples.

    Science.gov (United States)

    Duncan, Kyle D; Willis, Megan D; Krogh, Erik T; Gill, Christopher G

    2013-06-15

    High-throughput, automated analytical measurements are desirable in many analytical scenarios, as are rapid sample pre-screening techniques to identify 'positive' samples for subsequent measurements using more time-consuming conventional methodologies (e.g., liquid chromatography/mass spectrometry (LC/MS)). A miniature condensed-phase membrane introduction mass spectrometry (CP-MIMS) probe for the direct and continuous, on-line measurement of pharmaceuticals and environmental contaminants in small, complex samples is presented. A miniature polydimethylsiloxane hollow fibre membrane (PDMS-HFM) probe is coupled with an electrospray ionization (ESI) triple quadrupole mass spectrometer. Analytes are transported from the probe to the ESI source by a methanol acceptor phase. The probe can be autosampler mounted and directly inserted in small samples (≥400 μL) allowing continuous and simultaneous pptr-ppb level detection of target analytes (chlorophenols, triclosan, gemfibrozil, nonylphenol) in complex samples (artificial urine, beer, natural water, waste water, plant tissue). The probe has been characterized and optimized for acceptor phase flow rate, sample mixing and probe washing. Signal response times, detection limits and calibration data are given for selected ion monitoring (SIM) and tandem mass spectrometry (MS/MS) measurements of target analytes at trace levels. Comparisons with flow cell type CP-MIMS systems are given. Analyte depletion effects are evaluated for small samples (≥400 μL). On-line measurements in small volumes of complex samples, temporally resolved reaction monitoring and in situ/in vivo demonstrations are presented. The miniature CP-MIMS probe developed was successfully used for the direct, on-line detection of target analytes in small volumes (40 mL to 400 μL) of complex samples at pptr to low ppb levels. The probe can be readily automated as well as deployed for in situ/in vivo monitoring, including reaction monitoring, small sample

  6. Determination of thorium and light rare-earth elements in soil water and its high molecular mass organic fractions by inductively coupled plasma mass spectrometry and on-line-coupled size-exclusion chromatography.

    Science.gov (United States)

    Casartelli, Evelton A; Miekeley, Norbert

    2003-09-01

    Inductively coupled plasma mass spectrometry (ICP-MS) has been used for the determination of thorium and light rare-earth elements (LREEs) in soil and soil water samples from a mineral deposit (Morro do Ferro, Minas Gerais, Brazil). Size-exclusion chromatography (SEC) on-line coupled to ICP-MS and UV-detection was applied to verify possible association/complexation of these elements with organic matter in soil water separated by a centrifugation technique. Concentrations of DOC in soil waters are in the range of 10 to 500 mg L(-1) and correlate with the organic carbon content of the soil (r=0.950; p10,000 Da, with a retention time of about 10 min; 7000 to 8000 Da with retention times of 13 to 15 min; and 2000 to 4000 Da with retention times around 23 min. Elemental peaks associated with dissolved organic matter below 1000 Da were not observed, suggesting that complexation with simple plant organic acids or inorganic ligands is of minor importance in the environment studied in this work.

  7. First laser ions at an off-line mass separator of the ISAC facility at TRIUMF

    CERN Document Server

    Rauth, C; Horn, R; Lassen, J; Bricault, P; Wendt, K; 10.1016/j.nimb.2003.08.029

    2004-01-01

    For efficient and in particular for selective production of radioactive ion beams at on-line mass separator facilities the technique of resonance ionization laser ion sources (RILlS) has become the most powerful tool. In facilities like ISOLDE at CERN they nowadays represent the most commonly used type of ion source for rare short-lived isotopes, delivering highest suppression of isobaric contaminations. For a first off-line demonstration preparing the development and installation of such a laser ion source at the new ISAC facility at TRIUMF in Vancouver (Canada), an all solid state laser system developed at the University of Mainz (Germany), was transferred and tested there at an off-line test separator. The laser system consists of three tunable titanium:sapphire lasers with a repetition rate of 12 kHz, pulse length of ~30 ns, up to 2.5 W output power in the infrared to red spectral region and features additional frequency doubling units. With this system first RILIS studies were performed in a number of el...

  8. Comparison of direct infusion and on-line liquid chromatography/electrospray ionization mass spectrometry for the analysis of nucleic acids.

    Science.gov (United States)

    Huber, C G; Krajete, A

    2000-07-01

    The applicability of ion-pair reversed-phase high-performance liquid chromatography/electrospray ionization mass spectrometry (IP-RP-HPLC/ESI-MS) and direct infusion/ESI-MS to the characterization of nucleic acid mixtures was evaluated by the analysis of the reaction products obtained from solid-phase synthesis of a 39-mer oligonucleotide. IP-RP-HPLC/ESI-MS was performed using 200 microm i.d. capillary columns packed with octadecylated, micropellicular poly(styrene-divinylbenzene) particles and applying gradients of acetonitrile in 50 mM triethylammonium bicarbonate (TEAB). Three different solvent systems were utilized for direct infusion/ESI-MS with removal of metal cations by on-line cation exchange: (1) 10 mM triethylamine (TEA) in 50% aqueous acetonitrile, (2) 2.2 mM TEA, 400 mM hexafluoro-2-propanol (HFIP) in 20% aqueous methanol and (3) 50 mM TEAB in 10% aqueous acetonitrile. Owing to its separation capability, the highest selectivity and specificity were achieved with IP-RP-HPLC/ESI-MS, which, apart form the 39-mer target sequence, allowed the identification of two isobutyryl-protected target sequences and a 10-mer and 20-mer failure sequence. Direct infusion/ESI-MS with TEA-acetonitrile or TEA-HFIP-methanol as solvent revealed signals for the 39-mer in the m/z range 700-1600. The presence of derivatives containing one, two, three and four isobutyryl groups indicated that the hydrolysis of the protecting groups after solid-phase synthesis was not complete. Failure sequences could not be identified by direct infusion/ESI-MS under conditions favoring multiple charging of the analytes owing to the high chemical background and coincidental overlapping of m/z signals. However, efficient charge state reduction upon addition of carbonic acid to the electrosprayed solvent shifted the signals of the 39-mer and derivatives to m/z values >2400 and allowed the detection of seven different failure sequences, ranging from the 8-mer to the 23-mer, in the mixture.

  9. On-line two-dimensional capillary electrophoresis with mass spectrometric detection using a fully electric isolated mechanical valve.

    Science.gov (United States)

    Kohl, Felix J; Montealegre, Cristina; Neusüß, Christian

    2016-04-01

    CE is becoming more and more important in many fields of bioanalytical chemistry. Besides optical detection, hyphenation to ESI-MS detection is increasingly applied for sensitive identification purposes. Unfortunately, many CE techniques and methods established in research and industry are not compatible to ESI-MS since essential components of the background electrolyte interfere in ES ionization. In order to identify unknown peaks in established CE methods, here, a heart-cut 2D-CE separation system is introduced using a fully isolated mechanical valve with an internal loop of only 20 nL. In this system, the sample is separated using potentially any non-ESI compatible method in the first separation dimension. Subsequently, the portion of interest is cut by the internal sample loop of the valve and reintroduced to the second dimension where the interfering compounds are removed, followed by ESI-MS detection. When comparing the separation efficiency of the system with the valve to a system using a continuous capillary only a slight increase in peak width is observed. Ultraviolet/visible detection is integrated in the first dimension for switching time determination, enabling reproducible cutting of peaks of interest. The feasibility of the system is successfully demonstrated by a 2D analysis of a BSA tryptic digest sample using a nonvolatile (phosphate based) background electrolyte in the first dimension.

  10. On-Line, Gyro-Based, Mass-Property Identification for Thruster-Controlled Spacecraft Using Recursive Least Squares

    Science.gov (United States)

    Wilson, Edward; Lages, Chris; Mah, Robert; Clancy, Daniel (Technical Monitor)

    2002-01-01

    Spacecraft control, state estimation, and fault-detection-and-isolation systems are affected by unknown v aerations in the vehicle mass properties. It is often difficult to accurately measure inertia terms on the ground, and mass properties can change on-orbit as fuel is expended, the configuration changes, or payloads are added or removed. Recursive least squares -based algorithms that use gyro signals to identify the center of mass and inverse inertia matrix are presented. They are applied in simulation to 3 thruster-controlled vehicles: the X-38 and Mini-AERCam under development at NASA-JSC, and the SAM, an air-bearing spacecraft simulator at the NASA-Ames Smart Systems Research Lab (SSRL).

  11. On-Line Derivatization Gas Chromatography Ion Trap Mass Spectrometry for Determination of Endocrine Disruptors in Surface Water

    Energy Technology Data Exchange (ETDEWEB)

    Tzing, Shin-Hwa; Chang, Jia-Yaw; Ling, Yong-Chien

    2004-03-31

    A method has been developed for the determination of endocrine disruptors (EDs) (containing hydroxyl groups) in surface water from different sources. The surface water samples from different sites including school and local dormitory sewage effluents, lake water and river water were collected and analyzed. In this method, the pretreated sample is directly analyzed by GC-MS using on-line derivatization, where tetramethylammonium hydroxide (TMA-OH) was used as the derivatizing agent. Use of large-volume direct sample introduction (DSI) and co-injection of the sample and TMAOH avoids external contaminations as observed in conventional derivatization protocols. Additionally, the use of chemical ionization (CI) and CI-MS/MS could enable detection of EDs at lower concentrations and reduce the matrices' interference thereby enhancing detection sensitivity of EDs for quantification. In this work, the use of dichloromethane as CI reagent for EDs is reported for the first time and could detect EDs to concentrations as low as 0.5 pg/mL. The recovery ranged from 74 to 112 % and the relative standard derivations for replicate analyses ranged from 5 to 17 %. We hope that this method will be applicable for routine analysis of EDs with hydroxyl functional groups.

  12. Application of on-line electrochemistry/electrospray/tandem mass spectrometry to a quantification method for the antipsychotic drug zotepine in human serum.

    Science.gov (United States)

    Nozaki, Kazuyoshi; Osaka, Issey; Kawasaki, Hideya; Arakawa, Ryuichi

    2009-10-01

    A simple, rapid, and sensitive on-line liquid chromatographic electrochemistry/electrospray/tandem mass spectrometry (LC-EC/ESI-MS/MS) method for the determination of zotepine in human serum was developed using a new generated-electrochemically fragment ion, and was validated. A recent novel technique of LC-EC/ESI-MS/MS that combines LC-MS/MS and the on-line EC reaction is potentially applicable to developing a quantification method for drugs in biological samples. Newly formed products generated by the on-line EC cell are expected to provide appropriate precursor and product ions for the MS/MS determination method. This technique was successfully applied to a drug assay in a biological matrix. After adding imipramine (IS) to a 30-microL aliquot of human serum, the resulting sample was simply deproteinated with acetonitrile for a measurement. The analytical run time was 5 min. The calibration curve was linear in the concentration range of 10-2000 ng/mL. The intra-assay precision and accuracy were in the range of 1.8-8.9 and 98.4-113%, respectively.

  13. Integrated microfluidic system enabling (bio)chemical reactions with on-line MALDI-TOF mass spectrometry

    NARCIS (Netherlands)

    Brivio, Monica; Fokkens, Roel H.; Verboom, Willem; Reinhoudt, David N.; Tas, Niels R.; Goedbloed, Martijn; Berg, van den Albert

    2002-01-01

    A continuous flow micro total analysis system (μ-TAS) consisting of an on-chip microfluidic device connected to a matrix assisted laser desorption ionization [MALDI] time-of-flight [TOF] mass spectrometer (MS) as an analytical screening system is presented. Reaction microchannels and inlet/outlet re

  14. ARTICLES: Influence Factors on Particle Growth for On-line Aerosol Matrix-assisted Laser Desorption/Ionization Time-of-flight Mass Spectrometry

    Science.gov (United States)

    Xia, Wei-wei; Ti, Ru-fang; Zhang, Zi-Iiang; Zheng, Hai-yang; Fang, Li

    2010-06-01

    An evaporation/condensation flow cell was developed and interfaced with the matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectrometer for on-line bioaerosol detection and characterization, which allows matrix addition by condensation onto the laboratory-generated bioaerosol particles. The final coated particle exiting from the condenser is then introduced into the aerodynamic particle sizer spectrometer or home-built aerosol laser time-of-flight mass spectrometer, and its aerodynamic size directly effects on the matrix-to-analyte molar ratio, which is very important for MALDI technique. In order to observe the protonated analyte molecular ion, and then determine the classification of biological aerosols, the matrix-to-analyte molar ratio must be appropriate. Four experimental parameters, including the temperature of the heated reservoir, the initial particle size, its number concentration, and the matrix material, were tested experimentally to analyze their influences on the final particle size. This technique represents an on-line system of detection that has the potential to provide rapid and reliable identification of airborne biological aerosols.

  15. Impurity profiling of liothyronine sodium by means of reversed phase HPLC, high resolution mass spectrometry, on-line H/D exchange and UV/Vis absorption.

    Science.gov (United States)

    Ruggenthaler, M; Grass, J; Schuh, W; Huber, C G; Reischl, R J

    2017-09-05

    For the first time, a comprehensive investigation of the impurity profile of the synthetic thyroid API (active pharmaceutical ingredient) liothyronine sodium (LT3Na) was performed by using reversed phase HPLC and advanced structural elucidation techniques including high resolution tandem mass spectrometry (HRMS/MS) and on-line hydrogen-deuterium (H/D) exchange. Overall, 39 compounds were characterized and 25 of these related substances were previously unknown to literature. The impurity classification system recently developed for the closely related API levothyroxine sodium (LT4Na) could be applied to the newly characterized liothyronine sodium impurities resulting in a wholistic thyroid API impurity classification system. Furthermore, the mass-spectrometric CID-fragmentation of specific related substances was discussed and rationalized by detailed fragmentation pathways. Moreover, the UV/Vis absorption characteristics of the API and selected impurities were investigated to corroborate chemical structure assignments derived from MS data. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Automated on-line liquid–liquid extraction system for temporal mass spectrometric analysis of dynamic samples

    Energy Technology Data Exchange (ETDEWEB)

    Hsieh, Kai-Ta; Liu, Pei-Han [Department of Applied Chemistry, National Chiao Tung University, 1001 University Rd, Hsinchu, 300, Taiwan (China); Urban, Pawel L. [Department of Applied Chemistry, National Chiao Tung University, 1001 University Rd, Hsinchu, 300, Taiwan (China); Institute of Molecular Science, National Chiao Tung University, 1001 University Rd, Hsinchu, 300, Taiwan (China)

    2015-09-24

    Most real samples cannot directly be infused to mass spectrometers because they could contaminate delicate parts of ion source and guides, or cause ion suppression. Conventional sample preparation procedures limit temporal resolution of analysis. We have developed an automated liquid–liquid extraction system that enables unsupervised repetitive treatment of dynamic samples and instantaneous analysis by mass spectrometry (MS). It incorporates inexpensive open-source microcontroller boards (Arduino and Netduino) to guide the extraction and analysis process. Duration of every extraction cycle is 17 min. The system enables monitoring of dynamic processes over many hours. The extracts are automatically transferred to the ion source incorporating a Venturi pump. Operation of the device has been characterized (repeatability, RSD = 15%, n = 20; concentration range for ibuprofen, 0.053–2.000 mM; LOD for ibuprofen, ∼0.005 mM; including extraction and detection). To exemplify its usefulness in real-world applications, we implemented this device in chemical profiling of pharmaceutical formulation dissolution process. Temporal dissolution profiles of commercial ibuprofen and acetaminophen tablets were recorded during 10 h. The extraction-MS datasets were fitted with exponential functions to characterize the rates of release of the main and auxiliary ingredients (e.g. ibuprofen, k = 0.43 ± 0.01 h{sup −1}). The electronic control unit of this system interacts with the operator via touch screen, internet, voice, and short text messages sent to the mobile phone, which is helpful when launching long-term (e.g. overnight) measurements. Due to these interactive features, the platform brings the concept of the Internet-of-Things (IoT) to the chemistry laboratory environment. - Highlights: • Mass spectrometric analysis normally requires sample preparation. • Liquid–liquid extraction can isolate analytes from complex matrices. • The proposed system automates

  17. Multiple concurrent recursive least squares identification with application to on-line spacecraft mass-property identification

    Science.gov (United States)

    Wilson, Edward (Inventor)

    2006-01-01

    The present invention is a method for identifying unknown parameters in a system having a set of governing equations describing its behavior that cannot be put into regression form with the unknown parameters linearly represented. In this method, the vector of unknown parameters is segmented into a plurality of groups where each individual group of unknown parameters may be isolated linearly by manipulation of said equations. Multiple concurrent and independent recursive least squares identification of each said group run, treating other unknown parameters appearing in their regression equation as if they were known perfectly, with said values provided by recursive least squares estimation from the other groups, thereby enabling the use of fast, compact, efficient linear algorithms to solve problems that would otherwise require nonlinear solution approaches. This invention is presented with application to identification of mass and thruster properties for a thruster-controlled spacecraft.

  18. Monitoring of an esterification reaction by on-line direct liquid sampling mass spectrometry and in-line mid infrared spectrometry with an attenuated total reflectance probe

    Energy Technology Data Exchange (ETDEWEB)

    Owen, Andrew W.; McAulay, Edith A.J. [WestCHEM, Department of Pure and Applied Chemistry and CPACT, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL (United Kingdom); Nordon, Alison, E-mail: alison.nordon@strath.ac.uk [WestCHEM, Department of Pure and Applied Chemistry and CPACT, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL (United Kingdom); Littlejohn, David, E-mail: d.littlejohn@strath.ac.uk [WestCHEM, Department of Pure and Applied Chemistry and CPACT, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL (United Kingdom); Lynch, Thomas P. [WestCHEM, Department of Pure and Applied Chemistry and CPACT, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL (United Kingdom); Lancaster, J. Steven [Hull Research and Technology Centre, BP Chemicals, Hull, HU12 8DS (United Kingdom); Wright, Robert G. [Thermo Fisher Scientific, Winsford, Cheshire, CW7 3GA (United Kingdom)

    2014-11-07

    Highlights: • High efficiency thermal vaporiser designed and used for on-line reaction monitoring. • Concentration profiles of all reactants and products obtained from mass spectra. • By-product formed from the presence of an impurity detected by MS but not MIR. • Mass spectrometry can detect trace and bulk components unlike molecular spectrometry. - Abstract: A specially designed thermal vaporiser was used with a process mass spectrometer designed for gas analysis to monitor the esterification of butan-1-ol and acetic anhydride. The reaction was conducted at two scales: in a 150 mL flask and a 1 L jacketed batch reactor, with liquid delivery flow rates to the vaporiser of 0.1 and 1.0 mL min{sup −1}, respectively. Mass spectrometry measurements were made at selected ion masses, and classical least squares multivariate linear regression was used to produce concentration profiles for the reactants, products and catalyst. The extent of reaction was obtained from the butyl acetate profile and found to be 83% and 76% at 40 °C and 20 °C, respectively, at the 1 L scale. Reactions in the 1 L reactor were also monitored by in-line mid-infrared (MIR) spectrometry; off-line gas chromatography (GC) was used as a reference technique when building partial least squares (PLS) multivariate calibration models for prediction of butyl acetate concentrations from the MIR spectra. In validation experiments, good agreement was achieved between the concentration of butyl acetate obtained from in-line MIR spectra and off-line GC. In the initial few minutes of the reaction the profiles for butyl acetate derived from on-line direct liquid sampling mass spectrometry (DLSMS) differed from those of in-line MIR spectrometry owing to the 2 min transfer time between the reactor and mass spectrometer. As the reaction proceeded, however, the difference between the concentration profiles became less noticeable. DLSMS had advantages over in-line MIR spectrometry as it was easier to

  19. Polymer monolithic capillary microextraction on-line coupled with inductively coupled plasma-mass spectrometry for the determination of trace Au and Pd in biological samples

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xiaolan; He, Man; Chen, Beibei; Hu, Bin, E-mail: binhu@whu.edu.cn

    2014-11-01

    A novel method based on on-line polymer monolithic capillary microextraction (CME)-inductively coupled plasma mass spectrometry (ICP-MS) was developed for the determination of trace Au and Pd in biological samples. For this purpose, poly(glycidyl methacrylate-ethylene dimethacrylate) monolith was prepared and functionalized with mercapto groups. The prepared monolith exhibited good selectivity to Au and Pd, and good resistance to strong acid with a long life span. Factors affecting the extraction efficiency of CME, such as sample acidity, sample flow rate, eluent conditions and coexisting ion interference were investigated in detail. Under the optimal conditions, the limits of detection (LODs, 3σ) were 5.9 ng L{sup −1} for Au and 8.3 ng L{sup −1} for Pd, and the relative standard deviations (RSDs, c = 50 ng L{sup −1}, n = 7) were 6.5% for Au and 1.1% for Pd, respectively. The developed method was successfully applied to the determination of Au and Pd in human urine and serum samples with the recovery in the range of 84–118% for spiked samples. The developed on-line polymer monolithic CME-ICP-MS method has the advantages of rapidity, simplicity, low sample/reagent consumption, high sensitivity and is suitable for the determination of trace Au and Pd in biological samples with limited amount available and complex matrix. - Highlights: • An on-line CME-ICP-MS method was developed for Au and Pd analysis in human fluids. • Poly(GMA-EDMA-SH) monolith exhibited good selectivity for Au/Pd and acid-resistance. • The method is rapid, simple, and sensitive with low sample/reagents consumption.

  20. Ion reactions for isobar separation in accelerator mass spectrometry

    CERN Document Server

    Litherland, A E; Doupe, J P

    2003-01-01

    The use of resonant and near resonant keV ion reactions for isobar separation in AMS is discussed. It is shown that these and other ionic reactions can be useful provided that the multiple scattering is taken into account.

  1. Determination of paraben preservatives in seafood using matrix solid-phase dispersion and on-line acetylation gas chromatography-mass spectrometry.

    Science.gov (United States)

    Djatmika, Rosalina; Hsieh, Chih-Chung; Chen, Jhih-Ming; Ding, Wang-Hsien

    2016-11-15

    An effective method for determining four commonly detected paraben preservatives (methyl, ethyl, propyl and butyl paraben) in marketed seafood is presented. This method employs matrix solid-phase dispersion (MSPD) before identification and quantification of the paraben preservatives via on-line acetylation gas chromatography-mass spectrometry (GC-MS). Parameters affecting the extraction efficiency of MSPD were optimized through a Box-Behnken design method. Under optimal condition, 0.5-g of freeze-dried seafood was mixed with 0.5-g of anhydrous sodium sulfate, and dispersed with 1.0-g of Florisil using vortex. After that, the blend was transferred to a glass column containing 1.5-g of silica gel+C18 (w/w, 9:1), which acted as clean-up co-sorbents. Then, target analytes were eluted with 12mL of acetonitrile. The extract was then derivatized on-line in the GC injection-port through reaction with acetic anhydride, and the identity and quantity of the target analytes were determined by the GC-MS system. The limits of quantitation (LOQs) were 0.2 to 1.0ng/g (dry weight). Preliminary results showed that the total concentrations of four selected parabens ranged from 16.7 to 44.7ng/g (dry weight).

  2. Radio-frequency ion deflector for mass separation

    Energy Technology Data Exchange (ETDEWEB)

    Schlösser, Magnus, E-mail: magnus.schloesser@googlemail.com; Rudnev, Vitaly; Ureña, Ángel González, E-mail: laseres@pluri.ucm.es [Unidad de Láseres y Haces Moleculares, Instituto Plurisdisciplinar, Universidad Complutense de Madrid, Madrid 28040 (Spain)

    2015-10-15

    Electrostatic cylindrical deflectors act as energy analyzer for ion beams. In this article, we present that by imposing of a radio-frequency modulation on the deflecting electric field, the ion transmission becomes mass dependent. By the choice of the appropriate frequency, amplitude, and phase, the deflector can be used as mass filter. The basic concept of the new instrument as well as simple mathematic relations are described. These calculations and further numerical simulations show that a mass sensitivity is achievable. Furthermore, we demonstrate the proof-of-principle in experimental measurements, compare the results to those of from a 1 m linear time-of-flight spectrometer, and comment on the mass resolution of the method. Finally, some potential applications are indicated.

  3. Looking into individual coffee beans during the roasting process: direct micro-probe sampling on-line photo-ionisation mass spectrometric analysis of coffee roasting gases.

    Science.gov (United States)

    Hertz-Schünemann, Romy; Streibel, Thorsten; Ehlert, Sven; Zimmermann, Ralf

    2013-09-01

    A micro-probe (μ-probe) gas sampling device for on-line analysis of gases evolving in confined, small objects by single-photon ionisation time-of-flight mass spectrometry (SPI-TOFMS) was developed. The technique is applied for the first time in a feasibility study to record the formation of volatile and flavour compounds during the roasting process within (inside) or in the direct vicinity (outside) of individual coffee beans. A real-time on-line analysis of evolving volatile and semi-volatile organic compounds (VOC and SVOC) as they are formed under the mild pyrolytic conditions of the roasting process was performed. The soft-ionisation mass spectra depict a molecular ion signature, which is well corresponding with the existing knowledge of coffee roasting and evolving compounds. Additionally, thereby it is possible to discriminate between Coffea arabica (Arabica) and Coffea canephora (Robusta). The recognized differences in the roasting gas profiles reflect the differences in the precursor composition of the coffee cultivars very well. Furthermore, a well-known set of marker compounds for Arabica and Robusta, namely the lipids kahweol and cafestol (detected in their dehydrated form at m/z 296 and m/z 298, respectively) were observed. If the variation in time of different compounds is observed, distinctly different evolution behaviours were detected. Here, phenol (m/z 94) and caffeine (m/z 194) are exemplary chosen, whereas phenol shows very sharp emission peaks, caffeine do not have this highly transient behaviour. Finally, the changes of the chemical signature as a function of the roasting time, the influence of sampling position (inside, outside) and cultivar (Arabica, Robusta) is investigated by multivariate statistics (PCA). In summary, this pilot study demonstrates the high potential of the measurement technique to enhance the fundamental knowledge of the formation processes of volatile and semi-volatile flavour compounds inside the individual coffee bean.

  4. On-line analysis of secondary ozonides from cyclohexene and D-limonene ozonolysis using atmospheric sampling townsend discharge ionization mass spectrometry

    Science.gov (United States)

    Nøjgaard, J. K.; Nørgaard, A. W.; Wolkoff, P.

    An on-line technique has been developed for analysis of gas-phase oxidation products formed in a reaction flow tube using different reaction times, concentrations and humidities. Products of ozonolysis, including thermally labile secondary ozonides (SOZ), were directly introduced into an atmospheric sampling townsend discharge ionization (ASTDI) source coupled to a triple quadrupole mass spectrometer (MS). Instant changes in the product composition were monitored in the total-ion chromatogram, or by fragment ions in the collision activated dissociation mass spectra by use of MS/MS scan techniques. Assignment of the individual ions was accomplished by inspection of the products' mass spectra obtained by pre-concentration of the gas phase on a dedicated short column followed by chromatographic analysis. The observed reaction products correspond to those identified with other techniques. Of relevance for future mechanistic modelling, is the point that conditions of excess D-limonene favoured the formation of the D-limonene SOZ (major product), which was observed to be quite stable in dry and humid air, without oxidants. The D-limonene/ozone ratio was observed to be crucial for the stability of the SOZ, because it is prone to ozonolysis, and no SOZ could be detected in completely reacted 1:1 mixtures.

  5. On-line high-performance liquid chromatography-fluorescence detection-electrospray ionization-mass spectrometry profiling of human milk oligosaccharides derivatized with 2-aminoacridone.

    Science.gov (United States)

    Galeotti, Fabio; Coppa, Giovanni V; Zampini, Lucia; Maccari, Francesca; Galeazzi, Tiziana; Padella, Lucia; Santoro, Lucia; Gabrielli, Orazio; Volpi, Nicola

    2012-11-01

    A high-resolution normal-phase high-performance liquid chromatography-fluorescence detection-electrospray ionization-mass spectrometry separation and structural characterization of the main oligosaccharides along with lactose from human milk samples is described. A total of 22 commercially available oligosaccharides were fluorotagged with 2-aminoacridone and separated on an amide column and identified on the basis of their retention times and mass spectra. Derivatized species having mass lower than approximately 800 to 900 exhibited mainly [M-H](-1) anions, oligomers with mass up to approximately 1000 to 1100 were represented by both [M-H](-1) and [M-2H](-2) anions, and oligomers greater than approximately 1200 to 1300 were characterized by a charge state of -3. Furthermore, the retention times were directly related to the glycans' molecular mass. Human milk samples from the four groups of donors (Se±/Le±) were analyzed for their composition and amount of free oligosaccharides after rapid and simple prepurification and derivatization steps also in the presence of lactose in high content. This analytical approach enabled us to perform the determination of species not detected by traditional techniques, such as sialic acid, as well as of species present in low content easily mistaken with other peaks. Finally, labeled human milk oligosaccharides were analyzed without any interference from excess fluorophore or interference from proteins, peptides, salts, and other impurities normally present in this complex biological fluid.

  6. Penning trap for isobaric mass separation at IGISOL

    CERN Document Server

    Kolhinen, V; Hakala, J; Jokinen, A; Kopecky, S; Rinta-Antila, S; Szerypo, J; Äystö, J

    2003-01-01

    A cylindrical Penning trap has been built at the ion guide isotope separator facility IGISOL of the University of Jyvaeskylae. The main goal of the Penning trap application is to purify low-energy radioactive ion beams. The aim is to make isobarically pure beams. The technical description is presented.

  7. Penning trap for isobaric mass separation at IGISOL

    Energy Technology Data Exchange (ETDEWEB)

    Kolhinen, V.S. E-mail: veli.kolhinen@phys.jyu.fi; Eronen, T.; Hakala, J.; Jokinen, A.; Kopecky, S.; Rinta-Antila, S.; Szerypo, J.; Aeystoe, J

    2003-05-01

    A cylindrical Penning trap has been built at the ion guide isotope separator facility IGISOL of the University of Jyvaeskylae. The main goal of the Penning trap application is to purify low-energy radioactive ion beams. The aim is to make isobarically pure beams. The technical description is presented.

  8. Laser vaporization/ionization interface for coupling microscale separation techniques with mass spectrometry

    Science.gov (United States)

    Yeung, E.S.; Chang, Y.C.

    1999-06-29

    The present invention provides a laser-induced vaporization and ionization interface for directly coupling microscale separation processes to a mass spectrometer. Vaporization and ionization of the separated analytes are facilitated by the addition of a light-absorbing component to the separation buffer or solvent. 8 figs.

  9. Analysis of biogenic carbonates by inductively coupled plasma-mass spectrometry (ICP-MS). Flow injection on-line solid-phase preconcentration for trace element determination in fish otoliths.

    Science.gov (United States)

    Arslan, Z; Paulson, A J

    2002-04-01

    The aragonite deposits within the ear bones (otoliths) of teleost fish retain a chemical signal reflecting the life history of fish (similar to rings of trees) and the nature of fish habitats. Otoliths dissolved in acid solutions contain high concentrations of calcium and a variety of proteins. Elimination of matrix salts and organic interferences during preconcentration is essential for accurate determination of trace elements in otolith solutions by inductively coupled plasma-quadrupole mass spectrometry. An iminodiacetate-based chelating resin (Toyopearl AF-Chelate 650 M) has been used for on-line preconcentration and matrix separation for the determination of 31 transition and rare elements. Successful preconcentration of the elements was achieved at pH 5 by on-line buffering, except Mn which required pH 8.8. Sample solutions were loaded on to the column for 1 min at 3.2 mL min(-1), and then eluted directly into the mass spectrometer with 4% v/v nitric acid. This procedure enabled up to 25-fold preconcentration with successful removal of the calcium matrix. The effect of heat-assisted oxidation with concentrated nitric acid was investigated to eliminate the organic matrix. It was found that heating to dryness after dissolution and further mineralization with the acid significantly improved the retention of the transition elements. The method was validated by analysis of a certified reference material produced from saggittal otoliths of emperor snapper ( Lutjanus sebae), and then applied to the determination of trace metal concentrations in juvenile bluefin tuna ( Thunnus thynnus) from the Western Pacific Ocean.

  10. Analysis of biogenic carbonates by inductively coupled plasma-mass spectrometry (ICP-MS). Flow injection on-line solid-phase preconcentration for trace element determination in fish otoliths

    Energy Technology Data Exchange (ETDEWEB)

    Arslan, Z.; Paulson, A.J. [National Oceanic and Atmospheric Administration (NOAA), Northeast Fisheries Science Center (NFSC), James J. Howard Marine Sciences Laboratory, Highlands, NJ (United States)

    2002-04-01

    The aragonite deposits within the ear bones (otoliths) of teleost fish retain a chemical signal reflecting the life history of fish (similar to rings of trees) and the nature of fish habitats. Otoliths dissolved in acid solutions contain high concentrations of calcium and a variety of proteins. Elimination of matrix salts and organic interferences during preconcentration is essential for accurate determination of trace elements in otolith solutions by inductively coupled plasma-quadrupole mass spectrometry. An iminodiacetate-based chelating resin (Toyopearl AF-Chelate 650 M) has been used for on-line preconcentration and matrix separation for the determination of 31 transition and rare elements. Successful preconcentration of the elements was achieved at pH 5 by on-line buffering, except Mn which required pH 8.8. Sample solutions were loaded on to the column for 1 min at 3.2 mL min{sup -1}, and then eluted directly into the mass spectrometer with 4% v/v nitric acid. This procedure enabled up to 25-fold preconcentration with successful removal of the calcium matrix. The effect of heat-assisted oxidation with concentrated nitric acid was investigated to eliminate the organic matrix. It was found that heating to dryness after dissolution and further mineralization with the acid significantly improved the retention of the transition elements. The method was validated by analysis of a certified reference material produced from saggittal otoliths of emperor snapper (Lutjanus sebae), and then applied to the determination of trace metal concentrations in juvenile bluefin tuna (Thunnus thynnus) from the Western Pacific Ocean. (orig.)

  11. Single particle mass spectral signatures from vehicle exhaust particles and the source apportionment of on-line PM2.5 by single particle aerosol mass spectrometry.

    Science.gov (United States)

    Yang, Jian; Ma, Shexia; Gao, Bo; Li, Xiaoying; Zhang, Yanjun; Cai, Jing; Li, Mei; Yao, Ling'ai; Huang, Bo; Zheng, Mei

    2017-09-01

    In order to accurately apportion the many distinct types of individual particles observed, it is necessary to characterize fingerprints of individual particles emitted directly from known sources. In this study, single particle mass spectral signatures from vehicle exhaust particles in a tunnel were performed. These data were used to evaluate particle signatures in a real-world PM2.5 apportionment study. The dominant chemical type originating from average positive and negative mass spectra for vehicle exhaust particles are EC species. Four distinct particle types describe the majority of particles emitted by vehicle exhaust particles in this tunnel. Each particle class is labeled according to the most significant chemical features in both average positive and negative mass spectral signatures, including ECOC, NaK, Metal and PAHs species. A single particle aerosol mass spectrometry (SPAMS) was also employed during the winter of 2013 in Guangzhou to determine both the size and chemical composition of individual atmospheric particles, with vacuum aerodynamic diameter (dva) in the size range of 0.2-2μm. A total of 487,570 particles were chemically analyzed with positive and negative ion mass spectra and a large set of single particle mass spectra was collected and analyzed in order to identify the speciation. According to the typical tracer ions from different source types and classification by the ART-2a algorithm which uses source fingerprints for apportioning ambient particles, the major sources of single particles were simulated. Coal combustion, vehicle exhaust, and secondary ion were the most abundant particle sources, contributing 28.5%, 17.8%, and 18.2%, respectively. The fraction with vehicle exhaust species particles decreased slightly with particle size in the condensation mode particles. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Pressure-assisted electrokinetic injection for on-line enrichment in capillary electrophoresis-mass spectrometry: a sensitive method for measurement of ten haloacetic acids in drinking water.

    Science.gov (United States)

    Zhang, Huijuan; Zhu, Jiping; Aranda-Rodriguez, Rocio; Feng, Yong-Lai

    2011-11-07

    Haloacetic acids (HAAs) are by-products of the chlorination of drinking water containing natural organic matter and bromide. A simple and sensitive method has been developed for determination of ten HAAs in drinking water. The pressure-assisted electrokinetic injection (PAEKI), an on-line enrichment technique, was employed to introduce the sample into a capillary electrophoresis (CE)-electrospray ionization-tandem mass spectrometry system (ESI-MS/MS). HAAs were monitored in selected reaction monitoring mode. With 3 min of PAEKI time, the ten major HAAs (HAA10) in drinking water were enriched up to 20,000-fold into the capillary without compromising resolution. A simple solid phase clean-up method has been developed to eliminate the influence of ionic matrices from drinking water on PAEKI. Under conditions optimized for mass spectrometry, PAEKI and capillary electrophoresis, detection limits defined as three times ratio of signal to noise have been achieved in a range of 0.013-0.12 μg L(-1) for ten HAAs in water sample. The overall recoveries for all ten HAAs in drinking water samples were between 76 and 125%. Six HAAs including monochloro- (MCAA), dichloro- (DCAA), trichloro- (TCAA), monobromo- (MBAA), bromochloro- (BCAA), and bromodichloroacetic acids (BDCAA) were found in tap water samples collected.

  13. Organotin speciation in environmental matrices by automated on-line hydride generation-programmed temperature vaporization-capillary gas chromatography-mass spectrometry detection.

    Science.gov (United States)

    Serra, H; Nogueira, J M F

    2005-11-11

    In the present contribution, a new automated on-line hydride generation methodology was developed for dibutyltin and tributyltin speciation at the trace level, using a programmable temperature-vaporizing inlet followed by capillary gas chromatography coupled to mass spectrometry in the selected ion-monitoring mode acquisition (PTV-GC/MS(SIM)). The methodology involves a sequence defined by two running methods, the first one configured for hydride generation with sodium tetrahydroborate as derivatising agent and the second configured for speciation purposes, using a conventional autosampler and data acquisition controlled by the instrument's software. From the method-development experiments, it had been established that injector configuration has a great effect on the speciation of the actual methodology, particularly, the initial inlet temperature (-20 degrees C; He: 150 ml/min), injection volume (2 microl) and solvent characteristics using the solvent venting mode. Under optimized conditions, a remarkable instrumental performance including very good precision (RSD CRM 462, Nr. 330 dibutyltin: 68+/-12 ng/g; tributyltin: 54+/-15 ng/g on dry mass basis), using liquid-liquid extraction (LLE) and solid-phase extraction (SPE) sample enrichment and multiple injections (2 x 5 microl) for sensitivity enhancement. The methodology evidenced high reproducibility, is easy to work-up, sensitive and showed to be a suitable alternative to replace the currently dedicated analytical systems for organotin speciation in environmental matrices at the trace level.

  14. New on-line separation workflow of microbial metabolites via hyphenation of analytical and preparative comprehensive two-dimensional liquid chromatography.

    Science.gov (United States)

    Yan, Xia; Wang, Li-Juan; Wu, Zhen; Wu, Yun-Long; Liu, Xiu-Xiu; Chang, Fang-Rong; Fang, Mei-Juan; Qiu, Ying-Kun

    2016-10-15

    Microbial metabolites represent an important source of bioactive natural products, but always exhibit diverse of chemical structures or complicated chemical composition with low active ingredients content. Traditional separation methods rely mainly on off-line combination of open-column chromatography and preparative high performance liquid chromatography (HPLC). However, the multi-step and prolonged separation procedure might lead to exposure to oxygen and structural transformation of metabolites. In the present work, a new two-dimensional separation workflow for fast isolation and analysis of microbial metabolites from Chaetomium globosum SNSHI-5, a cytotoxic fungus derived from extreme environment. The advantage of this analytical comprehensive two-dimensional liquid chromatography (2D-LC) lies on its ability to analyze the composition of the metabolites, and to optimize the separation conditions for the preparative 2D-LC. Furthermore, gram scale preparative 2D-LC separation of the crude fungus extract could be performed on a medium-pressure liquid chromatograph×preparative high-performance liquid chromatography system, under the optimized condition. Interestingly, 12 cytochalasan derivatives, including two new compounds named cytoglobosin Ab (3) and isochaetoglobosin Db (8), were successfully obtained with high purity in a short period of time. The structures of the isolated metabolites were comprehensively characterized by HR ESI-MS and NMR. To be highlighted, this is the first report on the combination of analytical and preparative 2D-LC for the separation of microbial metabolites. The new workflow exhibited apparent advantages in separation efficiency and sample treatment capacity compared with conventional methods.

  15. Determination of parabens in human urine by optimal ultrasound-assisted emulsification microextraction and on-line acetylation gas chromatography-mass spectrometry.

    Science.gov (United States)

    Hui-Ting, Zhou; Ding, Erica M C; Ding, Wang-Hsien

    2017-07-15

    An effective and solvent-less method for the rapid determination of four commonly detected parabens (methyl-, ethyl-, propyl- and butyl-) in human urine samples is described. This method employed ultrasound-assisted emulsification microextraction (USAEME) before identification and quantitation of the parabens via on-line acetylation gas chromatography-mass spectrometry (GC-MS). Urine samples were enzymatically de-conjugated with β-glucuronidase and then extracted by an optimal USAEME procedure for the measurement of total concentrations of target analytes. The optimal USAEME parameters for one mL of urine sample (containing 0.1-g of sodium chloride), according to the Box-Behnken design method, are thus described: extractant of 200-μL of ethyl acetate, and ultrasonication for 1.0min and centrifugation at 7000rpm (3min). The supernatant was collected and evaporated until dry. Then the residue was re-dissolved in methanol (100-μL), and the extract was subjected to on-line acetylation GC-MS analysis. The limits of quantitation (LOQs) were less than 0.06ng/mL. Precisions for both intra- and inter-day analysis were calculated, and were less than 8%. Mean extraction recovery (known as trueness) was between 83 and 101% on three concentration levels. In human urine, the total concentrations of the four selected parabens, according to preliminary results, range from 0.3 to 124.5ng/mL for male, and from 27.2 to 246.3ng/mL for female. Female urine samples showed higher concentrations for the target parabens, which may indicate higher exposure due to lifestyle. This method permits accurate and high-throughput analysis of parabens for epidemiological studies. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Determination of Hg{sup 2+} by on-line separation and pre-concentration with atmospheric-pressure solution-cathode glow discharge atomic emission spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Li, Qing [Shanghai Institute of Ceramics, Chinese Academy of Science, Shanghai 200050 (China); Zhang, Zhen [Shanghai Institute of Ceramics, Chinese Academy of Science, Shanghai 200050 (China); School of Materials Science and Engineering, Shanghai University, Shanghai 200072 (China); Wang, Zheng, E-mail: wangzheng@mail.sic.ac.cn [Shanghai Institute of Ceramics, Chinese Academy of Science, Shanghai 200050 (China)

    2014-10-03

    Highlights: • A modified SBA-15 mesoporous silica (SH-SBA-15) was synthesized as a sorbent. • On-line SPE combined with SCGD-AES based on FIA was used to detect Hg{sup 2+} firstly. • A simple, low-cost Hg{sup 2+} analysis in a complex matrix was established. • The sensitive detection of Hg{sup 2+} was achieved with a detection limit of 0.75 μg L{sup −1}. - Abstract: A simple and sensitive method to determine Hg{sup 2+} was developed by combining solution-cathode glow discharge atomic emission spectrometry (SCGD-AES) with flow injection (FI) based on on-line solid-phase extraction (SPE). We synthesized L-cysteine-modified mesoporous silica and packed it in an SPE microcolumn, which was experimentally determined to possess a good mercury adsorption capacity. An enrichment factor of 42 was achieved under optimized Hg{sup 2+} elution conditions, namely, an FI flow rate of 2.0 mL min{sup −1} and an eluent comprised of 10% thiourea in 0.2 mol L{sup −1} HNO{sub 3}. The detection limit of FI–SCGD-AES was determined to be 0.75 μg L{sup −1}, and the precision of the 11 replicate Hg{sup 2+} measurements was 0.86% at a concentration of 100 μg L{sup −1}. The proposed method was validated by determining Hg{sup 2+} in certified reference materials such as human hair (GBW09101b) and stream sediment (GBW07310)

  17. Mass analysis of the components separated from printed circuit boards

    Directory of Open Access Journals (Sweden)

    Hana Charvátová

    2010-06-01

    Full Text Available Methods of effective and ecological recycling of printed circuit boards (PCBs are searched all over the world at this time.The material composition and temperature properties of PCB are necessary to be known for an optimal recycling technology. For thispurpose we analyzed weight ratio of the electronic components moulded on the selected kinds of PCBs and next we formulatedmathematic model of temperature field in PCB during a grinding process in that the metal layers are separated from the plasticelements. We present the obtained results in this paper.

  18. Peptide separations by on-line MudPIT compared to isoelectric focusing in an off-gel format: application to a membrane-enriched fraction from C2C12 mouse skeletal muscle cells.

    Science.gov (United States)

    Elschenbroich, Sarah; Ignatchenko, Vladimir; Sharma, Parveen; Schmitt-Ulms, Gerold; Gramolini, Anthony O; Kislinger, Thomas

    2009-10-01

    High-resolution peptide separation is pivotal for successful shotgun proteomics. The need for capable techniques propels invention and improvement of ever more sophisticated approaches. Recently, Agilent Technologies has introduced the OFFGEL fractionator, which conducts peptide separation by isoelectric focusing in an off-gel setup. This platform has been shown to accomplish high resolution of peptides for diverse sample types, yielding valuable advantages over comparable separation techniques. In this study, we deliver the first comparison of the newly emerging OFFGEL approach to the well-established on-line MudPIT platform. Samples from a membrane-enriched fraction isolated from murine C2C12 cells were subjected to replicate analysis by OFFGEL (12 fractions, pH 3-10) followed by RP-LC-MS/MS or 12-step on-line MudPIT. OFFGEL analyses yielded 1398 proteins (identified by 10,269 peptides), while 1428 proteins (11,078 peptides) were detected with the MudPIT approach. Thus, our data shows that both platforms produce highly comparable results in terms of protein/peptide identifications and reproducibility for the sample type analyzed. We achieve more accurate peptide focusing after OFFGEL fractionation with 88% of all peptides binned to a single fraction, as compared to 61% of peptides detected in only one step in MudPIT analyses. Our study suggests that both platforms are equally capable of high quality peptide separation of a sample with medium complexity, rendering them comparably valuable for comprehensive proteomic analyses.

  19. Normal phase liquid chromatography coupled to quadrupole time of flight atmospheric pressure chemical ionization mass spectrometry for separation, detection and mass spectrometric profiling of neutral sphingolipids and cholesterol.

    Science.gov (United States)

    Farwanah, Hany; Wirtz, Jennifer; Kolter, Thomas; Raith, Klaus; Neubert, Reinhard H H; Sandhoff, Konrad

    2009-10-01

    Many lipidomic approaches focus on investigating aspects of sphingolipid metabolism. Special emphasis is put on neutral sphingolipids and cholesterol and their interaction. Such an interest is attributed to the fact that those lipids are altered in a series of serious disorders including various sphingolipidoses. High performance thin-layer chromatography (HPTLC) has become a widely used technique for lipid analysis. However, mass spectrometric profiling is irreplaceable for gaining an overview about the various molecular species within a lipid class. In this work we have developed a sensitive method based on a gradient normal phase high performance liquid chromatography (HPLC) coupled to quadrupole time of flight (QTOF) atmospheric pressure chemical ionization mass spectrometry (APCI-MS) in positive mode, which for the first time enables separation, on-line detection, and mass spectrometric profiling of multiple neutral sphingolipids including ceramide, glucosylceramide, lactosylceramide, globotriaosylceramide, globotetraosylceramide, sphingomyelin as well as cholesterol within less than 15min. An important advantage of the presented HPLC/APCI-MS approach is that the separation pattern emulates the one obtained by an optimized HPTLC method with a multiple stage development. Thus, the lipid classes previously separated and quantified by HPTLC can be easily screened regarding their mass spectrometric profiles by HPLC/APCI-MS. In addition, the selected ionization conditions enable in-source fragmentation providing useful structural information. The methods (HPLC/APCI-MS and the optimized HPTLC) were applied for the analysis of the mentioned lipids in human fibroblasts. This approach is aimed basically at investigators who perform studies based on genetic modifications or treatment with pharmacological agents leading to changes in the biochemical pathways of neutral sphingolipids and cholesterol. In addition, it can be of interest for research on disorders related to

  20. On-line simultaneous and rapid separation of anions and cations from a single sample using dual-capillary sequential injection-capillary electrophoresis.

    Science.gov (United States)

    Gaudry, Adam J; Guijt, Rosanne M; Macka, Mirek; Hutchinson, Joseph P; Johns, Cameron; Hilder, Emily F; Dicinoski, Greg W; Nesterenko, Pavel N; Haddad, Paul R; Breadmore, Michael C

    2013-06-05

    A novel capillary electrophoresis (CE) approach has been developed for the simultaneous rapid separation and identification of common environmental inorganic anions and cations from a single sample injection. The method utilised a sequential injection-capillary electrophoresis instrument (SI-CE) with capacitively-coupled contactless conductivity detection (C(4)D) constructed in-house from commercial-off-the-shelf components. Oppositely charged analytes from a single sample plug were simultaneously injected electrokinetically onto two separate capillaries for independent separation and detection. Injection was automated and may occur from a syringe or be directly coupled to an external source in a continuous manner. Software control enabled high sample throughput (17 runs per hour for the target analyte set) and the inclusion of an isolation valve allowed the separation capillaries to be flushed, increasing throughput by removing slow migrating species as well as improving repeatability. Various environmental and industrial samples (subjected only to filtering) were analysed in the laboratory with a 3 min analysis time which allowed the separation of 23 inorganic and small organic anions and cations. Finally, the system was applied to an extended automated analysis of Hobart Southern Water tap water for a period of 48 h. The overall repeatability of the migration times of a 14 analyte standard sample was less than 0.74% under laboratory conditions. LODs ranged from 5 to 61 μg L(-1). The combination of automation, high confidence of peak identification, and low limits of detection make this a useful system for the simultaneous identification of a range of common inorganic anions and cations for discrete or continuous monitoring applications.

  1. Determination of Hg(2+) by on-line separation and pre-concentration with atmospheric-pressure solution-cathode glow discharge atomic emission spectrometry.

    Science.gov (United States)

    Li, Qing; Zhang, Zhen; Wang, Zheng

    2014-10-03

    A simple and sensitive method to determine Hg(2+) was developed by combining solution-cathode glow discharge atomic emission spectrometry (SCGD-AES) with flow injection (FI) based on on-line solid-phase extraction (SPE). We synthesized l-cysteine-modified mesoporous silica and packed it in an SPE microcolumn, which was experimentally determined to possess a good mercury adsorption capacity. An enrichment factor of 42 was achieved under optimized Hg(2+) elution conditions, namely, an FI flow rate of 2.0 mL min(-1) and an eluent comprised of 10% thiourea in 0.2 mol L(-1) HNO3. The detection limit of FI-SCGD-AES was determined to be 0.75 μg L(-1), and the precision of the 11 replicate Hg(2+) measurements was 0.86% at a concentration of 100 μg L(-1). The proposed method was validated by determining Hg(2+) in certified reference materials such as human hair (GBW09101b) and stream sediment (GBW07310).

  2. L-histidine functionalized multi-walled carbon nanotubes for on-line affinity separation and purification of immunoglobulin G in serum.

    Science.gov (United States)

    Du, Zhuo; Zhang, Suling; Zhou, Chanyuan; Liu, Miao; Li, Gongke

    2012-09-15

    In this work, the multi-walled carbon nanotubes were covalently functionalized with L-histidine (His-MWNTs) as online pseudospecific affinity adsorbent for immunoglobulin G (IgG) separation and purification with a simple surface modification method, using 1-ethyl-3-(3-dimethyaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxysuccinimde (NHS). The affinity of the His-MWNTs toward IgG was investigated in a microcolumn incorporated into a sequential injection system, which also involves an UV spectrometer with a flow cell for online real-time detection. The incorporation of histidine as affinity groups noticeably increased the selectivity and binding capacity of MWNTs for IgG and the His-MWNTs exhibited high retention and recovery rate of nearly 100% under optimized conditions. This separation and enrichment process made it possible to determine a lower concentration range of IgG in serum from 1.0-33 μg/mL with a detection limit of 0.3 μg/mL with a sampling volume of 4.0 mL. The static and dynamic adsorption capacities obtained were 267 mg of IgG/g His-MWNTs and 35 mg/g in aqueous solution, respectively, which are among the highest reported results in literatures employing affinity separation methods. Desorption of IgG from His-MWNTs could be accomplished by lowering the pH to 1.5 with glycine-HCl buffer. The practical application of His-MWNTs for separation of IgG in serum was evaluated with sodium dodecyl sulfate-polyacrylamide gel electrophoresis which confirmed that the purity of recovered IgG from human serum was over 85% and better than a commercial product.

  3. On-line extractive separation in flow injection analysis based on polymer inclusion membranes: a study on membrane stability and approaches for improving membrane permeability.

    Science.gov (United States)

    Zhang, Lujia L; Cattrall, Robert W; Ashokkumar, Muthupandian; Kolev, Spas D

    2012-08-15

    The effect of temperature on the sensitivity and sampling rate is studied for a flow injection analysis (FIA) system that uses a membrane separation cell fitted with a polymer inclusion membrane (PIM) for the determination of Zn(II). A temperature of 50 °C for the flowing donor and acceptor solutions and the membrane separation cell improves the sensitivity and the sampling rate relative to 20 °C up to 10-fold and 2-fold, respectively. Studies on the stability of the PIM are reported that show a limited loss of the membrane liquid phase into the aqueous phases used in the FIA system but this has exhibited a negligible effect on the amount of Zn(II) transported across the membrane. Most importantly, the extent of leaching of the PIM components is shown to depend on the nature of the aqueous phase with the membrane eventually reaching a stable composition. It is also shown that the application of ultrasound to the membrane separation cell leads to a slight increase in sensitivity without affecting the long term membrane stability.

  4. Characterisation of Phenolic Compounds in South African Plum Fruits (Prunus salicina Lindl. using HPLC Coupled with Diode-Array, Fluorescence, Mass Spectrometry and On-Line Antioxidant Detection

    Directory of Open Access Journals (Sweden)

    Dalene de Beer

    2013-05-01

    Full Text Available Phenolic compounds are abundant secondary metabolites in plums, with potential health benefits believed to be due to their antioxidant activity, amongst others. Phenolic characterisation of South African Prunus salicina Lindl. plums is necessary to fully evaluate their potential health benefits. An HPLC method using diode-array detection (DAD for quantification of phenolic compounds was improved and fluorescence detection (FLD was added for quantification of flavan-3-ols. Validation of the HPLC-DAD-FLD method showed its suitability for quantification of 18 phenolic compounds, including flavan-3-ols using FLD, and phenolic acids, anthocyanins and flavonols using DAD. The method was suitable for characterisation of the phenolic composition of 11 South African plum cultivars and selections, including various types with yellow and red skin and flesh. The method was used in conjunction with mass spectrometry (MS to identify 24 phenolic compounds. Neochlorogenic acid and cyanidin-3-O-glucoside were the major compounds in most of the plums, while cyanidin-3-O-glucoside was absent in Sun Breeze plums with yellow skin and flesh. Post-column on-line coupling of the ABTS•+ scavenging assay with HPLC-DAD enabled qualitative evaluation of the relative contribution of individual phenolic compounds to the antioxidant activity. The flavan-3-ols, neochlorogenic acid and cyanidin-3-O-glucoside displayed the largest antioxidant response peaks.

  5. Oxidative and inert pyrolysis on-line coupled to gas chromatography with mass spectrometric detection: On the pyrolysis products of tobacco additives.

    Science.gov (United States)

    Paschke, Meike; Hutzler, Christoph; Henkler, Frank; Luch, Andreas

    2016-11-01

    According to European legislation, tobacco additives may not increase the toxicity or the addictive potency of the product, but there is an ongoing debate on how to reliably characterize and measure such properties. Further, too little is known on pyrolysis patterns of tobacco additives to assume that no additional toxicological risks need to be suspected. An on-line pyrolysis technique was used and coupled to gas chromatography-mass spectrometry (GC/MS) to identify the pattern of chemical species formed upon thermal decomposition of 19 different tobacco additives like raw cane sugar, licorice or cocoa. To simulate the combustion of a cigarette it was necessary to perform pyrolysis at inert conditions as well as under oxygen supply. All individual additives were pyrolyzed under inert or oxidative conditions at 350, 700 and 1000°C, respectively, and the formation of different toxicants was monitored. We observed the generation of vinyl acrylate, fumaronitrile, methacrylic anhydride, isobutyric anhydride and 3-buten-2-ol exclusively during pyrolysis of tobacco additives. According to the literature, these toxicants so far remained undetectable in tobacco or tobacco smoke. Further, the formation of 20 selected polycyclic aromatic hydrocarbons (PAHs) with molecular weights of up to 278Da was monitored during pyrolysis of cocoa in a semi-quantitative approach. It was shown that the adding of cocoa to tobacco had no influence on the relative amounts of the PAHs formed. Copyright © 2016 Elsevier GmbH. All rights reserved.

  6. Determination of biocides and pesticides by on-line solid phase extraction coupled with mass spectrometry and their behaviour in wastewater and surface water

    Energy Technology Data Exchange (ETDEWEB)

    Singer, Heinz; Jaus, Sylvia; Hanke, Irene; Lueck, Alfred; Hollender, Juliane [Eawag, Swiss Federal Institute of Aquatic Science and Technology, Ueberlandstrasse 133, CH-8600 Duebendorf (Switzerland); Alder, Alfredo C., E-mail: alfredo.alder@eawag.c [Eawag, Swiss Federal Institute of Aquatic Science and Technology, Ueberlandstrasse 133, CH-8600 Duebendorf (Switzerland)

    2010-10-15

    This study focused on the input of hydrophilic biocides into the aquatic environment and on the efficiency of their removal in conventional wastewater treatment by a mass flux analysis. A fully automated method consisting of on-line solid phase extraction coupled to LC-ESI-MS/MS was developed and validated for the simultaneous trace determination of different biocidal compounds (1,2-benzisothiazoline-3-one (BIT), 3-Iodo-2-propynylbutyl-carbamate (IPBC), irgarol 1051 and 2-N-octyl-4-isothiazolinone (octhilinone, OIT), carbendazim, diazinon, diuron, isoproturon, mecoprop, terbutryn and terbutylazine) and pharmaceuticals (diclofenac and sulfamethoxazole) in wastewater and surface water. In the tertiary effluent, the highest average concentrations were determined for mecoprop (1010 ng/L) which was at comparable levels as the pharmaceuticals diclofenac (690 ng/L) and sulfamethoxazole (140 ng/L) but 1-2 orders of magnitude higher than the other biocidal compounds. Average eliminations for all compounds were usually below 50%. During rain events, increased residual amounts of biocidal contaminants are discharged to receiving surface waters. - Incomplete removal of biocides and pesticides during wastewater treatment.

  7. Simultaneous assessment of cholesterol absorption and synthesis in humans using on-line gas chromatography/ combustion and gas chromatography/pyrolysis/isotope-ratio mass spectrometry.

    Science.gov (United States)

    Gremaud, G; Piguet, C; Baumgartner, M; Pouteau, E; Decarli, B; Berger, A; Fay, L B

    2001-01-01

    A number of dietary components and drugs are known to inhibit the absorption of dietary and biliary cholesterol, but at the same time can compensate by increasing cholesterol synthesis. It is, therefore, necessary to have a convenient and accurate method to assess both parameters simultaneously. Hence, we validated such a method in humans using on-line gas chromatography(GC)/combustion and GC/pyrolysis/isotope-ratio mass spectrometry (IRMS). Cholesterol absorption was measured using the ratio of [(13)C]cholesterol (injected intravenously) to [(18)O]cholesterol (administered orally). Simultaneously, cholesterol synthesis was measured using the deuterium incorporation method. Our methodology was applied to 12 mildly hypercholesterolemic men that were given a diet providing 2685 +/- 178 Kcal/day (mean +/- SD) and 255 +/- 8 mg cholesterol per day. Cholesterol fractional synthesis rates ranged from 5.0 to 10.5% pool/day and averaged 7.36% +/- 1.78% pool/day (668 +/- 133 mg/day). Cholesterol absorption ranged from 36.5-79.9% with an average value of 50.8 +/- 15.4%. These values are in agreement with already known data obtained with mildly hypercholesterolemic Caucasian males placed on a diet similar to the one used for this study. However, our combined IRMS method has the advantage over existing methods that it enables simultaneous measurement of cholesterol absorption and synthesis in humans, and is therefore an important research tool for studying the impact of dietary treatments on cholesterol parameters.

  8. [Determination of 28 organochlorine and pyrethroid pesticides in pine nuts using solid-phase extraction and on-line gel permeation chromatography-gas chromatography/mass spectrometry].

    Science.gov (United States)

    Kang, Qinghe; Wu, Yan; Gao, Kaiyang; Li, Zhibin

    2009-03-01

    An analytical method has been developed for the determination of 28 organochlorine pesticides and pyrethroid pesticides in pine nuts. The sample was extracted With acetonitrile-water (4:1, v/v) as the extraction solution by means of high-speed homogenization. The crude extract was purified by an Aluminium-N solid phase extraction column to remove most of the fat and sterols in the sample, then on-line gel permeation chromatography-gas chromatography/ mass spectrometry (GPC-GC/MS) analysis was performed. The recoveries for the most of pesticides in the sample spiked with the standards of 0.05 mg/kg were 70%-120%, and the relative standard deviations were less than 15%. The limits of detection of 28 organochlorine pesti- and pyrethroid pesticides were 0.002-0.05 mg/kg. The linear relationship and the recovery results were satisfactory. The method is rapid, accurate, highly senstive, and can be used for the simultaneous determination of pesticide residues in pine nuts.

  9. On the implications of aerosol liquid water and phase separation for organic aerosol mass

    Data.gov (United States)

    U.S. Environmental Protection Agency — This dataset contains data presented in the figures of the paper "On the implications of aerosol liquid water and phase separation for organic aerosol mass"...

  10. Analysis of heterocyclic amines in hair by on-line in-tube solid-phase microextraction coupled with liquid chromatography−tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Kataoka, Hiroyuki, E-mail: hkataoka@shujitsu.ac.jp; Inoue, Tsutomu; Saito, Keita; Kato, Hisato; Masuda, Kazufumi

    2013-07-05

    Graphical abstract: Mutagenic and carcinogenic heterocyclic amines are accumulated in the hair of smoker. -- Highlights: •On-line in-tube solid-phase microextraction of heterocyclic amines was optimized. •Fourteen heterocyclic amines were simultaneously determined by LC–MS/MS. •Pico gram levels of heterocyclic amines could be easily analyzed within 15 min. •Heterocyclic amines could be quantitatively analyzed from several milligrams of hair. •The method is useful for the assessment of long-term exposure to heterocyclic amines. -- Abstract: Mutagenic and carcinogenic heterocyclic amines (HCAs) are formed during heating of various proteinaceous foods, but human exposure to HCAs has not yet been elucidated in detail. To assess long-term exposure to HCAs, we developed a simple and sensitive method for measuring HCAs in hair by automated on-line in-tube solid-phase microextraction (SPME) coupled with liquid chromatography–tandem mass spectrometry (LC–MS/MS). Using a Zorbax Eclipse XDB-C8 column, 16 HCAs were analyzed within 15 min. The optimum in-tube SPME conditions were 20 draw/eject cycles of 40 μL sample at a flow rate of 200 μL min{sup −1} using a Supel-Q PLOT capillary column as an extraction device. The extracted HCAs were easily desorbed from the column by passage of the mobile phase, with no carryover observed. This in-tube SPME LC–MS/MS method showed good linearity for HCAs in the range of 10–2000 pg mL{sup −1}, with correlation coefficients above 0.9989 (n = 18), using stable isotope-labeled HCA internal standards. The detection limits (S/N = 3) of 14 HCAs except for MeAαC and Glu-P-1 were 0.10–0.79 pg mL{sup −1}. This method was successfully utilized to analyze 14 HCAs in hair samples without any interference peaks, with quantitative limits (S/N = 10) of about 0.17–1.32 pg mg{sup −1} hair. Using this method, we evaluated the exposure to HCAs in cigarette smoke and the suitability of using hair HCAs as exposure biomarkers.

  11. First field application of a thermal desorption resonance-enhanced multiphoton-ionisation single particle time-of-flight mass spectrometer for the on-line detection of particle-bound polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Oster, Markus; Elsasser, Michael; Schnelle-Kreis, Jürgen; Zimmermann, Ralf

    2011-12-01

    The on-line analysis of single aerosol particles with mass spectrometrical methods is an important tool for the investigation of aerosols. Often, a single laser pulse is used for one-step laser desorption/ionisation of aerosol particles. Resulting ions are detected with time-of-flight mass spectrometry. With this method, the detection of inorganic compounds is possible. The detection of more fragile organic compounds and carbon clusters can be accomplished by separating the desorption and the ionisation in two steps, e.g. by using two laser pulses. A further method is, using a heated metal surface for thermal desorption of aerosol particles. If an ultraviolet laser is used for ionisation, a selective ionisation of polycyclic aromatic hydrocarbons (PAH) and alkylated PAH is possible via a resonance-enhanced multiphoton-ionisation process. Laser velocimetry allows individual laser triggering for single particles and additionally delivers information on aerodynamic particle diameters. It was shown that particles deriving from different combustion sources can be differentiated according to their PAH patterns. For example, retene, a C(4)-alkylated phenanthrene derivative, is a marker for the combustion of coniferous wood. In this paper, the first field application of a thermal desorption resonance-enhanced multiphoton-ionisation single particle time-of-flight mass spectrometer during a measurement campaign in Augsburg, Germany in winter 2010 is presented. Larger PAH-containing particles (i.e. with aerodynamic diameters larger than 1 μm), which are suspected to be originated by re-suspension processes of agglomerated material, were in the focus of the investigation. Due to the low concentration of these particles, an on-line virtual impactor enrichment system was used. The detection of particle-bound PAH in ambient particles in this larger size region was possible and in addition, retene could be detected on several particles, which allows to identify wood combustion as

  12. Conventional and Advanced Separations in Mass Spectrometry-Based Metabolomics: Methodologies and Applications

    Energy Technology Data Exchange (ETDEWEB)

    Heyman, Heino M.; Zhang, Xing; Tang, Keqi; Baker, Erin Shammel; Metz, Thomas O.

    2016-02-16

    Metabolomics is the quantitative analysis of all metabolites in a given sample. Due to the chemical complexity of the metabolome, optimal separations are required for comprehensive identification and quantification of sample constituents. This chapter provides an overview of both conventional and advanced separations methods in practice for reducing the complexity of metabolite extracts delivered to the mass spectrometer detector, and covers gas chromatography (GC), liquid chromatography (LC), capillary electrophoresis (CE), supercritical fluid chromatography (SFC) and ion mobility spectrometry (IMS) separation techniques coupled with mass spectrometry (MS) as both uni-dimensional and as multi-dimensional approaches.

  13. Development of an analytical method for the determination of the misuse in sports of boldenone through the analysis of urine by on-line coupling liquid chromatography-gas chromatography-combustion-isotope ratio mass spectrometry.

    Science.gov (United States)

    Toledano, R M; Díaz-Plaza, E M; Cortes, J M; Aragón, A; Vázquez, A M; Villén, J; Muñoz-Guerra, J

    2014-11-28

    Boldenone (Bo), androsta-1,4-dien-17β-ol-3-one, is an anabolic androgenic steroid not clinically approved for human application. Despite this, many cases are reported every year of athletes testing positive for Bo or its main metabolite 5β-androst-1-en-17β-ol-3-one (BoM). Recently the capability of different human intestinal bacteria to produce enzymes able to modify endogenous steroids in Bo has been demonstrated. When a urinary concentration of Bo and/or BoM between 5 and 30 ng/mL is measured a complementary analysis by gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS) must be carried out to discriminate the endogenous or exogenous origin. In the present work, a novel analytical method that couples LC-GC by means of the TOTAD interface with C-IRMS is described. The method is based on a first RPLC separation of unacetyled steroids, followed by acetylation and automated on-line LC-GC-C-IRMS, which includes a second RPLC clean-up of acetyl Bo and BoM, isolation of the two fractions in a fraction collector and their consecutive analysis by GC-C-IRMS. The method has been applied to the analysis of urine samples fortified at 5 and 10 ng/mL, where it has shown a good performance.

  14. Multielement trace determinations in A1 2O 3 ceramic powders by inductively coupled plasma mass spectrometry with special reference to on-line trace preconcentration

    Science.gov (United States)

    Pollmann, D.; Leis, F.; Tölg, G.; Tschöpel, P.; Broekaert, J. A. C.

    1994-12-01

    The use of inductively coupled plasma mass spectrometry (ICP-MS) for the determination of trace elements in Al 2O 3 powders is reported. Special interest is given to a preconcentration of the trace elements by on-line coupling of chromatography to ICP-MS. This is based on the complexation of Co, Cu, Cr, Fe, Ga, Mn, Ni, V and Zn with hexamethylene-dithiocarbamate (HMDC), their preconcentration on a C18 RP column by reversed phase liquid chromatography and their elution with CH 3OH-H 2O mixtures. A direct coupling of the HPLC system to the ICP-MS has been realized by high pressure pneumatic nebulization using desolvation. With the Chromatographie method developed, removal of the AI by at least 99% was achieved. For the trace elements V, Fe, Ni, Co, Cu and Ga, high and reproducible recoveries (ranging from 96-99%) were reached. The method developed has been shown to considerably enhance the power of detection as compared with direct procedures, namely down to 0.02-0.16 ( μg/g for V and Fe, respectively. The possibilities of the method are shown by the determinations of V, Mn, Fe, Ni, Co, Cu, Zn and Ga at the μg/g level in A1 2O 3 powders. The accuracy of the method at the 0.06 to 9.0 μg/g level for Co and Fe, respectively, is demonstrated by a comparison with results of independent methods from the literature.

  15. A laboratory flow reactor with gas particle separation and on-line MS/MS for product identification in atmospherically important reactions

    Directory of Open Access Journals (Sweden)

    J. F. Bennett

    2009-06-01

    Full Text Available A system to study the gas and particle phase products from gas phase hydrocarbon oxidation is described. It consists of a gas phase photochemical flow reactor followed by a diffusion membrane denuder to remove gases from the reacted products, or a filter to remove the particles. Chemical analysis is performed by an atmospheric pressure chemical ionization (APCI triple quadrupole mass spectrometer. A diffusion membrane denuder is shown to remove trace gases to below detectable limits so the particle phase can be studied. The system was tested by examining the products of the oxidation of m-xylene initiated by HO radicals. Dimethylphenol was observed in both the gas and particle phases although individual isomers could not be identified. Two furanone isomers, 5-methyl-2(3Hfuranone and 3-methyl-2(5Hfuranone were identified in the particulate phase, but the isobaric product 2,5 furandione was not observed. One isomer of dimethyl-nitrophenol was identified in the particle phase but not in the gas phase.

  16. A laboratory flow reactor with gas particle separation and on-line MS/MS for product identification in atmospherically important reactions

    Directory of Open Access Journals (Sweden)

    J. F. Bennett

    2009-12-01

    Full Text Available A system to study the gas and particle phase products from gas phase hydrocarbon oxidation is described. It consists of a gas phase photochemical flow reactor followed by a diffusion membrane denuder to remove gases from the reacted products, or a filter to remove the particles. Chemical analysis is performed by an atmospheric pressure chemical ionization (APCI triple quadrupole mass spectrometer. A diffusion membrane denuder is shown to remove trace gases to below detectable limits so the particle phase can be studied. The system was tested by examining the products of the oxidation of m-xylene initiated by HO radicals. Dimethylphenol was observed in both the gas and particle phases although individual isomers could not be identified. Two furanone isomers, 5-methyl-2(3Hfuranone and 3-methyl-2(5Hfuranone were identified in the particulate phase, but the isobaric product 2,5 furandione was not observed. One isomer of dimethyl-nitrophenol was identified in the particle phase but not in the gas phase.

  17. SPECIATION OF SELENIUM AND ARSENIC COMPOUNDS BY CAPILLARY ELECTROPHORESIS WITH HYDRODYNAMICALLY MODIFIED ELECTROOSMOTIC FLOW AND ON-LINE REDUCTION OF SELENIUM(VI) TO SELENIUM(IV) WITH HYDRIDE GENERATION INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRIC DETECTION

    Science.gov (United States)

    Capillary electrophoresis (CE) with hydride generation inductively coupled plasma mass spectrometry was used to determine four arsenicals and two selenium species. Selenate (SeVI) was reduced on-line to selenite (SeIV') by mixing the CE effluent with concentrated HCl. A microporo...

  18. An automated method for the analysis of phenolic acids in plasma based on ion-pairing micro-extraction coupled on-line to gas chromatography/mass spectrometry with in-liner derivatisation

    NARCIS (Netherlands)

    Peters, S.; Kaal, E.; Horsting, I.; Janssen, H.-G.

    2012-01-01

    A new method is presented for the analysis of phenolic acids in plasma based on ion-pairing ‘Micro-extraction in packed sorbent’ (MEPS) coupled on-line to in-liner derivatisation-gas chromatography-mass spectrometry (GC-MS). The ion-pairing reagent served a dual purpose. It was used both to improve

  19. On-line Mass Spectrometric Study of Heavy-Ion Induced Reactions at Energies up to 86 MeV/amu

    CERN Multimedia

    2002-01-01

    The aim of the experiment was to measure isotopic distributions of Li, Na, K, Rb, Cs and Fr as reaction fragments in heavy ion collisions. In order to get an overall view of the new energy range for heavy ions available from the SC, different energies and projectile-target combinations had to be studied. The data taking status is now finished. |1|2C and |1|8O beams were used in bombarding |1|2C, |9|3Nb, |1|8|1Ta and |2|3|8U in order to look at target fragmentation, projectile fragmentation and evaporative residues of spallation processes. The experimental apparatus is composed of three parts: \\item a)~A target-oven-ionizer assembly where selective thermal diffusion and selective surface ionization takes place in order to obtain a chemical separation of the reaction products. \\item b)~The mass spectrometer where the different-mass fragments are selected. \\item c)~An electrostatic ion beam line through which the fragments are transported to a low-background area where the detector (an electron multiplier) is lo...

  20. Characterization of phenolic compounds in Helichrysum melaleucum by high-performance liquid chromatography with on-line ultraviolet and mass spectrometry detection.

    Science.gov (United States)

    Gouveia, Sandra C; Castilho, Paula C

    2010-07-15

    Helicrysum melaleucum is a medicinal plant traditionally used in the islands of the Macaronesia region for the treatment of respiratory diseases. In this work, the phenolic compounds of Helicrysum melaleucum plants collected in different geographical locations of Madeira Island and their morphological parts (total aerial parts, leaves, flowers and stems) were extracted and analyzed separately by high-performance liquid chromatography/electrospray ionization tandem mass spectrometry (HPLC-DAD/ESI-MS(n)). A total of 68 compounds were characterized based mainly on their UV and mass spectra. These included derivatives of O-glycosylated flavonoids (flavonol and flavones type), quinic acid, caffeic acid, lignans and polyphenols. The flowers were found to be the morphological part with higher variety of phenolic compounds. The large differences in the phenolic composition of plants collected from different geographical locations allowed the identification of a few components, such as pinoresinol and methoxylated flavone derivatives, likely to be useful as geographical markers. Also, these results promote further comparison of the bioactivities of the different samples analyzed. This paper marks the first report on the chemical analysis of Helichrysum melaleucum species.

  1. Preliminary results on the determination of ultratrace amounts of cadmium in tea samples using a flow injection on-line solid phase extraction separation and preconcentration technique to couple with a sequential injection hydride generation atomic fluorescence spectrometry.

    Science.gov (United States)

    Duan, Taicheng; Song, Xuejie; Jin, Dan; Li, Hongfei; Xu, Jingwei; Chen, Hangting

    2005-10-31

    In this work, a method was developed for determination of ultra-trace levels of Cd in tea samples by atomic fluorescence spectrometry (AFS). A flow injection solid phase extraction (FI-SPE) separation and preconcentration technique, to on-line couple with a sequential injection hydride generation (SI-HG) technique is employed in this study. Cd was preconcentrated on the SPE column, which was made from a neutral extractant named Cyanex 923, while other matrix ions or interfering ions were completely or mostly separated off. Conditions for the SPE separation and preconcentration, as well as conditions for the HG technique, were studied. Due to the separation of interfering elements, Cd hydride generation efficiency could be greatly enhanced with the sole presence of Co(2+) with a concentration of 200mugL(-1), which is much lower than those in other works previously reported. Interferences on both the Cd separation and preconcentration, and Cd hydride generation (HG) were investigated; it showed that both the separation and preconcentration system, and the HG system had a strong anti-interference ability. The SPE column could be repeatedly used at least 400 times, a R.S.D. of 0.97% was obtained for 6 measurements of Cd with 0.2mugL(-1) and a correlation coefficiency of 1.0000 was obtained for the measurement of a series of solutions with Cd concentrations from 0.1 to 2mugL(-1). The method has a low detection limit of 10.8ngL(-1) for a 25mL solution and was successfully validated by using two tea standard reference materials (GBW08513 and GBW07605).

  2. 适用于时变系统的在线盲源分离算法研究%Research on on-line blind source separation algorithm for time-vary-ing system

    Institute of Scientific and Technical Information of China (English)

    邓大鹏; 李骏; 丁德强; 贺翥祯

    2016-01-01

    针对传统EASI算法收敛速率与稳态误差之间的矛盾,提出了一种基于估计函数期望的步长自适应算法(New Adaptive EASI),为了使这种算法能够更好地解决时变系统中不同条件下的盲源分离问题,提高信号的分离精度,建立了一种混合矩阵变化的在线检测机制,并将这种在线检测机制加入步长自适应算法中,对算法进行了改进.仿真实验表明,这种改进的步长自适应算法能够提高盲源分离初始阶段或是信道变化后分离初始阶段的信号恢复质量,解决源信号为非零均值信号时的盲源分离问题,并且能够准确地在线估计源信号的个数,实现信源数变化条件下的盲源分离.%Aiming at the contradiction between the convergence rate and the steady-state error of the traditional EASI algorithm, this paper presents a New Adaptive EASI algorithm based on the expectation of estimate function. In order to make the new algorithm be able to solve the BSS problems under different conditions of time-varying system better and improve the accuracy of separated signals, it sets up an on-line detection mechanism of the changes in mixing matrix and adds it to the New Adaptive EASI algorithm to modify the algorithm. Simulation results show that the modified New Adaptive EASI algorithm can improve the quality of separated signals in the initial stage of separation or just after the channel condition changes, do the on-line separation of nonzero mean mixed signals and accurately estimate the number of source signals online to solve the BSS problem under the condition that the number of the source signals varies during the separating process.

  3. Three decades of research using IGISOL technique at the University of Jyväskylä a portrait of the Ion Guide Isotope Separator On-Line facility in Jyväskylä

    CERN Document Server

    Eronen, Tommi; Jokinen, Ari; Kankainen, Anu; Moore, Iain; Penttilä, Heikki

    2014-01-01

    The IGISOL group at the University of Jyväskyla studies the properties of nuclei far off the line of beta stability. These studies are performed locally at the Jyväskylä Ion Guide Isotope Separator On-Line (IGISOL) facility, as well as at a number of other laboratories such as the ISOLDE facility in CERN, at GANIL and in Helmholzzentrum GSI, the location of the future radioactive beam facility FAIR. The group is also actively involved in work to support the development of international future facilities EURISOL and aforementioned FAIR. This book presents  carefully selected papers to portrait the work at IGISOL. Previously published in the journals Hyperfine Interactions and European Physical Journal A.

  4. Intensification of heat and mass transfer by ultrasound: application to heat exchangers and membrane separation processes.

    Science.gov (United States)

    Gondrexon, N; Cheze, L; Jin, Y; Legay, M; Tissot, Q; Hengl, N; Baup, S; Boldo, P; Pignon, F; Talansier, E

    2015-07-01

    This paper aims to illustrate the interest of ultrasound technology as an efficient technique for both heat and mass transfer intensification. It is demonstrated that the use of ultrasound results in an increase of heat exchanger performances and in a possible fouling monitoring in heat exchangers. Mass transfer intensification was observed in the case of cross-flow ultrafiltration. It is shown that the enhancement of the membrane separation process strongly depends on the physico-chemical properties of the filtered suspensions.

  5. Ion exchange separation of chromium from natural water matrix for stable isotope mass spectrometric analysis

    Science.gov (United States)

    Ball, J.W.; Bassett, R.L.

    2000-01-01

    A method has been developed for separating the Cr dissolved in natural water from matrix elements and determination of its stable isotope ratios using solid-source thermal-ionization mass spectrometry (TIMS). The separation method takes advantage of the existence of the oxidized form of Cr as an oxyanion to separate it from interfering cations using anion-exchange chromatography, and of the reduced form of Cr as a positively charged ion to separate it from interfering anions such as sulfate. Subsequent processing of the separated sample eliminates residual organic material for application to a solid source filament. Ratios for 53Cr/52Cr for National Institute of Standards and Technology Standard Reference Material 979 can be measured using the silica gel-boric acid technique with a filament-to-filament standard deviation in the mean 53Cr/52Cr ratio for 50 replicates of 0.00005 or less. (C) 2000 Elsevier Science B.V. All rights reserved.

  6. Rapid separation of phosphopeptides by microchip electrophoresis-electrospray ionization mass spectrometry.

    Science.gov (United States)

    Ollikainen, Elisa; Bonabi, Ashkan; Nordman, Nina; Jokinen, Ville; Kotiaho, Tapio; Kostiainen, Risto; Sikanen, Tiina

    2016-04-01

    Protein phosphorylation is a significant biological process, but separation of phosphorylated peptide isomers is often challenging for many analytical techniques. We developed a microchip electrophoresis (MCE) method for rapid separation of phosphopeptides with on-chip electrospray ionization (ESI) facilitating online sample introduction to the mass spectrometer (MS). With the method, two monophosphorylated positional isomers of insulin receptor peptide (IR1A and IR1B) and a triply phosphorylated insulin receptor peptide (IR3), all with the same amino acid sequence, were separated from the nonphosphorylated peptide (IR0) in less than one minute. For efficient separation of the positional peptide isomers from each other derivatization with 9-fluorenylmethyl reagents (either chloroformate, Fmoc-Cl, or N-succinimidyl carbonate, Fmoc-OSu) was required before the analysis. The derivatization improved not only the separation of the monophosphorylated positional peptide isomers in MCE, but also identification of the phosphorylation site based on MS/MS.

  7. Determination of denaturated proteins and biotoxins by on-line size-exclusion chromatography-digestion-liquid chromatography-electrospray mass spectrometry

    NARCIS (Netherlands)

    Carol, J.; Gorseling, M.C.J.K.; Jong, C.F. de; Lingeman, H.; Kientz, C.E.; Baar, B.L.M. van; Irth, H.

    2005-01-01

    A multidimensional analytical method for the rapid determination and identification of proteins has been developed. The method is based on the size-exclusion fractionation of protein-containing samples, subsequent on-line trypsin digestion and desalination, and reversed-phase high-performance liquid

  8. Determination of denaturated proteins and biotoxins by on-line size-exclusion chromatography-digestion-liquid chromatography-electrospray mass spectrometry

    NARCIS (Netherlands)

    Carol, J.; Gorseling, M.C.J.K.; Jong, C.F. de; Lingeman, H.; Kientz, C.E.; Baar, B.L.M. van; Irth, H.

    2005-01-01

    A multidimensional analytical method for the rapid determination and identification of proteins has been developed. The method is based on the size-exclusion fractionation of protein-containing samples, subsequent on-line trypsin digestion and desalination, and reversed-phase high-performance liquid

  9. Flow injection on-line dilution for multi-element determination in human urine with detection by inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Wang, Jianhua; Hansen, Elo Harald; Gammelgaard, Bente

    2001-01-01

    of 16.5 with on-line standard addition, and sup/ 103/Rh was used as internal standard to compensate for signal fluctuation. The procedure was validated by the analysis of two standard reference materials SRM 2670 (NIST) and Seronorm(TM) Trace Elements in Urine. Recovery experiments were performed...... urine samples. No correlations between the concentrations of the elements were observed....

  10. On-line laser spectroscopy with thermal atomic beams

    CERN Document Server

    Thibault, C; De Saint-Simon, M; Duong, H T; Guimbal, P; Huber, G; Jacquinot, P; Juncar, P; Klapisch, Robert; Liberman, S; Pesnelle, A; Pillet, P; Pinard, J; Serre, J M; Touchard, F; Vialle, J L

    1981-01-01

    On-line high resolution laser spectroscopy experiments have been performed in which the light from a CW tunable dye laser interacts at right angles with a thermal atomic beam. /sup 76-98/Rb, /sup 118-145 /Cs and /sup 208-213/Fr have been studied using the ionic beam delivered by the ISOLDE on-line mass separator at CERN while /sup 30-31/Na and /sup 38-47/K have been studied by setting the apparatus directly on-line with the PS 20 GeV proton beam. The principle of the method is briefly explained and some results concerning nuclear structure are given. The hyperfine structure, spins and isotope shifts of the alkali isotopes and isomers are measured. (8 refs).

  11. Star-galaxy separation strategies for WISE-2MASS all-sky infrared galaxy catalogues

    Science.gov (United States)

    Kovács, András; Szapudi, István

    2015-04-01

    We combine photometric information of the Wide-Field Infrared Survey Explorer (WISE) and Two Micron All Sky Survey (2MASS) all-sky infrared data bases, and demonstrate how to produce clean and complete galaxy catalogues for future analyses. Adding 2MASS colours to WISE photometry improves star-galaxy separation efficiency substantially at the expense of losing a small fraction of the galaxies. We find that 93 per cent of the WISE objects within W1 training set from the Sloan Digital Sky Survey PhotoObj table with known star-galaxy separation, and determined redshift distribution of our sample from the Galaxy and Mass Assembly spectroscopic survey. Varying the combination of photometric parameters input into our algorithm we show that W1WISE - J2MASS is a simple and effective star-galaxy separator, capable of producing results comparable to the multidimensional SVM classification. We present a detailed description of our star-galaxy separation methods, and characterize the robustness of our tools in terms of contamination, completeness, and accuracy. We explore systematics of the full sky WISE-2MASS galaxy map, such as contamination from moon glow. We show that the homogeneity of the full sky galaxy map is improved by an additional J2MASS galaxy catalogue we present in this paper covers 21 200 deg2 with dusty regions masked out, and has an estimated stellar contamination of 1.2 per cent and completeness of 70.1 per cent among 2.4 million galaxies with zmed ≈ 0.14. WISE-2MASS galaxy maps with well controlled stellar contamination will be useful for spatial statistical analyses, including cross-correlations with other cosmological random fields, such as the cosmic microwave background. The same techniques also yield a statistically controlled sample of stars as well.

  12. Flatland Position-Dependent-Mass: Polar Coordinates, Separability and Exact Solvability

    Directory of Open Access Journals (Sweden)

    Omar Mustafa

    2010-10-01

    Full Text Available The kinetic energy operator with position-dependent-mass in plane polar coordinates is obtained. The separability of the corresponding Schrödinger equation is discussed. A hypothetical toy model is reported and two exactly solvable examples are studied.

  13. Stimuli-responsive Membranes: Smart Tools for Controllable Mass-transfer and Separation Processes

    Institute of Scientific and Technical Information of China (English)

    褚良银; 谢锐; 巨晓洁

    2011-01-01

    As emerging artificial biomimetic membranes, smart or intelligent membranes that are able to respond to environmental stimuli are attracting ever-increasing interests from various fields. Their permeation properties including hydraulic permeability and diffusional permeability can be dramatically controlled or adjusted self-regulatively in response to small chemical and/or physical stimuli in their environments. Such environmental stimuli-responsive smart membranes could find myriad applications in numerous fields ranging from controlled release to separations. Here the trans-membrane mass-transfer and membrane separation is introduced as the beginning to initiate the requirement of smart membranes, and then bio-inspired design of environmental stimuli-responsive smart membranes and four essential elements for smart membranes are introduced and discussed. Next, smart membrane types and their applications as smart tools for controllable mass-transfer in controlled release and separations are reviewed. The research tooics in the near future are also suggested.

  14. Elimination of diastereomer interference to determine Telcagepant (MK-0974) in human plasma using on-line turbulent-flow technology and off-line solid-phase extraction coupled with liquid chromatography/tandem mass spectrometry.

    Science.gov (United States)

    Xu, Yang; Willson, Kenneth J; Anderson, Melanie D G; Musson, Donald G; Miller-Stein, Cynthia M; Woolf, Eric J

    2009-06-01

    To eliminate the diastereomer interference on Telcagepant (MK-0974) determination during clinical study support, on-line high turbulent-flow liquid chromatography (HTLC) methods, HTLC-A and HTLC-B that covered dynamic range of 0.5-500 nM and 5-5000 nM, respectively, were developed. To meet the requirement of rapid assay transfer among multiple laboratories and analysts, a solid-phase extraction (SPE) assay was derived from the existing HTLC-B assay under the same dynamic range. The on-line HTLC assays were achieved through direct injection of plasma samples, extraction of analyte with a Cohesive C18 column (50 mm x 0.5 mm, 50 microm), followed by HPLC separation on a FluoPhase RP column (100 mm x 2.1 mm, 5 microm) and MS/MS detection. The off-line SPE assay used Waters Oasis HLB microElution plate to extract the analytes from plasma matrix before injecting on a FluoPhase RP column (150 mm x 2.1 mm, 5 microm) for LC-MS/MS analysis. Under both on-line and off-line assay conditions, the diastereomer 1c was chromatographically separated from MK-0974. Cross-validation with the pooled samples demonstrated that both on-line and off-line assays provided comparable data with a difference of pros and cons of on-line and off-line assays with regard to man power involved in sample preparation, total analysis time, carryover, cost efficiency, and the requirement for assay transfer are discussed.

  15. Mass separation of deuterium and helium with conventional quadrupole mass spectrometer by using varied ionization energy

    Science.gov (United States)

    Yu, Yaowei; Hu, Jiansheng; Wan, Zhao; Wu, Jinhua; Wang, Houyin; Cao, Bin

    2016-03-01

    Deuterium pressure in deuterium-helium mixture gas is successfully measured by a common quadrupole mass spectrometer (model: RGA200) with a resolution of ˜0.5 atomic mass unit (AMU), by using varied ionization energy together with new developed software and dedicated calibration for RGA200. The new software is developed by using MATLAB with the new functions: electron energy (EE) scanning, deuterium partial pressure measurement, and automatic data saving. RGA200 with new software is calibrated in pure deuterium and pure helium 1.0 × 10-6-5.0 × 10-2 Pa, and the relation between pressure and ion current of AMU4 under EE = 25 eV and EE = 70 eV is obtained. From the calibration result and RGA200 scanning with varied ionization energy in deuterium and helium mixture gas, both deuterium partial pressures (PD2) and helium partial pressure (PHe) could be obtained. The result shows that deuterium partial pressure could be measured if PD2 > 10-6 Pa (limited by ultimate pressure of calibration vessel), and helium pressure could be measured only if PHe/PD2 > 0.45, and the measurement error is evaluated as 15%. This method is successfully employed in EAST 2015 summer campaign to monitor deuterium outgassing/desorption during helium discharge cleaning.

  16. Coupling sequential injection on-line preconcentration using a PTFE beads packed column to direct injection nebulization inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Wang, Jianhua; Hansen, Elo Harald

    2002-01-01

    An automated sequential injection on-line preconcentration procedure for trace metals by using a PTFE bead-packed microcolumn coupled to ICP-MS is described, and used for simultaneous analyses of cadmium and lead. In dilute nitric acid (0.5%, v/v), neutral complexes between the analytes and chela......An automated sequential injection on-line preconcentration procedure for trace metals by using a PTFE bead-packed microcolumn coupled to ICP-MS is described, and used for simultaneous analyses of cadmium and lead. In dilute nitric acid (0.5%, v/v), neutral complexes between the analytes...... and chelating reagent, diethyldithiophosphate (DDPA), are formed and adsorbed onto the surface of the PTFE beads. The adsorbed complexes are afterwards eluted with 20% nitric acid and the leading part of the eluate (40 mul) is stored in a sample loop (SL), the contents of which are subsequently transported, via...

  17. Automatic on-line monitoring of atmospheric volatile organic compounds: gas chromatography-mass spectrometry and gas chromatography-flame ionization detection as complementary systems.

    Science.gov (United States)

    de Blas, Maite; Navazo, Marino; Alonso, Lucio; Durana, Nieves; Iza, Jon

    2011-11-15

    Traditionally air quality networks have been carrying out the continuous, on-line measurement of volatile organic compounds (VOC) in ambient air with GC-FID. In this paper some identification and coelution problems observed while using this technique in long-term measurement campaigns are described. In order to solve these problems a GC-MS was set up and operated simultaneously with a GC-FID for C2-C11 VOCs measurement. There are few on-line, unattended, long term measurements of atmospheric VOCs performed with GC-MS. In this work such a system has been optimized for that purpose, achieving good repeatability, linearity, and detection limits of the order of the GC-FID ones, even smaller in some cases. VOC quantification has been made by using response factors, which is not frequent in on-line GC-MS. That way, the identification and coelution problems detected in the GC-FID, which may led to reporting erroneous data, could be corrected. The combination of GC-FID and GC-MS as complementary techniques for the measurement of speciated VOCs in ambient air at sub-ppbv levels is proposed. Some results of the measurements are presented, including concentration values for some compounds not found until now on public ambient air VOC databases, which were identified and quantified combining both techniques. Results may also help to correct previously published VOC data with wrongly identified compounds by reprocessing raw chromatographic data.

  18. Automatic on-line monitoring of atmospheric volatile organic compounds: Gas chromatography-mass spectrometry and gas chromatography-flame ionization detection as complementary systems

    Energy Technology Data Exchange (ETDEWEB)

    Blas, Maite de, E-mail: maite.deblas@ehu.es [Chemical and Environmental Engineering Department, University College of Technical Mining and Civil Engineering, University of the Basque Country, Colina de Beurco s/n, 48902 Barakaldo (Spain); Navazo, Marino; Alonso, Lucio; Durana, Nieves [Chemical and Environmental Engineering Department, School of Engineering, University of the Basque Country, Alameda de Urquijo s/n, 48013 Bilbao (Spain); Iza, Jon [Chemical and Environmental Engineering Department, Faculty of Pharmacy, University of the Basque Country, Paseo de la Universidad, 7, 01006, Vitoria-Gasteiz (Spain)

    2011-11-15

    Traditionally air quality networks have been carrying out the continuous, on-line measurement of volatile organic compounds (VOC) in ambient air with GC-FID. In this paper some identification and coelution problems observed while using this technique in long-term measurement campaigns are described. In order to solve these problems a GC-MS was set up and operated simultaneously with a GC-FID for C{sub 2}-C{sub 11} VOCs measurement. There are few on-line, unattended, long term measurements of atmospheric VOCs performed with GC-MS. In this work such a system has been optimized for that purpose, achieving good repeatability, linearity, and detection limits of the order of the GC-FID ones, even smaller in some cases. VOC quantification has been made by using response factors, which is not frequent in on-line GC-MS. That way, the identification and coelution problems detected in the GC-FID, which may led to reporting erroneous data, could be corrected. The combination of GC-FID and GC-MS as complementary techniques for the measurement of speciated VOCs in ambient air at sub-ppbv levels is proposed. Some results of the measurements are presented, including concentration values for some compounds not found until now on public ambient air VOC databases, which were identified and quantified combining both techniques. Results may also help to correct previously published VOC data with wrongly identified compounds by reprocessing raw chromatographic data.

  19. Real-time 2D separation by LC × differential ion mobility hyphenated to mass spectrometry.

    Science.gov (United States)

    Varesio, Emmanuel; Le Blanc, J C Yves; Hopfgartner, Gérard

    2012-03-01

    The liquid chromatography-mass spectrometry (LC-MS) analysis of complex samples such as biological fluid extracts is widespread when searching for new biomarkers as in metabolomics. The success of this hyphenation resides in the orthogonality of both separation techniques. However, there are frequent cases where compounds are co-eluting and the resolving power of mass spectrometry (MS) is not sufficient (e.g., isobaric compounds and interfering isotopic clusters). Different strategies are discussed to solve these cases and a mixture of eight compounds (i.e., bromazepam, chlorprothixene, clonapzepam, fendiline, flusilazol, oxfendazole, oxycodone, and pamaquine) with identical nominal mass (i.e., m/z 316) is taken to illustrate them. Among the different approaches, high-resolution mass spectrometry or liquid chromatography (i.e., UHPLC) can easily separate these compounds. Another technique, mostly used with low resolving power MS analyzers, is differential ion mobility spectrometry (DMS), where analytes are gas-phase separated according to their size-to-charge ratio. Detailed investigations of the addition of different polar modifiers (i.e., methanol, ethanol, and isopropanol) into the transport gas (nitrogen) to enhance the peak capacity of the technique were carried out. Finally, a complex urine sample fortified with 36 compounds of various chemical properties was analyzed by real-time 2D separation LC×DMS-MS(/MS). The addition of this orthogonal gas-phase separation technique in the LC-MS(/MS) hyphenation greatly improved data quality by resolving composite MS/MS spectra, which is mandatory in metabolomics when performing database generation and search.

  20. BINARY CEPHEIDS: SEPARATIONS AND MASS RATIOS IN 5 M {sub ☉} BINARIES

    Energy Technology Data Exchange (ETDEWEB)

    Evans, Nancy Remage; Karovska, Margarita; Tingle, Evan [Smithsonian Astrophysical Observatory, MS 4, 60 Garden Street, Cambridge, MA 02138 (United States); Bond, Howard E. [Department of Astronomy and Astrophysics, Pennsylvania State University, University Park, PA 16802 (United States); Schaefer, Gail H. [The CHARA Array, Georgia State University, P.O. Box 3965, Atlanta, GA 30302-3965 (United States); Mason, Brian D., E-mail: nevans@cfa.harvard.edu, E-mail: heb11@psu.edu, E-mail: schaefer@chara-array.org [US Naval Observatory, 3450 Massachusetts Avenue, NW, Washington, DC 20392-5420 (United States)

    2013-10-01

    Deriving the distribution of binary parameters for a particular class of stars over the full range of orbital separations usually requires the combination of results from many different observing techniques (radial velocities, interferometry, astrometry, photometry, direct imaging), each with selection biases. However, Cepheids—cool, evolved stars of ∼5 M {sub ☉}—are a special case because ultraviolet (UV) spectra will immediately reveal any companion star hotter than early type A, regardless of the orbital separation. We have used International Ultraviolet Explorer UV spectra of a complete sample of all 76 Cepheids brighter than V = 8 to create a list of all 18 Cepheids with companions more massive than 2.0 M {sub ☉}. Orbital periods of many of these binaries are available from radial-velocity studies, or can be estimated for longer-period systems from detected velocity variability. In an imaging survey with the Hubble Space Telescope Wide Field Camera 3, we resolved three of the companions (those of η Aql, S Nor, and V659 Cen), allowing us to make estimates of the periods out to the long-period end of the distribution. Combining these separations with orbital data in the literature, we derive an unbiased distribution of binary separations, orbital periods, and mass ratios. The distribution of orbital periods shows that the 5 M {sub ☉} binaries have systematically shorter periods than do 1 M {sub ☉} stars. Our data also suggest that the distribution of mass ratios depends on both binary separation and system multiplicity. The distribution of mass ratios as a function of orbital separation, however, does not depend on whether a system is a binary or a triple.

  1. On-line solid phase extraction-high performance liquid chromatography–isotope dilution–tandem mass spectrometry approach to quantify N,N-diethyl-m-toluamide and oxidative metabolites in urine

    Energy Technology Data Exchange (ETDEWEB)

    Kuklenyik, Peter; Baker, Samuel E.; Bishop, Amanda M.; Morales-A, Pilar; Calafat, Antonia M., E-mail: aic7@cdc.gov

    2013-07-17

    Graphical abstract: -- Highlights: •A fast assay to quantify the concentrations of N,N-Diethyl-m-Toluamide and two urinary metabolites was developed •It uses online SPE, reversed phase HPLC and tandem mass spectrometry •The method is precise and accurate with limits of detection ≤1 ng mL{sup −1} -- Abstract: Human exposure to N,N-diethyl-m-toluamide (DEET) occurs because of the widespread use of DEET as an active ingredient in insect repellents. However, information on the extent of such exposure is rather limited. Therefore, we developed a fast on-line solid phase extraction–high performance liquid chromatography–isotope dilution tandem mass spectrometry (HPLC-MS/MS) method to measure in urine the concentrations of DEET and two of its oxidative metabolites: N,N-diethyl-3-(hydroxymethyl)benzamide and 3-(diethylcarbamoyl)benzoic acid (DCBA). To the best of our knowledge, this is the first HPLC-MS/MS method for the simultaneous quantification of DEET and its select metabolites in human urine. After enzymatic hydrolysis of the conjugated species in 0.1 mL of urine, the target analytes were retained and pre-concentrated on a monolithic column, separated from each other and from other urinary biomolecules on a reversed-phase analytical column, and detected by atmospheric pressure chemical ionization in positive ion mode. The limits of detection ranged from 0.1 ng mL{sup −1} to 1.0 ng mL{sup −1}, depending on the analyte. Accuracy ranged between 90.4 and 104.9%, and precision ranged between 5.5 and 13.1% RSD, depending on the analyte and the concentration. We tested the usefulness of this method by analyzing 75 urine samples collected anonymously in the Southeastern United States in June 2012 from adults with no known exposure to DEET. Thirty eight samples (51%) tested positive for at least one of the analytes. We detected DCBA most frequently and at the highest concentrations. Our results suggest that this method can be used for the analysis of a large

  2. FI/SI on-line solvent extraction/back extraction preconcentration coupled to direct injection nebulization inductively coupled plasma mass spectrometry for determination of copper and lead

    DEFF Research Database (Denmark)

    Wang, Jianhua; Hansen, Elo Harald

    2002-01-01

    at a sample flow rate of 6.0 ml/min The precisions (RSD) at the 0.2 mug/1 level were 4.4% (Cu) and 4.8% (Pb), respectively. The applicability of the procedure is demonstrated for the determination of copper and lead in three certified reference materials and a urine sample.......An automated sequential injection on-line preconcentration procedure for determination of trace levels of copper and lead via solvent extraction/back extraction coupled to ICP-MS is described. In citrate buffer of pH 3, neutral complexes between the analytes and the chelating reagent, ammonium...

  3. 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.

    Science.gov (United States)

    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

  4. On-line coupling of solid-phase extraction with mass spectrometry for the analysis of biological samples. II. Determination of clenbuterol in urine using multiple-stage mass spectrometry in an ion-trap mass spectrometer

    NARCIS (Netherlands)

    van Hout, MWJ; Hofland, CM; Niederlander, HAG; de Jong, GJ

    2000-01-01

    Solid-phase extraction (SPE) was coupled to ion-trap mass spectrometry to determine clenbuterol in urine. For SPE a cartridge exchanger was used and, after extraction, the eluate was directly introduced into the mass spectrometer, For two types of cartridges, i.e. C-18 and polydivinylbenzene (PDVB),

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

    Science.gov (United States)

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

    2015-04-01

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

  6. Multidimensional Separation of Natural Products Using Liquid Chromatography Coupled to Hadamard Transform Ion Mobility Mass Spectrometry

    Science.gov (United States)

    Liu, Wenjie; Zhang, Xing; Knochenmuss, Richard; Siems, William F.; Hill, Herbert H.

    2016-05-01

    A high performance liquid chromatograph (HPLC)was interfaced to an atmospheric drift tube ion mobility time of flight mass spectrometry. The power of multidimensional separation was demonstrated using chili pepper extracts. The ambient pressure drift tube ion mobility provided high resolving powers up to 166 for the HPLC eluent. With implementation of Hadamard transform (HT), the duty cycle for the ion mobility drift tube was increased from less than 1% to 50%, and the ion transmission efficiency was improved by over 200 times compared with pulsed mode, improving signal to noise ratio 10 times. HT ion mobility and TOF mass spectrometry provide an additional dimension of separation for complex samples without increasing the analysis time compared with conventional HPLC.

  7. Stable Isotope Quantitative N-Glycan Analysis by Liquid Separation Techniques and Mass Spectrometry.

    Science.gov (United States)

    Mittermayr, Stefan; Albrecht, Simone; Váradi, Csaba; Millán-Martín, Silvia; Bones, Jonathan

    2017-01-01

    Liquid phase separation analysis and subsequent quantitation remains a challenging task for protein-derived oligosaccharides due to their inherent structural complexity and diversity. Incomplete resolution or co-detection of multiple glycan species complicates peak area-based quantitation and associated statistical analysis when optical detection methods are used. The approach outlined herein describes the utilization of stable isotope variants of commonly used fluorescent tags that allow for mass-based glycan identification and relative quantitation following separation by liquid chromatography (LC) or capillary electrophoresis (CE). Comparability assessment of glycoprotein-derived oligosaccharides is performed by derivatization with commercially available isotope variants of 2-aminobenzoic acid or aniline and analysis by LC- and CE-mass spectrometry. Quantitative information is attained from the extracted ion chromatogram/electropherogram ratios generated from the light and heavy isotope clusters.

  8. On-line analysis of penicillin blood levels in the live rat by combined microdialysis/fast-atom bombardment mass spectrometry.

    OpenAIRE

    Caprioli, R.M.; Lin, S. N.

    1990-01-01

    The combination of microdialysis and fast-atom bombardment mass spectrometry has been used to follow the pharmacokinetics of penicillin G directly in the blood-stream of a live rat. After the intramuscular injection of the antibiotic, the blood dialysate was allowed to flow into the mass spectrometer via the continuous-flow/fast-atom bombardment interface. Tandem mass spectrometry provided the means for isolating and recording the ion fragments produced from the drug as the dialysate was expo...

  9. Separation Techniques for Uranium and Plutonium at Trace Levels for the Thermal Ionization Mass Spectrometric Determination

    Energy Technology Data Exchange (ETDEWEB)

    Suh, M. Y.; Han, S. H.; Kim, J. G.; Park, Y. J.; Kim, W. H

    2005-12-15

    This report describes the state of the art and the progress of the chemical separation and purification techniques required for the thermal ionization mass spectrometric determination of uranium and plutonium in environmental samples at trace or ultratrace levels. Various techniques, such as precipitation, solvent extraction, extraction chromatography, and ion exchange chromatography, for separation of uranium and plutonium were evaluated. Sample preparation methods and dissolution techniques for environmental samples were also discussed. Especially, both extraction chromatographic and anion exchange chromatographic procedures for uranium and plutonium in environmental samples, such as soil, sediment, plant, seawater, urine, and bone ash were reviewed in detail in order to propose some suitable methods for the separation and purification of uranium and plutonium from the safeguards environmental or swipe samples. A survey of the IAEA strengthened safeguards system, the clean room facility of IAEA's NWAL(Network of Analytical Laboratories), and the analytical techniques for safeguards environmental samples was also discussed here.

  10. Target-guided separation of Bougainvillea glabra betacyanins by direct coupling of preparative ion-pair high-speed countercurrent chromatography and electrospray ionization mass-spectrometry.

    Science.gov (United States)

    Jerz, Gerold; Wybraniec, Sławomir; Gebers, Nadine; Winterhalter, Peter

    2010-07-02

    In this study, preparative ion-pair high-speed countercurrent chromatography was directly coupled to an electrospray ionization mass-spectrometry device (IP-HSCCC/ESI-MS-MS) for target-guided fractionation of high molecular weight acyl-oligosaccharide linked betacyanins from purple bracts of Bougainvillea glabra (Nyctaginaceae). The direct identification of six principal acyl-oligosaccharide linked betacyanins in the mass range between m/z 859 and m/z 1359 was achieved by positive ESI-MS ionization and gave access to the genuine pigment profile already during the proceeding of the preparative separation. Inclusively, all MS/MS-fragmentation data were provided during the chromatographic run for a complete analysis of substitution pattern. On-line purity evaluation of the recovered fractions is of high value in target-guided screening procedures and for immediate decisions about suitable fractions used for further structural analysis. The applied preparative hyphenation was shown to be a versatile screening method for on-line monitoring of countercurrent chromatographic separations of polar crude pigment extracts and also traced some minor concentrated compounds. For the separation of 760mg crude pigment extract the biphasic solvent system tert.-butylmethylether/n-butanol/acetonitrile/water 2:2:1:5 (v/v/v/v) was used with addition of ion-pair forming reagent trifluoroacetic acid. The preparative HSCCC-eluate had to be modified by post-column addition of a make-up solvent stream containing formic acid to reduce ion-suppression caused by trifluoroacetic acid and later significantly maximized response of ESI-MS/MS detection of target substances. A variable low-pressure split-unit guided a micro-eluate to the ESI-MS-interface for sensitive and direct on-line detection, and the major volume of the effluent stream was directed to the fraction collector for preparative sample recovery. The applied make-up solvent mixture significantly improved smoothness of the continuously

  11. Resonance-enhanced multiphoton ionization time-of-flight mass spectrometry for detection of nitrogen containing aliphatic and aromatic compounds: resonance-enhanced multiphoton ionization spectroscopic investigation and on-line analytical application.

    Science.gov (United States)

    Streibel, T; Hafner, K; Mühlberger, F; Adam, T; Zimmermann, R

    2006-01-01

    Resonance-enhanced multiphoton ionization (REMPI) combined with time-of-flight mass spectrometry (TOFMS) is an analytical method capable of on-line monitoring of trace compounds in complex matrices. A necessary prerequisite for substance selective detection is spectroscopic investigation of the target molecules. Several organic nitrogen compounds comprising aliphatic and aromatic amines, nitrogen heterocyclic compounds, and aromatic nitriles are spectroscopically investigated with a tunable narrow bandwidth optical parametric oscillator (OPO) laser system providing a scannable wavelength range between 220 and 340 nm. These species are known as possible precursors in fuel-NO formation from combustion of solid fuels such as biomass and waste. A newly conceived double inlet system was used in this study, which allows rapid change between effusive and supersonic molecular beams. The resulting REMPI spectra of the compounds are discussed with respect to electronic transitions that could be utilized for a selective ionization of these compounds in complex mixtures such as combustion and process gases. The practicability of this approach is demonstrated by wavelength selected on-line REMPI-TOFMS detection of aniline and cyanonaphthalene in the burning chamber of a waste incineration plant. REMPI mass spectra recorded at different excitation wavelengths as well as variations in time show the utilization of species-selective REMPI-TOFMS detection for on-line monitoring of crucial substances in pollutant formation.

  12. Charge variants characterization of a monoclonal antibody by ion exchange chromatography coupled on-line to native mass spectrometry: Case study after a long-term storage at +5°C.

    Science.gov (United States)

    Leblanc, Y; Ramon, C; Bihoreau, N; Chevreux, G

    2017-03-24

    Numerous putative post-translational modifications may induce variations of monoclonal antibodies charge distribution that can potentially affect their biological activity. The characterization and the monitoring of these charge variants are critical quality requirements to ensure stability and process consistency. Charge variants are usually characterized by preparative ion exchange chromatography, collection of fractions and subsequent reverse-phase liquid chromatography with mass spectrometry analysis. While this process can be automatized by on-line two-dimensional chromatography, it remains often complex and time consuming. For this reason, a straightforward on-line charge variant analysis method is highly desirable and analytical laboratories are actively pursuing efforts to overcome this challenge. In this study, a mixed mode ion exchange chromatographic method using volatile salts and coupled on-line to native mass spectrometry was developed in association with a middle-up approach for a detailed characterization of monoclonal antibodies charge variants. An aged monoclonal antibody, presenting a complex charge variant profile was successfully investigated by this methodology as a case study. Results demonstrate that deamidation of the heavy chain was the major degradation pathway after long-term storage at 5°C while oxidation was rather low. The method was also very useful to identify all the clipped forms of the antibody. Copyright © 2017 LFB Biotechnologies. Published by Elsevier B.V. All rights reserved.

  13. Mass, charge, and energy separation by selective acceleration with a traveling potential hill

    Science.gov (United States)

    Tung, L. Schwager; Barr, W. L.; Lowder, R. S.; Post, R. F.

    1996-10-01

    A traveling electric potential hill has been used to generate an ion beam with an energy distribution that is mass dependent from a monoenergetic ion beam of mixed masses. This effect can be utilized as a novel method for mass separation applied to identification or enrichment of ions (e.g., of elements, isotopes, or molecules). This theory for mass-selective acceleration is presented here and is shown to be confirmed by experiment and by a time-dependent particle-in-cell computer simulation. Results show that monoenergetic ions with the particular mass of choice are accelerated by controlling the hill potential and the hill velocity. The hill velocity is typically 20%-30% faster than the ions to be accelerated. The ability of the hill to pickup a particular mass uses the fact that small kinetic energy differences in the lab frame appear much larger in the moving hill frame. Ions will gain energy from the approaching hill if their relative energy in the moving hill frame is less than the peak potential of the hill. The final energy of these accelerated ions can be several times the source energy, which facilitates energy filtering for mass purification or identification. If the hill potential is chosen to accelerate multiple masses, the heaviest mass will have the greatest final energy. Hence, choosing the appropriate hill potential and collector retarding voltage will isolate ions with the lightest, heaviest, or intermediate mass. In the experimental device, called a Solitron, purified 20Ne and 22Ne are extracted from a ribbon beam of neon that is originally composed of 20Ne:22Ne in the natural ratio of 91:9. The isotopic content of the processed beam is determined by measuring the energy distribution of the detected current. These results agree with the theory. In addition to mass selectivity, our theory can also be applied to the filtration of an ion beam according to charge state or energy. Because of this variety of properties, the Solitron is envisioned to

  14. Sol-gel zirconia coating capillary microextraction on-line hyphenated with inductively coupled plasma mass spectrometry for the determination of Cr, Cu, Cd and Pb in biological samples.

    Science.gov (United States)

    Wu, Yiwei; Hu, Bin; Jiang, Zucheng; Feng, Yuqi; Lu, Peng; Li, Boyangzi

    2006-01-01

    A sol-gel zirconia coating was developed for the preconcentration/separation of trace Cr, Cu, Cd and Pb by capillary microextraction, and the adsorbed analytes were on-line eluted for detection using inductively coupled plasma mass spectrometry (ICP-MS). By immobilizing sol-gel zirconia on the inner surface of a fused-silica capillary, the sol-gel zirconia coating was simply prepared. Its adsorption properties, stability and the factors affecting the adsorption behaviors of Cr, Cu, Cd and Pb were investigated in detail. In the pH range from 7.8 to 10, the zirconia-coated capillary (35 cm x 0.15 mm) is selective towards Cr, Cu, Cd and Pb, and the analyzed ions could be desorbed quantitatively with 0.2 mL of 0.5 mol/L HNO(3) at a rate of 0.2 mL/min. With a consumption of 1.25 mL sample solution, an enrichment factor of 6.25, and detection limits (3sigma) of 9.9 pg/mL Cr, 17.9 pg/mL Cu, 4.5 pg/mL Cd and 3.7 pg/mL Pb were obtained. The precisions for nine replicate measurements of 1 ng/mL Cr, Cu, Cd and Pb were 4.9% Cr, 2.2% Cu, 2.0% Cd and 3.2% Pb (RSD), respectively. The proposed procedure has been applied to the determination of Cr, Cu, Cd and Pb in human urine, which was subjected to microwave-assisted digestion prior to analysis, and the recoveries for these elements were 89.2-101.8%. In order to validate the developed procedure, a NIES No.10-a Rice Flour-Unpolished certified reference material and a BCR No. 184 Bovine Muscle certified reference material were analyzed, and the results are in good agreement with the certified values. Copyright (c) 2006 John Wiley & Sons, Ltd.

  15. Review of zero-net-mass-flux jet and its application in separation flow control

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Since the zero-net-mass-flux (ZNMF) jet was first used as a laboratory flow control method in 1990’s, it has attracted much attention. The ZNMF jet has unique features such as compact actuator, no requirement for external air supply, complex piping, etc., and becomes a hot topic research subject in fluid mechanics. This review introduces the state of the art in the development of ZNMF jet in the quiescent fluid, the interaction of the ZNMF jet with the cross flow and its application in the separation flow control. The evolution of the vortex ring/pair and the spacial flow structure of the ZNMF in quicent fluid or cross flow are presented, as well as the key parameter effects. At last, the applications of ZNMF jet in the wake control of the circular cylinder, the separation control on the airfoil and the aerodynamic force or moment control on MAV/UAV are presented.

  16. Review of zero-net-mass-flux jet and its application in separation flow control

    Institute of Scientific and Technical Information of China (English)

    ZHANG PanFeng; WANG JinJun; FENG LiHao

    2008-01-01

    Since the zero-net-mass-flux (ZNMF) jet was first used as a laboratory flow control method in 1990's, it has attracted much attention. The ZNMF jet has unique features such as compact actuator, no requirement for external air supply, complex piping, etc., and becomes a hot topic research subject in fluid mechanics. This review introduces the state of the art in the development of ZNMF jet in the quiescent fluid, the interaction of the ZNMF jet with the cross flow and its application in the separation flow control. The evolution of the vortex ring/pair and the spacial flow structure of the ZNMF in quicent fluid or cross flow are presented, as well as the key parameter effects. At last, the applications of ZNMF jet in the wake control of the circular cylinder, the separation control on the airfoil and the aerodynamic force or moment control on MAV/UAV are presented.

  17. On-line coupling of solid-phase extraction with mass spectrometry for the analysis of biological samples III. Determination of prednisolone in serum

    NARCIS (Netherlands)

    van Hout, M.W.J.; Hofland, C.M; Niederlander, H.A G; Bruins, A.P.; de Zeeuw, R.A.; de Jong, G.J.

    2003-01-01

    Solid-phase extraction (SPE) was directly coupled to mass spectrometry (MS) to assess the feasibility of the system for the rapid determination of prednisolone in serum. A C-18 stationary phase allowed washing of the cartridge with 25% methanol. Elution was performed by switching the methanol

  18. On-line coupling of solid-phase extraction with mass spectrometry for the analysis of biological samples III. Determination of prednisolone in serum

    NARCIS (Netherlands)

    van Hout, MWJ; Hofland, CM; Niederlander, HAG; Bruins, AP; de Zeeuw, RA; de Jong, GJ

    2003-01-01

    Solid-phase extraction (SPE) was directly coupled to mass spectrometry (MS) to assess the feasibility of the system for the rapid determination of prednisolone in serum. A C-18 stationary phase allowed washing of the cartridge with 25% methanol. Elution was performed by switching the methanol percen

  19. Rapid chemical separations

    CERN Document Server

    Trautmann, N

    1976-01-01

    A survey is given on the progress of fast chemical separation procedures during the last few years. Fast, discontinuous separation techniques are illustrated by a procedure for niobium. The use of such techniques for the chemical characterization of the heaviest known elements is described. Other rapid separation methods from aqueous solutions are summarized. The application of the high speed liquid chromatography to the separation of chemically similar elements is outlined. The use of the gas jet recoil transport method for nuclear reaction products and its combination with a continuous solvent extraction technique and with a thermochromatographic separation is presented. Different separation methods in the gas phase are briefly discussed and the attachment of a thermochromatographic technique to an on-line mass separator is shown. (45 refs).

  20. Aerosol and trace gas vehicle emission factors measured in a tunnel using an Aerosol Mass Spectrometer and other on-line instrumentation

    Science.gov (United States)

    Chirico, Roberto; Prevot, Andre S. H.; DeCarlo, Peter F.; Heringa, Maarten F.; Richter, Rene; Weingartner, Ernest; Baltensperger, Urs

    2011-04-01

    In this study we present measurements of gas and aerosol phase composition for a mixed vehicle fleet in the Gubrist tunnel (Switzerland) in June 2008. PM 1 composition measurements were made with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (AMS) and a Multi Angle Absorption Photometer (MAAP). Gas-phase measurements of CO, CO 2, NO x and total hydrocarbons (THC) were performed with standard instrumentation. Weekdays had a characteristic diurnal pattern with 2 peaks in concentrations for all traffic related species corresponding to high vehicle density (˜300 ± 30 vehicles per 5 min) in the morning rush hour between 06:00 and 09:00 and in the afternoon rush hours from approximately 15:30 to 18:30. The emission factors (EF) of OA were heavily influenced by the OA mass loading. To exclude this partitioning effect, only organic aerosol mass concentrations from 60 μg m -3 to 90 μg m -3 were considered and for these conditions the EF(OA) value for HDV was 33.7 ± 2.3 mg km -1 for a temperature inside the tunnel of 20-25 °C. This value is not directly applicable to ambient conditions because it is derived from OA mass concentrations that are roughly a factor of 10 higher than typical ambient concentrations. An even higher EF(OA) HDV value of 47.4 ± 1.6 mg km -1 was obtained when the linear fit was applied to all data points including OA concentrations up to 120 μg m -3. Similar to the increasing EF, the OA/BC ratio in the tunnel was also affected by the organic loading and it increased by a factor of ˜3 over the OA range 10-120 μg m -3. This means that also the OA emission factors at ambient concentrations of around 5-10 μg m -3 would be 2-3 times lower than the emission factor given above. For OA concentrations lower than 40 μg m -3 the OA/BC mass ratio was below 1, while at an OA concentration of 100-120 μg m -3 the OA/BC ratio was ˜1.5. The AMS mass spectra (MS) acquired in the tunnel were highly correlated with the primary organic aerosol

  1. Base flow separation: A comparison of analytical and mass balance methods

    Science.gov (United States)

    Lott, Darline A.; Stewart, Mark T.

    2016-04-01

    Base flow is the ground water contribution to stream flow. Many activities, such as water resource management, calibrating hydrological and climate models, and studies of basin hydrology, require good estimates of base flow. The base flow component of stream flow is usually determined by separating a stream hydrograph into two components, base flow and runoff. Analytical methods, mathematical functions or algorithms used to calculate base flow directly from discharge, are the most widely used base flow separation methods and are often used without calibration to basin or gage-specific parameters other than basin area. In this study, six analytical methods are compared to a mass balance method, the conductivity mass-balance (CMB) method. The base flow index (BFI) values for 35 stream gages are obtained from each of the seven methods with each gage having at least two consecutive years of specific conductance data and 30 years of continuous discharge data. BFI is cumulative base flow divided by cumulative total discharge over the period of record of analysis. The BFI value is dimensionless, and always varies from 0 to 1. Areas of basins used in this study range from 27 km2 to 68,117 km2. BFI was first determined for the uncalibrated analytical methods. The parameters of each analytical method were then calibrated to produce BFI values as close to the CMB derived BFI values as possible. One of the methods, the power function (aQb + cQ) method, is inherently calibrated and was not recalibrated. The uncalibrated analytical methods have an average correlation coefficient of 0.43 when compared to CMB-derived values, and an average correlation coefficient of 0.93 when calibrated with the CMB method. Once calibrated, the analytical methods can closely reproduce the base flow values of a mass balance method. Therefore, it is recommended that analytical methods be calibrated against tracer or mass balance methods.

  2. Single photon ionization time-of-flight mass spectrometry with a pulsed electron beam pumped excimer VUV lamp for on-line gas analysis: setup and first results on cigarette smoke and human breath.

    Science.gov (United States)

    Mühlberger, F; Streibel, T; Wieser, J; Ulrich, A; Zimmermann, R

    2005-11-15

    Single-photon ionization (SPI) using vacuum ultraviolet (VUV) light produced by an electron beam pumped rare gas excimer source has been coupled to a compact and mobile time-of-flight mass spectrometer (TOFMS). The novel device enables real-time on-line monitoring of organic trace substances in complex gaseous matrixes down to the ppb range. The pulsed VUV radiation of the light source is employed for SPI in the ion source of the TOFMS. Ion extraction is also carried out in a pulsed mode with a short time delay with respect to ionization. The experimental setup of the interface VUV light source/time-of-flight mass spectrometer is described, and the novel SPI-TOFMS system is characterized by means of standard calibration gases. Limits of detection down to 50 ppb for aliphatic and aromatic hydrocarbons were achieved. First on-line applications comprised real-time measurements of aromatic and aliphatic trace compounds in mainstream cigarette smoke, which represents a highly dynamic fluctuating gaseous matrix. Time resolution was sufficient to monitor the smoking process on a puff-by-puff resolved basis. Furthermore, human breath analysis has been carried out to detect differences in the breath of a smoker and a nonsmoker, respectively. Several well-known biomarkers for smoke could be identified in the smoker's breath. The possibility for even shorter measurement times while maintaining the achieved sensitivity makes this new device a promising tool for on-line analysis of organic trace compounds in process gases or biological systems.

  3. Estimation of the bio-accessible fraction of Cr, As, Cd and Pb in locally available bread using on-line continuous leaching method coupled to inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Lamsal, Ram P; Beauchemin, Diane

    2015-03-31

    A previously developed, efficient and simple on-line leaching method was used to assess the maximum bio-accessible fraction (assuming no synergistic effect from other food and beverage) of potentially toxic elements (Cr, As, Cd and Pb) in whole wheat brown and white bread samples. Artificial saliva, gastric juice and intestinal juice were successively pumped into a mini-column, packed with bread (maintained at 37 °C) connected on-line to the nebulizer of an inductively coupled plasma mass spectrometry (ICP-MS) instrument equipped with a collision-reaction interface (CRI) using hydrogen as reaction gas to minimize carbon- and chlorine-based polyatomic interferences. In contrast to the conventional batch method to which it was compared, this approach provides real-time monitoring of potentially toxic elements that are continuously released during leaching. Mass balance for both methods was verified at the 95% confidence level. Results obtained from the whole wheat brown and white bread showed that the majority of Cr, Cd and Pb was leached by gastric juice but, in contrast, the majority of As was leached by saliva. While there was higher total content for elements in whole wheat bread than in white bread, a higher percentage of elements were bio-accessible in white bread than in whole wheat bread. Both the on-line and batch methods indicate that 40-98% of toxic elements in bread samples are bio-accessible. While comparison of total analyte concentrations with provisional tolerable daily intake values may indicate some serious health concern for children, when accounting for the bio-accessibility of these elements, bread consumption is found to be safe for all ages. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Determination of lead by hydride generation inductively coupled plasma mass spectrometry (HG-ICP-MS): on-line generation of plumbane using potassium hexacyanomanganate(III).

    Science.gov (United States)

    Yilmaz, Vedat; Arslan, Zikri; Rose, LaKeysha

    2013-01-25

    A hydride generation (HG) procedure has been described for determination of Pb by ICP-MS using potassium hexacyanomanganate(III), K(3)Mn(CN)(6), as an additive to facilitate the generation of plumbane (PbH(4)). Potassium hexacyanomanganate(III) was prepared in acidic medium as it was unstable in water. The stability of hexacyanomanganate(III) was examined in dilute solutions of HCl, HNO(3) and H(2)SO(4). The solutions prepared in 1% v/v H(2)SO(4) were found to be stable for over a period of 24h. The least suitable medium was 1% v/v HNO(3). For generation of plumbane, acidic hexacyanomanganate(III) and sample solutions were mixed on-line along a 5-cm long tygon tubing (1.14 mm i.d.) and then reacted with 2% m/v sodium borohydride (NaBH(4)). A concentration of 0.5% m/v K(3)Mn(CN)(6) facilitated the generation of PbH(4) remarkably. In comparison to H(2)SO(4), HCl provided broader working range for which optimum concentration was 1% v/v. No significant interferences were noted from transition metals and hydride forming elements, up to 0.5 μg mL(-1) levels, except Cu which depressed the signals severely. The depressive effects in the presence of 0.1 μg mL(-1) Cu were alleviated by increasing the concentration of K(3)Mn(CN)(6) to 2% m/v. Under these conditions, the sensitivity was enhanced by a factor of at least 42 to 48. The detection limit (3s) was 0.008 μg L(-1) for (208)Pb isotope. Average signal-to-noise ratio (S/N) ranged between 18 and 20 for 1.0 μg mL(-1) Pb solution. The accuracy of the method was verified by analysis of several certified reference materials, including Nearshore seawater (CASS-4), Bone ash (SRM 1400), and Mussel tissue (SRM 2976). The procedure was also successfully applied to the determination of Pb in coastal seawater samples by ICP-MS.

  5. Analysis of Protein Glycosylation and Phosphorylation Using Liquid Phase Separation, Protein Microarray Technology, and Mass Spectrometry

    Science.gov (United States)

    Zhao, Jia; Patwa, Tasneem H.; Pal, Manoj; Qiu, Weilian; Lubman, David M.

    2010-01-01

    Summary Protein glycosylation and phosphorylation are very common posttranslational modifications. The alteration of these modifications in cancer cells is closely related to the onset and progression of cancer and other disease states. In this protocol, strategies for monitoring the changes in protein glycosylation and phosphorylation in serum or tissue cells on a global scale and specifically characterizing these alterations are included. The technique is based on lectin affinity enrichment for glycoproteins, all liquid-phase two-dimensional fractionation, protein microarray, and mass spectrometry technology. Proteins are separated based on pI in the first dimension using chromatofocusing (CF) or liquid isoelectric focusing (IEF) followed by the second-dimension separation using nonporous silica RP-HPLC. Five lectins with different binding specificities to glycan structures are used for screening glycosylation patterns in human serum through a biotin–streptavidin system. Fluorescent phosphodyes and phosphospecific antibodies are employed to detect specific phosphorylated proteins in cell lines or human tissues. The purified proteins of interest are identified by peptide sequencing. Their modifications including glycosylation and phosphorylation could be further characterized by mass-spectrometry-based approaches. These strategies can be used in biological samples for large-scale glycoproteome/phosphoproteome screening as well as for individual protein modification analysis. PMID:19241043

  6. Extension of the two-dimensional mass channel cluster plot method to fast separations utilizing low thermal mass gas chromatography with time-of-flight mass spectrometry.

    Science.gov (United States)

    Fitz, Brian D; Synovec, Robert E

    2016-03-24

    Implementation of a data reduction and visualization method for use with high-speed gas chromatography and time-of-flight mass spectrometry (GC-TOFMS) is reported. The method, called the "2D m/z cluster method" facilitates analyte detection, deconvolution, and identification, by accurately measuring peak widths and retention times using a fast TOFMS sampling frequency (500 Hz). Characteristics and requirements for high speed GC are taken into consideration: fast separations with narrow peak widths and high peak capacity, rapid data collection rate, and effective peak deconvolution. Transitioning from standard GC (10-60+ minute separations) to fast GC (1-10 min separations) required consideration of how to properly analyze the data. This report validates use of the 2D m/z cluster method with newly developed GC technology that produces ultra-fast separations (∼1 min) with narrow analyte peak widths. Low thermal mass gas chromatography (LTM-GC) operated at a heating rate of 250 °C/min coupled to a LECO Pegasus III TOFMS analyzed a 115 component test mixture in 120 s with peak widths-at-base, wb (4σ), of 350 ms (average) to produce a separation with a high peak capacity, nc ∼ 340 (at unit resolution Rs = 1). The 2D m/z cluster method is shown to separate overlapped analytes to a limiting Rs ∼ 0.03, so the effective peak capacity was increased nearly 30-fold to nc ∼10,000 in the 120 s separation. The method, when coupled with LTM-GC-TOFMS, is demonstrated to provide unambiguous peak rank (i.e. the number of analytes per overlapped peak in the total ion current (TIC)), by visualizing locations of pure and chromatographically overlapped m/z. Hence, peak deconvolution and identification using MCR-ALS (multivariate curve resolution - alternating least squares) is demonstrated.

  7. Main polyphenols in the bitter taste of virgin olive oil. Structural confirmation by on-line high-performance liquid chromatography electrospray ionization mass spectrometry.

    Science.gov (United States)

    Gutiérrez-Rosales, F; Ríos, J J; Gómez-Rey, Ma L

    2003-09-24

    Twenty virgin olive oils of extra quality and different bitter intensity were submitted to sensory evaluation and to the determination of polyphenols. A linear regression analysis was carried out assuming, as an independent variable, bitter intensity perceived by tasters, as an independent variable, the concentration (mmol/kg) of dialdehydic and aldehydic forms oleuropein aglycon, and dialdehydic and aldehydic forms ligstroside aglycon. Structural confirmation of these compounds was done by online high-performance liquid chromatography-electrospray ionization-collison-induced dissociation-mass spectrometry. The results obtained demonstrate the essential role played by this compound in the bitter taste of virgin olive oil.

  8. Americium and plutonium separation by extraction chromatography for determination by accelerator mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Kazi, Zakir H. [Department of Earth Science, University of Ottawa, 140 Louis Pasteur Avenue, Ottawa K1N 6N5 (Canada); Cornett, Jack R., E-mail: jack.cornett@uottawa.ca [Department of Earth Science, University of Ottawa, 140 Louis Pasteur Avenue, Ottawa K1N 6N5 (Canada); Zhao, Xaiolei; Kieser, Liam [Department of Physics, University of Ottawa, 140 Louis Pasteur Avenue, Ottawa K1N 6N5 (Canada)

    2014-06-01

    Highlights: • Am and Pu were adsorbed and separated using a single extraction chromatography DGA column. • Pu was eluted from the column completely using on-column reduction of Pu(IV) to Pu(III). • ²⁴¹Am and 239,240Pu measurements by accelerator mass spectrometry (AMS) agree with the certified values in two SRMs. Abstract: A simple method was developed to separate Pu and Am using single column extraction chromatography employing N,N,N',N'-tetra-n-octyldiglycolamide (DGA) resin. Isotope dilution measurements of Am and Pu were performed using accelerator mass spectrometry (AMS) and alpha spectrometry. For maximum adsorption Pu was stabilized in the tetra valent oxidation state in 8 M HNO₃ with 0.05 M NaNO₂ before loading the sample onto the resin. Am(III) was adsorbed also onto the resin from concentrated HNO₃, and desorbed with 0.1 M HCl while keeping the Pu adsorbed. The on-column reduction of Pu(IV) to Pu(III) with 0.02 M TiCl₃ facilitated the complete desorption of Pu. Interferences (e.g. Ca²⁺, Fe³⁺) were washed off from the resin bed with excess HNO₃. Using NdF₃, micro-precipitates of the separated isotopes were prepared for analysis by both AMS and alpha spectrometry. The recovery was 97.7 ± 5.3% and 95.5 ± 4.6% for ²⁴¹Am and ²⁴²Pu respectively in reagents without a matrix. The recoveries of the same isotopes were 99.1 ± 6.0 and 96.8 ± 5.3% respectively in garden soil. The robustness of the method was validated using certified reference materials (IAEA 384 and IAEA 385). The measurements agree with the certified values over a range of about 1–100 Bq kg⁻¹. The single column separation of Pu and Am saves reagents, separation time, and cost.

  9. Americium and plutonium separation by extraction chromatography for determination by accelerator mass spectrometry.

    Science.gov (United States)

    Kazi, Zakir H; Cornett, Jack R; Zhao, Xaiolei; Kieser, Liam

    2014-06-04

    A simple method was developed to separate Pu and Am using single column extraction chromatography employing N,N,N',N'-tetra-n-octyldiglycolamide (DGA) resin. Isotope dilution measurements of Am and Pu were performed using accelerator mass spectrometry (AMS) and alpha spectrometry. For maximum adsorption Pu was stabilized in the tetra valent oxidation state in 8M HNO3 with 0.05 M NaNO2 before loading the sample onto the resin. Am(III) was adsorbed also onto the resin from concentrated HNO3, and desorbed with 0.1 M HCl while keeping the Pu adsorbed. The on-column reduction of Pu(IV) to Pu(III) with 0.02 M TiCl3 facilitated the complete desorption of Pu. Interferences (e.g. Ca(2+), Fe(3+)) were washed off from the resin bed with excess HNO3. Using NdF3, micro-precipitates of the separated isotopes were prepared for analysis by both AMS and alpha spectrometry. The recovery was 97.7±5.3% and 95.5±4.6% for (241)Am and (242)Pu respectively in reagents without a matrix. The recoveries of the same isotopes were 99.1±6.0 and 96.8±5.3% respectively in garden soil. The robustness of the method was validated using certified reference materials (IAEA 384 and IAEA 385). The measurements agree with the certified values over a range of about 1-100 Bq kg(-1). The single column separation of Pu and Am saves reagents, separation time, and cost.

  10. Separation and identification of neuropeptide Y, two of its fragments and their degradation products using capillary electrophoresis mass spectrometry

    NARCIS (Netherlands)

    Ensing, K; de Boer, Theo; Schreuder, N; de Zeeuw, RA

    1999-01-01

    This paper describes the development of an analytical method for the separation and identification of neuropeptide Y (NPY) and two important NPY fragments by capillary electrophoresis (CE) arid mass spectrometry (MS). A satisfactory separation and the highest sensitivity were obtained with formic ac

  11. Determination of bezafibrate, methotrexate, cyclophosphamide, orlistat and enalapril in waste and surface waters using on-line solid-phase extraction liquid chromatography coupled to polarity-switching electrospray tandem mass spectrometry.

    Science.gov (United States)

    Garcia-Ac, Araceli; Segura, Pedro A; Gagnon, Christian; Sauvé, Sébastien

    2009-04-01

    We developed a rapid method for the monitoring of five selected pharmaceuticals in the influent and effluent of municipal wastewater treatment plants (WWTP) as well as in the effluent-receiving waters. To that end, we optimized and validated an analytical method based on on-line solid-phase extraction (on-line SPE) coupled with reversed-phase liquid chromatography-switching polarity electrospray ionization-tandem mass spectrometry (LC-ESI(+/-)-MS/MS). The target analytes have a variable hydrophobic character and belong to various therapeutic classes including the lipid regulator bezafibrate, the chemotherapy drugs methotrexate and cyclophosphamide, the lipase inhibitor orlistat and the angiotensin converting enzyme (ACE) inhibitor used in the treatment of hypertension, enalapril. The method combines positive and negative voltage switching modes, therefore all analytes can be determined using a single injection and without any reduction in sensitivity. In order to detect traces of these compounds, a preconcentration step before detection is performed by loading 1.00 mL of sample in an on-line SPE cartridge and eluting from the cartridge using a reversed-phase liquid chromatography gradient. Analysis of wastewater and surface water samples was greatly affected by co-eluting matrix compounds, to compensate for matrix effects quantitation was therefore performed using standard additions. Method intra-day precision was less than 6.5% and limits of detection in fortified matrix effluent samples ranged from 9 to 20 ng L(-1). Four of the target pharmaceuticals were detected in the WWTP effluents, enalapril and bezafibrate being the most abundant compounds with concentrations of 35 and 239 ng L(-1), respectively. Concentrations of these same compounds in surface water samples from sites downstream in the St. Lawrence River were 8 and 63 ng L(-1), respectively, which was mainly due to dilution.

  12. On-line study of flavonoids of Trollius chinensis Bunge binding to DNA with ethidium bromide using a novel combination of chromatographic, mass spectrometric and fluorescence techniques.

    Science.gov (United States)

    Song, Zhiling; Wang, Hong; Ren, Biao; Zhang, Baobao; Hashi, Yuki; Chen, Shizhong

    2013-03-22

    The study of the interaction between drugs and DNA is an important way to understand the role of drug molecules. A novel online analytical method for this purpose combining high-performance liquid chromatography-diode array detector-electrospray ionization-ion-trap time-of-flight mass spectrometry (HPLC-DAD-ESI-IT-TOF-MS(n)) and DNA-ethidium bromide detection with a fluorescence detector (DNA-EB-FLD) was firstly developed, which could rapidly identify the chemical constituents and obtain the profile related to DNA binding activity. This method has been applied for a precise or probable identification of the chemical constituents by ultraviolet (UV) absorption and MS(n) data analysis, while the DNA binding profile has been characterized by directly measuring the fluorescence intensity of compound-DNA-EB. Using this method, Trollius chinensis Bunge was studied and 18 constituents were identified by MS(n) data; six of them (4'-methoxy-2″-O-(2‴-methylbutyryl)vitexin,2″-O-(3‴-methoxycaffeoyl)vitexin) and 4'-methoxy-2″-O-(2‴-methylbutyryl)orientin,acacetin-7-O-rutinoside,quercetin-3-O-xylosylglucoside,quercetin-3-O-arabinosylglucoside) were identified for the first time in T. chinensis Bunge, and 16 constituents accounted for its activity of binding to DNA. The established (HPLC-DAD-ESI-IT-TOF-MS(n) DNA-EB-FLD) system has proved to offer a useful strategy for correlating the chemical profile with the binding to DNA activities of the components without their isolation and purification, and may be used for multicomponent analysis of active substances in other herbs.

  13. Photon Scattering from the Stable Even-Mass Mo Isotopes Below the Neutron-Separation Energy

    Science.gov (United States)

    Rusev, G.; Hutcheson, A.; Kwan, E.; Tonchev, A. P.; Tornow, W.; Angell, C.; Hammond, S.; Karwowski, H. J.; Kelley, J. H.; Schwengner, R.; Dönau, F.; Wagner, A.

    2008-10-01

    We present results from photon-scattering experiments on the stable even-mass molybdenum isotopes below the neutron-separation energy carried out with bremsstrahlung at the superconducting electron accelerator ELBE at the Research Center Dresden-Rossendorf in Germany, and with monoenergetic photon beams at the HIγS facility at TUNL. We applied statistical methods in order to correct for the branching and cascade transitions and to determine the photoabsorption cross section. The obtained results allowed us to extend the tail of the Giant Dipole Resonance below the (,) threshold down to 4 MeV. The photoabsorption cross sections deduced from the present experiments show that the dipole strength increases with the neutron number of the Mo isotopes. The experimental results are discussed in the frame of Quasiparticle-Random-Phase-Approximation in a deformed basis which describe the increasing strength as a result of the deformation.

  14. Hollow fiber apparatus and use thereof for fluids separations and heat and mass transfers

    Science.gov (United States)

    Bikson, Benjamin; Etter, Stephen; Ching, Nathaniel

    2014-06-10

    A hollow fiber device includes a hollow fiber bundle, comprising a plurality of hollow fibers, a first tubesheet and a second tubesheet encapsulating respective distal ends of the hollow fiber bundle. The tubesheets have boreholes in fluid communication with bores of the hollow fibers. In at least one of the tubesheets, the boreholes are formed radially. The hollow fiber device can be utilized in heat exchange, in gas/gas, liquid/liquid and gas/liquid heat transfer, in combined heat and mass transfer and in fluid separation assemblies and processes. The design disclosed herein is light weight and compact and is particularly advantageous when the pressure of a first fluid introduced into the bores of hollow fibers is higher than the pressure on the shell side of the device.

  15. Advanced Multidimensional Separations in Mass Spectrometry: Navigating the Big Data Deluge

    Science.gov (United States)

    May, Jody C.; McLean, John A.

    2016-06-01

    Hybrid analytical instrumentation constructed around mass spectrometry (MS) is becoming the preferred technique for addressing many grand challenges in science and medicine. From the omics sciences to drug discovery and synthetic biology, multidimensional separations based on MS provide the high peak capacity and high measurement throughput necessary to obtain large-scale measurements used to infer systems-level information. In this article, we describe multidimensional MS configurations as technologies that are big data drivers and review some new and emerging strategies for mining information from large-scale datasets. We discuss the information content that can be obtained from individual dimensions, as well as the unique information that can be derived by comparing different levels of data. Finally, we summarize some emerging data visualization strategies that seek to make highly dimensional datasets both accessible and comprehensible.

  16. Identifying Gel-Separated Proteins Using In-Gel Digestion, Mass Spectrometry, and Database Searching: Consider the Chemistry

    Science.gov (United States)

    Albright, Jessica C.; Dassenko, David J.; Mohamed, Essa A.; Beussman, Douglas J.

    2009-01-01

    Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry is an important bioanalytical technique in drug discovery, proteomics, and research at the biology-chemistry interface. This is an especially powerful tool when combined with gel separation of proteins and database mining using the mass spectral data. Currently, few hands-on…

  17. Identifying Gel-Separated Proteins Using In-Gel Digestion, Mass Spectrometry, and Database Searching: Consider the Chemistry

    Science.gov (United States)

    Albright, Jessica C.; Dassenko, David J.; Mohamed, Essa A.; Beussman, Douglas J.

    2009-01-01

    Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry is an important bioanalytical technique in drug discovery, proteomics, and research at the biology-chemistry interface. This is an especially powerful tool when combined with gel separation of proteins and database mining using the mass spectral data. Currently, few hands-on…

  18. Experimental heat and mass transfer of the separated and coupled rotating desiccant wheel and heat wheel

    Energy Technology Data Exchange (ETDEWEB)

    Enteria, Napoleon; Yoshino, Hiroshi; Mochida, Akashi; Takaki, Rie [Graduate School of Engineering, Tohoku University, Sendai 980-8579 (Japan); Satake, Akira [Technical Research Institute, Maeda Corporation, Tokyo 179-8914 (Japan); Yoshie, Ryuichiro [Faculty of Engineering, Tokyo Polytechnic University, Atsugi 243-0297 (Japan); Mitamura, Tiruaki [Faculty of Engineering, Ashikaga Institute of Technology, Ashikaga 326-8558 (Japan); Baba, Seizo [Earth Clean Tohoku Co., Ltd., Sendai 984-0038 (Japan)

    2010-07-15

    The experimental evaluation of the separated and coupled rotating desiccant wheel and heat wheel is reported. The study aims to investigate the performance of the desiccant wheel and of the heat wheel both when operated separately and jointly. The performance evaluation of the desiccant wheel is based on its moisture removal capacity (MRC), moisture removal regeneration (MRR), and moisture mass balance (MMB). In addition, the study used the total energy balance (TEB), sensible coefficient of performance (COP{sub Sensible}), latent coefficient of performance (COP{sub Latent}) and, total coefficient of performance (COP{sub Total}). The performance of the heat wheel is based on its effectiveness. The COP{sub Sensible}, COP{sub Latent} and, COP{sub Total} are used in the performance evaluation of the coupled desiccant wheel and heat wheel. The general results of the study show that the MRC, MRR and MMB coupled with the TEB, COP{sub Latent}, COP{sub Sensible} and COP{sub Total} predict adequately the performance of the desiccant wheel. In addition, the coupled operation of the desiccant wheel and heat wheel, contributed to the reduction of the external thermal energy requirement for the regeneration of the desiccant wheel. This study can be applied in other researches seeking evaluation of the desiccant wheel, heat wheel, and their combined operation. Moreover, the data presented here are significant for the desiccant wheel benchmarking and for evaluation of the desiccant wheel models. (author)

  19. Separation and Analysis of Boron Isotope in High Plant by Thermal Ionization Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Qingcai Xu

    2015-01-01

    Full Text Available Knowledge of boron and its isotope in plants is useful to better understand the transposition and translocation of boron within plant, the geochemical behavior in the interface between soil and plant, and the biogeochemical cycle of boron. It is critical to develop a useful method to separate boron from the plant for the geochemical application of boron and its isotope. A method was developed for the extraction of boron in plant sample, whose isotope was determined by thermal ionization mass spectrometry. The results indicated that this method of dry ashing coupled with two-step ion-exchange chromatography is powerful for the separation of boron in plant sample with large amounts of organic matters completely. The ratios of boron isotope composition in those plant tissue samples ranged from -19.45‰ to +28.13‰ (total range: 47.58‰ with a mean value of 2.61±11.76‰ SD. The stem and root isotopic compositions were lower than those in flower and leaf. The molecular mechanism of boron isotope may be responsible for the observed variation of boron isotopic composition and are considered as a useful tool for the better understanding of boron cycling process in the environment and for the signature of living systems.

  20. Determination of trace metal ions via on-line separation and preconcentration by means of chelating Sepharose beads in a sequential injection lab-on-valve (SI-LOV) system coupled to electrothermal atomic absorption spectrometric detection

    DEFF Research Database (Denmark)

    Long, Xiangbao; Hansen, Elo Harald; Miró, Manuel

    2005-01-01

    . The samples are adjusted to pH 5.0 on-line in the system for optimum operation. The target ions are adsorbed by chelation on the surface of the beads, contained in a 20 mul microcolumn within the LOV, and following elution by 50 mul 2M nitric acid, the eluate is, as sandwiched by air segments, introduced...

  1. Determination of trace metal ions via on-line separation and preconcentration by means of chelating Sepharose beads in a sequential injection lab-on-valve (SI-LOV) system coupled to electrothermal atomic absorption spectrometric detection

    DEFF Research Database (Denmark)

    Long, Xiangbao; Hansen, Elo Harald; Miró, Manuel

    2005-01-01

    The analytical performance of an on-line sequential injection lab-on-valve (SI-LOV) system using chelating Sepharose beads as sorbent material for the determination of ultra trace levels of Cd(II), Pb(II) and Ni(II) by electrothermal atomic absorption spectrometry (ETAAS) is described and discussed...

  2. Separation Of Uranium And Plutonium Isotopes For Measurement By Multi Collector Inductively Coupled Plasma Mass Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Martinelli, R E; Hamilton, T F; Williams, R W; Kehl, S R

    2009-03-29

    Uranium (U) and plutonium (Pu) isotopes in coral soils, contaminated by nuclear weapons testing in the northern Marshall Islands, were isolated by ion-exchange chromatography and analyzed by mass spectrometry. The soil samples were spiked with {sup 233}U and {sup 242}Pu tracers, dissolved in minerals acids, and U and Pu isotopes isolated and purified on commercially available ion-exchange columns. The ion-exchange technique employed a TEVA{reg_sign} column coupled to a UTEVA{reg_sign} column. U and Pu isotope fractions were then further isolated using separate elution schemes, and the purified fractions containing U and Pu isotopes analyzed sequentially using multi-collector inductively coupled plasma mass spectrometer (MCICP-MS). High precision measurements of {sup 234}U/{sup 235}U, {sup 238}U/{sup 235}U, {sup 236}U/{sup 235}U, and {sup 240}Pu/{sup 239}Pu in soil samples were attained using the described methodology and instrumentation, and provide a basis for conducting more detailed assessments of the behavior and transfer of uranium and plutonium in the environment.

  3. Mass spectrometric analysis of electrophoretically separated allergens and proteases in grass pollen diffusates

    Directory of Open Access Journals (Sweden)

    Geczy Carolyn L

    2003-09-01

    Full Text Available Abstract Background Pollens are important triggers for allergic asthma and seasonal rhinitis, and proteases released by major allergenic pollens can injure airway epithelial cells in vitro. Disruption of mucosal epithelial integrity by proteases released by inhaled pollens could promote allergic sensitisation. Methods Pollen diffusates from Kentucky blue grass (Poa pratensis, rye grass (Lolium perenne and Bermuda grass (Cynodon dactylon were assessed for peptidase activity using a fluorogenic substrate, as well as by gelatin zymography. Following one- or two-dimensional gel electrophoresis, Coomassie-stained individual bands/spots were excised, subjected to tryptic digestion and analysed by mass spectrometry, either MALDI reflectron TOF or microcapillary liquid chromatography MS-MS. Database searches were used to identify allergens and other plant proteins in pollen diffusates. Results All pollen diffusates tested exhibited peptidase activity. Gelatin zymography revealed high Mr proteolytic activity at ~ 95,000 in all diffusates and additional proteolytic bands in rye and Bermuda grass diffusates, which appeared to be serine proteases on the basis of inhibition studies. A proteolytic band at Mr ~ 35,000 in Bermuda grass diffusate, which corresponded to an intense band detected by Western blotting using a monoclonal antibody to the timothy grass (Phleum pratense group 1 allergen Phl p 1, was identified by mass spectrometric analysis as the group 1 allergen Cyn d 1. Two-dimensional analysis similarly demonstrated proteolytic activity corresponding to protein spots identified as Cyn d 1. Conclusion One- and two-dimensional electrophoretic separation, combined with analysis by mass spectrometry, is useful for rapid determination of the identities of pollen proteins. A component of the proteolytic activity in Bermuda grass diffusate is likely to be related to the allergen Cyn d 1.

  4. Enhanced Mixture Separations of Metal Adducted Tetrasaccharides Using Frequency Encoded Ion Mobility Separations and Tandem Mass Spectrometry

    Science.gov (United States)

    Morrison, Kelsey A.; Bendiak, Brad K.; Clowers, Brian H.

    2016-10-01

    Using five isomeric tetrasaccharides in combination with seven multivalent metals, the impact on mobility separations and resulting CID spectra were examined using a hybrid ion mobility atmospheric pressure drift tube system coupled with a linear ion trap. By enhancing the duty cycle of the drift tube system using a linearly chirped frequency, the collision-induced dissociation spectra were encoded in the mobility domain according to the drift times of each glycan isomer precursor. Differential fragmentation patterns correlated with precursor drift times ensured direct assignment of fragments with precursor structure whether as individual standards or in a mixture of isomers. In addition to certain metal ions providing higher degrees of separation than others, in select cases more than one arrival time distribution was observed for a single pure carbohydrate isomer. These observations suggest the existence of alternative coordination sites within a single monomeric species, but more interesting was the observation of different fragmentation ion yields for carbohydrate dimers formed through metal adduction. Positive-ion data were also compared with negative-ion species, where dimer formation did not occur and single peaks were observed for each isomeric tetrasaccharide-alditol. This enhanced analytical power has implications not only for carbohydrate molecules but also for a wide variety of complex mixtures of molecules where dissociation spectra may potentially be derived from combinations of monomeric, homodimeric, and heterodimeric species having identical nominal m/z values.

  5. Enriching and Separating Primary Copper Impurity from Pb-3 Mass Pct Cu Melt by Super-Gravity Technology

    Science.gov (United States)

    Yang, Yuhou; Song, Bo; Song, Gaoyang; Yang, Zhanbing; Xin, Wenbin

    2016-10-01

    In this study, super-gravity technology was introduced in the lead bullion-refining process to investigate the enriching and separating laws of copper impurity from Pb-3 mass pct Cu melt. With the gravity coefficient G = 700 at the cooling rate of ν = 5 K min-1, the entire copper phase gathers at the upper area of the sample, and it is hard to find any copper particles at the bottom area of the sample. The floatation movement of copper phase was greatly intensified by super gravity and the mass pct of copper in tailing lead is up to 8.631 pct, while that in the refined lead is only 0.113 pct. The refining rate of lead bullion reached up to 94.27 pct. Copper-phase impurity can be separated effectively from Pb-3 mass pct Cu melt by filtration method in super-gravity field, and the separation efficiency increased with the increasing gravity coefficient in the range of G ≥ 10. After filtration at 613 K (340 °C) with gravity coefficient G = 100 for 10 minutes, the refined lead, with just 0.157 mass pct copper impurity, was separated to the bottom of the crucible, and the copper dross containing only 23.56 mass pct residual lead was intercepted by the carbon fiber felt, leading to the separation efficiency up to 96.18 pct (meaning a great reduction in metal loss).

  6. Nuclear magnetic resonance and liquid chromatography-mass spectrometry combined with an incompleted separation strategy for identifying the natural products in crude extract

    Energy Technology Data Exchange (ETDEWEB)

    Dai Dongmei; He Jiuming [Key Laboratory of Bioactive Substances and Resource Utilization of Chinese Herbal Medicine, Ministry of Education, Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College, 1 Xian Nong Tan Street, Beijing 100050 (China); Sun Ruixiang [Institute of Computing Technology, Chinese Academy of Sciences, Beijing 100080 (China); Zhang Ruiping [Key Laboratory of Bioactive Substances and Resource Utilization of Chinese Herbal Medicine, Ministry of Education, Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College, 1 Xian Nong Tan Street, Beijing 100050 (China); Aisa, Haji Akber [Xinjiang Technological Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi 830011 (China); Abliz, Zeper [Key Laboratory of Bioactive Substances and Resource Utilization of Chinese Herbal Medicine, Ministry of Education, Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College, 1 Xian Nong Tan Street, Beijing 100050 (China)], E-mail: zeper@imm.ac.cn

    2009-01-26

    NMR and LC-MS combined with an incompleted separation strategy were proposed to the simultaneous structure identification of natural products in crude extracts, and a novel method termed as NMR/LC-MS parallel dynamic spectroscopy (NMR/LC-MS PDS) was developed to discover the intrinsic correlation between retention time (Rt), mass/charge (m/z) and chemical shift ({delta}) data of the same constituent from mixture spectra by the co-analysis of parallelly visualized multispectroscopic datasets from LC-MS and {sup 1}H NMR. The extracted ion chromatogram (XIC) and {sup 1}H NMR signals deriving from the same individual constituent were correlated through fraction ranges and intensity changing profiles in NMR/LC-MS PDS spectrum due to the signal amplitude co-variation resulted from the concentration variation of constituents in a series of incompletely separated fractions. NMR/LC-MS PDS was applied to identify 12 constituents in an active herbal extract including flavonol glycosides, which was separated into a series of fractions by flash column chromatography. The complementary spectral information of the same individual constituent in the crude extract was discovered simultaneously from mixture spectra. Especially, two groups of co-eluted isomers were identified successfully. The results demonstrated that NMR/LC-MS PDS combined with the incompleted separation strategy achieved the similar function of on-line LC-NMR-MS analysis in off-line mode and had the potential for simplifying and accelerating the analytical routes for structure identification of constituents in herbs or their active extracts.

  7. An atmospheric pressure chemical ionization-ion-trap mass spectrometer for the on-line analysis of volatile compounds in foods: a tool for linking aroma release to aroma perception.

    Science.gov (United States)

    Le Quéré, Jean-Luc; Gierczynski, Isabelle; Sémon, Etienne

    2014-09-01

    An atmospheric pressure chemical ionization ion-trap mass spectrometer was set up for the on-line analysis of aroma compounds. This instrument, which has been successfully employed for some years in several in vitro and in vivo flavour release studies, is described for the first time in detail. The ion source was fashioned from polyether ether ketone and operated at ambient pressure and temperature making use of a discharge corona pin facing coaxially the capillary ion entrance of the ion-trap mass spectrometer. Linear dynamic ranges (LDR), limits of detection (LOD) and other analytical characteristics have been re-evaluated. LDRs and LODs have been found fully compatible with the concentrations of aroma compounds commonly found in foods. Thus, detection limits have been found in the low ppt range for common flavouring aroma compounds (for example 5.3 ppt (0.82 ppbV) for ethyl hexanoate and 4.8 ppt (1.0 ppbV) for 2,5-dimethylpyrazine). This makes the instrument applicable for in vitro and in vivo aroma release investigations. The use of dynamic sensory techniques such as the temporal dominance of sensations (TDS) method conducted simultaneously with in vivo aroma release measurements allowed to get some new insights in the link between flavour release and flavour perception.

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

    Energy Technology Data Exchange (ETDEWEB)

    Montesdeoca-Esponda, Sarah; Sosa-Ferrera, Zoraida; Santana-Rodriguez, Jose Juan [Universidad de Las Palmas de Gran Canaria, Departamento de Quimica, Las Palmas de Gran Canaria (Spain)

    2012-05-15

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

  9. Isomer separation and gas-phase configurations of organoruthenium anticancer complexes: ion mobility mass spectrometry and modeling.

    Science.gov (United States)

    Williams, Jonathan P; Bugarcic, Tijana; Habtemariam, Abraha; Giles, Kevin; Campuzano, Iain; Rodger, P Mark; Sadler, Peter J

    2009-06-01

    We have used ion mobility-mass spectrometry combined with molecular modeling for the separation and configurational analysis of three low-molecular-weight isomeric organoruthenium anticancer complexes containing ortho-, meta-, or para-terphenyl arene ligands. The isomers were separated using ion mobility based on traveling-wave technology and the experimentally determined collision cross sections were compared to theoretical calculations. Excellent agreement was observed between the experimentally and theoretically derived measurements.

  10. Mosquito mass rearing technology: a cold-water vortex device for continuous unattended separation of Anopheles arabiensis pupae from larvae.

    Science.gov (United States)

    Balestrino, Fabrizio; Gilles, Jérémie R L; Soliban, Sharon M; Nirschl, Anton; Benedict, Quentin E; Benedict, Mark Q

    2011-09-01

    In mass rearing of anopheline mosquitoes, pupae are usually separated from larvae on a daily basis to prevent unwanted adult emergence from trays. Depending on the device and species, 2 physical characteristics have most often been used for separation: buoyant density and size. In this report, we describe a system for continuous separation of Anopheles arabiensis larvae from pupae based on the natural difference in buoyant density and behavior between the 2 stages. We determined that temperatures 4-15 degrees C caused neither mortality nor reduction in likelihood of pupation or emergence. Separation improved as temperatures decreased down to 4 degrees C. We devised and demonstrated a 15 degrees C water vortex separator that we anticipate can process approximately 1 million larvae and pupae per hour with a < 0.3% pupal contamination rate and which operates unattended.

  11. Single photon ionization (SPI) via incoherent VUV-excimer light: robust and compact time-of-flight mass spectrometer for on-line, real-time process gas analysis.

    Science.gov (United States)

    Mühlberger, F; Wieser, J; Ulrich, A; Zimmermann, R

    2002-08-01

    Fast on-line detection of organic compounds from complex mixtures, such as industrial process gas streams, require selective and sensitive analytical methods. One feasible approach for this purpose is the use of mass spectrometry (MS) with a selective and soft (fragment-free) ionization technique, such as chemical ionization (CI) or photo ionization (PI). Single photon ionization (SPI) with vacuum ultraviolet (VUV) light is a particularly sof tionization technique, well-suited for detection of both aromatic and aliphatic species. Problematic, however, is the generation of the VUV light. In general, the vacuum ultraviolet (VUV) light sources for SPI-MS are based either on lasers (e.g., 118-nm radiation generated by frequency-tripling of the third harmonic of a Nd:YAG laser) or on conventional VUV lamps, such as deuterium lamps. Althoughthe laser-based techniques are very sophisticated and expensive, the conventional lamps have serious drawbacks regarding their optical parameters, such as low-output power, low spectral power density, and broad emission bands. In this work, a novel excimer VUV light source, in which an electron beam is used to form rare gas excimer species, is used. The excimer VUV light sourceproduces brilliant and intense VUV light. The novel VUV light source was coupled to a compact and mobile time-of-flight mass spectrometer (TOFMS). A special interface design, including optical (VUV optics) as well as electronic measures (e.g., pulsed ion extraction) was realized. The use of the excimer VUV lamp for SPI will allow the realization of very compact, rugged, and sensitive SPI-TOFMS devices, which preferably will be adapted for process analytical application or monitoring issues (e.g., chemical warfare detection). The excimer VUV-lamp technology delivers VUV light with a good beam quality and high-output power at low costs. Furthermore, it allows changing the emitted wavelength as well as the bandwidth of the excimer VUV lamp in t he 100-200-nm region

  12. Characterization of polysorbate 85, a nonionic surfactant, by liquid chromatography vs. ion mobility separation coupled with tandem mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Solak Erdem, Nilüfer; Alawani, Nadrah; Wesdemiotis, Chrys, E-mail: wesdemiotis@uakron.edu

    2014-01-15

    Graphical abstract: -- Highlights: •Liquid chromatography (LC) separates amphiphilic blends according to hydrophobicity. •Ion mobility (IM) spectrometry separates these blends based on molecular size/shape. •LC–MS provides the separation resolution needed for quantifying fatty acid content. •IM–MS enables rapid, solvent-free separation and the detection of trace components. •With either method, tandem MS allows to count the hydrophobic substituents. -- Abstract: Liquid chromatography (LC) and ion mobility (IM) separation have been coupled with mass spectrometry (MS) and tandem mass spectrometry (MS{sup 2}) to characterize a commercially important nonionic surfactant, polysorbate 85. The constituents of this amphiphilic blend contained a sorbitan or isosorbide core that was chain extended with poly(ethylene oxide) (PEO) and partially esterified at the PEO termini with oleic acid or, to a lesser extent, other fatty acids. Using interactive LC in reverse-phase mode, the oligomers of the surfactant were separated according to their hydrophobicity/hydrophilicity balance. On the other hand, IM spectrometry dispersed the surfactant oligomers by their charge and collision cross section (i.e. size/shape). With either separation method, an increased number of fatty ester groups and/or lack of the polar sorbitan (or isosorbide) core led to higher retention/drift times, enabling the separation of isobaric species or species with superimposed isotope patterns, so that their ester content could be conclusively identified by MS{sup 2}. LC–MS and IM–MS permitted the detection of several byproducts besides the major PEO-sorbitan oleate oligomers. LC–MS provides the separation resolution needed for quantitative determination of the degree of esterification. IM–MS, which minimizes analysis time and solvent use, is ideally suitable for a fast, qualitative survey of samples differing in their minor constituents or impurities.

  13. New Trends in on-line Marketing

    OpenAIRE

    Palkovič, Lukáš

    2011-01-01

    This bachelor thesis deals with new trend of internet marketing, it focuses especially on viral marketing. The theoretical part charasterizes the process of viral campaigns, furthermore deals with the components and aspects of on-line environment. Another separated chapter presents social networks, their place in viral marketing and at last but not least the viral video making process. The practical part contains different analyses of specific viral campaigns. The next and equally the last pa...

  14. Simple and quick determination of analgesics and other contaminants of emerging concern in environmental waters by on-line solid phase extraction coupled to liquid chromatography-tandem mass spectrometry.

    Science.gov (United States)

    Ferrer-Aguirre, Alejandra; Romero-González, Roberto; Vidal, J L Martínez; Frenich, Antonia Garrido

    2016-05-13

    A simple and quick analytical method has been developed for the determination of pharmaceutical compounds in water. An on-line solid-phase extraction (SPE) coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS) method has been optimized to determine 7 contaminants of emerging concern in environmental waters at ngL(-1) levels. This procedure requires minimal sample handling and small sample volume (900μL) with a total running time of 18min. Several SPE parameters were evaluated and optimized in order to achieve a high sample throughput. Therefore sample volume, carryover and reusability of the cartridges were evaluated. Performance characteristics were evaluated and good linearity was obtained (R(2)>0.98). Recoveries were evaluated in spiked samples at three concentrations and the values ranged from 71 to 104%. Intra and inter-day precision was lower than 10 and 13% respectively. Limits of quantification were equal to or lower than 10ngL(-1), except for 1,7-dimethylxanthine (20ngL(-1)) and ibuprofen (50ngL(-1)). The method was applied to 20 environmental water samples, and ibuprofen was the compound most widely detected at concentrations up to 42.06μgL(-1), whereas the other compounds were detected in fewer samples at lower concentrations (up to 15.99μgL(-1)).

  15. Automated on-line column-switching high performance liquid chromatography isotope dilution tandem mass spectrometry method for the quantification of bisphenol A, bisphenol F, bisphenol S, and 11 other phenols in urine.

    Science.gov (United States)

    Zhou, Xiaoliu; Kramer, Joshua P; Calafat, Antonia M; Ye, Xiaoyun

    2014-01-01

    Human exposure to bisphenol A (BPA) is widespread. However, in recent years, bisphenol analogs such as bisphenol S (BPS) and bisphenol F (BPF) are replacing BPA in the production of some consumer products. Because human exposure to these alternative bisphenols may occur, biomonitoring of these bisphenol analogs is warranted. In the present study, we developed and validated a sensitive and selective method that uses on-line solid phase extraction coupled to high performance liquid chromatography-isotope dilution tandem mass spectrometry with peak focusing to measure BPA, BPF, BPS, and 11 other environmental phenols in urine. The method required a small amount of sample (100μL) and minimal sample pretreatment. The limits of detection were 0.03ng/mL (BPS), 0.06ng/mL (BPF), 0.10ng/mL (BPA), and ranged from 0.1ng/mL to 1.0ng/mL for the other 11 phenols. In 100 urine samples collected in 2009-2012 from a convenience group of anonymous adults in the United States, of the three bisphenols, we detected BPA at the highest frequency and median concentrations (95%, 0.72ng/mL), followed by BPS (78%, 0.13ng/mL) and BPF (55%, 0.08ng/mL). This sensitive, rugged, and labor and cost-effective method could be used for the analysis of large number of samples for epidemiologic studies.

  16. 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.

    Science.gov (United States)

    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.

  17. Photo-ionisation mass spectrometry as detection method for gas chromatography. Optical selectivity and multidimensional comprehensive separations.

    Science.gov (United States)

    Zimmermann, Ralf; Welthagen, Werner; Gröger, Thomas

    2008-03-14

    Mass spectrometry (MS) with soft ionisation techniques (i.e. ionisation without fragmentation of the analyte molecules) for gaseous samples exhibits interesting analytical properties for direct analysis applications (i.e. direct inlet mass spectrometric on-line monitoring) as well as mass spectrometric detection method for gas chromatography (GC-MS). Commonly either chemical ionisation (CI) or field ionisation (FI) is applied as soft ionisation technology for GC-MS. An interesting alternative to the CI and FI technologies methods are photo-ionisation (PI) methods. PI overcomes some of the limitations of CI and FI and furthermore add some unique analytical properties. The resonance enhanced multi-photon ionisation (REMPI) method uses intense UV-laser pulses (wavelength range approximately 350-193 nm) for highly selective, sensitive and soft ionisation of predominately aromatic compounds. The single photon ionisation (SPI) method utilises VUV light (from lamps or laser sources, wavelengths range approximately 150-110 nm) can be used for a universal soft ionisation of organic molecules. In this article the historical development as well as the current status and concepts of gas chromatography hyphenated to photo-ionisation mass spectrometry are reviewed.

  18. Coupling Front-End Separations, Ion Mobility Spectrometry, and Mass Spectrometry For Enhanced Multidimensional Biological and Environmental Analyses

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Xueyun [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,; Wojcik, Roza [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,; Zhang, Xing [Skaggs School of Pharmacy and Pharmaceutical Sciences, Anschutz Medical Campus, University of Colorado, Denver, Colorado 80045; Ibrahim, Yehia M. [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,; Burnum-Johnson, Kristin E. [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,; Orton, Daniel J. [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,; Monroe, Matthew E. [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,; Moore, Ronald J. [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,; Smith, Richard D. [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,; Baker, Erin S. [Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352,

    2017-06-12

    Ion mobility spectrometry (IMS) is a widely used analytical technique for rapid molecular separations in the gas phase. IMS alone is useful, but its coupling with mass spectrometry (MS) and front-end separations has been extremely beneficial for increasing measurement sensitivity, peak capacity of complex mixtures, and the scope of molecular information in biological and environmental sample analyses. Multiple studies in disease screening and environmental evaluations have even shown these IMS-based multidimensional separations extract information not possible with each technique individually. This review highlights 3-dimensional separations using IMS-MS in conjunction with a range of front-end techniques, such as gas chromatography (GC), supercritical fluid chromatography (SFC), liquid chromatography (LC), solid phase extractions (SPE), capillary electrophoresis (CE), field asymmetric ion mobility spectrometry (FAIMS), and microfluidic devices. The origination, current state, various applications, and future capabilities for these multidimensional approaches are described to provide insight into the utility and potential of each technique.

  19. Two-dimensional separation of ionic species by hyphenation of capillary ion chromatography × capillary electrophoresis-mass spectrometry.

    Science.gov (United States)

    Beutner, Andrea; Kochmann, Sven; Mark, Jonas Josef Peter; Matysik, Frank-Michael

    2015-03-17

    The separation of complex mixtures such as biological or environmental samples requires high peak capacities, which cannot be established with a single separation technique. Therefore, multidimensional systems are in demand. In this work, we present the hyphenation of the two most important (orthogonal) techniques in ion analysis, namely, ion chromatography (IC) and capillary electrophoresis (CE), in combination with mass spectrometry. A modulator was developed ensuring a well-controlled coupling of IC and CE separations. Proof-of-concept measurements were performed using a model system consisting of nucleotides and cyclic nucleotides. The data are presented in a multidimensional contour plot. Analyte stacking in the CE separation could be exploited on the basis of the fact that the suppressed IC effluent is pure water.

  20. Formación on line On line learning

    Directory of Open Access Journals (Sweden)

    O. Grau-Perejoan

    2008-09-01

    Full Text Available La formación on line es una modalidad de enseñanza a distancia basada en las nuevas tecnologías. En este artículo se pretende hacer una introducción a base de describir a grandes rasgos sus características principales: asincronía, no presencialidad, comunicación escrita, función del profesor on line, así como los retos, los riesgos, las ventajas y los inconvenientes que plantea. Se exponen las diferencias entre la formación on line y la formación presencial, de manera que los docentes puedan adaptar de la mejor manera posible sus propuestas formativas a la modalidad on line. Se introduce el importantísimo papel de la planificación y de la fase de diseño y, finalmente, se repasan conceptos útiles para comprender mejor el mundo de la formación on line como son los conceptos entorno virtual de aprendizaje (EVA o Blended Learning (B-Learning.On line learning is a type of distance education based on new technologies. This article's aim is to introduce its main characteristics -asynchrony, non-presentiality, written communication, e-teacher role- as well as its challenges, risks, advantages and limitations. Differences between on line learning and face-to-face learning are presented in order to enable educational professionals to adapt their courses to the on line methodology. Planning and designing are introduced as key phases and, finally, useful concepts such as Virtual Learning Environment (VLE or Blended Learning (B-Learning are reviewed in order to achieve a better understanding of the on line learning field.

  1. Implementation of suitable flow injection/sequential injection on-line sample pretreatment schemes. Separation and preconcentration procedures for the determination of trace metal concentrations by ETAAS and/or ICPMS

    DEFF Research Database (Denmark)

    Hansen, Elo Harald; Wang, Jianhua

    Despite their excellent analytical chemical capacities, ETAAS and ICPMS, nevertheless, often require suitable pretreatment of the sample material in order to obtain the necessary sensitivity and selectivity. Either in order to separate/preconcentrate the analyte material, or because of the presen...

  2. Flow injection and sequential injection: The optimal solutions for executing appropriate on-line separation and preconcentration schemes for detection of trace-level concentrations of metals in complex matrices by ICPMS

    DEFF Research Database (Denmark)

    Hansen, Elo Harald

    as these adversely will impair its performance. In the lecture, selected examples of separation/preconcentration FI/SI-procedures for the determination of trace levels of metals will be presented, particular emphasis being placed on the use of the novel “lab-on-valve” (LOV) concept....

  3. Time-separated oscillatory fields for high-precision mass measurements on short-lived Al and Ca nuclides

    CERN Document Server

    George, S; Blank, B; Blaum, K; Breitenfeldt, M; Hager, U; Herfurth, F; Herlert, A; Kellerbauer, A G; Kluge, H J; Kretzschmar, M; Lunney, D; Savreux, R; Schwarz, S; Schweikhard, L; Yazidjian, C

    2008-01-01

    High-precision Penning trap mass measurements on the stable nuclide $^{27}$Al as well as on the short-lived radionuclides $^{26}$Al and $^{38,39}$Ca have been performed by use of radio-frequency excitation with time-separated oscillatory fields, i.e. Ramsey's method, as recently introduced for the excitation of the ion motion in a Penning trap, was applied. A comparison with the conventional method of a single continuous excitation demonstrates its advantage of up to ten times shorter measurements. The new mass values of $^{26,27}$Al clarify conflicting data in this specific mass region. In addition, the resulting mass values of the superallowed $\\beta$-emitter $^{38}$Ca as well as of the groundstate of the $\\beta$-emitter $^{26}$Al$^{m}$ confirm previous measurements and corresponding theoretical corrections of the ft-values.

  4. Identification of two-dimensional electrophoresis-separated proteins in human hepatoma cell by electrospray ion trap mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    As one of the most important analytical methods in proteome research, mass spectrometry was utilized to identify proteins separated by two-dimensional electrophoresis in the human hepatoma cell line BEL-7404. The protein spots were excised from the gel, followed by in-gel digestion, and the peptide mappings were analyzed by liquid chromatography electrospray ion trap mass spectrometer. Nine proteins were identified via database searching, according to the molecular weights and amino acid sequences of peptides, among which two proteins have not been identified in the other liver-cell database. The sequence coverage was 21%-72%. Furthermore, the relationship between the expressed proteins and the liver carcinoma was discussed.

  5. Mass Balance Reconciliation for Bilinear Systems: A Case Study of a Raw Mill Separator in a Typical Moroccan Cement Plant

    Directory of Open Access Journals (Sweden)

    S. Fellaou

    2016-06-01

    Full Text Available Stream flow rates and their several compositions are measured in a typical cement raw mill separator. In order to simultaneously reconcile flow and composition measurements in this circuit, the component mass balances was included as constraints which contain the products of flow rate and composition variables in the data reconciliation problem. In this paper, the effectiveness of simultaneous procedures for bilinear data reconciliation is established, the numerical problem constraints were coded in MATLAB and a mass balance model is built. Moreover, based on the difference between the measured and reconciled data it was found that it performs optimally.

  6. β-紫罗兰酮热裂解行为的初步探讨%Investigation of Pyrolysis Behavior ofβ-Ionone by on-line Pyrolysis-gas Chromatography/mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    赵瑞峰; 程侠; 叶荣飞; 林翔; 饶国华

    2014-01-01

    采用在线热裂解-气相色谱/质谱(Py-GC/MS )联用技术研究了在氦气氛围中β-紫罗兰酮在300、400、500、600、700、800℃下的热裂解行为,结果表明:①β-紫罗兰酮可以裂解生成48种物质;②在600℃以下只有10.765%的β-紫罗兰酮发生裂解;在700、800℃裂解加剧,有18.149%和21.286%的β-紫罗兰酮发生裂解;③同时随着裂解温度的升高,形成的危害性芳香烃类化合物的相对含量也逐渐增大。此外,根据主要裂解产物对β-紫罗兰酮的裂解机理进行了初步探讨。%β-Ionone was pyrolyzed under helium atmospheres at 300,400,500,600,700 and 800 ℃respectively,and the pyrolysates were analyzed by on-line gas chromatography /mass spectrometry (GC/MS).The results showed that (1 )Forty-eight substances were detected from the pyrolysates at 800 ℃;(2)At 600 ℃ only 10.765% ofβ-ionone was pyrolyzed.The pyrolysis reaction became more intensive at 700 and 800 ℃,18.149%and 21.286%ofβ-ionone was pyrolyzed;(3)the percentage of aromatic compounds increased with the increase of pyrolysis temperature.The possible pyrolysis mechanism ofβ-i-onone was preliminarily investigated based on the major pyrolysates.

  7. Separation and identification of Musa acuminate Colla (banana) leaf proteins by two-dimensional gel electrophoresis and mass spectrometry.

    Science.gov (United States)

    Lu, Y; Qi, Y X; Zhang, H; Zhang, H Q; Pu, J J; Xie, Y X

    2013-12-19

    To establish a proteomic reference map of Musa acuminate Colla (banana) leaf, we separated and identified leaf proteins using two-dimensional polyacrylamide gel electrophoresis (2D-PAGE) and mass spectrometry (MS). Tryptic digests of 44 spots were subjected to peptide mass fingerprinting (PMF) by matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) MS. Three spots that were not identified by MALDI-TOF MS analysis were identified by searching against the NCBInr, SwissProt, and expressed sequence tag (EST) databases. We identified 41 unique proteins. The majority of the identified leaf proteins were found to be involved in energy metabolism. The results indicate that 2D-PAGE is a sensitive and powerful technique for the separation and identification of Musa leaf proteins. A summary of the identified proteins and their putative functions is discussed.

  8. Heat and mass transfer in porous media phase separation at temperatures below the lambda-point of He-4

    Science.gov (United States)

    Yuan, S. W. K.; Frederking, T. H. K.

    1986-01-01

    Newtonian fluid motion, coupled to heat transfer via latent heat of phase transition, is well known from numerous studies of condensation and boiling. Considerably less knowledge is available for vapor-liquid phase separation in the absence of gravity effect on the transport phenomena. The present studies are focused on heat and mass transfer associated with vapor-liquid phase separation required for long-term storage of the cryogen liquid He II in space vessels. Though space conditions are the dominant mode of interest in advanced equipment, e.g. IR telescopes, the systems may be operated in principle during terrestrial conditions. The latter are considered in the present work. It emphasizes the linear regime including an extrapolation based on variable thermophysical properties. Data taken with a phase separation approach show departures from the linear regime prediction. They agree with a transport equation proposed for the nonlinear, turbulent regime.

  9. Ion Mobility Separations of Isomers based upon Long Path Length Structures for Lossless Ion Manipulations Combined with Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Liulin [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Ibrahim, Yehia M. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Baker, Erin S. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Aly, Noor A. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Hamid, Ahmed M. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Zhang, Xing [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Zheng, Xueyun [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Garimella, Sandilya V. B. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Webb, Ian K. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Prost, Spencer A. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Sandoval, Jeremy A. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Norheim, Randolph V. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Anderson, Gordon A. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Tolmachev, Aleksey V. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA; Smith, Richard D. [Biological Sciences Division and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Blvd Richland, WA 99352 USA

    2016-07-01

    Mass spectrometry (MS)-based multi-omic measurements, including proteomics, metabolomics, lipidomics, and glycomics, are increasingly transforming our ability to characterize and understand biological systems, but, presently have limitations due to the chemical diversity and range of abundances of biomolecules in complex samples. Advances addressing these challenges increasingly are based upon the ability to quickly separate, react and otherwise manipulate sample components for analysis by MS. Here we report on a new approach using Structures for Lossless Ion Manipulations (SLIM) to enable long serpentine path ion mobility spectrometry (IMS) separations followed by MS analyses. This approach provides previously unachieved mobility biomolecule isomer separations for biomolecular species, in conjunction with more effective ion utilization, and producing a basis for the improved characterization of very small samples.

  10. Heat and mass transfer in porous media phase separation at temperatures below the lambda-point of He-4

    Science.gov (United States)

    Yuan, S. W. K.; Frederking, T. H. K.

    1986-01-01

    Newtonian fluid motion, coupled to heat transfer via latent heat of phase transition, is well known from numerous studies of condensation and boiling. Considerably less knowledge is available for vapor-liquid phase separation in the absence of gravity effect on the transport phenomena. The present studies are focused on heat and mass transfer associated with vapor-liquid phase separation required for long-term storage of the cryogen liquid He II in space vessels. Though space conditions are the dominant mode of interest in advanced equipment, e.g. IR telescopes, the systems may be operated in principle during terrestrial conditions. The latter are considered in the present work. It emphasizes the linear regime including an extrapolation based on variable thermophysical properties. Data taken with a phase separation approach show departures from the linear regime prediction. They agree with a transport equation proposed for the nonlinear, turbulent regime.

  11. Rapid, high-purity chemical separation of molybdenum from iron meteorites for isotopic analysis by using thermal ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Qi-Lu; Masuda, Akimasa (Tokyo Univ. (Japan). Dept. of Chemistry)

    1992-05-01

    A chemical procedure has been developed, which combines both solvent extraction and anion exchange, so that microgram amounts of Mo can be cleanly, rapidly and efficiently separated from gram amounts of iron meteorites. Particular attention was directed to the complete separation of Mo from Zr and Ru. The isotopic abundance ratios of Mo can subsequently be determined with high accuracy by using thermal ionization mass spectrometry. The experiments indicate that the behaviour of Mo during solvent extraction and anion exchange is considerably different from that reported previously. In particular, it was found that there is a very narrow range of HCl concentrations within which it is possible to separate Mo from Fe by solvent extraction. The reproducibility and recovery of the method were examined by using inductively coupled plasma atomic emission spectrometry. (Author).

  12. On-line speciation of inorganic and methyl mercury in waters and fish tissues using polyaniline micro-column and flow injection-chemical vapour generation-inductively coupled plasma mass spectrometry (FI-CVG-ICPMS).

    Science.gov (United States)

    Krishna, M V Balarama; Chandrasekaran, K; Karunasagar, D

    2010-04-15

    A simple and efficient method for the determination of ultra-trace amounts of inorganic mercury (iHg) and methylmercury (MeHg) in waters and fish tissues was developed using a micro-column filled with polyaniline (PANI) coupled online to flow injection-chemical vapour generation-inductively coupled plasma mass spectrometry (FI-CVG-ICPMS) system. Preliminary studies indicated that inorganic and methyl mercury species could be separated on PANI column in two different speciation approaches. At pH extraction of the mercury species from biological samples, was used directly to separate MeHg from iHg in the fish tissues (tuna fish ERM-CE 463, ERM-CE 464 and IAEA-350) by PANI column using speciation procedure 1. The determined values were in good agreement with certified values. Under optimal conditions, the limits of detection (LODs) were 2.52 pg and 3.24 pg for iHg and MeHg (as Hg) respectively. The developed method was applied successfully to the direct determination of iHg and MeHg in various waters (tap water, lake water, ground water and sea-water) and the recoveries for the spiked samples were in the range of 96-102% for both the Hg species.

  13. Determination of saturated-hydrocarbon contamination in baby foods by using on-line liquid-gas chromatography and off-line liquid chromatography-comprehensive gas chromatography combined with mass spectrometry.

    Science.gov (United States)

    Mondello, Luigi; Zoccali, Mariosimone; Purcaro, Giorgia; Franchina, Flavio Antonio; Sciarrone, Danilo; Moret, Sabrina; Conte, Lanfranco; Tranchida, Peter Quinto

    2012-10-12

    The present contribution describes an investigation directed towards the use of a rapid heart-cutting multidimensional LC-GC-FID method for the analysis of mineral oil saturated hydrocarbons (MOSH), contained in different types of homogenized solid baby food (fish, meat and fruit products). The fish and meat products all contained vegetable oil (sunflower), potentially an important source of mineral-oil contamination. Sixteen commercial baby food samples were subjected to analysis, with various degrees of MOSH contamination (from 0.3mg/kg to circa 14 mg/kg) found. Hence, MOSH contamination was found not only in the meat and fish products, but also in the fruit ones. A fruit-based baby food was lab-made, using the ingredients reported on the commercial product, and was found to be contaminated. The single ingredients were then subjected to LC-GC analysis, with corn starch and sugar found to be the source of contamination. For confirmation of the analytical findings, three of the sixteen samples were analyzed in two separate laboratories, using two distinct LC-GC methods, based on different interfaces. The results were confirmed, in qualitative terms, by collecting the LC fractions, relative to some of the food samples, and subjecting them to comprehensive two-dimensional GC-quadrupole mass spectrometry. Thus, mass spectral data were attained for the saturated hydrocarbons. Copyright © 2012 Elsevier B.V. All rights reserved.

  14. 在线固相萃取-超高效液相色谱-串联质谱法测定乳制品中双酚A等4种内分泌干扰物%Determination of 4 Environmental Endocrine Disruptors Involving Bisphenol A in Dairy Products by On-line Solid Phase Extraction Coupled with Liquid Chromatography-Tandem Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    张品; 张晶; 陈洁君; 段鹤君; 邵兵

    2014-01-01

    A simple analytical method by means of on-line solid phase extraction followed liquid chromatography-tandem mass spectrometry ( SPE-LC-MS/MS) was developed for the simultaneous quantitation of 4 endocrine disruptors ( triclosan, triclocarban, bisphenol A and nonylphenol) in dairy products. Infant formula and milk samples were dissolved in acetic acid buffer and hydrolyzed by β-glucuronidase/arylsulfatase. Acetonitrile was used as the extract. Then, the mixture was freeze-centrifuged for 10 min and the supernatant was diluted with water, and analyzed via on-line SPE-LC-MS/MS. The sample extracts were concentrated by an Xbridge C8 cartridge and separated on a BEH C18 column with a gradient mobile phase of methanol and water; then analyzed by triple quadrupole mass spectrometry. Mass acquisition was conducted under negative electrospray ionization mode. Quantification was performed by isotopic internal standard calibration. Acceptable linearity (R2>0. 99) was achieved over the range of 0. 005-5. 0 μg/L, with limits of quantification of 0. 03-1. 0μg/kg. Average recoveries of four target compounds (spiked at three concentration levels) ranged from 80. 2%-106. 7%,with relative standard deviation less than 15%. Due to its rapidity, simplicity, and high sensitivity, the method is suitable for the analysis of endocrine disruptors in dairy products. It has been applied in the analysis of raw milk and milk products collected in Beijing. As a result, nonylphenol was found with a high detectable frequency.%建立了乳制品中三氯生、三氯卡班、双酚A和壬基酚4种内分泌干扰物的在线固相萃取超高压液相色谱-串联质谱(On-line SPE LC-MS/MS)检测方法。液态乳制品或奶粉样品中加入乙酸缓冲液,目标物经β-葡糖醛酸苷肽酶/芳基磺酸酯酶酶解后,用乙腈提取,冷冻离心10 min后,取上清液,用水稀释,在线固相萃取串联质谱法测定。样品溶液经Xbridge C8柱富集,BEH C18色谱柱分离,甲醇和

  15. A mass-balance model to separate and quantify colloidal and solute redistributions in soil

    Science.gov (United States)

    Bern, C.R.; Chadwick, O.A.; Hartshorn, A.S.; Khomo, L.M.; Chorover, J.

    2011-01-01

    Studies of weathering and pedogenesis have long used calculations based upon low solubility index elements to determine mass gains and losses in open systems. One of the questions currently unanswered in these settings is the degree to which mass is transferred in solution (solutes) versus suspension (colloids). Here we show that differential mobility of the low solubility, high field strength (HFS) elements Ti and Zr can trace colloidal redistribution, and we present a model for distinguishing between mass transfer in suspension and solution. The model is tested on a well-differentiated granitic catena located in Kruger National Park, South Africa. Ti and Zr ratios from parent material, soil and colloidal material are substituted into a mixing equation to quantify colloidal movement. The results show zones of both colloid removal and augmentation along the catena. Colloidal losses of 110kgm-2 (-5% relative to parent material) are calculated for one eluviated soil profile. A downslope illuviated profile has gained 169kgm-2 (10%) colloidal material. Elemental losses by mobilization in true solution are ubiquitous across the catena, even in zones of colloidal accumulation, and range from 1418kgm-2 (-46%) for an eluviated profile to 195kgm-2 (-23%) at the bottom of the catena. Quantification of simultaneous mass transfers in solution and suspension provide greater specificity on processes within soils and across hillslopes. Additionally, because colloids include both HFS and other elements, the ability to quantify their redistribution has implications for standard calculations of soil mass balances using such index elements. ?? 2011.

  16. Penning-trap Q-value determination of the Ga-71(v, e(-))Ge-71 reaction using threshold charge breeding of on-line produced isotopes

    NARCIS (Netherlands)

    Frekers, D.; Simon, M.C.; Andreoiu, C.; Bale, J. C.; Brodeur, M.; Brunner, T.; Chaudhuri, A.; Chowdhury, U.; Lopez-Urrutia, J. R. Crespo; Delheij, P.; Ejiri, H.; Ettenauer, S.; Gallant, A. T.; Gavrin, V.; Grossheim, A.; Harakeh, M. N.; Jang, F.; Kwiatkowski, A. A.; Lassen, J.; Lennarz, A.; Luichtl, M.; Ma, T.; Macdonald, T. D.; Mane, E.; Robertson, D.; Schultz, B. E.; Simon, V. V.; Teigelhoefer, A.; Dilling, J.

    2013-01-01

    We present a first direct Q-value measurement of the Ga-71(v, e(-))Ge-71 reaction using the TITAN mass-measurement facility at ISAC/TRIUMF. The measurements were performed in a Penning trap on neon-like Ga-71(21+) and Ge-71(22+) using isobar separation of the on-line produced mother and daughter

  17. Penning-trap Q-value determination of the Ga-71(v, e(-))Ge-71 reaction using threshold charge breeding of on-line produced isotopes

    NARCIS (Netherlands)

    Frekers, D.; Simon, M.C.; Andreoiu, C.; Bale, J. C.; Brodeur, M.; Brunner, T.; Chaudhuri, A.; Chowdhury, U.; Lopez-Urrutia, J. R. Crespo; Delheij, P.; Ejiri, H.; Ettenauer, S.; Gallant, A. T.; Gavrin, V.; Grossheim, A.; Harakeh, M. N.; Jang, F.; Kwiatkowski, A. A.; Lassen, J.; Lennarz, A.; Luichtl, M.; Ma, T.; Macdonald, T. D.; Mane, E.; Robertson, D.; Schultz, B. E.; Simon, V. V.; Teigelhoefer, A.; Dilling, J.

    2013-01-01

    We present a first direct Q-value measurement of the Ga-71(v, e(-))Ge-71 reaction using the TITAN mass-measurement facility at ISAC/TRIUMF. The measurements were performed in a Penning trap on neon-like Ga-71(21+) and Ge-71(22+) using isobar separation of the on-line produced mother and daughter nuc

  18. Separation of VX, RVX and GB Enantiomers Using Liquid ChromatographyTime-of-Flight Mass Spectrometry

    Science.gov (United States)

    2016-02-01

    a bandwidth of 4 nm) was referenced to a wavelength of 360 nm. An Agilent series 1200 fraction collector (Agilent Technologies; Santa Clara, CA) was...phosphorus compounds have four  bonds arranged through sp3 hybrid orbitals as occurs in tetrahedral carbon compounds. The first enantiomeric phosphorus...1200 Infinity series fraction collector was configured using the peak- time-based collection protocol, and the separated enantiomers were combined into

  19. Diffusion induced phase separation with crystallizable nylons. I. Mass transfer processes for nylon 4,6

    NARCIS (Netherlands)

    Bulte, A.M.W.; Bulte, A.M.W.; Mulder, M.H.V.; Smolders, C.A.; Smolders, C.A.; Strathmann, H.

    1996-01-01

    Mass transfer during membrane formation by means of phase inversion for a polymeric system with both a solid-liquid and a liquid-liquid equilibrium was studied on the basis of the theory developed by Reuvers and Smolders. During the first moments of immersion in the coagulation bath, the concentrati

  20. First spatial separation of a heavy ion isomeric beam with a multiple-reflection time-of-flight mass spectrometer

    Directory of Open Access Journals (Sweden)

    T. Dickel

    2015-05-01

    Full Text Available 211Po ions in the ground and isomeric states were produced via 238U projectile fragmentation at 1000 MeV/u. The 211Po ions were spatially separated in flight from the primary beam and other reaction products by the fragment separator FRS. The ions were energy-bunched, slowed-down and thermalized in a gas-filled cryogenic stopping cell (CSC. They were then extracted from the CSC and injected into a high-resolution multiple-reflection time-of-flight mass spectrometer (MR-TOF-MS. The excitation energy of the isomer and, for the first time, the isomeric-to-ground state ratio were determined from the measured mass spectrum. In the subsequent experimental step, the isomers were spatially separated from the ions in the ground state by an ion deflector and finally collected with a silicon detector for decay spectroscopy. This pioneering experimental result opens up unique perspectives for isomer-resolved studies. With this versatile experimental method new isomers with half-lives longer than a few milliseconds can be discovered and their decay properties can be measured with highest sensitivity and selectivity. These experiments can be extended to studies with isomeric beams in nuclear reactions.

  1. First spatial separation of a heavy ion isomeric beam with a multiple-reflection time-of-flight mass spectrometer

    Energy Technology Data Exchange (ETDEWEB)

    Dickel, T. [II. Physikalisches Institut, Justus-Liebig-Universität Gießen, 35392 Gießen (Germany); GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); Plaß, W.R., E-mail: Wolfgang.R.Plass@exp2.physik.uni-giessen.de [II. Physikalisches Institut, Justus-Liebig-Universität Gießen, 35392 Gießen (Germany); GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); Ayet San Andres, S. [GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); Ebert, J. [II. Physikalisches Institut, Justus-Liebig-Universität Gießen, 35392 Gießen (Germany); Geissel, H.; Haettner, E. [II. Physikalisches Institut, Justus-Liebig-Universität Gießen, 35392 Gießen (Germany); GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); Hornung, C. [II. Physikalisches Institut, Justus-Liebig-Universität Gießen, 35392 Gießen (Germany); Miskun, I. [II. Physikalisches Institut, Justus-Liebig-Universität Gießen, 35392 Gießen (Germany); GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); Pietri, S.; Purushothaman, S. [GSI Helmholtzzentrum für Schwerionenforschung GmbH, 64291 Darmstadt (Germany); and others

    2015-05-11

    {sup 211}Po ions in the ground and isomeric states were produced via {sup 238}U projectile fragmentation at 1000 MeV/u. The {sup 211}Po ions were spatially separated in flight from the primary beam and other reaction products by the fragment separator FRS. The ions were energy-bunched, slowed-down and thermalized in a gas-filled cryogenic stopping cell (CSC). They were then extracted from the CSC and injected into a high-resolution multiple-reflection time-of-flight mass spectrometer (MR-TOF-MS). The excitation energy of the isomer and, for the first time, the isomeric-to-ground state ratio were determined from the measured mass spectrum. In the subsequent experimental step, the isomers were spatially separated from the ions in the ground state by an ion deflector and finally collected with a silicon detector for decay spectroscopy. This pioneering experimental result opens up unique perspectives for isomer-resolved studies. With this versatile experimental method new isomers with half-lives longer than a few milliseconds can be discovered and their decay properties can be measured with highest sensitivity and selectivity. These experiments can be extended to studies with isomeric beams in nuclear reactions.

  2. Energy-Resolved Ion Mobility-Mass Spectrometry—A Concept to Improve the Separation of Isomeric Carbohydrates

    Science.gov (United States)

    Hoffmann, Waldemar; Hofmann, Johanna; Pagel, Kevin

    2014-03-01

    Recent works using ion mobility-mass spectrometry (IM-MS) have highlighted the power of this instrumental configuration to tackle one of the greatest challenges in glycomics and glycoproteomics: the existence of isobaric isomers. For a successful separation of species with identical mass but different structure via IM-MS, it is crucial to have sufficient IM resolution. In commercially available IM-MS instruments, however, this resolution is limited by the design of the instrument and usually cannot be increased at-will without extensive modifications. Here, we present a systematic approach to improve the resolving capability of IM-MS instruments using so-called energy-resolved ion mobility-mass spectrometry. The technique utilizes the fact that individual components in an isobaric mixture fragment at considerably different energies when activated in the gas phase via collision-induced dissociation (CID). As a result, certain components can be suppressed selectively at increased CID activation energy. Using a mixture of four isobaric carbohydrates, we show that each of the individual sugars can be resolved and unambiguously identified even when their drift times differ by as little as 3 %. However, the presented results also indicate that a certain difference in the gas-phase stability of the individual components is crucial for a successful separation via energy-resolved IM-MS.

  3. Energy-resolved ion mobility-mass spectrometry--a concept to improve the separation of isomeric carbohydrates.

    Science.gov (United States)

    Hoffmann, Waldemar; Hofmann, Johanna; Pagel, Kevin

    2014-03-01

    Recent works using ion mobility-mass spectrometry (IM-MS) have highlighted the power of this instrumental configuration to tackle one of the greatest challenges in glycomics and glycoproteomics: the existence of isobaric isomers. For a successful separation of species with identical mass but different structure via IM-MS, it is crucial to have sufficient IM resolution. In commercially available IM-MS instruments, however, this resolution is limited by the design of the instrument and usually cannot be increased at-will without extensive modifications. Here, we present a systematic approach to improve the resolving capability of IM-MS instruments using so-called energy-resolved ion mobility-mass spectrometry. The technique utilizes the fact that individual components in an isobaric mixture fragment at considerably different energies when activated in the gas phase via collision-induced dissociation (CID). As a result, certain components can be suppressed selectively at increased CID activation energy. Using a mixture of four isobaric carbohydrates, we show that each of the individual sugars can be resolved and unambiguously identified even when their drift times differ by as little as 3%. However, the presented results also indicate that a certain difference in the gas-phase stability of the individual components is crucial for a successful separation via energy-resolved IM-MS.

  4. Searching for Scatterers: High-Contrast Imaging of Young Stars Hosting Wide-Separation Planetary-Mass Companions

    CERN Document Server

    Bryan, Marta L; Knutson, Heather A; Kraus, Adam L; Hinkley, Sasha; Mawet, Dimitri; Nielsen, Eric L; Blunt, Sarah C

    2016-01-01

    We have conducted an angular differential imaging survey with NIRC2 at Keck in search of close-in substellar companions to a sample of seven systems with confirmed planetary-mass companions (PMCs) on wide orbits (>50 AU). These wide-separation PMCs pose significant challenges to all three possible formation mechanisms: core accretion plus scattering, disk instability, and turbulent fragmentation. We explore the possibility that these companions formed closer in and were scattered out to their present-day locations by searching for other massive bodies at smaller separations. The typical sensitivity for this survey is \\Delta K ~ 12.5 at 1". We identify eight candidate companions, whose masses would reach as low as one Jupiter mass if gravitationally bound. From our multi-epoch astrometry we determine that seven of these are conclusively background objects, while the eighth near DH Tau is ambiguous and requires additional monitoring. We rule out the presence of >7 M$_{\\rm Jup}$ bodies in these systems down to 1...

  5. A miniature system for separating aerosol particles and measuring mass concentrations.

    Science.gov (United States)

    Liang, Dao; Shih, Wen-Pin; Chen, Chuin-Shan; Dai, Chi-An

    2010-01-01

    We designed and fabricated a new sensing system which consists of two virtual impactors and two quartz-crystal microbalance (QCM) sensors for measuring particle mass concentration and size distribution. The virtual impactors utilized different inertial forces of particles in air flow to classify different particle sizes. They were designed to classify particle diameter, d, into three different ranges: d3.20 μm. The QCM sensors were coated with a hydrogel, which was found to be a reliable adhesive for capturing aerosol particles. The QCM sensor coated with hydrogel was used to measure the mass loading of particles by utilizing its characteristic of resonant frequency shift. An integrated system has been demonstrated.

  6. A Miniature System for Separating Aerosol Particles and Measuring Mass Concentrations

    Directory of Open Access Journals (Sweden)

    Dao Liang

    2010-04-01

    Full Text Available We designed and fabricated a new sensing system which consists of two virtual impactors and two quartz-crystal microbalance (QCM sensors for measuring particle mass concentration and size distribution. The virtual impactors utilized different inertial forces of particles in air flow to classify different particle sizes. They were designed to classify particle diameter, d, into three different ranges: d < 2.28 μm, 2.28 μm ≤ d ≤ 3.20 μm, d > 3.20 μm. The QCM sensors were coated with a hydrogel, which was found to be a reliable adhesive for capturing aerosol particles. The QCM sensor coated with hydrogel was used to measure the mass loading of particles by utilizing its characteristic of resonant frequency shift. An integrated system has been demonstrated.

  7. Flow analysis by using solenoid valves for As(III determination in natural waters by an on-line separation and pre-concentration system coupled to a tungsten coil atomizer

    Directory of Open Access Journals (Sweden)

    José Y. Neira

    2005-03-01

    Full Text Available A flow system coupled to a tungsten coil atomizer in an atomic absorption spectrometer (TCA-AAS was developed for As(III determination in waters, by extraction with sodium diethyldithiocarbamate (NaDDTC as complexing agent, and by sorption of the As(III-DDTC complex in a micro-column filled with 5 mg C18 reversed phase (10 µL dry sorbent, followed by elution with ethanol. A complete pre-concentration/elution cycle took 208 s, with 30 s sample load time (1.7 mL and 4 s elution time (71 µL. The interface and software for the synchronous control of two peristaltic pumps (RUN/ STOP, an autosampler arm, seven solenoid valves, one injection valve, the electrothermal atomizer and the spectrometer Read function were constructed. The system was characterized and validated by analytical recovery studies performed both in synthetic solutions and in natural waters. Using a 30 s pre-concentration period, the working curve was linear between 0.25 and 6.0 µg L-1 (r = 0.9976, the retention efficiency was 94±1% (6.0 µg L-1, and the pre-concentration coefficient was 28.9. The characteristic mass was 58 pg, the mean repeatability (expressed as the variation coefficient was 3.4% (n=5, the detection limit was 0.058 µg L-1 (4.1 pg in 71 µL of eluate injected into the coil, and the mean analytical recovery in natural waters was 92.6 ± 9.5 % (n=15. The procedure is simple, economic, less prone to sample loss and contamination and the useful lifetime of the micro-column was between 200-300 pre-concentration cycles.

  8. Isotope-Dilution Mass Spectrometry for Quantification of Urinary Active Androgens Separated by Gas Chromatography

    OpenAIRE

    Su Hyeon Lee; Man Ho Choi; Won-Yong Lee; Bong Chul Chung

    2010-01-01

    Cross reacting antibodies can cause an overestimation of the results of immunoassays. Therefore, alternative methodsare needed for the accurate quantification of steroids. Gas chromatography combined with isotope-dilution mass spectrometry(GC-IDMS) is developed to quantify urinary active androgens, testosterone, epitestosterone and dihydrotestosterone, which areclinically relevant androgens to both hair-loss and prostate diseases. The method devised involves enzymatic hydrolysis with β-glucur...

  9. Ion Mobility Separations of Isomers based upon Long Path Length Structures for Lossless Ion Manipulations Combined with Mass Spectrometry.

    Science.gov (United States)

    Deng, Liulin; Ibrahim, Yehia M; Baker, Erin S; Aly, Noor A; Hamid, Ahmed M; Zhang, Xing; Zheng, Xueyun; Garimella, Sandilya V B; Webb, Ian K; Prost, Spencer A; Sandoval, Jeremy A; Norheim, Randolph V; Anderson, Gordon A; Tolmachev, Aleksey V; Smith, Richard D

    2016-07-01

    Mass spectrometry (MS)-based multi-omic measurements, including proteomics, metabolomics, lipidomics, and glycomics, are increasingly transforming our ability to characterize and understand biological systems. Multi-omic analyses and the desire for comprehensive measurement coverage presently have limitations due to the chemical diversity and range of abundances of biomolecules in complex samples. Advances addressing these challenges increasingly are based upon the ability to quickly separate, react and otherwise manipulate sample components for analysis by MS. Here we report on a new approach using Structures for Lossless Ion Manipulations (SLIM) to enable long serpentine path ion mobility spectrometry (IMS) separations followed by MS analyses. This approach provides previously unachieved resolution for biomolecular species, in conjunction with more effective ion utilization, and a basis for greatly improved characterization of very small sample sizes.

  10. Simultaneous analysis of theanine, chlorogenic acid, purine alkaloids and catechins in tea samples with the help of multi-dimension information of on-line high performance liquid chromatography/electrospray-mass spectrometry.

    Science.gov (United States)

    Zhu, Xiaolan; Chen, Bo; Ma, Ming; Luo, Xubiao; Zhang, Fei; Yao, Shouzhuo; Wan, Zutian; Yang, Dajin; Hang, Hongwei

    2004-02-18

    A reverse phase high performance liquid chromatography (RP-HPLC) separation coupled with photo diode array detection (DAD) and electrospray ionization mass spectrometry (ESI-MS) detection was established for the analyzing of multiple bioactive compounds in tea and tea extracts. Theanine, chlorogenic acid, purine alkaloids and catechins were identified with authentic standard compounds and with MS-spectra. The content of theanine and catechins was measured by employing DAD and caffeine, chlorogenic acid, theobromine and theopylline by protonated molecular ion on selective ion recording (SIR) mode. The unity of LC/ESI-MS provides more qualitative and quantitative information comparing with general HPLC in the analysis of multi-components in tea, and complex extraction or sample pretreatment is unnecessary. The chromatogram acquired by using this method can be used as a bioactive components fingerprint for the quality control of tea and its extracts. With the help of multi-dimension information of HPLC-DAD-ESIMS, the compounds owning different chemical structure such as amino acid, catechins, etc. in tea and its extracts could be identified and determined in one run successfully.

  11. Determination of 3,4-methylenedioxymethamphetamine and its five main metabolites in rat urine by solid-phase extraction and high performance liquid chromatography with on line mass spectrometry.

    Science.gov (United States)

    Menet, Marie-Claude; Fonsart, Julien; Hervé, Françoise; Fompeydie, Dominique; Galliot-Guilley, Martine; Noble, Florence; Scherrmann, Jean-Michel

    2010-10-15

    The consumption of psychostimulant amphetamine-like drugs has increased significantly in recent years. Some MDMA metabolites are probably involved in the neurotoxicity and neurodegeneration caused by prolonged use rather than MDMA itself. We recently developed a method to analyze MDMA and its five main metabolites in rat plasma [7]. We have now fully validated this method to the quantification of these drugs in rat urine. We extracted MDMA and its metabolites with Oasis WCX cartridges, separated them on a Nucleodur C18 analytical column and quantified them by ion-trap mass spectrometry. Linearity was excellent: 12.5-1250ng/mL urine for HMA, HMMA, MDA and MDMA, 25-2500ng/mL for HHMA, and 150-7500ng/mL for HHA (r(2)>0.993 for all analytes). The lower limits of quantification were 12.5ng/mL urine for MDMA, MDA, HMA and HMMA, 25ng/mL for HHMA and 150ng/mL for HHA. Reproducibility was good (intra-assay precision=1.7-6.1%; inter-assay precision=0.6-5.7%), as was accuracy (intra-assay deviation=0.1-4.8%; inter-assay deviation=0.7-7.9%). Average recoveries were around 85.0%, except for HHMA (66.2%) and HHA (53.0%) (CVurine samples taken over 24h from rats given subcutaneous MDMA.

  12. Formation of residual nuclei with medium mass number in the reaction of protons with separated tin isotopes

    CERN Document Server

    Aleksandryan, V E; Balabekyan, A R; Danagulyan, A S; Kalinnikov, V G; Musulmanbekov, G; Rodionov, V K; Stegailov, V I; Frana, J

    2000-01-01

    The mechanism of formation of residual nuclei in the mass region 42<=A<=81 in the reactions of protons with separated tin isotopes at three protons energies 0.66, 1.0 and 8.1 GeV was investigated. The absolute cross-sections of the residual nuclei were compared with the theoretical ones calculated by the standard cascade-evaporation and the intranuclear cascad plus statistical multifragmentation models (INC+SMM). It was shown that at E sub p =8.1 GeV these nuclei may arise both from disintegration of the nucleus and as partners of several fragments.

  13. CERN Video News on line

    CERN Multimedia

    2003-01-01

    The latest CERN video news is on line. In this issue : an interview with the Director General and reports on the new home for the DELPHI barrel and the CERN firemen's spectacular training programme. There's also a vintage video news clip from 1954. See: www.cern.ch/video or Bulletin web page

  14. Enhancement of biological mass spectrometry by using separations based on changes in ion mobility (FAIMS and DMS).

    Science.gov (United States)

    Purves, Randy W

    2013-01-01

    Analysis of complex biological samples for low-level analytes by liquid chromatography-tandem mass spectrometry (LC-MS/MS) often requires additional selectivity. Differential mobility techniques (FAIMS and DMS) have been shown to enhance LC-MS/MS analyses by separating ions in the gas-phase on a millisecond timescale by use of a mechanism that is complementary to both liquid chromatography and mass spectrometry. In this overview, a simplified description of the operation of these devices is given and an example presented that illustrates the utility of FAIMS (DMS) for solving a challenging analytical assay. Important recent advances in the field, including work with gas modifiers, are presented, along with an outlook for the technology.

  15. Broad Separation of Isomeric Lipids by High-Resolution Differential Ion Mobility Spectrometry with Tandem Mass Spectrometry

    Science.gov (United States)

    Bowman, Andrew P.; Abzalimov, Rinat R.; Shvartsburg, Alexandre A.

    2017-08-01

    Maturation of metabolomics has brought a deeper appreciation for the importance of isomeric identity of lipids to their biological role, mirroring that for proteoforms in proteomics. However, full characterization of the lipid isomerism has been thwarted by paucity of rapid and effective analytical tools. A novel approach is ion mobility spectrometry (IMS) and particularly differential or field asymmetric waveform IMS (FAIMS) at high electric fields, which is more orthogonal to mass spectrometry. Here we broadly explore the power of FAIMS to separate lipid isomers, and find a 75% success rate across the four major types of glycero- and phospho- lipids ( sn, chain length, double bond position, and cis/ trans). The resolved isomers were identified using standards, and (for the first two types) tandem mass spectrometry. These results demonstrate the general merit of incorporating high-resolution FAIMS into lipidomic analyses.

  16. Electrophoretic separation techniques and their hyphenation to mass spectrometry in biological inorganic chemistry.

    Science.gov (United States)

    Holtkamp, Hannah; Grabmann, Gerlinde; Hartinger, Christian G

    2016-04-01

    Electrophoretic methods have been widely applied in research on the roles of metal complexes in biological systems. In particular, CE, often hyphenated to a sensitive MS detector, has provided valuable information on the modes of action of metal-based pharmaceuticals, and more recently new methods have been added to the electrophoretic toolbox. The range of applications continues to expand as a result of enhanced CE-to-MS interfacing, with sensitivity often at picomolar level, and evolved separation modes allowing for innovative sample analysis. This article is a followup to previous reviews about CE methods in metallodrug research (Electrophoresis, 2003, 24, 2023-2037; Electrophoresis, 2007, 28, 3436-3446; Electrophoresis, 2012, 33, 622-634), also providing a comprehensive overview of metal species studied by electrophoretic methods hyphenated to MS. It highlights the latest CE developments, takes a sneak peek into gel electrophoresis, traces biomolecule labeling, and focuses on the importance of early-stage drug development.

  17. On the implications of aerosol liquid water and phase separation for organic aerosol mass

    Science.gov (United States)

    Pye, Havala O. T.; Murphy, Benjamin N.; Xu, Lu; Ng, Nga L.; Carlton, Annmarie G.; Guo, Hongyu; Weber, Rodney; Vasilakos, Petros; Wyat Appel, K.; Hapsari Budisulistiorini, Sri; Surratt, Jason D.; Nenes, Athanasios; Hu, Weiwei; Jimenez, Jose L.; Isaacman-VanWertz, Gabriel; Misztal, Pawel K.; Goldstein, Allen H.

    2017-01-01

    Organic compounds and liquid water are major aerosol constituents in the southeast United States (SE US). Water associated with inorganic constituents (inorganic water) can contribute to the partitioning medium for organic aerosol when relative humidities or organic matter to organic carbon (OM / OC) ratios are high such that separation relative humidities (SRH) are below the ambient relative humidity (RH). As OM / OC ratios in the SE US are often between 1.8 and 2.2, organic aerosol experiences both mixing with inorganic water and separation from it. Regional chemical transport model simulations including inorganic water (but excluding water uptake by organic compounds) in the partitioning medium for secondary organic aerosol (SOA) when RH > SRH led to increased SOA concentrations, particularly at night. Water uptake to the organic phase resulted in even greater SOA concentrations as a result of a positive feedback in which water uptake increased SOA, which further increased aerosol water and organic aerosol. Aerosol properties, such as the OM / OC and hygroscopicity parameter (κorg), were captured well by the model compared with measurements during the Southern Oxidant and Aerosol Study (SOAS) 2013. Organic nitrates from monoterpene oxidation were predicted to be the least water-soluble semivolatile species in the model, but most biogenically derived semivolatile species in the Community Multiscale Air Quality (CMAQ) model were highly water soluble and expected to contribute to water-soluble organic carbon (WSOC). Organic aerosol and SOA precursors were abundant at night, but additional improvements in daytime organic aerosol are needed to close the model-measurement gap. When taking into account deviations from ideality, including both inorganic (when RH > SRH) and organic water in the organic partitioning medium reduced the mean bias in SOA for routine monitoring networks and improved model performance compared to observations from SOAS. Property updates from

  18. From User Comments to On-line Conversations

    OpenAIRE

    Wang, Chunyan; Ye, Mao; Huberman, Bernardo A.

    2012-01-01

    We present an analysis of user conversations in on-line social media and their evolution over time. We propose a dynamic model that accurately predicts the growth dynamics and structural properties of conversation threads. The model successfully reconciles the differing observations that have been reported in existing studies. By separating artificial factors from user behaviors, we show that there are actually underlying rules in common for on-line conversations in different social media web...

  19. Ricin as a weapon of mass terror--separating fact from fiction.

    Science.gov (United States)

    Schep, Leo J; Temple, Wayne A; Butt, Grant A; Beasley, Michael D

    2009-11-01

    In recent years there has been an increased concern regarding the potential use of chemical and biological weapons for mass urban terror. In particular, there are concerns that ricin could be employed as such an agent. This has been reinforced by recent high profile cases involving ricin, and its use during the cold war to assassinate a high profile communist dissident. Nevertheless, despite these events, does it deserve such a reputation? Ricin is clearly toxic, though its level of risk depends on the route of entry. By ingestion, the pathology of ricin is largely restricted to the gastrointestinal tract where it may cause mucosal injuries; with appropriate treatment, most patients will make a full recovery. As an agent of terror, it could be used to contaminate an urban water supply, with the intent of causing lethality in a large urban population. However, a substantial mass of pure ricin powder would be required. Such an exercise would be impossible to achieve covertly and would not guarantee success due to variables such as reticulation management, chlorination, mixing, bacterial degradation and ultra-violet light. By injection, ricin is lethal; however, while parenteral delivery is an ideal route for assassination, it is not realistic for an urban population. Dermal absorption of ricin has not been demonstrated. Ricin is also lethal by inhalation. Low doses can lead to progressive and diffuse pulmonary oedema with associated inflammation and necrosis of the alveolar pneumocytes. However, the risk of toxicity is dependent on the aerodynamic equivalent diameter (AED) of the ricin particles. The AED, which is an indicator of the aerodynamic behaviour of a particle, must be of sufficiently low micron size as to target the human alveoli and thereby cause major toxic effects. To target a large population would also necessitate a quantity of powder in excess of several metric tons. The technical and logistical skills required to formulate such a mass of powder to

  20. Analytical methods for proteome data obtained from SDS-PAGE multi-dimensional separation and mass spectrometry

    Directory of Open Access Journals (Sweden)

    Gun Wook Park

    2010-03-01

    Full Text Available For proteome analysis, various experimental protocols using mass spectrometry have been developed over thelast decade. The different protocols have differing performances and degrees of accuracy. Furthermore, the “best”protocol for a proteomic analysis of a sample depends on the purpose of the analysis, especially in connection withdisease proteomics, including biomarker discovery and therapeutics analyses of human serum or plasma. Theprotein complexity and the wide dynamic range of blood samples require high-dimensional separation technology.In this article, we review proteome analysis protocols in which both Sodium Dodecyl Sulfate-Polyacryl Amide GelElectrophoresis(SDS-PAGE and liquid chromatography are used for peptide and protein separations. Multidimensionalseparation technology supplies a high-quality dataset of tandem mass spectra and reveals signals fromlow-abundance proteins, although it can be time-consuming and laborious work. We survey shotgun proteomicsprotocols using SDS-PAGE and liquid chromatography and introduce bioinformatics tools for the analysis ofproteomics data. We also review efforts toward the biological interpretation of the proteome.

  1. Design of a single magnet separator with mass resolving power m/Δm ≈ 20, 000

    Science.gov (United States)

    Breitenfeldt, Martin; Augustin, Mathieu; Catherall, Richard; Giles, Tim; Schoerling, Daniel; Tveten, Gry M.

    2016-06-01

    ISOLDE at CERN is a leading radioactive ion beam facility. With its upgrade, the HIE-ISOLDE project, an increase in primary beam intensity and energy is envisaged and the aim is a significant increase in intensity of the exotic beams. The high resolution separator (HRS) after the upgrade is required to suppress contaminations almost completely when the masses differ to the beam of interest by Δm / m > 1 / 20, 000 . Here a 120° magnet with a bending radius of 1.25 m has been chosen. The magnetic rigidity is 0.625 Tm (B-field of 0.5 T) to allow for separation of molecules of up to a mass of 300 u. The magnet comprises a yoke in wedged H-type configuration for stability and precision and pole face conductors for focusing and compensation of aberrations. The concept was derived analytically, refined with the OPERA 2D software and tested with the ray-tracing module of OPERA 3D.

  2. Clean Air OnLine

    Energy Technology Data Exchange (ETDEWEB)

    Finney, D. [Environment Canada, Gatineau, PQ (Canada). Air Pollution Prevention Directorate

    2004-04-07

    This presentation describes Clean Air OnLine, a multi-tiered website dedicated to providing Canadians with information on air quality. The website is under development to support action to reduce air emissions, demonstrate the links between air emissions and environmental impacts, and enhance the understanding of sustainable community development issues such as health, energy, and urban sprawl. Partners in the Clean Air OnLine (CAOL) initiative include Environment Canada and the Clean Air Partnership which includes the Greater Toronto Area pilot project. The audience for CAOL includes municipal decision makers, local decision makers, community leaders, and the general public. The project provides Canadians with air pollution contextual information on pollution sources, pollutants, and related issues. It also provides information on health, environmental and economic impacts and the interrelationships with climate change issues and energy use. tabs., figs.

  3. On-line moisture analysis

    CERN Document Server

    Cutmore, N G

    2002-01-01

    Measurement of the moisture content of iron ore has become a key issue for controlling moisture additions for dust suppression. In most cases moisture content is still determined by manual or automatic sampling of the ore stream, followed by conventional laboratory analysis by oven drying. Although this procedure enables the moisture content to be routinely monitored, it is too slow for control purposes. This has generated renewed interest in on-line techniques for the accurate and rapid measurement of moisture in iron ore on conveyors. Microwave transmission techniques have emerged over the past 40 years as the dominant technology for on-line measurement of moisture in bulk materials, including iron ores. Alternative technologies have their limitations. Infra-red analysers are used in a variety of process industries, but rely on the measurement of absorption by moisture in a very thin surface layer. Consequently such probes may be compromised by particle size effects and biased presentation of the bulk mater...

  4. On-line cut-off technique and organic modifier addition aided signal enhancement for trace analysis of carbohydrates in cellulase hydrolysate by ion exclusion chromatography-electrospray ionization mass spectrometry.

    Science.gov (United States)

    Cheng, Cheanyeh; Tsai, Hsiang-Rong; Chang, Kuo-Chung

    2006-06-30

    Paper cellulose has been hydrolyzed with calcium alginate immobilized cellulase to produce carbohydrate products and the three trace sugars, galactose, arabinose, and mannose in the cellulase hydrolysate have been analyzed by HPIEC/ESI-MS. Applying the on-line cut-off technique to the HPIEC/ESI-MS can cut the high concentration glucose off to eliminate its interference on the peaks of minor sugars and enhance their signals from 1.1- to 1.6-fold. However, the on-line post column addition of 15% ethanol to the eluate can increase the signal of the three trace sugars, galactose, arabinose, and mannose up to 17-, 23-, and 11-fold, respectively, and make the corresponding detection limits as 0.04, 0.04, and 0.03 ppm. The accuracies of the quantitative analysis for the three trace sugars with the signal enhanced HPIEC/ESI-MS by the two enhancement methods were larger than 95%. The precisions of the analytical results were also greatly improved by the assistance of the two techniques and were less than 6.5%. The quantitative analysis of the three trace sugars was performed with the internal standard method and the internal standard (IS) was sorbitol. Overall, the signal enhancement of HPIEC/ESI-MS and quantification of the three trace sugars by the on-line cut-off technique and organic modifier addition was successful.

  5. Proteomic analysis of estrogen response of premalignant human breast cells using a 2-D liquid separation/mass mapping technique.

    Science.gov (United States)

    Zhao, Jia; Zhu, Kan; Lubman, David M; Miller, Fred R; Shekhar, Malthy P V; Gerard, Brigitte; Barder, Timothy J

    2006-07-01

    A 2-D liquid-phase separation method based on chromatofocusing and nonporous silica RP-HPLC followed by ESI-TOF-MS was used to analyze proteins in whole cell lysates from estrogen-treated and untreated premalignant, estrogen-responsive cell line MCF10AT1 cells. 2-D mass maps in the pH range 4.6-6.0 were generated with good correlation to theoretical M(r) values for intact proteins. Proteins were identified based on intact M(r), pI and PMF, or MS/MS sequencing. About 300 unique proteins were identified and 120 proteins in mass range 5-75 kDa were quantified upon treatment of estrogen. Around 40 proteins were found to be more highly expressed (>four-fold) and 17 were down-regulated (>four-fold) in treated cells. In our study, we found that many altered proteins have characteristics consistent with the development of a malignant phenotype. Some of them have a role in the ras pathway or play an important role in signal pathways. These changed proteins might be essential in the estrogen regulation mechanism. Our study highlights the use of the MCF10AT1 cell line to examine estrogen-induced changes in premalignant breast cells and the ability of the 2-D mass mapping technique to quantitatively study protein expression changes on a proteomic scale.

  6. Design and commissioning of a timestamp-based data acquisition system for the DRAGON recoil mass separator

    CERN Document Server

    Christian, G; Connolly, D; Fallis, J; Hutcheon, D; Olchanski, K; Ruiz, C

    2014-01-01

    The DRAGON recoil mass separator at TRIUMF exists to study radiative proton and alpha capture reactions, which are important in a variety of astrophysical scenarios. DRAGON experiments require a data acquisition system that can be triggered on either reaction product ($\\gamma$ ray or heavy ion), with the additional requirement of being able to promptly recognize coincidence events in an online environment. To this end, we have designed and implemented a new data acquisition system for DRAGON which consists of two independently triggered readouts. Events from both systems are recorded with timestamps from a $20$ MHz clock that are used to tag coincidences in the earliest possible stage of the data analysis. Here we report on the design, implementation, and commissioning of the new DRAGON data acquisition system, including the hardware, trigger logic, coincidence reconstruction algorithm, and live time considerations. We also discuss the results of an experiment commissioning the new system, which measured the ...

  7. Comprehensive ultra-performance liquid chromatographic separation and mass spectrometric analysis of eicosanoid metabolites in human samples.

    Science.gov (United States)

    Wang, Yan; Armando, Aaron M; Quehenberger, Oswald; Yan, Chao; Dennis, Edward A

    2014-09-12

    Over the past decade, the number of known eicosanoids has expanded immensely and we have now developed an ultra-performance liquid chromatography-electrospray ionization triple quadrupole mass spectrometric (UPLC-QTRAP/MS/MS) method to monitor and quantify numerous eicosanoids. The UPLC-QTRAP/MS/MS approach utilizes scheduled multiple reaction monitoring (MRM) to optimize sensitivity, number of metabolites that can be analyzed and the time requirement of the analysis. A total of 184 eicosanoids including 26 deuterated internal standards can be separated and monitored in a single 5min UPLC run. To demonstrate a practical application, human plasma samples were analyzed following solid-phase extraction (SPE) and the recovery rate and matrix effects were determined for the 26 deuterated internal standards added to the plasma. The method was validated and shown to be sensitive with the limit of quantitation at pg levels for most compounds, accurate with recovery rates of 70-120%, and precise with a CVeicosanoids.

  8. PHENIX on-line systems

    Energy Technology Data Exchange (ETDEWEB)

    Adler, S.S.; Allen, M.; Alley, G.; Amirikas, R.; Arai, Y.; Awes, T.C.; Barish, K.N.; Barta, F.; Batsouli, S.; Belikov, S.; Bennett, M.J.; Bobrek, M.; Boissevain, J.G.; Boose, S.; Britton, C.; Britton, L.; Bryan, W.L.; Cafferty, M.M.; Carey, T.A.; Chang, W.C.; Chi, C.Y.; Chiu, M.; Cianciolo, V.; Cole, B.A.; Constantin, P.; Cook, K.C.; Cunitz, H.; Desmond, E.J.; Ebisu, K.; Efremenko, Y.V.; El Chenawi, K.; Emery, M.S.; Engo, D.; Ericson, N.; Fields, D.E.; Frank, S.; Frantz, J.E.; Franz, A.; Frawley, A.D.; Fried, J.; Gannon, J.; Gee, T.F.; Gentry, R.; Giannotti, P.; Gustafsson, H.-A.; Haggerty, J.S.; Hahn, S.; Halliwell, J.; Hamagaki, H.; Hansen, A.G.; Hara, H.; Harder, J.; He, X.; Heistermann, F.; Hemmick, T.K.; Hibino, M.; Hill, J.C. E-mail: jhill@iastate.edu; Homma, K.; Jacak, B.V.; Jagadish, U.; Jia, J.; Kajihara, F.; Kametani, S.; Kamyshkov, Y.; Kandasamy, A.; Kang, J.H.; Kapustinsky, J.; Katou, K.; Kelley, M.A.; Kelly, S.; Kikuchi, J.; Kim, S.Y.; Kim, Y.G.; Kistenev, E.; Kotchetkov, D.; Kurita, K.; Lajoie, J.G.; Lenz, M.; Lenz, W.; Li, X.H.; Lin, S.; Liu, M.X.; Markacs, S.; Matathias, F.; Matsumoto, T.; Mead, J.; Mischke, R.E.; Mishra, G.C.; Moore, A.; Muniruzzamann, M.; Musrock, M.; Nagle, J.L.; Nandi, B.K.; Newby, J.; Nystrand, J.; O' Brien, E.; O' Connor, P.; Ohnishi, H.; Oskarsson, A.; Osterman, L.; Oyama, K.; Paffrath, L.; Pancake, C.E.; Pantuev, V.S.; Petridis, A.N.; Pisani, R.P.; Plagge, T.; Plasil, F.; Purschke, M.L.; Rankowitz, S.; Rao, R.; Rau, M.; Read, K.F.; Ryu, S.S.; Sakaguchi, T.; Sato, H.D.; Seto, R.; Shiina, T.; Silvermyr, D.; Simon-Gillo, J.; Simpson, M.; Sippach, W.; Skank, H.D.; Skutnik, S.; Sleege, G.A.; Smith, G.D.; Smith, M.; Stankus, P.W.; Steinberg, P.; Sugitate, T.; Sullivan, J.P.; Taketani, A.; Tamai, M.; Tanaka, Y.; Thomas, W.D.; Todd, R.; Toldo, F.; Turner, G.; Ushiroda, T.; Velkovska, J.; Hecke, H.W. van; Lith, M. van; Villatte, L.; Achen, W. von; Walker, J.W.; Wang, H.Q.; White, S.N.; Wintenberg, A.L.; Witzig, C.; Wood, L.[and others

    2003-03-01

    The PHENIX On-Line system takes signals from the Front End Modules (FEM) on each detector subsystem for the purpose of generating events for physics analysis. Processing of event data begins when the Data Collection Modules (DCM) receive data via fiber-optic links from the FEMs. The DCMs format and zero suppress the data and generate data packets. These packets go to the Event Builders (EvB) that assemble the events in final form. The Level-1 trigger (LVL1) generates a decision for each beam crossing and eliminates uninteresting events. The FEMs carry out all detector processing of the data so that it is delivered to the DCMs using a standard format. The FEMs also provide buffering for LVL1 trigger processing and DCM data collection. This is carried out using an architecture that is pipelined and deadtimeless. All of this is controlled by the Master Timing System (MTS) that distributes the RHIC clocks. A Level-2 trigger (LVL2) gives additional discrimination. A description of the components and operation of the PHENIX On-Line system is given and the solution to a number of electronic infrastructure problems are discussed.

  9. Quantitative Mass spectrometric Analysis of Ropivacaine and Bupivacaine in Authentic, Pharmaceutical and Spiked Human Plasma without Chromatographic Separation

    Directory of Open Access Journals (Sweden)

    Nahla N. Salama

    2009-01-01

    Full Text Available The present study employs time of flight mass spectrometry for quantitative analysis of the local anesthetic drugs ropivacaine and bupivacaine in authentic, pharmaceutical and spiked human plasma as well as in the presence of their impurities 2,6-dimethylaniline and alkaline degradation product. The method is based on time of flight electron spray ionization mass spectrometry technique without preliminary chromatographic separation and makes use of bupivacaine as internal standard for ropivacaine, which is used as internal standard for bupivacaine. A linear relationship between drug concentrations and the peak intensity ratio of ions of the analyzed substances is established. The method is linear from 23.8 to 2380.0 ng mL-1 for both drugs. The correlation coefficient was ≥0.996 in authentic and spiked human plasma. The average percentage recoveries in the ranges of 95.39%–102.75% was obtained. The method is accurate (% RE < 5% and reproducible with intra- and inter-assay precision (RSD% < 8.0%. The quantification limit is 23.8 ng mL-1 for both drugs. The method is not only highly sensitive and selective, but also simple and effective for determination or identification of both drugs in authentic and biological fluids. The method can be applied in purity testing, quality control and stability monitoring for the studied drugs.

  10. Solvent Separating Secondary Metabolites Directly from Biosynthetic Tissue for Surface-Assisted Laser Desorption Ionisation Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    David Rudd

    2015-03-01

    Full Text Available Marine bioactive metabolites are often heterogeneously expressed in tissues both spatially and over time. Therefore, traditional solvent extraction methods benefit from an understanding of the in situ sites of biosynthesis and storage to deal with heterogeneity and maximize yield. Recently, surface-assisted mass spectrometry (MS methods namely nanostructure-assisted laser desorption ionisation (NALDI and desorption ionisation on porous silicon (DIOS surfaces have been developed to enable the direct detection of low molecular weight metabolites. Since direct tissue NALDI-MS or DIOS-MS produce complex spectra due to the wide variety of other metabolites and fragments present in the low mass range, we report here the use of “on surface” solvent separation directly from mollusc tissue onto nanostructured surfaces for MS analysis, as a mechanism for simplifying data annotation and detecting possible artefacts from compound delocalization during the preparative steps. Water, ethanol, chloroform and hexane selectively extracted a range of choline esters, brominated indoles and lipids from Dicathais orbita hypobranchial tissue imprints. These compounds could be quantified on the nanostructured surfaces by comparison to standard curves generated from the pure compounds. Surface-assisted MS could have broad utility for detecting a broad range of secondary metabolites in complex marine tissue samples.

  11. Optimal hydrograph separation using a recursive digital filter constrained by chemical mass balance, with application to selected Chesapeake Bay watersheds

    Science.gov (United States)

    Raffensperger, Jeff P.; Baker, Anna C.; Blomquist, Joel D.; Hopple, Jessica A.

    2017-06-26

    Quantitative estimates of base flow are necessary to address questions concerning the vulnerability and response of the Nation’s water supply to natural and human-induced change in environmental conditions. An objective of the U.S. Geological Survey National Water-Quality Assessment Project is to determine how hydrologic systems are affected by watershed characteristics, including land use, land cover, water use, climate, and natural characteristics (geology, soil type, and topography). An important component of any hydrologic system is base flow, generally described as the part of streamflow that is sustained between precipitation events, fed to stream channels by delayed (usually subsurface) pathways, and more specifically as the volumetric discharge of water, estimated at a measurement site or gage at the watershed scale, which represents groundwater that discharges directly or indirectly to stream reaches and is then routed to the measurement point.Hydrograph separation using a recursive digital filter was applied to 225 sites in the Chesapeake Bay watershed. The recursive digital filter was chosen for the following reasons: it is based in part on the assumption that groundwater acts as a linear reservoir, and so has a physical basis; it has only two adjustable parameters (alpha, obtained directly from recession analysis, and beta, the maximum value of the base-flow index that can be modeled by the filter), which can be determined objectively and with the same physical basis of groundwater reservoir linearity, or that can be optimized by applying a chemical-mass-balance constraint. Base-flow estimates from the recursive digital filter were compared with those from five other hydrograph-separation methods with respect to two metrics: the long-term average fraction of streamflow that is base flow, or base-flow index, and the fraction of days where streamflow is entirely base flow. There was generally good correlation between the methods, with some biased

  12. On-line sample treatment - Capillary gas chromatography

    NARCIS (Netherlands)

    Goosens, EC; de Jong, D; de Jong, GJ; Brinkman, UAT

    1998-01-01

    Sample pretreatment is often the bottleneck of a trace level analytical procedure. In order to increase performance, increasing attention is therefore being devoted to combining sample pretreatment on-line with the separation technique that has to be used. In the present review, a variety of procedu

  13. On-line digestion system for protein characterization and proteome analysis.

    Science.gov (United States)

    López-Ferrer, Daniel; Petritis, Konstantinos; Lourette, Natacha M; Clowers, Brian; Hixson, Kim K; Heibeck, Tyler; Prior, David C; Pasa-Tolić, Ljiljana; Camp, David G; Belov, Mikhail E; Smith, Richard D

    2008-12-01

    An efficient on-line digestion system that reduces the number of sample manipulation steps has been demonstrated for high-throughput proteomics. By incorporating a pressurized sample loop into a liquid chromatography-based separation system, both sample and enzyme (e.g., trypsin) can be simultaneously introduced to produce a complete, yet rapid digestion. Both standard proteins and a complex Shewanella oneidensis global protein extract were digested and analyzed using the automated online pressurized digestion system coupled to an ion mobility time-of-flight mass spectrometer, an ion trap mass spectrometer, or both. The system denatured, digested, and separated product peptides in a manner of minutes, making it amenable to on-line high-throughput applications. In addition to simplifying and expediting sample processing, the system was easy to implement and no cross-contamination was observed among samples. As a result, the online digestion system offers a powerful approach for high-throughput screening of proteins that could prove valuable in biochemical research (rapid screening of protein-based drugs).

  14. Automatically Detecting and Tracking Coronal Mass Ejections. I. Separation of Dynamic and Quiescent Components in Coronagraph Images

    Science.gov (United States)

    Morgan, Huw; Byrne, Jason P.; Habbal, Shadia Rifai

    2012-06-01

    Automated techniques for detecting and tracking coronal mass ejections (CMEs) in coronagraph data are of ever increasing importance for space weather monitoring and forecasting. They serve to remove the biases and tedium of human interpretation, and provide the robust analysis necessary for statistical studies across large numbers of observations. An important requirement in their operation is that they satisfactorily distinguish the CME structure from the background quiescent coronal structure (streamers, coronal holes). Many studies resort to some form of time differencing to achieve this, despite the errors inherent in such an approach—notably spatiotemporal crosstalk. This article describes a new deconvolution technique that separates coronagraph images into quiescent and dynamic components. A set of synthetic observations made from a sophisticated model corona and CME demonstrates the validity and effectiveness of the technique in isolating the CME signal. Applied to observations by the LASCO C2 and C3 coronagraphs, the structure of a faint CME is revealed in detail despite the presence of background streamers that are several times brighter than the CME. The technique is also demonstrated to work on SECCHI/COR2 data, and new possibilities for estimating the three-dimensional structure of CMEs using the multiple viewing angles are discussed. Although quiescent coronal structures and CMEs are intrinsically linked, and although their interaction is an unavoidable source of error in any separation process, we show in a companion paper that the deconvolution approach outlined here is a robust and accurate method for rigorous CME analysis. Such an approach is a prerequisite to the higher-level detection and classification of CME structure and kinematics.

  15. Conception of PIPERADE: A high-capacity Penning-trap mass separator for high isobaric contamination at DESIR

    Energy Technology Data Exchange (ETDEWEB)

    Minaya Ramirez, E., E-mail: minaya@ipno.in2p3.fr [Max-Planck-Institut für Kernphysik, 69117 Heidelberg (Germany); Alfaurt, P.; Aouadi, M.; Ascher, P.; Blank, B. [Centre d’Etudes Nucléaires de Bordeaux-Gradignan (France); Blaum, K. [Max-Planck-Institut für Kernphysik, 69117 Heidelberg (Germany); Cam, J.-F. [Laboratoire de Physique Corpusculaire, Caen (France); Chauveau, P. [Grand Accélérateur National d’Ions Lourds CEA/DSM-CNRS-IN2P3, Caen (France); Daudin, L. [Centre d’Etudes Nucléaires de Bordeaux-Gradignan (France); Delahaye, P. [Grand Accélérateur National d’Ions Lourds CEA/DSM-CNRS-IN2P3, Caen (France); Delalee, F. [Centre d’Etudes Nucléaires de Bordeaux-Gradignan (France); Dupré, P. [Centre de Sciences Nucléaires et de Sciences de la Matière, Orsay (France); El Abbeir, S.; Gerbaux, M.; Grévy, S.; Guérin, H. [Centre d’Etudes Nucléaires de Bordeaux-Gradignan (France); Lunney, D. [Centre de Sciences Nucléaires et de Sciences de la Matière, Orsay (France); Metz, F. [Max-Planck-Institut für Kernphysik, 69117 Heidelberg (Germany); Naimi, S. [Riken, 2-1 Hirosawa, Wako, Saitama 351-0198 (Japan); Perrot, L. [Institut de Physique Nucléaire, Orsay (France); and others

    2016-06-01

    The DESIR (decay, excitation and storage of radioactive ions) facility at GANIL-SPIRAL2 will receive a large variety of exotic nuclei at low energy (up to 60 keV) with high intensities. However, the production methods of radioactive beams are non selective, limiting the purity of the beams of interest. Moreover, the high precision needed for nuclear structure and astrophysics studies using beta decay spectroscopy, laser spectroscopy and trap-based experiments at DESIR requires highly pure samples of exotic nuclei. The aim of the double-Pennig-trap mass separator PIPERADE is to deliver large and very pure samples of exotic nuclei to the different experiments in DESIR. New excitation schemes and a large inner diameter of the first trap will mitigate space charge effects to attempt trapping of up to 10{sup 5} ions per pulse. The purification cycle will be performed in a few milliseconds so that short-lived nuclei can be purified. To extract the nuclides of interest from the large amount of isobaric contaminants, a resolving power of 10{sup 5} is mandatory. Afterwards the ions of interest will be accumulated in the second trap until they constitute a sufficiently pure sample for the measurements. The status of the project is presented.

  16. Enhancing glycan isomer separations with metal ions and positive and negative polarity ion mobility spectrometry-mass spectrometry analyses

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Xueyun; Zhang, Xing; Schocker, Nathaniel S.; Renslow, Ryan S.; Orton, Daniel J.; Khamsi, Jamal; Ashmus, Roger A.; Almeida, Igor C.; Tang, Keqi; Costello, Catherine E.; Smith, Richard D.; Michael, Katja; Baker, Erin S.

    2016-09-07

    Glycomics has become an increasingly important field of research since glycans play critical roles in biology processes ranging from molecular recognition and signaling to cellular communication. Glycans often conjugate with other biomolecules such as proteins and lipids, and alter their properties and functions, so understanding the effect glycans have on cellular systems is essential. However the analysis of glycans is extremely difficult due to their complexity and structural diversity (i.e., the number and identity of monomer units, and configuration of their glycosidic linkages and connectivities). In this work, we coupled ion mobility spectrometry with mass spectrometry (IMS-MS) to characterize glycan standards and biologically important isomers of synthetic αGal-containing O-glycans including glycotopes of the protozoan parasite Trypanosoma cruzi, which is the causative agent of Chagas disease. IMS-MS results showed significant differences for the glycan structural isomers when analyzed in positive and negative polarity and complexed with different metal cations. These results suggest specific metal ions or ion polarities could be used to target and baseline separate glycan isomers of interest with IMS-MS.

  17. Combined Reversed Phase HPLC, Mass Spectrometry, and NMR Spectroscopy for a Fast Separation and Efficient Identification of Phosphatidylcholines

    Directory of Open Access Journals (Sweden)

    Jan Willmann

    2011-01-01

    Full Text Available In respect of the manifold involvement of lipids in biochemical processes, the analysis of intact and underivatised lipids of body fluids as well as cell and tissue extracts is still a challenging task, if detailed molecular information is required. Therefore, the advantage of combined use of high-pressure liquid chromatography (HPLC, mass spectrometry (MS, and nuclear magnetic resonance (NMR spectroscopy will be shown analyzing three different types of extracts of the ubiquitous membrane component phosphatidylcholine. At first, different reversed phase modifications were tested on phosphatidylcholines (PC with the same effective carbon number (ECN for their applicability in lipid analysis. The results were taken to improve the separation of three natural PC extract types and a new reversed phase (RP-HPLC method was developed. The individual species were characterized by one- and two-dimensional NMR and positive or negative ion mode quadrupole time of flight (q-TOF-MS as well as MS/MS techniques. Furthermore, ion suppression effects during electrospray ionisation (ESI, difficulties, limits, and advantages of the individual analytical techniques are addressed.

  18. Direct determination of melamine in dairy products by gas chromatography/mass spectrometry with coupled column separation

    Energy Technology Data Exchange (ETDEWEB)

    Xu Xiaomin [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou, 310028 (China); Zhejiang Provincial Center for Disease Control and Prevention, Hangzhou, 310051 (China); Ren Yiping [Zhejiang Provincial Center for Disease Control and Prevention, Hangzhou, 310051 (China); Zhu Yun [Xinjiang Uygur Autonomous Region Center for Disease Control and Prevention, Urumchi, 830002 (China); Cai Zengxuan; Han Jianlong; Huang Baifen [Zhejiang Provincial Center for Disease Control and Prevention, Hangzhou, 310051 (China); Zhu Yan, E-mail: zhuyan@zju.edu.cn [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou, 310028 (China)

    2009-09-14

    A coupled capillary column system was developed for the qualitative and quantitative determination of melamine with isotope internal standard in dairy products by gas chromatography/mass spectrometry (GC/MS) without derivatization. A 30 m of DB-5ms ((5%-phenyl)-methylpolysiloxane, 0.25 mm i.d., 0.25 {mu}m df) coupled with a 1.5 m of Innowax (polyethylene glycol, 0.32 mm i.d., 0.25 {mu}m df) by a quartz capillary column connector was introduced as separation column. Three advantages were discussed for the coupled system. The sample was fortified with a ring-labeled {sup 13}C{sub 3}{sup 15}N{sub 3}-melamine as an isotope internal standard and extracted by 1% of trichloroacetic acid aqueous solution. 2.2% of lead acetate solution was then added to deposit protein in the sample matrix. After purification by cation exchange cartridge, the sample solution was directly injected and detected by GC/MS. A six-point calibration curve ranging from 0.05 to 2 mg kg{sup -1} of melamine in sample was used to establish instrument response. The recovery was 93.9-102% with relative standard deviation from 3.1 to 8.7% when isotope internal standard used. The calculated method detection limit was 0.01 mg kg{sup -1}.

  19. Design and commissioning of a timestamp-based data acquisition system for the DRAGON recoil mass separator

    Energy Technology Data Exchange (ETDEWEB)

    Christian, G.; Fallis, J.; Hutcheon, D.; Olchanski, K.; Ruiz, C. [TRIUMF, Vancouver (Canada); Akers, C. [TRIUMF, Vancouver (Canada); University of York, Department of Physics, Heslington, York (United Kingdom); Connolly, D. [Colorado School of Mines, Department of Physics, Golden, CO (United States)

    2014-04-15

    The DRAGON recoil mass separator at TRIUMF exists to study radiative proton and alpha capture reactions, which are important in a variety of astrophysical scenarios. DRAGON experiments require a data acquisition system that can be triggered on either reaction product (γ-ray or heavy ion), with the additional requirement of being able to promptly recognize coincidence events in an online environment. To this end, we have designed and implemented a new data acquisition system for DRAGON, which consists of two independently triggered readouts. Events from both systems are recorded with timestamps from a 20 MHz clock that are used to tag coincidences in the earliest possible stage of the data analysis. Here we report on the design, implementation, and commissioning of the new DRAGON data acquisition system, including the hardware, trigger logic, coincidence reconstruction algorithm, and live time considerations. We also discuss the results of an experiment commissioning the new system, which measured the strength of the E{sub c.m.} = 1113 keV resonance in the {sup 20} Ne(p, γ){sup 21} Na radiative proton capture reaction. (orig.)

  20. Enantiomeric separation of free L- and D-amino acids in hydrolyzed protein fertilizers by capillary electrophoresis tandem mass spectrometry.

    Science.gov (United States)

    Sánchez-Hernández, Laura; Serra, Nuria Sierras; Marina, María Luisa; Crego, Antonio L

    2013-05-29

    Two capillary electrophoresis-tandem mass spectrometry (CE-MS(2)) methods were optimized in this work using cyclodextrins (CDs) as chiral selectors in order to determine the degree of racemization of the free amino acids contained in different hydrolyzed protein fertilizers used as plant biostimulants. The methodologies developed were characterized by the specificity of MS(2) experiments enabling the identification of all protein amino acids, except for cysteine. The enantiomeric separation of up to 14 amino acids was achieved with resolutions above 1.0 and limits of detection between 0.02 and 0.8 μM. The methods were applied to the analysis of complex samples such as hydrolyzed protein fertilizers to evaluate the presence of d-amino acids after different kinds of hydrolysis treatments. The results corroborated the absence or almost negligible presence of enantiomeric conversions of the L-amino acids into D-amino acids in the case of fertilizers obtained by enzymatic hydrolysis, as well as the high racemization rate for those obtained through a chemical hydrolysis.

  1. Compact ultrafast orthogonal acceleration time-of-flight mass spectrometer for on-line gas analysis by electron impact ionization and soft single photon ionization using an electron beam pumped rare gas excimer lamp as VUV-light source.

    Science.gov (United States)

    Mühlberger, F; Saraji-Bozorgzad, M; Gonin, M; Fuhrer, K; Zimmermann, R

    2007-11-01

    Orthogonal acceleration time-of-flight mass spectrometers (oaTOFMS), which are exhibiting a pulsed orthogonal extraction of ion bunches into the TOF mass analyzer from a continuous primary ion beam, are well-suited for continuous ionization methods such as electron impact ionization (EI). Recently an electron beam pumped rare gas excimer lamp (EBEL) was introduced, which emits intensive vacuum UV (VUV) radiation at, e.g., 126 nm (argon excimer) and is well suited as the light source for soft single photon ionization (SPI) of organic molecules. In this paper, a new compact oaTOFMS system which allows switching between SPI, using VUV-light from an EBEL-light source, and conventional EI is described. With the oaTOFMS system, EBEL-SPI and EI mass spectral transients can be recorded at very high repetition rates (up to 100 kHz), enabling high duty cycles and therefore good detection efficiencies. By using a transient recorder card with the capability to perform on-board accumulation of the oaTOF transients, final mass spectra with a dynamic range of 106 can be saved to the hard disk at a rate of 10 Hz. As it is possible to change the ionization modes (EI and SPI) rapidly, a comprehensive monitoring of complex gases with highly dynamic compositions, such as cigarette smoke, is possible. In this context, the EI based mass spectra address the bulk composition (compounds such as water, oxygen, carbon dioxide, etc. in the up to percentage concentration range) as well as some inorganic trace gases such as argon, sulfur dioxide, etc. down to the low ppm level. The EBEL-SPI mass spectra on the other hand are revealing the organic composition down to the lower ppb concentration range.

  2. HPLC separation and GC-MS identification of the polar components of coal liquids. [High pressure liquid chromatography, gas chromatography-mass spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Satoh, M.; Tanabe, K.; Uchino, H.; Yokoyama, S.; Sanada, Y.

    1984-01-01

    The polar components in the 200-400 C fraction of Akabira coal liquids were separated by high pressure liquid chromatography using an amine-based column. By varying the CHCl/sub 3/ concentration in the solvent, basic, neutral and acid fractions were obtained. These were then investigated separately using infrared spectroscopy, flame ionization detection-gas chromatography and gas chromatography-mass spectroscopy. The basic fraction contained alkyltetrahydroquinolines, the neutral fraction, alkylphenols and alkylcarbazoles; and the acid fraction, alkylphenols. 15 references.

  3. Proteomic profiling of amniotic fluid in premature labor using two-dimensional liquid separation and mass spectrometry

    Science.gov (United States)

    Bujold, Emmanuel; Romero, Roberto; Kusanovic, Juan Pedro; Erez, Offer; Gotsch, Francesca; Chaiworapongsa, Tinnakorn; Gomez, Ricardo; Espinoza, Jimmy; Vaisbuch, Edi; Kim, Yeon Mee; Edwin, Samuel; Pisano, Mike; Allen, Beth; Podust, Vladimir N.; Dalmasso, Enrique A.; Rutherford, Jennifer; Rogers, Wade; Moser, Allan; Yoon, Bo Hyun; Barder, Tim

    2011-01-01

    Objective Simultaneous analysis of the protein composition of biological fluids is now possible. Such an approach can be used to identify biological markers of disease and to understand the pathophysiology of disorders that have eluded classification, diagnosis, and treatment. The purpose of this study was to analyze the differences in protein composition in amniotic fluid of patients in preterm labor. Study Design Amniotic fluid was obtained by amniocenteses from three groups of women with preterm labor and intact membranes: (1) women without intra-amniotic infection/inflammation (IAI) who delivered at term; (2) women without intra-amniotic IAI who delivered a preterm neonate; and (3) women with IAI. Intra-amniotic infection was defined as a positive amniotic fluid culture for microorganisms. Intra-amniotic inflammation was defined as an elevated amniotic fluid interleukin (IL)-6 (≥2.3 ng/mL). Two-dimensional (2D) chromatography was used for analysis. The first dimension separated proteins by isoelectric point, while the second, by the degree of hydrophobicity. 2D protein maps were generated using different experimental conditions (reducing agents as well as protein concentration). The maps were used to discern subsets of isoelectric point/hydrophobicity containing differentially expressed proteins. Protein identification of differentially expressed fractions was conducted with mass spectrometry. ELISA immunoassays as well as surface-enhanced laser desorption/ionization time-of-flight mass spectrometry (SELDI-TOF MS)--based on-chip antibody capture immunoassay were also used for confirmation of a specific protein that was differentially expressed. Results 1) Amniotic fluid protein composition can be analyzed using a combination of 2D liquid chromatography and mass spectrometry for the identification of proteins differentially expressed in patients in preterm labor; 2) While total insulin-like growth factor-binding protein-1 (IGFBP-1) concentration did not change

  4. Proteomic profiling of amniotic fluid in preterm labor using two-dimensional liquid separation and mass spectrometry.

    Science.gov (United States)

    Bujold, Emmanuel; Romero, Roberto; Kusanovic, Juan Pedro; Erez, Offer; Gotsch, Francesca; Chaiworapongsa, Tinnakorn; Gomez, Ricardo; Espinoza, Jimmy; Vaisbuch, Edi; Mee Kim, Yeon; Edwin, Samuel; Pisano, Mike; Allen, Beth; Podust, Vladimir N; Dalmasso, Enrique A; Rutherford, Jennifer; Rogers, Wade; Moser, Allan; Yoon, Bo Hyun; Barder, Tim

    2008-10-01

    Simultaneous analysis of the protein composition of biological fluids is now possible. Such an approach can be used to identify biological markers of disease and to understand the pathophysiology of disorders that have eluded classification, diagnosis, and treatment. The purpose of this study was to analyze the differences in protein composition of the amniotic fluid of patients in preterm labor. Amniotic fluid was obtained by amniocentesis from three groups of women with preterm labor and intact membranes: (1) women without intra-amniotic infection/inflammation (IAI) who delivered at term, (2) women without IAI who delivered a preterm neonate, and (3) women with IAI. Intra-amniotic infection was defined as a positive amniotic fluid culture for microorganisms. Intra-amniotic inflammation was defined as an elevated amniotic fluid interleukin (IL)-6 (> or =2.3 ng/mL). Two-dimensional (2D) chromatography was used for analysis. The first dimension separated proteins by isoelectric point, while the second, by the degree of hydrophobicity. 2D protein maps were generated using different experimental conditions (reducing agents as well as protein concentration). The maps were used to discern subsets of isoelectric point/hydrophobicity containing differentially expressed proteins. Protein identification of differentially expressed fractions was conducted with mass spectrometry. Enzyme-linked immunosorbent assays (ELISA) as well as surface-enhanced laser desorption/ionization time-of-flight mass spectrometry (SELDI-TOF MS)-based on-chip antibody capture immunoassays were also used for confirmation of a specific protein that was differentially expressed. (1) Amniotic fluid protein composition can be analyzed using a combination of 2D liquid chromatography and mass spectrometry for the identification of proteins differentially expressed in patients in preterm labor. (2) While total insulin-like growth factor-binding protein-1 (IGFBP-1) concentration did not change, IGFBP-1

  5. Separate and combined associations of body-mass index and abdominal adiposity with cardiovascular disease : collaborative analysis of 58 prospective studies

    NARCIS (Netherlands)

    Wormser, David; Kaptoge, Stephen; Di Angelantonio, Emanuele; Wood, Angela M.; Pennells, Lisa; Thompson, Alex; Sarwar, Nadeem; Kizer, Jorge R.; Lawlor, Debbie A.; Nordestgaard, Borge G.; Ridker, Paul; Salomaa, Veikko; Stevens, June; Woodward, Mark; Sattar, Naveed; Collins, Rory; Thompson, Simon G.; Whitlock, Gary; Danesh, John

    2011-01-01

    Background Guidelines differ about the value of assessment of adiposity measures for cardiovascular disease risk prediction when information is available for other risk factors. We studied the separate and combined associations of body-mass index (BMI), waist circumference, and waist-to-hip ratio wi

  6. Separate and combined associations of body-mass index and abdominal adiposity with cardiovascular disease: collaborative analysis of 58 prospective studies

    DEFF Research Database (Denmark)

    Wormser, David; Kaptoge, Stephen; Di Angelantonio, Emanuele

    2011-01-01

    Guidelines differ about the value of assessment of adiposity measures for cardiovascular disease risk prediction when information is available for other risk factors. We studied the separate and combined associations of body-mass index (BMI), waist circumference, and waist-to-hip ratio with risk...

  7. Optimization of on-line hydrogen stable isotope ratio measurements of halogen- and sulfur-bearing organic compounds using elemental analyzer–chromium/high-temperature conversion isotope ratio mass spectrometry (EA-Cr/HTC-IRMS)

    Science.gov (United States)

    Gehre, Matthias; Renpenning, Julian; Geilmann, Heike; Qi, Haiping; Coplen, Tyler B.; Kümmel, Steffen; Ivdra, Natalija; Brand, Willi A.; Schimmelmann, Arndt

    2017-01-01

    Rationale: Accurate hydrogen isotopic analysis of halogen- and sulfur-bearing organics has not been possible with traditional high-temperature conversion (HTC) because the formation of hydrogen-bearing reaction products other than molecular hydrogen (H2) is responsible for non-quantitative H2 yields and possible hydrogen isotopic fractionation. Our previously introduced, new chromium-based EA-Cr/HTC-IRMS (Elemental Analyzer–Chromium/High-Temperature Conversion Isotope Ratio Mass Spectrometry) technique focused primarily on nitrogen-bearing compounds. Several technical and analytical issues concerning halogen- and sulfur-bearing samples, however, remained unresolved and required further refinement of the reactor systems.

  8. High-throughput cytochrome P450 (CYP) inhibition screening via cassette probe-dosing strategy. I. Development of direct injection/on-line guard cartridge extraction/tandem mass spectrometry for the simultaneous detection of CYP probe substrates and their metabolites.

    Science.gov (United States)

    Bu, H Z; Magis, L; Knuth, K; Teitelbaum, P

    2000-01-01

    A highly efficient direct injection/on-line guard cartridge extraction/tandem mass spectrometry (DI-GCE/MS/MS) method utilizing electrospray polarity switching was developed for the simultaneous detection of probe substrates and marker metabolites of seven human hepatic cytochrome P450 (CYP) isozymes: CYP1A2, 2A6, 3A4, 2C9, 2C19, 2D6 and 2E1. Microsomal incubations were terminated with formic acid, centrifuged, and the resulting supernatants were injected for analysis by DI-GCE/MS/MS. This method employed an extremely short C(18) cartridge (4 mm in length) which allowed rapid cleanup of sample matrices while retaining the analytes an appropriate time (2. 0-2.2 min). From 1.5 to 2.7 min the effluent was directed to the mass spectrometer for detection otherwise diverted to waste. As a result of the efficient on-line extraction, matrix (e.g., salts and proteins) suppression was minimized. In addition, no visible source contamination was observed and system performance (chromatographic and mass spectrometric) did not significantly deteriorate after 500 consecutive injections. Electrospray polarity switching was strategically executed on a Micromass Quattro II mass spectrometer by establishing dummy ion transitions to protect the analytes from the interference of the overwhelming noise which was unavoidable for the first transition scanned following each polarity switch. This unique strategy led to the simultaneous detection of seven CYP probe substrates and seven corresponding marker metabolites (12 by positive mode and 2 by negative mode).

  9. Determination of free cortisol and free cortisone in human urine by on-line turbulent flow chromatography coupled to fused-core chromatography-tandem mass spectrometry (TFC-HPLC-MS/MS).

    Science.gov (United States)

    Sánchez-Guijo, Alberto; Hartmann, Michaela F; Shi, Lijie; Remer, Thomas; Wudy, Stefan A

    2014-01-01

    Urinary free cortisol and urinary free cortisone are decisive markers for the diagnosis of syndromes related to the dysfunction of the adrenal gland or to evaluate certain enzymatic disorders. Here, we present a new method, designed for routine laboratory use, which enables quick determination of these analytes with minor sample workup. Turbulent flow chromatography shortens sample preparation, and connection to a fused-core particle-packed column (rugged amide-embedded C18 phase) permits a rapid and effective separation of the analytes, as well as additional separation from other related and isobaric compounds present in urine. Urinary isobaric compounds were successfully identified. The method requires only 100 μl of urine supernatant per sample. The total time between injections is 9.5 min. The solvents used for both turbulent and analytical chromatography are water and methanol, and the relatively low flows needed during the method resulted in an extended life of the columns. Linearity showed a R (2) > 0.994. Limit of detection and limit of quantification are 0.5 and 1.0 ng/ml for cortisone and 1.0 and 2.0 ng/ml for cortisol. Recoveries ranged from 99.7 to 109.1 % for cortisone and from 98.7 to 102.9 % for cortisol. Accuracy values (relative errors) for intra- and inter-assay experiments were always below 8 %, whereas precision (percent CV) ranged from 3.7 to 10.7 %. No matrix effects were detected during the validation process. The reproducibility for each analyte's retention time was excellent, with a coefficient of variation always below 0.2 %. The final validation step included the study of urine samples from healthy children and from children previously diagnosed with corticoidal disorders. The high selectivity achieved enables quick data handling.

  10. 行业竞争力导向的在线大规模定制产品族规模优化方法%Size Optimization Method for On-line Mass Customization of Product Family

    Institute of Scientific and Technical Information of China (English)

    伊辉勇; 刘伟

    2011-01-01

    客户导向的产品族规模优化方法在与竞争对手产品族相比时并不一定能使在线定制服务提供商获得竞争优势,还需要考虑竞争对手产品族对其产品族规模的影响.产品族规模优化应该在满足工程技术约束和制造规模经济性的基础上,引入产品功能配置元和结构配置元,结合客户需求强度和偏好分析,构建了行业竞争力导向的在线大规模定制产品族规模优化方法,最后结合案例证明该方法的有效性.%Manufacturers are now offering product customization services to the end customer. Customer satisfaction becomes important for manufacturers to stay competitive. Satisfying customers with the product family is difficult for a company to achieve. To achieve competitive advantages, a company may need to consider potential influence of competitive product family. The product family is defined from the perspectives of engineering design and manufacturing. The concept can help people understand product features and component configuration elements. We use a survey to evaluate competitiveness of product family for known and unknown family structure of competitive products. Product family size optimization method and steps for on-line mags customization of industrial competitiveness-oriented is built.In the first part, this paper discusses the concept of product family. We use the concept to build topological structure of product family. The product family scale is defined from the perspectives of engineering design and manufacturing. In the second part, we discuss the use of product family scale optimization model to gain competitiveness. We evaluate the product family structure of competitors through the screening and identification of industry competitors, the comparison and evaluation of product family, and the optimization of product family structure and size. When the product family structure of competitors is unknown, we directly evaluate product family and

  11. Continuous Flow Liquid Microjunction Surface Sampling Probe Connected On-line with HPLC/MS for Spatially Resolved Analysis of Small Molecules and Proteins

    Energy Technology Data Exchange (ETDEWEB)

    Van Berkel, Gary J [ORNL; Kertesz, Vilmos [ORNL

    2013-01-01

    RATIONALE: A continuous flow liquid microjunction surface sampling probe extracts soluble material from surfaces for direct ionization and detection by MS. Demonstrated here is the on-line coupling of such a probe with HPLC/MS enabling extraction, separation and detection of small molecules and proteins from surfaces in a spatially resolved (~0.5 mm diameter spots) manner. Methods: A continuous flow liquid microjunction surface sampling probe was connected to a 6-port, 2-position valve for extract collection and injection to an HPLC column. A QTRAP 5500 hybrid triple quadrupole linear ion trap equipped with a Turbo V ion source operated in positive ESI mode was used for all experiments. System operation was tested with extraction, separation and detection of propranolol and associated metabolites from drug dosed tissues and proteins from dried sheep blood spots on paper. Results: Confirmed in the tissue were the parent drug and two different hydroxypropranolol glucuronides. The mass spectrometric response for these compounds from different locations in the liver showed an increase with increasing extraction time (5, 20 and 40 s extractions). For on-line separation and detection/identification of extracted proteins from dried sheep blood spots, two major protein peaks dominated the chromatogram and could be correlated with the expected masses for the hemoglobin and chains. Conclusions: Spatially resolved sampling, separation, and detection of small molecules and proteins from surfaces can be accomplished using a continuous flow liquid microjunction surface sampling probe coupled on-line with HPLC/MS detection.

  12. High resolution LC-ESI-TOF-mass spectrometry method for fast separation, identification, and quantification of 12 isoflavones in soybeans and soybean products.

    Science.gov (United States)

    Lee, Mi Jin; Chung, Ill-Min; Kim, Hunjung; Jung, Mun Yhung

    2015-06-01

    A high resolution LC-ESI-TOF-MS analytical method was established for the rapid isolation, identification, and quantification of 12 isoflavones in soybean and soybean products. Individual isoflavones were identified on the basis of the accurate mass data of their respective protonated mass ions, Na or K adduct ions, fragment ions, and isotope ion patterns. The protonated mass ions of isoflavones were extracted for their quantification in soybean products. Twelve different isoflavones in the soybean products were fully separated, identified and quantified within 12min separation time. The established LC-TOF/MS was an effective analytical method for the simultaneous characterization and quantification of isoflavones with exceptionally short analytical time, high selectivity, a high linearity (r(2)>0.992) in a wide range, low LOD and LOQ, high precision, inter-and intra-day repeatability, and no significant matrix effect. Furthermore, it requires simple sample preparation procedure (solvent extraction, dilution, and syringe filtration).

  13. The development of a rugged, field portable membrane introduction tandem mass spectrometer and its use as an on-line monitor for volatile and semi-volatile organic compounds in the Alberta Oil Sands

    Energy Technology Data Exchange (ETDEWEB)

    Nicholas, Davey [Applied Environmental Research Laboratories (Canada)

    2011-07-01

    In Alberta, steam assisted gravity drainage is a process often used to enhance oil recovery from open pit mining or heavy oil reservoirs. This process releases volatile and semi-volatile organic compounds (VOC/SVOC) into the atmosphere or process waters. Thus a field portable analytical instrument is needed to monitor VOC/SVOC. The aim of this paper is to present the development of such a tool and its results. A field portable membrane introduction tandem mass spectrometer was developed through a multiyear collaboration between Statoil, NTNU and Griffin. This technology can analyze both atmospheric and aqueous environmental samples. Calibrations of the system were carried out in a laboratory and the system was then tested in two field trials in the Alberta oil sands. This work gives results of these different tests and explores the use of thermally assisted membrane interfaces and in-membrane trap and release strategies.

  14. Synthesis of internal labeled standards of melatonin and its metabolite N1-acetyl-N2-formyl-5-methoxykynuramine for their quantification using an on-line liquid chromatography-electrospray tandem mass spectrometry system.

    Science.gov (United States)

    Almeida, Eduardo A; Klitzke, Clécio F; Martinez, Glaucia R; Medeiros, Marisa H G; Di Mascio, Paolo

    2004-01-01

    Melatonin (N-acetyl-5-methoxytryptamine) is implicated in physiologic changes related to light-dark cycles and has been recently found to display antioxidant properties. It is known that the reaction of melatonin with certain reactive oxygen and nitrogen species, such as hydrogen peroxide and singlet oxygen, produces N1-acetyl-N2-formyl-5-methoxykynuramine (AFMK). We report herein on the development of a new liquid chromatography/tandem mass spectrometry (LC/ESI/MS-MS) assay to quantitatively determine melatonin and AFMK. The stable isotopic internal standard of melatonin-D3 was synthesized by the reaction of 5-methoxytryptamine with deuterated acetyl chloride (CD3COCl). Labeled AFMK (AFMK-D3) was obtained after photooxidation of melatonin-D3. The predominant ion [M + H]+ in the full scan mass spectra of melatonin, melatonin-D3, AFMK and AFMK-D3 were located, respectively, at m/z = 233, 236, 265 and 268. The collision-induced dissociation of the molecules revealed a predominant fragment at m/z = 174 for melatonin and melatonin-D3 (loss of the N-acetyl group), and at m/z = 178 for AFMK and AFMK-D3 (loss of both the N-acetyl and the N-formyl groups). The m/z transitions from 233 to 174 (melatonin), from 236 to 174 (melatonin-D3), from 265 to 178 (AFMK), and from 268 to 178 (AFMK-D3) were therefore chosen for the multiple reaction monitoring detection experiments, ensuring a high specificity and an accurate quantification of melatonin and AFMK in human plasma.

  15. PSYM-WIDE: A Survey for Large-separation Planetary-mass Companions to Late Spectral Type Members of Young Moving Groups

    Science.gov (United States)

    Naud, Marie-Eve; Artigau, Étienne; Doyon, René; Malo, Lison; Gagné, Jonathan; Lafrenière, David; Wolf, Christian; Magnier, Eugene A.

    2017-09-01

    We present the results of a direct imaging survey for very large separation (>100 au), low-mass companions around 95 nearby young K5–L5 stars and brown dwarfs. They are high-likelihood candidates or confirmed members of the young (≲150 Myr) β Pictoris and AB Doradus moving groups (ABDMG) and the TW Hya, Tucana–Horologium, Columba, Carina, and Argus associations. Images in i\\prime and z\\prime filters were obtained with the Gemini Multi-Object Spectrograph (GMOS) on Gemini South to search for companions down to an apparent magnitude of z\\prime ∼ 22–24 at separations ≳20″ from the targets and in the remainder of the wide 5.‧5 × 5.‧5 GMOS field of view. This allowed us to probe the most distant region where planetary-mass companions could be gravitationally bound to the targets. This region was left largely unstudied by past high-contrast imaging surveys, which probed much closer-in separations. This survey led to the discovery of a planetary-mass (9–13 {M}{Jup}) companion at 2000 au from the M3V star GU Psc, a highly probable member of ABDMG. No other substellar companions were identified. These results allowed us to constrain the frequency of distant planetary-mass companions (5–13 {M}{Jup}) to {0.84}-0.66+6.73% (95% confidence) at semimajor axes between 500 and 5000 au around young K5–L5 stars and brown dwarfs. This is consistent with other studies suggesting that gravitationally bound planetary-mass companions at wide separations from low-mass stars are relatively rare.

  16. Oligosaccharide mapping of heparinase I-treated heparins by hydrophilic interaction liquid chromatography separation and online fluorescence detection and electrospray ionization-mass spectrometry characterization.

    Science.gov (United States)

    Galeotti, Fabio; Volpi, Nicola

    2016-05-06

    Oligosaccharide mapping based on enzyme cleavage provides a useful molecular fingerprint of the heparin structure revealing detailed structural information regarding its sequence and the content of part of the ATIII-binding region. This approach is performed by strong-anion exchange (SAX)-HPLC separation which is incompatible with MS requiring purification of oligosaccharides for their conclusive identification. We report a novel oligosaccharide mapping strategy based on the HILIC separation of the main heparin disaccharides/oligosaccharides released by heparinase I, fluorotagged with 2-aminoacridone and on-line detected by a fluorescence detector and characterized by ESI-MS. The application of a polar solvent having a high pH with acetonitrile avoided desulfation enabling a simple and accurate structural oligosaccharide assignment. Oligosaccharide mapping, or merely complete disaccharide composition, may be performed on nanogram-scale by the fluorescence detector vs micrograms useful for classical SAX-HPLC. Additionally, only widely commercially available heparin lyase I is necessary, without the use of expensive heparinases II and III. Contrary to SAX-HPLC, this novel HILIC approach is able to separate and identify the saturated trisulfated disaccharide belonging to the non-reducing end of heparin chains. Finally, the content of 3-O-sulfo groups of the ATIII-binding region is determined.

  17. Are on-line currencies virtual banknotes?

    OpenAIRE

    Stephen F. Quinn; William Roberds

    2003-01-01

    The history of money is marked by innovations that have expanded the role of "inside money"-money created by the private sector. For instance, the past few years have seen the development of several types of on-line payment arrangements, some of which have been dubbed "on-line currencies." ; This article examines the likely success or failure of on-line currencies by means of a historical analogy. The discussion compares the introduction of on-line currencies to the debut of the bearer bankno...

  18. On-Line Impact Load Identification

    Directory of Open Access Journals (Sweden)

    Krzysztof Sekuła

    2013-01-01

    Full Text Available The so-called Adaptive Impact Absorption (AIA is a research area of safety engineering devoted to problems of shock absorption in various unpredictable scenarios of collisions. It makes use of smart technologies (systems equipped with sensors, controllable dissipaters and specialised tools for signal processing. Examples of engineering applications for AIA systems are protective road barriers, automotive bumpers or adaptive landing gears. One of the most challenging problems for AIA systems is on-line identification of impact loads, which is crucial for introducing the optimum real-time strategy of adaptive impact absorption. This paper presents the concept of an impactometer and develops the methodology able to perform real-time impact load identification. Considered dynamic excitation is generated by a mass M1 impacting with initial velocity V0. An analytical formulation of the problem, supported with numerical simulations and experimental verifications is presented. Two identification algorithms based on measured response of the impacted structure are proposed and discussed. Finally, a concept of the AIA device utilizing the idea of impactometer is briefly presented.

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

    Science.gov (United States)

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

    2009-02-01

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

  20. Separation of small molecular peptides with the same amino acid composition but different sequences by high performance liquid chromatography-electrospray ionization-mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Peptidomics has emerged as a new discipline in recent years. Mass spectrometry (MS) is the most universal and efficient tool for structure identification of proteins and peptides. However,there is a limitation for the identification of peptides with the same amino acid composition but different se-quences because these peptides have identical mass spectra of molecular ions. This paper presents a high performance liquid chromatography-electrospray ionization-mass spectrometry (HPLC-ESI-MS) method for the separation of small molecular peptides with the same amino acid composition but dif-ferent sequences. Two tripeptides of Gly-Ser-Phe and Gly-Phe-Ser were used as a model sample. The separation behavior has been investigated and the separation conditions have been optimized. Under the optimum conditions,good repeatability was achieved. The developed method could provide a helpful reference for the separation of other peptides with the same amino acid composition but different sequences in the study of proteomics and peptidomics.

  1. On line routing per mobile phone

    DEFF Research Database (Denmark)

    Bieding, Thomas; Görtz, Simon; Klose, Andreas

    2009-01-01

    On-line routing is concerned with building vehicle routes in an ongoing fashion in such a way that customer requests arriving dynamically in time are efficiently and effectively served. An indispensable prerequisite for applying on-line routing methods is mobile communication technology. Addition...

  2. 呼气中挥发性硫化物的质子转移反应质谱在线检测%On-line Detection of Volatile Sulfur Compounds in Breath Gas by Proton Transfer Reaction Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    沈成银; 王鸿梅; 黄超群; 陆燕; 夏磊; 陈小景; 王宏志; 储焰南

    2015-01-01

    利用自主研制的高灵敏呼气检测质子转移反应质谱( PTR-MS),对一名口臭受试者的口腔吹出气体、鼻子呼出气体和口腔内气体分别进行多组分实时监测,发现了该受试者呼气中3种引起口臭的挥发性硫化物( VSCs)的来源并不相同,其中甲硫醇主要来源于口腔,硫化氢和二甲基硫则主要来源于肺或呼吸道。本研究不仅发现了口腔内气体在PTR-MS呼气监测过程中的特征变化趋势,还分析了呼出气体中3种VSCs的来源,对于呼气的正确采样和检测具有重要的指导意义。%To develop a kind of noninvasive method of breath diagnosis in diseases, much attention has been paid to the study of the relation between diseases and volatile organic compounds in human breath gas. However, the gas in oral cavity was usually ignored in many studies of breath gas. The bad breath odor of a participant was studied by a home-made proton transfer reaction mass spectrometer( PTR-MS) . The breath via the mouth, breath via the nose and the air in the mouth cavity were monitored with the mode of multiple ion detect scans. The results show that three different volatile sulfur compounds that cause bad breath odor should be attributed to different sources. The source of methyl mercaptan in breath is oral cavity, and the source of hydrogen sulphide and dimethylsulfide in breath is lung or respiratory tract. The related result is very important to sampling and detection of breath gas.

  3. Separating the Chaff from the Oats: Evidence for a Conceptual Distinction between Count Noun and Mass Noun Aggregates

    Science.gov (United States)

    Middleton, Erica L.; Wisniewski, Edward J.; Trindel, Kelly A.; Imai, Mutsumi

    2004-01-01

    The English language makes a grammatical distinction between count nouns and mass nouns. For example, count nouns but not mass nouns can be pluralized and can appear with the indefinite article. Some scholars dismiss the distinction as an arbitrary convention of language whereas others suggest that it is conceptually based. The present studies…

  4. Automated 2D peptide separation on a 1D nano-LC-MS system

    DEFF Research Database (Denmark)

    Taylor, Paul; Nielsen, Peter A; Trelle, Morten Beck;

    2009-01-01

    the on-line separation of highly complex peptide mixtures directly coupled with mass spectrometry-based identification. Here, we present a variation of the traditional MudPIT protocol, combining highly sensitive chromatography using a nanoflow liquid chromatography system (nano-LC) with a two...

  5. Ultra high performance liquid chromatography with tandem mass spectrometry for rapid separation and identification of main constituents in Chinese herbal formula Xuan Hu Suo San.

    Science.gov (United States)

    Tang, Huaqi; Zhang, Xinyue; Luo, Shilin; Shang, Fei; Chen, Jianping; Wang, Jinghong; Duan, Xiaojie; Gao, Xiaoyan; Sun, Yikun

    2017-02-15

    Xuan Hu Suo San (XHSS) is a traditional Chinese medicine that has been extensively applied in the treatment of osteoarthritis for many years, however, its chemical composition has not yet been elucidated. Thus, a rapid, efficient, and precise method based on ultra high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry was applied in both positive- and negative-ion modes to rapidly separate and identify the main chemical ingredients in XHSS for the first time. Finally, with the optimised separation and detection method, a total of 57 compounds were simultaneously separated within 13 min, among which 14 compounds were confirmed by comparing retention time and MS data with reference standards and others were tentatively identified by comparing with reference literatures. This rapid and sensitive approach is highly useful for the identification and characterisation of chemical constituents, and provides fundamental and extensive information supporting further metabolic and pharmacokinetic studies of XHSS.

  6. CAPILLARY ELECTROPHORESIS-ELECTROSPRAY MASS SPECTRA OF THE HERBICIDES PARAQUAT AND DIQUAT

    Science.gov (United States)

    The positive ion electrospray mass spectra of the quaternary ammonium salt herbicides paraquat and diquat are examined by on-line separation with capillary electrophoresis (CE) and by direct infusion of the analytes. The analytes are separated by CE in 7-10 min at pH 3.9 in 50% m...

  7. Escapist Motives for On-line Gaming and Strengthening of Weak Ties

    DEFF Research Database (Denmark)

    Sudzina, Frantisek; Razmerita, Liana

    Due to advances of technology including faster and ubiquitously ac-cessible Internet connection, on-line gaming have grown tremendously in the last couple of years. The aim of this paper is to investigate whether escapist mo-tives for playing games are linked to strengthening of weak ties through...... on-line gaming. The research investigates Facebook and other on-line games separate-ly. A surprising result is that while most of the investigated escapist motives are positively correlated with strengthening of weak ties, the mundane breaking motive is negatively correlated with strengthening...

  8. On-line identification of lysergic acid diethylamide (LSD) in tablets using a combination of a sweeping technique and micellar electrokinetic chromatography/77 K fluorescence spectroscopy.

    Science.gov (United States)

    Fang, Ching; Liu, Ju-Tsung; Lin, Cheng-Huang

    2003-03-01

    This work describes a novel method for the accurate determination of lysergic acid diethylamide (LSD) in tablets. A technique involving sweeping-micellar electrokinetic chromatography (MEKC) was used for the initial on-line concentration and separation, after which a cryogenic molecular fluorescence experiment was performed at 77 K. Using this approach, not only the separation of LSD from the tablet extract was achieved, but on-line spectra were readily distinguishable and could be unambiguously assigned. The results are in agreement with analyses by gas chromatography-mass spectrometry (GC-MS). Thus, this method, which was found to be accurate, sensitive and rapid, has the potential for use as a reliable complementary method to GC-MS in such analyses.

  9. On-line matrix addition for detecting aerosol particles

    Institute of Scientific and Technical Information of China (English)

    ZHOU; Liuzhu; ZHU; Yuan; GUO; Xiaoyong; ZHAO; Wenwu; ZHENG; Haiyang; Gu; Xuejun; FANG; Li; ZHANG; Weijun

    2006-01-01

    Single aerosol particles were measured by matrix-assisted laser desorption/ionization (MALDI) with an aerosol time-of-flight mass spectrometer (ATOFMS). The inlet to the ATOFMS was coupled with an evaporation/condensation flow cell that allowed matrix addition by condensation onto the particles. The coated particles entered the ion source through three-stage differentially pumped capillary inlet and were then ionized by a focused 266 nm Nd:YAG laser. The mass spectra and aerodynamic size of the single particles can be obtained simultaneously. The on-line matrix addition technique makes it possible to identify biological aerosols in real-time.

  10. Effect of bend separation distance on the mass transfer in back-to-back pipe bends arranged in a 180° configuration

    Science.gov (United States)

    Chen, X.; Le, T.; Ewing, D.; Ching, C. Y.

    2016-12-01

    The mass transfer to turbulent flow through back-to-back pipe bends arranged in a 180° configuration with different lengths of pipe between the bends was measured using a dissolving gypsum test section in water. The measurements were performed for bends with a radius of curvature of 1.5 times the pipe diameter ( D) at a Reynolds numbers of 70,000 and Schmidt number of 1280. The maximum mass transfer in the bends decreased from approximately 1.8 times the mass transfer in the upstream pipe when there was no separation distance between the bends to 1.7 times when there was a 1 D or 5 D length of pipe between the bends. The location of the maximum mass transfer was on the inner sidewall downstream of the second bend when there was no separation distance between the bends. This location changed to the inner wall at the beginning of the second bend when there was a 1 D long pipe between the bends, and to the inner sidewall at the end of the first bend when there was a 5 D long pipe between the bends.

  11. Quantitative separation of the influence of copper (II) chloride mass migration on the chemo-responsive shape memory effect in polyurethane shape memory polymer

    Science.gov (United States)

    Lu, Haibao; Lu, Chunrui; Huang, Wei Min; Leng, Jinsong

    2016-10-01

    Chemo-responsive shape memory effect in polyurethane shape memory polymer (SMP) composite triggered by mass migration of copper (II) chloride (CuCl2) has been experimentally demonstrated. In this study, we present a comprehensive study on quantitative separation of the effect of CuCl2 particle mass migration on the chemo-responsive shape recovery behavior of polyurethane SMP composites with different concentrations of CuCl2 particles. It is found that the SMP is featured with a critical release rate of the mechanical energy storage associated with the shape recovery behavior due to mass migration of the CuCl2 particle. A sequence of molecular interactions among CuCl2 particles, polyurethane macromolecules and water molecules, i.e., assembly of the CuCl2 particle with polyurethane macromolecules, and then disassembly and dissolution of the CuCl2 particle in water, results in an acceleration of water-induced shape recovery of polyurethane SMP. This study focuses on the quantitative separation of the influence of mass migration on the chemo-responsive shape recovery behavior of polyurethane SMP in response to water. It is expected to promote and achieve the actuation of chemo-responsive SMPs in a fully controllable manner.

  12. Mechanical coupling between two innovative theories on erosion, transportation and phase-separation: Solving some long-standing problems in mass flows

    Science.gov (United States)

    Pudasaini, Shiva P.; Fischer, Jan-Thomas; Mergili, Martin

    2017-04-01

    Debris flows are gravity driven mixture flows of soil, sand, rock and water. The solid particles and viscous fluid governs the rheological properties, and their coupling significantly influences the dynamics. For example, debris flows can dramatically increase their volume and destructive potential, and become exceptionally mobile by entraining bed material. The mixture composition can evolve to strikingly change the spatial distribution of particles and fluid, and thus frictional and viscous resistance. So, erosion-deposition and phase-separation between solid and fluid, which strongly depend on material composition, play a critical role in debris flow dynamics. Proper understanding of these complex physical processes is very important in accurate description of impact forces, inundation areas, landscape evolution and developing reliable mitigation plans. Predicting the underlying processes of erosion, phase-separation and deposition in debris flow are long-standing challenges. However, due to lack of data and suitable models, there exists no runout prediction method that includes observed processes of erosion of dry and saturated beds, entrainment and diffusion of eroded material, grain sorting, phase-separation, levee/lobe formation and evolution of deposition patterns. Based on innovative mechanical models for erosion-deposition (Pudasaini and Fischer, 2016a) and phase-separation (Pudasaini and Fischer, 2016b) that explicitly consider changes in local flow compositions, and their basic/potential validations, we present a novel, unified, efficient and fully coupled solution method to these true multi-phase, three-dimensional mass flow problems. As debris flows are better described by a three-phase mixture that include viscous fluid, and fine and coarse grains as compared to often used single-phase models, we propose model extensions that consists of three-phases including yield strength. Thus, we present an advanced mass flow simulation model aiming to

  13. On-line generalized Steiner problem

    Energy Technology Data Exchange (ETDEWEB)

    Awerbuch, B.; Azar, Y.; Bartal, Y. [Tel Aviv Univ. (Israel)

    1996-12-31

    The Generalized Steiner Problem (GSP) is defined as follows. We are given a graph with non-negative weights and a set of pairs of vertices. The algorithm has to construct minimum weight subgraph such that the two nodes of each pair are connected by a path. We consider the on-line generalized Steiner problem, in which pairs of vertices arrive on-line and are needed to be connected immediately. We give a simple O(log{sup 2} n) competitive deterministic on-line algorithm. The previous best online algorithm (by Westbrook and Yan) was O({radical}n log n) competitive. We also consider the network connectivity leasing problem which is a generalization of the GSP. Here edges of the graph can be either bought or leased for different costs. We provide simple randomized O(log{sup 2} n) competitive algorithm based on the on-line generalized Steiner problem result.

  14. The war against on-line piracy

    OpenAIRE

    Harris, Julian

    2011-01-01

    A summary by Julian Harris, Deputy General Editor Amicus Curiae, of US attempts to control what it identifies as rogue Internet sites engaged in on-line piracy and opposition to such legislative moves.

  15. Topographical and Chemical Imaging of a Phase Separated Polymer Using a Combined Atomic Force Microscopy/Infrared Spectroscopy/Mass Spectrometry Platform.

    Science.gov (United States)

    Tai, Tamin; Karácsony, Orsolya; Bocharova, Vera; Van Berkel, Gary J; Kertesz, Vilmos

    2016-03-01

    In this paper, the use of a hybrid atomic force microscopy/infrared spectroscopy/mass spectrometry imaging platform was demonstrated for the acquisition and correlation of nanoscale sample surface topography and chemical images based on infrared spectroscopy and mass spectrometry. The infrared chemical imaging component of the system utilized photothermal expansion of the sample at the tip of the atomic force microscopy probe recorded at infrared wave numbers specific to the different surface constituents. The mass spectrometry-based chemical imaging component of the system utilized nanothermal analysis probes for thermolytic surface sampling followed by atmospheric pressure chemical ionization of the gas phase species produced with subsequent mass analysis. The basic instrumental setup, operation, and image correlation procedures are discussed, and the multimodal imaging capability and utility are demonstrated using a phase separated poly(2-vinylpyridine)/poly(methyl methacrylate) polymer thin film. The topography and both the infrared and mass spectral chemical images showed that the valley regions of the thin film surface were comprised primarily of poly(2-vinylpyridine) and hill or plateau regions were primarily poly(methyl methacrylate). The spatial resolution of the mass spectral chemical images was estimated to be 1.6 μm based on the ability to distinguish surface features in those images that were also observed in the topography and infrared images of the same surface.

  16. On-Line Acquisitions by LOLITA

    Directory of Open Access Journals (Sweden)

    Frances G. Spigai

    1970-12-01

    Full Text Available The on-line acquisition program (LOLITA in use at the Oregon State University Library is described in terms of development costs, equipment requirements, and overall design philosophy. In particular, the record format and content of records in the on-order file, and the on-line processing of these records (input, search, correction, output using a cathode ray tube display terminal are detailed.

  17. ACSEPP On-Line Electronic Payment Protocol

    Institute of Scientific and Technical Information of China (English)

    WANG Shao-bin; ZHU Xian; HONG Fan

    2004-01-01

    With analyzing the existing on-line electronic payment protocols, this paper presents a new on-line electronic payment protocol named ACSEPP: Anonymous, Convenient and Secure Electronic Payment Protocol.Its aim is to design a practical electronic payment protocol which is both secure and convenient.Without using PKI_CA frame, it realized the anonymity of consumer and merchant, the convenient of handling, the low cost of maintenance and the security.

  18. GPS Separator

    CERN Multimedia

    2016-01-01

    Footage of the 70 degree ISOLDE GPS separator magnet MAG70 as well as the switchyard for the Central Mass and GLM (GPS Low Mass) and GHM (GPS High Mass) beamlines in the GPS separator zone. In the GPS20 vacuum sector equipment such as the long GPS scanner 482 / 483 unit, faraday cup FC 490, vacuum valves and wiregrid piston WG210 and WG475 and radiation monitors can also be seen. Also the RILIS laser guidance and trajectory can be seen, the GPS main beamgate switch box and the actual GLM, GHM and Central Beamline beamgates in the beamlines as well as the first electrostatic quadrupoles for the GPS lines. Close up of the GHM deflector plates motor and connections and the inspection glass at the GHM side of the switchyard.

  19. First on-line $\\beta$-NMR on oriented nuclei magnetic dipole moments of the $\

    CERN Document Server

    Giles, T; Stone, N J; Van Esbroeck, K; White, G; Wöhr, A; Veskovic, M; Towner, I S; Mantica, P F; Prisciandaro, J I; Morrissey, D J; Fedosseev, V; Mishin, V I; Köster, U; Walters, W B

    2000-01-01

    The first fully on-line use of the angular distribution of $\\beta$ - emission in detection of NMR of nuclei oriented at low temperatures is reported. The magnetic moments of the single valence particle, intermediate mass, isotopes $^{67}$Ni($\

  20. Monolithic Superhydrophobic Polymer Layer with Photopatterned Virtual Channel for the Separation of Peptides Using Two-Dimensional Thin Layer Chromatography-Desorption Electrospray Ionization Mass Spectrometry

    Science.gov (United States)

    Han, Yehua; Levkin, Pavel; Abarientos, Irene; Liu, Huwei; Svec, Frantisek; Fréchet, Jean M.J.

    2010-01-01

    Superhydrophobic monolithic porous polymer layers with a photopatterned hydrophilic channel have been prepared. These layers were used for two-dimensional thin layer chromatography of peptides. The 50 μm thin poly(butyl methacrylate-co-ethylene dimethacrylate) layers supported onto 4.0 × 3.3 cm glass plates were prepared using UV-initiated polymerization in a simple glass mold. Photografting of a mixture of 2-acrylamido-2-methyl-1-propanesulfonic acid and 2-hydroxyethyl methacrylate carried out through a mask afforded a 600 μm wide virtual channel along one side of the layer. This channel, which contains ionizable functionalities, enabled the first dimension separation in ion exchange mode. The aqueous mobile phase migrates only through the channel due to the large difference in surface tension at the interface of the hydrophilic channel and the superhydrophobic monolith. The unmodified part of the layer featuring hydrophobic chemistry was then used for the reversed phase separation in the orthogonal second dimension. Practical application of our technique was demonstrated with a rapid 2D separation of a mixture of model peptides differing in hydrophobicity and isoelectric point using a combination of ion-exchange and reversed phase modes. In the former mode, the peptides migrated 11 mm in less than 1 min. Detection of fluorescently labeled peptides was achieved through UV light visualization. Separation of the native peptides was monitored directly using a desorption electrospray ionization (DESI) source coupled to a mass spectrometer. Unidirectional surface scanning with the DESI source was found suitable to determine both the location of each separated peptide and its molecular mass. PMID:20151661

  1. Determination of ultra-low level 129I in vegetation using pyrolysis for iodine separation and accelerator mass spectrometry measurements

    DEFF Research Database (Denmark)

    Hou, Xiaolin; Wang, Yanyun

    2016-01-01

    Radioactive isotopes of iodine are the most common radiological toxins from nuclear accidents due to their high release and high enrichment in human thyroid. Among the radioactive isotopes, long-lived 129I can not only be used for the estimation of the radioactive risk of short-lived radioactive...... isotopes of iodine to humans and ecosystems, but also for the investigation of the biogeochemical cycle and environmental behavior of iodine. Accurate determination of 129I in various environmental and biological samples is the key issue for these purposes. Due to its beta decay, low specific activity...... and ultra-low concentration in normal environmental and biological samples, it is important to efficiently separate iodine from the sample matrix and sensitively measure 129I. However, the complicated chemical properties of iodine and high organic content in biological samples make efficient separation...

  2. Cull sow knife-separable lean content evaluation at harvest and lean mass content prediction equation development.

    Science.gov (United States)

    Abell, Caitlyn E; Stalder, Kenneth J; Hendricks, Haven B; Fitzgerald, Robert F

    2012-07-01

    The objectives of this study were to develop a prediction equation for carcass knife-separable lean within and across USDA cull sow market weight classes (MWC) and to determine carcass and individual primal cut knife separable lean content from cull sows. There were significant percent lean and fat differences in the primal cuts across USDA MWC. The two lighter USDA MWC had a greater percent carcass lean and lower percent fat compared to the two heavier MWC. In general, hot carcass weight explained the majority of carcass lean variation. Additionally, backfat was a significant variation source when predicting cull sow carcass lean. The findings support using a single lean prediction equation across MWC to assist processors when making cull sow purchasing decisions and determine the mix of animals from various USDA MWC that will meet their needs when making pork products with defined lean:fat content.

  3. Characterization of gel-separated glycoproteins using two-step proteolytic digestion combined with sequential microcolumns and mass spectrometry

    DEFF Research Database (Denmark)

    Larsen, Martin Røssel; Højrup, Peter; Roepstorff, Peter

    2005-01-01

    Protein glycosylation can be vital for changing the function or physiochemical properties of a protein. Abnormal glycosylation can lead to protein malfunction, resulting in severe diseases. Therefore, it is important to develop techniques for characterization of such modifications in proteins...... present a new technique that allows characterization of low amounts of glycoproteins separated by gel electrophoresis. The method takes advantage of sequential specific and nonspecific enzymatic treatment followed by selective purification and characterization of the glycopeptides using graphite powder...

  4. Modeling of mass transfer of Phospholipids in separation process with supercritical CO2 fluid by RBF artificial neural networks

    Science.gov (United States)

    An artificial Radial Basis Function (RBF) neural network model was developed for the prediction of mass transfer of the phospholipids from canola meal in supercritical CO2 fluid. The RBF kind of artificial neural networks (ANN) with orthogonal least squares (OLS) learning algorithm were used for mod...

  5. Determination of plutonium isotopes (238Pu, 239Pu, 240Pu, 241Pu) in environmental samples using radiochemical separation combined with radiometric and mass spectrometric measurements.

    Science.gov (United States)

    Xu, Yihong; Qiao, Jixin; Hou, Xiaolin; Pan, Shaoming; Roos, Per

    2014-02-01

    This paper reports an analytical method for the determination of plutonium isotopes ((238)Pu, (239)Pu, (240)Pu, (241)Pu) in environmental samples using anion exchange chromatography in combination with extraction chromatography for chemical separation of Pu. Both radiometric methods (liquid scintillation counting and alpha spectrometry) and inductively coupled plasma mass spectrometry (ICP-MS) were applied for the measurement of plutonium isotopes. The decontamination factors for uranium were significantly improved up to 7.5 × 10(5) for 20 g soil compared to the level reported in the literature, this is critical for the measurement of plutonium isotopes using mass spectrometric technique. Although the chemical yield of Pu in the entire procedure is about 55%, the analytical results of IAEA soil 6 and IAEA-367 in this work are in a good agreement with the values reported in the literature or reference values, revealing that the developed method for plutonium determination in environmental samples is reliable. The measurement results of (239+240)Pu by alpha spectrometry agreed very well with the sum of (239)Pu and (240)Pu measured by ICP-MS. ICP-MS can not only measure (239)Pu and (240)Pu separately but also (241)Pu. However, it is impossible to measure (238)Pu using ICP-MS in environmental samples even a decontamination factor as high as 10(6) for uranium was obtained by chemical separation.

  6. A single-step pesticide extraction and clean-up multi-residue analytical method by selective pressurized liquid extraction followed by on-line solid phase extraction and ultra-high-performance liquid chromatography-tandem mass spectrometry for complex matrices.

    Science.gov (United States)

    Rodrigues, Elsa Teresa; Pardal, Miguel Ângelo; Salgueiro-González, Noelia; Muniategui-Lorenzo, Soledad; Alpendurada, Maria Fátima

    2016-06-24

    Pesticides, a group of compounds linked to human activity, may, when in toxic levels, have a profound effect on water quality, and hence result in adverse consequences to aquatic life and ultimately to human health. Analytical challenges arise when successfully trying to determine these levels in environmental complex matrices. Therefore, fast, simple, sensitive and selective analytical methodologies for multi-residue determination of pesticides (atrazine, azoxystrobin, bentazon, λ-cyhalothrin, penoxsulam and terbuthylazine) in sediment, macrophytes (algae and aquatic plants) and aquatic animals were developed and validated. The established methods were matrix-dependent and were based on Selective Pressurized Liquid Extraction (SPLE) followed by on-line Solid Phase Extraction and Ultra Performance Liquid Chromatography-tandem Mass Spectrometry (on-line SPE-UPLC-ESI-MS/MS). This cutting-edge research methodology uses a small amount of sample, is time saving and reduces the use of organic solvents in compliance with Green Chemistry principles. The analytical features were adequate for all compounds in all studied matrices. The established methodology was applied on real marine samples and no pesticide concentrations above their respective method quantification limits were measured in sediments or aquatic plants. However, terbuthylazine was found in the macroalgae Ulva spp. (108ngg(-1)dw) and all the prospected pesticides were measured above their respective method quantification limits in the bivalve Scrobicularia plana (atrazine: 48ngg(-1)dw, azoxystrobin: 64ngg(-1)dw, bentazon: 33ngg(-1)dw, λ-cyhalothrin: 2531ngg(-1)dw, penoxsulam: 50ngg(-1)dw, and terbuthylazine: 44ngg(-1)dw).

  7. Separation of polar mushroom toxins by mixed-mode hydrophilic and ionic interaction liquid chromatography-electrospray ionization-mass spectrometry.

    Science.gov (United States)

    Chung, Wai-cheung; Tso, Sau-ching; Sze, Sai-tim

    2007-02-01

    Reversed-phase liquid chromatography (RPLC) is commonly used to analyze nonvolatile contaminants and naturally occurring toxins in foods. However, polar compounds, such as hydrophilic polypeptides and quaternary ammonium salts, are often not satisfactorily separated by RPLC and present a challenge for analytical scientists. In this study, hydrophilic interaction liquid chromatography (HILIC), on an amide-based stationary phase in combination with electrospray ionization (ESI) tandem mass spectrometry (MS-MS), is successfully employed to simultaneously separate polar mushroom toxins, including amanitins and phallotoxins, which are cyclic oligopeptides and muscarine, a quaternary ammonium compound, in mushrooms. The sensitivity of different ionization modes is studied, and the positive ionization mode is found to provide a more sensitive and effective tool for the unambiguous identification of the concerned polar toxins because of their characteristic fragmentation patterns. The properties of the mobile phase are also found to have significant impacts on the separation. At a high acetonitrile (ACN) concentration, hydrophilic interaction dominates, and all analytes under study demonstrate a much higher affinity with the stationary phase. The addition of methanol (MeOH) as a modifier could further enhance the HILIC separation for amanitins, phallotoxins, and muscarine. Valley-to-valley separation is achieved upon the optimatizatiqn of the mobile phase (comprising of ACN, MeOH, and ammonium formate buffer at pH approximately 3.5) and the solvent gradient. HILIC coupled with ESI-MS-MS is demonstrated to be a novel technique for the simultaneous separation and confirmatory analysis of the concerned polar toxins by providing an environment of solubility and retention that could not be achieved through the use of RPLC.

  8. Toward 'omic scale metabolite profiling: a dual separation-mass spectrometry approach for coverage of lipid and central carbon metabolism.

    Science.gov (United States)

    Ivanisevic, Julijana; Zhu, Zheng-Jiang; Plate, Lars; Tautenhahn, Ralf; Chen, Stephen; O'Brien, Peter J; Johnson, Caroline H; Marletta, Michael A; Patti, Gary J; Siuzdak, Gary

    2013-07-16

    Although the objective of any 'omic science is broad measurement of its constituents, such coverage has been challenging in metabolomics because the metabolome is comprised of a chemically diverse set of small molecules with variable physical properties. While extensive studies have been performed to identify metabolite isolation and separation methods, these strategies introduce bias toward lipophilic or water-soluble metabolites depending on whether reversed-phase (RP) or hydrophilic interaction liquid chromatography (HILIC) is used, respectively. Here we extend our consideration of metabolome isolation and separation procedures to integrate RPLC/MS and HILIC/MS profiling. An aminopropyl-based HILIC/MS method was optimized on the basis of mobile-phase additives and pH, followed by evaluation of reproducibility. When applied to the untargeted study of perturbed bacterial metabolomes, the HILIC method enabled the accurate assessment of key, dysregulated metabolites in central carbon pathways (e.g., amino acids, organic acids, phosphorylated sugars, energy currency metabolites), which could not be retained by RPLC. To demonstrate the value of the integrative approach, bacterial cells, human plasma, and cancer cells were analyzed by combined RPLC/HILIC separation coupled to ESI positive/negative MS detection. The combined approach resulted in the observation of metabolites associated with lipid and central carbon metabolism from a single biological extract, using 80% organic solvent (ACN:MeOH:H2O 2:2:1). It enabled the detection of more than 30,000 features from each sample type, with the highest number of uniquely detected features by RPLC in ESI positive mode and by HILIC in ESI negative mode. Therefore, we conclude that when time and sample are limited, the maximum amount of biological information related to lipid and central carbon metabolism can be acquired by combining RPLC ESI positive and HILIC ESI negative mode analysis.

  9. Formación on line

    Directory of Open Access Journals (Sweden)

    O. Grau-Perejoan

    Full Text Available La formación on line es una modalidad de enseñanza a distancia basada en las nuevas tecnologías. En este artículo se pretende hacer una introducción a base de describir a grandes rasgos sus características principales: asincronía, no presencialidad, comunicación escrita, función del profesor on line, así como los retos, los riesgos, las ventajas y los inconvenientes que plantea. Se exponen las diferencias entre la formación on line y la formación presencial, de manera que los docentes puedan adaptar de la mejor manera posible sus propuestas formativas a la modalidad on line. Se introduce el importantísimo papel de la planificación y de la fase de diseño y, finalmente, se repasan conceptos útiles para comprender mejor el mundo de la formación on line como son los conceptos entorno virtual de aprendizaje (EVA o Blended Learning (B-Learning.

  10. Aluminum and phosphorus separation: application to preparation of target from brain tissue for {sup 26}Al determination by accelerator mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Brauer, Russell D.; Robertson, J. David; Sharma, Pankaj; Yokel, Robert A. E-mail: ryokel1@pop.uky.edu

    1999-04-01

    Acid digested brain containing 4 mg added {sup 27}Al was ashed at 1000 deg. C to prepare an Al{sub 2}O{sub 3} target for accelerator mass spectrometry (AMS) analysis of {sup 26}Al. A glass-like material usually resulted which was thought to be aluminum (Al) oxyphosphate. The separation of Al and phosphate was investigated. Al, but not phosphate, was bound by a cation exchange resin (AG 50-X8). Hydrofluoric acid eluted the Al from the resin. Removal of phosphate from acid digested brain by this method produced an amorphous material after ashing that was easier to recover from the porcelain crucible and had a higher AMS beam current. This procedure to separate Al from phosphate may have utility in other applications.

  11. IgY14 and SuperMix immunoaffinity separations coupled with liquid chromatography-mass spectrometry for human plasma proteomic biomarker discovery

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Tujin; Zhou, Jianying; Gritsenko, Marina A.; Hossain, Mahmud; Camp, David G.; Smith, Richard D.; Qian, Weijun

    2012-02-01

    Interest in the application of advanced proteomics technologies to human blood plasma- or serum-based clinical samples for the purpose of discovering disease biomarkers continues to grow; however, the enormous dynamic range of protein concentrations in these types of samples (often >10 orders of magnitude) represents a significant analytical challenge, particularly for detecting low-abundance candidate biomarkers. In response, immunoaffinity separation methods for depleting multiple high- and moderate-abundance proteins have become key tools for enriching low-abundance proteins and enhancing detection of these proteins in plasma proteomics. Herein, we describe IgY14 and tandem IgY14-Supermix separation methods for removing 14 high-abundance and up to 60 moderate-abundance proteins, respectively, from human blood plasma and highlight their utility when combined with liquid chromatography-tandem mass spectrometry for interrogating the human plasma proteome.

  12. IgY14 and SuperMix immunoaffinity separations coupled with liquid chromatography-mass spectrometry for human plasma proteomics biomarker discovery.

    Science.gov (United States)

    Shi, Tujin; Zhou, Jian-Ying; Gritsenko, Marina A; Hossain, Mahmud; Camp, David G; Smith, Richard D; Qian, Wei-Jun

    2012-02-01

    Interest in the application of advanced proteomics technologies to human blood plasma- or serum-based clinical samples for the purpose of discovering disease biomarkers continues to grow; however, the enormous dynamic range of protein concentrations in these types of samples (often >10 orders of magnitude) represents a significant analytical challenge, particularly for detecting low-abundance candidate biomarkers. In response, immunoaffinity separation methods for depleting multiple high- and moderate-abundance proteins have become key tools for enriching low-abundance proteins and enhancing detection of these proteins in plasma proteomics. Herein, we describe IgY14 and tandem IgY14-Supermix separation methods for removing 14 high-abundance and up to 60 moderate-abundance proteins, respectively, from human blood plasma and highlight their utility when combined with liquid chromatography-tandem mass spectrometry for interrogating the human plasma proteome.

  13. Radiochemical Separation and Measurement by Mass Spectrometry with Magnetic Sector with Inductively Coupled Plasma source (ICP-SFMS of Plutonium Isotopes in Soil Samples

    Directory of Open Access Journals (Sweden)

    C. O. Torres-Cortés

    2016-08-01

    Full Text Available The aim of this work is twofold: to optimize the radiochemical separation of Plutonium (Pu from soil samples, and to measure the Pu concentration. Soil samples were prepared using acid digestion assisted by microwaves; then, Pu purification was carried out with Pu AG1X8 resin. Pu isotopes were measured using Mass Spectrometry with Magnetic Sector with Inductively Coupled Plasma source (ICP-SFMS. In order to reduce the interference due to the presence of 238UH+ in the samples a desolvation system (Apex was used. The limit of detection (LOD of Pu was determined. The efficiency of Pu recovery from soil samples varies from 70 to 93%.

  14. Determination of Ultralow Level 129I/127I in Natural Samples by Separation of Microgram Carrier Free Iodine and Accelerator Mass Spectrometry Detection

    DEFF Research Database (Denmark)

    Hou, Xiaolin; Zhou, Weijian; Chen, Ning;

    2010-01-01

    a carrier free method using coprecipitation of AgI with AgCl for preparing micrograms of iodine target, associated with combustion using a tube furnace for separating iodine from solid samples and anion exchange chromatography for preconcentrating iodine from a large volume of water. An accelerator mass...... of 129I/127I, and a detection limit of this method for 129I is calculated to be 105 atoms. This will allow us to accurately determine 129I in prenuclear geological samples of low iodine concentration with 129I/127I of 10−12, such as loess, soil, coral, rock, sediment, and groundwater. Some samples...

  15. Separation and characterization of phenolic compounds in fennel (Foeniculum vulgare) using liquid chromatography-negative electrospray ionization tandem mass spectrometry.

    Science.gov (United States)

    Parejo, Irene; Jauregui, Olga; Sánchez-Rabaneda, Ferran; Viladomat, Francesc; Bastida, Jaume; Codina, Carles

    2004-06-16

    Liquid chromatography (LC) diode array detection (DAD) coupled to negative electrospray ionization (ESI) tandem mass spectrometry (MS/MS) was used for the rapid and sensitive identification of water-soluble phenolic compounds in fennel waste. The plant material was first extracted and then chromatographed on Sephadex LH-20 to afford seven fractions, each of them being subjected to LC-MS analysis. Identification of the compounds was carried out by interpretation of UV, MS, and MS/MS spectra. Forty-two phenolic substances were identified, 27 of which had not previously been reported in fennel, including hydroxycinnamic acid derivatives, flavonoid glycosides, and flavonoid aglycons.

  16. On line routing per mobile phone

    DEFF Research Database (Denmark)

    Bieding, Thomas; Görtz, Simon; Klose, Andreas

    2009-01-01

    . Additionally it is of utmost importance that the employed communication system is suitable integrated with the firm’s enterprise application system and business processes. On basis of a case study, we describe in this paper a system that is cheap and easy to implement due to the use of simple mobile phones......On-line routing is concerned with building vehicle routes in an ongoing fashion in such a way that customer requests arriving dynamically in time are efficiently and effectively served. An indispensable prerequisite for applying on-line routing methods is mobile communication technology...

  17. Educational On-Line Gaming Propensity

    DEFF Research Database (Denmark)

    Sudzina, Frantisek; Razmerita, Liana; Kirchner, Kathrin

    2014-01-01

    Educational on-line games are promising for new generations of students who are grown up digital. Th e new generations of students are technology savvy and spend lots of time on the web and on social networks. Based on an exploratory study, this article investigates the factors that infl uence...... students’ willingness to participate in serious games for teaching/learning. Th is study investigates the relationship between students’ behavior on Facebook, Facebook games, and their attitude toward educational on-line games. Th e results of the study reveal that the early adopters of educational games...

  18. The new on-line Czech Food Composition Database.

    Science.gov (United States)

    Machackova, Marie; Holasova, Marie; Maskova, Eva

    2013-10-01

    The new on-line Czech Food Composition Database (FCDB) was launched on http://www.czfcdb.cz in December 2010 as a main freely available channel for dissemination of Czech food composition data. The application is based on a complied FCDB documented according to the EuroFIR standardised procedure for full value documentation and indexing of foods by the LanguaL™ Thesaurus. A content management system was implemented for administration of the website and performing data export (comma-separated values or EuroFIR XML transport package formats) by a compiler. Reference/s are provided for each published value with linking to available freely accessible on-line sources of data (e.g. full texts, EuroFIR Document Repository, on-line national FCDBs). LanguaL™ codes are displayed within each food record as searchable keywords of the database. A photo (or a photo gallery) is used as a visual descriptor of a food item. The application is searchable on foods, components, food groups, alphabet and a multi-field advanced search. Copyright © 2013 Elsevier Ltd. All rights reserved.

  19. DEVELOPMENT OF AN ON-LINE COAL WASHABILITY ANALYZER

    Energy Technology Data Exchange (ETDEWEB)

    J.D. Miller; C.L. Lin; G.H. Luttrell; G.T. Adel; Barbara Marin

    2001-06-26

    Washability analysis is the basis for nearly all coal preparation plant separations. Unfortunately, there are no on- line techniques for determining this most fundamental of all coal cleaning information. In light of recent successes at the University of Utah, it now appears possible to determine coal washability on-line through the use of x-ray computed tomography (CT) analysis. The successful development of such a device is critical to the establishment of process control and automated coal blending systems. In this regard, Virginia Tech, Terra Tek Inc., and U.S. coal producers have joined with the University of Utah and to undertake the development of an X-ray CT-based on- line coal washability analyzer with financial assistance from DOE. Each project participant brought special expertise to the project in order to create a new dimension in coal cleaning technology. The project involves development of appropriate software and extensive testing/evaluation of well-characterized coal samples from operating coal preparation plants. Data collected to date suggest that this new technology is capable of serving as a universal analyzer that can not only provide washability analysis, but also particle size distribution analysis, ash analysis, and perhaps pyritic sulfur analysis.

  20. DEVELOPMENT OF AN ON-LINE COAL WASHABILITY ANALYZER

    Energy Technology Data Exchange (ETDEWEB)

    J.D. Miller

    1999-09-30

    Washability analysis is the basis for nearly all coal preparation plant separations. Unfortunately, there are no on-line techniques for determining this most fundamental of all coal cleaning information. In light of recent successes at the University of Utah, it now appears possible to determine coal washability on-line through the use of x-ray computed tomography (CT) analysis. The successful development of such a device is critical to the establishment of process control and automated coal blending systems. In this regard, Virginia Tech, Terra Tek Inc., and several eastern coal companies have joined with the University of Utah and agreed to undertake the development of a x-ray CT-based on-line coal washability analyzer with financial assistance from DOE. The three-year project will cost $594,571, of which 33% ($194,575) will be cost-shared by the participants. The project involves development of appropriate software and extensive testing/evaluation of well-characterized coal samples from operating coal preparation plants. Each project participant brings special expertise to the project which is expected to create a new dimension in coal cleaning technology. Finally, it should be noted that the analyzer may prove to be a universal analyzer capable of providing not only washability analysis, but also particle size distribution analysis, ash analysis and perhaps pyritic sulfur analysis.

  1. A fast and sensitive method for the separation of carotenoids using ultra-high performance supercritical fluid chromatography-mass spectrometry.

    Science.gov (United States)

    Jumaah, Firas; Plaza, Merichel; Abrahamsson, Victor; Turner, Charlotta; Sandahl, Margareta

    2016-08-01

    In this study, a rapid and sensitive ultra-high performance supercritical fluid chromatography-mass spectrometry (UHPSFC-MS) method has been developed and partially validated for the separation of carotenoids within less than 6 min. Six columns of orthogonal selectivity were examined, and the best separation was obtained by using a 1-aminoanthracene (1-AA) column. The length of polyene chain as well as the number of hydroxyl groups in the structure of the studied carotenoids determines their differences in the physiochemical properties and thus the separation that is achieved on this column. All of the investigated carotenoids were baseline separated with resolution values greater than 1.5. The effects of gradient program, back pressure, and column temperature were studied with respect to chromatographic properties such as retention and selectivity. Electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) were compared in both positive and negative mode, using both direct infusion and hyphenated with UHPSFC. The ESI in positive mode provided the highest response. The coefficient of determination (R (2)) for all calibration curves were greater than 0.998. Limit of detection (LOD) was in the range of 2.6 and 25.2 ng/mL for α-carotene and astaxanthin, respectively, whereas limit of quantification (LOQ) was in the range of 7.8 and 58.0 ng/mL for α-carotene and astaxanthin, respectively. Repeatability and intermediate precision of the developed UHPSFC-MS method were determined and found to be RSD supercritical fluid extracts of microalgae and rosehip. Graphical Abstract Ultra-high performance supercritical fluid chromatography-a rapid separation method for the analysis of carotenoids in rosehip and microalgae samples.

  2. Separating climate-induced mass transfers and instrumental effects from tectonic signal in repeated absolute gravity measurements

    Science.gov (United States)

    Van Camp, M.; Viron, O.; Avouac, J. P.

    2016-05-01

    We estimate the signature of the climate-induced mass transfers in repeated absolute gravity measurements based on satellite gravimetric measurements from the Gravity Recovery and Climate Experiment (GRACE) mission. We show results at the globe scale and compare them with repeated absolute gravity (AG) time behavior in three zones where AG surveys have been published: Northwestern Europe, Canada, and Tibet. For 10 yearly campaigns, the uncertainties affecting the determination of a linear gravity rate of change range 3-4 nm/s2/a in most cases, in the absence of instrumental artifacts. The results are consistent with what is observed for long-term repeated campaigns. We also discuss the possible artifact that can result from using short AG survey to determine the tectonic effects in a zone of high hydrological variability. We call into question the tectonic interpretation of several gravity changes reported from stations in Tibet, in particular the variation observed prior to the 2015 Gorkha earthquake.

  3. Biodegradation testing of chemicals with high Henry’s constants – separating mass and effective concentration reveals higher rate constants

    DEFF Research Database (Denmark)

    Birch, Heidi; Andersen, Henrik Rasmus; Comber, Mike

    During simulation-type biodegradation tests, volatile chemicals will continuously partition between water phase and headspace. This study addressed how (1) this partitioning affects biodegradation test results and (2) it can be accounted for by combining mass balance and dynamic biodegradation...... Microextraction (HS-SPME) was applied directly on the test systems to measure substrate depletion by biodegradation relative to abiotic controls. HS-SPME was also applied to determine air to water partitioning ratios. Water phase biodegradation rate constants, kwater, were up to 72 times higher than test system...... biodegradation rate constants, ksystem. True water phase degradation rate constants facilitate extrapolation to other air-water systems and are more suitable input parameters for aquatic exposure and fate models. As such, they should be considered more appropriate for risk assessments than test system rate...

  4. ON-LINE DOCUMENTS CONTENT MANAGEMENT

    Directory of Open Access Journals (Sweden)

    VASILESCU RAMONA VIOLETA

    2010-05-01

    Full Text Available This paper outlines the steps and technologies used in developing an on-line application server with many desktop clients, and with high power processing for a wide range of input documents to obtain searchable documents on the highest portability standards, PDF and PDF /A.

  5. Selective separation, detection of zotepine and mass spectral characterization of degradants by LC-MS/MS/QTOF

    Institute of Scientific and Technical Information of China (English)

    M.V.N. Kumar Talluri; Naveen Reddy Kandimalla; Raju Bandu; Divya Chundi; Ramesh Marupaka; Ragampeta Srinivas

    2014-01-01

    A simple, precise, accurate stability-indicating gradient reversed-phase high-performance liquid chromatographic (RP-HPLC) method was developed for the quantitative determination of zotepine (ZTP) in bulk and pharmaceutical dosage forms in the presence of its degradation products (DPs). The method was developed using Phenomenex C18 column (250 mm ~ 4.6 mm i.d., 5 mm) with a mobile phase containing a gradient mixture of solvents, A (0.05%trifluoroacetic acid (TFA), pH ¼ 3.0) and B (acetonitrile). The eluted compounds were monitored at 254 nm;the run time was within 20.0 min, in which ZTP and its DPs were well separated, with a resolution of 41.5. The stress testing of ZTP was carried out under acidic, alkaline, neutral hydrolysis, oxidative, photolytic and thermal stress conditions. ZTP was found to degrade significantly in acidic, photolytic, thermal and oxidative stress conditions and remain stable in basic and neutral conditions. The developed method was validated with respect to specificity, linearity, limit of detection, limit of quantification, accuracy, precision and robustness as per ICH guidelines. This method was also suitable for the assay determination of ZTP in pharmaceutical dosage forms. The DPs were characterized by LC-MS/MS and their fragmentation pathways were proposed.

  6. Selective separation, detection of zotepine and mass spectral characterization of degradants by LC–MS/MS/QTOF

    Directory of Open Access Journals (Sweden)

    M.V.N. Kumar Talluri

    2014-04-01

    Full Text Available A simple, precise, accurate stability-indicating gradient reversed-phase high-performance liquid chromatographic (RP–HPLC method was developed for the quantitative determination of zotepine (ZTP in bulk and pharmaceutical dosage forms in the presence of its degradation products (DPs. The method was developed using Phenomenex C18 column (250 mm×4.6 mm i.d., 5 µm with a mobile phase containing a gradient mixture of solvents, A (0.05% trifluoroacetic acid (TFA, pH=3.0 and B (acetonitrile. The eluted compounds were monitored at 254 nm; the run time was within 20.0 min, in which ZTP and its DPs were well separated, with a resolution of >1.5. The stress testing of ZTP was carried out under acidic, alkaline, neutral hydrolysis, oxidative, photolytic and thermal stress conditions. ZTP was found to degrade significantly in acidic, photolytic, thermal and oxidative stress conditions and remain stable in basic and neutral conditions. The developed method was validated with respect to specificity, linearity, limit of detection, limit of quantification, accuracy, precision and robustness as per ICH guidelines. This method was also suitable for the assay determination of ZTP in pharmaceutical dosage forms. The DPs were characterized by LC–MS/MS and their fragmentation pathways were proposed.

  7. Rapid chiral separation of atenolol, metoprolol, propranolol and the zwitterionic metoprolol acid using supercritical fluid chromatography-tandem mass spectrometry - Application to wetland microcosms.

    Science.gov (United States)

    Svan, Alfred; Hedeland, Mikael; Arvidsson, Torbjörn; Jasper, Justin T; Sedlak, David L; Pettersson, Curt E

    2015-08-28

    A method for enantiomeric separation of the three β-blocking agents atenolol, metoprolol, propranolol and the zwitterionic metoprolol acid, a major metabolite of both metoprolol and in environmental matrices also atenolol, has been developed. By use of supercritical fluid chromatography and the polysaccharide-based Chiralpak(®) IB-3, all four compounds were simultaneously enantiomerically separated (Rs>1.5) within 8min. Detection was performed using tandem mass spectrometry, and to avoid isobaric interference between the co-eluting metoprolol and metoprolol acid, the achiral column Acquity(®) UPC(2) BEH 2-EP was attached ahead of to the chiral column. Carbon dioxide with 18% methanol containing 0.5% (v/v) of the additives trifluoroacetic acid and ammonia in a 2:1 molar ratio were used as mobile phase. A post column make-up flow (0.3mL/min) of methanol containing 0.1% (v/v) formic acid was used to enhance the positive electrospray ionization. Detection was carried out using a triple quadrupole mass spectrometer operating in the selected reaction monitoring mode, using one transition per analyte and internal standard. The method was successfully applied for monitoring the enantiomeric fraction change over time in a laboratory scale wetland degradation study. It showed good precision, recovery, sensitivity and low effect of the sample matrix.

  8. Detection of activity and mass spectrometric identification of mouse liver carboxylesterase and aldehyde dehydrogenase separated by non-denaturing two-dimensional electrophoresis after extraction with detergents.

    Science.gov (United States)

    Shimazaki, Youji; Manabe, Takashi

    2005-05-20

    To examine the activities and identity of enzymes associated with organelles such as microsomes and mitochondria, proteins from mouse liver were extracted using the non-ionic detergents Nonidet P-40 (NP-40), polyoxyethylene sorbitan monooleate (Tween 80), polyoxyethylene isooctylphenyl ester (Triton X), n-octyl beta-D-glucoside (octyl glycoside) or anionic detergent sodium dodecylsulfate (SDS) after the removal of cytosolic proteins. The proteins extracted by detergents were separated by non-denaturing two-dimensional electrophoresis (2-DE). The activities of esterase and aldehyde dehydrogenase were retained by non-denaturing 2-DE after treatment with each non-ionic detergent, but the activities were reduced or lost when the proteins were extracted with more than 0.5% SDS. For proteomic analysis of the organelle-associated proteins in mouse liver, proteins were separated by non-denaturing 2-DE and were identified using electrospray ionization tandem mass spectrometry (ESI-MS/MS) after the proteins were solubilized by octyl glycoside, NP-40 and 0.1% SDS. Several organelle-associated proteins such as carboxylesterase, aldehyde dehydrogenase, glucose regulated protein and HSP60 were identified. These results indicate that the activities and identity of detergent-soluble enzymes can be examined by this non-denaturing 2-DE and mass spectrometry.

  9. Rapid screening of transferrin-binders in the flowers of Bauhinia blakeana Dunn by on-line high-performance liquid chromatography-diode-array detector-electrospray ionization-ion-trap-time-of-flight-mass spectrometry-transferrin-fluorescence detection system.

    Science.gov (United States)

    Liu, Meixian; Dong, Jing; Lin, Zongtao; Niu, Yanyan; Zhang, Xiaotian; Jiang, Haixiu; Guo, Ning; Li, Wei; Wang, Hong; Chen, Shizhong

    2016-06-10

    Transferrin (Transferrin, TRF, TF) has drawn increasing attention in cancer therapy due to its potential applications in drug delivery. TF receptor, highly expressed in tumor cells, recognizes and transports Fe(3+)-TF into cells to release iron into cytoplasm. Thus, discovering TF-binding compounds has become an active research area and is of great importance for target therapy. In this study, an on-line analysis method was established for screening TF-binding compounds from the flowers of Bauhinia blakeana Dunn using a high-performance liquid chromatography-diode-array detector-multi-stage mass spectrometry-transferrin-fluorescence detector (HPLC-DAD-MS(n)-TF-FLD) method. As a result, 33 of 80 identified or tentatively characterized compounds in the sample were TF-binding active. Twenty-five flavonol glycosides and eight phenolic acids were identified as TF-binders. Twelve of these active compounds together with six standard compounds were used to study the dose-response effects and structure-activity relationships of flavonoids and phenolic acids. The method was validated by vitexin with a good linearity in the range of concentrations used in the study. The limit of detection for vitexin was 0.1596 nmol. Our study indicated that the established method is simple, rapid and sensitive for screening TF-binding active compounds in the extract of Bauhinia blakeana Dunn, and therefore is important for discovering potential anti-cancer ingredients from complex samples for TF related drug delivery.

  10. Characterization of a condensed-phase membrane introduction mass spectrometry (CP-MIMS) interface using a methanol acceptor phase coupled with electrospray ionization for the continuous on-line quantitation of polar, low-volatility analytes at trace levels in complex aqueous samples.

    Science.gov (United States)

    Duncan, K D; McCauley, E P B; Krogh, E T; Gill, C G

    2011-05-15

    We report the development and application of a capillary hollow fibre membrane interface using methanol as an acceptor phase to deliver target analytes to an electrospray ionization source and a triple quadrupole mass spectrometer. Superior fluid handling systems lead to greater signal stability and membrane integrity for the continuous on-line monitoring of polar and charged analytes in complex aqueous samples with detection limits in the parts-per-trillion to parts-per-billion range. The system can be operated in either a continuous flow or a stopped acceptor flow mode - the latter giving rise to greater sensitivity. We report detection limits, enrichment factors and signal response times for selected analytes with polydimethylsiloxane and Nafion® polymer membrane interfaces. In addition, we demonstrate the use of this interface to detect pharmaceuticals and other contaminants in natural water and artificial urine. The improved sensitivity and analytical response times of our CP-MIMS system make it possible to continuously monitor dynamic chemical systems with temporal resolutions on the order of minutes. Presented is a comparison of the performance of CP-MIMS versus direct infusion electrospray ionization, demonstrating the potential advantages over direct infusion for trace analyte measurements in complex, high ionic strength samples. Furthermore, by continuously flowing a reaction mixture in a closed loop over the interface, we demonstrate the use of the system as an in situ reaction-monitoring platform for the chlorination of a model organic compound in aqueous solution. Copyright © 2011 John Wiley & Sons, Ltd.

  11. On-Line Mass Spectrometry Detection of Heavy Metals by Electrothermal Vaporization-Assisted Pulsed Corona Discharge Ionization Source under Ambient Conditions%基于电热蒸发辅助脉冲电晕放电大气压离子化源的重金属污染在线质谱检测技术

    Institute of Scientific and Technical Information of China (English)

    周建光; 林静; 张涛; 张体强; 牟颖

    2011-01-01

    A home-made electrothermal vaporization-assisted pulsed corona discharge atmospheric pressure ionization source was developed for coupling with a time-of-flight mass spectrometer for on-line detection of heavy metals in water samples. Experimental results show that vanadium, chromium, manganese, arsenic,including arsenic, chromium, which are great harmful to the environment, could be detected. The source has a simple structure, convenient operation, low energy consumption, and is easy to use, with a high sensitivity.The limit of detection can get to 10-13-10-12 g, and the method can be used online.%研制电热蒸发辅助脉冲电晕放电大气压离子化源,将其与飞行时间质谱耦合联用,建立了重金属污染的在线检测方法.实验结果表明,该方法对V,Cr,Mn,As等主要重金属污染物检测性能较好,灵敏度高,检出限一般可达10-13~10-12 g,具有结构简单、操作方便、能耗低等特点,实现了在线监测.

  12. A field survey of metal binding to metallothionein and other cytosolic ligands in liver of eels using an on-line isotope dilution method in combination with size exclusion (SE) high pressure liquid chromatography (HPLC) coupled to Inductively Coupled Plasma time-of-flight Mass Spectrometry (ICP-TOFMS).

    Science.gov (United States)

    Van Campenhout, Karen; Goenaga Infante, Heidi; Goemans, Geert; Belpaire, Claude; Adams, Freddy; Blust, Ronny; Bervoets, Lieven

    2008-05-15

    The effect of metal exposure on the accumulation and cytosolic speciation of metals in livers of wild populations of European eel with special emphasis on metallothioneins (MT) was studied. Four sampling sites in Flanders showing different degrees of heavy metal contamination were selected for this purpose. An on-line isotope dilution method in combination with size exclusion (SE) high pressure liquid chromatography (HPLC) coupled to Inductively Coupled Plasma time-of-flight Mass Spectrometry (ICP-TOFMS) was used to study the cytosolic speciation of the metals. The distribution of the metals Cd, Cu, Ni, Pb and Zn among cytosolic fractions displayed strong differences. The cytosolic concentration of Cd, Ni and Pb increased proportionally with the total liver levels. However, the cytosolic concentrations of Cu and Zn only increased above a certain liver tissue threshold level. Cd, Cu and Zn, but not Pb and Ni, were largely associated with the MT pool in correspondence with the environmental exposure and liver tissue concentrations. Most of the Pb and Ni and a considerable fraction of Cu and Zn, but not Cd, were associated to High Molecular Weight (HMW) fractions. The relative importance of the Cu and Zn in the HMW fraction decreased with increasing contamination levels while the MT pool became progressively more important. The close relationship between the cytosolic metal load and the total MT levels or the metals bound on the MT pool indicates that the metals, rather than other stress factors, are the major factor determining MT induction.

  13. On-line Identification of the DC motor Parameters by using Least Mean Square Recursive Method

    Directory of Open Access Journals (Sweden)

    Marian Gaiceanu

    2014-09-01

    Full Text Available The on-line least square parameters (electrical and mechanical identification method of the separately DC motor is presented in this paper. The parameters of the DC machine are time dependent; therefore, for the DC drive control the on-line parameters identification procedure is mandatory. By knowing accurately the DC motor parameters, the parameters of the DC speed and current cascade controllers can be obtained.

  14. Indirect chiral separation of new recreational drugs by gas chromatography-mass spectrometry using trifluoroacetyl-L-prolyl chloride as chiral derivatization reagent.

    Science.gov (United States)

    Weiß, Jennifer A; Mohr, Stefan; Schmid, Martin G

    2015-03-01

    New recreational drugs such as amphetamine-, cathinone, and benzofury derivatives gained high popularity on the drug market in recent years. They can be purchased via the Internet from different providers and online portals. Most of these compounds are chiral, which makes the development of chiral separation methods necessary. Besides this, it is useful to find out if the compounds were sold as racemic mixtures. Also, it is important to check whether the new psychoactive compounds contain further ingredients or impurities. The aim of this research was the continuation of the application of a method for indirect chiral separation of 24 new psychoactive compounds recently purchased via the Internet. After derivatization with the chiral derivatization reagent trifluoroacetyl-L-prolyl chloride, chromatographic separation of diastereomers was achieved using a 30 m HP5-MS capillary column. As carrier gas, helium was used with a constant flow of 1.0 ml/min. Three different column temperature programs were tested. Under optimum conditions 13 out of 24 compounds were successfully resolved into their enantiomers obtaining Rs values up to 7.0. The use of a single quadrupole mass spectrometer as the detector allowed the identification of the compounds in multicomponent samples.

  15. Rapid and Green Separation of Mono- and Diesters of Monochloropropanediols by Ultrahigh Performance Supercritical Fluid Chromatography-Mass Spectrometry Using Neat Carbon Dioxide as a Mobile Phase.

    Science.gov (United States)

    Jumaah, Firas; Jędrkiewicz, Renata; Gromadzka, Justyna; Namieśnik, Jacek; Essén, Sofia; Turner, Charlotta; Sandahl, Margareta

    2017-09-20

    This study demonstrates the effect of column selectivity and density of supercritical carbon dioxide (SC-CO2) on the separation of monochloropropanediol (MCPD) esters, known as food toxicants, using SC-CO2 without addition of cosolvent in ultrahigh performance supercritical fluid chromatography-mass spectrometry (UHPSFC-MS). This study shows that over 20 2-monochloropropanediol (2-MCPD) and 3-monochloropropanediol (3-MCPD) mono- and diesters are separated on a 2-picolylamine column in less than 12 min. The presence and position of a hydroxyl group in the structure, the number of unsaturated bonds, and the acyl chain length play a significant role in the separation of MCPD esters. The flow rate, backpressure, and column oven temperature, which affect the density of the mobile phase, were shown to have a substantial impact on retention, efficiency, and selectivity. The developed method was successfully applied for the determination of MCPD esters in refined oils and showed a close to excellent green analysis score using the Analytical Eco-Scale.

  16. Gadolinium speciation with Tetradentate, N-donor extractants for minor actinide/lanthanide separation: an XRD, mass spectrometry and EPR study

    Energy Technology Data Exchange (ETDEWEB)

    Whittaker, D.M. [School of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL (United Kingdom); Sharrad, C.A. [School of Chemical Engineering and Analytical Science, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom); Research Centre for Radwaste and Decommissioning, Dalton Nuclear Institute, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom); Sproules, S. [Photon Science Institute, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom); WestCHEM, School of Chemistry, University of Glasgow, Glasgow G12 8QQ (United Kingdom)

    2013-07-01

    The hydrophobic organic molecules CyMe{sub 4}-BTPhen (1) and CyMe{sub 4}-BTBP (2) have been developed and tuned over many years to be able to separate the trivalent actinides from the trivalent lanthanides (Ln) selectively in bi-phasic solvent extraction processes for the separation of the long-lived radio-toxic minor actinides from spent nuclear fuel. The ability of these N-donor ligands to perform this separation is poorly understood, as is their speciation with the metal ions when extracted into the organic phase. Our previous work has shown Ln{sup 3+} speciation to be largely 1:2 Ln:L in nature with another small molecule, either water or nitrate, occupying a cavity between the tetradentate bound N-donor ligands. The identity of the small molecule changes across the lanthanide series, and here we continue investigations into this speciation. Complexes of these N-donor ligands with Gd{sup 3+} have been synthesised and characterised by X-ray crystallography, mass spectrometry and EPR spectroscopy. We show that the N-donor ligands have no effect on the electronic configuration of Gd{sup 3+} and that the lanthanide contraction with the steric rigidity of the N-donor ligand appears to determine the size of the cavity between the coordinated ligands. This in turn appears to control the identity of the small molecule on the ninth site in the 1:2 Gd:L species. (authors)

  17. Escapist Motives for On-line Gaming and Strengthening of Weak Ties

    DEFF Research Database (Denmark)

    Sudzina, Frantisek; Razmerita, Liana

    Due to advances of technology including faster and ubiquitously accessible Internet connection, on-line gaming have grown tremendously in the last couple of years. The aim of this paper is to investigate whether escapist motives for playing games are linked to strengthening of weak ties through on......-line gaming. The research investigates Facebook and other on-line games separately. A surprising result is that while most of the investigated escapist motives are positively correlated with strengthening of weak ties, the mundane breaking motive is negatively correlated with strengthening of weak ties....

  18. Associations of adult separation anxiety disorder with conflict-related trauma, ongoing adversity, and the psychosocial disruptions of mass conflict among West Papuan refugees.

    Science.gov (United States)

    Tay, Alvin Kuowei; Rees, Susan; Kareth, Moses; Silove, Derrick

    2016-03-01

    Refugees commonly experience traumatic events that threaten the self and close others, suggesting the possibility that they may experience overlapping symptoms of posttraumatic stress disorder (PTSD) and separation anxiety disorder (SAD). We examine this possibility among West Papua refugees (n = 230) displaced to Port Moresby, Papua New Guinea. We also examine associations between the combined PTSD-SAD construct and indices of past trauma exposure, ongoing adversity, and the psychosocial disruptions caused by mass conflict and displacement. We applied culturally adapted interview modules to assess symptoms of PTSD, SAD, traumatic events (TEs), ongoing adversity, and 5 psychosocial dimensions. Latent class analysis identified a PTSD class (23%), a posttraumatic (PT) SAD class (22%), and a low-symptom class (55%). Compared with the low-symptom class, both the PTSD and PT-SAD classes endorsed higher levels of exposure to all domains of TEs (conflict-related trauma, witnessing murder, childhood related adversities, traumatic losses, and health stress) and ongoing adversity (access to health care, displacement/separation, safety in the community, and access to basic needs), but the 2 comorbid groups did not differ on these indices. The PT-SAD class alone scored higher than the low-symptom reference class in relation to disruptions to the psychosocial domains (safety/security, bonds/network, access to justice, roles/identities, existential meaning) and higher than the PTSD class on safety/security, justice and roles/identities. Our findings suggest that the PT-SAD pattern may represent a response to the most severe forms of psychosocial disruptions of mass conflict among refugees. A focus on separation anxiety may enhance psychotherapies designed to treat PTSD in refugees. (PsycINFO Database Record

  19. Biodegradation testing of chemicals with high Henry's constants - Separating mass and effective concentration reveals higher rate constants.

    Science.gov (United States)

    Birch, Heidi; Andersen, Henrik R; Comber, Mike; Mayer, Philipp

    2017-05-01

    During simulation-type biodegradation tests, volatile chemicals will continuously partition between water phase and headspace. This study addressed how (1) this partitioning affects test results and (2) can be accounted for by combining equilibrium partition and dynamic biodegradation models. An aqueous mixture of 9 (semi)volatile chemicals was first generated using passive dosing and then diluted with environmental surface water producing concentrations in the ng/L to μg/L range. After incubation for 2 h to 4 weeks, automated Headspace Solid Phase Microextraction (HS-SPME) was applied directly on the test systems to measure substrate depletion by biodegradation relatively to abiotic controls. HS-SPME was also applied to determine air to water partitioning ratios. Biodegradation rate constants relating to the chemical in the water phase, kwater, were generally a factor 1 to 11 times higher than biodegradation rate constants relating to the total mass of chemical in the test system, ksystem, with one exceptional factor of 72 times for a long chain alkane. True water phase degradation rate constants were found (i) more appropriate for risk assessment than test system rate constants, (ii) to facilitate extrapolation to other air-water systems and (iii) to be better defined input parameters for aquatic exposure and fate models.

  20. [Fast separation and identification of nine carcinogenic dyes in textiles using liquid chromatography-electrospray tandem mass spectrometry].

    Science.gov (United States)

    Ding, Youchao; Cao, Xizhong; Wu, Lina; Zhang, Qian

    2008-09-01

    A qualitative method of the identification of nine carcinogenic dyes prohibited in textiles was developed using high performance liquid chromatography-tandem mass spectrometry interfaced with electro-spray ionization (HPLC-ESI-MS/MS) in the selective reaction monitoring (SRM) mode. The dyes were extracted from textiles composed of natural or chemical fibers by methanol under ultrasounication, and then eluted with gradient by acetonitrile and 5 mmol/L ammonium acetate from an RP-C18 column with two segments in effluents. The first effluents accommodated Acid Red 26, Direct Blue 6, Direct Black 38 and Direct Red 28 with negative ionization mode, while the second accommodated Basic Red 9, Basic Violet 14, Disperse Blue 1, Disperse Orange 11 and Disperse Yellow 3 with positive ionization mode. Thus the investigated compounds could be identified simultaneously with single-run analysis no matter which type of the fibre the sample was and no matter which category of the dye the analyte was. The established method was successfully applied to identify the carcinogenic dyes in textile samples through comparing the chromatographic retention time and the relative abundance of characteristic product ions with the standards.

  1. Implementation of suitable flow injection/sequential-sample separation/preconcentration schemes for determination of trace metal concentrations using detection by electrothermal atomic absorption spectrometry and inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Hansen, Elo Harald; Wang, Jianhua

    2002-01-01

    Various preconditioning procedures encomprising appropriate separation/preconcentration schemes in order to obtain optimal sensitivity and selectivity characteristics when using electrothermal atomic absorption spectrometry (ETAAS) and inductively coupled plasma mass spectrometry (ICPMS) are pres...

  2. Separating Autotrophic and Heterotrophic Contributions to Soil Respiration in Maize-Based Agroecosystems Using Stable Carbon Isotope Ratio Mass Spectrometry.

    Science.gov (United States)

    Amos, B.; Walters, D. T.; Madhavan, S.; Arkebauer, T. J.; Scoby, D. L.

    2005-12-01

    Any effort to establish a carbon budget for a growing crop by means of a thorough accounting of all C sources and sinks will require the ability to discriminate between autotrophic and heterotrophic contributions to soil surface CO2 flux. Autotrophic soil respiration (Ra) is defined as combined root respiration and the respiration of soil microorganisms residing in the rhizosphere and using root-derived carbohydrates as an energy source, while heterotrophic respiration (Rh) is defined as the respiration of soil microorganisms and macroorganisms not directly under the influence of the live root system and using SOM as an energy source. We partition soil surface CO2 flux into its autotrophic and heterotrophic components by combining root exclusion with stable carbon isotope techniques in production scale (~65 ha) maize-based agroecosystems. After flux measurements, small chambers are placed on collars in both root excluded shields and in non-root excluded soil, ambient headspace CO2 is removed using a soda lime trap, and soil-respired C is allowed to collect in the chambers. Soil respiration samples are then collected in 12mL evacuated exetainers and analyzed for δ13C by means of a Finnigan Delta-S isotope ratio mass spectrometer interfaced with a Thermo Finnigan GasBench II and a cryogenic trap to increase CO2 concentration. These δ13C measurements were made throughout the 2005 growing season in maize fields representing three agroecosystems: irrigated continuous maize, irrigated maize-soybean rotation, and rainfed maize soybean rotation. Estimates of autotrophic and heterotrophic soil respiration along with other results of this study will be presented.

  3. 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.

    Science.gov (United States)

    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.

  4. Implementation of suitable flow injection/sequential-sample separation/preconcentration schemes for determination of trace metal concentrations using detection by electrothermal atomic absorption spectrometry and inductively coupled plasma mass spectrometry

    DEFF Research Database (Denmark)

    Hansen, Elo Harald; Wang, Jianhua

    2002-01-01

    Various preconditioning procedures encomprising appropriate separation/preconcentration schemes in order to obtain optimal sensitivity and selectivity characteristics when using electrothermal atomic absorption spectrometry (ETAAS) and inductively coupled plasma mass spectrometry (ICPMS) are pres......Various preconditioning procedures encomprising appropriate separation/preconcentration schemes in order to obtain optimal sensitivity and selectivity characteristics when using electrothermal atomic absorption spectrometry (ETAAS) and inductively coupled plasma mass spectrometry (ICPMS...... prior to detection are effected in a microconduit placed on top of an SI selection valve....

  5. Analysis of metal-binding proteins separated by non-denaturating gel electrophoresis using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS).

    Science.gov (United States)

    Becker, J Susanne; Mounicou, Sandra; Zoriy, Miroslav V; Becker, J Sabine; Lobinski, Ryszard

    2008-09-15

    Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) have become established as very efficient and sensitive biopolymer and elemental mass spectrometric techniques for studying metal-binding proteins (metalloproteins) in life sciences. Protein complexes present in rat tissues (liver and kidney) were separated in their native state in the first dimension by blue native gel electrophoresis (BN-PAGE). Essential and toxic metals, such as zinc, copper, iron, nickel, chromium, cadmium and lead, were detected by scanning the gel bands using quadrupole LA-ICP-MS with and without collision cell as a microanalytical technique. Several proteins were identified by using MALDI-TOF-MS together with a database search. For example, on one protein band cut from the BN-PAGE gel and digested with the enzyme trypsin, two different proteins - protein FAM44B and cathepsin B precursor - were identified. By combining biomolecular and elemental mass spectrometry, it was possible to characterize and identify selected metal-binding rat liver and kidney tissue proteins.

  6. Educational On-Line Gaming Propensity

    DEFF Research Database (Denmark)

    Sudzina, Frantisek; Razmerita, Liana; Kirchner, Kathrin

    2014-01-01

    Educational on-line games are promising for new generations of students who are grown up digital. Th e new generations of students are technology savvy and spend lots of time on the web and on social networks. Based on an exploratory study, this article investigates the factors that infl uence...... students’ willingness to participate in serious games for teaching/learning. Th is study investigates the relationship between students’ behavior on Facebook, Facebook games, and their attitude toward educational on-line games. Th e results of the study reveal that the early adopters of educational games...... are likely to be students, who are young, have only a few Facebook connections, who currently play Facebook game(s). Furthermore, the study emphasizes that there may be differences between students coming from various countries....

  7. Separating refractory and non-refractory particulate chloride and estimating chloride depletion by aerosol mass spectrometry in a marine environment

    Directory of Open Access Journals (Sweden)

    I. Nuaaman

    2015-01-01

    Full Text Available Aerosol composition and concentration measurements along the coast of California were obtained using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS onboard the research vessel Atlantis during the CalNex study in 2010. This paper focuses on the measurement of aerosol chloride using the HR-AMS that can be ambiguous in regions with significant quantities of sea salt aerosols. This ambiguity arises due to large differences in the sensitivity of the HR-AMS to refractory chloride species (i.e., NaCl and non refractory chloride species (i.e., NH4Cl, HCl, etc.. Using the HR-AMS, the aerosol chloride signal is typically quantified using ion signals for 35Cl+, H35Cl+, 37Cl+ and H37Cl+ (HxCl+. During this study, the highest aerosol chloride signal was observed during sea sweep experiments when the source of the aerosol chloride was NaCl present in artificially generated sea salt aerosols even though the HR-AMS has significantly lower sensitivity to such refractory species. Other prominent ion signals that arise from NaCl salt were also observed at m/z 22.99 for Na+ and m/z 57.96 for Na35Cl+ during both sea sweep experiments and during periods of ambient measurements. Thus, refractory NaCl contributes significantly to the HxCl+ signal, interfering with attempts to quantify non sea salt chloride (nssCl. It was found that during ambient aerosol measurements, the interference in the HxCl+ signal from sea salt chloride (ssCl was as high as 89%, but with a study wide average of 10%. The Na35Cl+ ion signal was found to be a good tracer for NaCl. We outline a method to establish nssCl in the ambient aerosols by subtracting the sea salt chloride (ssCl signal from the HxCl+ signal. The ssCl signal is derived from the Na35Cl+ ion tracer signal and the HxCl+ to Na35Cl+ ratio established from the sea sweep experiments. Ambient submicron concentrations of ssCl were also established using the

  8. Connecting to On-line Data

    Science.gov (United States)

    Eichhorn, G.; Astrophysics Datacenter Executive Committee (ADEC)

    2004-05-01

    The Astrophysics Datacenter Executive Committee (ADEC) is coordinating the development of a system to facilitate the linking to on-line data. This system has three components: 1. Unique dataset identifiers. 2. A verification system for identifiers. 3. Permanent links to on-line data sets. 1. The ADEC has agreed on a naming scheme for data sets that allows for the unique identification of any data set. The ADEC data centers will clearly mark their data with these identifiers to allow the generation of links to these data. 2. Each data center has a utility that can check whether a data set identifier is a valid identifier at that center. A central verifier allows third parties access to these individual verifiers through a single portal. 3. The central verifier also provides permanent links to data sets through a central link forwarding system. This makes it possible to move data sets between data centers while maintaining the permanent links. The ADEC plans to first use this system to implement the linking from the literature to on-line data in a collaboration with the AAS and the University of Chicago Press for the AAS journals.

  9. A THERMAL INFRARED IMAGING STUDY OF VERY LOW MASS, WIDE-SEPARATION BROWN DWARF COMPANIONS TO UPPER SCORPIUS STARS: CONSTRAINING CIRCUMSTELLAR ENVIRONMENTS

    Energy Technology Data Exchange (ETDEWEB)

    Bailey, Vanessa; Hinz, Philip M.; Su, Kate Y. L.; Hoffmann, William F.; Rieke, George; Rodigas, Timothy; Skemer, Andrew; Vaitheeswaran, Vidhya [Steward Observatory, University of Arizona, 933 N. Cherry Ave., Tucson, AZ 85721 (United States); Currie, Thayne [Department of Astronomy and Astrophysics, University of Toronto, 50 St. George Street, Toronto, ON M5S 3H4 (Canada); Esposito, Simone; Pinna, Enrico; Puglisi, Alfio [Osservatorio Astrofisico di Arcetri, Largo Enrico Fermi 5, I-50125 Firenze (Italy); Hill, John M. [Large Binocular Telescope Observatory, University of Arizona, 933 N. Cherry Ave., Tucson, AZ 85721 (United States); Jones, Terry [School of Physics and Astronomy, University of Minnesota, 116 Church St. SE, Minneapolis, MN 55455 (United States); Kim, Jihun [College of Optical Sciences, University of Arizona, 1630 E. University Blvd., Tucson, AZ 85721 (United States); Leisenring, Jarron; Meyer, Michael [Institut fuer Angewandte Physik, Eidgenoessische Technische Hochschule-Zuerich, CH-8093 (Switzerland); Murray-Clay, Ruth; Skrutskie, Michael F. [Harvard-Smithsonian Center for Astrophysics, Harvard University, 60 Garden St., Cambridge, MA 02138 (United States); Nelson, Matthew J., E-mail: vbailey@as.arizona.edu [Department of Astronomy, University of Virginia, Charlottesville, VA 22904 (United States); and others

    2013-04-10

    We present a 3-5 {mu}m LBT/MMT adaptive optics imaging study of three Upper Scorpius stars with brown dwarf (BD) companions with very low masses/mass ratios (M{sub BD} <25 M{sub Jup}; M{sub BD}/M{sub *} Almost-Equal-To 1%-2%) and wide separations (300-700 AU): GSC 06214, 1RXS 1609, and HIP 78530. We combine these new thermal IR data with existing 1-4 {mu}m and 24 {mu}m photometry to constrain the properties of the BDs and identify evidence for circumprimary/circumsecondary disks in these unusual systems. We confirm that GSC 06214B is surrounded by a disk, further showing that this disk produces a broadband IR excess due to small dust near the dust sublimation radius. An unresolved 24 {mu}m excess in the system may be explained by the contribution from this disk. 1RXS 1609B exhibits no 3-4 {mu}m excess, nor does its primary; however, the system as a whole has a modest 24 {mu}m excess, which may come from warm dust around the primary and/or BD. Neither object in the HIP 78530 system exhibits near- to mid-IR excesses. We additionally find that the 1-4 {mu}m colors of HIP 78530B match a spectral type of M3 {+-} 2, inconsistent with the M8 spectral type assigned based on its near-IR spectrum, indicating that it may be a low-mass star rather than a BD. We present new upper limits on additional low-mass companions in the system (<5 M{sub Jup} beyond 175 AU). Finally, we examine the utility of circumsecondary disks as probes of the formation histories of wide BD companions, finding that the presence of a disk may disfavor BD formation near the primary with subsequent outward scattering.

  10. Electrospray micromixer chip for on-line derivatization and kinetic studies.

    Science.gov (United States)

    Abonnenc, Mélanie; Dayon, Loïc; Perruche, Brice; Lion, Niels; Girault, Hubert H

    2008-05-01

    An electrospray microchip for mass spectrometry comprising an integrated passive mixer to carry out on-chip chemical derivatizations is described. The microchip fabricated using UV-photoablation is composed of two microchannels linked together by a liquid junction. Downstream of this liquid junction, a mixing unit made of parallel oblique grooves is integrated to the microchannel in order to create flow perturbations. Several mixer designs are evaluated. The mixer efficiency is investigated both by fluorescence study and mass spectrometric monitoring of the tagging reaction of cysteinyl peptides with 1,4-benzoquinone. The comparisons with a microchip without a mixing unit and a kinetic model are used to assess the efficiency of the mixer showing tagging kinetics close to that of bulk reactions in an ideally mixed reactor. As an ultimate application, the electrospray micromixer is implemented in a LC-MS workflow. On-line derivatization of albumin tryptic peptides after a reversed-phase separation and counting of their cysteines drastically enhance the protein identification.

  11. On-line determination of anions in pulp mills by capillary electrophoresis (CE); Tehdasoloissa tapahtuva anionien kapillaarielektroforeettinen on-line maeaeritys ja sen hyoedyntaeminen prosessivalvonnassa - MPKY 02

    Energy Technology Data Exchange (ETDEWEB)

    Kokkonen, R.; Holmberg, M.; Vainikka, V. [Finnish Pulp and Paper Research Institute, Espoo (Finland)

    1998-12-31

    The aim of the study was to set-up a process control system for on-line measurement of certain anions. Typical anions which forms precipitates in pulp and paper mills are oxalate, carbonate and sulphate. Thus it is important to develop a continuous process analyzing system to control concentration levels of this anions. For the preliminary tests of continuous determinations of chloride and sulphate anions in tap water a simple on-line system was build in KCL (The Finnish Pulp and Paper Research Institute) and connected to a capillary electroforesis apparatus. In the preliminary tests a chromate buffer (ph = 7.6) was used. Separation of chloride and sulphate was excellent but the stability of buffer was not good enough and it was usable only for few hours. After experimental studies VTT developed a stable capillary electrophoresis method based on mixed amine buffer and this was selected for an on-line method for determination of anions in process waters of the pulp and paper industry. In the preliminary on-line test (r = 20) repeatabilities of migration times of sulphate and chloride with the chromate buffer were < 5 % (RSD) and peak heights < 15 % (RSD). With the mixed amine buffer repeatabilities were better. The preliminary tests showed that it is possible to connect a capillary electrophoresis system to on-line measurements. For the moment no commercial on-line CE apparatus is available. (orig.)

  12. An Interface for Sensitive Analysis of Monoamine Neurotransmitters by Ion-Pair Chromatography–ESI-MS with Continuous On-Line Elimination of Ion-Pair Reagents

    OpenAIRE

    Shi,Shuyun; Zhao, Binqing; Yagnik, Gargey; Zhou, Feimeng

    2013-01-01

    A challenge in coupling ion-pair chromatography (IPC) on-line with electrospray ionization-mass spectrometry (ESI-MS) is that the nonvolatile ion-pair reagent (e.g., alkyl sulfate for amines or tetrabutylammonium for carboxylic acids) in the mobile phase suppresses the ESI-MS signals in the gas phase and their accumulation can clog the MS sampling interface. Consequently, IPC–ESI-MS is conducted either with a volatile ion-pair reagent, which could compromise the analyte separation efficiency,...

  13. Nuclear spins of the isomers /sup 191m-185m/Hg determined by on-line quantum-beat spectroscopy

    CERN Document Server

    Kremmling, H; Fischer, H G; Kluge, H J; Kühl, T; Schüssler, H A

    1979-01-01

    The nuclear spins of the very neutron-deficient /sup 191m-185m/Hg isomers were measured on line at the mass separator ISOLIDE at CERN using pulsed-laser excitation and observation of the time-resolved quantum beats from selected hyperfine-structure states. The spins of these isomers are with I=13/2 equal to those of the long-lived isomers /sup 199m-193m/Hg already known. The persistence of this spin value for eight isomers is explained by the model of rotation-aligned coupling. (12 refs).

  14. Using GPS and absolute gravity observations to separate the effects of present-day and Pleistocene ice-mass changes in South East Greenland

    Science.gov (United States)

    van Dam, T.; Francis, O.; Wahr, J.; Khan, S. A.; Bevis, M.; van den Broeke, M. R.

    2017-02-01

    Measurements of vertical crustal uplift from bedrock sites around the edge of the Greenland ice sheet (GrIS) can be used to constrain present day mass loss. Interpreting any observed crustal displacement around the GrIS in terms of present day changes in ice is complicated, however, by the glacial isostatic adjustment (GIA) signal. With GPS observations alone, it is impossible to separate the uplift driven by present day mass changes from that due to ice mass changes in the past. Wahr et al. (1995) demonstrated that viscoelastic surface displacements were related to the viscoelastic gravity changes through a proportionality constant that is nearly independent of the choice of Earth viscosity or ice history model. Thus, by making measurements of both gravity and surface motion at a bedrock site, the viscoelastic effects could be removed from the observations and we would be able to constrain present day ice mass changes. Alternatively, we could use the same observations of surface displacements and gravity to determine the GIA signal. In this paper, we extend the theory of Wahr et al. (1995) by introducing a constant, Z, that represents the ratio between the elastic changes in gravity and elastic uplift at a particular site due to present day mass changes. Further, we combine 20 yrs of GPS observations of uplift with eight absolute gravity observations over the same period to determine the GIA signal near Kulusuk, a site on the southeastern side of the GrIS, to experimentally demonstrate the theory. We estimate that the GIA signal in the region is 4.49 ± 1.44mm/yr and is inconsistent with most previously reported model predictions that demonstrate that the GIA signal here is negative. However, as there is very little in situ data to constrain the GIA rate in this part of Greenland, the Earth model or the ice history reconstructions could be inaccurate (Khan et al., 2016). Improving the estimate of GIA in this region of Greenland will allow us to better determine

  15. Separation of silver ions and starch modified silver nanoparticles using high performance liquid chromatography with ultraviolet and inductively coupled mass spectrometric detection

    Energy Technology Data Exchange (ETDEWEB)

    Hanley, Traci A.; Saadawi, Ryan; Zhang, Peng; Caruso, Joseph A., E-mail: joseph.caruso@uc.edu; Landero-Figueroa, Julio

    2014-10-01

    The production of commercially available products marketed to contain silver nanoparticles is rapidly increasing. Species-specific toxicity is a phenomenon associated with many elements, including silver, making it imperative to develop a method to identify and quantify the various forms of silver (namely, silver ions vs. silver nanoparticles) possibly present in these products. In this study a method was developed using high performance liquid chromatography (HPLC) with ultraviolet (UV–VIS) and inductively coupled mass spectrometric (ICP-MS) detection to separate starch stabilized silver nanoparticles (AgNPs) and silver ions (Ag{sup +}) by cation exchange chromatography with 0.5 M nitric acid mobile phase. The silver nanoparticles and ions were baseline resolved with an ICP-MS response linear over four orders of magnitude, 0.04 mg kg{sup −1} detection limit, and 90% chromatographic recovery for silver solutions containing ions and starch stabilized silver nanoparticles smaller than 100 nm.

  16. Separation of silver ions and starch modified silver nanoparticles using high performance liquid chromatography with ultraviolet and inductively coupled mass spectrometric detection

    Science.gov (United States)

    Hanley, Traci A.; Saadawi, Ryan; Zhang, Peng; Caruso, Joseph A.; Landero-Figueroa, Julio

    2014-10-01

    The production of commercially available products marketed to contain silver nanoparticles is rapidly increasing. Species-specific toxicity is a phenomenon associated with many elements, including silver, making it imperative to develop a method to identify and quantify the various forms of silver (namely, silver ions vs. silver nanoparticles) possibly present in these products. In this study a method was developed using high performance liquid chromatography (HPLC) with ultraviolet (UV-VIS) and inductively coupled mass spectrometric (ICP-MS) detection to separate starch stabilized silver nanoparticles (AgNPs) and silver ions (Ag+) by cation exchange chromatography with 0.5 M nitric acid mobile phase. The silver nanoparticles and ions were baseline resolved with an ICP-MS response linear over four orders of magnitude, 0.04 mg kg- 1 detection limit, and 90% chromatographic recovery for silver solutions containing ions and starch stabilized silver nanoparticles smaller than 100 nm.

  17. Detection and quantification of some plant growth regulators in a seaweed-based foliar spray employing a mass spectrometric technique sans chromatographic separation.

    Science.gov (United States)

    Prasad, Kamalesh; Das, Arun Kumar; Oza, Mihir Deepak; Brahmbhatt, Harshad; Siddhanta, Arup Kumar; Meena, Ramavatar; Eswaran, Karuppanan; Rajyaguru, Mahesh Rameshchandra; Ghosh, Pushpito Kumar

    2010-04-28

    The sap expelled from the fresh harvest of Kappaphycus alvarezii , a red seaweed growing in tropical waters, has been reported to be a potent foliar spray. Tandem mass spectrometry of various organic extracts of the sap confirmed the presence of the plant growth regulators (PGRs) indole 3-acetic acid, gibberellin GA(3), kinetin, and zeatin. These PGRs were quantified in fresh state and after 1 year of storage by ESI-MS without recourse to chromatographic separation. Quantification was validated against HPLC data. The results may be useful in correlating with the efficacy of the sap. The methodology was extended to two other seaweeds. The method developed is convenient and precise and may find application in other agricultural formulations containing these growth hormones.

  18. Direct Separation of Pregabalin Enantiomers Using a Zwitterionic Chiral Selector by High Performance Liquid Chromatography Coupled to Mass Spectrometry and Ultraviolet Detection

    Directory of Open Access Journals (Sweden)

    Lakshmi Narayana Chennuru

    2016-11-01

    Full Text Available The chromatographic resolution of pregabalin enantiomers has been often achieved by derivatization of the molecule, in order to reach enough sensitivity at low concentrations of the minor enantiomer present in the active principle. In the present article, the development and optimization of two liquid chromatographic methods are presented for the direct resolution of pregabalin enantiomers on a chiral stationary phase (CSP containing a zwitterionic selector derived from cinchona alkaloid and sulfonic acid (CHIRALPAK ZWIX. The key parameters for the separation as well as the compatibility of chromatographic conditions with different detection modes (ultraviolet and mass spectrometry were investigated. The resulting methods were found to be selective, of high performance and low limits of detection (2 µg/mL by UV and 1 ng/mL by MS, respectively and quantification (6 µg/mL by UV and 5 ng/mL by MS, respectively for the minor enantiomer which is considered as a chiral impurity.

  19. Enhanced capabilities for imaging gangliosides in murine brain with matrix-assisted laser desorption/ionization and desorption electrospray ionization mass spectrometry coupled to ion mobility separation.

    Science.gov (United States)

    Škrášková, Karolina; Claude, Emmanuelle; Jones, Emrys A; Towers, Mark; Ellis, Shane R; Heeren, Ron M A

    2016-07-15

    The increased interest in lipidomics calls for improved yet simplified methods of lipid analysis. Over the past two decades, mass spectrometry imaging (MSI) has been established as a powerful technique for the analysis of molecular distribution of a variety of compounds across tissue surfaces. Matrix-assisted laser desorption/ionization (MALDI) MSI is widely used to study the spatial distribution of common lipids. However, a thorough sample preparation and necessity of vacuum for efficient ionization might hamper its use for high-throughput lipid analysis. Desorption electrospray ionization (DESI) is a relatively young MS technique. In DESI, ionization of molecules occurs under ambient conditions, which alleviates sample preparation. Moreover, DESI does not require the application of an external matrix, making the detection of low mass species more feasible due to the lack of chemical matrix background. However, irrespective of the ionization method, the final information obtained during an MSI experiment is very complex and its analysis becomes challenging. It was shown that coupling MSI to ion mobility separation (IMS) simplifies imaging data interpretation. Here we employed DESI and MALDI MSI for a lipidomic analysis of the murine brain using the same IMS-enabled instrument. We report for the first time on the DESI IMS-MSI of multiply sialylated ganglioside species, as well as their acetylated versions, which we detected directly from the murine brain tissue. We show that poly-sialylated gangliosides can be imaged as multiply charged ions using DESI, while they are clearly separated from the rest of the lipid classes based on their charge state using ion mobility. This represents a major improvement in MSI of intact fragile lipid species. We additionally show that complementary lipid information is reached under particular conditions when DESI is compared to MALDI MSI.

  20. A novel phosphoprotein analysis scheme for assessing changes in premalignant and malignant breast cell lines using 2D liquid separations, protein microarrays and tandem mass spectrometry.

    Science.gov (United States)

    Patwa, Tasneem H; Wang, Yanfei; Miller, Fred R; Goodison, Steve; Pennathur, Subramaniam; Barder, Timothy J; Lubman, David M

    2008-01-01

    An analysis of phosphorylation changes that occur during cancer progression would provide insights into the molecular pathways responsible for a malignant phenotype. In this study we employed a novel coupling of 2D-liquid separations and protein microarray technology to reveal changes in phosphoprotein status between premalignant (AT1) and malignant (CA1a) cell lines derived from the human MCF10A breast cell lines. Intact proteins were first separated according to their isoelectric point and hydrophobicities, then arrayed on SuperAmine glass slides. Phosphoproteins were detected using the universal, inorganic phospho-sensor dye, ProQ Diamond. Using this dye, out of 140 spots that were positive for phosphorylation, a total of 85 differentially expressed spots were detected over a pH range of 7.2 to 4.0. Proteins were identified and their peptides sequenced by mass spectrometry. The strategy enabled the identification of 75 differentially expressed phosphoproteins, from which 51 phosphorylation sites in 27 unique proteins were confirmed. Interestingly, the majority of differentially expressed phosphorylated proteins observed were nuclear proteins. Three regulators of apoptosis, Bad, Bax and Acinus, were also differentially phosphorylated in the two cell lines. Further development of this strategy will facilitate an understanding of the mechanisms involved in malignancy progression and other disease-related phenotypes.

  1. Nanoliter-volume protein enrichment, tryptic digestion, and partial separation based on isoelectric points by CE for MALDI mass spectral analysis.

    Science.gov (United States)

    Nesbitt, Chandra A; Jurcic, Kristina; Yeung, Ken K-C

    2008-01-01

    Sequence-specific proteolysis is an important part of protein identification by MS. Digestion of protein is commonly performed in-solution, in sample vials with volumes ranging from milli- to microliters. When digestion is performed with a sample volume below 1 microL, handling of solution and potential sample loss via adsorption become significant issues. In this report, a proof of concept for the digestion of a small volume protein solution inside a capillary was demonstrated using a discontinuous buffer system previously studied (Nesbitt, C. A., et al. J. Chromatogr. A 2005, 1073, 175-180). Upon voltage application, a pH junction was created by the discontinuous buffer. Using myoglobin as an example, the protein molecules were enriched at the junction with an estimated volume of a few nanoliters. A protease, trypsin, was then introduced to myoglobin at the junction by coenrichment to induce in-capillary digestion. The voltage application was then suspended to provide the necessary time (2 h) for the proteolysis to proceed. When completed, voltage application was resumed, and the discontinuous buffer reconcentrated the peptides formed from digestion. Importantly, the refocused peptides appeared to roughly elute according to their pIs, resulting in a partial separation. Direct sample deposition from capillary was performed to facilitate mass spectral analysis by MALDI. The partial separation, according to pI, offered the potential benefits of MALDI MS signal enhancement and provided supplementary pI information for peptide identity assignment.

  2. 在线热裂解-气相色谱/质谱联用技术分析葫芦巴净油的热裂解产物%Analysis of Pyrolysates from Fenugreek Absolute by On-Line Pyrolysis-Gas Chromatography/Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    叶荣飞; 程侠; 宋森川; 李峰; 黄飞; 任成龙; 宋化灿

    2015-01-01

    采用在线热裂解-气相色谱/质谱(Py-GC/MS)联用技术研究了氦气氛围中葫芦巴净油在300、400、500、600、700、800℃下的热裂解行为。结果表明:①在上述条件下共鉴定出86种裂解产物,主要是酯、酸、醇、烯烃类化合物;②裂解温度低于500℃时,检测到的成分基本相同;③裂解温度从600℃升至800℃,检测到危害性的苯系物种类增多、相对含量增大。此外,对葫芦巴净油裂解产物的致香机理和苯系物的形成机理进行了简单讨论。%Fenugreek absolute was pyrolyzed under helium atmospheres at 300,400,500,600,700 and 800 ℃,respectively.The pyrolysates were analyzed by on-line gas chromatography/mass spectrometry (GC/MS).The results showed that,first,eighty-six constituents were identified,and the major of the pyrolysates were esters,acids,alcohols and alkenes.Second,the pyrolysates were almost same at lower temperature (300~500 ℃).Third,more and more benzene derivates were identified with higher per-centage with increasing temperature (600~800 ℃).In addition,the flavor mechanism and the attribu-tion of benzene compounds were investigated.

  3. Determination of ultralow level 129I/127I in natural samples by separation of microgram carrier free iodine and accelerator mass spectrometry detection.

    Science.gov (United States)

    Hou, Xiaolin; Zhou, Weijian; Chen, Ning; Zhang, Luyuan; Liu, Qi; Luo, Maoyi; Fan, Yukun; Liang, Wangguo; Fu, Yunchong

    2010-09-15

    Separation of carrier free iodine from low iodine level samples and accurate measurement of ultralow level (129)I in micrograms of iodine target are essential but a bottleneck in geological dating of terrestrial system and tracer research using naturally produced (129)I. In this work, we present a carrier free method using coprecipitation of AgI with AgCl for preparing micrograms of iodine target, associated with combustion using a tube furnace for separating iodine from solid samples and anion exchange chromatography for preconcentrating iodine from a large volume of water. An accelerator mass spectrometry was used to measure ultralow level (129)I in micrograms of iodine target. The recovery of iodine in the entire separation procedure is higher than 80% and 65% for solid and water samples, respectively. One microgram iodine in the target (AgI-AgCl) can produce a stable (127)I signal for AMS measurement of (129)I/(127)I, and a detection limit of this method for (129)I is calculated to be 10(5) atoms. This will allow us to accurately determine (129)I in prenuclear geological samples of low iodine concentration with (129)I/(127)I of 10(-12), such as loess, soil, coral, rock, sediment, and groundwater. Some samples with low iodine content have been successfully analyzed, and the lowest value of the (129)I/(127)I ratio of 2 × 10(-11) was observed in 23.5 and 63.5 m loess samples collected in the Loess Plateau, China. The developed method sheds light on a wide application in earth science.

  4. A Refreshable, On-line Cache for HST Data Retrieval

    Science.gov (United States)

    Fraquelli, Dorothy A.; Ellis, Tracy A.; Ridgaway, Michael; DPAS Team

    2016-01-01

    We discuss upgrades to the HST Data Processing System, with an emphasis on the changes Hubble Space Telescope (HST) Archive users will experience. In particular, data are now held on-line (in a cache) removing the need to reprocess the data every time they are requested from the Archive. OTFR (on the fly reprocessing) has been replaced by a reprocessing system, which runs in the background. Data in the cache are automatically placed in the reprocessing queue when updated calibration reference files are received or when an improved calibration algorithm is installed. Data in the on-line cache are expected to be the most up to date version. These changes were phased in throughout 2015 for all active instruments.The on-line cache was populated instrument by instrument over the course of 2015. As data were placed in the cache, the flag that triggers OTFR was reset so that OTFR no longer runs on these data. "Hybrid" requests to the Archive are handled transparently, with data not yet in the cache provided via OTFR and the remaining data provided from the cache. Users do not need to make separate requests.Users of the MAST Portal will be able to download data from the cache immediately. For data not in the cache, the Portal will send the user to the standard "Retrieval Options Page," allowing the user to direct the Archive to process and deliver the data.The classic MAST Search and Retrieval interface has the same look and feel as previously. Minor changes, unrelated to the cache, have been made to the format of the Retrieval Options Page.

  5. Detection of bacteria from biological mixtures using immunomagnetic separation combined with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

    Science.gov (United States)

    Madonna, A.J.; Basile, F.; Furlong, E.; Voorhees, K.J.

    2001-01-01

    A rapid method for identifying specific bacteria from complex biological mixtures using immunomagnetic separation coupled to matrix-assisted laser desorption/ionization time-of-flight mass spectrometry has been developed. The technique employs commercially available magnetic beads coated with polycolonal antibodies raised against specific bacteria and whole cell analysis by MALDI-MS. A suspension of a bacterial mixture is mixed with the immunomagnetic beads specific for the target microorganism. After a short incubation period (20 mins) the bacteria captured by the beads are washed, resuspended in deionized H2O and directly applied onto a MALDI probe. Liquid suspensions containing bacterial mixtures can be screened within 1 h total analysis time. Positive tests result in the production of a fingerprint mass spectrum primarily consisting of protein biomarkers characteristic of the targeted microorganism. Using this procedure, Salmonella choleraesuis was isolated and detected from standard bacterial mixtures and spiked samples of river water, human urine, and chicken blood. Copyright ?? 2001 John Wiley & Sons, Ltd.

  6. Chromatographic enrichment and subsequent separation of nickel and vanadyl porphyrins from natural seeps and molecular characterization by positive electrospray ionization FT-ICR mass spectrometry.

    Science.gov (United States)

    Putman, Jonathan C; Rowland, Steven M; Corilo, Yuri E; McKenna, Amy M

    2014-11-04

    We report a novel chromatographic method to enrich and separate nickel and vanadyl porphyrins from a natural seep sample and combine molecular level characterization by positive-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Vanadyl and nickel porphyrin model compound elution from primary secondary amine (PSA) stationary phase combined with UV-vis spectroscopy confirms enrichment and subsequent fractionation of nickel and vanadyl porphyrins into polarity-based subfractions. A more than 100-fold increase in signal-to-noise ratio for nickel porphyrins enables unequivocal elemental composition assignment confirmed by isotopic fine structure for all isotopes >1% relative abundance, and the first mass spectral identification of (61)Ni porphyrin isotopologues derived from natural seeps. Oxygen-containing vanadyl porphyrins and sulfur-containing vanadyl porphyrins are isolated in the same fraction simultaneously from the same sample. We provide the first chromatographic evidence of carboxylic acid functionalities peripheral to the porphyrin core, in agreement with previous studies.

  7. A Thermal Infrared Imaging Study of Very Low-Mass, Wide Separation Brown Dwarf Companions to Upper Scorpius Stars: Constraining Circumstellar Environments

    CERN Document Server

    Bailey, Vanessa; Currie, Thayne; Su, Kate Y L; Esposito, Simone; Hill, John M; Hoffmann, William F; Jones, Terry; Kim, Jihun; Leisenring, Jarron; Meyer, Michael; Murray-Clay, Ruth; Nelson, Matthew J; Pinna, Enrico; Puglisi, Alfio; Rieke, George; Rodigas, Timothy; Skemer, Andrew; Skrutskie, Michael F; Vaitheeswaran, Vidhya; Wilson, John C

    2013-01-01

    We present a 3-5um LBT/MMT adaptive optics imaging study of three Upper Scorpius stars with brown dwarf (BD) companions with very low-masses/mass ratios (M_BD < 25M_Jup; M_BD / M_star ~ 1-2%), and wide separations (300-700 AU): GSC 06214, 1RXS 1609, and HIP 78530. We combine these new thermal IR data with existing 1-4um and 24um photometry to constrain the properties of the BDs and identify evidence for circumprimary/secondary disks in these unusual systems. We confirm that GSC 06214B is surrounded by a disk, further showing this disk produces a broadband IR excess due to small dust near the dust sublimation radius. An unresolved 24um excess in the system may be explained by the contribution from this disk. 1RXS 1609B exhibits no 3-4um excess, nor does its primary; however, the system as a whole has a modest 24um excess, which may come from warm dust around the primary and/or BD. Neither object in the HIP 78530 system exhibits near- to mid-IR excesses. We additionally find that the 1-4um colors of HIP 7853...

  8. Simultaneous determination of 3-monochloropropane-1,2-diol and acrylamide in food by gas chromatography-triple quadrupole mass spectrometry with coupled column separation.

    Science.gov (United States)

    Xu, Xiao-min; He, Hua-li; Zhu, Yan; Feng, Liang; Ying, Ying; Huang, Bai-fen; Shen, Hai-tao; Han, Jian-long; Ren, Yi-ping

    2013-01-14

    Both 3-monochloropropane-1,2-diol (3-MCPD) and acrylamide are contaminants found in heat-processed foods and their related products. A quantitative method was developed for the simultaneous determination of both contaminants in food by gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS). The analytes were purified and extracted by the matrix solid-phase dispersion extraction (MSPDE) technique with Extrelut NT. A coupled column (a 3 m Innowax combined with a 30 m DB-5 ms) was developed to separate both compounds efficiently without derivatization. Triple quadrupole mass spectrometry in multiple reaction monitoring mode (MRM) was applied to suppress matrix interference and obtain good sensitivity in the determination of both analytes. The limit of detection (LOD) in the sample matrix was 5 μg kg(-1) for 3-MCPD or acrylamide. The average recoveries for 3-MCPD and acrylamide in different food matrices were 90.5-107% and 81.9-95.7%, respectively, with the intraday relative standard deviations (RSDs) of 5.6-13.5% and 5.3-13.4%, respectively. The interday RSDs were 6.1-12.6% for 3-MCPD and were 5.0-12.8% for acrylamide. Both contaminants were found in samples of bread, fried chips, fried instant noodles, soy sauce, and instant noodle flavoring. Neither 3-MCPD nor acrylamide was detected in the samples of dairy products (solid or liquid samples) and non-fried instant noodles. Copyright © 2012 Elsevier B.V. All rights reserved.

  9. Total on-line purchasing system (TOPS)

    Energy Technology Data Exchange (ETDEWEB)

    Collins, N.

    1995-11-01

    The Information Management Division (IMD) at LLNL is developing a new purchasing system for the Procurement Department. The first major development of this new system is called, {open_quotes}Total On-Line Purchasing System{close_quotes} (TOPS). TOPS will help speed up the requisitioning process by having requisitions electronically entered by requesters and electronically sent to buyers to be put on Purchase Orders. The new purchasing system will use Electronic Commerce (EC)/Electronic Data Interchange (EDI), to help increase transaction flows for shipping notices, RFQs, Quotes, Purchase Orders, and Invoices. ANSI X.12 is the EDI standard that this new EC will use.

  10. Investigations of on-line process analysis in batchwise and continuous ethanol production using Zymomonas mobilis. Untersuchungen zur on-line Prozessanalyse bei der satzweisen und kontinuierlichen Ethanolproduktion mit Zymomonas mobilis

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, W.

    1985-01-01

    A fermentation unit was connected to a process computer for on-line data acquisition, process observation and SPC control. The continuous measurement of relevant process parameters was to enable off-line modelling of growth and product formation of the bacterium Zymomonas mobilis. A continuous analysis of substrate and product concentrations beyond the conventional instrumentation of bioreactors was made possible by using membrane separation processes with subsequent detection of components. A glucose detection method adaptable to glucose was developed. Exhaust gas, dissolved gas and volatile components were measured using a mass spectrometer convected to the reactor. Data acquisition, data analysis and system control were carried out using the process computer system CASFA (= Computer Automation System for Fermentation Systems on the Laboratory Scale).

  11. Characterization of oligosaccharides with capillary high performance anion exchange chromatography hyphenated to pulsed amperometric detection and ion trap mass spectrometry : application to the analysis of human lysosomal disorders

    NARCIS (Netherlands)

    Bruggink, Cornelis

    2013-01-01

    The development of a capillary ion chromatograph is described together with a matching desalter. This desalter made it possible to use on-line a mass spectrometer. The mass spectrometer enables partly to characterize carbohydrates eluting from the anion exchange column. This separation technology is

  12. On-line and Mobil Learning Activities

    Science.gov (United States)

    Ackerman, S. A.; Whittaker, T. M.; Jasmin, T.; Mooney, M. E.

    2012-12-01

    Introductory college-level science courses for non-majors are critical gateways to imparting not only discipline-specific information, but also the basics of the scientific method and how science influences society. They are also indispensable for student success to degree. On-line, web-based homework (whether on computers or mobile devices) is a rapidly growing use of the Internet and is becoming a major component of instruction in science, replacing delayed feedback from a few major exams. Web delivery and grading of traditional textbook-type questions is equally effective as having students write them out for hand grading, as measured by student performance on conceptual and problem solving exams. During this presentation we will demonstrate some of the interactive on-line activities used to teach concepts and how scientists approach problem solving, and how these activities have impacted student learning. Evaluation of the activities, including formative and summative, will be discussed and provide evidence that these interactive activities significantly enhance understanding of introductory meteorological concepts in a college-level science course. More advanced interactive activities are also used in our courses for department majors, some of these will be discussed and demonstrated. Bring your mobile devices to play along! Here is an example on teaching contouring: http://profhorn.aos.wisc.edu/wxwise/contour/index.html

  13. The Monitor System for the LHCb on-line farm

    CERN Document Server

    Bonifazi, F; Carbone, A; Galli, D; Gregori, D; Marconi, U; Peco, G; Vagnoni, V

    2005-01-01

    The aim of the LHCb on-line farm Monitor System is to keep under control all the working indicators which are relevant for the farm operation, and to set the appropriate alarms whenever an error or a critical condition comes up. Since the most stressing tasks of the farm are the data transfer and processing, relevant indicators includes the CPU and the memory load of the system, the network interface and the TCP/IP stack parameters, the rates of the interrupts raised by the network interface card and the detailed status of the running processes. The monitoring of computers’ physical conditions (temperatures, fan speeds and motherboard voltages) are the subject of a separate technical note, since they are accessed in a different way, by using the IPMI protocol.

  14. On-line control of the nonlinear dynamics for synchrotrons

    Science.gov (United States)

    Bengtsson, J.; Martin, I. P. S.; Rowland, J. H.; Bartolini, R.

    2015-07-01

    We propose a simple approach to the on-line control of the nonlinear dynamics in storage rings, based on compensation of the nonlinear resonance driving terms using beam losses as the main indicator of the strength of a resonance. The correction scheme is built on the analysis of the resonance driving terms in first perturbative order and on the possibility of using independent power supplies in the sextupole magnets, which is nowadays present in many synchrotron light sources. Such freedom allows the definition of "smart sextupole knobs" attacking each resonance separately. The compensation scheme has been tested at the Diamond light source and proved to be effective in opening up the betatron tune space, resonance free, available to the electron beam and to improve the beam lifetime.

  15. FLOW INJECTION ON-LINE SEPARATION AND SPECTROPHOTOMETRIC DETERMINATION OF TRACES OF LEAD IN ENVIRONMENTAL SAMPLES%环境样品中痕量铅的流动注射在线分离及分光光度检测

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A flow injection method has been developed for the determination of lead in environmental samples by use of on-line preconcentration on a Pb*SpecTM column and spectrophotometric detection. The lead in sample solutions was adsorbed selectively on the column from 1mol*l-1 nitric acid and the retained lead was eluted with 0.1mol*l-1 ammonium oxalate.4-(2-pyridylazo)resorcinol (PAR) was used as a chromogenic reagent at pH 10 and the absorbance of Pb-PAR complex was monitored at 530 nm. The pumps, valves and spectrophotometer were controlled by a personal computer. The detection limit (3σ) was 3ng of lead. The RSD is 1.7% at a level of 0.4μg lead. The proposed method was successfully applied to the determination of lead in fly ash of an incinerator for industrial waste and in river water certified reference material provided by the Japan Society for Analytical Chemistry.

  16. PI-TOF/MS法逐口在线分析卷烟主流烟气中7种有机物%On-line Puff-by-puff Analysis of Seven Organic Compounds in Mainstream Cigarette Smoke by Photo-Ionization-Time-of-Flight Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    庞永强; 姜兴益; 罗彦波; 李雪; 朱风鹏; 陈再根

    2015-01-01

    In order to investigate the puff-by-puff release characteristics of mainstream cigarette smoke, a photo-ionization-time-of-flight mass spectrometry (PI-TOF/MS) method was developed for on-line analyzing seven organic compounds (acetaldehyde, 1, 3-butadiene, acetone, isoprene, 2-butanone, benzene and toluene) in mainstream cigarette smoke. The constant volume sampling of mainstream cigarette smoke was achieved by a constant flow orifice, the smoke was directly introduced into the ion source of PI-TOF/MS through a sampling tube with a heating unit. The results showed that: 1) The intra-day and inter-day repeatabilities were good with the relative standard deviations (RSDs) less than 15%, exclusive of the first and the last puffs, where the deviations were larger due to cigarette lighting and variable puff volume, respectively. 2) The RSDs between the results of 1R5F and 3R4F reference cigarettes determined by this method and the mean test values of CORESTA collaborative experiments were less than 10%. 3) The deliveries of different compounds in single puff differed obviously, as did the deliveries between different puffs. This method is simple, fast, accurate, and suitable for the on-line puff-by-puff analysis of mainstream cigarette smoke.%为了考察卷烟抽吸过程中主流烟气的逐口释放特征,建立了在线分析卷烟主流烟气中乙醛、1,3-丁二烯、丙酮、异戊二烯、2-丁酮、苯和甲苯7种有机物的光致电离飞行时间质谱(PI-TOF/MS)方法。通过标准恒流孔实现卷烟烟气的定量取样,烟气经带加热装置的采样管引入PI-TOFMS离子源内进行分析。结果表明:①方法日内重复性、日间重复性良好,除第1口和最后1口由于点火过程及抽吸容量不同而导致变异较大外,其他口的RSD均小于15%;②1R5F和3R4F参比卷烟的测试结果与CORESTA共同实验测试平均值的相对偏差在10%以内;③不同化合物的逐口释放量存在较大

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

    Science.gov (United States)

    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.

  18. The non-Newtonian heat and mass transport of He 2 in porous media used for vapor-liquid phase separation. Ph.D. Thesis

    Science.gov (United States)

    Yuan, S. W. K.

    1985-01-01

    This investigation of vapor-liquid phase separation (VLPS) of He 2 is related to long-term storage of cryogenic liquid. The VLPS system utilizes porous plugs in order to generate thermomechanical (thermo-osmotic) force which in turn prevents liquid from flowing out of the cryo-vessel (e.g., Infrared Astronomical Satellite). An apparatus was built and VLPS data were collected for a 2 and a 10 micrometer sintered stainless steel plug and a 5 to 15 micrometer sintered bronze plug. The VLPS data obtained at high temperature were in the nonlinear turbulent regime. At low temperature, the Stokes regime was approached. A turbulent flow model was developed, which provides a phenomenological description of the VLPS data. According to the model, most of the phase separation data are in the turbulent regime. The model is based on concepts of the Gorter-Mellink transport involving the mutual friction known from the zero net mass flow (ZNMF) studies. The latter had to be modified to obtain agreement with the present experimental VLPS evidence. In contrast to the well-known ZNMF mode, the VLPS results require a geometry dependent constant (Gorter-Mellink constant). A theoretical interpretation of the phenomenological equation for the VLPS data obtained, is based on modelling of the dynamics of quantized vortices proposed by Vinen. In extending Vinen's model to the VLPS transport of He 2 in porous media, a correlation between the K*(GM) and K(p) was obtained which permits an interpretation of the present findings. As K(p) is crucial, various methods were introduced to measure the permeability of the porous media at low temperatures. Good agreement was found between the room temperature and the low temperature K(p)-value of the plugs.

  19. On-Line Hyperspectral Transmittance Imaging for Internal Defect Detection of Pickling Cucumbers

    Science.gov (United States)

    Hyperspectral imaging technique under transmittance mode was investigated for detection of internal defect in pickling cucumbers such as carpel suture separation or hollow cucumbers caused by mechanical stress. A prototype of on-line hyperspectral transmittance imaging system was developed for real...

  20. On-Line Real Time Realization and Application of Adaptive Fuzzy Inference Neural Network

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    In this paper,a modeling algorithm developed by transferring the adaptive fuzzy inference neural network into an on-line real time algorithm,combining the algorithm with conventional system identification method and applying them to separate identification of nonlinear mu Iti-variable systems is introduced and discussed.

  1. Characterizing Low Molecular Weight Organic Matter in Arctic Polygonal Tundra Soils to Identify Biogeochemical Hotspots Using a Dual-Separation, High-Resolution Mass Spectrometry Approach

    Science.gov (United States)

    Ladd, M.; Wullschleger, S. D.; Iversen, C. M.; Hettich, R.

    2016-12-01

    Reliably modeling biogeochemical processes (e.g. decomposition, plant-microbial competition for nutrients) across spatial or temporal scales requires elucidating the chemical composition of low molecular weight (LMW) dissolved soil organic matter (DOM). Our understanding is limited, however, by the wide-ranging physicochemical properties and high fluxes of these compounds, posing major challenges in detection, isolation, and quantification. Here, we developed and evaluated a sensitive, non-targeted approach to characterize LMW DOM in the Arctic, a unique system that is warming at a rate twice that of the global average and may have significant feedbacks to global C and N cycles. Soil cores were collected from a continuous permafrost, polygonal tundra landscape near Barrow, Alaska (71° 16' N) and sectioned into 5 cm increments. Water and salt extracts from each section were filtered and injected onto C18 reversed-phase or zwitterionic-type hydrophilic interaction chromatography (ZIC-pHILIC) columns for separation. LMW DOM profiles were obtained using high-resolution mass spectrometry (HRMS), and unique features, known and unknown, were characterized by LC retention time, accurate mass (m/z), and molecular fragmentation pattern. Coupling two orthogonal chromatographic separations with HRMS enabled the characterization of hundreds of analytes in a single measurement providing enhanced, high-throughput coverage of LMW DOM from soil extracts. The complexity and relative/absolute intensities of LMW DOM features (e.g. organic acids, amino sugars, peptides) varied across polygon type (high- or low-centered), extract condition, and with depth, providing an information-rich, molecular signal of LMW DOM availability across scales. Comprehensively profiling this complex mixture of small molecules of both biotic and abiotic origin provides a chemical signature of biological function, allowing for more reliable predictions of how discrete, molecular-scale processes may control

  2. Aprender a innovar: una experiencia on line

    Directory of Open Access Journals (Sweden)

    Joaquín MORENO MARCHAL

    2014-11-01

    Full Text Available La creatividad y la innovación se han convertido en recursos clave en la denominada sociedad del conocimiento, que bien podría ser también llamada sociedad de la innovación. Pero innovar es una actividad compleja, que integra la aplicación de múltiples capacidades, el pensamiento divergente y convergente, la gestión de equipos humanos, la comunicación. Ahora bien, a innovar se puede, y se debe, aprender. Aprender a innovar es un reto y también una obligación para el conjunto del sistema educativo en todos sus niveles. Partiendo de estas consideraciones este trabajo expone una experiencia de aprendizaje de la creatividad y de la innovación a través de un curso totalmente on line basado en la plataforma MOODLE, en el marco del Programa de Formación Permanente de la Universidad de Cádiz. Se presenta un modelo del proceso de innovación, denominado CREALAB, de elaboración propia. Este modelo se ha utilizado como base del proceso de aprendizaje de la creatividad y de la innovación y en el diseño del curso, está organizado en torno a actividades y tiene un carácter iterativo y realimentado. Se presentan además el conjunto del diseño metodológico y los resultados obtenidos en las dos ediciones celebradas hasta el momento. El diseño del curso totalmente on line y los resultados alcanzados permiten estimar un alto potencial de aplicación, tanto a nivel personal como a nivel organizacional.

  3. On-line chemical composition analyzer development

    Energy Technology Data Exchange (ETDEWEB)

    Roberts, M.J.; Garrison, A.A.; Muly, E.C.; Moore, C.F.

    1992-02-01

    The energy consumed in distillation processes in the United States represents nearly three percent of the total national energy consumption. If effective control of distillation columns can be accomplished, it has been estimated that it would result in a reduction in the national energy consumption of 0.3%. Real-time control based on mixture composition could achieve these savings. However, the major distillation processes represent diverse applications and at present there does not exist a proven on-line chemical composition sensor technology which can be used to control these diverse processes in real-time. This report presents a summary of the findings of the second phase of a three phase effort undertaken to develop an on-line real-time measurement and control system utilizing Raman spectroscopy. A prototype instrument system has been constructed utilizing a Perkin Elmer 1700 Spectrometer, a diode pumped YAG laser, two three axis positioning systems, a process sample cell land a personal computer. This system has been successfully tested using industrially supplied process samples to establish its performance. Also, continued application development was undertaken during this Phase of the program using both the spontaneous Raman and Surface-enhanced Raman modes of operation. The study was performed for the US Department of Energy, Office of Industrial Technologies, whose mission is to conduct cost-shared R D for new high-risk, high-payoff industrial energy conservation technologies. Although this document contains references to individual manufacturers and their products, the opinions expressed on the products reported do not necessarily reflect the position of the Department of Energy.

  4. On-line sample processing involving microextraction techniques as a front-end to atomic spectrometric detection for trace metal assays: A review

    Energy Technology Data Exchange (ETDEWEB)

    Miró, Manuel, E-mail: manuel.miro@uib.es [FI-TRACE Group, Department of Chemistry, Faculty of Sciences, University of the Balearic Islands, E-07122 Palma de Mallorca, Illes Balears (Spain); Hansen, Elo Harald [Granåsen 93, DK-2800 Kgs. Lyngby (Denmark)

    2013-06-11

    Graphical abstract: -- Highlights: •Role of flow injection in automation of microextraction techniques for metal assays. •On-line coupling of liquid phase microextraction (LPME) to atomic spectrometry. •Critical evaluation of on-line single drop and dispersive LPME. •On-line coupling of micro-solid phase extraction (μSPE) to atomic spectrometry. •Critical appraisal of magnetic/carbon nanoparticles and biomass for on-line μSPE. -- Abstract: Within the last decade, liquid-phase microextraction (LPME) and micro-solid phase extraction (μSPE) approaches have emerged as substitutes for conventional sample processing procedures for trace metal assays within the framework of green chemistry. This review surveys the progress of the state of the art in simplification and automation of microextraction approaches by harnessing to the various generations of flow injection (FI) as a front end to atomic absorption spectrometry (AAS), atomic fluorescence spectrometry (AFS) or inductively coupled plasma atomic emission spectrometry or mass spectrometry (ICP-AES/MS). It highlights the evolution of flow injection analysis and related techniques as vehicles for appropriate sample presentation to the detector and expedient on-line matrix separation and pre-concentration of trace levels of metals in troublesome matrices. Rather than being comprehensive this review is aimed at outlining the pros and cons via representative examples of recent attempts in automating green sample preparation procedures in an FI or sequential injection (SI) mode capitalizing on single-drop microextraction, dispersive liquid-phase microextraction and advanced sorptive materials including carbon and metal oxide nanoparticles, ion imprinted polymers, superparamagnetic nanomaterials and biological/biomass sorbents. Current challenges in the field are identified and the synergetic combination of flow analysis, nanotechnology and metal-tagged biomolecule detection is envisaged.

  5. Separation and analysis of trace volatile formaldehyde in aquatic products by a MoO₃/polypyrrole intercalative sampling adsorbent with thermal desorption gas chromatography and mass spectrometry.

    Science.gov (United States)

    Ma, Yunjian; Zhao, Cheng; Zhan, Yisen; Li, Jianbin; Zhang, Zhuomin; Li, Gongke

    2015-05-01

    An in situ embedded synthesis strategy was developed for the preparation of a MoO3 /polypyrrole intercalative sampling adsorbent for the separation and analysis of trace volatile formaldehyde in aquatic products. Structural and morphological characteristics of the MoO3 /polypyrrole intercalative adsorbent were investigated by a series of characterization methods. The MoO3 /polypyrrole sampling adsorbent possessed a higher sampling capacity and selectivity for polar formaldehyde than commonly used commercial adsorbent Tenax TA. Finally, the MoO3 /polypyrrole adsorbent was packed in the thermal desorption tube that was directly coupled to gas chromatography with mass spectrometry for the analysis of trace volatile formaldehyde in aquatic products. Trace volatile formaldehyde from real aquatic products could be selectively sampled and quantified to be 0.43-6.6 mg/kg. The detection limit was achieved as 0.004 μg/L by this method. Good recoveries for spiked aquatic products were achieved in range of 75.0-108% with relative standard deviations of 1.2-9.0%. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. A supersonic jet target for the cross section measurement of the 12C(α, γ)16O reaction with the recoil mass separator ERNA

    Science.gov (United States)

    Rapagnani, D.; Buompane, R.; Di Leva, A.; Gialanella, L.; Busso, M.; De Cesare, M.; De Stefano, G.; Duarte, J. G.; Gasques, L. R.; Morales Gallegos, L.; Palmerini, S.; Romoli, M.; Tufariello, F.

    2017-09-01

    12C(α, γ)16O cross section plays a key-role in the stellar evolution and nucleosynthesis of massive stars. Hence, it must be determined with the precision of about 10% at the relevant Gamow energy of 300 keV. The ERNA (European Recoil mass separator for Nuclear Astrophysics) collaboration measured, for the first time, the total cross section of 12C(α, γ)16O by means of the direct detection of the 16O ions produced in the reaction down to an energy of Ecm = 1.9 MeV. To extend the measurement at lower energy, it is necessary to limit the extension of the He gas target. This can be achieved using a supersonic jet, where the oblique shock waves and expansion fans formed at its boundaries confine the gas, which can be efficiently collected using a catcher. A test version of such a system has been designed, constructed and experimentally characterized as a bench mark for a full numerical simulation using FV (Finite Volume) methods. The results of the commissioning of the jet test version and the design of the new system that will be used in combination with ERNA are presented and discussed.

  7. High performance liquid chromatography/ion-trap mass spectrometry for separation and simultaneous determination of ethynylestradiol, gestodene, levonorgestrel, cyproterone acetate and desogestrel.

    Science.gov (United States)

    Matejícek, David; Kubán, Vlastimil

    2007-04-11

    A fast and highly sensitive high performance liquid chromatographic/ion-trap mass spectrometric method (LC/MS) has been developed for simultaneous determination of ethynylestradiol (EE2), gestodene (GES), levonorgestrel (LNG), cyproterone acetate (CPA) and desogestrel (DES). Among three types of sorbents tested (C8, C18 and phenyl) from two suppliers, the best separation was achieved on reverse phase Zorbax SB-Phenyl column using aqueous methanol as a mobile phase. A linear gradient profile from 70 up to 100% (v/v) in 7th min, kept constant at 100% up to 10th min and followed by a negative gradient to 70% of methanol up to 12th min was used for elution. Applicability of electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) and influence of the mobile phase composition, its flow rate, capillary/vaporizer temperature of API source and in-source fragmentor voltage ionization are discussed. The on-column limits of quantification (10S/N) were 300 pg of EE2, 14 pg of GES and LNG, 4 pg of CPA and 960 pg of DES per injection (1 microL) using APCI with data collection in selected ion monitoring (SIM) mode. The analytical performance of the method was evaluated using the determination of EE2, GES, LNG, CPA and DES in contraceptives and river water samples.

  8. The transesterification of rapeseed and waste sunflower oils: Mass-transfer and kinetics in a laboratory batch reactor and in an industrial-scale reactor/separator setup.

    Science.gov (United States)

    Klofutar, B; Golob, J; Likozar, B; Klofutar, C; Zagar, E; Poljansek, I

    2010-05-01

    We have investigated the transesterification of rapeseed (RO) and waste sunflower (SO) oils with methanol in the presence of potassium hydroxide as a catalyst. The transesterification of tri-acylglycerols was first conducted in a batch reactor. The effect of the temperature on the reaction rates was studied at a constant molar ratio of the alcohol to tri-acylglycerols (6:1) and for a constant concentration of the catalyst (1.0wt%). Size-exclusion chromatography and (1)H NMR spectroscopy were used to quantitatively monitor the transesterification reaction. The mass-transfer coefficients of the tri-acylglycerols during the initial transesterification stage were found to be 0.2-1.2x10(-5)mmin(-1), depending on the type of oil and the temperature. Calculated activation energies implied that at higher temperatures the formation of mono-acylglycerols and glycerole was favored for the SO (93kJ/mol for the forward and 48kJ/mol for the backward reaction) and the RO (47kJ/mol for the forward and 36kJ/mol for the backward reaction), respectively. For the continuous industrial reactor/separator setup, the optimum methanol recycle ratio was established as 0.0550.

  9. Influence of visualization on consumption during on-line shopping

    OpenAIRE

    Hictaler, Urška

    2013-01-01

    This diploma work studies the influence of visualization on consumption during on-line shopping. The first part of the thesis starts with key areas of visualization, consumption and on-line shopping. Visualization, areas of use, human perception and ways of product presentation in on-line shops are defined discussed first. Next, consumption, consumers and factors that influence their decisions and satisfaction are defined. The last topic in the first part of the thesis discusses on-line shopp...

  10. On-Line Learning: One Way to Bring People Together

    Science.gov (United States)

    Goff-Kfouri, Carol Ann

    2006-01-01

    The purpose of this study was to demonstrate the benefits of on-line learning for adult learners and to further demystify three common misconceptions concerning on-line learning: students certainly do receive support from their on-line professors, the professor is pro-active rather than passive, and students may be more motivated to learn than in…

  11. A Distributed System for Learning Programming On-Line

    Science.gov (United States)

    Verdu, Elena; Regueras, Luisa M.; Verdu, Maria J.; Leal, Jose P.; de Castro, Juan P.; Queiros, Ricardo

    2012-01-01

    Several Web-based on-line judges or on-line programming trainers have been developed in order to allow students to train their programming skills. However, their pedagogical functionalities in the learning of programming have not been clearly defined. EduJudge is a project which aims to integrate the "UVA On-line Judge", an existing…

  12. Electrochemically-Modulated Separations for Material Accountability Measurements

    Energy Technology Data Exchange (ETDEWEB)

    Arrigo, Leah M.; Liezers, Martin; Douglas, Matthew; Green, Michael A.; Farmer, Orville T.; Schwantes, Jon M.; Peper, Shane M.; Duckworth, Douglas C.

    2010-05-07

    The Safeguards community recognizes that an accurate and timely measurement of accountable material mass at the head-end of the facility is critical to a modern materials control and accountability program at fuel reprocessing plants. For material accountancy, it is critical to detect both acute and chronic diversions of nuclear materials. Therefore, both on-line nondestructive (NDA) and destructive analysis (DA) approaches are desirable. Current methods for DA involve grab sampling and laboratory based column extractions that are costly, hazardous, and time consuming. Direct on-line gamma measurements of Pu, while desirable, are not possible due to contributions from other actinide and fission products. A technology for simple, online separation of targeted materials would benefit both DA and NDA measurements.

  13. SOL: INNOVACIÓN ON-LINE

    Directory of Open Access Journals (Sweden)

    Rubén Faúndez

    2007-11-01

    Full Text Available Las aplicaciones de simulación tienden a ser cada vez más cercanas a usuarios e industrias. Sin embargo, muchas de ellas no poseen ni la capacidad ni el conocimiento como para desarrollar internamente sus modelos de simulación. Por este motivo, y como una forma de apoyar la toma de decisiones basándose en modelos de simulación, se presenta la plataforma SOL (Simulación On Line. La metodología completa de trabajo, así como la interacción entre SOL, Empresa y Asesor, son presentadas. Su base de datos, los niveles de usuarios, sus funcionalidades, y la creación automatizada de información grafica y visual, también son explicadas. En el caso de aplicación, el uso de SOL para apoyar la toma de decisiones en una operación de movimiento de material, permite a los tomadores de decisión acceder a análisis robustos basados en información extraída de los modelos de simulación. SOL, al almacenar información, funcionar vía web, generar análisis automatizados y crear visualizaciones, permite cumplir con las expectativas de los usuarios respecto a una solución integral en simulación.

  14. A Geochemical Mass-Balance Method for Base-Flow Separation, Upper Hillsborough River Watershed, West-Central Florida, 2003-2005 and 2009

    Science.gov (United States)

    Kish, G.R.; Stringer, C.E.; Stewart, M.T.; Rains, M.C.; Torres, A.E.

    2010-01-01

    Geochemical mass-balance (GMB) and conductivity mass-balance (CMB) methods for hydrograph separation were used to determine the contribution of base flow to total stormflow at two sites in the upper Hillsborough River watershed in west-central Florida from 2003-2005 and at one site in 2009. The chemical and isotopic composition of streamflow and precipitation was measured during selected local and frontal low- and high-intensity storm events and compared to the geochemical and isotopic composition of groundwater. Input for the GMB method included cation, anion, and stable isotope concentrations of surface water and groundwater, whereas input for the CMB method included continuous or point-sample measurement of specific conductance. The surface water is a calcium-bicarbonate type water, which closely resembles groundwater geochemically, indicating that much of the surface water in the upper Hillsborough River basin is derived from local groundwater discharge. This discharge into the Hillsborough River at State Road 39 and at Hillsborough River State Park becomes diluted by precipitation and runoff during the wet season, but retains the calcium-bicarbonate characteristics of Upper Floridan aquifer water. Field conditions limited the application of the GMB method to low-intensity storms but the CMB method was applied to both low-intensity and high-intensity storms. The average contribution of base flow to total discharge for all storms ranged from 31 to 100 percent, whereas the contribution of base flow to total discharge during peak discharge periods ranged from less than 10 percent to 100 percent. Although calcium, magnesium, and silica were consistent markers of Upper Floridan aquifer chemistry, their use in calculating base flow by the GMB method was limited because the frequency of point data collected in this study was not sufficient to capture the complete hydrograph from pre-event base-flow to post-event base-flow concentrations. In this study, pre-event water

  15. Laser-ablation electrospray ionization mass spectrometry with ion mobility separation reveals metabolites in the symbiotic interactions of soybean roots and rhizobia

    Energy Technology Data Exchange (ETDEWEB)

    Stopka, Sylwia A. [Department of Chemistry, W. M. Keck Institute for Proteomics Technology and Applications, The George Washington University, Washington DC 20052 USA; Agtuca, Beverly J. [Divisions of Plant Sciences and Biochemistry, C. S. Bond Life Sciences Center, University of Missouri, Columbia MO 65211 USA; Koppenaal, David W. [Environmental Molecular Sciences Laboratory, Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Paša-Tolić, Ljiljana [Environmental Molecular Sciences Laboratory, Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Stacey, Gary [Divisions of Plant Sciences and Biochemistry, C. S. Bond Life Sciences Center, University of Missouri, Columbia MO 65211 USA; Vertes, Akos [Department of Chemistry, W. M. Keck Institute for Proteomics Technology and Applications, The George Washington University, Washington DC 20052 USA; Anderton, Christopher R. [Environmental Molecular Sciences Laboratory, Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA

    2017-05-23

    Technologies enabling in situ metabolic profiling of living plant systems are invaluable for understanding physiological processes and could be used for rapid phenotypic screening (e.g., to produce plants with superior biological nitrogen fixing ability). The symbiotic interaction between legumes and nitrogen-fixing soil bacteria results in a specialized plant organ (i.e., root nodule), where the exchange of nutrients between host and endosymbiont occurs. Laser ablation electrospray ionization mass spectrometry (LAESI-MS) is a method that can be performed under ambient conditions requiring minimal sample preparation. Here, we employed LAESI-MS to explore the well-characterized symbiosis between soybean (Glycine max L. Merr.) and its compatible symbiont, Bradyrhizobium japonicum. The utilization of ion mobility separation (IMS) improved the molecular coverage, selectivity, and identification of the detected biomolecules. Specifically, incorporation of IMS resulted in an increase of 153 detected metabolites in the nodule samples. The data presented demonstrates the advantages of using LAESI-IMS-MS for the rapid analysis of intact root nodules, uninfected root segments, and free-living rhizobia. Untargeted pathway analysis revealed several metabolic processes within the nodule (e.g., zeatin, riboflavin, and purine synthesis). Compounds specific to the uninfected root and bacteria were also detected. Lastly, we performed depth-profiling of intact nodules to reveal the location of metabolites to the cortex and inside the infected region, and lateral profiling of sectioned nodules confirmed these molecular distributions. Our results established the feasibility of LAESI-IMS-MS for the analysis and spatial mapping of plant tissues, with its specific demonstration to improve our understanding of the soybean-rhizobial symbiosis.

  16. Mathematical modeling of separated two-phase turbulent reactive flows using a filtered mass density function approach for large eddy simulation

    Science.gov (United States)

    Carrara, Mark David

    2006-04-01

    The overall objective of this dissertation is the development of a modeling and simulation approach for turbulent two-phase chemically reacting flows. A new full velocity-scalar filtered mass density function (FMDF) formulation for large eddy simulation (LES) of a separated two-phase flow is developed. In this formulation several terms require modeling that include important conditionally averaged phase-coupling terms (PCT). To close the PCT a new derivation of the local instantaneous two-phase equations is presented and important identities are derived relating the PCT to surface averages. The formulation is then applied for two particle laden flow cases and solved using a full particle based Monte-Carlo numerical solution procedure. The first case is a temporally developing counter-current mixing layer dilutely seeded with evaporating water droplets. Validation studies reveal excellent agreement of the full particle method to previous hybrid FDF studies and direct numerical simulations for single-phase flows. One-way coupled simulations reveal that the overall dispersion is maximized with unity Stokes number droplets. Two-way coupled simulations reveal the advantages of two FDF approaches where the subgrid variation of droplet properties are explicitly taken into account. Comparisons of the fully-coupled FDF approach are compared to more approximate means of determining phase-coupling based on filtered properties and local and compounded global errors are assessed. The second case considered is the combustion aluminum particles. A new mechanistic model for the ignition and combustion of aluminum particulate is developed that accounts for unsteady heating, melting, heterogeneous surface reactions (HSR) and quasi-steady burning. Results of this model agree well with experimental data for overall burn rates and ignition times. Two-phase simulations of aluminum particulate seeded mixing layer reveal the variations in flame radius resulting in local extinguishment

  17. Simultaneous Determination of 34 Pesticide Residues in Vegetable Oil by QuEChERS-on-line Gel Permeation Chromatography-Gas Chromatography-Mass Spectrometry%QuEChERS-在线凝胶色谱-气相色谱-质谱法测定植物油中34种农药残留

    Institute of Scientific and Technical Information of China (English)

    阮华; 荣维广; 宋宁慧; 吉文亮; 刘华良; 马永建

    2014-01-01

    A method for the simultaneous determination of 34 pesticides in sunflower oil, soybean oil and corn oil was developed. The samples were extracted and purified by a modified QuEChERS method, and then the supernatant was analyzed by on-line gel permeation chromatography-gas chromatography-mass spectrometry ( GPC-GC-MS ) . The linear range was from 0 . 01 to 0 . 2 mg/L with a good correlation coefficients ( r≥0. 9913). The average recoveries of 31 pesticides (except p,p′-DDE, p,p′-DDD, p,p′-DDT. For detail, please reference to section 3 . 6 ) ranged from 70 . 3% to 115 . 4%, 69 . 5% to 112 . 6% and 70 . 2% to 116 . 1%spiked at 0. 05 μg/g and 0. 1 μg/g with the relative standard deviations (RSDs, n=6) less than 13. 3%, 13. 5% and 12. 1% in sunflower oil, soybean oil and corn oil samples, respectively. The LODs of this method ranged from 0. 0692 to 2. 28, 0. 0559 to 2. 01 and 0. 0584 to 2. 14μg/kg (S/N=3) in sunflower oil, soybean oil and corn oil samples respectively. The convenient operation and versatility of this method are suitable for the fast screening and detection of 34 pesticide residues in sunflower oil, soybean oil and corn oil.%建立了葵花油、大豆油和玉米油中34种中高毒农药的快速筛查方法。样品采用改进的QuEChERS方法进行提取净化,提取液采用在线GPC-GC-MS检测。结果表明,34种农药在0.01~0.2 mg/L范围内具有良好的线性关系,相关系数为0.9913~0.9997。除p,p′-DDE, p,p′-DDD, p,p′-DDT外的31种农药在葵花油、大豆油和玉米油中的检出限分别为0.0692~2.28μg/kg,0.0559~2.01μg/kg,0.0584~2.14μg/kg;在0.05和0.1μg/g添加水平的平均回收率分别为70.3%~115.4%,69.5%~112.6%,70.2%~116.1%;相对标准偏差(RSD, n=6)分别为2.9%~13.3%,3.9%~13.5%,4.2%~12.1%。本方法具有操作便捷、快速等特点,适用于葵花油、大豆油和玉米油中34种农药残留的快速筛查与检测。

  18. High-accuracy mass determination of unstable cesium and barium isotopes

    CERN Document Server

    Ames, F; Beck, D; Bollen, G; De Saint-Simon, M; Jertz, R; Kluge, H J; Kohl, A; König, M; Lunney, M D; Martel, I; Moore, R B; Otto, T; Patyk, Z; Raimbault-Hartmann, H; Rouleau, G; Savard, G; Schark, E; Schwarz, S; Schweikhard, L; Stolzenberg, H; Szerypo, J

    1999-01-01

    Direct mass measurements of short-lived Cs and Ba isotopes have been performed with the tandem Penning trap mass spectrometer ISOLTRAP installed at the on-line isotope separator ISOLDE at CERN. Typically, a mass resolving power of 600 000 and an accuracy of $\\delta \\mbox{m} \\approx 13$ keV have been obtained. The masses of $^{123,124,126}$Ba and $^{122m}$Cs were measured for the first time. A least-squares adjustment has been performed and the experimental masses are compared with theoretical ones, particularly in the frame of a macroscopic-microscopic model.

  19. Determination of anions with an on-line capillary electrophoresis method; Anionien on-line maeaeritys kapillaarielektroforeesilla - MPKT 10

    Energy Technology Data Exchange (ETDEWEB)

    Siren, H.; Saerme, T.; Kotiaho, T.; Hiissa, T.; Savolahti, P.; Komppa, V. [VTT Chemical Technology, Espoo (Finland)

    1998-12-31

    The aim of the study was to set-up an on-line capillary electrophoresis method for determination of anions in process waters of pulp and paper industry with exporting the results to the process control system of the mill. The quantification is important, since it will give information about the possible causes of precipitation. In recent years, the capillary electrophoresis (CE) due to its high separation efficiency has been shown as a method to take into consideration when analyzing chemical species ranging from small inorganic anions to different macromolecules. Many compounds are not easily detected in their native state, why analysis methods must be developed to improve their detection. Especially, small inorganic and organic anions which do not have chromophores are not sensitive enough for direct-UV detection. In such analyses the anions are mostly detected with indirect-UV technique. Capillary electrophoresis instruments are used to analyze samples in off-line, which seldom represent the situation in process. Therefore, on-line instrument technology with autoanalyzing settings will be needed in quality control. The development of a fully automatic capillary electrophoresis system is underway in co-operation with KCL (The Finnish Pulp and Paper Research Institute). In our research, we have first concentrated on the determination of sulphate in waters of paper industry. The method used for detection of sulphate is based on indirect-UV detection with CE, where the background electrolyte (BGE) is an absorbing mixture of secondary amines. The whole procedure for quantification of sulphate is performed within 15 minutes, after which a new sample is analyzed automatically. The only sample pretreatment is filtration, which is necessary before analysis. The concentrations of sulphate in process waters tested were between 300 and 800 ppm. Our tests show that a simultaneous determination of chloride, sulphate, nitrate, nitrite, sulphite, carbonate and oxalate is also

  20. Direct mass measurements beyond the proton drip-line

    CERN Document Server

    Rauth, C; Blaum, K; Block, M; Chaudhuri, A; Eliseev, S; Ferrer, R; Habs, D; Herfurth, F; Hessberger, F P; Hofmann, S; Kluge, H J; Maero, G; Martin, A; Marx, G; Mukherjee, M; Neumayr, J B; Plass, W R; Quint, W; Rahaman, S; Rodríguez, D; Scheidenberger, C; Schweikhard, L; Thirolf, P G; Vorobjev, G; Weber, C; Di, Z

    2007-01-01

    First on-line mass measurements were performed at the SHIPTRAP Penning trap mass spectrometer. The masses of 18 neutron-deficient isotopes in the terbium-to-thulium region produced in fusion-evaporation reactions were determined with relative uncertainties of about $7\\cdot 10^{-8}$, nine of them for the first time. Four nuclides ($^{144, 145}$Ho and $^{147, 148}$Tm) were found to be proton-unbound. The implication of the results on the location of the proton drip-line is discussed by analyzing the one-proton separation energies.

  1. Robust on-line monitoring of biogas processes; Robusta maettekniker on-line foer optimerad biogasproduktion

    Energy Technology Data Exchange (ETDEWEB)

    Nordberg, Aake; Hansson, Mikael; Kanerot, Mija; Krozer, Anatol; Loefving, Bjoern; Sahlin, Eskil

    2010-03-15

    Although demand for biomethane in Sweden is higher than ever, many Swedish codigestion plants are presently operated below their designed capacity. Efforts must be taken to increase the loading rate and guarantee stable operation and high availability of the plants. There are currently no commercial systems for on-line monitoring, and due to the characteristics of the material, including corrosion and tearing, robust applications have to be developed. The objective of this project was to identify and study different monitoring technologies with potential for on-line monitoring of both substrate mixtures and anaerobic digester content. Based on the prerequisites and demands at Boraas Energi och Miljoe AB's (BEMAB, the municipal energy and waste utility in the city of Boraas, Sweden) biogas plant, the extent of the problems, measurement variables and possible ways of managing these issues have been identified and prioritized. The substrate mixtures in question have a high viscosity and are inhomogeneous with variation in composition, which calls for further homogenization, dilution and filtration to achieve high precision in the necessary analyses. Studies of using different mixers and mills showed that the particle size (800 mum) needed for on-line COD measurement could not be achieved. The problem of homogenization can be avoided if indirect measurement methods are used. Laboratory tests with NIR (near-infra red spectroscopy) showed that VS can be predicted (R2=0,78) in the interval of 2-9% VS. Furthermore, impedance can give a measurement of soluble components. However, impedance is not sensitive enough to give a good measurement of total TS. Microwave technology was installed at the production plant and showed a faster response to changes in TS than the existing TS-sensor. However, due to technical problems, the evaluation only could be done during a limited period of ten days. BEMAB will continue the measurements and evaluation of the instrument. The

  2. Comprehensive two-dimensional liquid chromatography: Ion chromatography × reversed-phase liquid chromatography for separation of low-molar-mass organic acids

    NARCIS (Netherlands)

    S.S. Brudin; R.A. Shellie; P.R. Haddad; P.J. Schoenmakers

    2010-01-01

    In the work presented here a novel approach to comprehensive two-dimensional liquid chromatography is evaluated. Ion chromatography is chosen for the first-dimension separation and reversed-phase liquid chromatography is chosen for the second-dimension separation mode. The coupling of these modes is

  3. Force-reflecting teleoperation of robots based on on-line correction of a virtual model

    Institute of Scientific and Technical Information of China (English)

    LIU Wei; SONG Aiguo; LI Huijun

    2007-01-01

    Virtual reality is an effective method to eliminate the influence of time delay.However,it depends on the precision of the virtual model.In this paper,we introduce a method that corrects the virtual model on-line to establish a more precise model.The geometric errors of the virtual model were corrected on-line by overlapping the graphics over the images and also by syncretizing the position and force information from the remote.Then the sliding average least squares (SALS)method was adopted to determine the mass,damp,and stiffness of the remote environment and use this information to amend the dynamic model of the environment.Experimental results demonstrate that the on-line correction method we proposed can effectively reduce the impact caused by time delay,and improve the operational performance of the teleoperation system.

  4. DOE-EPRI On-Line Monitoring Implementation Guidelines

    Energy Technology Data Exchange (ETDEWEB)

    E. Davis, R. Bickford

    2003-01-02

    Industry and EPRI experience at several plants has shown on-line monitoring to be very effective in identifying out-of-calibration instrument channels or indications of equipment-degradation problems. The EPRI implementation project for on-line monitoring has demonstrated the feasability of on-line monitoring at several participating nuclear plants. The results have been very enouraging, and substantial progress is anticipated in the coming years.

  5. Poss On-line (Personalisation of Self-Service Solutions across On-line platforms)

    DEFF Research Database (Denmark)

    Nielsen, Janni; Nielsen, Lene; Jespersen, Mikkel

    2005-01-01

    The project on Personalisation of Self-service Solutions across On-line Platforms (POSS ON-LINE) focuses on users, clients, and self-service solutions. It is based on the understanding that clients and users are different and have different goals, and that self-service takes place in different co...... at the process of development. However, we lack methods to predict user behaviour without having to deal with huge amounts of data and data from both quantitative data as well as life world observations are required....... the client and the user. The system gathers data about the user, which enables the client to push information to the user. Personalisation enables graphic user interface design that is personalised and relevant to the individual user and invites the user to get access to information with less strain....... Personalisation of self-service solutions is promising and IT companies are experiencing an increase in the clients' demands. At the same time the development of solutions moves within a shorter and shorter time span. Hence the process of innovations is paced and there is an increasing need of new ways of looking...

  6. The Resonance Ionization Laser Ion Source RILIS - leading all-rounder of on-line ion sources

    Energy Technology Data Exchange (ETDEWEB)

    Rothe, Sebastian [CERN, Geneva (Switzerland); Institut fuer Physik, Univ. Mainz (Germany); Fedosseev, Valentin; Fink, Daniel; Seliverstov, Maxim [CERN, Geneva (Switzerland); Rossel, Ralf [CERN, Geneva (Switzerland); Institut fuer Physik, Univ. Mainz (Germany); Hochschule RheinMain, Wiesbaden (Germany); Wendt, Klaus [Institut fuer Physik, Univ. Mainz (Germany)

    2012-07-01

    The resonance ionization laser ion source (RILIS) of the on-line isotope separator facility ISOLDE at CERN, is based on the method of stepwise resonant laser excitation and ionization of atoms. The element selectivity of the RILIS complements the mass selection process of the ISOLDE separator magnets to provide high purity ion beams of many isotopes. The RILIS, which now includes two complementary and independent tunable laser systems (dye and titanium:sapphire lasers), has been significantly improved since its first demonstration of selective ionization of Yb isotopes in 1992. Today, on account of the high degree of selectivity for the 27 elements now offered, the annual operation of RILIS exceeds 2500 h, making it the most versatile and commonly used ion source at ISOLDE. The use of a narrow band dye laser enables precision in-source laser spectroscopy of isotope shifts and hyperfine structures of isotopes far from stability as well as the production of isomer pure beams as has been demonstrated for Ag, Cu, Pb, Bi, Po, and Tl. A recent upgrade of the RILIS comprises the incorporation of a complementary all solid state laser system as well as the Laser Ion Source Trap (LIST), which greatly enhances selectivity by suppressing any surface ionized isobars.

  7. Applications of on-line weak affinity interactions in free solution capillary electrophoresis

    DEFF Research Database (Denmark)

    Heegaard, Niels H H; Nissen, Mogens H; Chen, David D Y

    2002-01-01

    The impressive selectivity offered by capillary electrophoresis can in some cases be further increased when ligands or additives that engage in weak affinity interactions with one or more of the separated analytes are added to the electrophoresis buffer. This on-line affinity capillary...... enantiomers and on using capillary electrophoresis to characterize such interactions quantitatively. We describe the equations for binding isotherms, illustrate how selectivity can be manipulated by varying the additive concentrations, and show how the methods may be used to estimate binding constants. On......-line affinity capillary electrophoresis methods are especially valuable for enantiomeric separations and for functional characterization of the contents of biological samples that are only available in minute quantities....

  8. On-line catalytic upgrading of biomass fast pyrolysis products

    Institute of Scientific and Technical Information of China (English)

    LU Qiang; ZHU XiFeng; LI WenZhi; ZHANG Ying; CHEN DengYu

    2009-01-01

    Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) was employed to achieve fast pyrolysis of biomass and on-line analysis of the pyrolysis vapors. Four biomass materials (poplar wood, fir wood, cotton straw and rice husk) were pyrolyzed to reveal the difference among their products. Moreover, catalytic cracking of the pyrolysis vapors from cotton straw was performed by using five catalysts, including two microporous zeolites (HZSM-5 and HY) and three mesoporous catalysts (ZrO2&TiO2, SBA-15 and AI/SBA-15). The results showed that the distribution of the pyrolytic products from the four materials differed a little from each other, while catalytic cracking could significantly alter the pyrolytic products. Those important primary pyrolytic products such as levoglucosen, hydroxyacetaldehyde and 1-hydroxy-2-propanone were decreased greatly after catalysis. The two microporous zeolites were ef-fective to generate high yields of hydrocarbons, while the three mesoporous materials favored the formation of furan, furfural and other furan compounds, as well as acetic acid.

  9. A novel phosphoprotein analysis scheme for assessing changes in premalignant and malignant breast cell lines using 2D liquid separations, protein microarrays and tandem mass spectrometry

    OpenAIRE

    Patwa, Tasneem H; Wang, Yanfei; Miller, Fred R.; Goodison, Steve; Pennathur, Subramaniam; Timothy J Barder; David M Lubman

    2008-01-01

    An analysis of phosphorylation changes that occur during cancer progression would provide insights into the molecular pathways responsible for a malignant phenotype. In this study we employed a novel coupling of 2D-liquid separations and protein microarray technology to reveal changes in phosphoprotein status between premalignant (AT1) and malignant (CA1a) cell lines derived from the human MCF10A breast cell lines. Intact proteins were first separated according to their isoelectric point and ...

  10. Production of neutron deficient rare isotope beams at IGISOL; on-line and off-line studies

    Energy Technology Data Exchange (ETDEWEB)

    Huikari, J. E-mail: jussi.huikari@phys.jyu.fi; Dendooven, P.; Jokinen, A.; Nieminen, A.; Penttilae, H.; Peraejaervi, K.; Popov, A.; Rinta-Antila, S.; Aeystoe, J

    2004-08-01

    This article reports on recent on-line yield measurements employing the light-ion and heavy-ion reaction-based ion guide systems and new results on {alpha}-recoil ion transport properties in ion guides with and without electric fields. In addition, the presently used ion guide designs for fusion evaporation reactions are introduced. The present study investigated different schemes for ion extraction from the gas cell. The addition of an extra ring electrode between the traditional skimmer electrode and the exit hole led to transmission independent of the primary beam intensity as opposed to strong intensity dependence observed earlier with the plain skimmer only. Furthermore, the mass resolving power of the IGISOL mass separator was increased to 1100 as compared to 250 with the skimmer system when using the RF-sextupole for the extraction from the heavy-ion ion guide. As a new method, the possibility to increase the ion guide efficiency by injecting electrons into the stopping volume is introduced. The efficiency of the electron emitter ion guide was a factor of ten higher in off-line conditions. Also, the influence of the buffer gas purity on the ion survival is discussed.

  11. On-line radiochemical assay for monoamine oxidase utilizing high-performance liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Nissinen, E.; Linko-Loeppoenen SMae; Maennistoe P4

    1984-12-01

    A fast and sensitive assay for the determination of monoamine oxidase activity was developed. The method is based on the separation and quantitation of /sup 14/C-labeled assay products by high-performance liquid chromatography, which is interfaced directly into a flow-through radioactivity detector. This allows on-line quantitation of the radioactive compounds with picomole sensitivity. The method makes possible the complete separation and detection of the deaminated products of monoamine oxidase A and B substrates benzylamine and 5-hydroxytryptamine, respectively. This assay has been applied to the measurement of monoamine oxidase A and B activities in rat brain.

  12. On-line method of determining utilization factor in Hg-196 photochemical separation process

    Science.gov (United States)

    Grossman, Mark W.; Moskowitz, Philip E.

    1992-01-01

    The present invention is directed to a method for determining the utilization factor [U] in a photochemical mercury enrichment process (.sup.196 Hg) by measuring relative .sup.196 Hg densities using absorption spectroscopy.

  13. Capillary Separation: Micellar Electrokinetic Chromatography

    Science.gov (United States)

    Terabe, Shigeru

    2009-07-01

    Micellar electrokinetic chromatography (MEKC), a separation mode of capillary electrophoresis (CE), has enabled the separation of electrically neutral analytes. MEKC can be performed by adding an ionic micelle to the running solution of CE without modifying the instrument. Its separation principle is based on the differential migration of the ionic micelles and the bulk running buffer under electrophoresis conditions and on the interaction between the analyte and the micelle. Hence, MEKC's separation principle is similar to that of chromatography. MEKC is a useful technique particularly for the separation of small molecules, both neutral and charged, and yields high-efficiency separation in a short time with minimum amounts of sample and reagents. To improve the concentration sensitivity of detection, several on-line sample preconcentration techniques such as sweeping have been developed.

  14. ON-LINE PREEMPTIVE SCHEDULING ON UNIFORM MACHINES

    Institute of Scientific and Technical Information of China (English)

    ZHANG Yuzhong; WANG Shouyang; Bo Chen; ZHANG Shuxia

    2001-01-01

    We address the problem of preemptively schedule on-line jobs on arbitrary muniformly related machines with the objective of minimizing the schedule length. We provide the first on-line algorithm for this general problem, and show that the algorithm being the speeds of the m machines.

  15. From Off-line to On-line Handwriting Recognition

    NARCIS (Netherlands)

    Lallican, P.; Viard-Gaudin, C.; Knerr, S.

    2004-01-01

    On-line handwriting includes more information on time order of the writing signal and on the dynamics of the writing process than off-line handwriting. Therefore, on-line recognition systems achieve higher recognition rates. This can be concluded from results reported in the literature, and has been

  16. On-Line and Off-Line Assessment of Metacognition

    Science.gov (United States)

    Saraç, Seda; Karakelle, Sema

    2012-01-01

    The study investigates the interrelationships between different on-line and off-line measures for assessing metacognition. The participants were 47 fifth grade elementary students. Metacognition was assessed through two off-line and two on-line measures. The off-line measures consisted of a teacher rating scale and a self-report questionnaire. The…

  17. On-line characterization of a hybridoma cell culture process.

    Science.gov (United States)

    Zhou, W; Hu, W S

    1994-06-20

    The on-line determination of the physiological state of a cell culture process requires reliable on-line measurements of various parameters and calculations of specific rates from these measurements. The cell concentration of a hybridoma culture was estimated on-line by measuring optical density (OD) with a laser turbidity probe. The oxygen uptake rate (OUR) was determined by monitoring dynamically dissolved oxygen concentration profiles and closing oxygen balances in the culture. The base addition for neutralizing lactate produced by cells was also monitored on-line via a balance. Using OD and OUR measurements, the specific growth and specific oxygen consumption rates were determined on-line. By combining predetermined stoichiometric relationships among oxygen and glucose consumption and lactate production, the specific glucose consumption and lactate production rates were also calculated on-line. Using these on-line measurements and calculations, the hybridoma culture process was characterized on-line by identifying the physiological states. They will also facilitate the implementation of nutrient feeding strategies for fed-batch and perfusion cultures. (c) 1994 John Wiley & Sons, Inc.

  18. On-line optimal control of greenhouse crop cultivation.

    NARCIS (Netherlands)

    Straten, van G.

    1996-01-01

    Thus far, optimal control has primarily been investigated for seasonal crop growth optimization. On-line aspects have received much less attention. The decomposition between long term strategies and on-line control, however, is not trivial. Appreciable losses occur when set-points generated by seaso

  19. On-line optimal control of greenhouse crop cultivation.

    NARCIS (Netherlands)

    Straten, van G.

    1996-01-01

    Thus far, optimal control has primarily been investigated for seasonal crop growth optimization. On-line aspects have received much less attention. The decomposition between long term strategies and on-line control, however, is not trivial. Appreciable losses occur when set-points generated by seaso

  20. Determining the solution conformational entropy of oligosaccharides by SEC with on-line viscometry detection.

    Science.gov (United States)

    Morris, Mallory J; Striegel, André M

    2014-06-15

    Introduced here is a method for determining the solution conformational entropy of oligosaccharides (-ΔS) that relies on the on-line coupling of size-exclusion chromatography (SEC), an entropically-controlled separation technique, and differential viscometry (VISC). Results from this SEC/VISC method were compared, for the same injections of the same sample dissolutions and under identical solvent/temperature conditions, to results from a benchmark SEC/differential refractometry (SEC/DRI) method which has been applied successfully over the last decade to determining -ΔS of a variety of mono-, di-, and oligosaccharides. The accuracy (as compared to SEC/DRI) and precision of SEC/VISC were found to be excellent, as was the sensitivity of the viscometer in the oligomeric region. The experiments presented here contrast three sets of (1→4)-β-d-oligosaccharides, namely manno-, cello-, and N-acetylchitooligosaccharides of degree of polymerization (DP) 2 through 6. For each series, the dependence of -ΔS on DP was found to be monotonic while, between series, differences at each DP could be ascribed to either the additional degrees of freedom imparted by large, multi-atomic substituent groups, or to the presence or absence of additional intramolecular hydrogen bonds, depending on the axial versus equatorial arrangement of particular hydroxyl groups. An hypothesis is advanced to explain the unexpectedly high sensitivity of viscometric detection for low-molar-mass analytes. The method presented can be extended to the analysis of oligosaccharides other than those studied here. Published by Elsevier Ltd.

  1. High-accuracy mass determination of neutron-rich rubidium and strontiumiIsotopes

    CERN Document Server

    Raimbault-Hartmann, H; Beck, D; Bollen, G; De Saint-Simon, M; Kluge, H J; König, M; Moore, R B; Schwarz, S; Savard, G; Szerypo, J

    2002-01-01

    The penning-trap mass spectrometer ISOLTRAP, installed at the on-line isotope separator ISOLDE at CERN, has been used to measure atomic masses of $^{88,89,90m,91,92,93,94}$Rb and $^{91- 95}$Sr. Using a resolving power of R $\\!\\scriptstyle\\approx$1 million a mass accuracy of typically 10 keV was achieved for all nuclides. Discrepancies with older data are analyzed and discussed, leading to corrections to those data. Together with the present ISOLTRAP data these corrected data have been used in the general mass adjustment.

  2. Algorithms for semi on-line multiprocessor scheduling problems

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    In the classical multiprocessor scheduling problems, it is assumed that the problems are considered in off-line or on-line environment. But in practice, problems are often not really off-line or on-line but somehow in between. This means that, with respect to the on-line problem, some further information about the tasks is available, which allows the improvement of the performance of the best possible algorithms. Problems of this class are called semi on-line ones. The authors studied two semi on-line multiprocessor scheduling problems, in which, the total processing time of all tasks is known in advance, or all processing times lie in a given interval. They proposed approximation algorithms for minimizing the makespan and analyzed their performance guarantee. The algorithms improve the known results for 3 or more processor cases in the literature.

  3. Separation and identification of polyphenols in apple pomace by high-speed counter-current chromatography and high-performance liquid chromatography coupled with mass spectrometry.

    Science.gov (United States)

    Cao, Xueli; Wang, Cong; Pei, Hairun; Sun, Baoguo

    2009-05-01

    Apple pomace, a by-product in the processing of apple juice, was investigated as a potential source of polyphenols. Two methods of separation and purification of polyphenols from apple pomace extract were established by combination of gel chromatography with high-speed counter-current chromatography (HSCCC) and solvent extraction with HSCCC, respectively. The optimal separation was performed on a Sephadex LH-20 column using gradient aqueous ethanol as eluting solvent from 0% to 100% in increments of 10%. HPLC analysis indicated that main polyphenols existed in fractions eluted between 40% and 50% aqueous ethanol. The fractions of interest from column were separated by HSCCC with the solvent system hexane-ethyl acetate-1% aqueous acetic acid (0.5:9.5:10, v/v/v). Ethyl acetate fractionation of the apple pomace extract followed by direct HSCCC separation by the same solvent system in the volume ratio of 1:9:10 also produced a good separation of the main polyphenols of interest. Six high-purity polyphenols were achieved tentatively and identified by HPLC/MS: chlorogenic acid (1, m/z 354), quercetin-3-glucoside/quercetin-3-glacaside (2, m/z 464), quercetin-3-xyloside (3, m/z 434), phloridzin (4, m/z 436), quercetin-3-arabinoside (5, m/z 434), and quercetin-3-rhamnoside (6, m/z 448). These results provided a preliminary foundation for further development and exploration of apple pomace.

  4. Separation and identification of moxifloxacin impurities in drug substance by high-performance liquid chromatography coupled with ultraviolet detection and Fourier transform ion cyclotron resonance mass spectrometry

    Institute of Scientific and Technical Information of China (English)

    Cai Sheng Wu; Zhi Xin Jia; Bao Ming Ning; Jin Lan Zhang; Song Wu

    2012-01-01

    In this paper,a high-performance liquid chromatography coupled with ultraviolet detection and Fourier transform-ion cyclotron resonance mass spectrometry (HPLC-UV/FTICRMS) method was described for the investigation of impurity profile in moxifloxacin (MOX) drug substance and chemical reference substance.Ten impurities were detected by HPLC-UV,while eight impurities were identified by using the high accurate molecular mass combined with multiple-stage mass spectrometric data and fragmentation rules.In addition,to our knowledge,five impurities were founded for the first time in MOX drug substance.

  5. Mass measurements on radioactive isotopes using the ISOLTRAP spectrometer

    CERN Document Server

    Dilling, J; Kluge, H J; Kohl, A; Lamour, E; Marx, G; Schwarz, S C; Bollen, G; Kellerbauer, A G; Moore, R B; Henry, S

    2000-01-01

    ISOLTRAP is a Penning trap mass spectrometer installed at the on line isotope separator ISOLDE at CERN. Direct measurements of the masses of short lived radio isotopes are performed using the existing triple trap system. This consists of three electromagnetic traps in tandem: a Paul trap to accumulate and bunch the 60 keV dc beam, a Penning trap for cooling and isobar separation, and a precision Penning trap for the determination of the masses by cyclotron resonance. Measurements of masses of unknown mercury isotopes and in the vicinity of doubly magic /sup 208/Pb are presented, all with an accuracy of delta m/m approximately=1*10/sup -7/. Developments to replace the Paul trap by a radiofrequency quadrupole ion guide system to increase the collection efficiency are presently under way and the status is presented. (10 refs).

  6. Precise atomic masses of neutron-rich Br and Rb nuclei close to the r-process path

    CERN Document Server

    Rahaman, S; Eronen, T; Hager, U; Hakala, J; Jokinen, A; Kankainen, A; Karvonen, P; Moore, I D; Pentillä, H; Rinta-Antila, S; Rissanen, J; Saastamoinen, A; Sonoda, T; Äystö, J

    2007-01-01

    The Penning trap mass spectrometer JYFLTRAP, coupled to the Ion-Guide Isotope Separator On-Line (IGISOL) facility at Jyvaskyla, was employed to measure the atomic masses of neutron rich 85 to 92Br and 94 to 97Rb isotopes with a typical accuracy less than 10 keV. Discrepancies with the older data are discussed. Comparison to different mass models is presented. Details of nuclear structure, shell and subshell closures are investigated by studying the two-neutron separation energy and the shell gap energy.

  7. Precise atomic masses of neutron-rich Br and Rb nuclei close to the r-process path

    Energy Technology Data Exchange (ETDEWEB)

    Rahaman, S.; Hager, U.; Elomaa, V.V.; Eronen, T.; Hakala, J.; Jokinen, A.; Kankainen, A.; Karvonen, P.; Moore, I.D.; Penttilae, H.; Rinta-Antila, S.; Rissanen, J.; Saastamoinen, A.; Sonoda, T.; Aeystoe, J. [University of Jyvaeskylae, Department of Physics (YFL) (Finland)

    2007-04-15

    The Penning trap mass spectrometer JYFLTRAP, coupled to the Ion-Guide Isotope Separator On-Line (IGISOL) facility at Jyvaeskylae, was employed to measure the atomic masses of neutron-rich {sup 85-92}Br and {sup 94-97}Rb isotopes with a typical accuracy less than 10keV. Discrepancies with the older data are discussed. Comparison to different mass models is presented. Details of nuclear structure, shell and subshell closures are investigated by studying the two-neutron separation energy and the shell gap energy. (orig.)

  8. Masses of neutron-rich Ni and Cu isotopes and the shell closure at Z=28,N=40

    Energy Technology Data Exchange (ETDEWEB)

    Rahaman, S.; Hakala, J.; Elomaa, V.V.; Eronen, T.; Hager, U.; Jokinen, A.; Kankainen, A.; Moore, I.D.; Penttilae, H.; Rinta-Antila, S.; Rissanen, J.; Saastamoinen, A.; Weber, C.; Aeystoe, J. [University of Jyvaeskylae, Department of Physics, P.O. Box 35 (YFL) (Finland)

    2007-10-15

    The Penning trap mass spectrometer JYFLTRAP, coupled to the Ion Guide Isotope Separator On-Line (IGISOL) facility at Jyvaeskylae, was employed to measure the atomic masses of neutron-rich {sup 70-73}Ni and {sup 73,} {sup 75}Cu isotopes with a typical accuracy less than 5 keV. The mass of {sup 73}Ni was measured for the first time. Comparisons with the previous data are discussed. Two-neutron separation energies show a weak subshell closure at {sup 68} {sub 28}Ni{sub 40}. A well established proton shell gap is observed at Z=28. (orig.)

  9. MODULAR RESEARCH EQUIPMENT FOR ON-LINE INSPECTION IN ADVANCED MANUFACTURING SYSTEMS

    Directory of Open Access Journals (Sweden)

    Davrajh, S.

    2012-11-01

    Full Text Available The significance of inspection processes increases when producing parts with high levels of customer input. These processes must adapt to variations in significant product characteristics. Mass customisation and reconfigurable manufacturing are currently being researched as ways to respond to high levels of customer input. This paper presents the research and development of modular inspection equipment that was designed to meet the on-line quality requirements of mass customisation and reconfigurable manufacturing environments. Simulated results were analysed for application in an industrial environment. The implementation of the equipment in South Africa is briefly discussed. The research indicates that manufacturers need only invest in the required equipment configurations when they are needed for on-line inspection.

  10. A gas chromatograph/mass spectrometry method for determining isotopic distributions in organic compounds used in the chemical approach to stable isotope separation

    Energy Technology Data Exchange (ETDEWEB)

    Martinez, A.M.; Spall, W.D.; Smith, B.F.

    1990-01-01

    A variety of gas chromatograph/mass spectrometry (GC/MS) methods have been developed to resolve benzene, benzophenone, anthracene, fluorenone, and their respective stable isotope analogs from other components by gas chromatography. The ratio of stable isotope-labeled material to natural isotopic abundance compounds is determined from the mass spectra averaged across the chromatographic peak. Both total ion and selective ion chromatographic approaches were used for relative data and comparison. 9 refs., 11 tabs.

  11. Plasma source mass spectrometry in experimental nutrition.

    Science.gov (United States)

    Barnes, R M

    1998-01-01

    The development and commercial availability of plasma ion source, specifically inductively coupled plasma, mass spectrometers (ICP-MS) have significantly extended the potential application of stable isotopes for nutritional modeling. The status of research and commercial ICP-MS instruments, and their applications and limitations for stable isotopic studies are reviewed. The consequences of mass spectroscopic resolution and measurement sensitivity obtainable with quadrupole, sector, time-of-flight, and trap instruments on stable isotope analysis are examined. Requirements for reliable isotope measurements with practical biological samples including tissues and fluids are considered. The possibility for stable isotope analysis in chemically separated compounds (speciation) also is explored. On-line compound separations by chromatography or electrophoresis, for example, have been combined instrumentally with ICP-MS. Som possibilities and requirements are described for stable isotope speciation analysis.

  12. 在线净化液相色谱串联质谱法测定动物源食品中金刚烷胺的残留%Determination of Amantadine Residues in Foods of Animal Origin by On-line Cleanup Liquid Chromatography-Tandem Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    艾连峰; 马育松; 陈瑞春; 郭春海; 康占省

    2013-01-01

    建立了在线净化液相色谱串联质谱法测定动物源食品中金刚烷胺的残留.样品用甲醇-1%三氯乙酸或乙腈提取,提取液用阳离子交换在线净化柱(Cyclone MCX)净化,5%氨水-甲醇溶液将分析物洗脱转入至Capcell Pak MG C18分析柱,经色谱分离后,用串联质谱检测.方法的定量限(LOQ)牛奶为0.25 μg/kg,动物组织和鸡蛋为0.5 μg/kg,在0.1~20 μg/L浓度范围内呈良好线性,线性相关系数大于0.9995.方法在3个水平的添加回收率为83.3%~93.6%,相对标准偏差在3.5% ~5.9%之间.方法简单快速,回收率高,重现性好,适用于动物源食品中金刚烷胺残留的定量及确证分析.%A new method using online cleanup technology combined with tandem mass spectrometry (MS/MS) has been developed for determination of amantadine residues in foods of animal origin.The manual sample preparation was limited to extraction of simples by methanol-1% trichloroactic acid (50∶ 50,V/V) or acetonitrile.The extract was online purified on cyclone MCX column where the sample matrix was washed away while the analytes were retained.Subsequently,the analytes were eluted from the extraction column onto the analytical column (Capcell Pak MG C18 column) by means of 5% ammonia hydroxide methanol solution prior to chromatographic separation and MS/MS detection.The limit of quantization (LOQ) for milk was 0.25 μg/kg,and for animal tissues and egg was 0.5 μg/kg.The linearity is satisfactory with a correlation coefficient of >0.9995 at concentrations ranging from O.1 to 20 μg/L.Average recoveries of the analytes fortified at three levels were range from 83.3% to 93.6%,and the relative standard deviations were range from 3.5% to 5.9%.The method is suitable for quantitative analysis and confirmation of amantadine residues in foods of animal origin.

  13. BRAMA, a Broad Range Atomic Mass Analyzer for the ISL

    Energy Technology Data Exchange (ETDEWEB)

    Nitschke, J.M. [Lawrence Berkeley Lab., CA (United States)

    1994-05-01

    An alternative to conventional on-line isotope separators for use in radioactive beam facilities is described. It consists of an analyzer with a static magnetic field that is capable of separating a wide mixture of (radioactive) ions into mass bins ranging from 6 to 240 u. If incorporated into the ISL, BRAMA would make several low-energy radioactive beams available for experiments simultaneously, in addition to the beam that is being delivered to the post-accelerator. A preliminary ion-optical geometry is discussed.

  14. Electroextraction separation of dyestuffs

    Energy Technology Data Exchange (ETDEWEB)

    Luo, G.S.; Yu, M.J.; Jiang, W.B.; Zhu, S.L.; Dai, Y.Y. [Tsinghua Univ., Beijing (China). Dept. of Chemical Engineering

    1999-03-01

    Electroseparation technologies have prospects for significant growth well into the next century. Electroextraction, a coupled separation technique of solvent extraction with electrophoresis, was used to remove dyestuffs from their aqueous stream. A study on the characteristics of the separation technique was carried out with n-butanol/acid-chrom blue K/water and n-butanol/methyl blue/water as working systems. A continuous separation equipment was designed and sued in this work. The influences of two-phase flow, field strength, and concentration of the feed on the recovery of solute were studied. The results showed that much higher recovery of solute with less solvent consumption could be achieved by using this technique to remove dyes from their aqueous streams, especially for the separation of the dilute solution. When the field strength is increased, the recovery and mass flux increase. When the feed flow rate and the initial solute concentration are increased, the recovery decreases and the mass flux increases.

  15. Capillary electrophoresis-mass spectrometry of carbohydrates.

    Science.gov (United States)

    Zaia, Joseph

    2013-01-01

    The development of methods for capillary electrophoresis (CE) with on-line mass spectrometric detection (CE/MS) is driven by the need for accurate, robust, and sensitive glycomics analysis for basic biomedicine, biomarker discovery, and analysis of recombinant protein therapeutics. One important capability is to profile glycan mixtures with respect to the patterns of substituents including sialic acids, acetate, sulfate, phosphate, and other groups. There is additional need for an MS-compatible separation system capable of resolving carbohydrate isomers. This chapter summarizes applications of CS/MS to analysis of carbohydrates, glycoproteins, and glycopeptides that have appeared since 2008. Readers are referred to recent comprehensive reviews covering earlier publications.

  16. ELECTROCHEMICALLY-MODULATED SEPARATIONS FOR SAFEGUARDS MEASUREMENTS

    Energy Technology Data Exchange (ETDEWEB)

    Green, Michael A.; Arrigo, Leah M.; Liezers, Martin; Orton, Christopher R.; Douglas, Matthew; Peper, Shane M.; Schwantes, Jon M.; Hazelton, Sandra G.; Duckworth, Douglas C.

    2010-08-11

    A critical objective of materials accountability in safeguards is the accurate and timely analysis of fuel reprocessing streams to detect both abrupt and prolonged diversions of nuclear materials. For this reason both on-line nondestructive (NDA) and destructive analysis (DA) approaches are sought-after. Current methods for DA involve grab sampling and laboratory based column extractions that are costly, hazardous, and time consuming. While direct on-line gamma measurements of Pu are desirable, they are not possible due to contributions from other actinides and fission products. Researchers at Pacific Northwest National Laboratory are currently investigating electrochemically-modulated separation (EMS) as a straightforward, cost-effective technology for selective separation of Pu or U from aqueous reprocessing streams. The EMS selectivity is electrochemically controlled and results from the sorption of Pu4+ and U4+ redox states onto the anodized target electrode, allowing for selective accumulation of U or Pu from nitric acid streams to be turned “on” or “off.” It is envisioned that this technology can be utilized to isolate Pu for both NDA and DA analysis. For the NDA approach, rapid Pu analysis by gamma-ray spectroscopy could be performed after chemical clean-up of activation and fission products by EMS. Likewise, in the DA approach, EMS could be used to retain and concentrate the Pu in nanogram quantities on the electrode surface to be transported to the lab for analysis using high precision mass spectrometry. Due to the challenges associated with complex matrices, a systematic investigation of the redox-dependent accumulation of Pu using EMS was necessary, and results will be presented. Approaches to mitigate interelement effects using large surface area cells will also be discussed. The EMS chemistry and spectroscopy for Pu isolation and measurement will be presented, proof-of-principle measurements will be described, and the application of this

  17. On-line sample-pre-treatment schemes for trace-level determinations of metals by coupling flow injection or sequential injection with ICP-MS

    DEFF Research Database (Denmark)

    Wang, Jianhua; Hansen, Elo Harald

    2003-01-01

    for on-line matrix separation and pre-concentration of trace levels of metals with detection by ICP-MS. It highlights some of the frequently applied on-line, sample-pre-treatment schemes, including solid phase extraction (SPE), on-wall molecular sorption and precipitate/(co)-precipitate retention using...... a polytetrafluoroethylene (PTFE) knotted reactor (KR), solvent extraction-back extraction and hydride/vapor generation. It also addresses a novel, robust approach, whereby the protocol of SI-LOV-bead injection (BI) on-line separation and pre-concentration of ultra-trace levels of metals by a renewable microcolumn...

  18. On-line Autonomous Learning Based on Leamerg Expectation

    Institute of Scientific and Technical Information of China (English)

    李利娜

    2008-01-01

    On-line autonomous learning of College English is one of the important reforms in colleges recently.This paper aims to explore the changes of teachers'role in the new on-line setting.The article first reviews the theoretical study of learner autonomy,then makes a practical investigation into the attitude and expectation learners have on teachers through a self-designed questionnaire,and explores that teachers should make an adjustment to their role orientation and changes their roles into motivators,evaluators and resources supphers in the new on-line setting.

  19. On-line Classical Guitar Course: Blogs for Music Education

    OpenAIRE

    José Luis Navarro; Gilles Lavigne; G. Guadalupe Martínez Salgado

    2009-01-01

    This article introduces an on-line course constructed by means of a blog. The tool was the main goal of a research project titled “Develop, Implementation and evaluation of a Hybrid Course Face to face-On Line for Teaching the Beginning to Play the Classical Guitar”. This work was a three steep project in which it was implemented, applied and evaluated. The on-line course was intended to prepare the students to learn the basic principles to start in classical music with the guitar. The result...

  20. Understanding on-line community: the affordances of virtual space

    Directory of Open Access Journals (Sweden)

    Karen Ruhleder

    2002-01-01

    Full Text Available Increasing numbers of on-line venues for learning are emerging as virtual communities become more accessible and commonplace. This paper looks at one particular virtual community, an on-line degree programme at the University of Illinois, Urbana-Champaign, which offers an M.S. in Library and Information Science (called LEEP. It draws on a framework presented by Mynatt, et al. (1998, which provides a lens for talking about on-line community as a set of affordances. This framework is applied to illustrate the interactions, artefacts, and expectations that shape this community.